TW201008996A

TW201008996A - Curable composition for imprint, curing object using the same, manufacturing method thereof and member for liquid crystal display device

Info

Publication number: TW201008996A
Application number: TW098122172A
Authority: TW
Inventors: Hiroyuki Yonezawa; Akinori Fujita; Takashi Takayanagi
Original assignee: Fujifilm Corp
Priority date: 2008-07-02
Filing date: 2009-07-01
Publication date: 2010-03-01
Also published as: TWI438235B; CN101620376B; JP5306903B2; JP2010034513A; KR20100004052A; CN101620376A

Abstract

An object of the present invention is to provide a curable composition for imprint having good imprint ability and photo-curability, as well as mechanical characteristics, various durability, especially photo-curability, thermal resistance and elastic-recovery rate are excellent, and provide a manufacturing method thereof and member for liquid crystal display device. Provided is a curable composition for imprint characterized in that contains photo-polymeric monomer, photo polymerization initiator and anti-oxidant, in which a content of the said photo-polymeric monomer is 0.3-7 mass%, and the said anti-oxidant is anyone of only hindered phenol-based anti-oxidant, only semi-hindered phenol-based anti-oxidant, mixture of hindered phenol-based anti-oxidant and semi-hindered phenol-based anti-oxidant or only hindered amine-based anti-oxidant.

Description

.201008996 六、發明說明：【發明所屬之技術領域】本發明係關於壓印用硬化性組成物、使用它之硬化物及其製造方法以及使用該硬化物之液晶顯示裝置用構件。【先前技術】壓印法方面，提議有使用熱可塑性樹脂作爲被加工材料之熱壓印法（例如，參照非專利文獻1 )、與使用光硬化性組成物之光壓印（例如，參照非專利文獻2)的2種技術。熱參壓印法的情形，係將模具（mold)按壓於加熱至玻璃轉移溫度以上之高分子樹脂，冷卻後將模具脫膜，以將微細構造轉印至基板上之樹脂。該方法由於亦可應用於各種樹脂材料及玻璃材料，故在各方面之應用受到期待。例如，下述專利文獻1及2中揭示利用熱可塑性樹脂，廉價地形成奈米圖案之熱壓印方法。另一方面，透過透明模具或透明基材照射光線，使光 ❹ 硬化性組成物光硬化之光壓印法，在模具之按壓時不需要加熱轉印圖案的材料，可在室溫進行壓印。最近，尙有組合此兩者之優點的製作奈米流延法、3維積層構造之逆向壓印方法等新發展之報告。此種壓印法中，已提議有如下在奈米規模之應用技術。第一技術係藉由高精度位置摻合與高積體化，取代先前的微影術而成爲應用於高密度半導體積體電路之製作、或液晶顯示器之電晶體的製作等。第二技術係成型之形狀 _ /1^ 嫌 .201008996 (圖案）本身具有功能，可應用作爲各種奈米技術之要素零件、或作爲構造構件者’其實例可舉出各種微.奈米光學元件或高密度記錄媒體、光學薄膜、平面顯示器中的構造構件等。又，作爲另外之其他技術，係藉由微米構造與奈米構造之同時一體成型、或簡單的層間位置摻合以構築積層構造，而應用於 //-TAS(Micro-Total Analysis System)或生物晶片之製作。第三技術係利用高精度之位置摻合與高積體化，取代先前的微影術而成爲適用於高密度半導體積體電路之製作、或液晶顯示器之電晶體的製作等。包括前述技術，關於此等應用之壓印法的實用化組合係日漸活躍。茲說明前述第一技術中高密度半導體積體電路製作之應用例。近年來，半導體積體電路係進展微細化、積體化，作爲用以實現其微細加工之圖案轉印技術之光微影術裝置的高精度化已有進展。然而，相對於額外的微細化之要求，難以滿足微細圖案解像性、裝置成本、生產量三者。對此，作爲用以低成本進行微細圖案形成之技術，已提議使用壓印微影術技術，尤其是使用奈米壓印微影術技術（光奈米壓印法）》例如，下述專利文獻1中揭示使用矽晶圓作爲剛性打印頭（stamp)使用，藉由圖案轉印而形成25 nm以下之微細構造的奈米壓印技術。隨著此趨勢，爲了將奈米壓印微影術應用於半導體積體電路之製作，已開始活躍地進行模具與樹脂的剝離性、壓印均勻性、圖案轉印精度等爲始的性質的檢討。 \[Technical Field] The present invention relates to a curable composition for imprint, a cured product using the same, a method for producing the same, and a member for a liquid crystal display device using the cured product. [Prior Art] In the imprint method, a thermal imprint method using a thermoplastic resin as a material to be processed (for example, refer to Non-Patent Document 1) and photo-imprinting using a photocurable composition are proposed (for example, reference to non- Two techniques of Patent Document 2). In the case of the thermal embossing method, a mold is pressed against a polymer resin heated to a temperature higher than the glass transition temperature, and after cooling, the mold is released to transfer the fine structure to the resin on the substrate. Since this method can also be applied to various resin materials and glass materials, applications in various fields are expected. For example, Patent Documents 1 and 2 below disclose a hot stamping method in which a nano pattern is inexpensively formed by using a thermoplastic resin. On the other hand, a photoimprint method in which a light-curing composition is light-cured by a transparent mold or a transparent substrate, and the material of the transfer pattern is not required to be heated when the mold is pressed, and can be imprinted at room temperature. . Recently, there have been reports on new developments such as the nano-casting method and the reverse imprint method of 3-dimensional laminated structure combined with the advantages of both. In this imprint method, the following application techniques on the nanometer scale have been proposed. The first technique is applied to the fabrication of high-density semiconductor integrated circuits or the fabrication of transistors for liquid crystal displays by high-precision position blending and high integration, instead of prior lithography. The shape of the second technology is _ /1 ^ 嫌.201008996 (pattern) itself has a function, can be applied as a component of various nanotechnology, or as a structural member's examples of which can be exemplified by various micro-nano optical components Or high-density recording media, optical films, structural members in flat displays, and the like. Further, as another technique, it is applied to a //-TAS (Micro-Total Analysis System) or a living body by integrally molding a micro-structure and a nanostructure at the same time, or by simply mixing the interlayer positions to construct a laminated structure. Fabrication of wafers. The third technique utilizes high-precision position blending and high integration to replace the prior lithography to be suitable for the fabrication of high-density semiconductor integrated circuits or the fabrication of transistors for liquid crystal displays. Including the aforementioned techniques, the practical combination of imprinting methods for such applications is increasingly active. An application example of the fabrication of the high-density semiconductor integrated circuit in the first technique will be described. In recent years, the semiconductor integrated circuit has been progressively refined and integrated, and the precision of the photolithography apparatus as a pattern transfer technique for realizing microfabrication has progressed. However, it is difficult to satisfy the fine pattern resolution, the device cost, and the throughput in comparison with the requirements of additional miniaturization. In view of this, as a technique for performing fine pattern formation at a low cost, it has been proposed to use an imprint lithography technique, in particular, a nanoimprint lithography technique (photon nanoimprint method). For example, the following patents Document 1 discloses the use of a tantalum wafer as a rigid printhead to form a finely structured nanoimprint technique of 25 nm or less by pattern transfer. With this trend, in order to apply nanoimprint lithography to the fabrication of semiconductor integrated circuits, active properties such as mold-resin peelability, imprint uniformity, and pattern transfer precision have been actively developed. Review. \

