201036997 六、發明說明： 【發明所屬之技術領域】 本發明係有關一種含有甘油（曱基）丙烯酸酯 (glycerine (meth)acrylate)為原料之胺酯（甲基）丙稀酸 酯（urethane (meth)acrylate)的樹脂組成物。更且，本發 明之樹脂組成物的硬化皮膜由於其硬度、與基材之密著 性、耐刮傷性等優異，捲曲小且亦少有龜裂的產生，因此 可使用作為塑膠膜或小型框體之外塗層（overcoat)。 【先前技術】 目前，除了加工性、透明性之外，在輕量、廉價、光 學特性等各方面優異的塑膠正運用於產業界中。然而，由 於塑膠比玻璃等柔軟而有易於傷及表面之缺點，因此，一 般係在表面上進行外塗層劑的塗佈。外塗層劑之中，以提 高表面硬度為目的之硬塗層劑（hard coating agent)，已 知有聚矽氧（silicone)系塗料、丙烯酸系塗料、三聚氰胺 系塗料等熱硬化梨等數量眾多之物。其中以聚矽氧系硬塗 層劑因性能、品質優異而為主要使用者，然在另一方面卻 有硬化時間長、高價位之缺點。 為此而開發出一種彌補聚矽氧系硬塗層劑之缺點的感 光性之丙烯酸系硬塗劑（參照專利文獻1)而使用。丙烯酸 糸硬塗層劑係經由务、外線專放射線之知射而立即硬化’且 加工處理速度迅速。並且，由於硬度、耐到傷性等優異且 價廉，因而成為硬塗層劑領域之主流。尤其適用在聚酯等 膜的連續加工。 4 321753 201036997 塑膠膜方面係有：肀 氯乙稀膜系膜、聚碳酸醋膜、 性而言，以聚醋膜最被=使臈等’從各種優異特 作為防麵飛散之膜、或汽心旨膜係廣泛地使用 系統廚具之表面防污膜—Ί、白板用表層膜、 視、觸控板、液晶顯示、電子將材料中之⑽平面電 EL顯示___二二示謂p)、有機201036997 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to an urethane (meth) acrylate containing glycerine (meth) acrylate as a raw material. ) acrylate) resin composition. Further, since the cured film of the resin composition of the present invention is excellent in hardness, adhesion to a substrate, scratch resistance, etc., and has little curl and little cracking, it can be used as a plastic film or a small film. Overcoat outside the frame. [Prior Art] In addition to workability and transparency, plastics that are excellent in light weight, low cost, and optical properties are currently used in the industry. However, since the plastic is softer than glass and has a disadvantage of easily damaging the surface, the coating of the overcoating agent is generally performed on the surface. Among the overcoating agents, a hard coating agent for the purpose of improving the surface hardness is known to have a large number of heat-hardened pears such as a silicone coating, an acrylic coating, and a melamine coating. Things. Among them, the polyoxygen-based hard coater is mainly used because of its excellent performance and quality, but on the other hand, it has the disadvantages of long hardening time and high price. For this reason, a photosensitive acrylic hard coating agent (refer to Patent Document 1) which compensates for the defects of the polyoxygen-based hard coat agent has been developed and used. The acrylic enamel hard coating agent is immediately hardened by the radiation of the external and external radiation, and the processing speed is rapid. Further, it is excellent in hardness, scratch resistance, and the like, and is inexpensive, and thus has become the mainstream in the field of hard coat agents. It is especially suitable for continuous processing of films such as polyester. 4 321753 201036997 Plastic film is made up of: 肀 肀 膜 膜 、 、 、 、 、 、 、 、 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚The purpose of the film system is to widely use the surface antifouling film of the system kitchen utensils - Ί, white surface film, visual, touch panel, liquid crystal display, electronic (10) planar electric EL display ___ 二二示说 p) ,organic
G 話及電腦，播放器等的=二主體及開關、行動電 ^ 1寺的電子機盗框體。該等皆為了不 "而k上硬塗層。並且，除了塑膠之膜以外，亦可 對聚反酸^或丙晞酸等之薄片或基板施以硬塗層，而於光 碟或背光周邊的液晶相關構件中使用。 近年來’謀求除了耐刮傷性以外之作為硬塗層性能的 機此性。例如，在設有膜之CRT、LCD、PDP等之顯示體中， 因反射而難以觀看顯示體之晝面’且眼睛亦容易疲勞，因 此’依用途不同而需要進行能防止表面反射之硬塗層處理 (參照專利文獻2)。 除了需求賦予機能性之硬塗層，另外對於硬塗層原本 提升硬度之目的亦進行檢討。例如：專利文獻3中，經由 在樹脂組成物中添加多官能胺酯丙烯酸酯而謀求硬度的提 升。然而’由於所使用之多官能胺酯丙烯酸酯之硬化收縮 大’而出現龜裂的產生等問題。更且，其添加量或組成整 體之構成亦有限制。 含有使甘油（甲基）丙烯酸酯（a)與多元異氰酸酯 (polyisocyanate)化合物（b)反應而得之胺酯（甲基）丙埽 321753 201036997 is曰的樹n成物係記載於專利文獻4以及專利文獻5 中。專，^獻4中記載-種成為以質量平均分子量10, 00。 以上之聚合物及三(丙烯醢氧乙基)異氰脲酸酯為必須之印 刷配線隸焊__㈣㈣収用讀脂組成物，然 並未要求硬度切到傷性，亦未考相I料。在專利文 獻5 _記載-種含有經改f之氧切微粒的立體造塑用組 成物’然而料_卻無任何記載。 [先前專利文獻] [專利文獻] [專利文獻1]曰本特開平9_侧4號公報 [專利文獻2]日本特開平9_1459G3號公報 [專利文獻3]日本如2幅_U3648號公報 [專利文獻4]日本特開日3 62-290705號公報 [專利文獻5]曰本特開平9-87513號公報 【發明内容】 [發明所欲解決之課題] 而嘗臈變薄的傾向中，為了開發更堅硬之外塗 膜的f 料本身之硬度高者、提高交聯度、設定增 專方法’然而卻有龜裂的產生、由於係厚膜交 度k局會產生捲曲等之問題。 物明之目的係為改善上述缺點而提供—種樹脂組 成物可塗成厚膜且硬度優異，同時所賦予 [用以解^會發生—錢裂，从魏狀收縮率低 L用以解決課題之手段] 6 321753 201036997 本發明者料解決上述課如專㈣志進行檢討之社 果’發現具有特定之化合物及級成的樹脂組成物可解決上 述問題，遂而完成本發明。 、 亦即’本發明係有關下述樹脂組成物： ⑴-種樹脂組成物，係包含：使甘油（曱基）丙烯動 與月旨環式多元異氰酸醋化合物反應而得之胺醋（甲基） Ο 酸醋（A)、（曱基）丙稀酸醋⑻、以及光聚合起始劑（〇。、 ⑵-種樹脂組成物，係包含：使甘油（甲基）丙馳醋⑷ 及⑷以狀（甲基）丙烯酸醋⑹）與多元異氛酸醋化合物 (b)反應而得之胺醋（甲基）丙稀酸g旨（η)、（甲基）丙婦酸 酯（B)、以及光聚合起始劑（c)。 (3)如上述（1)或（2)所記載之樹脂組成物，係作為外塗層使 用。 [發明效果] 如依本發明，即提供一種可獲得硬化時之收縮率低、 〇具有高硬度且不發生捲曲或龜裂的硬化皮膜之樹脂組成物 以及利用該樹脂組成物之外塗層劑。 【實施方式】 [用以實施發明之型態] 以下’對本發明進行詳細說明。 本發明之樹脂組成物中所使用的胺酯（甲基）丙婦酸醋 (A)係使甘油（甲基）丙稀酸酯（a)與多元異氰酸酯化合物（b) 反應而得。甘油（甲基）丙烯酸酯（a)所具有之（甲基）丙歸醯 基之數並無特別限定。 321753 201036997 本發明之樹脂组成物中所使用的胺酯（曱基）丙烯酸酯 (A 1)係使甘油（甲基）丙烯酸醋（&)及（a)以外之（甲基）丙 婦酉文S曰（a 1)與多元異氰酸酯化合物（匕）反應而得。甘油（甲 基）丙烯酸酯（a)所具有之（甲基）丙烯醯基之數並無特別限 定。 本發明之樹脂組成物中所使用的甘油（甲基）丙烯酸酯 (a)可列舉如：甘油二丙烯酸酯、甘油二甲基丙烯酸酯、甘 油單丙烯酸酯單甲基丙烯酸酯、二甘油三丙烯酸酯、二甘 油三甲基丙烯酸自旨等。其中以甘油二丙稀_、甘油二甲 基丙烯酸酯、甘油單丙烯酸酯單甲基丙烯酸酯為佳。 本發明之樹脂組成物中所使用的（a)以外之（曱基）丙 烯酸醋U-D ’只要是具有活性氫基者即可而純別限定， 可列舉如：含有羥基之（曱基）丙烯酸酯、新戊四醇 (pentaerythri to 1)類、羥甲基類、環氧基丙烯酸酯類等單 B月έ ·多官能的（曱基）丙豨酸酯。 (a)以外之（甲基）丙烯酸酯（a-1)之例可列舉如：（甲美） 丙稀酸2,乙醋、（甲基）两稀酸2_經丙醋、（甲基）丙婦ς 4-經丁酯、環己燒二甲醇單（甲基）丙稀酸醋、聚乙二醇單 (甲基）丙烯酸醋、聚丙二醇單（曱基）丙烯_、（甲基）丙 稀酸2-祕-3-苯氧基丙§旨等含錢基之（甲基）丙婦酸 醋；新戊四醇三（甲基）丙烯酸醋、新戍四醇四丙稀酸醋、 二新戊四醇三（甲基）丙_醋、二新戍四醇四（甲基）丙婦 酸酯、二新戊四醇五（曱基）丙烯酸醋、二新戊四醇六（甲基） 丙烯酸醋、二新戊四醇二（甲基）丙婦酸§|等新戊四醇類； 321753 201036997 ，經f基丙K甲基）丙_醋等㈣基類；雙紛A二環 氧基丙烯酸酯等環氧基丙烯酸酯類。 义 而且，該等（a)以外之（甲基）丙烤酸醋（ 混合2種以上使用。 平领次 本發明之樹腊組成物中可使用的⑷以外之（甲基）丙 烯酸醋（a-Ι)係以多宫能之（甲基）丙婦酸酯為佳，以3土官能 以上之（甲基）丙稀酸酯更佳，其中尤以新戊四醇三丙稀酸 _、新戊四醇四丙稀酸酯、二新戊四醇五丙_醋、二新 戊四醇六丙稀酸酯或該等之混合物為佳。 本發明之樹脂組成物令可使甩的多元異氛酸酉旨化合物 (b)只要為1分子中含有2個以上異氰酸基之化合物，則無 ，別限定’其例可列舉如：脂肪族系多元異氰酸g旨化合物、 芳香族系多元異氰酸酯化合物、脂環式多元異氰酸酯、該 等之三聚體或多聚體化合物、縮二脲（biuret)型多元異氰 酸酯、脲基甲酸酯（all〇phanate)型多元異氰酸酯等。三聚 〇體或多聚體化合物係指3個異氰酸基形成i或2個以上異 氰脲酸酯（isocyanurate)環構造之化合物。更且，多元異 氰酸酯化合物（b)可單獨或混合2種以上使用。 脂肪族系多元異氰酸酯化合物之例可列舉如：1，6_六 亞曱基一異氰酸醋、異佛爾酮二異氰酸醋、氫化伸甲苯二 異氰酸酯、氫化伸苯二甲基二異氰酸酯、氫化二苯基甲烷 一異氰酸酯、1，3-環己烧二異氰酸酯、l，4-環己烷二異氰 酸醋、二環己基曱烷-4, 4，-二異氰酸酯、間-四甲基苯二甲 基二異氰酸酯、對-四甲基苯二曱基二異氰酸酯、i，4_四亞 9 321753 201036997 曱基二異氰酸酯、1，12-十二（亞甲基）二異氰酸酯、2,2,4- 二甲基環己烧二異氰酸酯、2, 4, 4-三甲基環己烷二異氰酸 醋、2, 2, 4-三甲基六亞甲基二異氰酸酯、2,4,4_三甲基六 亞甲基二異氰酸酯、離胺酸二異氰酸酯、降莰烷二異氰酸 酯等。 芳香族系多元異氰酸酯化合物之例可列舉如：伸甲苯 二異氰酸酯、伸苯基二甲二異氰酸酯、二苯基甲烷二異氰 酉夂酉曰I 5-奈—異氰酸酯、二曱基聯苯胺（t〇Hdine)二異 氰酸酯、1，4-伸苯二異氰酸酯、1, 6_伸苯二異氰酸酯等。 脂裱式多元異氰酸酯之例可列舉如：環己烷二異氰酸 酯、氳化伸甲苯二異氰酸酯、二曱基環己烷二異氰酸酯、 4’4-亞甲基雙（環己基異氰酸酯）、異佛爾酮二異氰酸酯、 一環庚烧二異氰酸酯、降莰烧二異氰酸酯等。 本發明中之多元異氰酸酯化合物（b)係以脂肪族系多 元異氰酸酯化合物為佳’以脂環式多元異氰酸酯更佳，尤 以異佛爾酮二異氰酸酯以及異佛爾酮二異氰酸酯之三聚體 或多聚體化合物等為最佳。 本發明中所使用之胺酯（甲基）丙烯酸酯（〇係經由使 :油（甲基）丙烯酸酯（a)與多元異氰酸酯化合物（1〇(以脂 環式夕元異氰酸酯化合物為佳）反應而得。（A_ 1)可經由使 甘油（甲基）丙烯酸酯（a)及（a)以外之（甲基）丙烯酸酯（a」） 與多元異氰酸酯化合物（b)反應而得。（A)與（Ay)可分別單 獨地在本發明之樹脂組成物中使用，亦可合併使用。相對 於甘油（甲基）丙烯酸醋（a)與（a)以外之（甲基）丙稀酸酯 321753 10 201036997 (a-l)中的1當量活性氫基，多元異氰酸酯化合物（b)中 異氰酸基當量一般在0.1至50當量之範圍，以〇】 υ. 1 至 10 當量之範圍為佳。反應溫度一般在30至150°c，以5() i 10 0 °c之範圍為佳。反應之終點係以與過量的正丁基胺反應、 並以1N鹽酸反滴定的方法算出殘餘之異氰酸酯量，以異^ 酸酯成為0.5質量％以下時作為終點。 Ο 〇 以縮短該等反應時間為目的亦可添加觸媒。該觸媒可 使用鹼性觸媒以及酸性觸媒之任一種。鹼性觸媒之例可歹4 舉如：吡啶、吡咯、三乙基胺、二乙基胺、二丁基胺、气 等胺類；三丁基膦、三苯基膦等膦類。酸性觸媒之例可列 舉如：環烷酸銅、環烷酸鈷、環烷酸辞、三丁氧基銘、四 丁氧基三鈦、四丁氧基锆等金屬烷氧化物類；氯化銘等路 易士酸類；2-乙基己烷錫、三月桂酸辛基錫、二月桂酸_ 丁基錫、二乙酸辛基錫等錫化合物。該等觸媒之添加量相 對於100質量份之多元異氰酸酯化合物（b)，一般為〇工質 量份以上1質量份以下。 、 另外，在反應時，為防止反應中之聚合而宜使用卩且％ 劑（例如：對甲氧基齡（p-methoxyphenol)、2, 4-二甲武 第二丁基驗、3-經基硫驗、對苯酿；、2，.5-二經基〜對苯酿 吩噻嗪（phenothiazine)等），該阻聚劑之使用量相對於反 應混合物係〇.〇1質量％以上1質量％以下，較佳者為〇的 質量％以上0.5質量％以下。反應溫度為60至15(rc，以 至120°C為佳。 本發明之樹脂組成物中，以本發明之樹脂組成物的固 321753 11 201036997 形分作為100質量％時，上述（A)及/或（A-l)之使用量係一 般在5質量％以上97質量％以下，以21質量％以上80質量％ 以下為佳。 本發明中所使用之（甲基）丙烯酸酯（幻並無特別限 定’惟可列舉如：單官能（甲基）丙烯酸酯、2官能（甲基） 丙烯酸酯、3宫能以上之（子基）丙烯酸酯、聚酯（$基）丙 烯酸酯、胺酯（甲基）丙烯酸酯低聚體、聚酯（甲基）丙烯酸 酯低聚體、環氧基（曱基）丙烯酸酯低聚體等。 