201008996 茲說明前述第二技術中·在液晶顯示器（LCD)、電漿顯示器（PDP)等平面顯示器之光壓印法的應用例。隨著LCD 基板、PDP基板之大型化、與高精細化的動向，近年來係注目取代在薄膜電晶體（TFT)或電極板之製造時所使用的先前之光微影術法的壓印微影術作爲廉價之微影術，而必須開發取代先前之光微影術法所使用之蝕刻光阻的光硬化性光阻。又，作爲LCD等構造構件，對於規定所用之透明保護膜材料、或液晶顯示器中等胞溝（cell gap)的間隔材 ® 等，亦開始檢討壓印法之應用。此種構造構件用之光阻係與上述的鈾刻光阻相異，由於最終殘存於平面顯示器面板等之顯示器内，故稱爲「永久光阻」或「永久膜」。作爲適用先前光微影術技術之永久膜，可舉例如設在液晶面板的TFT基板上之保護膜、或爲了減低R、G、B層間的段差且賦予對ITO膜在濺鍍製膜時之高溫處理的耐性而設在彩色濾光片上的保護膜等。此等保護膜（永久膜）之 0 形成中，由於要求塗布膜之均勻性、超過200°C之加熱處理後高的光透過性、耐擦傷性等各種特性，故要求滿足此等特性之壓印用硬化性組成物的開發。又，前述液晶顯示器中所用的間隔材，通常係在彩色濾光片形成後或前述彩色濾光片用保護膜形成後，在彩色濾光片基板上使用光硬化性組成物，藉由光微影術形成約10// m〜20 μ m大小的圖案，進一步藉由後烘烤加熱硬化所形成。此種前述液晶顯示器中所用的間隔材，除了硬度、圖案精度等，特別要求 201008996 高彈性回復率，已尋求滿足此等特性之壓印用硬化性組成物的開發。再者，壓印法中，必須提高形成有圖案之模具表面凹部的腔體内之壓印用硬化性組成物的流動性。又，必須改善模具與光阻之間的剝離性同時改善光阻與基材（基板、支撐體）之間的密接性。如上所述，在壓印微影術所用之材料的要求特性係依照應用的用途而多有不同。然而，關於壓印用組成物，雖然以往有例如關於黏度之期待的記載，但是迄今仍沒有適合各用途之材料的設計指南的報告例。因此，作爲永久膜之主要技術課題，已舉出圖案精度、耐熱性、硬度等多種課題。將壓印用硬化性組成物用作爲永久膜的情況亦與使用習知的丙烯酸樹脂等光阻相同，（1)圖案轉印精度（壓印微影術之壓印性）、（2)耐熱性、 (3)硬化性之賦予係爲重要。作爲光壓印用硬化性組成物特有之課題，除了上述（1) 〜（3)之性能以外，機械特性之一，能夠承受作爲永久膜使用之（4)高彈性回復率之賦予係爲重要。再者，設計壓印用硬化性組成物的組成物時，除上述（1)〜（4)點外，同時必須確保（5)光阻在模具的凹部之流動性，必須在無溶劑或少量溶劑使用下之低黏度化（較佳爲5mPa.s以下）、與（6)爲了作爲電氣電路之構造構件使用必須改善、考慮電壓特性，組成物設計的技術性難度係更加提高。 .201008996 近年來，爲了抑制退色，已提議在壓印用硬化性組成物中使用抗氧化劑（參照專利文獻3、專利文獻4)。然而，實際上現狀係尙未檢討將抗氧化劑用於壓印用硬化性組成物。又，檢討將習知抗氧化劑添加於其他用途之光硬化性組成物。例如，可舉例爲了防止在光碟用接著劑組成物中貼合的金屬面之氧化、且提高接著劑之接著力（專利文獻 5) 。在同文獻中記載於光硬化性組成物中使用小於0.2質量 %之抗氧化劑的例子，但沒有暗示滿足壓印性、耐熱性、光硬化性、高彈性回復率、低黏度化、電壓特性等壓印用硬化性組成物所需求之特性的記載。特別是在使用少於0.2 質量％之抗氧化劑的例子中，組成物的黏度變爲 3 8 0mPa.s(25°C )，非爲可應用於專利文獻5所記載之謀求低黏度化組成物的壓印用硬化性組成物。又，以改善黏度爲目的，已報告在活性光線硬化型噴墨用組成物中添加0.1 5質量％抗氧化劑之實例（專利文獻 6) 。然而，在同文獻中雖有關於黏度之改善的記述，但卻沒有關於壓印性、耐熱性、光硬化性、高彈性回復率及電壓特性之記載。如專利文獻5與專利文獻6所記載，在光硬化性樹脂組成物中添加抗氧化劑之公知文獻的目的係爲了防止空氣中的氧導致之氧化、或爲了低黏度化，以往係有進行以上之詳細檢討。又，在熱硬化性樹脂添加抗氧化劑之公知文 .201008996 獻的目的亦爲抑制在加熱時氧化導致之樹脂變色。〔先前技術文獻〕〔專利文獻〕〔專利文獻1〕美國專利第5,772,905號公報〔專利文獻2〕美國專利第5,956,21 6號公報〔專利文獻3〕特開2008-105414號公報〔專利文獻4〕特開2008-92099號公報〔專利文獻5〕特開2002-256228號公報〔專利文獻6〕特開2006- 1 24636號公報〔非專利文獻〕〔非專利文獻 1〕S.Chou 等人：Appl. Phys. Lett. Vol.67, 3 1 14(1995) 〔非專利文獻 2〕M.Colbun 等人：Proc.SPIE,Vol. 3676,379 (1999) 【發明內容】 φ [發明所欲解決之課題] 有鑑於上述課題，將上述專利文獻6所記載之組成物原樣地用於壓印用途，明白在耐熱性、彈性回復率及電壓特性方面，爲不良者。本發明之目的係提供一種具有良好壓印性與光硬化性，且機械特性、各種耐久性、其中光硬化性、耐熱性及彈性回復率優良的壓印用硬化性組成物、使用它之硬化物及其製造方法以及液晶顯示裝置用構件。更具體而言，本 .201008996 發明之目的係提供一種尤其適合於平面顯示器等之透明保護膜或間隔材等之永久膜的壓印用硬化性組成物。 [解決課題之手段] 基於上述課題，本案發明人等進行鑽硏探討，結果發現藉由使壓印用硬化性組成物中含有特定量的抗氧化劑，可設計出完全滿足上述（1)〜（6)之特性的組成物，其中尤其可得（4)高彈性回復率的組成物。亦即，發現藉由下述手段可解決上述課題。 ^ [1] 一種壓印用硬化性組成物，其特徵在於：其係含有A) 光聚合性單體、B)光聚合起始劑、C)抗氧化劑之光壓印用組成物，其中前述A)光聚合性單體之含量爲80〜99質量 %，前述C)抗氧化劑之含量爲0.3〜7質量％，前述C)抗氧化劑係僅爲受阻酚系抗氧化劑、僅爲半受阻酚系抗氧化劑、受阻酚系抗氧化劑與半受阻酚系抗氧化劑之混合物、或僅爲受阻胺系抗氧化劑中的任一者。 φ [2]如[1]所記載之壓印用硬化性組成物，其中前述抗氧化劑係僅由半受阻酚系抗氧化劑所構成。 [3] —種壓印用硬化性組成物，其特徵在於：其係含有A) 光聚合性單體、B)光聚合起始劑、C)抗氧化劑之光壓印用組成物，其中前述A)光聚合性單體之含量爲80〜99質量 %，前述C)抗氧化劑之含量爲0.3〜7質量％，前述C)抗氧化劑爲受阻酚系抗氧化劑與硫醚系抗氧化劑之混合物、或半受阻酚系抗氧化劑與硫醚系抗氧化劑之混合物》 -10- 201008996 [4] 如[3]所記載之壓印用硬化性組成物，其中前述抗氧化劑爲半受阻酚系與硫醚系之混合物。 [5] 如[1]〜[4]中任一項所記載之壓印用組成物，其中前述抗氧化劑之含量爲0.5〜5質量％。 [6] 如[1]〜[5]中任一項所記載之壓印用組成物，其彈性回復率爲70%以上。 [7] —種硬化物，其特徵係使如[1]〜[6]中任一項所記載之壓印用硬化性組成物硬化而成。 [8] —種液晶顯示裝置用構件，其特徵係包括如[7]所記載之硬化物。 [9] 一種硬化物之製造方法，其特徵係包括：將如[1]〜[7] 中任一項所記載之壓印用硬化性組成物塗布在基材上而形成圖案形成層之步驟、將模具按壓於前述圖案形成層表面之步驟、與對前述圖案形成層照射光之步驟。〇 [10]如[9]所記載之硬化物之製造方法，其係進一步包括將經照射光之前述圖案形成層進行加熱之步驟。 [發明效果] 根據本發明，可提供一種加熱硬化後之圖案精度、表面硬度、光透過性及耐熱性優異的壓印用硬化性組成物、使用它之硬化物及其製造方法以及液晶顯示裝置用構件。【實施方式】 [實施發明之形態] -11- .201008996 以下針對本發明之内容加以詳細説明。本案說明書中使用「〜」，係指包括其前後所記載數値爲下限値及上限値。又’在本說明書中，「（甲基）丙烯酸酯」係表示「丙嫌酸酯」及「甲基丙烯酸酯」，「（甲基）丙烯酸」係表示「丙烯酸」及「甲基丙烯酸」，「（甲基）丙烯醯基」係表示「丙烯醯基」及「甲基丙烯醯基」。再者，本說明書中，「單體」與「單分子」係同義。本發明中之單體係與寡聚物及聚合物不同，指重量平均分子量爲1,000以下之化合物。本說明書中，「官能基」係指與聚合相關的基。又，在本發明所說的壓印係可包括約數十nm〜數十从m之尺寸的圖案轉印，亦包括奈米壓印，非爲限定奈米等級者。又，在本說明書中，「受阻酚系抗氧化劑」與「半受阻酚系」係不重複之槪念，明確地區別。 φ [壓印用硬化性組成物] 本發明之壓印用硬化性組成物（以下，簡稱爲「本發明之組成物」）係含有光聚合性單體、光聚合起始劑、抗氧化劑之光壓印用組成物，前述光聚合性單體之含量爲80〜 99.質量％，前述抗氧化劑之含量爲0.3〜7質量％。再者，本發明之壓印用硬化性組成物的第一態樣的特徵在於前述抗氧化劑係僅爲受阻酚系抗氧化劑、僅爲半受阻酚系抗氧化劑、受阻酚系抗氧化劑與半受阻酚系抗氧化劑之混合 -12- .201008996 物、或僅爲受阻胺系抗氧化劑中的任一者。另一方面，本發明之壓印用硬化性組成物第二態樣的特徵在於前述抗氧化劑係受阻酚系抗氧化劑與硫醚系抗氧化劑之混合物、或半受阻酚系抗氧化劑與硫醚系抗氧化劑之混合物》本發明之組成物除了含有特定範圍的量之光聚合性單體與光聚合起始劑，尙含有特定範圍的量之抗氧化劑，藉此可同時達成高水準的壓印性、光硬化性、耐熱性、電壓特性，再者，亦可使彈性回復率成爲高水準。由於從先前的抗氧化劑之功能無法預期提高彈性回復率之效果，故提高彈性回復率係特別驚奇的效果。又，本發明之壓印用硬化性組成物可廣泛地用於光壓印微影術（包括光奈米壓印微影術），可具有如下特徴。 (1) 本發明之組成物由於在室溫之溶液流動性優異，因此該組成物可容易地流入模具凹部之腔體内，因爲不易吸入大氣而引起氣泡缺陷，在模具凸部或凹部均不易在光硬化後殘留殘渣。 (2) 將本發明之組成物硬化後之硬化膜由於機械性質優異、塗膜與基材之密接性優良、且塗膜與模具之剝離性優異，因此在剝除模具時不會引起圖案崩塌或在塗膜表面產生黏絲性（stringness)而引起表面龜裂，故可形成良好的圖案（良好的壓印性）。 (3) 由於塗布均勻性，因此適合於大型基材之塗布·微細加工領域等。 -13- .201008996 (4) 因爲光硬化性、耐熱性、彈性回復率等機械特性高，因此適合作爲永久膜。 (5) 由於電壓特性優異，故適合於電子電路用材料等。因此，本發明之壓印用硬化性組成物可適合應用於例如，迄今難以發展之半導體積體電路或液晶顯示裝置用構件（尤其是液晶顯示器之薄膜電晶體、液晶彩色濾光片之保護膜、間隔材、其他液晶顯示裝置用構件之微細加工用途等），亦可廣泛地應用於其他用途，例如，電漿顯示器面板用隔壁材、平面螢幕、微電動機械系統（MEMS)、感應元件、光碟、高密度記憶體磁碟等之磁氣記錄媒體、繞射光柵或浮雕全息圖等之光學零件、奈米裝置、光學裝置、光學薄膜或偏光元件、有機電晶體、彩色濾光片、表塗層、柱材、液晶配向用肋材、微透鏡陣列、免疫分析晶片、DNA分離晶片、微反應器、奈米生化裝置、光導波路、濾光器、液晶光子晶體（photonic liquid crystal)等之製作。 φ (光聚合性單體）在本發明之壓印用硬化性組成物中含有光聚合性單體。本發明之組成物藉由含有光聚合性單體，可在光照射後得到良好的圖案精度（壓印性）。在本發明，「光聚合性單體j係指可藉由光照射引發聚合反應以形成高分子量體之單體。作爲在本發明所用之光聚合性單體的主要功能，可依目的適當選擇組成物之黏度調整或硬化膜之機械特性。從 -14- 201008996 組成物之黏度調整的觀點來看，較佳爲使用低黏度之光聚合性單體。又，爲了提升硬化物之圖案精度，組成物之黏度通常較佳爲1 8mPa · s以下，其目的係以使用盡可能低黏度之聚合性單體爲佳。光聚合性單體的黏度係與分子量、分子間相互作用等相關，因此光自由基聚合性單量的低黏度化係可藉由考慮低分子量、低分子間相互作用而達成。在本發明所用之光聚合性單體從調整組成物之黏度的觀點來看，較佳爲具有lOOmPa _s以下的黏度之化合物、更佳爲50mPa*s以下、特佳爲10mPa，s以下。本發明中光聚合性單體的重量平均分子量從調整組成物之黏度的觀點來看，較佳爲500以下、更佳爲100〜 400、特佳爲100〜300。又，本發明中光聚合性單體所具有之光自由基聚合性官能基，可舉例如具有乙烯性不飽和鍵之官能基，以（甲基）丙烯酸基、乙烯基、烯丙基苯乙烯基爲較佳。本發明之組 φ 成物所含的光聚合性單體可爲1種，亦可爲2種以上。又，本發明之組成物亦可並用具有光自由基聚合性官能基之光聚合性單體、不含有其之光聚合性單體（例如，具有陽離子性聚合性基之聚合性單體）。又，從賦予硬化膜之機械特性的觀點來看，以使用二官能以上之多官能單體爲較佳。此種多官能單體必然因分子量變大而黏度提高，由於組成物之高黏度化也會使圖案精度降低。所以’本發明所用之聚合性單體係考慮黏度調 -15- 201008996 整用之低黏度單分子與用以賦予硬化膜之機械特性賦予的多官能單分子之組合、或本發明中之氧雜環丁烷（oxetane) 化合物或官能性酸酐之組合，加以綜合性地選擇。在本發明之壓印用硬化性組成物，全組成物中光聚合性單體的含量，從光照射後之圖案精度的觀點來看，以20 〜90質量％爲較佳、以30〜70質量％爲更佳。惟，本發明中光聚合性單體的含量係如上述，係考慮本發明之組成物中具有自由基聚合性官能基之化合物的含量來決定》參在本發明，可僅含1種之倍半砂氧院（silsesquioxane) 化合物，亦可含2種以上。又，本發明之組成物中，倍半矽氧烷化合物以含1〜40質量％之比例爲較佳、以含1〜20 質量％之比例爲更佳。藉由成爲此範圍，可兼具組成物黏度與硬化膜的機械特性。本發明中光聚合性單體可舉出具有1個含有乙烯性不飽和鍵的基之聚合性不飽和單體（單官能之聚合性不飽和 φ 單體）。具體而言，對苯二甲酸2-丙烯醯氧基乙酯、對苯二甲酸2-丙烯醯氧基2-羥基乙酯、六氫對苯二甲酸2-丙烯醯氧基乙酯、對苯二甲酸2-丙烯醯氧基丙酯、丙烯酸2-乙基 -2-丁基丙二醇酯、（甲基）丙烯酸2-乙基己酯、（甲基）丙烯酸2-乙基己基卡必醇酯、（甲基）丙烯酸2-羥基丁酯、（甲基）丙烯酸2-羥基乙酯、（甲基）丙烯酸2-羥基丙酯、（甲基）丙烯酸2-甲氧基乙酯、（甲基）丙烯酸3-甲氧基丁酯、（甲基）丙烯酸4-羥基丁酯、丙烯酸酸二聚物、（甲基）丙烯酸苄酯、 -16- 201008996 丁二醇單（甲基）丙烯酸酯、（甲基）丙烯酸丁氧基乙酯、（甲基）丙烯酸丁酯、（甲基）丙烯酸十六烷酯、環氧乙烷改質（以下稱爲「EO」。）（甲基）丙烯酸甲酚酯、（甲基）丙烯酸二丙二醇酯、（甲基）丙烯酸乙氧基化苯酯、（甲基）丙烯酸乙酯、 (甲基）丙烯酸異戊酯、（甲基）丙烯酸異丁酯、（甲基）丙烯酸異辛酯、（甲基）丙烯酸環己酯、（甲基）丙烯酸異冰片酯、（甲基）丙烯酸二環戊酯、（甲基）丙烯酸二環戊基氧基乙酯、（甲基）丙烯酸異肉豆蔻酯、（甲基）丙烯酸月桂酯、（甲基）丙烯 ❹ 酸甲氧基二丙二醇酯、（甲基）丙烯酸甲氧基三丙二醇酯、（甲基）丙烯酸甲氧基聚乙二醇酯、（甲基）丙烯酸甲氧基三乙二醇酯、（甲基）丙烯酸甲酯、新戊二醇苯甲酸酯（甲基）丙烯酸酯、（甲基）丙烯酸壬基苯氧基聚乙二醇酯、（甲基）丙烯酸壬基苯氧基聚丙二醇酯、（甲基）丙烯酸辛酯、（甲基）丙烯酸對異丙苯基苯氧基乙二醇酯、表氯醇（以下稱爲「ECH」）改質丙烯酸苯氧酯、（甲基）丙烯酸苯氧基乙酯、（甲基）丙烯酸苯 φ 氧基二乙二醇酯、（甲基）丙烯酸苯氧基六乙二醇酯、（甲基）丙烯酸苯氧基四乙二醇酯、（甲基）丙烯酸聚乙二醇酯、（甲基）丙烯酸聚乙二醇-聚丙二醇酯、（甲基）丙烯酸聚丙二醇酯、（甲基）丙烯酸硬脂酯、EO改質（甲基）丙烯酸琥珀酸酯、 (甲基）丙烯酸tert-丁酯、（甲基）丙烯酸三溴苯酯、EO改質（甲基）丙烯酸三溴苯酯、（甲基）丙烯酸三-十二烷酯、p-異丙烯基苯酚、苯乙烯、α-甲基苯乙烯、丙烯腈、乙烯基咔唑、丙烯酸乙基氧雜環丁烷基甲酯。 -17- 201008996 再者，可例示乙烯基三氯矽烷、乙烯基參（yS -甲氧基乙氧基）矽烷、乙烯基三乙氧基矽烷、乙烯基三甲氧基矽烷等之乙烯基矽烷、3-甲基丙烯醯氧基丙基甲基二甲氧基矽烷、3-甲基丙烯醯氧基丙基三甲氧基矽烷、3_丙烯醯氧基丙基三甲氧基矽烷等之（甲基）丙烯醯氧基矽烷。此等之中，本發明特別適合使用丙烯酸酯單分子。又，作爲本發明之光聚合性單體，亦可較佳使用具有 2個含有乙烯性不飽和鍵的基之二官能聚合性不飽和單體。作爲前述二官能聚合性不飽和單體的實例，可例示二乙二醇單乙基醚（甲基）丙烯酸酯、二羥甲基二環戊烷二（甲基）丙烯酸酯、二（甲基）丙烯酸化三聚氰酸酯、二（甲基）丙烯酸1，3-丁二醇酯、二（甲基）丙烯酸ι，4-丁二醇酯、E0改質二（甲基）丙烯酸1，6-己二醇酯、ECH改質二（甲基）丙烯酸 1,6-己二醇酯、丙烯酸烯丙氧基聚乙二醇酯、二（甲基）丙烯酸1,9-壬二醇酯、EO改質雙酚A二（甲基）丙烯酸酯、p〇改 φ 質雙酚A二（甲基）丙烯酸酯、改質雙酚a二（甲基）丙烯酸酯、EO改質雙酚F二（甲基）丙烯酸酯、ECH改質二丙烯酸六氫酞酸酯、二（甲基）丙烯酸羥基三甲基乙酸新戊二醇酯、二（甲基）丙烯酸新戊二醇酯、EO改質二丙烯酸新戊二醇酯、環氧丙烷（以後稱爲「p〇」。）改質二丙烯酸新戊二醇酯、己內酯改質羥基三甲基乙酸酯新戊二醇、硬脂酸改質二（甲基）丙烯酸新戊四醇酯、ECH改質二（甲基）丙烯酸駄酸酯、聚（乙二醇-丁二醇）二（甲基）丙烯酸酯、聚（丙二醇_ -18- 201008996 丁二醇）二（甲基）丙烯酸酯、聚酯（二）丙烯酸酯、二（甲基）丙烯酸聚乙二醇酯、二（甲基）丙烯酸聚丙二醇酯、ECH改質二（甲基）丙烯酸丙二醇酯、矽酮二（甲基）丙烯酸酯、二（甲基）丙烯酸三乙二醇酯、二（甲基）丙烯酸四乙二醇酯、（二）丙烯酸三環癸烷二甲醇酯、新戊二醇改質三羥甲基丙烷二 (甲基）丙烯酸酯、二（甲基）丙烯酸三丙二醇酯、EO改質二（甲基）丙烯酸三丙二醇酯、三丙三醇二（甲基）丙烯酸酯、二（甲基）丙烯酸二丙二醇酯、二乙烯基乙烯脲、二乙烯基丙烯脲、（甲基）丙烯酸二環戊烯酯、（甲基）丙烯酸二環戊烯基氧基乙酯、二（甲基）丙烯酸二環戊基酯。此等之中，二（甲基）丙烯酸新戊二醇酯、二（甲基）丙烯酸1,9-壬二醇酯、二（甲基）丙烯酸三丙二醇酯、二（甲基）丙烯酸四乙二醇酯、二（甲基）丙烯酸羥基三甲基乙酸新戊二醇酯、二（甲基）丙烯酸聚乙二醇酯、（甲基）丙烯酸二環戊烯酯、（甲基）丙烯酸二環戊烯基氧基乙酯、二（甲基）丙烯酸 φ 二環戊基酯等係特別適合用於本發明。作爲本發明中之光聚合性單體，亦可較佳使用具有3 個以上之含有乙烯性不飽和鍵的基的多官能聚合性不飽和單體。作爲前述多官能聚合性不飽和單體的實例，可舉出 ECH改質三（甲基）丙烯酸丙三醇酯、EO改質三（甲基）丙烯酸丙三醇酯、PO改質三（甲基）丙烯酸丙三醇酯、三丙烯酸新戊四醇酯、E◦改質磷酸三丙烯酸酯、三羥甲基丙烷三（甲基）丙烯酸酯、己內酯改質三羥甲基丙烷三（甲基）丙烯酸 -19- 201008996 酯、EO改質三羥甲基丙烷三（甲基）丙烯酸酯、p〇改質三羥甲基丙烷三（甲基）丙烯酸酯、參（丙烯醯氧基乙基）三聚氰酸酯、六（甲基）丙烯酸二新戊四醇酯、己內酯改質六（甲基）丙烯酸二新戊四醇酯、五（甲基）丙烯酸二新戊四醇羥酯、烷基改質五（甲基）丙烯酸二新戊四醇酯、聚（甲基）丙烯酸二新戊四醇酯、烷基改質二新戊四醇三（甲基）丙烯酸酯、二-三羥甲基丙烷四（甲基）丙烯酸酯、四（甲基）丙烯酸新戊四醇乙氧酯、四（甲基）丙烯酸新戊四醇酯等。參此等之中，E0改質三（甲基）丙烯酸丙三醇酯、p〇改質三（甲基）丙烯酸丙三醇酯 '三羥甲基丙烷三（甲基）丙烯酸酯、E0改質三羥甲基丙烷三（甲基）丙烯酸酯、p〇改質三羥甲基丙烷三（甲基）丙烯酸酯、六（甲基）丙烯酸二新戊四醇酯、四（甲基）丙烯酸新戊四醇乙氧酯、四（甲基）丙烯酸新戊四醇酯等係特別適合用於本發明。本發明所用之光聚合性單體，亦可使用乙烯基醚化合 φ 物。前述乙烯基醚化合物係可由公知之物加以適當選擇’例如，2-乙基己基乙烯基醚、丁二醇-1，4-二乙烯基醚、二乙二醇單乙烯基醚、二乙二醇單乙烯基醚、乙二醇二乙烯基醚、三乙二醇二乙烯基醚、1,2-丙二醇二乙烯基醚、1，3-丙二醇二乙烯基醚、1,3-丁二醇二乙烯基醚、1，4-丁二醇二乙烯基醚、丁二醇二乙烯基醚、新戊二醇二乙烯基醚、三羥甲基丙烷三乙烯基醚、三羥甲基乙烷三乙烯基醚、己二 -20- 201008996 醇二乙烯基醚、四乙二醇二乙烯基醚、新戊四醇二乙缔基醚、新戊四醇三乙烯基醚、新戊四醇四乙烯基醚、山梨糖醇四乙烯基醚、山梨糖醇五乙烯基醚、乙二醇二乙烯乙嫌基醚、二乙一醇二乙嫌乙嫌基醚、乙二醇二丙嫌乙嫌基酸、三乙二醇二乙烯乙烯基醚、三羥甲基丙烷三乙烯乙烯基醚、三羥甲基丙烷二乙烯乙烯基醚、新戊四醇二乙烯乙稀基醚、新戊四醇三乙烯乙烯基醚、新戊四醇四乙烯乙燦基醚、1，1，1-參〔4-(2-乙烯氧基乙氧基）苯基〕乙烷、雙酣參八二乙烯氧基乙基醚等。此等乙嫌基酸化合物係可利用例如，Stephen. C. Lapin Polymers Paint Colour Journal.179(4237)、321(1988)所記載之方法’即藉由多元醇或多元苯酚與乙炔之反應、或多$ 醇或多元苯酚與鹵化烷基乙烯基醚之反應予以合成，此等係可1種單獨或組合2種以上來使用。又，本發明所用之光聚合性單體亦可採用苯乙烯衍生 φ 物。作爲苯乙烯衍生物，可舉出例如，P-甲氧基苯乙嫌、 P-甲氧基-々·甲基苯乙烯、P-羥基苯乙烯等。其他可與本發明之單官能聚合物倂用之苯乙烯衍生物，可列舉例如，苯乙烯、p -甲基苯乙烯、P -甲氧基苯乙烯、/3-甲基苯乙烯、P-甲基·ζδ-甲基苯乙烯、甲基苯乙烯、Ρ-甲氧基甲基苯乙烯、Ρ·羥基苯乙烯等。再者，在本發明中，亦可使用乙烯基萘衍生物，例如可列舉1_乙烯基萘、〇：-甲基-1-乙烯基萘、甲基-1-乙烯基萘、4•甲基 -21- 201008996 -1-乙烯基萘、4-甲氧基-1-乙烯基萘等。又’爲了提升與模具之剝離性及塗布性，亦可將（甲基）丙烯酸三氟乙酯、（甲基）丙烯酸五氟乙酯、（甲基）丙烯酸（全氟丁基）乙酯、（甲基）丙烯酸全氟丁基·羥基丙酯、（甲基）丙烯酸（全氟己基）乙酯、（甲基）丙烯酸八氟戊酯、（甲基）丙烯酸全氟辛基乙酯、（甲基）丙烯酸四氟丙基酯等之具有氟原子之化合物作爲本發明中之光聚合性單體使用或與本發明中之光聚合性單體倂用。〇再者’本發明所用之光聚合性單體可摻合丙烯基醚及丁烯基醚。例如1-十二烷基-1-丙烯基醚、1-十二烷基-1-丁烯基醚、1-丁烯氧基甲基-2-降冰片烯、1-4-二（1-丁烯氧基）丁烷、1,10-二（1-丁烯氧基）癸烷、1，4-二（1-丁烯氧基甲基）環己烷、二乙二醇二（1-丁烯基）醚、1，2,3-三（1-丁烯氧基）丙烷、丙烯基醚丙烯碳酸酯等係可適合使用。本發明之壓印用硬化性組成物中，作爲本發明所用之 Q 光聚合性單體’亦可含有具有含光自由基聚合性官能基的氧雜環丁烷環之化合物（以下，簡稱爲「氧雜環丁烷化合物」或「氧雜環丁烷單分子」）作爲光聚合性單體。本發明之組成物爲含有具氧雜環丁烷環之化合物時，因可藉由加熱得到優良硬度而較佳。本發明中具有氧雜環丁烷環之化合物所含的氧雜環丁烷環構造（氧雜環丁烷基）之數目，從硬化速度與硬化膜物性的觀點來看’以1〜4爲較佳、以1〜3爲更佳。 -22- 201008996 又，本發明中具有氧雜環丁烷環之化合物的總碳數，從組成物之黏度減低的觀點來看，以5〜50爲較佳、以5 〜20爲更佳。本發明中具有氧雜環丁烷環的化合物之分子量，從組成物之黏度減低的觀點來看，以100〜1000爲較佳、以100 〜400爲更佳。又，作爲本發明中之光聚合性單體的氧雜環丁烷化合物係具有光自由基聚合性官能基。作爲前述光自由基聚合性官能基，可舉出例如，具有乙烯性不飽和鍵之官能基，以（甲基）丙烯酸基、乙烯基、烯丙基、苯乙烯基爲較佳。本發明中具有氧雜環丁烷環之化合物所含的光自由基聚合性基之數目，從光照射時之圖案精度與基板之密接性的観點來看，以1〜4爲較佳、以1〜2爲更佳。本發明之組成物中所含的具有氧雜環丁烷環之化合物可爲1種、亦可爲 2種以上。又，本發明之組成物亦可並用具有光自由基聚 Φ 合性官能基之氧雜環丁烷化合物、與不含其之氧雜環丁烷化合物。倂用具有光自由基聚合性官能基之化合物U)、與不具有其之氧雜環丁烷化合物（y)時，從光照射後之圖案精度與抑制加熱時未反應成分揮發抑制的觀點來看，其含有比（X: y，基準爲X)以1/2〜5/1爲較佳、以1/1〜2/1爲更佳。又，本發明之壓印用硬化性組成物，只要不違背本發明之主旨，除了作爲光聚合性單體以外，亦可含具有氧雜環丁烷環之化合物。 -23- 201008996 在本發明之壓印用硬化性組成物，全組成物中氧雜環丁烷化合物的含量，從光照射後之圖案精度的觀點來看，以5〜50質量％爲較佳、以1〇〜30質量％爲更佳。惟，本發明中具有氧雜環丁烷環之化合物爲具有光自由基聚合性官能基時，其含量係如上述，可考慮本發明之組成物中具有自由基聚合性官能基之化合物的含量來加以決定。此時’具有光自由基聚合性官能基之氧雜環丁烷化合物的含量’係由與具有其他自由基聚合性官能基之化合物的含量 ❿ 之關係、或與不具有光自由基聚合性官能基之氧雜環丁烷化合物的含量之關係來適當決定。作爲本發明中具有氧雜環丁烷基之化合物，可列舉例如，3-乙基-3-羥基甲基氧雜環丁烷（商品名：OXT-101、東亞合成（股）製）、1,4-雙[[(3-乙基-3-氧雜環丁烷基）甲氧基] 甲基]苯（商品名：OXT-121、東亞合成（股）製）、3-乙基- 3-(苯氧基甲基）氧雜環丁烷（商品名：OXT-211、東亞合成（股） φ 製）、二[1-乙基（3-氧雜環丁烷基）]甲基醚（商品名： OXT.221、東亞合成（股）製）、3-乙基- 3-(2-乙基己氧基甲基）氧雜環丁烷（商品名：ΌΧΤ-212、東亞合成（股）製）、4,4’-雙 [3-乙基-(3-氧雜環丁烷基）甲氧基甲基]聯苯（商品名： ETERNACOLLOXBP、宇部興產（股）製）、倍半矽氧烷改質型氧雜環丁烷（商品名：OX-SQ、東亞合成（股）製）、氧雜環丁烷（甲基）丙烯酸酯（商品名：OXE-10、30、大阪有機化學（股）製）等。 -24- 201008996 本發明之壓印用硬化性組成物亦可含有官能性酸酐。本發明之酸酐化合物具有作爲前述氧雜環丁烷化合物之硬化劑的功能。本發明之組成物含有官能性酸酐時，由於在加熱硬化後可得髙表面硬度而較佳。本發明中所謂「官能性酸酐」，係酮酸2分子經脫水縮合之化合物，藉由加熱等與其他官能基化學鍵結者。作爲前述官能性酸酐酐，可列舉例如，酞酸酐類、檸康酸酐類、琥珀酸酐類、丙酸酐類、馬來酸酐類、醋酸酐 ❹ 類等，從黏度減低與組成物安定性的觀點來看，以酞酸酐類、馬來酸酐類爲較佳。又，本發明中官能性酸酐的總碳數，從組成物之黏度減低的觀點來看，以10〜100爲較佳、以10〜50爲更佳。本發明中官能性酸酐之分子量，從組成物之黏度減低的觀點來看，以100〜1000爲較佳、以100〜500爲更佳。又，前述官能性酸酐，從使光聚合性單體爲前述範圍 φ 之觀點來看，以具有光自由基聚合性官能基爲較佳。前述光自由基聚合性官能基，可列舉例如具有乙烯性不飽和鍵之官能基’以（甲基）丙烯酸基、乙烯基、烯丙基、苯乙烯基爲較佳。本發明中官能性酸酐所含之光自由基聚合性基的數目，從光照射時之圖案精度及與基板之密接性的觀點來看，以1〜3爲較佳、以1〜2爲更佳。本發明之組成物中所含的官能性酸酐可爲1種、亦可爲2種以上。又，本發明之組成物亦可倂用具有光自由基聚合性官能基之官能 -25- 201008996 性酸酐、與不具有其之官能性酸酐。倂用具有光自由基聚合性官能基之化合物（q)、與不具有其之官能性酸酐（w)時，從光照射後之圖案精度與抑制加熱時未反應成分揮發的觀點來看，其含有比（q: w，基準爲q)以1/2〜5/1爲較佳、以 1/1〜2Π爲更佳。在本發明之壓印用硬化性組成物，全組成物中官能性酸酐的含量，從光照射後之圖案精度的觀點來看，以5〜 50質量％爲較隹、以10〜30質量％爲更佳。惟，本發明中 ® 之官能性酸酐具有光自由基聚合性官能基時，其含量係如上述，可考慮本發明之組成物中具有自由基聚合性官能基之化合物的含量來加以決定。此時，具有光自由基聚合性官能基之官能性酸酐的含量係由與具有其他自由基聚合性官能基之化合物的含量之關係、或與不具有光自由基聚合性官能基之官能性酸酐的含量之關係來加以適當決定。又，在本發明之壓印用硬化性組成物，本發明之氧雜 g 環丁烷化合物U)與官能性酸酐（b)之含有比（a : b，基準爲 a)，從盡可能減少未反應官能基的量之觀點來看，以3/1〜 1/3爲較佳、以2/1〜1/2爲更佳。作爲本發明中之官能性酸酐’可列舉例如甲基 -1，2,3,6-四氫酞酸酐（商品名：EPICLON B570、大日本油墨化學工業（股）製）、甲基-六氫酞酸酐（商品名：EPIC LON B650、大曰本油墨化學工業（股）製）、甲基-3,6-內亞甲基 -1，2,3,6-四氫酞酸酐（商品名：厘11八(：-?、曰立化成工業（股） -26- 201008996 製）、4-甲基六氫酞酸酐（商品名：RIKACID Μ H-700、新曰本理化（股）製）、無水檸康酸、十二烯琥珀酸酐（商品名： RIKACID DDSA、新日本理化（股）製）、丙三醇雙（苯三甲酸酐）一乙酸酯（商品名：RIKACID MTA-10、新曰本理化（股）製）、日本Zeon(股）製之Quinhard -200(商品名）、日本環氧樹脂（股）製之 EPICURE YH-3 06(商品名）、Aldrich試藥 (P25205 、 294152,B9750 、 B4600 、 412287 、 N818 、 N1607 、 330736)等。接著，針對本發明中之光聚合性單體的較佳調合形態加以説明。本發明之壓印用硬化性組成物係組成物中光聚合性單體的總含量爲80〜99質量％。「光聚合性單體」係指例如（甲基）丙烯酸基、乙烯基、烯丙基等之具有含乙烯性不飽和鍵之自由基聚合性官能基的化合物。例如，前述具有氧雜環丁烷環之化合物之氧雜環丁烷（甲基）丙烯酸酯，由於（甲基）丙烯酸基爲自由基聚合性官能基，故符合前述光聚合性單體。本發明之組成物中光聚合性單體之總含量若小於80 質量％時，則即使進行光照射亦不能充分硬化，無法將模具圖案精度良好地進行轉印，硬化膜之硬度等物性亦不充分。又，本發明之組成物中具有自由基聚合性官能基之化合物的總含量大於99質量％時，光自由基聚合起始劑或界面活性劑等添加劑沒充分功效，圖案精度、硬化膜之物性 -27- 201008996 惡化。從圖案精度與硬化膜物性的觀點來看’本發明之組成物中具有自由基聚合性官能基之化合物的總含量以60〜 99質量％爲較佳、以80〜98質量％爲更佳。前述單官能之聚合性不飽和單體通常係作爲反應性稀釋劑使用，有效降低本發明之組成物的黏度，通常係添加總聚合性不飽和單體的10質量％以上。較佳爲添加20〜 80質量％、更佳爲25〜70質量％、特佳爲30〜60質量％之範圍。 e 前述單官能之聚合性不飽和單體由於作爲反應性稀釋劑更爲，故以添加總聚合性不飽和單體之1 0質量％以上爲較佳。前述具有2個含不飽和鍵的基之單體（二官能聚合性不飽和單體）較佳爲以總聚合性不飽和單體的90質量％以下、更佳爲80質量％以下、特佳爲70質量％以下之範圍予以添加。單官能及二官能聚合性不飽和單體之比例較佳爲 φ 以總聚合性不飽和單體之1〜95質量％、更佳爲3〜95質量 %、特佳爲5〜90質量％的範圍予以添加。具有3個以上前述含不飽和鍵的基之多官能聚合性不飽和單體之比例較佳爲以總聚合性不飽和單體之80質量％以下、更佳爲70質量 %以下、特佳爲60質量％以下的範圍來添加。藉由使具有3 個以上聚合性含不飽和鍵的基之聚合性不飽和單體之比例爲80質量％以下，因可降低組成物之黏度而較佳。 (光自由基聚合起始劑） -28- 201008996 本發明之壓印用硬化性組成物係含光自由基聚合起始劑。本發明之組成物藉由含有利用光照射可起始自由基聚合反之光自由基聚合起始劑，可使光照射後之圖案精度變爲良好。光自由基聚合起始劑，本發明所用之光自由基聚合起始劑的含量係以全組成物中例如0.1〜15質量％爲較佳、更佳爲0.2〜12質量％、特佳爲0.3〜10質量％。使用2 種以上之光聚合起始劑時，其合計量係爲前述範圍。前述光自由基聚合起始劑之比例爲0.1質量％以上 e 時，感度（速硬化性）、解像性、線邊緣粗糙性、塗膜強度有提升的傾向而較佳。另一方面，藉由使光自由基聚合起始劑之比例爲15質量％以下，光透過性、著色性、處理性等有提高的傾向而較佳。至今，在含染料及/或顏料之噴墨用組成物或液晶顯示器彩色濾光片用組成物，雖以對較佳光聚合起始劑及/或光酸產生劑之添加量進行各種檢討，但關於壓印用等之光壓印微影術用硬化性組成物之較佳光聚 φ 合起始劑及/或光酸產生劑的添加量並無報告。亦即，在含染料及/或顔料之系統中，此等係具有作爲自由基捕集劑之功用，對光聚合性、感度造成影響。考慮到此點，在此等用途中光聚合起始劑的添加量係經最適化。另一方面，在本發明之組成物，染料及/或顏料並非必須成分，光聚合起始劑之最適範圍有時係與噴墨用組成物或液晶顯示器彩色濾光片用組成物等之領域相異。本發明所用之光自由基聚合起始劑係摻合對所使用 -29- 201008996 之光源的波長具有.活性且使用產生適當活性種者。本發明所使用之光自由基聚合起始劑可採用例如市售之起始劑。此等實例可列舉可由 Ciba公司取得之 Irgacure(註冊商標）2959 : (1-[4-(2-羥基乙氧基）苯基]-2-羥基-2-甲基-1-丙院-1-酮、Irgacure(註冊商標）184: (1-經基環己基苯基酮）、Irgacure(註冊商標）50: (1-羥基環己基苯基酮、二苯甲酮）、Irgacure (註冊商標）651: (2,2-二甲氧基-1，2-二苯基乙烷-1-酮）、Irgacure(註冊商標）369: (2-苄基-2-二甲 ® 基胺基-1-(4-味啉基苯基）丁酮-1)、Irgacure(註冊商標）907 : (2·甲基-1[4-甲基硫苯基]-2-味啉代丙烷-1-酮、Irgacure(註冊商標）819:(雙（2,4,6-三甲基苯甲醯基）-苯基膦、 Irgacure(註冊商標）1 800 :(雙（2,6-二甲氧基苯甲醯基）-2,4,4-三甲基-戊基膦，1-羥基-環己基-苯基-酮）、 Irgacure(註冊商標）1 800 :(雙（2,6-二甲氧基苯甲醯基）-2,4,4-三甲基-戊基膦，2-羥基-2-甲基-1-苯基-1-丙烷·1-0 酮）、Irgacure(註冊商標）ΟΧΕ01 : (1,2-辛烷二酮，1·[4-(苯基硫）苯基]-2-(0-苯甲醯基肟）、Darocur(註冊商標）1173: (2-羥基-2-甲基-1-苯基-1·丙烷-1-酮）、Darocur(註冊商標）1116、1398、1174 及 1020、CGI242:(乙酮，1-[9-乙基- 6-(2-甲基苯甲醯基）-9H-咔唑-3-基]-1-(0-乙醯基肟）；可由BASF 公司取得之Lucirin TPO : (2,4,6-三甲基苯甲醯基二苯基膦）、Lucirin TP0-L : (2,4,6-三甲基苯甲醯基乙氧基苯基膦）；ESACURE 可由日本 SiberHegner 公司取得之 -30- 201008996 ESACURE1001M ： (1-[4-苯甲醯基苯基锍基]苯基]-2 -甲基 -2-(4-甲基苯基碾基）丙烷-1-酮、可由^4-1414旭電化公司取得之 Adeka Optomer(註冊商標）N-1414:(咔唑·苯酮系）、 A d e k a 0 p t 〇 m e r (註冊商標）N -1 7 1 7 :(叱陡系）、A d e k a Optomer(註冊商標）N- 1 606:(三阱系）；三和化學製之TFE-三阱：（2-[2-(呋喃-2-基）乙烯基]-4,6-雙（三氯甲基）-l，3,5-三阱）、三和化學製之TME-三畊：（2-[2-(5-甲基呋喃·2-基）乙烯基]-4,6-雙（三氯甲基）-1，3,5-三哄）、三和化學製之1^-三畊：（2-(4-甲氧基苯基）-4,6-雙（三氯甲基）-1，3,5·三畊）、 MIDORI化學製TAZ-113 : (2-[2-(3,4-二甲氧基苯基）乙烯基]-4,6-雙（三氯甲基）-1，3,5-三阱）、MIDORI化學製 TAZ-108(2-(3,4-二甲氧基苯基）-4,6-雙（三氯甲基）-1，3,5_三畊）、二苯甲酮、4,4*-雙二乙基胺基二苯甲酮、甲基-2-二苯甲酮、4-苯甲醯基-4’-甲基二苯基硫醚、4-苯基二苯甲酮、乙基米其勒酮、2-氯噻吨酮、2-甲基噻吨酮、2-異丙基噻吨酮、4-異丙基噻吨酮、2,4-二乙基噻吨酮、1-氯-4-丙氧基噻吨酮、2 -甲基噻吨酮、噻吨酮銨鹽、苯偶姻、4,4’-二甲氧基苯偶姻、苯偶姻甲基醚、苯偶姻乙基醚、苯偶姻異丙基醚、苯偶姻異丁基醚、苄基二甲基縮酮、1，1，卜三氯苯乙酮、二乙氧基苯乙酮及二苯并環庚酮、〇 -苯甲醯基安息香酸甲酯、2-苯甲醯基萘、4-苯甲醯基聯苯、4-苯甲醯基二苯基醒、 1,4-苯甲醯基苯、苄基、10-丁基-2-氯吖啶酮、[4_(甲基苯基硫）苯基]苯基甲烷）、2 -乙基蒽醌、2,2 -雙（2-氯苯 -31- 201008996 基）4,5,4’，5’-肆（3,4,5-三甲氧基苯基）1,2’-聯咪唑、2,2-雙（〇-氯苯基）4,5,4’，5’-四苯基-1,2’-聯咪唑、參（4-二甲基胺基苯基）甲烷、乙基-4-(二甲基胺基）苯甲酸酯、2-(二甲基胺基）乙基苯甲酸酯、丁氧基乙基_4-(二甲基胺基）苯甲酸酯等。 (抗氧化劑）本發明之壓印用硬化性組成物亦可含抗氧化劑。本發明之壓印用硬化性組成物之第一態樣的特徵在於前述抗氧化劑僅爲受阻酚系抗氧化劑、僅爲半受阻酚系抗氧化劑、爲受阻酚系抗氧化劑與半受阻酚系抗氧化劑之混合物、或僅爲受阻胺系抗氧化劑中之任一者。另一方面，本發明之壓印用硬化性組成物第二態樣的特徵在於前述抗氧化劑爲受阻酚系抗氧化劑與硫醚系抗氧化劑之混合物、或半受阻酚系抗氧化劑與硫醚系抗氧化劑之混合物。本發明之特徴係藉由使用在上述本發明之2種態樣的 0 抗氧化劑，可舉出提升光硬化性、耐熱性、彈性回復率之點。鑑於添加習知抗氧化劑之光硬化性樹脂組成物領域的技術，以本發明之上述2種態樣來添加抗氧化劑，達成本發明之組成物效果後而提升硬化膜的彈性回復率，其係特別驚人的效果。又，受阻酚系或半受阻酚系抗氧化劑以外之苯酚系抗氧化劑由於聚合阻礙大因而不佳。本發明之壓印用硬化性組成物所用之抗氧化劑的含 -32- 201008996 量爲全組成物中的0.3〜7質量％、較佳爲0.5〜5質量％、更佳爲1.5〜5質量％。使用2種以上之抗氧化劑時，使其合計量爲前述範圍。若前述抗氧化劑之含量爲0.3質量％以上時，因耐熱性、彈性回復率提升而較佳，若在7質量％以下時，因光硬化性提升而較佳。又，若前述抗氧化劑的含量爲0.5質量％以上時，因可更使耐熱性及彈性回復率提升而更佳，若爲5質量％以下時，因可更提升光硬化性而更佳。再者，若前述抗氧化劑之含量爲1.5質量％以上時，因可更進一步地提升耐熱性及彈性回復率，因此特佳爲1.5 〜5質量％。本發明之受阻酚系抗氧化劑係具有以下述一般式（1) 所示之構造的物質。201008996 An application example of the photoimprint method of a flat panel display such as a liquid crystal display (LCD) or a plasma display (PDP) in the second technique described above will be described. With the increase in the size of the LCD substrate and the PDP substrate, and the trend toward high definition, in recent years, attention has been paid to the replacement of the previous photolithography method used in the manufacture of thin film transistors (TFTs) or electrode plates. As a cheap lithography, shadows must develop photocurable photoresists that replace the etch photoresist used in previous photolithography. Further, as a structural member such as an LCD, the application of the imprint method has been reviewed for a transparent protective film material to be used, or a spacer material for a cell gap of a liquid crystal display. The photoresist for such a structural member is different from the above-described uranium engraved photoresist, and is eventually referred to as "permanent photoresist" or "permanent film" because it eventually remains in a display such as a flat panel display panel. As a permanent film to which the prior photolithography technique is applied, for example, a protective film provided on a TFT substrate of a liquid crystal panel, or a step of reducing the gap between the R, G, and B layers and imparting a film to the ITO film during sputtering can be used. A protective film or the like provided on a color filter for resistance to high-temperature treatment. In the formation of such a protective film (permanent film), since the uniformity of the coating film, the high light transmittance after heat treatment exceeding 200 ° C, and the scratch resistance are required, it is required to satisfy the pressure of these characteristics. Development of a hardening composition for printing. Further, the spacer used in the liquid crystal display is usually formed after the color filter is formed or after the protective film for the color filter is formed, and a photocurable composition is used on the color filter substrate by light micro The shadow formed a pattern of about 10//m to 20 μm in size and was further formed by post-baking heat hardening. In addition to the hardness and pattern precision, the spacer used in the above liquid crystal display particularly requires a high elastic recovery rate of 201008996, and development of a hardenability composition for imprint which satisfies these characteristics has been sought. Further, in the imprint method, it is necessary to improve the fluidity of the curable composition for imprinting in the cavity in which the recess of the mold surface is formed. Further, it is necessary to improve the peeling property between the mold and the photoresist while improving the adhesion between the photoresist and the substrate (substrate, support). As noted above, the required characteristics of the materials used in embossing lithography vary widely depending on the application. However, although the composition for imprinting has been described in the past, for example, regarding the expectation of viscosity, there have been no reports of design guidelines for materials suitable for each application. Therefore, as a main technical problem of the permanent film, various problems such as pattern accuracy, heat resistance, and hardness have been cited. The case where the curable composition for imprint is used as the permanent film is also the same as that of the conventional acrylic resin, (1) pattern transfer precision (imprinting of imprint lithography), and (2) heat resistance. (3) The imparting of the hardening property is important. As a problem specific to the curable composition for photoimprinting, in addition to the properties (1) to (3) above, one of the mechanical properties can withstand the imparting of a high elastic recovery rate as a permanent film (4). . Further, when designing the composition of the curable composition for imprinting, in addition to the above points (1) to (4), it is necessary to ensure (5) the fluidity of the photoresist in the concave portion of the mold, and it is necessary to have no solvent or a small amount. Low viscosity under solvent use (preferably 5mPa. s below) and (6) In order to use as a structural member of an electric circuit, it is necessary to improve and consider the voltage characteristics, and the technical difficulty of the composition design is further improved. . 201008996 In recent years, in order to suppress discoloration, it has been proposed to use an antioxidant in a curable composition for imprint (see Patent Document 3 and Patent Document 4). However, in fact, the current situation does not review the use of antioxidants for the hardening composition for imprinting. Further, a photocurable composition in which a conventional antioxidant is added to other uses is reviewed. For example, in order to prevent oxidation of the metal surface to be bonded to the adhesive composition for a disc, and to improve the adhesion of the adhesive (Patent Document 5). It is described in the same literature that the photocurable composition is less than 0. An example of the antioxidant of 2% by mass, but does not imply a description of characteristics required for a hardening composition for imprinting such as imprintability, heat resistance, photocurability, high elastic recovery, low viscosity, and voltage characteristics. Especially when using less than 0. In the example of 2% by mass of the antioxidant, the viscosity of the composition is changed to 380 mPa. s (25 ° C) is not a curable composition for imprinting which is applied to a low-viscosity composition described in Patent Document 5. Further, for the purpose of improving the viscosity, it has been reported that 0 is added to the active light-curable ink-jet composition. An example of 15% by mass of an antioxidant (Patent Document 6). However, although there is a description about the improvement of viscosity in the same literature, there is no description about imprintability, heat resistance, photocurability, high elastic recovery rate, and voltage characteristics. As disclosed in Patent Document 5 and Patent Document 6, a known document in which an antioxidant is added to a photocurable resin composition is intended to prevent oxidation by oxygen in the air or to lower the viscosity. Detailed review. Further, a publicly known article in which an antioxidant is added to a thermosetting resin. The purpose of 201008996 is also to suppress the discoloration of the resin caused by oxidation during heating. [Prior Art Document] [Patent Document 1] [Patent Document 1] US Pat. No. 5,772,905 (Patent Document 2) US Pat. No. 5,956,216 (Patent Document 3) JP-A-2008-105414 (Patent Document 4) [Patent Document 5] JP-A-2002-256228 (Patent Document 6) JP-A-2006- 1 24636 (Non-Patent Document) [Non-Patent Document 1] S. Chou et al.: Appl. Phys. Lett. Vol. 67, 3 1 14 (1995) [Non-Patent Document 2] M. Colbun et al.: Proc. SPIE, Vol. 3676, 379 (1999) [Problems to be Solved by the Invention] In view of the above-mentioned problems, the composition described in Patent Document 6 is used as it is for imprinting, and heat resistance and elastic recovery rate are understood. And the voltage characteristics are bad. An object of the present invention is to provide a hardenable composition for embossing which has good embossability and photocurability, and which is excellent in mechanical properties, various durability, photohardness, heat resistance and elastic recovery, and hardening thereof. And a method for producing the same, and a member for a liquid crystal display device. More specifically, this. 201008996 The object of the invention is to provide a curable composition for imprinting which is particularly suitable for a permanent film such as a transparent protective film or a spacer for a flat panel display or the like. [Means for Solving the Problem] Based on the above-mentioned problems, the inventors of the present invention conducted a drill collar investigation and found that it is possible to design the above-mentioned (1) to (1) to be completely satisfied by including a specific amount of an antioxidant in the curable composition for imprinting. 6) A composition of the characteristics in which (4) a composition having a high elastic recovery ratio is particularly available. That is, it has been found that the above problems can be solved by the following means. [1] A curable composition for embossing, comprising: a) a photopolymerizable monomer, B) a photopolymerization initiator, and C) an optical imprint composition for an antioxidant, wherein the aforementioned A) the content of the photopolymerizable monomer is 80 to 99% by mass, and the content of the above-mentioned C) antioxidant is 0. 3 to 7 mass%, the above-mentioned C) antioxidant is only a hindered phenol-based antioxidant, only a semi-hindered phenol-based antioxidant, a mixture of a hindered phenol-based antioxidant and a semi-hindered phenol-based antioxidant, or only a hindered amine system. Any of the antioxidants. [2] The curable composition for imprint according to [1], wherein the antioxidant is composed only of a semi-hindered phenol-based antioxidant. [3] A curable composition for embossing, comprising: a) a photopolymerizable monomer, B) a photopolymerization initiator, and C) an antioxidant for photoimprint composition, wherein A) the content of the photopolymerizable monomer is 80 to 99% by mass, and the content of the above-mentioned C) antioxidant is 0. 3 to 7 mass%, the above C) antioxidant is a mixture of a hindered phenol antioxidant and a thioether antioxidant, or a mixture of a semi-hindered phenol antioxidant and a thioether antioxidant -10- 201008996 [4] [3] The curable composition for imprint described above, wherein the antioxidant is a mixture of a semi-hindered phenol system and a thioether system. [5] The composition for imprint according to any one of [1] to [4] wherein the content of the antioxidant is 0. 5 to 5 mass%. [6] The composition for imprint according to any one of [1] to [5], which has an elastic recovery ratio of 70% or more. [7] A cured product obtained by curing the curable composition for imprint according to any one of [1] to [6]. [8] A member for a liquid crystal display device, characterized by comprising the cured product according to [7]. [9] A method of producing a cured product, comprising the step of applying a curable composition for imprint according to any one of [1] to [7] on a substrate to form a pattern forming layer. And a step of pressing the mold on the surface of the pattern forming layer and a step of irradiating the pattern forming layer with light. [10] The method for producing a cured product according to [9], which further comprises the step of heating the pattern forming layer irradiated with light. According to the present invention, it is possible to provide a curable composition for imprinting which is excellent in pattern accuracy, surface hardness, light transmittance, and heat resistance after heat curing, a cured product using the same, a method for producing the same, and a liquid crystal display device. Use components. [Embodiment] [Formation of the Invention] -11- . 201008996 The contents of the present invention are described in detail below. The use of "~" in this manual refers to the number of 値 before and after the lower limit 値 and upper limit 値. In the present specification, "(meth)acrylate" means "acrylic acid ester" and "methacrylate", and "(meth)acrylic acid" means "acrylic acid" and "methacrylic acid". "(Meth)acrylonitrile" means "acryloyl" and "methacryl". In addition, in this specification, "monomer" is synonymous with "single molecule". The single system in the present invention is different from the oligomer and the polymer, and refers to a compound having a weight average molecular weight of 1,000 or less. In the present specification, "functional group" means a group related to polymerization. Further, the imprinting system according to the present invention may comprise a pattern transfer of a size of from about several tens of nanometers to several tens of meters, and also includes nanoimprinting, not limited to the nanometer level. Further, in the present specification, the "hindered phenol-based antioxidant" and the "semi-hindered phenol-based" are not clearly distinguished, and are clearly distinguished. Φ [curable composition for imprinting] The curable composition for imprint of the present invention (hereinafter, simply referred to as "the composition of the present invention") contains a photopolymerizable monomer, a photopolymerization initiator, and an antioxidant. The composition for photoimprinting, the content of the photopolymerizable monomer is 80 to 99. % by mass, the content of the aforementioned antioxidant is 0. 3 to 7 mass%. Further, the first aspect of the curable composition for imprint of the present invention is characterized in that the antioxidant is only a hindered phenol-based antioxidant, only a semi-hindered phenol-based antioxidant, a hindered phenol-based antioxidant, and a semi-blocked Mixture of phenolic antioxidants -12- . 201008996, or just one of the hindered amine antioxidants. On the other hand, the second aspect of the curable composition for imprint of the present invention is characterized in that the antioxidant is a mixture of a hindered phenol-based antioxidant and a thioether-based antioxidant, or a semi-hindered phenol-based antioxidant and a thioether system. Mixture of Antioxidant The composition of the present invention contains a specific range of amount of photopolymerizable monomer and photopolymerization initiator, and contains a specific range of antioxidants, thereby achieving high level of imprintability at the same time. Moreover, photohardenability, heat resistance, and voltage characteristics, and the elastic recovery rate can also be made high. Since the effect of the elastic recovery rate cannot be expected from the function of the previous antioxidant, it is particularly surprising that the elastic recovery rate is improved. Further, the curable composition for imprint of the present invention can be widely used for photoimprint lithography (including photon lithography), and can have the following features. (1) Since the composition of the present invention is excellent in fluidity at a solution at room temperature, the composition can easily flow into the cavity of the concave portion of the mold, and it is difficult to inhale the atmosphere to cause bubble defects, which is difficult in the convex portion or the concave portion of the mold. The residue remains after photohardening. (2) The cured film obtained by curing the composition of the present invention is excellent in mechanical properties, excellent in adhesion between the coating film and the substrate, and excellent in peeling property between the coating film and the mold, so that pattern peeling is not caused when the mold is peeled off. Or a stringness is generated on the surface of the coating film to cause surface cracking, so that a good pattern (good embossability) can be formed. (3) Due to uniform coating properties, it is suitable for coating and micromachining of large substrates. -13- . 