單官能（甲基）丙烯酸酯之例可列舉如：丙烯醯基嗎啉 (acryioyimorphoiine) ; (f 基）丙烯酸 2_ 羥丙酯、（甲基） 丙烯酸4-羥丁酯等含有羥基之（甲基）丙烯酸酯；環己烷 -1,4-一甲醇單（甲基）丙烯酸酯、（曱基）丙烯酸四氫呋喃曱 酉曰、（甲基）丙烯酸異莰酯、（曱基）丙烯酸二環戊酯、（甲基） 丙烯酸二環戊烯酯、（甲基）丙烯酸二環戊烯氧基乙酯等^旨 肪族（甲基）丙烯酸酯；（甲基）丙烯酸苯氧基乙酯、（聚）乙 氧基（甲基）丙烯酸苯酯、（甲基）丙烯酸對異丙苯基苯氧基 乙醋、（甲基）丙烯酸三溪苯氧基乙醋、（曱基）丙烯酸苯^ 基以旨、（甲基）丙烯酸2-經基-3-苯氧基丙醋、苯基紛（聚） 乙氧基（曱基）丙烯酸酯、苯基酚環氧基（曱基）丙烯酸酯等 芳香族（曱基）丙烯酸酯。 2官能（曱基）丙烯酸酯之例可列舉如·· u—丁二醇二 (甲基）丙烯酸醋、1，6-己二醇二（曱基）丙烯酸酷、u 一壬 二醇二（甲基）丙烯酸醋、三環癸烧二甲醇（甲基）丙稀酸 酉旨、雙盼Α(聚）乙氧基二（甲基）丙烯酸醋、魏Α(聚）丙氧 321753 12 201036997 . 基二（甲基）丙烯酸酯、雙酚F(聚）乙氧基二（甲基）丙婦酸 酯、乙二醇二（曱基）丙烯酸酯、（聚）乙二醇二（甲基）丙烯 酸酯、羥基特戊酸新戊二醇酯之ε —己内酯加成物之二（甲 基）丙烯酸酯（例如：日本化藥（股）製造之KAyARAI) HX-220、HX-620 等）等。 3官能以上之多官能（甲基）丙烯酸酯之例可列舉如： 二-三羥甲基丙烷四（甲基）丙烯酸酯、三羥甲基丙烷三（甲 ❹基）丙烯酸酯、三羥甲基辛烷四（甲基）丙烯酸酯、三羥甲基 丙烷聚乙氧基三（甲基）丙烯酸酯、三羥甲基丙烷（聚）丙氧 基三（甲基）丙烯酸酯、三羥甲基丙烷（聚）乙氧基（聚）丙氧 基三（甲基）丙烯酸酯等羥甲基類；新戊四醇三（甲基）丙烯 酸酯、新戊四醇聚乙氧基四（甲基）丙烯酸酯、新戊四醇（聚） 丙氧基四（甲基）丙烯酸酯、新戊四醇四（甲基）丙烯酸酯、 一新戊四醇四（甲基）丙烯酸酯、二新戊四醇五（甲基）丙烯 酸酯、二新戊四醇六（甲基）丙烯酸酯等新戊四醇類；三[(曱 〇基）丙埽醯乳基乙基]異氰脲酸醋、經己内酯改質之異氰脲 酸三[(甲基）丙烯醯氧基乙基]酯等；雙酚A二環氧基丙烯 I Ss等ί哀氧基丙稀酸醋類。 (聚）酯（曱基）丙稀酸酯之例可列舉如：乙二醇、二乙 〜醇、二乙二醇、丙二醇、二丙二醇、三丙二醇、新戊二 醇、聚乙二醇、聚丙二醇等二醇類、丨，4_丁二醇、16—己 二醇、1，8-辛二醇、1，9-壬二醇、2_甲基4,8-辛二醇、3_ 甲基1’5戊一醇、2, 4-二乙基-1,5-戊二醇、2-丁基-2- 乙基-1,3-丙二醇等直鏈或分支的烷二醇類、環己烷-丨“一 321753 13 201036997 二甲醇等脂環式烷二醇類、雙酚A(聚）乙氧基二醇或雙酚A (聚）丙氧基一醇等二醇化合物與上述二元酸或其酐的反應 物之（聚）酯二醇與（甲基）丙烯酸之反應物等。 胺酯（曱基）丙烯酸酯低聚體之例可列舉如：使二醇化 合物（例如：乙二醇、二乙二醇、三乙二醇、丙二醇、二丙 二醇、三丙二醇、丨，4—丁二醇、新戊二醇、丨，6—己二醇、 1，8-辛二醇、i，9_壬二醇、2一甲基“，^辛二醇、3—甲基 -1，5-戊二醇、2,4_二乙基戊二醇、2_ 丁基_2_乙基 -1,3-丙二醇、環己烷一 1>4_二甲醇、聚乙二醇、聚丙二醇、 雙酚A聚乙氧基二醇、雙酚A聚丙氧基二醇等）、或該等二 醇化合物與二元酸或其酐（例如：琥珀酸、己二酸、壬二酸、 ，聚酸、異酞酸、義酸、賴或該等之酐）的反應物之聚 酉曰醇與有機多元異氰酸醋（例如：四亞甲基二显着醢 六亞f基二異氰酸酯、2,2,4_三^基六亞甲基二異氰 駄酉曰、2’4, 4-三曱基六亞曱基二異氰酸酯等鏈狀飽和烴異 氰酸酯、異佛爾酮二異氰酸酉旨、降获燒二異氰酸醋、二環 己基甲垸二異氰酸酯、亞甲基雙（4_環己基異氛酸醋）、氫 化=苯基甲燒二異氰酸醋、氳化二甲苯二異氰酸醋、氮化 甲本二異氰酸酯等環狀飽和烴異氰酸酯、2,4一伸甲苯二異 氰H 1,3-伸苯二甲基二異氰酸g旨、對伸笨二異氰酸醋、 士3’-二子基_4,4，_二異氰酸醋、6_異丙約，3_苯基二異 、1，5-萘二異氰酸醋等芳香族多元異氛酸醋）反應， u後再加成含有經基之（甲基）丙稀酸醋的反應物等。 (聚）酯（甲基）丙烯酸酯低聚體之例可列舉如··上述二 321753 14 201036997 醇化合物與上述二元酸或其酐之反應物的（聚）酯二醇與 (甲基）丙烯酸之反應物等。 〃 本發明之樹脂組成物中，以本發明之樹脂組成物的固 形分作為1〇〇質量％時，上述（Β)成分之使用量係一般在〇 質量％以上94質量％以下，以20質量％以上79質量％以下為 佳。 * Ο Ο 本發明之樹脂組成物中，依需要而使用的光聚合起始 劑（C)之例可列舉如：安息香（benzoin)、安息香甲_、安 息香乙醚、安息香丙醚、安息香異丁醚等安息香類；苯乙 酮、2,2-· —乙氧•基—2-本基苯乙酮、ι，ΐ-二氯苯乙嗣、2一 羥基-2-曱基-苯基丙烷-1-酮、二乙氧基笨乙酮、卜經基環 己基苯基酮、2-曱基-1-[4-(甲硫基）苯基]-2_嗎啉基丙燒 -：!-酮等苯乙酮類；2-乙基蒽醌、2-第三丁基蒽醌、2_氯策 酉昆、2 -戊基恩酿專恩S昆類，2，4 _二乙基嗟嘲_ (2, 4-diethylthioxanthone)、2-異丙基噻噸鲷、2一氣養嘴 酮等噻噸酮類；苯乙酮二曱基縮酮、苯偶醯二甲基縮酿^ (benzil dimethyl ketal)等縮酮類；二苯甲調、苯甲酿 基-4’-曱基二苯基硫醚、4, 4’-二甲基胺基二苯甲_等二笨 曱酮類；2, 4, 6-三甲基苯曱酸基二苯基氧化膦、雙（2 & g 三甲基苯甲醯基）苯基氧化膦等氧化膦類等。並且，具體而 言，可容易從市面上獲得汽巴精化公司(Ciba Specialty Chemicals)製造之Irgacure 184(1-羥基環己基苯基酿j)、 Irgacure 907(2-甲基-1_(4-(曱硫基）苯基）-2-嗎琳基丙 烷-卜酮）、BASF公司製造之Lucirin TP0(2, 4, 6-三甲基苯 321753 15 201036997 該等可單獨或混合2種以 甲醯基二苯基氧化膦）等。並且， 上使用。 形分作為1〇〇質量％時， 質量％以上10質量％以下， 本發明讀敝成物巾’林發日狀樹驗成物的固 上述（C)成分之使用量係一般在〇 以1質量％以上7質量％以下為佳。 並且，本發明中亦可使用硬化促進劑（D)。可使用之硬 化促進劑之例可列舉如：三乙醇胺、二乙醇胺、N_乙基二 乙醇胺2甲胺基乙基苯曱酸醋、二甲胺基苯乙嗣、對二 甲胺基苯曱酸異胺酯、EPA等胺類；2—疏基苯并書唾等供 氫體（hydrogen donor)。以本發明之樹脂組成物的固形分 作為100質K時’該等硬化促進劑之使用量係一般在〇質 量％以上5質量％以下。 本發明之樹脂組成物中，依需要而使用的稀釋劑（E) 之例可列舉如：丁内酯、r-戊内酯、7 _己内酯、r_ 庚内δ曰、α-乙醯基—r _丁内酯、ε _己内酯等内酯類；二 %烷、1’ 2-二曱氧基曱烷、二乙二醇二曱醚、二乙二醇二 乙醚、一乙二醇二丁醚、丙二醇單曱醚、丙二醇單乙醚、 三乙二醇二甲醚、三乙二醇二乙醚、四乙二醇二甲醚、四 乙一醇二乙醚等醚類；碳酸伸乙酯、碳酸伸丙酯等碳酸酯 類，曱基乙基酮、曱基異丁基g同、環己酮、苯乙酮等酮類； 酚、甲酚、二甲酚等酚類；乙酸乙酯、乙酸丁酯、乳酸乙 酉曰、乙基溶纖劑乙酸酯（ethyi cellosolve acetate)、丁 基溶纖劑乙酸酯、卡必醇乙酸酯、丁基卡必醇乙酸酯、丙 二醇單曱醚乙酸酯等酯類；曱苯、二曱苯、二乙苯、環己 321753 16 201036997 烷等烴類；三氯乙烷、四氯乙烷、單氯笨等_化烴類等； 石油醚、石油腦（petroleum naphtha)等石油系溶劑等有 溶劑類；2H，3H-四氟丙醇等氟系醇類、全氟丁基^美醚 全氟丁基乙基醚等氫氟趟類；曱醇、乙醇、異丙醇、正 醇等醇類；兼具酮與醇雙方性能之二丙酮醇等。該等可$ 獨或混合2種以上使用。 本發明之樹脂組成物中，相對於本發明樹脂紐成物之 總量，上述（E)成分之使用量係在〇質量％以上90質量％以 〇 下之範圍’以〇質量°/◦以上80質量％以下為佳。 ° 更且，本發明之樹脂組成物中，亦可依所需而在本發 明之感光性樹脂組成物中添加流平劑、消泡劑、紫外、線吸 收劑、光安定劑、抗氧化劑、阻聚劑、交聯劑等，以賦予 各個目的之機能性。流平劑可列舉如：氟系化合物、聚石夕 氧系化合物、丙烯酸系化合物等；紫外線吸收劑可列舉如： 苯并三0坐系化合物、二苯曱酮系化合物、三哄系化合物等. ❹光安定劑可列舉如：受阻胺系化合物、苯曱酸酯系化合物 等；抗氧化劑可列舉如：驗系化合物等；阻聚劑可列舉如： 曱氧基酚、甲基氫醌、氫醌等；交聯劑可列舉如：上述多 元異氰酸酯類、三聚氰胺化合物等。 本發明之樹脂組成物可經由將上述（A)成分、（A-1)成 分、（B)成分、（C)成分，及依所需之（的金分、'務)喊分以 及其它成分以任意順序混合而獲得。 — 本發明之樹脂組成物係在基材上塗布上述樹脂組成 物，使該樹脂組成物在乾燥後之膜厚一般成為0. lym以上 321753 201036997 50 # m以下，以1 # m以上20 // m以下為佳，並在乾燥後經 由照射紫外線而形成硬化膜即可獲得。 基材膜之例可列舉如：聚酯、聚丙烯、聚乙烯、聚丙 烯酸酯、聚碳酸酯、三醋酸纖維素、聚醚砜、環烯烴系聚 合物等。所使用之膜可為設有花樣或易接著層者、經電暈 處理等之表面處理者、經脫模處理者。 上述樹脂組成物之塗佈方法之例可列舉如：棒式塗 佈、線棒式塗佈、氣刀塗佈、凹版印刷塗佈、反向式凹版 印刷塗佈、微凹板印刷塗佈、微反向式凹版印刷塗佈、模 具式塗佈、浸潰塗佈、旋轉塗佈、喷霧塗佈等。 為了硬化可照射紫外線，但亦可使用電子束等。經由 紫外線硬化時，光源係使用具有氤燈、高壓水銀燈、金屬 鹵素燈等之紫外線照射裝置，可依所需而調整光量、光源 的配置等。在使用高壓水銀燈時，相對於1盞具有80至 120W/cm2能量之燈，以輸送速度5至60m/分鐘使之硬化者 為佳。另外，經由電子束使之硬化時，以使用具有100至 500eV能量之電子束加速裝置者為佳，此時亦可不使用光 聚合起始劑（C)。 本發明之樹脂組成物係作為印墨；鋁、鐵、銅等金屬； 氯乙烯、丙烯酸、聚碳酸酯、聚對酞酸伸乙酯、聚乙烯、 聚丙烯等塑膠；玻璃等陶瓷材料；木材、紙、印刷紙、纖 維等之各種塗佈材，而可使用在表面處理劑、結合劑 (binder)、塑膠材料、成形材料、積層板、接著劑、黏著 劑等之用途。更具體之用途係可使用在平凸版印墨、柔版 18 321753 201036997 印墨（f 1 exographic ink)、凹版印墨、網版印墨等印墨領 域；光面漆領域；紙塗佈劑領域；木工用塗料領域；飲料 罐用塗佈劑或印刷印墨領域；軟包裝膜塗佈劑、印刷印墨 或黏著劑、感熱紙、感熱膜用塗佈劑、印刷印墨、接著劑、 黏著劑或光纖塗佈劑、成型加工用膜塗佈劑等之用途上。 在上述用途中，本發明之樹脂組成物在硬化時的收縮 率低，具有高硬度，且並無產生捲曲或龜裂之情形，因此 特別有用於塑膠膜或小型框體之硬塗層劑等之用途上。 ❹（實施例） 以下，經由實施例而更詳加說明本發明，然本發明並 不受限於該等實施例。並且，實施例中，如無特別限定，「份」 係表示「質量份」。 合成例1 在備有回流冷卻器、攪拌機、溫度計、溫度調節裝置 之反應器中，添加甘油單丙稀酸醋•單甲基丙烯酸酉旨 Q 344. 35g(l. 54莫耳）、作為阻聚劑之4-甲氧基酚0. 25g、 作為胺酯化反應觸媒之二月桂酸二丁基錫0. 25g並攪拌至 均勻，使内部溫度成為50°C。接著於内部溫度不超出80 °〇下，滴入異佛爾酮二異氰酸酯155. 65g(0. 70莫耳），添 加後於80°C反應，在NC0含量成為0. 1%以下之時點結束反 應，得到胺酯丙烯酸酯。 合成例2 在備有回流冷卻器、攪拌機、溫度計、溫度調節裝置 之反應器中，添加甘油單丙烯酸酯•單甲基丙烯酸酯 19 321753 201036997 262. 60g(l. 17莫耳）、甲基乙基酮125. 00g、作為阻聚劑之 4-曱氧基酚0. 25g、作為胺酯化反應觸媒之二月桂酸二丁 基錫0. 25g並攪拌至均勻，使内部溫度成為50°C。接著於 内部溫度不超出80°C下，滴入T-1890(異佛爾酮二異氰酸 酯3聚體）237.4(^(0.36莫耳），添加後於80°0：反應，在 NC0含量成為0.1%以下之時點結束反應，得到含有80%胺 酯丙烯酸酯的樹脂溶液。 合成例3 在備有回流冷卻器、攪拌機、溫度計、溫度調節裝置 之反應器中，添加甘油單丙烯酸酯•單甲基丙烯酸酯 187. 14g(0. 84莫耳）、新戊四醇三丙烯酸酯與新戊四醇四 丙烯酸酯之混合物（質量份混合比：65/35 ;羥基當量： 458.9g/Eq)187.08g(0.41莫耳）、作為阻聚劑之4-曱氧基 酚0. 25g、作為胺酯化反應觸媒之二月桂酸二丁基錫0. 25g 並攪拌至均勻，使内部溫度成為50°C。接著於内部温度不 超出80°C下滴入異佛爾酮二異氰酸酯125.78g(0.57莫 耳），添加後於80°C反應，在N⑶含量成為0. 1%以下之時 點結束反應，得到胺酯丙烯酸酯。 合成例4 在備有回流冷卻器、攪拌機、溫度計、溫度調節裝置 之反應器中，添加甘油單丙烯酸酯•單甲基丙烯酸酯80. 42g (0. 36莫耳）、新戊四醇三丙烯酸酯與新戊四醇四丙烯酸酯 之混合物（質量份混合比：65/35 ;羥基當量：458.9g/Eq) 240. 83g(0. 52莫耳）、甲基乙基酮125. 00g、作為阻聚劑之 20 321753 201036997 4-曱氧基酚0. 25g、作為胺酯化反應觸媒之二月桂酸二丁 基錫0.25g並攪拌至均勻，使内部溫度成為5(TC。接著於 内部溫度不超出80°C下滴入T -1890(異佛爾酮二異氰酸酯 3聚體）178. 75g(〇.27莫弄），添加後於8〇°C反應，在NCO 含量成為0.1%以下之時點結束反應’得到含有80%胺酯丙 烯酸醋的樹脂溶液。 合成例5 在備有回流冷卻器、授摔機、溫度计、溫度調節裝置 之反應器中，添加甘油單丙烯酸酯•單甲基丙烯酸酯 149. 51g(0. 67莫耳）、新戊四醇三丙烯酸酯與新戊四醇四 丙烯酸酯之混合物（質量份混合比：65/35 ;羥基當量： 458. 9g/Eq)149. 50g(0. 33 莫耳）、甲基乙基酮 125. 00g、作 為阻聚劑之4-曱氧基酚〇. 25g、作為胺酯化反應觸媒之二 月桂酸二丁基錫0.25g並攪拌至均勻’使内部溫度成為50 ◦C。接著於内部溫度不超出8〇°C下滴入T-1890(異佛爾酮 ◎二異氰酸酯3聚體）200. 99g(〇. 3〇莫耳），添加後於80°C 反應，在NC0含量成為0. 1%以下之時點結束反應，得到含 有80%胺酯丙烯酸酯的樹脂溶液。 合成例6 在備有回流冷卻器、攪拌機、溫度計、溫度調節裝置 之反應器中，添加甘油單丙烯酸酯•單曱基丙烯酸酯 209. 60g(0. 94莫荨）、新戊四醇三丙烯酸酯與新戊四醇四 丙烯酸酯之混合物（質量份混合比：65/35 ;羥基當量： 458. 9g/Eq)70. 〇7g(〇. 15 莫耳）、甲基乙基酮 125. 00g、作 21 321753 201036997 為阻聚劑之4-曱氧基酚0. 25g、作為胺酯化反應觸媒之二 月桂酸二丁基錫0. 25g並攪拌至均勻，使内部溫度成為50 °C。接著於内部溫度不超出80°C下滴入T-1890(異佛爾酮 二異氰酸酯3聚體）220. 34g(0. 33莫耳），添加後於80°C 中反應，在N⑶含量成為0. 1 %以下之時點結束反應，得到 含有80%胺酯丙烯酸酯的樹脂溶液。 合成例7 在備有回流冷卻器、攪拌機、溫度計、溫度調節裝置 之反應器中，添加甘油單丙烯酸酯•單曱基丙烯酸酯 197.71g(0.88莫耳）、二新戊四醇五丙烯酸酯與二新戊四 醇六丙烯酸酯之混合物（質量份混合比：40/60 ;羥基當量： 1311. 2g/Eq)197. 69g(0. 15莫耳）、作為阻聚劑之4-甲氧基 酚0. 25g、作為胺酯化反應觸媒之二月桂酸二丁基錫0. 25g 並攪拌至均勻，使内部溫度成為50°C。接著於内部溫度不 超出80°C下滴入異佛爾酮二異氰酸酯104.60g(0.47莫 耳），添加後於80°C反應，在NCO含量成為0. 1%以下之時 點結束反應，得到胺酯丙烯酸酯。 合成例8 在備有回流冷卻器、攪拌機、溫度計、溫度調節裝置 之反應器中，添加甘油單丙烯酸酯•單甲基丙烯酸酯 163.51g(0.73莫耳）、二新戊四醇五丙烯酸酯與二新戊四 醇六丙烯酸酯之混合物（質量份混合比：40/60 ;羥基當量： 1311. 2g/Eq)163. 49g(0. 36 莫耳）、曱基乙基酮 125. 00g、 作為阻聚劑之4-曱氧基酚0. 25g、作為胺酯化反應觸媒之 22 321753 201036997 一。月桂馱一丁基錫〇. 25g並攪拌至均勻，使内部溫度成為 50C。接著於内部溫度不超出8〇。〇下滴入了_189〇(異佛爾 酮-異3聚體）173. Qig(〇. 26莫耳），添加後於80 °C反應’在NC0含量成$ 〇·1%以下之時點結束反應，得到 含有80%胺酯丙烯酸酯的樹脂溶液。 比較合成例1 在備有回流冷卻器、攪拌機、溫度計、溫度調節裝置 之反應器中，添加甘油單丙烯酸酯•單甲基丙烯酸酯 372.58g(l.67莫耳）、作為阻聚劑之4_甲氧基酚〇.25忌、 作為胺Sa化反應觸媒之二月桂酸二丁基錫〇. 並攪拌至 均勻，使内部溫度成為5〇t：。接著於内部溫度不超出8〇 C下滴入六亞甲基二異氰酸酯127.42g(0.76莫耳），添加 後於反應’在_含量成為1%以下之時點結束反 應，得到胺酯丙烯酸酯。 比較合成例2 在備有回流冷卻器、攪拌機、溫度計、溫度調節裝置 之反應器中，添加新戊四醇三丙烯酸酯與新戊四醇四丙烯 酸酯之混合物(質量份混合比:65/35:羥基當量:458.9g/Eq) 4〇9· 77g(0.89莫耳）、作為阻聚劑之4一甲氧基酚〇.25g、 作為胺酯化反應觸媒之二月桂酸二丁基錫〇 並攪拌至 均勻使内邻度成為5〇。〇。接著滴入異佛爾酮二異氰酸 酯90.23g(0.41莫耳）且使内部溫度不超出8〇。〇，添加後 於80 C中反應’在NCO含量成為0. 1%以下之時間點結束反 應’得到胺酯丙烯酸§旨。 23 . 321753 201036997 比較合成例3 在備有回流冷卻器、攪拌機、溫度計、溫度調節裝置 之反應器中，添加二新戊四醇五丙烯酸醋與二新戊四醇六 丙烯酸酯之混合物（質量份混合比：40/60 ;羥基當量： 1311.2g/Eq)464. 23g(0.35莫耳）、作為阻聚劑之4-甲氧基 酚0. 25g、作為胺酯化反應觸媒之二月桂酸二丁基錫0. 25g 並攪拌至均勻，使内部溫度成為50°C。接著於内部溫度不 超出80°C下滴入異佛爾酮二異氰酸酯35.77g(0. 16莫 耳），添加後於80°C中反應，在上述NCO含量成為0. 1%以 下之時點結束反應，得到胺酯丙烯酸酯。 實施例1至10以及比較例1至5 將調配有表1及表2所示材料之樹脂組成物以棒式塗 佈器塗佈於經易接著處理之PET膜（膜厚125# m)上，以約 80至100 °C乾燥後，經紫外線照射器（japan Storage Battery Co. Ltd. : CS30L-1-1)以高壓水銀燈：i20W/cm; 燈高度：10cm;輸送帶速度：l〇m/分鐘（能量：約300roW/cm2、 約200mJ/cm2)之條件使其硬化，得到膜厚約之硬塗層 膜。同時’表1及表2中之單位以「份」表示。 321753 24 201036997 [表l] 實施例1 實施例2 實施例3 實施例4 實施例5 實施例6 實施例7 實施例8 實施例9 實施例10 合成例1之化合物 30 合成例2之化合物 37.5 50 合成例3之化合物 30 合成例4之化合物 37.5 合成例5之化合物 37.5 50 合成例6之化合物 37.5 合成例7之化合物 30 合成例8之化合物 37.5 DPHA *1 20 20 20 20 20 20 20 20 10 10 ΜΕΚ η 50 42.5 50 42.5 42.5 42.5 50 42.5 40 40 Irg. 184 5 5 5 5 5 5 5 5 5 5G words and computers, players, etc. = two main body and switch, mobile electric ^ 1 temple electronic pirate frame. These are all not for " and k hard coating. Further, in addition to the plastic film, a thin coating or a substrate such as a polyacid or a propionate may be applied to the liquid crystal related member around the optical disk or the backlight. In recent years, it has been sought to be a hard coat layer in addition to scratch resistance. For example, in a display body such as a CRT, an LCD, or a PDP provided with a film, it is difficult to view the face of the display body due to reflection and the eyes are easily fatigued. Therefore, it is necessary to perform hard coating to prevent surface reflection depending on the application. Layer processing (refer to Patent Document 2). In addition to the need to impart a functional hard coat, the hard coat is also reviewed for its original purpose of improving hardness. For example, in Patent Document 3, the hardness is increased by adding a polyfunctional amine ester acrylate to the resin composition. However, there is a problem that cracks occur due to the large hardening shrinkage of the polyfunctional amine ester acrylate used. Moreover, the amount of addition or composition of the whole is also limited. A tree n-form containing an amine ester (methyl) propylene 321753 201036997 is obtained by reacting glycerin (meth) acrylate (a) with a polyisocyanate compound (b) is described in Patent Document 4 and Patent Document 5. Specifically, it is described in 4, which has a mass average molecular weight of 10, 00. The above polymer and tris(propylene oxyethyl) isocyanurate are necessary for the printed wiring. __(4) (4) The fat reading composition is accepted, but the hardness is not required to be cut to the point of injury. Patent Document 5 _ describes a composition for three-dimensional plasticization containing modified oxygen-cut particles. However, there is no description. [Patent Document 1] [Patent Document 1] Japanese Patent Laid-Open Publication No. Hei 9-9459G3 (Patent Document 3) Japanese Patent Publication No. _U3648 [Patent Document 5] Japanese Patent Laid-Open No. Hei. No. Hei 9-87513 (Patent Document 5). The hardness of the coating material is higher, the hardness of the coating material itself is higher, the degree of crosslinking is increased, and the specialization method is set. However, there is a problem that cracks are generated, and curling occurs due to the thick film crossing degree. The purpose of the object is to improve the above-mentioned shortcomings. The resin composition can be coated into a thick film and has excellent hardness, and at the same time, it is given [to solve the problem that it will occur - the crack is formed, and the shrinkage rate from the Wei shape is low to solve the problem. Means] 6 321 753 201036997 The inventors of the present invention have solved the above problems by solving the above-mentioned problems, such as the fact that the resin composition having a specific compound and composition can be solved, and the present invention has been completed. That is, the present invention relates to the following resin composition: (1) a resin composition comprising: an amine vinegar obtained by reacting glycerol (mercapto) propylene with a cyclical cyclic polyisocyanate compound ( Methyl) phthalic acid vinegar (A), (mercapto) acrylic acid vinegar (8), and a photopolymerization initiator (〇., (2) - a resin composition comprising: glycerol (methyl) propylene vinegar (4) And (4) an amine acetonate (methyl) acrylic acid obtained by reacting a (meth)acrylic acid vinegar (6)) with a polyvalent oleic acid vinegar compound (b), (η), (methyl) propionate ( B), and a photopolymerization initiator (c). (3) The resin composition according to the above (1) or (2), which is used as an overcoat layer. [Effect of the Invention] According to the present invention, there is provided a resin composition which can obtain a hardened film having a low shrinkage ratio at the time of hardening, has a high hardness and which does not curl or crack, and a coating agent using the resin composition . [Embodiment] [Mode for carrying out the invention] The present invention will be described in detail below. The amine ester (methyl) acetoacetate (A) used in the resin composition of the present invention is obtained by reacting glycerin (meth) acrylate (a) with a polyvalent isocyanate compound (b). The number of the (meth) propyl group to be contained in the glycerin (meth) acrylate (a) is not particularly limited. 321753 201036997 The amine ester (mercapto) acrylate (A 1) used in the resin composition of the present invention is glycerin (meth) acrylate (&) and (meth) gamma The formula S曰(a 1) is obtained by reacting a polyisocyanate compound (匕). The number of (meth)acrylonitrile groups of the glycerol (meth) acrylate (a) is not particularly limited. The glycerin (meth) acrylate (a) used in the resin composition of the present invention may, for example, be glycerin diacrylate, glycerin dimethacrylate, glycerin monoacrylate monomethacrylate or diglycerin triacrylate. Ester, diglycerin trimethacrylate, etc. Among them, propylene dipropylene hydride, glycerin dimethyl acrylate, and glycerin monoacrylate monomethacrylate are preferred. The (mercapto)acrylic acid vinegar UD ' other than (a) used in the resin composition of the present invention is not particularly limited as long as it has an active hydrogen group, and examples thereof include a hydroxyl group-containing (mercapto) acrylate. , pentaerythri to 1 type, hydroxymethyl group, epoxy acrylate, etc., such as mono-Ben, polyfunctional (fluorenyl) propionate. Examples of the (meth) acrylate (a-1) other than (a) include, for example, (methyl methacrylate) acrylic acid 2, ethyl ketone, (methyl) diacid 2 propyl vinegar, (methyl) ) 乙妇ς 4-butyl butyl ester, cyclohexene dimethanol mono (meth) acrylate vinegar, polyethylene glycol mono (meth) acrylate vinegar, polypropylene glycol mono (mercapto) propylene _, (methyl Acetate 2-carbo-3-phenoxypropionate (meth) vinegar vinegar; neopentyl alcohol tris(meth)acrylic acid vinegar Vinegar, dipentaerythritol tris(methyl)propane vinegar, diterpene tetraol