201008996 (4) It is suitable as a permanent film because of its high mechanical properties such as light hardenability, heat resistance and elastic recovery. (5) Since it is excellent in voltage characteristics, it is suitable for materials for electronic circuits. Therefore, the curable composition for imprint of the present invention can be suitably applied to, for example, a semiconductor integrated circuit or a member for a liquid crystal display device which has hitherto been difficult to develop (especially a thin film transistor of a liquid crystal display, a protective film of a liquid crystal color filter) , spacers, and other micro-processing applications for liquid crystal display devices, etc.), can also be widely used in other applications, such as partition walls for plasma display panels, flat screens, micro electromechanical systems (MEMS), sensing elements, Optical components such as magnetic recording media such as optical disks and high-density memory disks, optical components such as diffraction gratings or embossed holograms, nanodevices, optical devices, optical films or polarizing elements, organic transistors, color filters, and watches Coating, column, liquid crystal alignment rib, microlens array, immunoassay wafer, DNA separation wafer, microreactor, nano biochemical device, optical waveguide, filter, photonic liquid crystal, etc. Production. φ (Photopolymerizable monomer) The photopolymerizable monomer is contained in the curable composition for imprint of the present invention. The composition of the present invention can provide good pattern precision (imprint property) after light irradiation by containing a photopolymerizable monomer. In the present invention, the "photopolymerizable monomer j" means a monomer which can initiate a polymerization reaction by light irradiation to form a high molecular weight body. As a main function of the photopolymerizable monomer used in the present invention, it can be appropriately selected depending on the purpose. The viscosity of the composition is adjusted or the mechanical properties of the cured film. From the viewpoint of viscosity adjustment of the composition of-14-201008996, it is preferred to use a photopolymerizable monomer having a low viscosity. Further, in order to improve the pattern precision of the cured product, The viscosity of the composition is usually preferably 18 mPa·s or less, and the purpose is to use a polymerizable monomer having a viscosity as low as possible. The viscosity of the photopolymerizable monomer is related to molecular weight, intermolecular interaction, and the like. The photo-radical polymerizable single-component low-viscosity system can be achieved by considering low molecular weight and low intermolecular interaction. The photopolymerizable monomer used in the present invention is preferably from the viewpoint of adjusting the viscosity of the composition. It is a compound having a viscosity of 100 mPa _s or less, more preferably 50 mPa*s or less, particularly preferably 10 mPa or less. The weight average molecular weight of the photopolymerizable monomer in the present invention is adjusted from the composition. The viewpoint of the viscosity is preferably 500 or less, more preferably 100 to 400, and particularly preferably 100 to 300. Further, the photoradical polymerizable functional group of the photopolymerizable monomer in the present invention can be exemplified. The functional group having an ethylenically unsaturated bond is preferably a (meth)acrylic group, a vinyl group or an allylstyrene group. The photopolymerizable monomer contained in the group φ of the present invention may be 1 In addition, the photopolymerizable monomer having a photoradical polymerizable functional group and a photopolymerizable monomer not containing the photopolymerizable monomer (for example, having a cationic polymerization) may be used in combination with the composition of the present invention. Further, from the viewpoint of imparting mechanical properties to the cured film, it is preferred to use a difunctional or higher polyfunctional monomer. Such a polyfunctional monomer necessarily has a viscosity due to a large molecular weight. Increasing, because of the high viscosity of the composition, the pattern precision is also lowered. Therefore, the polymerizable single system used in the present invention considers the viscosity adjustment -15 - 201008996. The low viscosity single molecule used for the whole is used to impart mechanical properties to the cured film. Polyfunctional single molecule A combination of these, or a combination of an oxetane compound or a functional anhydride in the present invention, is selected in a comprehensive manner. In the curable composition for imprint of the present invention, the photopolymerizable single in the entire composition The content of the body is preferably from 20 to 90% by mass, more preferably from 30 to 70% by mass, from the viewpoint of pattern accuracy after light irradiation. However, the content of the photopolymerizable monomer in the present invention is as follows. The above is considered in consideration of the content of the compound having a radical polymerizable functional group in the composition of the present invention. In the present invention, only one type of silsesquioxane compound may be contained, or two types may be contained. Further, in the composition of the present invention, the sesquioxane compound is preferably contained in a proportion of from 1 to 40% by mass, more preferably from 1 to 20% by mass. By being in this range, it is possible to combine both the viscosity of the composition and the mechanical properties of the cured film. In the photopolymerizable monomer of the present invention, a polymerizable unsaturated monomer (monofunctional polymerizable unsaturated φ monomer) having one group containing an ethylenically unsaturated bond may be mentioned. Specifically, 2-propenyloxyethyl terephthalate, 2-propenyloxy 2-hydroxyethyl terephthalate, 2-propenyloxyethyl hexahydroterephthalate, p-benzene 2-propenyl propyl propyl dicarboxylate, 2-ethyl-2-butyl propylene glycol acrylate, 2-ethylhexyl (meth) acrylate, 2-ethylhexyl carbitol (meth) acrylate , 2-hydroxybutyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, (methyl) ) 3-methoxybutyl acrylate, 4-hydroxybutyl (meth) acrylate, acrylate acid dimer, benzyl (meth) acrylate, -16-201008996 butanediol mono (meth) acrylate, Butyloxyethyl (meth)acrylate, butyl (meth)acrylate, hexadecyl (meth)acrylate, modified with ethylene oxide (hereinafter referred to as "EO".) (meth)acrylic acid Phenolic ester, dipropylene glycol (meth)acrylate, ethoxylated phenyl (meth)acrylate, ethyl (meth)acrylate, isoamyl (meth)acrylate , isobutyl (meth)acrylate, isooctyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, (methyl) Dicyclopentyloxyethyl acrylate, isomyristyl (meth)acrylate, lauryl (meth)acrylate, methoxydipropylene glycol (meth) acrylate, methoxy (meth)acrylate Tripropylene glycol ester, methoxypolyethylene glycol (meth)acrylate, methoxytriethylene glycol (meth)acrylate, methyl (meth)acrylate, neopentyl glycol benzoate ( Methyl) acrylate, decyl phenoxy polyethylene glycol (meth) acrylate, decyl phenoxy propylene glycol (meth) acrylate, octyl (meth) acrylate, (meth) acrylate Phenyl phenoxyethylene glycol ester, epichlorohydrin (hereinafter referred to as "ECH") modified phenoxy acrylate, phenoxyethyl (meth) acrylate, benzene φ oxy (meth) acrylate Diethylene glycol ester, phenoxy hexaethylene glycol (meth)acrylate, (meth) propylene Acid phenoxytetraethylene glycol ester, polyethylene glycol (meth)acrylate, polyethylene glycol-polypropylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, hard (meth)acrylate Fatty ester, EO modified (meth)acrylic acid succinate, tert-butyl (meth)acrylate, tribromophenyl (meth)acrylate, EO modified tribromophenyl (meth)acrylate, (A Tris-dodecyl acrylate, p-isopropenylphenol, styrene, α-methylstyrene, acrylonitrile, vinylcarbazole, ethyl oxetanemethyl acrylate. -17- 201008996 Further, a vinyl decane such as vinyl trichloromethane, vinyl ginseng (yS-methoxyethoxy) decane, vinyl triethoxy decane or vinyl trimethoxy decane can be exemplified. 3-methyl propylene methoxy propyl methyl dimethoxy decane, 3-methyl propylene methoxy propyl trimethoxy decane, 3- propylene methoxy propyl trimethoxy decane, etc. ) propylene decyloxydecane. Among these, the present invention is particularly suitable for the use of acrylate single molecules. Further, as the photopolymerizable monomer of the present invention, a difunctional polymerizable unsaturated monomer having two groups containing an ethylenically unsaturated bond can be preferably used. As an example of the aforementioned difunctional polymerizable unsaturated monomer, diethylene glycol monoethyl ether (meth) acrylate, dimethylol dicyclopentane di(meth) acrylate, di(methyl) can be exemplified. Acrylic cyanurate, 1,3-butylene glycol di(meth)acrylate, ι,4-butylene glycol di(meth)acrylate, E0 modified di(meth)acrylic acid 1, 6-hexanediol ester, ECH modified 1,6-hexanediol di(meth)acrylate, allyloxypolyethylene glycol acrylate, 1,9-nonanediol di(meth)acrylate EO modified bisphenol A di(meth) acrylate, p 〇 φ bisphenol A di(meth) acrylate, modified bisphenol a di (meth) acrylate, EO modified bisphenol F Di(meth)acrylate, ECH modified hexahydrofurfurate diacrylate, hydroxytrimethylacetate neopentyl glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, EO modification Neopentyl glycol diacrylate, propylene oxide (hereinafter referred to as "p〇".) modified neopentyl glycol diacrylate, caprolactone modified hydroxytrimethyl acetate neopentyl , stearic acid modified di(meth)acrylic acid pentaerythritol ester, ECH modified di(meth)acrylic acid decanoate, poly(ethylene glycol-butanediol) di(meth)acrylate, poly (propylene glycol _ -18- 201008996 butane diol) di(meth) acrylate, polyester (di) acrylate, polyethylene glycol di(meth) acrylate, polypropylene glycol di(meth) acrylate, ECH Modification of propylene glycol di(meth)acrylate, ketone ketone di(meth) acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, (di)acrylic acid Cyclodecane dimethanol ester, neopentyl glycol modified trimethylolpropane di(meth) acrylate, tripropylene glycol di(meth)acrylate, EO modified tripropylene glycol di(meth)acrylate, three Glycerol di(meth)acrylate, dipropylene glycol di(meth)acrylate, divinylethylene urea, divinyl propylene urea, dicyclopentenyl (meth) acrylate, (meth) acrylate Cyclopentenyloxyethyl ester, dicyclopentyl di(meth)acrylate. Among these, neopentyl glycol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, tripropylene glycol di(meth)acrylate, tetraethyl bis(meth)acrylate Glycol ester, hydroxytrimethylacetate neopentyl glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, dicyclopentenyl (meth)acrylate, (meth)acrylic acid Cyclopentenyloxyethyl ester, φ dicyclopentyl di(meth)acrylate, and the like are particularly suitable for use in the present invention. As the photopolymerizable monomer in the present invention, a polyfunctional polymerizable unsaturated monomer having three or more groups containing an ethylenically unsaturated bond can also be preferably used. Examples of the polyfunctional polymerizable unsaturated monomer include ECH-modified tris(meth)acrylic acid glycerol ester, EO-modified tris(meth)acrylic acid glycerol ester, and PO-modified tris(A). Base) glycerol acrylate, neopentyl glycol triacrylate, E ◦ modified phosphoric acid triacrylate, trimethylolpropane tri (meth) acrylate, caprolactone modified trimethylolpropane tri Methyl)acrylic acid-19- 201008996 ester, EO modified trimethylolpropane tri(meth)acrylate, p〇 modified trimethylolpropane tri(meth)acrylate, ginseng Carboxylic acid ester, tricresyl hexa(meth) acrylate, caprolactone modified hexamethyl (meth) acrylate pentaerythritol, penta (meth) acrylate pentaerythritol Hydroxyester, alkyl modified pentaerythritol penta(meth)acrylate, dipentaerythritol poly(meth)acrylate, alkyl modified dipentaerythritol tri(meth)acrylate, Di-trimethylolpropane tetra(meth)acrylate, neopentyl glycol tetra(meth)acrylate, tetra(methyl) The new acid esters of pentaerythritol and the like. Among them, E0 modified tris(meth)acrylic acid glycerol ester, p〇 modified tris(meth)acrylic acid glycerol ester trimethylolpropane tri(meth)acrylate, E0 modified Trimethylolpropane tri(meth)acrylate, p〇modified trimethylolpropane tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tetra(meth)acrylic acid Neopentyl glycol ethoxylate, neopentyl tetra(meth)acrylate, and the like are particularly suitable for use in the present invention. The photopolymerizable monomer used in the present invention may also be a vinyl ether compound. The above vinyl ether compound can be appropriately selected from known ones, for example, 2-ethylhexyl vinyl ether, butanediol-1,4-divinyl ether, diethylene glycol monovinyl ether, diethylene glycol Alcohol monovinyl ether, ethylene glycol divinyl ether, triethylene glycol divinyl ether, 1,2-propylene glycol divinyl ether, 1,3-propanediol divinyl ether, 1,3-butanediol Divinyl ether, 1,4-butanediol divinyl ether, butanediol divinyl ether, neopentyl glycol divinyl ether, trimethylolpropane trivinyl ether, trimethylolethane Trivinyl ether, hexamethylene-20- 201008996 alcohol divinyl ether, tetraethylene glycol divinyl ether, neopentyl alcohol diethyl ether ether, neopentyl alcohol trivinyl ether, neopentyl alcohol Vinyl ether, sorbitol tetravinyl ether, sorbitol pentavinyl ether, ethylene glycol divinyl b-ethyl ether, diethylene glycol diethylene glycol suspected ether, ethylene glycol dipropylene Acid, triethylene glycol divinyl vinyl ether, trimethylolpropane triethylene vinyl ether, trimethylolpropane divinyl vinyl ether, neopentyl alcohol divinyl vinyl Ether, neopentyl alcohol triethylene vinyl ether, neopentyl alcohol tetraethylene ethylene ether, 1,1,1-gin[4-(2-vinyloxyethoxy)phenyl]ethane, double Ginseng octavinyloxyethyl ether and the like. These B-acidic compounds are available, for example, Stephen. C. Lapin Polymers Paint Colour Journal. The method described in 179 (4237) and 321 (1988) is synthesized by reacting a polyhydric alcohol or a polyhydric phenol with acetylene, or by reacting an alcohol or a polyhydric phenol with a halogenated alkyl vinyl ether. One type may be used alone or in combination of two or more. Further, the photopolymerizable monomer used in the present invention may also be a styrene-derived φ material. The styrene derivative may, for example, be P-methoxyphenethyl, P-methoxy-oxime methylstyrene or P-hydroxystyrene. Other styrene derivatives which can be used in combination with the monofunctional polymer of the present invention include, for example, styrene, p-methylstyrene, P-methoxystyrene, /3-methylstyrene, P-. Methyl·ζδ-methylstyrene, methylstyrene, anthracene-methoxymethylstyrene, anthracene hydroxystyrene, and the like. Further, in the present invention, a vinyl naphthalene derivative can also be used, and examples thereof include 1-vinylnaphthalene, anthracene:-methyl-1-vinylnaphthalene, methyl-1-vinylnaphthalene, and 4·A. Base-21- 201008996 -1-vinylnaphthalene, 4-methoxy-1-vinylnaphthalene, and the like. Further, in order to improve the peelability and coatability with the mold, trifluoroethyl (meth)acrylate, pentafluoroethyl (meth)acrylate, (perfluorobutyl)ethyl (meth)acrylate, Perfluorobutyl-hydroxypropyl (meth)acrylate, (perfluorohexyl)ethyl (meth)acrylate, octafluoropentyl (meth)acrylate, perfluorooctylethyl (meth)acrylate, A compound having a fluorine atom such as tetrafluoropropyl methacrylate is used as the photopolymerizable monomer in the present invention or in combination with the photopolymerizable monomer in the present invention. Further, the photopolymerizable monomer used in the present invention may be blended with a propenyl ether and a butenyl ether. For example, 1-dodecyl-1-propenyl ether, 1-dodecyl-1-butenyl ether, 1-butoxymethyl-2-norbornene, 1-4-di(1) -butenyloxy)butane, 1,10-bis(1-butoxy)decane, 1,4-bis(1-butoxymethyl)cyclohexane, diethylene glycol di 1-butenyl)ether, 1,2,3-tris(1-butenyloxy)propane, propylene ether propylene carbonate, or the like can be suitably used. In the curable composition for imprint of the present invention, the Q-ray polymerizable monomer used in the present invention may further contain a compound having an oxetane ring containing a photoradical polymerizable functional group (hereinafter, simply referred to as An "oxetane compound" or an "oxetane single molecule" is used as a photopolymerizable monomer. When the composition of the present invention contains a compound having an oxetane ring, it is preferred because it can be heated to have excellent hardness. The number of the oxetane ring structure (oxetanyl group) contained in the compound having an oxetane ring in the present invention is from 1 to 4 from the viewpoints of the curing rate and the physical properties of the cured film. Preferably, it is preferably 1 to 3. Further, the total carbon number of the compound having an oxetane ring in the present invention is preferably from 5 to 50, more preferably from 5 to 20, from the viewpoint of reducing the viscosity of the composition. The molecular weight of the compound having an oxetane ring in the present invention is preferably from 100 to 1,000, more preferably from 100 to 400, from the viewpoint of reducing the viscosity of the composition. Further, the oxetane compound which is a photopolymerizable monomer in the present invention has a photoradical polymerizable functional group. The photo-radical polymerizable functional group may, for example, be a functional group having an ethylenically unsaturated bond, and preferably a (meth)acrylic group, a vinyl group, an allyl group or a styryl group. The number of photoradical polymerizable groups contained in the compound having an oxetane ring in the present invention is preferably from 1 to 4 from the viewpoint of the pattern accuracy at the time of light irradiation and the adhesion between the substrates. It is better to use 1~2. The compound having an oxetane ring contained in the composition of the present invention may be one type or two or more types. Further, the composition of the present invention may be used in combination with an oxetane compound having a photoradical polyfunctionality functional group and an oxetane compound not containing the same. When the compound U) having a photoradical polymerizable functional group and the oxetane compound (y) having no photo-polymerizable functional group are used, the pattern accuracy after light irradiation and the suppression of volatilization of unreacted components during heating are suppressed. It is preferable that the ratio (X: y, the reference is X) is preferably 1/2 to 5/1, more preferably 1/1 to 2/1. Further, the curable composition for imprint of the present invention may contain a compound having an oxacyclobutane ring in addition to the photopolymerizable monomer, as long as it does not deviate from the gist of the present invention. -23-201008996 In the curable composition for imprint of the present invention, the content of the oxetane compound in the total composition is preferably 5 to 50% by mass from the viewpoint of pattern accuracy after light irradiation. It is preferably 1 to 30% by mass. However, when the compound having an oxetane ring in the present invention has a photoradical polymerizable functional group, the content thereof is as described above, and the content of the compound having a radical polymerizable functional group in the composition of the present invention can be considered. To decide. In this case, the 'content of the oxetane compound having a photoradical polymerizable functional group' is derived from the relationship with the content ❿ of the compound having another radical polymerizable functional group or with no photo radical polymerizable function. The relationship between the content of the oxetane compound is appropriately determined. The compound having an oxetanyl group in the invention may, for example, be 3-ethyl-3-hydroxymethyloxetane (trade name: OXT-101, manufactured by Toagosei Co., Ltd.), 1 , 4-bis[[(3-ethyl-3-oxetanyl)methoxy]methyl]benzene (trade name: OXT-121, manufactured by East Asia Synthetic Co., Ltd.), 3-ethyl- 3-(phenoxymethyl)oxetane (trade name: OXT-211, East Asia Synthetic (R) φ), bis[1-ethyl(3-oxetanyl)]methyl Ether (trade name: OXT. 221, East Asian synthesis (stock), 3-ethyl-3-(2-ethylhexyloxymethyl) oxetane (trade name: ΌΧΤ-212, manufactured by East Asia Synthetic Co., Ltd.), 4 , 4'-bis[3-ethyl-(3-oxetanyl)methoxymethyl]biphenyl (trade name: ETERNACOLLOXBP, manufactured by Ube Industries, Ltd.), sesquiterpene oxide modification Amino oxetane (trade name: OX-SQ, manufactured by Toagosei Co., Ltd.), oxetane (meth) acrylate (trade name: OXE-10, 30, Osaka Organic Chemicals Co., Ltd.) System) and so on. -24- 201008996 The curable composition for imprint of the present invention may further contain a functional acid anhydride. The acid anhydride compound of the present invention has a function as a curing agent for the aforementioned oxetane compound. When the composition of the present invention contains a functional acid anhydride, it is preferred to obtain a surface hardness after heat curing. In the present invention, the "functional acid anhydride" is a compound obtained by dehydrating condensation of two molecules of keto acid, and is chemically bonded to other functional groups by heating or the like. Examples of the functional anhydride anhydrides include phthalic anhydrides, citraconic anhydrides, succinic anhydrides, propionic anhydrides, maleic anhydrides, and acetic anhydrides, and the like, from the viewpoint of viscosity reduction and composition stability. It is preferable to use phthalic anhydride or maleic anhydride. Further, in the present invention, the total carbon number of the functional acid anhydride is preferably from 10 to 100, more preferably from 10 to 50, from the viewpoint of reducing the viscosity of the composition. The molecular weight of the functional acid anhydride in the present invention is preferably from 100 to 1,000, more preferably from 100 to 500, from the viewpoint of reducing the viscosity of the composition. Further, the functional acid anhydride is preferably a photoradical polymerizable functional group from the viewpoint of setting the photopolymerizable monomer to the above range φ. The photoradical polymerizable functional group may, for example, be a functional group having an ethylenically unsaturated bond, and a (meth)acrylic group, a vinyl group, an allyl group or a styrene group is preferred. In the present invention, the number of photo-radical polymerizable groups contained in the functional acid anhydride is preferably from 1 to 3, more preferably from 1 to 2, from the viewpoint of pattern accuracy at the time of light irradiation and adhesion to a substrate. good. The functional acid anhydride contained in the composition of the present invention may be one type or two or more types. Further, the composition of the present invention may be a functional group having a photoradical polymerizable functional group, -25-201008996, and a functional acid anhydride having no such. When the compound (q) having a photoradical polymerizable functional group and the functional acid anhydride (w) having no functional group are used, the pattern accuracy after light irradiation and the suppression of volatilization of unreacted components during heating are considered. The content ratio (q: w, reference q) is preferably 1/2 to 5/1, more preferably 1/1 to 2 Å. In the curable composition for imprint of the present invention, the content of the functional acid anhydride in the total composition is from 5 to 50% by mass, more preferably from 10 to 30% by mass, from the viewpoint of pattern accuracy after light irradiation. For better. However, in the case where the functional anhydride of ® in the present invention has a photoradical polymerizable functional group, the content thereof is as described above, and can be determined in consideration of the content of the compound having a radical polymerizable functional group in the composition of the present invention. In this case, the content of the functional acid anhydride having a photoradical polymerizable functional group is a relationship with the content of a compound having another radical polymerizable functional group or a functional anhydride having no photoradical polymerizable functional group. The relationship between the content is appropriately determined. Further, in the curable composition for imprint of the present invention, the content ratio of the oxa g cyclobutane compound U) of the present invention to the functional acid anhydride (b) (a: b, the reference is a) is reduced as much as possible. From the viewpoint of the amount of the unreacted functional group, it is preferably 3/1 to 1/3, more preferably 2/1 to 1/2. The functional anhydride in the present invention is, for example, methyl-1,2,3,6-tetrahydrophthalic anhydride (trade name: EPICLON B570, manufactured by Dainippon Ink Chemicals Co., Ltd.), methyl-hexahydrogen Anthraquinone anhydride (trade name: EPIC LON B650, manufactured by Otsuka Ink Chemical Industry Co., Ltd.), methyl-3,6-endomethyl-1,2,3,6-tetrahydrophthalic anhydride (trade name: PCT 11 8 (:-?, 曰立化成工业有限公司) - 4-methyl hexahydrophthalic anhydride (trade name: RIKACID Μ H-700, Xinyi physics and chemistry (share) system), Anhydrous citraconic acid, dodecene succinic anhydride (trade name: RIKACID DDSA, manufactured by Nippon Chemical and Chemical Co., Ltd.), glycerol bis(benzenetricarboxylic anhydride) monoacetate (trade name: RIKACID MTA-10, Xinyi) This physicochemical (share) system), Japan's Zeon (share) Quinhard-200 (trade name), Japan Epoxy resin (stock) EPICURE YH-3 06 (trade name), Aldrich reagent (P25205, 294152, B9750, B4600, 412287, N818, N1607, 330736), etc. Next, a preferred blending form of the photopolymerizable monomer in the present invention will be described. The total content of the photopolymerizable monomer in the curable composition for imprinting of the present invention is from 80 to 99% by mass. "Photopolymerizable monomer" means, for example, (meth)acrylic group, vinyl group, or alkene. a compound having a radically polymerizable functional group containing an ethylenically unsaturated bond, such as a propyl group, for example, an oxetane (meth) acrylate having a compound having an oxetane ring, When the total amount of the photopolymerizable monomer in the composition of the present invention is less than 80% by mass, the acrylic group is not sufficiently hardened by light irradiation. The mold pattern cannot be transferred accurately, and the physical properties such as the hardness of the cured film are also insufficient. Further, when the total content of the compound having a radical polymerizable functional group in the composition of the present invention is more than 99% by mass, the light is free. Additives such as a base polymerization initiator or a surfactant are not sufficiently effective, and the pattern accuracy and physical properties of the cured film are deteriorated from -27 to 201008996. From the viewpoint of pattern accuracy and physical properties of the cured film, 'this The total content of the compound having a radical polymerizable functional group in the composition of the composition is preferably 60 to 99% by mass, more preferably 80 to 98% by mass. The monofunctional polymerizable unsaturated monomer is usually used as a reaction. The use of the diluent is effective to reduce the viscosity of the composition of the present invention, and is usually 10% by mass or more of the total polymerizable unsaturated monomer, preferably 20 to 80% by mass, more preferably 25 to 70% by mass. It is particularly preferably in the range of 30 to 60% by mass. e Since the monofunctional polymerizable unsaturated monomer is more preferably a reactive diluent, it is preferred to add 10% by mass or more of the total polymerizable unsaturated monomer. The monomer having two groups containing an unsaturated bond (difunctional polymerizable unsaturated monomer) is preferably 90% by mass or less, more preferably 80% by mass or less, based on the total polymerizable unsaturated monomer. It is added in the range of 70% by mass or less. The ratio of the monofunctional and difunctional polymerizable unsaturated monomers is preferably φ to 1 to 95% by mass, more preferably 3 to 95% by mass, particularly preferably 5 to 90% by mass based on the total of the polymerizable unsaturated monomers. The scope is added. The proportion of the polyfunctional polymerizable unsaturated monomer having three or more unsaturated bond-containing groups is preferably 80% by mass or less, more preferably 70% by mass or less, based on the total polymerizable unsaturated monomer. It is added in the range of 60 mass% or less. When the ratio of the polymerizable unsaturated monomer having three or more polymerizable unsaturated bond-containing groups is 80% by mass or less, the viscosity of the composition can be lowered, which is preferable. (Photoradical polymerization initiator) -28 - 201008996 The curable composition for imprint of the present invention contains a photoradical polymerization initiator. The composition of the present invention can make the pattern precision after light irradiation good by including a radical polymerization which can be initiated by light irradiation and a photoradical polymerization initiator. The photoradical polymerization initiator, the photoradical polymerization initiator used in the present invention is contained in the total composition, for example, 0. 1 to 15% by mass is preferably, more preferably 0. 2 to 12% by mass, particularly preferably 0. 3 to 10% by mass. When two or more kinds of photopolymerization initiators are used, the total amount thereof is in the above range. The ratio of the aforementioned photoradical polymerization initiator is 0. When the amount is 1% by mass or more, the sensitivity (speed hardenability), the resolution, the line edge roughness, and the coating film strength tend to be improved. On the other hand, when the ratio of the photo-radical polymerization initiator is 15% by mass or less, the light transmittance, the coloring property, the handleability, and the like tend to be improved. In the inkjet composition containing a dye and/or a pigment or a composition for a color filter of a liquid crystal display, various evaluations have been made on the addition amount of a preferred photopolymerization initiator and/or photoacid generator. However, the addition amount of the preferred photopolymerization initiator and/or photoacid generator for the curable composition for photoimprint lithography for imprinting or the like has not been reported. That is, in a system containing a dye and/or a pigment, these have a function as a radical trapping agent, and have an influence on photopolymerizability and sensitivity. In view of this, the amount of the photopolymerization initiator added in these applications is optimized. On the other hand, in the composition of the present invention, the dye and/or the pigment are not essential components, and the optimum range of the photopolymerization initiator may be in the field of an inkjet composition or a liquid crystal display color filter composition or the like. Different. The photoradical polymerization initiator used in the present invention is blended with the wavelength of the light source used in -29-201008996. Active and used to produce the appropriate active species. The photoradical polymerization initiator used in the present invention may be, for example, a commercially available initiator. Examples of such an example include Irgacure (registered trademark) 2959 available from Ciba Corporation: (1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propanol-1 -ketone, Irgacure (registered trademark) 184: (1-cyclohexyl phenyl ketone), Irgacure (registered trademark) 50: (1-hydroxycyclohexyl phenyl ketone, benzophenone), Irgacure (registered trademark) 651: (2,2-dimethoxy-1,2-diphenylethane-1-one), Irgacure (registered trademark) 369: (2-benzyl-2-dimethylamino group-1 -(4-tyrosolinylphenyl)butanone-1), Irgacure (registered trademark) 907 : (2·methyl-1[4-methylthiophenyl]-2-zinolinepropan-1-one , Irgacure (registered trademark) 819: (bis(2,4,6-trimethylbenzylidene)-phenylphosphine, Irgacure (registered trademark) 1 800 : (bis(2,6-dimethoxybenzene) Mercapto)-2,4,4-trimethyl-pentylphosphine, 1-hydroxy-cyclohexyl-phenyl-one), Irgacure (registered trademark) 1 800 : (double (2,6-dimethoxy) Benzomethane)-2,4,4-trimethyl-pentylphosphine, 2-hydroxy-2-methyl-1-phenyl-1-propane·1-0 ketone), Irgacure (registered trademark) ΟΧΕ01 : (1,2-octanedione, 1·[4-(phenylthio)phenyl) ]-2-(0-Benzylmercaptopurine), Darocur (registered trademark) 1173: (2-hydroxy-2-methyl-1-phenyl-1·propan-1-one), Darocur (registered trademark) 1116, 1398, 1174 and 1020, CGI242: (ethanone, 1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-1-(0-乙醯基肟); Lucirin TPO available from BASF: (2,4,6-trimethylbenzhydryldiphenylphosphine), Lucirin TP0-L: (2,4,6-trimethylbenzene Methionylethoxyphenylphosphine; ESACURE available from Siber Hegner, Japan -30- 201008996 ESACURE1001M : (1-[4-Benzylmercaptophenyl]phenyl]-2-methyl-2- (4-methylphenyl)-propan-1-one, Adeka Optomer (registered trademark) N-1414: (carbazole benzophenone), A deka 0 pt 取得 available from ^4-1414 SolOC Corporation Mer (registered trademark) N -1 7 1 7 : (叱 steep system), A deka Optomer (registered trademark) N-1 606: (three-well system); three-chemical TFE-three-well: (2-[ 2-(furan-2-yl)vinyl]-4,6-bis(trichloromethyl)-l,3,5-triad), tri-chemical TME-three tillage: (2-[2 -(5-methylfuran-2-yl)vinyl] -4,6-bis(trichloromethyl)-1,3,5-triazine), Sanhe Chemical 1^-three tillage: (2-(4-methoxyphenyl)-4,6 - bis(trichloromethyl)-1,3,5·three tillage), MIDORI chemical TAZ-113 : (2-[2-(3,4-dimethoxyphenyl)vinyl]-4, 6-bis(trichloromethyl)-1,3,5-triad), MIDORI chemical TAZ-108 (2-(3,4-dimethoxyphenyl)-4,6-bis(trichloro) Methyl)-1,3,5_three tillage), benzophenone, 4,4*-bisdiethylaminobenzophenone, methyl-2-benzophenone, 4-benzamide 4- 4'-methyl diphenyl sulfide, 4-phenyl benzophenone, ethyl melamine, 2-chlorothioxanthone, 2-methyl thioxanthone, 2-isopropyl thiophene Tons of ketone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 1-chloro-4-propoxythioxanthone, 2-methylthioxanthone, thioxanthone ammonium salt, Benzoin, 4,4'-dimethoxybenzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl di Methyl ketal, 1,1, trichloroacetophenone, diethoxyacetophenone and dibenzocycloheptanone, methyl benzyl-benzoguanidinobenzoate, 2-benzylidene , 4-benzylidenebiphenyl, 4-benzylidene diphenyl ketone, 1,4-benzylidene benzene, benzyl, 10-butyl-2-chloroacridone, [4_(A Phenylthio)phenyl]phenylmethane), 2-ethylanthracene, 2,2-bis(2-chlorobenzene-31- 201008996 base) 4,5,4',5'-肆(3, 4,5-trimethoxyphenyl) 1,2'-biimidazole, 2,2-bis(indolyl-chlorophenyl) 4,5,4',5'-tetraphenyl-1,2'-linked Imidazole, ginseng (4-dimethylaminophenyl)methane, ethyl-4-(dimethylamino)benzoate, 2-(dimethylamino)ethyl benzoate, butyl Oxyethyl 4- 4-(dimethylamino)benzoate or the like. (Antioxidant) The curable composition for imprint of the present invention may contain an antioxidant. The first aspect of the curable composition for imprint of the present invention is characterized in that the antioxidant is only a hindered phenol-based antioxidant, only a semi-hindered phenol-based antioxidant, a hindered phenol-based antioxidant, and a semi-hindered phenolic anti-oxidant. A mixture of oxidizing agents, or only one of the hindered amine-based antioxidants. On the other hand, the second aspect of the curable composition for imprint of the present invention is characterized in that the antioxidant is a mixture of a hindered phenol-based antioxidant and a thioether-based antioxidant, or a semi-hindered phenol-based antioxidant and a thioether system. a mixture of antioxidants. The characteristic of the present invention is the point of using the zero antioxidant of the above-described two aspects of the present invention, which enhances photocurability, heat resistance and elastic recovery. In view of the technique of adding a photo-curable resin composition of a conventional antioxidant, an antioxidant is added in the above two aspects of the present invention, and the elastic recovery rate of the cured film is improved after the effect of the composition of the present invention is achieved. Particularly amazing results. Further, the phenol-based antioxidant other than the hindered phenol-based or semi-hindered phenol-based antioxidant is not preferable because of a large polymerization inhibition. The antioxidant used in the curable composition for imprint of the present invention contains -32 - 201008996 in an amount of 0. 3 to 7 mass%, preferably 0. 5 to 5 mass%, more preferably 1. 5 to 5 mass%. When two or more kinds of antioxidants are used, the total amount thereof is in the above range. If the content of the aforementioned antioxidant is 0. When the amount is 3% by mass or more, the heat resistance and the elastic recovery rate are preferably improved, and when the amount is 7% by mass or less, the photocurability is improved. Further, if the content of the aforementioned antioxidant is 0. When the amount is 5% by mass or more, the heat resistance and the elastic recovery rate are further improved, and when the amount is 5% by mass or less, the photocurability is further improved. Furthermore, if the content of the aforementioned antioxidant is 1. When the amount is 5 mass% or more, the heat resistance and the elastic recovery rate can be further improved, so that it is particularly preferably 1. 5 to 5 mass%. The hindered phenol-based antioxidant of the present invention has a structure represented by the following general formula (1).