tetra(methyl)propanate, dipentaerythritol penta(indenyl)acrylic acid vinegar, dipentaerythritol (methyl) acrylic acid vinegar, dipentaerythritol di(methyl) propyl ketone § | and other pentaerythritol; 321753 201036997, by f-propyl K methyl) propyl vinegar, etc. (four) base class; An epoxy acrylate such as A di-epoxy acrylate. And (meth)acrylic acid vinegar (a) other than (4) which can be used in the wax composition of the present invention. -Ι) is preferably a poly(methylene) propionate, and a (meth) acrylate of more than 3 earth functions, especially pentaerythritol triacrylate _, Pentaerythritol tetrapropyl acrylate, dine pentaerythritol pentapropyl vinegar, dinepentaerythritol hexaacrylate or a mixture thereof. Preferably, the resin composition of the present invention allows for the diversity of bismuth The anaerobic acid-based compound (b) is not limited as long as it is a compound containing two or more isocyanate groups in one molecule, and examples thereof include aliphatic aliphatic polyisocyanate g-based compounds and aromatics. A polyisocyanate compound, an alicyclic polyisocyanate, such a trimer or multimer compound, a biuret-type polyisocyanate, an all-phanphan type polyisocyanate, etc. A steroidal or multimeric compound means that three isocyanato groups form i or more than two isocyanurates (isocyanura) Further, the polyisocyanate compound (b) may be used alone or in combination of two or more. Examples of the aliphatic polyisocyanate compound include, for example, 1,6-hexamethylene-isocyanuric acid , isophorone diisocyanate, hydrogenated toluene diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane monoisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane Alkane diisocyanate, dicyclohexyldecane-4,4,-diisocyanate, m-tetramethylphenyldimethyl diisocyanate, p-tetramethylphenyldidecyl diisocyanate, i, 4_4 Sub 9 321753 201036997 decyl diisocyanate, 1,12-dodecyl (methylene) diisocyanate, 2,2,4-dimethylcyclohexanyl diisocyanate, 2,4,4-trimethylcyclohexane Diisocyanate, 2, 2, 4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, diazonic acid diisocyanate, norbornane diisocyanate, etc. Examples of the aromatic polyisocyanate compound include, for example, toluene diisocyanate and phenylene diisocyanate. Acid ester, diphenylmethane diisocyanide I 5-na-isocyanate, dimercaptobenzidine (t〇Hdine) diisocyanate, 1,4-phenylene diisocyanate, 1,6_benzobenzene Isocyanate, etc. Examples of the lipid oxime polyisocyanate include, for example, cyclohexane diisocyanate, oxime toluene diisocyanate, dinonylcyclohexane diisocyanate, 4'4-methylenebis(cyclohexyl isocyanate), Isophorone diisocyanate, monocycloheptyl diisocyanate, decane diisocyanate, etc. The polyisocyanate compound (b) in the present invention is preferably an aliphatic polyisocyanate compound, and is preferably an alicyclic polyisocyanate. In particular, isophorone diisocyanate and a trimer or multimer compound of isophorone diisocyanate are preferred. The amine ester (meth) acrylate used in the present invention is obtained by reacting an oil (meth) acrylate (a) with a polyvalent isocyanate compound (1 〇 (preferably an alicyclic quaternary isocyanate compound) (A-1) can be obtained by reacting a glycerol (meth) acrylate (a) and a (meth) acrylate (a) other than (a) with a polyvalent isocyanate compound (b). And (Ay) may be used separately in the resin composition of the present invention, or may be used in combination. Compared with glycerol (meth)acrylic acid (a) and (a) other than (meth) acrylate 321753 10 201036997 (al) 1 equivalent of active hydrogen group, the isocyanate group equivalent of the polyisocyanate compound (b) is generally 0. 1 to 50 equivalents, to 〇 υ. A range of 1 to 10 equivalents is preferred. The reaction temperature is usually from 30 to 150 ° C, preferably in the range of 5 () i 10 0 °c. The end point of the reaction was calculated by reacting with an excess of n-butylamine and back titrating with 1 N hydrochloric acid to calculate the amount of residual isocyanate. When it is 5 mass% or less, it is an end point. Ο 触 A catalyst can also be added for the purpose of shortening the reaction time. The catalyst may be any of a basic catalyst and an acidic catalyst. Examples of the basic catalyst include pyridine, pyrrole, triethylamine, diethylamine, dibutylamine, gas and the like; and phosphines such as tributylphosphine and triphenylphosphine. Examples of the acidic catalyst include metal alkoxides such as copper naphthenate, cobalt naphthenate, naphthenic acid, tributoxy, tetrabutoxytrititanium, and tetrabutoxyzirconium; Huaming and other Lewis acids; 2-ethylhexyltin, octyltin trilaurate, dilaurate _ butyl tin, octyl tin diacetate and other tin compounds. The amount of the catalyst added is usually 1 part by mass or more based on 100 parts by mass of the polyvalent isocyanate compound (b). Further, in the reaction, in order to prevent polymerization in the reaction, it is preferred to use a hydrazine and a % agent (for example, p-methoxyphenol, 2, 4-dimethyl sulfonate, 3-termination) Base sulfur test, benzene brewing; 2,. 5-di- yl-p-phenylene phenothiazine, etc.), the amount of the polymerization inhibitor used relative to the reaction mixture system. 〇1% by mass or more and 1% by mass or less, preferably 〇% by mass or more. 5 mass% or less. The reaction temperature is 60 to 15 (rc, preferably 120 ° C.) In the resin composition of the present invention, when the solid content of the resin composition of the present invention is 321753 11 201036997 as 100% by mass, the above (A) and / The amount of use of (Al) is generally 5% by mass or more and 97% by mass or less, and preferably 21% by mass or more and 80% by mass or less. The (meth) acrylate used in the present invention (the illusion is not particularly limited) However, examples thereof include monofunctional (meth) acrylate, bifunctional (meth) acrylate, (sub) acrylate of 3 gongs or more, polyester ($ acrylate), and amine ester (methyl). Acrylate oligomer, polyester (meth) acrylate oligomer, epoxy (fluorenyl) acrylate oligomer, etc. Examples of monofunctional (meth) acrylates include acrylonitrile? Acryioyimorphoiine; (f)acrylic acid 2-hydroxypropyl ester, (meth)acrylic acid 4-hydroxybutyl ester and other hydroxyl group-containing (meth) acrylate; cyclohexane-1,4-monomethyl alcohol (methyl) Acrylate, (mercapto)acrylic acid tetrahydrofuran, (methyl) Isodecyl enoate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, etc. Ester; phenoxyethyl (meth)acrylate, phenyl (poly)ethoxy(meth)acrylate, p-cumylphenoxyacetate (meth)acrylate, trioxene (meth)acrylate Ethyl acetoacetate, (mercapto)acrylic acid phenyl group, (meth)acrylic acid 2-carbyl-3-phenoxypropyl acetonate, phenyl phthalate (poly)ethoxy (indenyl) acrylate, An aromatic (fluorenyl) acrylate such as phenylphenol epoxy (fluorenyl) acrylate. Examples of the bifunctional (fluorenyl) acrylate include, for example, u-butylene glycol di(meth)acrylate vinegar. 