一般式（1) OHGeneral formula (1) OH

L1 —般式（1)中、R1及R2係各自獨立地表示tert-丁基或 •C(R4R5)_R6，R3表示氫原子、或碳數1〜6之分枝或直鏈的可具有取代基之烷基，L1表示一價取代基。R4及R5係各自獨立地表示氫原子或甲基，R6表示下述一般式（2)所示之構造的取代基。 -33- 201008996 -般式泛)L1 In the general formula (1), R1 and R2 each independently represent tert-butyl or •C(R4R5)_R6, and R3 represents a hydrogen atom, or a branched or linear carbon number of 1 to 6 may have a substitution. The alkyl group, L1 represents a monovalent substituent. R4 and R5 each independently represent a hydrogen atom or a methyl group, and R6 represents a substituent of the structure represented by the following general formula (2). -33- 201008996 - general style)

L2 —般式（2)中、X1表示氫原子、烷基、羥基、（甲基）丙烯酸酯基、羧基，X1爲羥基時R7表示ter t-丁基，X1爲羥基以外時R7表示氫原子、碳數1〜6之分枝或直鏈的可具有取代基之烷基，R8表示氫原子、或碳數1〜6之分枝或直鏈的可具有取代基之烷基，L2表示一價取代基，*表示鍵結部位。在一般式（1)，前述R1及前述R2較佳爲tert-丁基》前述R3較佳爲氫原子。前述R4及R5較佳爲氫原子。前述L1較佳爲氫原子、或碳數1〜6之分枝或直鏈的可具有取代基之烷基、烷氧基。更佳爲具有甲基、烷氧基或胺基作爲取代基之碳數1〜4的烷基。前述R6爲複數時，複數個R6係可彼此不同或相同。在一般式（2)，前述X1較佳爲氫原子、烷基、羥基、（甲基）丙烯酸酯基、羧基，更佳爲羥基。前述X1爲羥基以外時，前述R7較佳爲氫原子、甲基、 tert-丁基，更佳爲tert-丁基。前述R8較佳爲氫原子》 -34- 201008996 前述L2係與前述L1之較佳範圍相同。受阻酚系抗氧化劑之具體例可列舉2·，6-二-tert-丁基苯酚、2,6-二-tert-丁基-4-甲基苯酚、2,2’-亞甲基雙（6-tert-丁基-4-甲基苯酚）等。又，本發明係不限於此等具體例的實例。本發明中半受阻酚系抗氧化劑係具有下述一般式（3) 所示之構造的物質。L2 In the general formula (2), X1 represents a hydrogen atom, an alkyl group, a hydroxyl group, a (meth) acrylate group or a carboxyl group, and when X1 is a hydroxyl group, R7 represents a ter t-butyl group, and when X1 is a hydroxyl group, R7 represents a hydrogen atom. a branched or straight-chain alkyl group having a substituent of 1 to 6 carbon atoms, R 8 represents a hydrogen atom, or a branched or straight-chain alkyl group having a carbon number of 1 to 6, and L 2 represents a A valence substituent, * indicates a bond site. In the general formula (1), the above R1 and the above R2 are preferably tert-butyl. The above R3 is preferably a hydrogen atom. The above R4 and R5 are preferably a hydrogen atom. The above L1 is preferably a hydrogen atom or a branched or linear alkyl group or alkoxy group having a carbon number of 1 to 6. More preferably, it is an alkyl group having 1 to 4 carbon atoms which has a methyl group, an alkoxy group or an amine group as a substituent. When the above R6 is a complex number, the plurality of R6 systems may be different from each other or the same. In the general formula (2), the above X1 is preferably a hydrogen atom, an alkyl group, a hydroxyl group, a (meth) acrylate group or a carboxyl group, more preferably a hydroxyl group. When X1 is other than a hydroxyl group, R7 is preferably a hydrogen atom, a methyl group or a tert-butyl group, more preferably a tert-butyl group. The above R8 is preferably a hydrogen atom" -34 - 201008996 The above L2 system is the same as the preferred range of the above L1. Specific examples of the hindered phenol-based antioxidant include 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-4-methylphenol, and 2,2'-methylenebis ( 6-tert-butyl-4-methylphenol) and the like. Further, the present invention is not limited to the examples of the specific examples. The semi-hindered phenol-based antioxidant of the present invention has a structure represented by the following general formula (3).

一般式（3) OHGeneral formula (3) OH

一般式（3)中，R11表示氫原子或甲基，R12表示tert-丁基或- C(R14R15)-R“，R13表示氫原子、或碳數1〜6之分枝或直鏈的可具有取代基之烷基，L11表示一價取代基。R14及 φ Rl5係各自獨立地表示氫原子或甲基，R16表示下述一般式（4) 所示之構造的取代基。一般式（4) X”In the general formula (3), R11 represents a hydrogen atom or a methyl group, R12 represents tert-butyl or -C(R14R15)-R", and R13 represents a hydrogen atom or a branched or straight chain having a carbon number of 1 to 6. The alkyl group having a substituent, L11 represents a monovalent substituent, R14 and φ Rl5 each independently represent a hydrogen atom or a methyl group, and R16 represents a substituent of the structure represented by the following general formula (4). ) X"

-35- 201008996 —般式（4)中，X11表示氫原子、烷基、羥基、（甲基）丙烯酸酯基、羧基，X"爲羥基時，R17表示氫原子或甲基， X11爲羥基以外時，R17表示氫原子、碳數1〜6之分枝或直鏈的可具有取代基之烷基，R18表示氫原子、或碳數1〜6 之分枝或直鏈的可具有取代基之烷基，L12表示一價取代基、*表示鍵結部位。在一般式（3)，前述R11較佳爲甲基。前述R12較佳爲tert-丁基。胃前述R13較佳爲氫原子。前述R14及R15較佳爲氫原子。前述L11係與前述L1之較佳範圍相同。在一般式（4)，前述X11較佳爲氫原子、烷基、羥基、 (甲基）丙烯酸酯基、羧基、更佳爲羥基。前述X11爲羥基時，前述R17較佳爲tert-丁基。前述X11爲羥基以外時，前述R17較佳爲氫原子、甲 φ 基、tert-丁基，更佳爲甲基。前述R8較佳爲氫原子。前述L2係與前述L1之較佳範圍相同。作爲半受阻酚系抗氧化劑之具體例，可列舉2-甲基 -6-tert-丁基苯酚、2-甲基-6-tert-丁基-4-甲基苯酚、6-tert-丁基-4-甲基苯酚、6-tert-丁基-4-甲基苯酚、2,2’-亞甲基雙 (4,6-二甲基苯酚）等。又，本發明係不限於此等具體例之例不 ° -36- 201008996 本發明之受阻胺系抗氧化劑並無特別限定，可例示具有下述一般式（5)所示之構造作爲部分構造之化合物。 -般式（5) R21-35- 201008996 In the general formula (4), X11 represents a hydrogen atom, an alkyl group, a hydroxyl group, a (meth) acrylate group or a carboxyl group, and when X is a hydroxy group, R17 represents a hydrogen atom or a methyl group, and X11 is a hydroxyl group. When R17 represents a hydrogen atom, a branched group having a carbon number of 1 to 6 or a linear alkyl group which may have a substituent, and R18 represents a hydrogen atom, or a branched or straight chain having a carbon number of 1 to 6 may have a substituent. Alkyl group, L12 represents a monovalent substituent, and * represents a bond site. In the general formula (3), the above R11 is preferably a methyl group. The aforementioned R12 is preferably tert-butyl. The aforementioned R13 of the stomach is preferably a hydrogen atom. The above R14 and R15 are preferably a hydrogen atom. The aforementioned L11 is the same as the preferred range of the above L1. In the general formula (4), the above X11 is preferably a hydrogen atom, an alkyl group, a hydroxyl group, a (meth) acrylate group, a carboxyl group, or more preferably a hydroxyl group. When X11 is a hydroxyl group, R17 is preferably a tert-butyl group. When X11 is other than a hydroxyl group, R17 is preferably a hydrogen atom, a methyl group or a tert-butyl group, more preferably a methyl group. The above R8 is preferably a hydrogen atom. The aforementioned L2 system is the same as the preferred range of the above L1. Specific examples of the semi-hindered phenol antioxidant include 2-methyl-6-tert-butylphenol, 2-methyl-6-tert-butyl-4-methylphenol, and 6-tert-butyl. 4-methylphenol, 6-tert-butyl-4-methylphenol, 2,2'-methylenebis(4,6-dimethylphenol), and the like. In addition, the present invention is not limited to the specific examples of the present invention. The hindered amine-based antioxidant of the present invention is not particularly limited, and the structure represented by the following general formula (5) can be exemplified as a partial structure. Compound. - General (5) R21

鮝基前述R21以表示氫原子、或碳數1〜6之分枝或直鏈的有取代基之烷基、烷氧基爲較佳，以氫原子或烷氧基爲更佳。前述L21之較佳範圍係與前述L1之較佳範圍相同。作爲受阻胺系抗氧化劑之具體例，可舉出雙（2,2,6,6- ❿ 四甲基-4-哌啶基）癸二酸酯、雙（N-甲基-2,2,6,6-四甲基-4- 脈陡基）癸二酸酯、^!^-雙（2,2,6,6-四甲基-4-哌啶基）-1，6- 六亞甲基二胺、2-甲基-2-(2,2,6,6-四甲基-4-哌啶基）胺基 •^(2,2,6,6-四甲基-4-哌啶基）丙醢胺、肆（2,2,6,6-四甲基-4- 峨陡基）（1，2,3,4-丁烷四羧酸酯、聚〔{6-(1,1，3,3-四甲基丁基）亞胺基-1，3,5-三畊- 2,4 -二基}{(2,2,6,6-四甲基-4-哌啶基）亞胺基}六甲基{(2,2,6,6-四甲基-4-哌啶基）亞胺基丨〕、聚〔（6-味咻基-丨，3,5_三阱-24_二基）丨（2,2,6,6-四甲基-4-哌啶基）亞胺基}六甲川{(2,2,6,6-四甲基-4-哌啶基）亞胺基}〕、 -37- 201008996 琥珀酸二甲基與1-(2-羥基乙基）-4-羥基- 2,2,6,6-四甲基哌啶之縮聚物、N，N’-4,7-肆〔4,6-雙{N-丁基項-(1，2,2,6,6-五甲基-4-哌啶基）胺基}·1,3,5-三哄-2-基〕-4,7-二氮雜癸烷 -1，10-二胺等。又，本發明係不限於此等具體例之例示。本發明之硫醚系抗氧化劑係以一般式R-S-R’所示之化合物。在此R及R’係分別爲烷基或烷基酯基，以烷基酯基爲較佳。作爲前述硫醚系抗氧化劑的實例，可列舉硫代二丙酸二·十三烷酯等。又，本發明係不限於此等具體例之例示。又，本發明之範圍外的苯酚系抗氧化劑係具有以下一般式（6)所示之構造的物質。一般式（6)The above R21 is preferably an alkyl group or an alkoxy group which represents a hydrogen atom or a branched or linear chain having 1 to 6 carbon atoms, and more preferably a hydrogen atom or an alkoxy group. The preferred range of the aforementioned L21 is the same as the preferred range of the above L1. Specific examples of the hindered amine-based antioxidant include bis(2,2,6,6-fluorene tetramethyl-4-piperidyl)sebacate and bis(N-methyl-2,2, 6,6-tetramethyl-4-pulsyl) sebacate, ^!^-bis(2,2,6,6-tetramethyl-4-piperidinyl)-1,6-hexa Methyldiamine, 2-methyl-2-(2,2,6,6-tetramethyl-4-piperidinyl)amine•^(2,2,6,6-tetramethyl-4- Piperidinyl) propylamine, hydrazine (2,2,6,6-tetramethyl-4-indole) (1,2,3,4-butane tetracarboxylate, poly[{6-( 1,1,3,3-tetramethylbutyl)imido-1,3,5-trinyl- 2,4-diyl}{(2,2,6,6-tetramethyl-4- Piperidinyl)imino}hexamethyl{(2,2,6,6-tetramethyl-4-piperidinyl)imide ruthenium], poly[(6-misodecyl-indole, 3, 5_Triso-24-diyl) ruthenium (2,2,6,6-tetramethyl-4-piperidinyl)imino}hexamethine{(2,2,6,6-tetramethyl- 4-piperidinyl)imine}], -37- 201008996 dimethyl succinate and 1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine Polycondensate, N,N'-4,7-oxime [4,6-bis{N-butyl term-(1,2,2,6,6-pentamethyl-4-piperidinyl)amino} ·1,3,5-triazin-2-yl]-4,7-diazadecane-1 Further, the present invention is not limited to the specific examples of the above. The thioether-based antioxidant of the present invention is a compound represented by the general formula RS-R'. Here, the R and R' systems are respectively The alkyl group or the alkyl ester group is preferably an alkyl ester group. Examples of the thioether-based antioxidant include ditridecyl thiodipropionate and the like. Further, the present invention is not limited thereto. Further, the phenolic antioxidant other than the range of the present invention has a structure represented by the following general formula (6). General formula (6)

—般式（6)中、R31及R32表示氫原子或甲基，R33及L31 表示一價取代基。在本發明之壓印用硬化性組成物第一態樣，前述抗氧化劑係僅由半受阻酚系抗氧化劑構成，由更提高抗氧化能力、減低聚合阻礙、提升光硬化性之觀點來看爲更佳。又，在本發明之壓印用硬化性組成物第二態樣，前述抗氧化劑爲半受阻酚系與硫醚系之混合物，由更提高抗氧 -38- .201008996 化能力、減低聚合阻礙、提升光硬化性之觀點來看爲更佳。前述抗氧化劑係可抑制因熱或光照射導致退色及臭氧、活性氧、NOx、SOx(x爲整數）等之各種氧化性氣體等至退色。尤其是本發明藉由添加抗氧化劑具有可防止硬化膜之著色、減低因分解導致之膜厚減少的優點。作爲前述抗氧化劑之市售品，可列舉商品名Irganox 1010、1 03 5、1 076、1 222(以上 Ciba Geigy(股）製）、商品名 AntigeneP、3C、F.R、Sumilizer S、Sumilizer GA80(住友化 ® 學工業（股）製）、商品名 ADK STAB AO70、AO80、 AO503((股）ADEKA製）等》此等可單獨使用，亦可混合使用。又，前述抗氧化劑係可藉由公知之方法來合成。 (界面活性劑）本發明之壓印用硬化性組成物亦可含界面活性劑。本發明所用之界面活性劑係總組成物中含有例如，0.0 0 1〜5 質量％、較佳爲0.002〜4質量％、更佳爲0.005〜3質量％。使 φ 用2種以上之界面活性劑時，係使其合計量爲前述範圍。界面活性劑若佔組成物中0.00 1〜5質量％之範圍時，塗布均勻性之效果良好，不易引起因界面活性劑過多導致之模具轉印特性惡化。作爲前述界面活性劑，以含氟系界面活性劑、矽酮系界面活性劑及氟·矽酮系界面活性劑之至少1種爲較佳，以含氟系界面活性劑與矽酮系界面活性劑兩找或含氟.矽酮系界面活性劑爲更佳，以含氟.矽酮系界面活性劑爲最佳。 -39· 201008996 而且’前述氟系界面活性劑及矽酮系界面活性劑以非離子性之界面活性劑爲較佳。在此’ 「氟·矽酮系界面活性劑」係指具氟系界面活性劑及矽酮系界面活性劑兩者之要件。藉由使用此種界面活性劑，可解決將本發明之壓印硬化性組成物塗布在半導體元件製造用之矽晶圓、液晶元件製造用之方形玻璃基板、鉻膜、鉬膜、鉬合金膜、钽膜、鉬合金膜、氮化矽膜、非晶矽酮膜、摻雜有氧化錫之氧化銦（ITO)膜或氧化錫膜等之形成有各種膜的基板上時所引起的輝紋、鱗狀模樣（光阻膜之乾燥不均）等塗布不良的問題。又，可提升本發明之組成物在模具凹部之腔體内的流動性、提升模具與光阻之間的剝離性、提升光阻與基板間之密接性、減低組成物之黏度。尤其是本發明之壓印組成物藉由添加前述界面活性劑，可大幅改善塗布均勻性，在使用旋轉塗布機或狹縫掃瞄塗布機之塗布中，可得無關基板尺寸之良好的塗布適性。In the general formula (6), R31 and R32 represent a hydrogen atom or a methyl group, and R33 and L31 represent a monovalent substituent. In the first aspect of the curable composition for imprint of the present invention, the antioxidant is composed only of a semi-hindered phenol-based antioxidant, and is improved from the viewpoint of further improving oxidation resistance, reducing polymerization inhibition, and improving photocurability. Better. Further, in the second aspect of the curable composition for imprint of the present invention, the antioxidant is a mixture of a semi-hindered phenol-based and a thioether-based compound, and the anti-oxidation-38-201008996 is improved, and the polymerization inhibition is reduced. It is better to improve the light hardenability. The antioxidant can suppress fading of various oxidizing gases such as discoloration and ozone, active oxygen, NOx, and SOx (x is an integer) due to heat or light irradiation. In particular, the present invention has the advantage of preventing the coloration of the cured film and reducing the film thickness due to decomposition by adding an antioxidant. Commercial products of the above-mentioned antioxidants include Irganox 1010, 1 03 5, 1 076, and 1 222 (manufactured by Ciba Geigy Co., Ltd.), trade names Antigene P, 3C, FR, Sumilizer S, and Sumilizer GA80 (Sumitomo). Chemical Industry Co., Ltd., trade name: ADK STAB AO70, AO80, AO503 (made by Adeka), etc. These may be used alone or in combination. Further, the antioxidant can be synthesized by a known method. (Surfactant) The curable composition for imprint of the present invention may further contain a surfactant. The total surfactant composition used in the present invention contains, for example, 0.01 to 5% by mass, preferably 0.002 to 4% by mass, more preferably 0.005 to 3% by mass. When two or more kinds of surfactants are used for φ, the total amount is made into the above range. When the surfactant is in the range of 0.001 to 5% by mass in the composition, the effect of uniformity of coating is good, and deterioration of mold transfer characteristics due to excessive surfactant is less likely to occur. As the surfactant, at least one of a fluorine-containing surfactant, an anthrone-based surfactant, and a fluoroneketone-based surfactant is preferable, and a surfactant of a fluorine-containing surfactant and an anthrone is interfacially active. The agent is two or fluorine-containing. The anthrone-based surfactant is more preferable, and the fluorine-containing anthrone-based surfactant is preferred. -39· 201008996 Further, the fluorine-based surfactant and the anthrone-based surfactant are preferably a nonionic surfactant. Here, the "fluoroneketone-based surfactant" means both a fluorine-based interface active agent and an anthrone-based surfactant. By using such a surfactant, it is possible to solve the problem that the imprint-curable composition of the present invention is applied to a wafer for manufacturing a semiconductor element, a prismatic glass substrate for producing a liquid crystal element, a chromium film, a molybdenum film, or a molybdenum alloy film. a ridge film, a molybdenum alloy film, a tantalum nitride film, an amorphous fluorene film, an indium oxide (ITO) film doped with tin oxide, or a tin oxide film, etc. There is a problem of poor coating such as a scaly appearance (drying unevenness of the photoresist film). Further, the fluidity of the composition of the present invention in the cavity of the concave portion of the mold can be improved, the peeling property between the mold and the photoresist can be improved, the adhesion between the photoresist and the substrate can be improved, and the viscosity of the composition can be reduced. In particular, the imprint composition of the present invention can greatly improve coating uniformity by adding the above-mentioned surfactant, and good coating suitability irrespective of substrate size can be obtained in coating using a spin coater or a slit sweep coater. .

可用於本發明之非離子性氟系界面活性劑的實例，可舉出商品名Fluorad FC-4 30、FC-431(住友3M(股）製）、商品名 Surflon S-382(旭硝子（股）製）、EFTOP EF-122A、122B、 122C 、 EF-121 、 EF-126 、 EF-127 、 MF-100(TOCHEMExamples of the nonionic fluorine-based surfactant which can be used in the present invention include the trade names Fluorad FC-4 30, FC-431 (manufactured by Sumitomo 3M Co., Ltd.), and the trade name Surflon S-382 (Asahi Glass Co., Ltd.). EFTOP EF-122A, 122B, 122C, EF-121, EF-126, EF-127, MF-100 (TOCHEM)