1,6-hexanediol bis(indenyl) acrylate, u-glycol diol di(meth)acrylic acid vinegar, tricyclic tert-doped dimethanol (methyl) acrylate acid, double anticipation (poly) Ethoxy bis(meth)acrylic acid vinegar, Wei Wei (poly) propoxy oxygen 321753 12 201036997 . Di-(meth) acrylate, bisphenol F (poly) ethoxy di(methyl) propionate, ethylene glycol di(decyl) acrylate, (poly)ethylene glycol di(methyl) Acrylate, bis(meth)acrylate of ε-caprolactone adduct of hydroxypivalic acid neopentyl glycol ester (for example: KAyARAI manufactured by Nippon Kayaku Co., Ltd.) HX-220, HX-620, etc. )Wait. Examples of the trifunctional or higher polyfunctional (meth) acrylates include di-trimethylolpropane tetra(meth)acrylate, trimethylolpropane tris(methyl decyl) acrylate, and trishydroxyl Octyl octane tetra(meth) acrylate, trimethylolpropane polyethoxy tri(meth) acrylate, trimethylolpropane (poly) propoxy tri(meth) acrylate, trishydroxyl Hydroxymethyl groups such as propane (poly)ethoxy (poly) propoxy tri(methyl) acrylate; neopentyl alcohol tri(meth) acrylate, neopentyl alcohol poly ethoxy tetra (a) Acrylate, neopentyl alcohol (poly) propoxy tetra (meth) acrylate, neopentyl alcohol tetra (meth) acrylate, neopentyl alcohol tetra (meth) acrylate, two new Pentaerythritol penta (meth) acrylate, neopentyl alcohol such as dipentaerythritol hexa(meth) acrylate; tris[(indenyl) propyl acetonyl ethyl] isocyanuric acid vinegar , [[meth) propylene methoxyethyl] isocyanurate modified by caprolactone; bisphenol A di-epoxy propylene I Ss, etc. . Examples of the (poly)ester (mercapto) acrylate include ethylene glycol, diethyl alcohol, diethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, neopentyl glycol, polyethylene glycol, Glycols such as polypropylene glycol, hydrazine, 4-butanediol, 16-hexanediol, 1,8-octanediol, 1,9-nonanediol, 2-methyl 4,8-octanediol, 3_ Linear or branched alkanediols such as methyl 1'5-pentanol, 2,4-diethyl-1,5-pentanediol, 2-butyl-2-ethyl-1,3-propanediol a cyclohexane-oxime "a 321753 13 201036997 di-alkyl alcohol such as an alicyclic alkanediol, a bisphenol A (poly) ethoxy diol or a bisphenol A (poly) propoxy monool A reaction product of a (poly)ester diol and a (meth)acrylic acid of a reactant of the above dibasic acid or an anhydride thereof, etc. Examples of the amine ester (mercapto) acrylate oligomer are exemplified by a diol compound ( For example: ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, hydrazine, 4-butanediol, neopentyl glycol, hydrazine, 6-hexanediol, 1,8-octane Glycol, i, 9-nonanediol, 2-methyl", octyl diol, 3-methyl-1,5- Pentandiol, 2,4-diethylpentanediol, 2-butyl-2-n-1,3-propanediol, cyclohexane-1<4-dimethanol, polyethylene glycol, polypropylene glycol, double Phenol A polyethoxy diol, bisphenol A polypropoxy diol, etc.), or diol compounds and dibasic acids or anhydrides thereof (for example: succinic acid, adipic acid, sebacic acid, polyacid) a polydecyl alcohol of a reactant of isophthalic acid, an acid, an acid or an anhydride thereof, and an organic polyisocyanate (for example, tetramethylene di-significant hexa-f-di-isocyanate, 2, Chain-like saturated hydrocarbon isocyanate such as 2,4_trisylhexamethylene diisocyanide or 2'4,4-tridecylhexamethylene diisocyanate, isophorone diisocyanate , obtained by burning diisocyanate, dicyclohexylformamidine diisocyanate, methylene bis(4_cyclohexylisophthalic acid vinegar), hydrogenation = phenyl ketone diisocyanate, hydrazine xylene Cyclic saturated hydrocarbon isocyanate such as isocyanic acid vinegar or carbonitrile diisocyanate, 2,4-methyl-toluene diisocyanate H 1,3- phenylenedidimethyl diisocyanate, and stupid diisocyanate Vinegar, 3'-dibasic _4,4,_diisocyanate 6_isopropyl, 3_phenyl diiso, 1,5-naphthalene diisocyanate, etc., aromatic polyiso-acidic acid vinegar) reaction, after u addition to the base (meth)acrylic acid The reaction of vinegar, etc. Examples of the (poly)ester (meth) acrylate oligomer include (poly)ester diol and (meth) of the reactant of the above-mentioned two 321753 14 201036997 alcohol compound and the above dibasic acid or its anhydride. Acrylic reactants, etc. In the resin composition of the present invention, when the solid content of the resin composition of the present invention is 1% by mass, the amount of the above (Β) component is generally 〇% by mass or more and 94% by mass or less, and 20% by mass. More than 79% by mass or less is preferred. * Ο Ο The photopolymerization initiator (C) used in the resin composition of the present invention may, for example, be benzoin, benzoin A, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl ether. Benzoin; acetophenone, 2,2---ethoxy-yl- 2-benylacetophenone, ι, ΐ-dichlorophenylacetamidine, 2-hydroxy-2-indolyl-phenylpropane- 1-ketone, diethoxyacetophenone, p-cyclohexyl phenyl ketone, 2-mercapto-1-[4-(methylthio)phenyl]-2 morpholinylpropanone-:!-ketone And other acetophenones; 2-ethyl hydrazine, 2-tert-butyl fluorene, 2 chloropice, 2 - pentyl enriched S Kun, 2,4 _ diethyl 嗟 mock _ (2, 4-diethylthioxanthone), 2-isopropyl thioxanthene, 2 gas ketone ketone and other thioxanthone; acetophenone didecyl ketal, benzoin dimethyl condensate ^ (benzil dimethyl) Ketal) and other ketals; dibenzoate, benzoyl-4'-mercaptodiphenyl sulfide, 4, 4'-dimethylaminobenzonitrile, etc.; Oxidation of 4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2 & g trimethylbenzylidene)phenylphosphine oxide And so on. Further, in particular, Irgacure 184 (1-hydroxycyclohexylphenyl styrene j) and Irgacure 907 (2-methyl-1_(4-) manufactured by Ciba Specialty Chemicals can be easily obtained from the market. (曱thio)phenyl)-2-morphinylpropane-buxone), Lucirin TP0 manufactured by BASF Corporation (2, 4, 6-trimethylbenzene 321753 15 201036997 These may be used alone or in combination with 2 Mercaptodiphenylphosphine oxide) and the like. Also, use it on. When the content is 1% by mass, the mass% is not more than 10% by mass, and the amount of the above-mentioned (C) component of the invention is as follows: It is preferable that the mass% is 7% by mass or more. Further, in the present invention, a hardening accelerator (D) can also be used. Examples of the hardening accelerator which can be used include, for example, triethanolamine, diethanolamine, N-ethyldiethanolamine 2 methylaminoethylphthalic acid vinegar, dimethylaminophenidinium, p-dimethylaminophenylhydrazine. An acid isobaric acid ester, an amine such as EPA; or a hydrogen donor such as a thiol benzopyrene. When the solid content of the resin composition of the present invention is 100 K, the amount of the hardening accelerator used is generally 5% by mass or more and 5% by mass or less. Examples of the diluent (E) to be used in the resin composition of the present invention include, for example, butyrolactone, r-valerolactone, 7-caprolactone, r_gyne δ曰, α-acetonitrile. Lactams such as ri-r-butyrolactone and ε-caprolactone; di-alkane, 1' 2-dimethoxy decane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and one Ethers such as diol dibutyl ether, propylene glycol monoterpene ether, propylene glycol monoethyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether; Carbonates such as esters and propyl carbonate; ketones such as mercaptoethyl ketone, decyl isobutyl g, cyclohexanone, acetophenone; phenols such as phenol, cresol and xylenol; Ester, butyl acetate, acetaminophen, ethyl ethyi cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate, propylene glycol monoterpene Esters such as ether acetate; terphenyl, diphenylbenzene, diethylbenzene, cyclohexane 321753 16 201036997 hydrocarbons such as alkane; trichloroethane, tetrachloroethane, monochlorobenzene, etc., hydrocarbons, etc.; Ether, stone Solvents such as petroleum solvents such