PRODUCTS(股）製）、商品名 PF-63 6、PF-6320、PF-656、 PF-6520(均爲 OMNOVA Solutions, Inc.)、商品名 FUTAGENT FT250、FT25 1、DFX18(均爲 NE0S (股）製）、商品名 UNIDAIN -40- 201008996 DS-401 > DS-403 ' DS-451 (均爲DAIKIN工業（股）製）、商品名 MEGAFAC171、172、173、178K、178A、（均爲大日本油墨化學工業（股）製）^ 又，作爲非離子性之前述矽酮系界面活性劑的實例，可舉出商品名SI-10系列（竹本油脂（股）製）、MEGAFAC PEINTAD 31(大日本油墨化學工業（股）製）、KP-341(信越化學工業（股）製）。又，作爲前述氟·矽酮系界面活性劑的實例，可舉出 ^ 商品名 Χ-70-090、Χ-70-09 1、Χ-70-092、Χ-70-093 (均爲信越化學工業（股）製）、商品名]^£〇人卩人〇11-08、又1^-4(均爲大曰本油墨化學工業（股）製）。 (其他成分）本發明之組成物除前述成分外，亦可視需要添加非聚合性分子、聚合物成分、脫膜劑、有機金屬偶合劑、聚合抑制劑、紫外線吸收劑、光安定劑、抗老化劑、可塑劑、 φ 密接促進劑、熱聚合起始劑、光鹼產生劑、著色劑、彈性體粒子、光增感劑、鹼性化合物、及其他流動調整劑、消泡劑、分散劑等。本發明之組成物，爲了密接性之賦予、硬化膜物性之控制的目的，可添加前述非聚合性分子。此種非聚合性分子之添加量可依照在本發明之範圍內能控制光聚合性分子之添加量的範圍加以決定。作爲此種非聚合性分子，可舉出例如如癸二酸二辛酯之烷酯、（硫）尿素化合物、有機微 -41 - 201008996 粒子、無機微粒子等。在本發明之組成物，爲了更提高交聯密度，可在達成本發明之目的的範圍內摻合分子量比前述多官能之其他聚合性單體大的多官能寡聚物。作爲具有光自由基聚合性之多官能寡聚物，可舉出酯丙烯酸酯、聚胺基甲酸酯丙烯酸酯、聚醚丙烯酸酯、環氧基丙烯酸酯等之各種丙烯酸酯寡聚物、三甲氧基矽烷基丙基丙烯酸酯之水解縮合物。寡聚物成分之添加量，相對於除去組成物之溶劑以外的成分而言，以0〜30質量％爲較佳、更佳爲0〜20質量％、進一步較佳爲0〜10質量％、最佳爲0〜5質量％。本發明之壓印用硬化性組成物，從改良壓印適性、硬化性等之觀點來看，亦可進一步含有聚合物成分。前述聚合物成分以在側鏈具有聚合性官能基之聚合物爲較佳。前述聚合物成分之重量平均分子量，從與聚合性化合物之相溶性的觀點來看，以2000〜100000爲較佳、以5000〜50000 爲更佳。聚合物成分之添加量相對於除去組成物之溶劑的成分而言，以0〜30質量％爲較佳、更佳爲0〜20質量％、進 —步較佳爲0〜10質量％、最佳爲2質量％以下。又，從圖案形成性的観點來看，樹脂成分以盡可能少爲較佳，較佳爲除了界面活性劑、微量添加劑外，不含樹脂成分。爲了進一步提升剝離性，本發明之組成物可任意地摻合脫膜劑。具體而言，添加目的係可將壓付於本發明之組成物的層之模具不引起樹脂層之表面龜裂或殘留而完美地 -42- 201008996 剝離。脫膜劑可使用先前公知之脫膜劑，例如，矽酮系脫膜劑、聚乙烯蠟、醯胺蠟、特弗龍粉末（特弗龍爲註冊商標）等之固形蠟、氟系、磷酸酯系化合物等之任一者。又，亦可使此等脫膜劑附著於模具。當前述矽酮系脫膜劑係與本發明所用之前述光硬化性樹脂組合時，從模具之剝離性特別良好，不易引起殘留現象。前述矽酮系脫膜劑係以有機聚矽氧烷構造爲基本構造之脫膜劑，例如，含有未改質或改質矽油、三甲基矽氧 w 基矽酸之聚矽氧烷、矽酮系丙烯酸樹脂等即符合，通常在硬塗層用組成物所用之矽酮系均平劑亦可適用。前述改質矽油係將聚矽氧烷之側鏈及/或末端改質而成者，可分爲反應性矽油與非反應性矽油。作爲反應性矽油，可舉出胺基改質、環氧基改質、羧基改質、甲醇改質、甲基丙烯酸改質、锍基改質、苯酚改質、單末端反應性、異種官能基改質等。作爲非反應性矽油，可舉出聚醚改質、 Q 甲基苯乙烯基改質、烷基改質、高級脂肪酯改質、親水性特殊改質、高級烷氧基改質、高級脂肪酸改質、氟改質等。亦可對一個聚矽氧烷分子進行2種以上的如前述之改質方法。 BIJ述改質砂油較佳爲具有與組成物成分之適度相溶性。特別是，使用對在組成物中視需要所摻合之其他塗膜形成成分具有反應性的反應性矽油時，由於將本發明之組成物在經硬化的硬化膜中利用化學鍵固定，故不易引起該 -43- 201008996 硬化膜之密接性阻礙、污染、劣化等之問題。在蒸鍍步驟中提升與蒸鍍層的密接性方面特別有效。又，以（甲基）丙烯醯基改質矽酮、乙烯基改質矽酮等之具有光硬化性的官能基改質而成的矽酮之情形，由於與本發明之組成物進行交聯，因此硬化後之特性優異。前述含有三甲基矽氧基矽酸之聚矽氧烷係在表面容易滲出且剝離性優良，且即使滲出表面密接性亦優良，與金屬蒸鍍或表塗層之密接性亦優良方面而言爲較佳。 W 前述脫膜劑可僅添加1種或組合2種以上。在本發明之壓印用硬化性組成物添加脫膜劑時，較佳爲在組成物總量中摻合0.001〜10質量％之比例、更佳爲添加0.01〜5質量％之範圍。當脫膜劑之含量爲0.01〜5質量％之範圔内時，模具與壓印用硬化性組成物層之剝離性提升效果變好，而且可抑制組成物之塗覆時的收縮導致塗膜面之表面龜裂問題產生、在製品中基材自身或接近的層發生 φ 例如阻礙蒸鍍層之密接性、轉印時之皮膜破壞等（膜強度變得太弱）。本發明之組成物爲了提高具有微細凹凸圖案之表面構造的耐熱性、強度、或與金屬蒸鍍層之密接性，亦可摻合有機金屬偶合劑。又，有機金屬偶合劑因亦具有促進熱硬化反應之效果故有效。作爲前述有機金屬偶合劑，例如可使用矽烷偶合劑、鈦偶合劑、鉻偶合劑、鋁偶合劑、錫偶合劑等之各種偶合劑。 -44- .201008996 可用於本發明之組成物的矽烷偶合劑，可列舉例如’ /5 -(3,4-環氧基環己基）乙基三甲氧基矽烷、r-環氧丙氧基丙基三甲氧基矽烷、7*·環氧丙氧基丙基甲基二乙氧基矽烷等之環氧基矽烷；N-卢-(胺基乙基）-r-胺基丙基三甲氧基矽烷、N-/3-(胺基乙基）-r-胺基丙基甲基二甲氧基矽烷、 r -胺基丙基三甲氧基矽烷、N-苯基-r -胺基丙基三甲氧基矽烷等之胺基矽烷；及作爲其他矽烷偶合劑，可舉出r-锍基丙基三甲氧基矽烷、r-氯丙基甲基二甲氧基矽烷、氯丙基甲基二乙氧基矽烷等。作爲前述鈦偶合劑，可舉出例如’異丙基三異硬脂醯基鈦酸酯、異丙基三-十二烷基苯颯基鈦酸酯、異丙基參（二辛基焦磷酸酯）鈦酸酯、四異丙基雙（二辛基亞磷酸酯）鈦酸酯、四辛基雙（二-十三烷基亞磷酸酯）鈦酸酯、四（2,2-二烯丙氧基甲基）雙（二-十三烷基）亞磷酸酯鈦酸酯、雙（二辛基焦磷酸酯）氧基乙酸酯鈦酸酯、雙（二辛基焦磷酸酯）乙烯鈦酸酯、異丙基三辛醯基鈦酸酯、異丙基二甲基丙烯酸異硬脂醯基鈦酸酯、異丙基異硬脂醯基二丙烯酸鈦酸酯、異丙基三（二辛基磷酸酯）鈦酸酯、異丙基三異丙苯基苯基鈦酸酯、異丙基三（N-胺基乙基.胺基乙基）鈦酸酯、二異丙苯基苯基氧基乙酸酯鈦酸酯、二異硬脂醯基乙烯鈦酸酯等。作爲前述鉻偶合劑，可舉出例如’四- η-丙氧基鉻、四 -丁氧基锆、四乙醯基丙酮酸锆、二丁氧基雙（乙醯基丙酮酸）锆、三丁氧基乙基乙醯乙酸锆、丁氧基乙醯基丙酮酸酯 -45- 201008996 雙（乙基乙醯乙酸）鉻等。作爲前述鋁偶合劑，可舉出例如’異丙酸鋁、單sec-丁氧基二異丙酸鋁'sec-丁酸鋁、乙酸鋁、乙基乙醯乙酸酯二異丙酸鋁、參（乙基乙醯乙酸）鋁、烷基乙醯乙酸酯二異丙酸鋁、一乙醯基丙酮酸酯雙（乙基乙醯乙酸）鋁、參（乙醯基乙醯乙酸）鋁等。前述有機金屬偶合劑能夠以在本發明之壓印用硬化性組成物之固體成分總量中佔0.001〜10質量％之比例任意地摻合。藉由使有機金屬偶合劑之比例爲0.001質量％以上，在耐熱性、強度、與蒸鍍層之密接性賦予的提升方面有更有效的傾向。另一方面，藉由使有機金屬偶合劑之比例爲10質量％以下，具有可抑制組成物之安定性、成膜性之缺損的傾向而較佳。本發明之壓印用硬化性組成物爲了提升儲存安定性等，亦可摻合聚合抑制劑。作爲前述聚合抑制劑，可使用例如，氫醌、tert-丁基氫醌、兒茶酚、氫醌單甲基醚等之苯酚類；苯醌、二苯基苯醌等之醌類；啡噻畊類；銅類等。聚合抑制劑以相對於本發明之組成物之總量而言爲0.001 〜10質量％之比例任意地摻合爲較佳。本發明之壓印用硬化性組成物中亦可使用紫外線吸收劑。前述紫外線吸收劑之市售品可舉出Tinuvin P、234、 320、326、327、328、213(以上，Ciba Geigy(股）製）、PRODUCTS (stock), trade name PF-63 6, PF-6320, PF-656, PF-6520 (both OMNOVA Solutions, Inc.), trade name FUTAGENT FT250, FT25 1, DFX18 (both NE0S (shares) )), product name UNIDAIN -40- 201008996 DS-401 > DS-403 'DS-451 (both DAIKIN Industrial Co., Ltd.), trade names MEGAFAC171, 172, 173, 178K, 178A, (all are large) In addition, as an example of the nonionic ketone-based surfactant, the product name is SI-10 series (made by Takeshi Oil Co., Ltd.), and MEGAFAC PEINTAD 31 (large Japan Ink Chemical Industry Co., Ltd.), KP-341 (Shin-Etsu Chemical Industry Co., Ltd.). Further, examples of the fluoroneketone-based surfactant include product names Χ-70-090, Χ-70-09 1, Χ-70-092, and Χ-70-093 (both Shin-Etsu Chemical Co., Ltd.) Industrial (share) system, the product name] ^ 〇卩卩 -08 -08 -08 -08 -08 -08 -08 -08 -08 -08 -08 -08 -08 -08 -08 -08 -08 -08 -08 -08 -08 -08 -08 -08 -08 -08 -08 -08 -08 (Other components) In addition to the above components, the composition of the present invention may optionally contain a non-polymerizable molecule, a polymer component, a release agent, an organic metal coupling agent, a polymerization inhibitor, an ultraviolet absorber, a light stabilizer, and an anti-aging property. Agent, plasticizer, φ adhesion promoter, thermal polymerization initiator, photobase generator, colorant, elastomer particles, photosensitizer, basic compound, and other flow regulators, defoamers, dispersants, etc. . In the composition of the present invention, the non-polymerizable molecule may be added for the purpose of imparting adhesion and controlling the physical properties of the cured film. The amount of such a non-polymerizable molecule to be added can be determined in accordance with the range in which the amount of the photopolymerizable molecule can be controlled within the range of the present invention. Examples of such a non-polymerizable molecule include alkyl esters such as dioctyl sebacate, (sulfuric) urea compounds, organic micro-41 - 201008996 particles, and inorganic fine particles. In the composition of the present invention, in order to further increase the crosslinking density, a polyfunctional oligomer having a molecular weight larger than that of the above polyfunctional other polymerizable monomer can be blended in the range in which the object of the present invention is attained. Examples of the polyfunctional oligomer having photo-radical polymerizability include various acrylate oligomers such as ester acrylate, polyurethane acrylate, polyether acrylate, and epoxy acrylate, and the top three. A hydrolysis condensate of oxonium propyl acrylate. The amount of the oligomer component added is preferably from 0 to 30% by mass, more preferably from 0 to 20% by mass, even more preferably from 0 to 10% by mass, based on the component other than the solvent from which the composition is removed. The optimum is 0 to 5 mass%. The curable composition for imprint of the present invention may further contain a polymer component from the viewpoint of improving the embossability and the hardenability. The above polymer component is preferably a polymer having a polymerizable functional group in a side chain. The weight average molecular weight of the above polymer component is preferably from 2,000 to 100,000, more preferably from 5,000 to 50,000, from the viewpoint of compatibility with the polymerizable compound. The amount of the polymer component added is preferably from 0 to 30% by mass, more preferably from 0 to 20% by mass, more preferably from 0 to 10% by mass, most preferably from 0 to 10% by mass, based on the component of the solvent from which the composition is removed. Preferably, it is 2% by mass or less. Further, from the viewpoint of pattern formation, the resin component is preferably as small as possible, and it is preferred that the resin component is not contained in addition to the surfactant and the trace additive. In order to further improve the peelability, the composition of the present invention may optionally incorporate a release agent. Specifically, the purpose of the addition is that the mold which is pressed against the layer of the composition of the present invention can be peeled off perfectly from the surface of the resin layer without causing cracking or residue of the surface of the resin layer. As the release agent, a previously known release agent such as an anthrone-based release agent, a polyethylene wax, a guanamine wax, a Teflon powder (Teflon is a registered trademark), or the like, a solid wax, a fluorine-based, or a phosphoric acid may be used. Any of ester compounds and the like. Further, these release agents can also be attached to the mold. When the fluorenone-based release agent is combined with the photocurable resin used in the present invention, the release property from the mold is particularly excellent, and it is less likely to cause a residual phenomenon. The anthrone-based release agent is a release agent having a basic structure of an organic polyoxymethane, for example, a polyoxane or an anthracene containing unmodified or modified eucalyptus oil, trimethyl fluorinated fluorenyl decanoic acid. A ketone-based acrylic resin or the like is suitable, and an anthrone-based leveling agent which is usually used for a composition for a hard coat layer is also applicable. The modified eucalyptus oil is obtained by modifying the side chain and/or the terminal of the polyoxyalkylene, and is classified into a reactive eucalyptus oil and a non-reactive eucalyptus oil. Examples of the reactive eucalyptus oil include amine group modification, epoxy group modification, carboxyl group modification, methanol modification, methacrylic acid modification, thiol modification, phenol modification, single terminal reactivity, and heterofunctional groups. Reform and so on. Examples of the non-reactive eucalyptus oil include polyether modification, Q methyl styrene modification, alkyl modification, higher fatty ester modification, hydrophilic special modification, higher alkoxy modification, and higher fatty acid modification. Quality, fluorine modification, etc. It is also possible to carry out two or more modifications as described above for one polyoxyalkylene molecule. The BIJ described modified sand oil preferably has a moderate compatibility with the composition components. In particular, when a reactive eucalyptus oil which is reactive with other coating film forming components blended as needed in the composition is used, since the composition of the present invention is fixed by chemical bonding in the cured cured film, it is difficult to cause the -43- 201008996 The problem of adhesion, corrosion, deterioration, etc. of the cured film. It is particularly effective in improving the adhesion to the vapor-deposited layer in the vapor deposition step. Further, in the case of an anthrone having a photocurable functional group such as a (meth) acrylonitrile-based fluorenone or a vinyl modified fluorenone, it is crosslinked with the composition of the present invention. Therefore, the properties after hardening are excellent. The polyoxyalkylene containing trimethylphosphonium decanoic acid is excellent in peeling property on the surface, and is excellent in peelability, and is excellent in adhesion to the surface of the exudation surface, and is excellent in adhesion to metal vapor deposition or surface coating. It is better. W The above-mentioned release agent may be added alone or in combination of two or more. When the release agent is added to the curable composition for imprint of the present invention, it is preferably blended in a proportion of 0.001 to 10% by mass, more preferably 0.01 to 5% by mass, based on the total amount of the composition. When the content of the release agent is in the range of 0.01 to 5% by mass, the peeling property-improving effect of the mold and the hardenable composition layer for imprinting is improved, and the shrinkage at the time of coating of the composition can be suppressed to cause the coating film. The surface cracking problem occurs on the surface, and the substrate itself or the adjacent layer in the product causes φ, for example, adhesion between the vapor deposition layer and film breakage at the time of transfer (the film strength becomes too weak). The composition of the present invention may be blended with an organic metal coupling agent in order to improve the heat resistance, strength, or adhesion to the metal deposition layer of the surface structure having the fine uneven pattern. Further, the organometallic coupling agent is effective because it also has an effect of promoting the thermosetting reaction. As the organometallic coupling agent, for example, various coupling agents such as a decane coupling agent, a titanium coupling agent, a chrome coupling agent, an aluminum coupling agent, and a tin coupling agent can be used. -44- .201008996 The decane coupling agent which can be used in the composition of the present invention may, for example, be ' /5 -(3,4-epoxycyclohexyl)ethyltrimethoxydecane, r-glycidoxypropane Epoxy decane such as trimethoxy decane, 7*·glycidoxypropylmethyldiethoxy decane; N-lu-(aminoethyl)-r-aminopropyltrimethoxy Decane, N-/3-(aminoethyl)-r-aminopropylmethyldimethoxydecane, r-aminopropyltrimethoxydecane, N-phenyl-r-aminopropyl Amino decane such as trimethoxy decane; and as other decane coupling agent, r-mercaptopropyltrimethoxydecane, r-chloropropylmethyldimethoxydecane, chloropropylmethyldi Ethoxy decane and the like. Examples of the titanium coupling agent include 'isopropyl triisostearyl decyl titanate, isopropyl tri-dodecyl phenyl fluorenyl titanate, and isopropyl hydrazine (dioctyl pyrophosphate). Ester) titanate, tetraisopropylbis(dioctylphosphite) titanate, tetraoctylbis(di-tridecylphosphite) titanate, tetrakis(2,2-diene) Propyloxymethyl)bis(di-tridecyl)phosphite titanate, bis(dioctylpyrophosphate)oxyacetate titanate, bis(dioctylpyrophosphate)ethylene Titanate, isopropyl trioctyl decyl titanate, isostearyl isopropyl methacrylate, isopropyl isostearyl bis acrylate, isopropyl tris(dioctyl) Phosphate) titanate, isopropyl triisopropylphenyl phenyl titanate, isopropyl tris(N-aminoethyl.aminoethyl) titanate, diisopropylphenyl phenyl Oxyacetate titanate, diisostearate vinyl titanate, and the like. Examples of the chrome coupling agent include 'tetra-n-propoxy chromium, tetra-butoxy zirconium, zirconium tetraethyl phthalate, zirconium dibutoxy bis(ethyl decyl pyruvate), and the like. Zirconium ethoxide, butyl acetoxyacetate - 45- 201008996 bis (ethyl acetoacetate) chromium. Examples of the aluminum coupling agent include aluminum isopropylate, aluminum sec-butoxydiisopropylate s-aluminum succinate, aluminum acetate, ethyl acetoacetate, aluminum diisopropylate, and the like. Refractory (ethyl acetoacetate) aluminum, alkyl acetoacetate aluminum diisopropylate, acetoacetate bis(ethyl acetonitrile) aluminum, ginseng (ethylene acetonitrile) aluminum Wait. The organometallic coupling agent can be arbitrarily blended in a proportion of 0.001 to 10% by mass based on the total solid content of the curable composition for imprint of the present invention. When the ratio of the organic metal coupling agent is 0.001% by mass or more, the heat resistance, the strength, and the adhesion to the vapor-deposited layer are more effectively promoted. On the other hand, when the ratio of the organic metal coupling agent is 10% by mass or less, it is preferable to suppress the stability of the composition and the film formability. The curable composition for imprint of the present invention may be blended with a polymerization inhibitor in order to improve storage stability and the like. As the polymerization inhibitor, for example, a phenol such as hydroquinone, tert-butylhydroquinone, catechol or hydroquinone monomethyl ether; an anthracene such as benzoquinone or diphenylphenylhydrazine; Tillage; copper, etc. The polymerization inhibitor is preferably blended at a ratio of 0.001 to 10% by mass based on the total amount of the composition of the present invention. An ultraviolet absorber can also be used as the curable composition for imprint of the present invention. Commercial products of the ultraviolet absorber include Tinuvin P, 234, 320, 326, 327, 328, and 213 (above, Ciba Geigy Co., Ltd.).