as petroleum (petroleum naphtha); fluoroalcohols such as 2H, 3H-tetrafluoropropanol, and hydrofluoroquinones such as perfluorobutyl methacrylate and perfluorobutyl ethyl ether; Alcohols such as ethanol, isopropanol and n-alcohol; diacetone alcohol having both ketone and alcohol properties. These can be used alone or in combination of two or more. In the resin composition of the present invention, the amount of the component (E) used in the total amount of the resin composition of the present invention is in the range of 〇% by mass or more and 90% by mass in the range of 〇 〇 ° ° ◦ ◦ ◦ 80% by mass or less is preferred. Further, in the resin composition of the present invention, a leveling agent, an antifoaming agent, an ultraviolet ray, a line absorbing agent, a photostabilizer, an antioxidant, and the like may be added to the photosensitive resin composition of the present invention as needed. A polymerization inhibitor, a crosslinking agent, etc., to impart functionality for each purpose. Examples of the leveling agent include a fluorine-based compound, a polyoxo-based compound, and an acrylic compound; and examples of the ultraviolet absorber include a benzotriene compound, a benzophenone compound, a triterpenoid compound, and the like. . Examples of the luminescent stabilizer include a hindered amine compound and a benzoate compound; the antioxidant may, for example, be a test compound; and the polymerization inhibitor may, for example, be methoxyphenol, methylhydroquinone or hydrogen. The crosslinking agent may, for example, be the above-mentioned polyvalent isocyanate or melamine compound. The resin composition of the present invention can be obtained by substituting the above-mentioned (A) component, (A-1) component, (B) component, (C) component, and the desired gold component and other components. Obtained by mixing in any order. The resin composition of the present invention is coated with the above resin composition on a substrate, and the film thickness of the resin composition after drying is generally 0. Lym or more 321753 201036997 50 # m or less, preferably 1 # m or more and 20 // m or less, and after drying, a cured film can be obtained by irradiating ultraviolet rays. Examples of the substrate film include polyester, polypropylene, polyethylene, polyacrylate, polycarbonate, cellulose triacetate, polyether sulfone, and cycloolefin polymer. The film to be used may be a surface treatment person having a pattern or an easy-to-layer layer, a corona treatment or the like, and a mold release treatment. Examples of the coating method of the resin composition include bar coating, wire bar coating, air knife coating, gravure coating, reverse gravure coating, and micro gravure coating. Micro reverse gravure coating, die coating, dip coating, spin coating, spray coating, and the like. In order to harden, ultraviolet rays may be irradiated, but an electron beam or the like may also be used. When the ultraviolet light is hardened, an ultraviolet ray irradiation device such as a xenon lamp, a high pressure mercury lamp, or a metal halogen lamp is used as the light source, and the amount of light and the arrangement of the light source can be adjusted as needed. When a high-pressure mercury lamp is used, it is preferable to harden it at a conveying speed of 5 to 60 m/min with respect to a lamp having an energy of 80 to 120 W/cm2. Further, when it is hardened by an electron beam, it is preferable to use an electron beam acceleration device having an energy of 100 to 500 eV, and in this case, the photopolymerization initiator (C) may not be used. The resin composition of the present invention is used as an ink; a metal such as aluminum, iron or copper; a plastic such as vinyl chloride, acrylic acid, polycarbonate, polyethylene terephthalate, polyethylene or polypropylene; ceramic material such as glass; wood For various coating materials such as paper, printing paper, and fiber, it can be used for a surface treatment agent, a binder, a plastic material, a molding material, a laminate, an adhesive, an adhesive, or the like. More specific uses can be used in the printing area of flat relief printing ink, flexographic 18 321753 201036997 ink (f 1 exographic ink), gravure ink, screen printing ink, etc.; smooth surface paint; paper coating agent field Woodworking coatings; coatings for printing cans or printing inks; flexible packaging film coatings, printing inks or adhesives, thermal papers, coatings for thermal films, printing inks, adhesives, adhesives Or use of a fiber coating agent, a film coating agent for molding processing, or the like. In the above-mentioned use, the resin composition of the present invention has a low shrinkage rate at the time of curing, has a high hardness, and does not cause curling or cracking, and thus has a hard coating agent for a plastic film or a small frame. Its use. (Embodiment) Hereinafter, the present invention will be described in more detail by way of examples, but the invention is not limited to the examples. Further, in the examples, "parts" means "parts by mass" unless otherwise specified. Synthesis Example 1 In a reactor equipped with a reflux condenser, a stirrer, a thermometer, and a temperature adjusting device, glycerin monoacrylic acid acrylate and monomethacrylic acid were added. 35g (l. 54 moles, 4-methoxyphenol as a polymerization inhibitor. 25g, dibutyltin dilaurate as an amine esterification reaction catalyst. 25 g and stirred until uniform, so that the internal temperature became 50 °C. Then, after the internal temperature does not exceed 80 °, the isophorone diisocyanate 155 is added dropwise. 65g (0. 70 mol), after adding at 80 ° C, the content of NC0 becomes 0. The reaction was terminated at a time of 1% or less to obtain an amine ester acrylate. Synthesis Example 2 In a reactor equipped with a reflux condenser, a stirrer, a thermometer, and a temperature adjusting device, glycerin monoacrylate monomethacrylate was added 19 321753 201036997 262. 60g (l. 17 moles, methyl ethyl ketone 125. 00g, 4-nonoxyphenol as a polymerization inhibitor. 25 g, dibutyltin dilaurate as an amine esterification reaction catalyst. 25 g and stirred until uniform, so that the internal temperature became 50 °C. Then, T-1890 (isophorone diisocyanate trimer) was added dropwise at an internal temperature of not more than 80 ° C. 4 (^(0. 36 mol), after addition at 80 ° 0: reaction, the NC0 content becomes 0. The reaction was terminated at a time of 1% or less to obtain a resin solution containing 80% of an amine acrylate. Synthesis Example 3 In a reactor equipped with a reflux condenser, a stirrer, a thermometer, and a temperature adjusting device, glycerin monoacrylate mono methacrylate was added. 14g (0. 84 moles, a mixture of pentaerythritol triacrylate and neopentyl alcohol tetraacrylate (mass parts mixing ratio: 65/35; hydroxyl equivalent: 458. 9g/Eq) 187. 08g (0. 41 moles, 4-nonoxyl phenol as a polymerization inhibitor. 25g, dibutyltin dilaurate as an amine esterification reaction catalyst. 25 g and stirred until uniform, so that the internal temperature became 50 °C. Then, isophorone diisocyanate 125 is added dropwise at an internal temperature of not more than 80 ° C. 78g (0. 57 mol), after the addition at 80 ° C reaction, the N (3) content becomes 0. The reaction was terminated at a time of 1% or less to obtain an amine ester acrylate. Synthesis Example 4 In a reactor equipped with a reflux condenser, a stirrer, a thermometer, and a temperature adjusting device, glycerin monoacrylate/monomethacrylate was added. 42g (0. 36 moles, a mixture of pentaerythritol triacrylate and neopentyl alcohol tetraacrylate (mass parts mixing ratio: 65/35; hydroxyl equivalent: 458. 9g/Eq) 240. 83g (0. 52 moles, methyl ethyl ketone 125. 00g, as a polymerization inhibitor 20 321753 201036997 4-decyloxyphenol 0. 25 g, dibutyltin dilaurate as an amine esterification reaction catalyst. 25g and stirred until uniform, so that the internal temperature becomes 5 (TC. Then, T -1890 (isophorone diisocyanate trimer) is added dropwise at an internal temperature not exceeding 80 ° C. 75g (〇. 27 Mo,) After the addition, the reaction was carried out at 8 ° C, and the NCO content became 0. The reaction was terminated at a time of 1% or less to obtain a resin solution containing 80% of an amino acid acrylate. Synthesis Example 5 In a reactor equipped with a reflux condenser, a ripper, a thermometer, and a temperature adjusting device, glycerin monoacrylate mono methacrylate was added. 51g (0. 67 moles, a mixture of pentaerythritol triacrylate and neopentyl alcohol tetraacrylate (mass parts mixing ratio: 65/35; hydroxyl equivalent: 458. 9g/Eq) 149. 50g (0. 33 Mole), methyl ethyl ketone 125. 00g, 4-anthoxyphenolphthalein as a polymerization inhibitor. 25g, as an amine esterification reaction catalyst, dibutyltin laurate 0. 25 g and stir until uniform 'to make the internal temperature 50 ◦C. Then, T-1890 (isophorone ◎ diisocyanate trimer) was added dropwise at an internal temperature of not more than 8 ° C. 99g (〇. 3〇莫耳), after the addition, the reaction at 80 ° C, the content of NC0 becomes 0. The reaction was terminated at a time of 1% or less to obtain a resin solution containing 80% of an amine acrylate. Synthesis Example 6 In a reactor equipped with a reflux condenser, a stirrer, a thermometer, and a temperature adjusting device, glycerin monoacrylate mono acrylate was added. 60g (0. 94 Mo荨), a mixture of pentaerythritol triacrylate and neopentyl alcohol tetraacrylate (mass parts mixing ratio: 65/35; hydroxyl equivalent: 458. 9g/Eq) 70. 〇7g (〇. 15 moles, methyl ethyl ketone 125. 00g, for 21 321753 201036997 is a polymerization inhibitor 4-anthoxyphenol 0. 25g, as an amine esterification reaction catalyst, dibutyltin laurate 0. 25 g and stir until uniform, so that the internal temperature became 50 °C. Then, T-1890 (isophorone diisocyanate trimer) 220 is added dropwise at an internal temperature of not more than 80 ° C. 34g (0. 33 mol), after the addition, the reaction was carried out at 80 ° C, and the content of N(3) became 0. The reaction was terminated at a time of 1% or less to obtain a resin solution containing 80% of an amine acrylate. Synthesis Example 7 In a reactor equipped with a reflux condenser, a stirrer, a thermometer, and a temperature adjusting device, glycerin monoacrylate/monodecyl acrylate was added. 71g (0. a mixture of 88 moles, dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (mass parts mixing ratio: 40/60; hydroxyl equivalent: 1311. 2g/Eq) 197. 69g (0. 15 moles, 4-methoxy phenol as a polymerization inhibitor. 25g, dibutyltin dilaurate as an amine esterification reaction catalyst. 25 g and stirred until uniform, so that the internal temperature became 50 °C. Then, isophorone diisocyanate 104 is added dropwise at an internal temperature of not more than 80 ° C. 60g (0. 47 moles), after the addition, reacted at 80 ° C, and the NCO content became 0. The reaction was terminated at a time of 1% or less to obtain an amine ester acrylate. Synthesis Example 8 In a reactor equipped with a reflux condenser, a stirrer, a thermometer, and a temperature adjusting device, glycerin monoacrylate mono methacrylate was added. 51g (0. 73 moles, a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (mass parts mixing ratio: 40/60; hydroxyl equivalent: 1311. 2g/Eq) 163. 49g (0. 36 Moer), mercapto ethyl ketone 125. 00g, 4-nonoxyphenol as a polymerization inhibitor. 25g, as a catalyst for amine esterification reaction 22 321753 201036997 one. Laurel 驮 butyl tin bismuth. 25 g and stirred until uniform, so that the internal temperature became 50C. Then the internal temperature does not exceed 8 〇. _189〇(isophorone-isotrimer) was added to the underarm. Qig (〇. 26 moles, and reacted at 80 °C after the addition. The reaction was terminated when the NC0 content was less than or equal to 1% to obtain a resin solution containing 80% of an amine acrylate. Comparative Synthesis Example 1 In a reactor equipped with a reflux condenser, a stirrer, a thermometer, and a temperature regulating device, glycerin monoacrylate monomethacrylate was added. 58g (l. 67 moles, 4_methoxyphenolphthalein as a polymerization inhibitor. 25 bogey, dibutyltin dilaurate as a catalyst for the amine Sa reaction. Stir well until the internal temperature becomes 5 〇t:. Then, hexamethylene diisocyanate 127 is added dropwise at an internal temperature of not more than 8 ° C. 42g (0. 76 moles, after the addition, the reaction was completed at the point when the content of _ was 1% or less to obtain an amine ester acrylate. Comparative Synthesis Example 2 A mixture of neopentyl alcohol triacrylate and neopentyl alcohol tetraacrylate was added to a reactor equipped with a reflux condenser, a stirrer, a thermometer, and a temperature adjusting device (mass parts mixing ratio: 65/35) : hydroxyl equivalent: 458. 9g/Eq) 4〇9· 77g(0. 89 mole), 4-methoxy phenolphthalein as a polymerization inhibitor. 25 g of dibutyltin dilaurate as an amine esterification reaction catalyst was stirred until uniform to bring the internal affinity to 5 Å. Hey. Next, isophorone diisocyanate was added dropwise. 23g (0. 41 Moules) and the internal temperature does not exceed 8 〇. 〇, after the addition, reacted at 80 C. The NCO content became 0. The reaction is terminated at a time point of 1% or less to obtain an amine ester acrylic acid. twenty three . 321753 201036997 Comparative Synthesis Example 3 In a reactor equipped with a reflux condenser, a stirrer, a thermometer, and a temperature adjusting device, a mixture of dinepentaerythritol pentaacrylate and dipentaerythritol hexaacrylate was added (mass ratio mixing ratio) : 40/60 ; hydroxyl equivalent: 1311. 2g/Eq) 464. 23g (0. 35 moles, 4-methoxy phenol as a polymerization inhibitor. 25g, dibutyltin dilaurate as an amine esterification reaction catalyst. 25 g and stirred until uniform, so that the internal temperature became 50 °C. Then, isophorone diisocyanate is added dropwise at an internal temperature of not more than 80 ° C. 77g (0. 16 mol), after the addition, the reaction was carried out at 80 ° C, and the above NCO content became 0. The reaction was terminated at a time of 1% to obtain an amine ester acrylate. Examples 1 to 10 and Comparative Examples 1 to 5 The resin compositions prepared with the materials shown in Tables 1 and 2 were coated on a PET film (film thickness 125# m) which was easily treated by a bar coater. After drying at about 80 to 100 ° C, it is passed through a UV illuminator (japan Storage Battery Co. Ltd. : CS30L-1-1) Hardened by high pressure mercury lamp: i20W/cm; lamp height: 10cm; conveyor speed: l〇m/min (energy: about 300roW/cm2, about 200mJ/cm2) A hard coating film of about thickness. At the same time, the units in Tables 1 and 2 are indicated by "parts". 321753 24 201036997 [Table 1] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Compound of Synthesis Example 30 Compound of Synthesis Example 2 37. 5 50 Compound of Synthesis Example 3 Compound of Synthesis Example 4 37. 5 Compound of Synthesis Example 5 37. 5 50 Compound of Synthesis Example 37. 5 Compound of Synthesis Example 7 Compound of Synthesis Example 37. 5 DPHA *1 20 20 20 20 20 20 20 20 10 10 ΜΕΚ η 50 42. 5 50 42. 5 42. 5 42. 5 50 42. 5 40 40 Irg. 184 5 5 5 5 5 5 5 5 5 5