Sumisorb 110' 130、140、220、250、300、320、340、350、 -46- 201008996 400(以上，住友化學工業（股）製）等。紫外線吸收劑較佳爲以相對於壓印用硬化性組成物之總量而言0.01〜10質量％之比例任意地摻合。本發明之壓印用硬化性組成物中亦可使用光安定劑。前述光安定劑之市售品，可舉出Tinuvin 292、144、 622LD (以上，CibaGeigy(股）製）、SanolLS-770、765、292、 2626、1114、744(以上，三共化成工業（股）製）等。光安定劑較佳爲以相對於壓印用硬化性組成物之總量而言0.0 1〜 W 10質量％之比例任意地摻合。本發明之壓印用硬化性組成物中亦可使用抗老化劑。前述抗老化劑之市售品，可舉出Antigene W、S、P、 3C、6C、RD-G、FR、AW(以上，住友化學工業（股）製）等。抗老化劑較佳爲以相對於壓印用硬化性組成物之總量而言 0.01〜10質量％之比例任意地摻合。在本發明之壓印用硬化性組成物中，爲了調整與基板 φ 之接著性或膜的柔軟性、硬度等，可添加可塑劑。較佳可塑劑之具體例，例如，對苯二甲酸二辛酯、對苯二甲酸二十二烷酯、二辛酸三乙二醇酯、對苯二甲酸二甲基乙二醇酯、三甲酚基磷酸酯、己二酸二辛酯、癸二酸二丁酯、三乙醯基丙三醇、己二酸二甲酯、己二酸二乙酯、己二酸二 (η-丁基）酯、辛二酸二甲酯、辛二酸二乙酯、辛二酸二（n-丁基）酯等，可塑劑係能夠以組成物中之30質量％以下任意地添加。較佳爲20質量％以下、更佳爲10質量％以下。爲得 • 47- .201008996 可塑劑之添加效果，以o.i質量％以上爲較佳。在本發明之壓印用硬化性組成物爲了調整與基板之接著性等，亦可添加密接促進劑。作爲前述密接促進劑，可使用苯并咪唑類或聚苯并咪唑類、低級羥基烷基取代吡啶衍生物、含氮雜環化合物、尿素或硫尿素、有機磷化合物、8-羥喹啉、4-羥基喋啶、1,10-菲繞啉、2,2’-聯吡啶衍生物、苯并三唑類、有機磷化合物與苯二胺化合物、2-胺基-1-苯基乙醇、N-苯基乙醇胺、N-乙基二乙醇胺、N-乙基 m 二乙醇胺、N-乙基乙醇胺及衍生物、苯并唾唑衍生物等。密接促進劑在組成物中較佳爲20質量％以下、更佳爲10質量 %以下、進一步較佳爲5質量％以下。爲得密接促進劑之添加效果，以0.1質量％以上爲較佳。使本發明之組成物硬化時，亦可視需要添加熱聚合起始劑。作爲較佳之熱聚合起始劑，可列舉例如過氧化物、偶氮化合物。具體例可舉出苯甲醯基過氧化物、tert-丁基-Q 過氧化苯甲酸酯、偶氮雙異丁腈等。熱聚合起始劑較佳爲組成物中之8.0質量％以下、更佳爲6.0質量％以下、進一步較佳爲4.0質量％以下。爲得熱聚合起始劑之添加效果，以 3.0質量％以上爲較佳。本發明之壓印用硬化性組成物爲了調整圖案形狀、感度等之目的，亦可視需要添加光鹼產生劑。作爲光鹼產生劑，可舉出例如，2-硝基苄基環己基胺基甲酸酯、三苯基甲醇、0-胺甲醯基羥基醯胺、〇-胺甲醯基肟、[[(2,6-二硝 48 - 201008996 基苄基）氧基]羰基]環己基胺、雙[[(2-硝基苄基）氧基]羰基] 己烷1，6-二胺、4-(甲基硫苯甲醯基）-1-甲基味啉基乙院、（4-味啉基苯甲酿基）-1-节基-1-二甲基胺基丙院、N-(2-硝基苄基氧基擬基）吡咯院、六氣合鈷（III)參（三苯基甲基硼酸鹽）、2-苄基-2-二甲基胺基-1-(4-味啉基苯基）-丁酮、2,6-二甲基-3,5-二乙醯基-4-(2’-硝基苯基）-1，4-二氫吡啶、2,6-二甲基-3,5-二乙醯基-4-(2’，4’-二硝基苯基）-丨，4-二氫吡啶等。在本發明之壓印用硬化性組成物，爲了提升塗膜的辨識性等之目的，亦可任意地添加著色劑。在不損及本發明之目的的範圍，著色劑可使用在UV噴墨組成物、彩色濾光片用組成物及CCD圖像感應用組成物等所用之顏料或染料。可用於本發明之顏料，可使用先前公知的各種無機顏料或有機顏料。作爲無機顏料，可舉出金靥氧化物、金屬錯鹽等所示之金屬化合物，具體而言可舉出鐵、鈷、鋁、鎘、鉛、銅、鈦、鎂、鉻、鋅、銻等之金屬氧化物、金屬複合氧化物。作爲有機顏料，可例示C.I.顏料黃11，24, 31，53, 83, 99, 108, 109, 110, 138, 139,151，154，167、C.I.顏料橙 36, 38, 43、C.I.顔料紅 105, 122，149, 150，155, 171，175，176，177, 209、C.I.顏料紫 19, 23, 32, 39、C.I.顏料藍 1，2, 15，16, 22, 60，66、C.I.顏料綠 7，36，37、C.I.顏料棕 25，28、C.I.顔料黑1，7及碳黑。著色劑相對於組成物之總量，較佳爲掺合 0.001〜2質量％之比例。 •49- .201008996 又，在本發明之壓印用硬化性組成物，爲了提升機械強度、柔軟性等目的，亦可添加作爲任意成分之彈性體粒子。在本發明之組成物可添加作爲任意成分之彈性體粒子的平均粒子尺寸較佳爲10nm〜7 00nm、更佳爲30〜 3OOnm。例如聚丁二烯、聚異戊二烯、丁二烯/丙烯腈共聚物、苯乙烯/ 丁二烯共聚物、苯乙烯/異戊二烯共聚物、乙烯 /丙烯共聚物、乙烯/ α-烯烴系共聚物、乙烯/ α-烯烴/聚烯共聚物、丙烯酸橡膠、丁二烯/(甲基）丙烯酸酸酯共聚物、苯乙烯/ 丁二烯嵌段共聚物、苯乙烯/異戊二烯嵌段共聚物等之彈性體粒子。又，可使用將此等彈性體粒子以甲基丙烯酸甲酯聚合物、甲基丙烯酸甲酯/甲基丙烯酸縮水甘油酯共聚物等被覆而成的芯/殼型粒子。彈性體粒子亦可爲交聯構造。作爲彈性體粒子之市售品，可舉出例如，Resinous Bond RKB(Resinous化成（股）製）、Techno MBS-61、MBS-69(以上，Techno Polymer(股）製）等。此等彈性體粒子係可單獨或組合2種以上而使用。本發明之組成物中的彈性體成分之含有比例較佳爲1〜35質量％、更佳爲2〜30質量％、特佳爲3〜20質量％。再者，本發明之壓印用硬化性組成物中除了光自由基聚合起始劑以外，亦可添加光增感劑以調整UV領域之波長。在本發明可使用之典型增感劑可舉出揭示於Crivell0〔 -50- 201008996 V. Crivello，Adv. in Polymer Sci，62，1 (1 984)〕者、具體而言，芘、茈、吖啶橙、噻吨酮、2-氯噻吨酮、苯并黃素、 N-乙烯基咔唑、9,10-二丁氧基蒽、蒽醌、香豆素、酮香豆素、菲、樟腦輥、啡噻畊衍生物等。在本發明之組成物爲了硬化收縮之抑制、提升熱安定性等目的，亦可任意地添加鹼性化合物。作爲鹼性化合物，可舉出胺與喹啉及喹哄等含氮雜環化合物、鹼性鹼金屬化合物、鹼性鹼土類金屬化合物等。此等之中，從與光聚合成單分子之相溶性方面而言，以胺爲較佳，例如可舉出，辛基胺、萘基胺、二甲苯二胺、二苄基胺、二苯基胺、二丁基胺、二辛基胺、二甲基苯胺、奎寧環、三丁基胺、三辛基胺、四甲基乙烯二胺、四甲基-1,6-六亞甲基二胺、六亞甲基四胺及三乙醇胺等。本發明之組成物爲了提升光硬化性，亦可添加鏈移動劑。作爲前述鏈移動劑，具體而言可舉出4-雙（3-锍基丁基氧基）丁烷、1，3,5-參（3-锍基丁基氧基乙基）1，3,5-三哄-2,4,6(111，31^，511)-三酮、新戊四醇肆（3-锍基丁酸酯）。又，本發明之壓印用硬化性組成物在調製時之水分量較佳爲2.0質量％以下、更佳爲1.5質量％、進一步較佳爲1.0 質量％以下。藉由使調製時之水分量爲2.0質量％以下，可使本發明之組成物之保存性更安定。又，在本發明之壓印用硬化性組成物亦可使用溶劑。前述有機溶劑的含量在全組成物中以3質量％以下爲較佳。 -51- .201008996 亦即，本發明之組成物較佳爲含有如前述；官能之其他單體作爲反應性稀釋劑，故並以溶解本發明之組成物之成分的有機溶劑物中，有機溶劑的含量較佳爲3質量％以下以下，特佳爲未含有。如此，本發明之組有機溶劑者，在反應性稀釋劑將不溶解之本發明之組成物的情況、或微調整黏度時加。本發明之組成物中可較佳使用的有機光壓印用硬化性組成物或光阻通常所用的本發明所用之化合物溶解及均勻分散，且應，即無特別限定。作爲前述有機溶劑，可舉例如，甲醇，四氫呋喃等之醚類；乙二醇單甲基醚、乙乙二醇甲基乙基醚、乙二醇單乙基醚等之賽路蘇乙酸酯、乙基賽路蘇乙酸酯等之乙肇酯類；二乙二醇單甲基醚、二乙二醇二乙二甲基醚、二乙二醇乙基甲基醚、二乙二乙二醇單丁基醚等之二乙二醇類；丙二醇丙二醇乙基醚乙酸酯等之丙二醇烷基醚乙二甲苯等之芳香族烴類；丙酮、甲基乙基画環己酮、4-羥基-4-甲基-2-戊酮、2-庚酮等丙酸乙酯、2-羥基-2-甲基丙酸甲酯、2-羥酯、乙氧基醋酸乙酯、羥基醋酸乙酯、2- 之單官能及/或二非一定要含有用。本發明之組成、更佳爲2質量％成物未必是不含化合物等溶解成，亦可任意地添溶劑之種類爲在溶劑，只要能將不與此等成分反 •乙醇等之醇類；二醇二甲基醚、二醇醚類：甲基二醇烷基醚乙酸基醚、二乙二醇醇單乙基醚、二甲基醚乙酸酯、酸酯類；甲苯、同、甲基異丁酮、之酮類；2·羥基基-2-甲基丙酸乙羥基-2-甲基丁烷 -52- 201008996 酸甲酯、3-甲氧基丙酸甲酯、3-甲氧基丙酸乙酯、3-乙氧基丙酸甲酯、3-乙氧基丙酸乙酯、醋酸乙酯、醋酸丁酯、乳酸甲酯、乳酸乙基等之乳酸酯類等之酯類等。再者，N-甲基甲醯胺、N，N-二甲基甲醯胺、N-甲基甲醯苯胺、N-甲基乙醯胺、N，N-二甲基乙醯胺、N-甲基吡咯烷酮、二甲基亞碾、苄基乙基醚、二己基醚、丙酮基丙酮、異佛爾酮、己酸、辛酸、1-辛醇、1-壬醇、苄基醇、醋酸苄酯、安息香酸乙酯、草酸二乙酯、馬來酸二乙酯、T-丁 ❹ 內酯、碳酸乙烯酯、碳酸丙烯酯、苯基賽路蘇乙酸酯等之高沸點溶劑。此等係可1種單獨使用，亦可倂用2種以上。此等之中，特佳爲甲氧基丙二醇乙酸酯、2-羥基丙快酸乙酯、3-甲氧基丙酸甲酯、3-乙氧基丙酸乙酯、乳酸乙酯、環己酮、甲基異丁基酮、2-庚酮等。本發明之壓印用硬化性組成物之表面張力以在18〜 3 0mN/m的範圍爲較佳、以在20〜28mN/m之範圍爲更佳。藉 Q 由成爲如此範圍，可得提升表面平滑性之效果。又，本發明之壓印用硬化性組成物在調製時之水分量較佳爲2.0質量％以下、更佳爲1.5質量％、進一步較佳爲1.0 質量％以下。藉由使調製時之水分量爲2.0質量％以下，可使本發明之組成物之保存性更爲安定。針對本發明之壓印用硬化性組成物之黏度加以説明。本發明中的黏度只要沒有特別限定，即是指25 °C之黏度。本發明之壓印用硬化性組成物在25 °C之黏度以3〜 -53- 201008996 18mPa*s爲較佳、進一步較佳爲5〜15mPa*s、特佳爲7〜 12mPa_s。藉由使本發明之組成物之黏度成爲3mPa*s以上，有不易產生基板塗布適性之問題或膜之機械強度降低的傾向。具體而言，藉由使黏度爲3mPa*s以上，可抑制在組成物之塗布時產生表面不均、或在塗布時組成物從基板流出而較佳。又，黏度爲3mPa*s以上之組成物亦比黏度小於3mPa •s之組成物容易調製。另一方面，藉由使本發明之組成物之黏度成爲18mPa*s，即使是使具有微細凹凸圖案之模具密接於組成物的情形，組成物亦可流入模具凹部的腔體内、不易帶入大氣，因此不容易引起氣泡缺陷，在模具凸部於光硬化後不易殘留殘渣而較佳。又，本發明之組成物之黏度爲18mPa ·8以下時，於微細圖案的形成上黏度不造成影響〇通常，組成物之黏度係可藉由摻雜黏度相異的各種單體、寡聚物、聚合物來調整。爲了將本發明之壓印用硬化 Φ 性組成物之黏度在前述範圍内設計，較佳爲添加單分子黏度在5.0mPa_s以下之組成物以調整黏度。 [硬化物之製造方法] 接著，針對使用本發明之壓印用硬化性組成物的硬化物（尤其是微細凹凸圖案）之形成方法加以説明。經由將本發明之壓印用硬化性組成物塗布在基板或支撐體（基材）上而形成圖案形成層之步驟、在前述圖案形成層表面按壓模具之步驟、及對前述圖案形成層照射光之步驟將本發明之 -54- 201008996 組成物硬化，藉此可形成微細·的凹凸圖案。尤其在本發明中，爲使硬化物之硬化度提升，以進一步含在光照射後加熱圖案形成層之步驟爲較佳。即，較佳爲本發明之壓印用硬化性組成物係以光及熱來硬化。藉由本發明之硬化物之製造方法而得的硬化物之圖案精密度、硬化性、光透過性優良，可特別適用於液晶彩色濾光片之保護膜、間隔材、其他液晶顯示裝置用構件。具體而言，在基材（基板或支撐體）上塗布至少由本發明之組成物構成之圖案形成層，視需要使其而形成由本發明之組成物所構成的層（圖案形成層）以製作圖案受容體（在基材上設有圖案形成層者），且將模具壓接於該圖案受容體的圖案形成層表面，而進行轉印模具圖案之加工，藉由光照射及加熱使微細凹凸圖案形成層硬化。光照射及加熱亦可經由複數次來進行。藉由本發明之圖案形成方法（硬化物之製造方法）的光壓印微影亦可積層化或多重圖案化，亦可與通常之熱壓印組合使用。又，作爲本發明之壓印用硬化性組成物之應用，亦可在基板或支撐體上塗布本發明之組成物，將由該組成物構成的層曝光、硬化、視需要使乾燥（烘烤），藉以製作表塗層或絕緣膜等之永久膜。在液晶顯示器（LCD)等所用之永久膜（構造構件用之光阻）中，爲了不阻礙顯示器之動作，宜極力避免金屬或有機物之離子性雜質混入光阻中，其濃度爲lOOOppm以下、 -55- 201008996 宜爲lOOppm以下》以下，針對使用本發明之壓印用硬化性組成物而成的硬化物之製造方法（圖案形成方法（圖案轉印方法））加以具體敘述。在本發明之硬化物之製造方法，首先將本發明之組成物塗布於基材上以形成圖案形成層。作爲將本發明之壓印用硬化性組成物塗布於基材上時的塗布方法，可利用一般習知之塗布方法，例如浸塗法、空氣刀塗法、簾幕塗布法、線棒塗布法、凹版塗布法、擠壓塗布法、旋轉塗布法、挾縫掃瞄法等，藉由進行塗布而形成。又，本發明之組成物所構成的圖案形成層之膜厚係依照使用用途而相異，約爲0.05ym〜30/zm。又，亦可將本發明之組成物利用多重塗布予以塗布。而且，在基材與本發明之組成物所構成的圖案形成層之間，亦可形成例如平坦化層等之其他有機層。藉此，由於圖案形成層與基板不直接相接，可防止對基板之灰塵附著或基板之損傷等。用以塗布本發明之壓印用硬化性組成物的基材（基板或支撐體）係可依照各種用途加以選擇，例如，石英、玻璃、光學薄膜、陶瓷材料、蒸鍍膜、磁性膜、反射膜、Ni、Cu、 Cr、Fe等之金屬基板、紙、SOG(旋塗玻璃（spin on glass))、聚酯薄膜、聚碳酸酯薄膜、聚醯亞胺薄膜等之聚合物基板、 TFT陣列基板、PDP之電極板、玻璃或透明塑膠基板、ITO 或金屬等之導電性基材、絕緣性基材、矽酮、氮化矽酮、 -56- 201008996 聚矽酮、氧化矽酮、非晶矽酮等之半導體製作基板等，無特別限制。又，基材的形狀也沒有特別限定，可爲板狀亦可爲圓筒狀。再者，如後述之前述基材依照與模具之組合等，可選擇光透過性或非光透過性者。接著，在本發明之硬化物之製造方法，爲了將圖案轉印於圖案形成層，將模具壓合（按壓）於圖案形成層表面。藉此，可將在模具之按壓表面預先形成的微細圖案轉印至圖案形成層。 v 使用本發明之壓印用硬化性組成物的光壓印微影術係在模具材及/或基板之至少一者必須選擇光透過性材料。在適用於本發明之光壓印微影術，在基材上塗布本發明之壓印用硬化性組成物以形成圖案形成層，在其表面按壓光透過性的模具，並從模具內面照射光，使前述圖案形成層硬化。又，亦可將本發明之壓印用硬化性組成物塗布於光透過性基材上，將模具按壓於其上，從基材內面照射 Φ 光，以使壓印用硬化性組成物硬化。前述光照射可在附著模具之狀態進行，也可在模具剝離後進行，在本發明中，較佳爲以密接模具之狀態進行。可用於本發明之模具係使用具有欲轉印之圖案的模具。前述模具上之圖案可藉由例如光微影術或電子射線描畫法等’依所希望的加工精度形成圖案，惟在本發明中，模具圖案形成方法係無特殊限制。在本發明所用之光透過性模具材係無特別限定，只要 -57- 201008996 爲具有預定強度、耐久性者即可。具體而言，可例示玻璃、石英、PMMA、聚碳酸酯樹脂等之光透明性樹脂、透明金屬蒸鍍膜 '聚二甲基矽氧烷等之柔軟膜、光硬化膜、金屬膜等。在本發明使用透明基板時，所使用之非光透過型模具材沒有特別限定’只要爲具有預定強度者即可。具體而言，可例示陶瓷材料、蒸鍍膜、磁性膜、反射膜、Ni、Cu、Cr、 Fe等之金屬基板、SiC、矽酮、氮化矽酮、聚矽酮、氧化矽酮、非晶矽酮等之基板等，沒有特殊限制。又，模具之形狀亦無特殊限制，板狀模具、圓筒狀模具均可。圓筒狀模具係適用於特別需要轉印之連續生產性的情形。在本發明之硬化物之製造方法所用的模具，爲了提升壓印用硬化性組成物與模具表面之剝離性，亦可進行脫膜處理。作爲此種模具，可爲經進行矽酮系或氟系等之矽烷偶合劑之處理者，例如也適合使用DAIKIN工業（股）製之 OPTOOL DSX、或住友3M(股）製之Novec EGC-1720等市售脫膜劑。使用本發明之組成物進行光壓印微影術時，本發明之硬化物之製造方法通常係以模具壓力爲10大氣壓以下來進行。藉由使模具壓力爲10大氣壓以下，模具或基板不易變形且具有提高圖案精度的傾向。又，由於施加壓力低，因此有可縮小裝置的傾向，從此點而言亦爲較佳。模具壓力較佳爲選擇在模具凸部的壓印用硬化性組成物之殘膜變 -58- 201008996 少之範圍，可確保模具轉印之均勻性。在本發明之硬化物之製造方法，對前述圖案形成層照射光之步驟中光照射的照射量，只要爲比硬化所需之照射量爲足夠大即可。硬化所需要之照射量係視壓印用硬化性組成物之不飽和鍵的消耗量或硬化膜的膠黏性加以適當決定。又，在適用於本發明的光壓印微影術，光照射時之基板溫度通常係以室溫進行，惟爲提高反應性亦可邊加熱邊 ® 進行光照射。在光照射的前階段，若控制爲真空狀態，則可防止氣泡混入、抑制氧混入所致之反應性降低，具有提升模具與壓印用硬化性組成物之密接性的效果，故亦可以真空狀態進行光照射。又，本發明之硬化物之製造方法中，光照射時之較佳真空度爲lOla〜常壓之範圍。用以使本發明之壓印用硬化性組成物硬化的光並無特別限定，可列舉例如高能量電離放射線、近紫外、遠紫 φ 外、可視、紅外等範圍之波長的光或放射線。作爲高能量電離放射線源，藉由例如科克勞夫型加速器、凡德格拉夫型加速器、線性加速器、貝他加速器（betatron)、迴旋加速器等之加速器加速之電子射線，係工業上使用最爲便利且經濟，亦可使用其他由放射性同位素或原子爐等所放射之 7線、X線、α線、中子線、質子線等之放射線。作爲紫外線源，可舉出例如紫外線螢光燈、低壓水銀燈、高壓水銀燈、超高壓水銀燈、氙燈、碳弧燈、太陽燈等。放射線 -59- 201008996 包括例如微波、EUV。又，LED、半導體雷射光、或248nm 之KrF準分子雷射光或193nmArF準分子雷射等之半導體之微細加工所用的雷射光亦可適用於本發明。此等光係可使用單色光，亦可使用複數種波長相異的光（混合光）。於曝光時，宜使曝光照度爲lmW/cm2〜50mW/cm2之範圍。藉由爲lmW/cm2以上，因可縮短曝光時間而可提高生產性，藉由成爲50mW/cm2以下，具有可抑制因產生副反應所致之永久膜特性劣化的傾向，故較佳。曝光量宜爲 ® 5mJ/cm2〜1 000mJ/cm2之範圍。若爲5mJ/cm2以上，可防止曝光邊限變得狹窄，光硬化不足而在模具附著未反應物等問題發生。又，曝光量若爲1000m〗/cm2以下，可抑制因組成物之分解導致永久膜劣化。再者，於曝光時，爲防止氧導致自由基聚合之阻礙，亦可流通氮、氬等之惰性氣體，控制氧濃度爲小於l〇〇mg/L。在本發明之硬化物之製造方法中，藉由光照射使圖案 φ 形成層硬化後，較佳爲包括加熱經硬化之圖案使其進一步硬化的步驟（後烘烤步驟）。而且，加熱在從光照射後之圖案形成層剝離模具的前後之任一時點進行皆可，以在模具剝離後加熱圖案形成層爲較佳。於光照射後加熱硬化本發明之組成物的熱，以150〜280°C爲較佳、以200〜25 0t爲更佳。又，賦予熱之時間，以5〜60分鐘爲較佳、以15〜 4 5分鐘爲更佳。在本發明，光壓印微影術之光照射只要比硬化所需要 -60-Sumisorb 110' 130, 140, 220, 250, 300, 320, 340, 350, -46-201008996 400 (above, Sumitomo Chemical Industries Co., Ltd.) and the like. The ultraviolet absorber is preferably blended at a ratio of 0.01 to 10% by mass based on the total amount of the curable composition for imprint. A light stabilizer can also be used as the curable composition for imprint of the present invention. The commercial products of the above-mentioned light stabilizers include Tinuvin 292, 144, 622LD (above, CibaGeigy Co., Ltd.), SanolLS-770, 765, 292, 2626, 1114, 744 (above, Sankyo Chemical Industry Co., Ltd.) System) and so on. The light stabilizer is preferably blended at a ratio of from 0.01 to W10% by mass based on the total amount of the curable composition for imprint. An anti-aging agent can also be used in the curable composition for imprint of the present invention. Examples of the commercial product of the anti-aging agent include Antigene W, S, P, 3C, 6C, RD-G, FR, and AW (above, Sumitomo Chemical Industries Co., Ltd.). The anti-aging agent is preferably blended at a ratio of 0.01 to 10% by mass based on the total amount of the curable composition for imprint. In the curable composition for imprint of the present invention, a plasticizer may be added in order to adjust the adhesion to the substrate φ or the flexibility, hardness, and the like of the film. Specific examples of preferred plasticizers, for example, dioctyl terephthalate, behenyl terephthalate, triethylene glycol dioctanoate, dimethyl glycol terephthalate, tricresol Phosphate, dioctyl adipate, dibutyl sebacate, triethylene glyceryl triglyceride, dimethyl adipate, diethyl adipate, di(η-butyl) adipate The ester, the dimethyl suberate, the diethyl dioctate, the di(n-butyl) suberate, and the like can be arbitrarily added in an amount of 30% by mass or less of the composition. It is preferably 20% by mass or less, more preferably 10% by mass or less. For the addition effect of the plasticizer, it is preferable to use o.i mass% or more. In the curable composition for imprint of the present invention, an adhesion promoter may be added in order to adjust the adhesion to the substrate or the like. As the adhesion promoter, benzimidazoles or polybenzimidazoles, lower hydroxyalkyl-substituted pyridine derivatives, nitrogen-containing heterocyclic compounds, urea or sulfur urea, organophosphorus compounds, 8-hydroxyquinoline, 4 can be used. -hydroxyacridine, 1,10-phenanthroline, 2,2'-bipyridine derivative, benzotriazole, organophosphorus compound and phenylenediamine compound, 2-amino-1-phenylethanol, N - phenylethanolamine, N-ethyldiethanolamine, N-ethylm diethanolamine, N-ethylethanolamine and derivatives, benzoxazole derivatives, and the like. The adhesion promoter is preferably 20% by mass or less, more preferably 10% by mass or less, even more preferably 5% by mass or less, based on the composition. In order to obtain the effect of adding the adhesion promoter, it is preferably 0.1% by mass or more. When the composition of the present invention is hardened, a thermal polymerization initiator may be added as needed. As a preferable thermal polymerization initiator, a peroxide and an azo compound are mentioned, for example. Specific examples thereof include benzammonium peroxide, tert-butyl-Q peroxybenzoate, azobisisobutyronitrile, and the like. The thermal polymerization initiator is preferably 8.0% by mass or less, more preferably 6.0% by mass or less, still more preferably 4.0% by mass or less. The effect of adding the thermal polymerization initiator is preferably 3.0% by mass or more. The curable composition for imprint of the present invention may be added with a photobase generator as needed for the purpose of adjusting the shape, sensitivity, and the like. The photobase generator may, for example, be 2-nitrobenzylcyclohexylcarbamate, triphenylmethanol, 0-amine methyl hydroxy hydroxy guanamine, hydrazine-amine methyl hydrazide, [[ (2,6-dinitrogen 48 - 201008996 benzyl)oxy]carbonyl]cyclohexylamine, bis[[(2-nitrobenzyl)oxy]carbonyl]hexane 1,6-diamine, 4- (methylthiobenzhydryl)-1-methylmorpholinyl phenyl, (4-glyphosylbenzoyl)-1-phenyl-1-methylaminopropyl, N-( 2-nitrobenzyloxy-p-pyridylpyrrolium, hexa-cobalt (III) ginseng (triphenylmethylborate), 2-benzyl-2-dimethylamino-1-(4- Phenyl phenyl)-butanone, 2,6-dimethyl-3,5-diethylindol-4-(2'-nitrophenyl)-1,4-dihydropyridine, 2,6 - dimethyl-3,5-diethylinden-4-(2',4'-dinitrophenyl)-indole, 4-dihydropyridine and the like. In the curable composition for imprint of the present invention, a coloring agent may be arbitrarily added for the purpose of improving the visibility of the coating film and the like. The coloring agent can be used for a pigment or dye used in a UV inkjet composition, a color filter composition, a CCD image sensing composition, or the like, without departing from the object of the present invention. As the pigment which can be used in the present invention, various inorganic pigments or organic pigments previously known can be used. Examples of the inorganic pigment include a metal compound represented by a gold ruthenium oxide or a metal salt, and specific examples thereof include iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, ruthenium, and the like. Metal oxides, metal composite oxides. As the organic pigment, CI Pigment Yellow 11, 24, 31, 53, 83, 99, 108, 109, 110, 138, 139, 151, 154, 167, CI Pigment Orange 36, 38, 43 and CI Pigment Red 105, 122 can be exemplified. , 149, 150, 155, 171, 175, 176, 177, 209, CI Pigment Violet 19, 23, 32, 39, CI Pigment Blue 1, 2, 15, 16, 22, 60, 66, CI Pigment Green 7, 36, 37, CI Pigment Brown 25, 28, CI Pigment Black 1, 7 and carbon black. The colorant is preferably blended in a ratio of 0.001 to 2% by mass based on the total amount of the composition. Further, in the curable composition for imprint of the present invention, elastomer particles which are optional components may be added for the purpose of improving mechanical strength and flexibility. The average particle size of the elastomer particles which can be added as an optional component in the composition of the present invention is preferably from 10 nm to 700 nm, more preferably from 30 to 300 nm. For example, polybutadiene, polyisoprene, butadiene/acrylonitrile copolymer, styrene/butadiene copolymer, styrene/isoprene copolymer, ethylene/propylene copolymer, ethylene/α- Olefin-based copolymer, ethylene/α-olefin/polyene copolymer, acrylic rubber, butadiene/(meth)acrylate copolymer, styrene/butadiene block copolymer, styrene/isoprene Elastomer particles such as an alkyl block copolymer. Further, core/shell type particles in which the elastomer particles are coated with a methyl methacrylate polymer, a methyl methacrylate/glycidyl methacrylate copolymer or the like can be used. The elastomer particles can also be crosslinked. The commercially available product of the elastomer particles may, for example, be Resinous Bond RKB (manufactured by Resinous Chemical Co., Ltd.), Techno MBS-61, MBS-69 (manufactured by Techno Polymer Co., Ltd.) or the like. These elastomer particles may be used singly or in combination of two or more. The content of the elastomer component in the composition of the present invention is preferably from 1 to 35 % by mass, more preferably from 2 to 30% by mass, particularly preferably from 3 to 20% by mass. Further, in addition to the photoradical polymerization initiator, the curable composition for imprint of the present invention may be added with a photosensitizer to adjust the wavelength in the UV region. Typical sensitizers which can be used in the present invention are disclosed in Crivell 0 [-50-201008996 V. Crivello, Adv. in Polymer Sci, 62, 1 (1 984)], specifically, 芘, 茈, 吖Pyridine orange, thioxanthone, 2-chlorothioxanthone, benzoxanthin, N-vinylcarbazole, 9,10-dibutoxyanthracene, hydrazine, coumarin, ketocoumarin, phenanthrene, Camphor roller, thiophene derivative, etc. The composition of the present invention may optionally be added with a basic compound for the purpose of suppressing the hardening shrinkage and improving the thermal stability. The basic compound may, for example, be a nitrogen-containing heterocyclic compound such as an amine or quinoline or quinacrid, a basic alkali metal compound or a basic alkaline earth metal compound. Among these, an amine is preferable in terms of compatibility with photopolymerization into a single molecule, and examples thereof include octylamine, naphthylamine, xylenediamine, dibenzylamine, and diphenyl. Amine, dibutylamine, dioctylamine, dimethylaniline, quinuclidine, tributylamine, trioctylamine, tetramethylethylenediamine, tetramethyl-1,6-hexamethylene Diamine, hexamethylenetetramine and triethanolamine. The composition of the present invention may be added with a chain shifting agent in order to enhance photocurability. Specific examples of the chain shifting agent include 4-bis(3-mercaptobutyloxy)butane and 1,3,5-gin(3-mercaptobutyloxyethyl) 1,3. , 5-tritero-2,4,6(111,31^,511)-trione, pentaerythritol bismuth (3-mercaptobutyrate). Further, the moisture content of the curable composition for imprint of the present invention is preferably 2.0% by mass or less, more preferably 1.5% by mass, still more preferably 1.0% by mass or less. When the water content at the time of preparation is 2.0% by mass or less, the preservability of the composition of the present invention can be made more stable. Further, a solvent may be used as the curable composition for imprint of the present invention. The content of the organic solvent is preferably 3% by mass or less based on the total composition. -51-.201008996 That is, the composition of the present invention is preferably an organic solvent containing the other monomer as described above as a reactive diluent and solubilizing the components of the composition of the present invention, an organic solvent. The content is preferably 3% by mass or less, and particularly preferably not contained. Thus, the organic solvent of the present invention is added in the case where the reactive diluent is not dissolved in the composition of the present invention or when the viscosity is finely adjusted. The curable composition for organic photoimprint or the compound used in the present invention which is usually used for the resist is dissolved and uniformly dispersed in the composition of the present invention, and is not particularly limited. The organic solvent may, for example, be an ether such as methanol or tetrahydrofuran; or celecoxib acetate such as ethylene glycol monomethyl ether, ethylene glycol methyl ethyl ether or ethylene glycol monoethyl ether. Ethyl esters such as ethyl celecoxib acetate; diethylene glycol monomethyl ether, diethylene glycol diethylene glycol ether, diethylene glycol ethyl methyl ether, diethylene glycol An aromatic hydrocarbon such as diol glycol monoether such as diol monobutyl ether; propylene glycol alkyl ether such as propylene glycol propylene glycol ethyl ether acetate; acetone, methyl ethyl hexanone, 4 Ethyl propionate such as hydroxy-4-methyl-2-pentanone or 2-heptanone, methyl 2-hydroxy-2-methylpropionate, 2-hydroxy ester, ethyl ethoxyacetate, hydroxyacetic acid Ethyl ester, 2-monofunctional and/or secondary are not necessarily included. The composition of the present invention, more preferably 2% by mass, is not necessarily dissolved in a compound or the like, and the type of the solvent may be optionally added as a solvent, as long as alcohols such as ethanol are not reacted with these components; Glycol dimethyl ether, glycol ethers: methyl glycol alkyl ether acetate ether, diethylene glycol alcohol monoethyl ether, dimethyl ether acetate, acid ester; toluene, the same, a Isobutyl ketone, ketones; 2 hydroxy-2-methylpropanoic acid hydroxy-2-methylbutane-52- 201008996 methyl ester, methyl 3-methoxypropionate, 3-methyl Ester esters of ethyl oxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, etc. Classes, etc. Further, N-methylformamide, N,N-dimethylformamide, N-methylformamide, N-methylacetamide, N,N-dimethylacetamide, N -methylpyrrolidone, dimethyl submilling, benzyl ethyl ether, dihexyl ether, acetone acetone, isophorone, hexanoic acid, octanoic acid, 1-octanol, 1-nonanol, benzyl alcohol, acetic acid High boiling point solvent such as benzyl ester, ethyl benzoate, diethyl oxalate, diethyl maleate, T-butyrolactone, ethylene carbonate, propylene carbonate, phenyl racelus acetate. These may be used alone or in combination of two or more. Among these, methoxypropanediol acetate, ethyl 2-hydroxypropionate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl lactate, and a ring are particularly preferred. Hexanone, methyl isobutyl ketone, 2-heptanone, and the like. The surface tension of the curable composition for imprint of the present invention is preferably in the range of 18 to 30 mN/m, more preferably in the range of 20 to 28 mN/m. By using Q to be such a range, the effect of improving surface smoothness can be obtained. Further, the moisture content of the curable composition for imprint of the present invention is preferably 2.0% by mass or less, more preferably 1.5% by mass, still more preferably 1.0% by mass or less. When the water content at the time of preparation is 2.0% by mass or less, the preservability of the composition of the present invention can be made more stable. The viscosity of the curable composition for imprint of the present invention will be described. The viscosity in the present invention means a viscosity at 25 ° C unless otherwise specified. The curable composition for imprint of the present invention preferably has a viscosity at 25 ° C of 3 to -53 to 201008996 18 mPa*s, more preferably 5 to 15 mPa*s, particularly preferably 7 to 12 mPa_s. When the viscosity of the composition of the present invention is 3 mPa*s or more, there is a problem that the substrate coating property is less likely to occur or the mechanical strength of the film is lowered. Specifically, by setting the viscosity to 3 mPa*s or more, it is possible to suppress occurrence of surface unevenness at the time of coating of the composition or to flow out of the substrate from the substrate at the time of coating. Further, a composition having a viscosity of 3 mPa*s or more is also easily modulated than a composition having a viscosity of less than 3 mPa·s. On the other hand, when the viscosity of the composition of the present invention is 18 mPa*s, even if the mold having the fine uneven pattern is adhered to the composition, the composition can flow into the cavity of the concave portion of the mold, and it is not easy to bring in Atmospheric, it is not easy to cause bubble defects, and it is preferable that the mold convex portion is less likely to remain after the photocuring. Further, when the viscosity of the composition of the present invention is 18 mPa·8 or less, the viscosity does not affect the formation of the fine pattern. Generally, the viscosity of the composition can be obtained by doping various monomers and oligomers having different viscosity. , polymer to adjust. In order to design the viscosity of the hardening Φ composition for imprinting of the present invention within the above range, it is preferred to add a composition having a single molecule viscosity of 5.0 mPa_s or less to adjust the viscosity. [Method for Producing the cured product] Next, a method of forming a cured product (particularly, a fine uneven pattern) using the curable composition for imprint of the present invention will be described. a step of forming a pattern forming layer by applying the curable composition for imprint of the present invention onto a substrate or a support (substrate), a step of pressing a mold on the surface of the pattern forming layer, and irradiating the pattern forming layer with light The step of hardening the composition of the present invention -54 to 201008996, whereby a fine concavo-convex pattern can be formed. In particular, in the present invention, in order to increase the degree of hardening of the cured product, it is preferred to further include a step of heating the pattern forming layer after the light irradiation. That is, it is preferred that the curable composition for imprint of the present invention is cured by light and heat. The cured product obtained by the method for producing a cured product of the present invention is excellent in precision, hardenability, and light transmittance, and is particularly suitably used for a protective film for a liquid crystal color filter, a spacer, and other members for a liquid crystal display device. Specifically, a pattern forming layer composed of at least a composition of the present invention is applied onto a substrate (substrate or support), and a layer (pattern forming layer) composed of the composition of the present invention is formed as necessary to form a pattern. The receiving body (the pattern forming layer is provided on the substrate), and the mold is crimped to the surface of the pattern forming layer of the pattern receiving body, and the transfer mold pattern is processed, and the fine concave and convex pattern is made by light irradiation and heating. The layer is hardened. Light irradiation and heating can also be carried out several times. The photoimprint lithography by the pattern forming method (the method for producing a cured product) of the present invention may be laminated or multi-patterned, or may be used in combination with usual hot stamping. Further, as the application of the curable composition for imprint of the present invention, the composition of the present invention may be applied onto a substrate or a support, and a layer composed of the composition may be exposed, hardened, and dried (baked) as necessary. To make a permanent film such as a surface coating or an insulating film. In a permanent film (photoresist for a structural member) used in a liquid crystal display (LCD) or the like, in order not to hinder the operation of the display, it is preferable to prevent the ionic impurities of the metal or organic substance from being mixed into the photoresist at a concentration of 1000 ppm or less. 55-201008996 is preferably 100 ppm or less. Hereinafter, a method for producing a cured product (pattern forming method (pattern transfer method)) using the curable composition for imprint of the present invention will be specifically described. In the method for producing a cured product of the present invention, the composition of the present invention is first applied onto a substrate to form a pattern forming layer. As a coating method when the curable composition for imprint of the present invention is applied onto a substrate, a conventional coating method such as a dip coating method, an air knife coating method, a curtain coating method, a wire bar coating method, or the like can be used. A gravure coating method, an extrusion coating method, a spin coating method, a quilting scanning method, or the like is formed by coating. Further, the film thickness of the pattern forming layer composed of the composition of the present invention varies depending on the intended use, and is about 0.05 ym to 30/zm. Further, the composition of the present invention may be applied by multiple coating. Further, another organic layer such as a planarization layer may be formed between the substrate and the pattern forming layer composed of the composition of the present invention. Thereby, since the pattern forming layer does not directly contact the substrate, dust adhesion to the substrate, damage to the substrate, and the like can be prevented. The substrate (substrate or support) for applying the curable composition for imprint of the present invention can be selected according to various uses, for example, quartz, glass, optical film, ceramic material, vapor deposited film, magnetic film, reflective film. , metal substrate of Ni, Cu, Cr, Fe, etc., polymer substrate of paper, SOG (spin on glass), polyester film, polycarbonate film, polyimide film, etc., TFT array substrate , PDP electrode plate, glass or transparent plastic substrate, conductive substrate such as ITO or metal, insulating substrate, fluorenone, fluorenone, -56- 201008996 polyfluorenone, fluorenone, amorphous 矽The semiconductor production substrate or the like of a ketone or the like is not particularly limited. Further, the shape of the substrate is not particularly limited, and may be a plate shape or a cylindrical shape. Further, as described above, the substrate may be selected to have light transmittance or non-light transmittance in accordance with a combination with a mold or the like. Next, in the method for producing a cured product of the present invention, in order to transfer a pattern onto the pattern forming layer, the mold is pressed (pressed) on the surface of the pattern forming layer. Thereby, the fine pattern previously formed on the pressing surface of the mold can be transferred to the pattern forming layer. v Photoimprint lithography using the curable composition for imprint of the present invention At least one of the mold material and/or the substrate must select a light transmissive material. In the photoimprint lithography suitable for the present invention, the curable composition for imprint of the present invention is applied onto a substrate to form a pattern forming layer, and a light transmissive mold is pressed on the surface thereof, and is irradiated from the inner surface of the mold. Light causes the aforementioned pattern forming layer to harden. Further, the curable composition for imprint of the present invention may be applied onto a light-transmitting substrate, and a mold may be pressed thereon to irradiate Φ light from the inner surface of the substrate to harden the curable composition for imprinting. . The light irradiation may be carried out in a state in which the mold is attached, or may be performed after the mold is peeled off. In the present invention, it is preferable to carry out the state in which the mold is adhered. A mold which can be used in the present invention uses a mold having a pattern to be transferred. The pattern on the mold can be patterned by a desired processing precision such as photolithography or electron ray drawing, but in the present invention, the mold pattern forming method is not particularly limited. The light-transmitting mold material used in the present invention is not particularly limited as long as -57-201008996 has a predetermined strength and durability. Specifically, a light-transparent resin such as glass, quartz, PMMA or polycarbonate resin, a transparent film of a transparent metal vapor-deposited film such as polydimethyl siloxane or a photocured film or a metal film can be exemplified. When the transparent substrate is used in the present invention, the non-light transmitting type mold material to be used is not particularly limited as long as it has a predetermined strength. Specifically, a ceramic material, a vapor deposited film, a magnetic film, a reflective film, a metal substrate such as Ni, Cu, Cr, or Fe, SiC, anthrone, fluorenone, fluorenone, fluorenone, or amorphous can be exemplified. The substrate such as an anthrone or the like is not particularly limited. Further, the shape of the mold is not particularly limited, and a plate mold or a cylindrical mold may be used. The cylindrical mold is suitable for the case where continuous productivity of transfer is particularly required. The mold used in the method for producing a cured product of the present invention may be subjected to a release treatment in order to improve the peeling property between the curable composition for imprint and the surface of the mold. As such a mold, those which are subjected to a decane coupling agent such as an anthrone or a fluorine-based one may be, for example, an OPTOOL DSX manufactured by DAIKIN Industries Co., Ltd. or a Novec EGC-1720 manufactured by Sumitomo 3M Co., Ltd. And other commercially available release agents. When photoimprint lithography is carried out using the composition of the present invention, the method for producing a cured product of the present invention is usually carried out at a mold pressure of 10 atm or less. When the mold pressure is 10 atm or less, the mold or the substrate is less likely to be deformed and the pattern accuracy tends to be improved. Further, since the applied pressure is low, there is a tendency to reduce the size of the device, and it is also preferable from this point of view. The mold pressure is preferably selected from the range of the residual film of the hardenable composition for imprinting of the mold to be less than -58 to 201008996, and the uniformity of the transfer of the mold can be ensured. In the method for producing a cured product of the present invention, the amount of irradiation of light in the step of irradiating light to the pattern forming layer may be sufficiently larger than the amount of irradiation required for curing. The amount of irradiation required for hardening is appropriately determined depending on the consumption of the unsaturated bond of the hardenable composition for imprint or the adhesiveness of the cured film. Further, in the photoimprint lithography which is suitable for the present invention, the substrate temperature at the time of light irradiation is usually carried out at room temperature, but it is also possible to heat the side while heating to improve the reactivity. In the pre-light irradiation stage, if it is controlled to be in a vacuum state, it is possible to prevent the bubble from entering and suppress the decrease in reactivity due to oxygen incorporation, and to improve the adhesion between the mold and the hardenable composition for imprinting, so vacuum can be used. The state is illuminated by light. Further, in the method for producing a cured product of the present invention, the preferred degree of vacuum at the time of light irradiation is in the range of from 10 la normal pressure to normal pressure. The light for curing the curable composition for imprint of the present invention is not particularly limited, and examples thereof include light or radiation having a wavelength in a range of high-energy ionizing radiation, near-ultraviolet light, far-purple φ, visible, infrared, or the like. As a high-energy ionizing radiation source, the electron beam accelerated by an accelerator such as a Krokoff type accelerator, a Vandergrave type accelerator, a linear accelerator, a betatron, a cyclotron, etc. is the most industrially used. Convenient and economical, it is also possible to use other radiation such as 7-line, X-ray, α-line, neutron line, or proton line emitted by a radioisotope or an atomic furnace. Examples of the ultraviolet light source include ultraviolet fluorescent lamps, low-pressure mercury lamps, high-pressure mercury lamps, ultra-high pressure mercury lamps, xenon lamps, carbon arc lamps, and sun lamps. Radiation -59- 201008996 Includes, for example, microwave, EUV. Further, laser light for microfabrication of semiconductors such as LEDs, semiconductor laser light, or 248 nm KrF excimer laser light or 193 nm ArF excimer laser light can also be applied to the present invention. These light systems can use monochromatic light or a plurality of different wavelengths of light (mixed light). When exposing, the exposure illuminance should be in the range of lmW/cm2 to 50 mW/cm2. When it is lmW/cm2 or more, the production time can be improved by shortening the exposure time, and when it is 50 mW/cm2 or less, it is preferable to suppress deterioration of permanent film characteristics due to side reactions. The exposure should be in the range of ® 5mJ/cm2 to 1 000mJ/cm2. When the thickness is 5 mJ/cm2 or more, it is possible to prevent the exposure margin from becoming narrow, and the problem of insufficient photohardening and adhesion of unreacted materials to the mold occurs. Further, when the exposure amount is 1000 m/cm 2 or less, deterioration of the permanent film due to decomposition of the composition can be suppressed. Further, at the time of exposure, in order to prevent oxygen from causing blockage of radical polymerization, an inert gas such as nitrogen or argon may be passed to control the oxygen concentration to be less than 10 mg/L. In the method for producing a cured product of the present invention, after the pattern φ is formed into a layer by light irradiation, it is preferred to include a step of heating the hardened pattern to further harden (post-baking step). Further, heating may be performed at any point before and after the pattern-forming layer is peeled off from the pattern after the light irradiation, and it is preferable to heat the pattern-forming layer after the mold is peeled off. The heat of the composition of the present invention which is heat-hardened after light irradiation is preferably 150 to 280 ° C, more preferably 200 to 25 0 t. Further, the time for applying heat is preferably 5 to 60 minutes, more preferably 15 to 45 minutes. In the present invention, the light irradiation of photoimprint lithography is only required to be hardened by -60-