[表2] 比較例1 比較例2 比較例3 比較例4 比較例5 比較合成例1之化合物 30 比較合成例2之化合物 30 比較合成例3之化合物 30 合成例2之化合物 12.5 DPHA 20 20 20 50 40 MEK 50 50 50 50 47.5 Irg. 184 5 5 5 5 5 (註） *1 :日本化藥（股）製造之KAYARAD DPHA(二新戊四醇五丙 浠酸S旨/六丙烯酸S旨混合物） *2 :曱基乙基酮 25 321753 201036997 *3 :汽巴精化公司（股）製造之1-羥基環己基苯基酮 對實施例1至10以及比較例1至5所得硬塗膜進行下 述項目之評估，將其結果示於表3。 (鉛筆硬度） 依照JIS K 5600-5-4，使用鉛筆刮痕試驗機，測定上 述組成之塗佈膜的鉛筆硬度。詳而言之，係在具有欲測定 之硬化皮膜的聚酯膜上，將鉛筆以45°之角度從上方施加 750g之荷重並刮劃5mm左右，以5次中有4次以上無刮痕 之鉛筆的硬度表示。 (密著性） 在耐光性試驗後之膜表面以刀具劃上十字痕，並於其 上貼上玻璃膠帶，再以90°之角度使其剝離。 〇：無剝離現象 X :有剝離現象 (耐刮傷性） 對鋼絲棉# 0000條施加200g/cm2之荷重並反覆10 次，以肉眼確認傷痕狀態。 〇：無傷痕 X :有傷痕 (捲曲） 將具有欲測定之硬化皮膜的聚酯膜裁切成5cmx5cm， 在80°C之乾燥爐中放置1小時後，使其回復室溫。在水平 之台上分別測定翹起的四邊之高度，並將四邊之和作為測 定值（單位：mm)。此時，基材本身之捲曲為0mm。 26 321753 201036997 ·> (黏性） 將調配有表1及表2所示材料之樹脂組成物以棒式塗 佈器塗佈於經易接著處理之PET膜（膜厚125/zm)上，於約 80至l〇〇°c乾燥後，將塗膜以脫脂棉擦拭，評估膜之黏性。 評估 〇·脫脂棉未沾黏 X :脫脂棉之棉絮沾黏在塗膜上 (外觀) 〇 以肉眼判斷表面之龜裂、白化、模糊等狀態。 評估 〇 ·良好 x :明顯產生龜裂 (硬化收縮率） 在合成例1至8、比較合成例1至3所得之化合物中 添加作為光聚合劑之3質量％之Irg. 184，在玻璃基板上以 合成例8 之化合物方面，[Table 2] Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Compound 30 of Synthesis Example 1 Comparative Compound 30 of Synthesis Example 2 Comparative Compound 30 of Synthesis Example 3 Compound 12.5 of Synthesis Example 2 DPHA 20 20 20 50 40 MEK 50 50 50 50 47.5 Irg. 184 5 5 5 5 5 (Note) *1 : KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd. (dipentaerythritol pentapropanoic acid S / hexaacrylic acid S mixture *2 : mercapto ethyl ketone 25 321753 201036997 *3 : 1-hydroxycyclohexyl phenyl ketone manufactured by Ciba Specialty Chemicals Co., Ltd. The hard coating films obtained in Examples 1 to 10 and Comparative Examples 1 to 5 were subjected to The evaluation of the following items shows the results in Table 3. (Pencil Hardness) The pencil hardness of the coating film of the above composition was measured in accordance with JIS K 5600-5-4 using a pencil scratch tester. Specifically, on the polyester film having the hardened film to be measured, the pencil is applied with a load of 750 g from above at an angle of 45° and scratched by about 5 mm, and four or more times of five times without scratches. The hardness of the pencil is expressed. (Adhesion) After the light resistance test, the surface of the film was cut with a cross mark, and a glass tape was attached thereto, and peeled off at an angle of 90°. 〇: No peeling phenomenon X: Peeling phenomenon (scratch resistance) A load of 200 g/cm 2 was applied to the steel wool # 0000 and repeated 10 times to confirm the flaw state with the naked eye. 〇: no scratches X: scratches (curl) The polyester film having the hardened film to be measured was cut into 5 cm x 5 cm, placed in a drying oven at 80 ° C for 1 hour, and then returned to room temperature. The heights of the four sides of the warp are measured on the horizontal table, and the sum of the four sides is taken as the measured value (unit: mm). At this time, the curl of the substrate itself was 0 mm. 26 321753 201036997 ·> (viscosity) The resin composition prepared with the materials shown in Tables 1 and 2 was applied to a PET film (film thickness 125/zm) which was easily treated by a bar coater. After drying at about 80 to 10 ° C, the film was wiped with absorbent cotton to evaluate the adhesion of the film. Evaluation 〇·The absorbent cotton is not sticky X: The cotton wool of the absorbent cotton is adhered to the coating film (appearance) 〇 The surface is cracked, whitened, and blurred. Evaluation 良好·Good x: Significant cracking (hardening shrinkage ratio) In the synthesis examples 1 to 8, the compounds obtained in Comparative Synthesis Examples 1 to 3 were added with 3% by mass of Irg. 184 as a photopolymerization agent on a glass substrate. In terms of the compound of Synthesis Example 8,
硬化收縮率= 〇棒式塗佈器進行塗佈，使用紫外線照射器照射紫外線，得 到膜厚約2〇〇 硬化物。惟在合成例2、合成例4至6、 面’係使作為溶劑之MEK從含有胺酯 。硬化收縮率係從25°C時 重與硬化物的液體比重依據下述之算式 (膜比重-液體比重）/膜比重χ1 〇〇 321753 27 201036997 [表3] 鉛筆硬度 密著性 耐刮傷性 捲曲 黏性 外觀 實施例1 2H 〇 〇 10 X 〇 實施例2 2H 〇 〇 10 〇 〇 實施例3 3H 〇 〇 14 X 〇 實施例4 3H 〇 〇 17 X 〇 實施例5 3H 〇 〇 13 〇 〇 實施例6 3H 〇 〇 11 〇 〇 實施例7 3H 〇 〇 17 X 〇 實施例8 3H 〇 〇 17 X 〇 實施例9 2H 〇 〇 11 〇 〇 實施例10 3H 〇 〇 12 〇 〇 比較例1 2H 〇 〇 20 X 〇 比較例2 3H 〇 〇 22 X 〇 比較例3 3H 〇 〇 28 X 〇 比較例4 3H 〇 〇 35 X 〇 比較例5 3H 〇 〇 28 X 〇 [表4] 硬化收縮率 合成例1之化合物 8 合成例2之化合物 8 合成例3之化合物 9 合成例4之化合物 9 合成例5之化合物 8 合成例6之化合物 8 合成例7之化合物 9 合成例8之化合物 9 比較合成例1之化合物 12 比較合成例2之化合物 11 比較合成例3之化合物 10 28 321753 201036997 化皮發明—成物之硬 亦無龜料情形好，且播曲小， 所構成的坡醋(⑶丙稀酸醋之實施例;、公 t之黏性良好。並且，由表4之結果㈣白 =:Γ成Γ所含的胺酯⑽)丙婦酸醋由於硬化 ㈣上=^帽蝴編靖卩制效果。 明之樹脂組成物所得的硬塗膜具 =、，，硬化時之收縮率… 龜裂的產生。S此，本發明之樹脂 膜或小型桓體之外塗層。 I用作為塑膠 【圖式簡單說明】 無。 【主要元件符號說明】 無 321753 29Hardening shrinkage = coating by a pry bar coater, and ultraviolet rays were irradiated with an ultraviolet ray irradiator to obtain a cured product having a film thickness of about 2 Å. However, in Synthesis Example 2, Synthesis Examples 4 to 6, and Surface, MEK as a solvent was contained from an amine ester. The hardening shrinkage ratio is the liquid specific gravity of the hardened material from 25 ° C according to the following formula (film specific gravity - liquid specific gravity) / film specific gravity χ 1 〇〇 321753 27 201036997 [Table 3] Pencil hardness tightness scratch resistance Curl-viscous appearance Example 1 2H 〇〇10 X 〇Example 2 2H 〇〇10 〇〇Example 3 3H 〇〇14 X 〇Example 4 3H 〇〇17 X 〇Example 5 3H 〇〇13 〇〇Implementation Example 6 3H 〇〇11 〇〇 Example 7 3H 〇〇 17 X 〇 Example 8 3H 〇〇 17 X 〇 Example 9 2H 〇〇 11 〇〇 Example 10 3H 〇〇 12 〇〇 Comparative Example 1 2H 〇〇 20 X 〇Comparative Example 2 3H 〇〇22 X 〇Comparative Example 3 3H 〇〇28 X 〇Comparative Example 4 3H 〇〇35 X 〇Comparative Example 5 3H 〇〇28 X 〇[Table 4] Hardening shrinkage ratio Synthesis Example 1 Compound 8 Synthesis Example 2 Compound 8 Synthesis Example 3 Compound 9 Synthesis Example 4 Compound 9 Synthesis Example 5 Compound 8 Synthesis Example 6 Compound 8 Synthesis Example 7 Compound 9 Synthesis Example 8 Compound 9 Comparative Synthesis Example 1 Compound 12 Compare Compound 11 of Synthesis Example 2 Comparing the compound of Synthesis Example 3 28 321753 201036997 The invention of the skin--the hard and non-turtle material of the product is good, and the smear is small, and the savanna of the vinegar is formed (the embodiment of the acrylic acid vinegar; The result is good. Moreover, the result of Table 4 (four) white =: the amine ester (10) contained in Γ Γ 丙 丙 丙 妇 由于 由于 由于 由于 由于 由于 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四The hard coating film obtained by the resin composition of the Ming =,,, the shrinkage rate at the time of hardening... The occurrence of cracks. Here, the resin film of the present invention or the outer coating of the small carcass. I used as a plastic [Simple description of the diagram] None. [Main component symbol description] None 321753 29