201008996 之照射量爲夠大即可。硬化所需要之照射量裔影術用硬化性組，成物之不飽和鍵之消耗量或瑪性加以決定。 β 又，適用於本發明之光壓印微影術中，3 板溫度通常係以室溫進行，惟爲提高反應性β 進行光照射。在光照射的前階段，若控制爲ϊ 可防止氣泡混入、抑制氧混入所致之反應性降提升模具與壓印微影術用硬化性組成物之密g 故宜在真空狀態進行光照射。在本發明，較il 在lO^Pa〜常壓之範圍進行。本發明之壓印用硬化性組成物係混合後，藉由以例如，孔徑0.05//m〜5.〇Aim之知濾，而可調製爲溶液。壓印用硬化性組成物之常係在0°C〜100°C之範圍進行。過濾可爲多R 可重複多數次。又，亦可將經過濾的液體進f 濾所使用之材質可使用聚乙烯樹脂、聚丙烯樹耐綸樹脂等，並無特別限定。 [硬化物] 藉由上述本發明之硬化物之製造方法拜明硬化物係可作爲用於液晶顯示器（LCD)等之構件用光阻）或蝕刻光阻來使用。又，前述永^ 後裝瓶於加侖瓶或夸脫瓶等之容器，進行運$ 時，爲了防止劣化，亦可將容器内以惰性氮写丨依照壓印微丨化膜之膠黏 ί照射時之基 :可邊加熱邊 :空狀態，則 r低，因具有丨性之效果， i之真空度係上述各成分 ϊ濾器進行過混合·溶解通穿段進行，亦 ί再過濾。過脂、氟樹脂、形成的本發永久膜（構造、膜係在製造 ί、保管，此 5氬等取代。 -61- 201008996 時於管制保控、度輸溫運可於亦又質The amount of exposure for 201008996 is large enough. The amount of exposure required for hardening is determined by the hardening group, the consumption of the unsaturated bond of the adult or the nature. Further, in the photoimprint lithography of the present invention, the temperature of the three sheets is usually carried out at room temperature, but the light is irradiated by increasing the reactivity β. In the pre-light irradiation stage, if it is controlled to be ϊ, it is possible to prevent the bubble from entering and suppress the reactivity caused by the oxygen intrusion. To improve the density of the mold and the squeezing lithography hardening composition, it is preferable to perform light irradiation in a vacuum state. In the present invention, it is carried out in the range of lO^Pa~atmospheric pressure. The curable composition for imprint of the present invention is mixed and then pulverized into a solution by, for example, a pore size of 0.05//m to 5. 〇Aim. The hardening composition for imprinting is usually carried out in the range of 0 °C to 100 °C. Filtration can be repeated multiple times for multiple R. Further, the material used for the filtration of the filtered liquid may be, for example, a polyethylene resin or a polypropylene resin, and is not particularly limited. [Cured material] The above-described method for producing a cured product of the present invention is used in the case where the cured product can be used as a photoresist for a member such as a liquid crystal display (LCD) or an etching resist. In addition, when the bottle is bottled in a gallon bottle or a quart bottle for a long time, in order to prevent deterioration, the container may be written with inert nitrogen according to the adhesive of the imprinted micro-deposited film. Base of time: can be heated side: empty state, then r is low, because of the effect of 丨, the vacuum degree of i is the above-mentioned components ϊ filter is mixed and dissolved through the section, and then filtered. Peracid, fluororesin, formed permanent film (structure, film system in manufacturing, storage, this 5 argon, etc.. -61- 201008996 in the regulation of control, degree of transport can also be qualitative

爲變至之光膜遮久以永’ 止然防當更。了圍爲範 , 之溫°c 常 ο 不進行反應的程度爲較佳。本發明之硬化物的彈性回復率從適合用來作爲液晶顯示裝置用構件之觀點來看，以70%以上爲較佳、以75% 以上爲更佳、80%以上爲特佳。 [液晶顯示裝置用構件] 又，本發明之壓印用硬化性組成物可適用來作爲半導馨體積體電路、記錄材料、液晶顯示裝置用構件，其中以液晶顯示裝置用構件爲較佳，以作爲平面顯示器等之蝕刻光阻爲更佳。利用本發明之壓印用組成物作爲蝕刻光阻時，首先使用形成有例如Si〇2等薄膜的矽晶圓等作爲基材，在基材上藉由本發明之硬化物之製造方法形成奈米等級的微細圖案。然後，濕蝕刻時使用氟化氫等、乾鈾刻時使用CF4等 φ 蝕刻氣體進行蝕刻’藉此可在基材上形成希望的圖案。 [實施例] 以下舉出實施例更具體地説明本發明。以下實施例所示之材料、使用量、比例、處理内容、處理順序等只要不脫離本發明之宗旨’皆可做適當變更。因此，本發明之範圍係不限於以下所示之具體例。 [實施例1] 在下述表2所示之組成加入下述表1記載之光聚合性 -62- 201008996 單體Ml〜M3、下述光自性劑W _ 1及W · 2、下述; 印用硬化性組成物。又由基聚合起始劑P-1、下述界面活坑氧化劑AO 1，調製實施例1之壓，表2中的數値爲質量％。In order to change to the light film, it will last forever. The temperature is always the same as the temperature, and the degree of non-reaction is preferred. The elastic recovery rate of the cured product of the present invention is preferably 70% or more, more preferably 75% or more, and still more preferably 80% or more from the viewpoint of being suitable as a member for a liquid crystal display device. [Member for liquid crystal display device] The curable composition for imprint of the present invention can be suitably used as a semi-conductive body bulk circuit, a recording material, and a member for a liquid crystal display device, and among them, a member for a liquid crystal display device is preferable. It is more preferable to use an etching resist as a flat display or the like. When the composition for imprint of the present invention is used as an etching resist, first, a germanium wafer or the like on which a thin film such as Si〇2 is formed is used as a substrate, and a nanometer is formed on the substrate by the method for producing a cured product of the present invention. A fine pattern of grades. Then, when wet etching is performed, hydrogen fluoride or the like is used, and when dry uranium engraving is performed, etching is performed using φ etching gas such as CF4, whereby a desired pattern can be formed on the substrate. [Examples] Hereinafter, the present invention will be more specifically described by way of examples. The materials, the amounts, the ratios, the processing contents, the processing order, and the like shown in the following examples can be appropriately changed without departing from the gist of the invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. [Example 1] The photopolymerizable-62-201008996 monomers M1 to M3 described below in Table 1 and the following photoinitiators W _ 1 and W · 2 were added to the compositions shown in Table 2 below; A hardening composition is printed. Further, the pressure of Example 1 was prepared from the base polymerization initiator P-1 and the following interface oxidant AO 1, and the number 値 in Table 2 was % by mass.

參 -63- 201008996 [表1 ]参-63- 201008996 [Table 1]

略稱 .. 商品名製造商光聚潍單體 Ml (單官能丙烯酸單分子） Viscoat#160 大阪有機化學工業 M2 (二官能丙烯酸單分子） NPGDA 曰本化藥 M3 (三官能丙烯酸單分子） Aronix M309 東亞合成 M4 (氧雜環丁烷單分子） OXT221 東亞合成 M5 (氧雜環丁烷單分子） OXTIOl 東亞合成 M6 獮氧挪分子） Celloxide 2021P 戴西爾化學 M7 (單官能丙嫌酸單分子） Viscoat#155 大阪有機化學工業 M8 (單官能甲基丙嫌酸單分子）甲基丙烯酸酸縮水甘油酯東京化成 M9 (二官能丙嫌酸單分子） FA-129AS 曰立化成 M10 (二官能丙烯酸單分子） Light-acrylate 3EG-A 共榮公司化學 Mil (單官能丙烯酸單分子） KBM5103 信越化學工業非聚合性 C1 癸二酸二辛酯住友化學光聚合起始劑 PI1 (光自由基聚合起始劑） TPO-L 日本Siber PI2 (光陽離子聚合起始簡 Irgacure 250 Ciba 界面活性劑 W1 (非離子系界面活性勛 PioninD6315 w油脂 W2(|R系界面活性劑） MEGAFACF780F 大日本油墨化學工業 W3 嗽酮系界面活性劑） KF-352A 信越化學工業矽焼偶合劑 SCI KBM903 信越化學工業抗氧化劑 A01(受阻酚系） ADK STAB AO-60 Adeka Japan A02(半受阻酚系） Sumilizer GA-80 住友化學 A03(苯酚系） Irganox E 201 Ciba A〇4(受阻胺系） ADK STAB LA-68 Adeka Japan A〇5(硫醚系） ADK STAB AO-503 Adeka Japan A06(硫醚系） Irganox 1035FF Ciba -64- 201008996 [實施例2〜66、比較例1〜21及25〜37] 除了改爲下述表2〜6之組成以外，與實施例1之成物相同地進行，得此等組成物。 [比較例22〜24] 將特開2006-124636號公報之表18所記載的No.8、 Νο·9及No.ll之中除去顏料，調製爲比較例22〜24之組成物。前述No.8係不含抗氧化劑，前述No.9係含0.15質量 %之Sumilizer MDP-S(住友化學工業製）作爲受阻酚系抗氧化劑，前述 No.ll係含有 0.15質量％之 Hostavin N-24(Clariant公司製）作爲受阻胺系抗氧化劑。 [壓印用硬化性組成物之評價] 針對各實施例及比較例的組成物，依照下述評價方法對壓印性、光硬化性、耐熱性、彈性回復率及電壓特性進行測定·評價。結果示於下述表2〜表6。 <壓印性> 轉印於光阻之圖案係評價能夠以何種程度再現模具之形狀。具體而言，對各組成物，以膜厚成爲3.0;/m的方式旋塗於玻璃基板上。將經旋塗之塗布基膜安置在0RC公司製之以高壓水銀燈（燈具功率2000mW/cm2)爲光源的壓印裝置，以模具加壓力0.8kN、曝光中的真空度爲lOTorr(約 1.33xl04Pa)之條件，以模具按壓，模具係使用具有10/zm 之線/間距圖案且溝槽深度爲4.0/^m的材質爲聚二甲基矽氧烷（將東麗·道康寧（股）製之「SILPOT184」以80°C 60分鐘 •65- 201008996 硬化而成）之物’然後，從模具表面以240nU/cm2的條件進行曝光。曝光後去除模具，得到光阻圖案。然後，將所得光阻圖案在烘箱以230°C、30分鐘加熱，使完全硬化。利用掃瞄型電子顯微鏡及光學顯微鏡觀察轉印後之圖案形狀，依照以下基準評價圖案形狀。 5:模具形狀的轉印率爲95 %以上。 4:模具形狀的轉印率爲90%以上、小於95%。 3 :模具形狀的轉印率爲80%以上、小於90%。 ® 2 :模具形狀的轉印率爲7 0 %以上、小於8 0 %。 1 :模具形狀的轉印率爲小於7 0 % » <光硬化性之評價> 將各組成物以膜厚成爲3.0# m的方式旋塗於玻璃基板上，不壓著模具，在氮氛圍氣下以10mW、300m〗/cm2的條件進行曝光。然後，在膜的表面壓付塑膠薄膜，評價剝除塑膠薄膜時的殘留痕跡情形（膠黏性），測定光硬化性。 A 5:完全沒有殘留痕跡。 4 :雖有殘留痕跡，但數秒內消失。 3 :雖有殘留痕跡，但數分內消失。 2:殘留痕跡，時間經過也亦未消失。 1 :膜未硬化。 <耐熱性> 將各組成物以膜厚成爲3.0 的方式旋塗於玻璃基板上，不壓著模具，在氮氛圍氣下以l〇mW、300m】/cm2的 -66 - .201008996 條件進行曝光。然後，在烘箱以23 0°C、15分鐘加熱使硬化。測定在烘箱烘烤前後之膜厚，求得其減少率’依照下述基準評價加熱所致之膜減少率（膜減少）。 5:230°(：-15〇111丨11之烘烤前後的膜減少爲5%以下。 4 : 230°C -150min之烘烤前後的膜減少爲5%以上、小於 10%。 3 : 230°C -150min之烘烤前後的膜減少爲10%以上、小於1 5 %。 Φ 2: 230°C-150min之烘烤前後的膜減少爲15%以上、小於20%。 1 : 23(TC -150min之烘烤前後的膜減少爲20%以上。 <彈性回復率之評價> 將各組成物以膜厚成爲3.0 的方式旋塗於玻璃基板上，不壓著模具，在氮氛圍氣下以10mW-200mJ進行曝光。之後在烘箱以230°C、30分鐘加熱使硬化，將硬化所 φ 得的膜做成 20x30x4# m的柱狀，以島津製作所製 DUH-W201測定彈性回復率。 5 :彈性回復率爲80%以上。 4 :彈性回復率爲75 %以上、小於80%。 3 :彈性回復率爲70%以上、小於75%。 2 :彈性回復率爲60%以上、小於75%。 1 :彈性回復率爲小於60%。 <電壓特性之評價> -67- 201008996 將各組成物以膜厚成爲3.0 的方式旋塗於玻璃基板上，不壓著模具，在氮氛圍氣下以10mW-200mJ進行曝光。之後在烘箱以230°C、30分鐘加熱使硬化，依照同心環法測定硬化所得的膜之體積電阻，測定電壓特性。將所得電壓特性依照下述評價進行評價。 5:體積電阻爲1χ10Ε15Ω ·πι以上。 4 :體積電阻爲5χ10Ε14 Ω . m以上、小於1χ1〇Ε15 Ω . m。 3:體積電阻爲1χ10Ε14Ω .m以上、小於5χ10Ε14Ω .m。 ❹ 2:體積電阻爲1X10E13 Ω .m以上、小於1χ1〇Ε14Ω .m。 1 :體積電阻小於1χ1〇Ε13Ω ·ιη。在此，實施例1〜7及比較例26係僅使用受阻酚系抗氧化劑之態樣，改變抗氧化劑之添加量。實施例8〜1 4及比較例27係僅使用半受阻酚系抗氧化劑之態樣.，改變抗氧化劑之添加量進行比較。實施例15〜21及比較例28係僅使用半受阻酚系抗氧化劑之態樣，改變抗氧化劑之添加量 φ 進行比較。實施例22〜28及比較例29係使用受阻酚系抗氧化劑與硫醚系抗氧化劑的混合物之態樣，改變抗氧化劑之添加量進行比較。實施例29〜35及比較例30係使用半受阻酚系抗氧化劑與硫醚系抗氧化劑的混合物之態樣，改變抗氧化劑之添加量進行比較。實施例36、37及比較例17 〜2 1係在僅使用半受阻酚系抗氧化劑之態樣中，比較進一步添加非聚合性分子C1使添加量增加的情形。實施例3 8 〜44、比較例25及比較例3 1係進行在僅使用半受阻酚系 -68- 201008996 抗氧化劑之態樣中，將實施例8〜14的光聚合性單體M1〜 M3變更爲光聚合性氧雜環丁烷化合物M4〜M6且改變添加量之比較。又，比較例1係進行不添加抗氧化劑時的比較。比較例2係進行不添加光聚合起始劑時的比較。比較例3 〜8係使用苯酚系抗氧化劑改變添加量，與本發明實施例之特定抗氧化劑的效果做比較。比較例9及1 0係使用苯酚系抗氧化劑使光聚合起始劑之添加量增加時的比較例。比較例11〜16係僅單獨使用硫醚系抗氧化劑改變添加量，與本發明實施例之特定抗氧化劑的效果做比較。將特開 2006-124636號公報之表18所記載之Νο·8、No.9及Νο·11 之中的顏料除去之比較例22〜24與本案之實施例1〜44全盤性地比較。 ❹ -69- 201008996Abbreviation: Trade name manufacturer, photopolymerization monomer Ml (monofunctional acrylic single molecule) Viscoat#160 Osaka Organic Chemical Industry M2 (difunctional acrylic single molecule) NPGDA 曰本化药M3 (trifunctional acrylic single molecule) Aronix M309 East Asian synthesis M4 (oxetane single molecule) OXT221 East Asian synthesis M5 (oxetane single molecule) OXTIOl East Asian synthesis M6 oxime molecule) Celloxide 2021P Daisy chemical M7 (monofunctional acrylic acid single molecule Viscoat#155 Osaka Organic Chemical Industry M8 (monofunctional methyl propylene monoacid) diglycol methacrylate Tokyo Chemical M9 (difunctional acrylic acid monomolecular) FA-129AS 曰立化成M10 (difunctional acrylic acid) Single molecule) Light-acrylate 3EG-A Co., Ltd. Chemically Mil (monofunctional acrylic single molecule) KBM5103 Shin-Etsu Chemical Industry Non-polymeric C1 Dioctyl sebacate Sumitomo Chemical Photopolymerization initiator PI1 (Photoradical polymerization initiation Agent) TPO-L Japan Siber PI2 (Photocation Polymerization Startup Irgacure 250 Ciba Surfactant W1 (Nonionic Interface Interacting PioninD6315 w Grease) W2 (|R-based surfactant) MEGAFACF780F Dainippon ink chemical industry W3 ketone-based surfactant) KF-352A Shin-Etsu Chemical Industry 矽焼 coupling agent SCI KBM903 Shin-Etsu Chemical Industry Anti-oxidant A01 (hindered phenolic) ADK STAB AO- 60 Adeka Japan A02 (semi-hindered phenol system) Sumilizer GA-80 Sumitomo Chemical A03 (phenol system) Irganox E 201 Ciba A〇4 (hindered amine system) ADK STAB LA-68 Adeka Japan A〇5 (thioether system) ADK STAB AO-503 Adeka Japan A06 (thioether system) Irganox 1035FF Ciba -64- 201008996 [Examples 2 to 66, Comparative Examples 1 to 21, and 25 to 37] In addition to the composition of Tables 2 to 6 below, The composition of Example 1 was carried out in the same manner, and the composition was obtained. [Comparative Examples 22 to 24] Among the No. 8, Νο·9 and No. 11 described in Table 18 of JP-A-2006-124636, The pigment was prepared into the composition of Comparative Examples 22 to 24. The No. 8 contained no antioxidant, and the No. 9 contained 0.15% by mass of Sumilizer MDP-S (manufactured by Sumitomo Chemical Co., Ltd.) as a hindered phenol-based antioxidant. The aforementioned No. ll contains 0.15% by mass of Hostavin N-24 (manufactured by Clariant Co., Ltd.). A hindered amine-based antioxidant. [Evaluation of the curable composition for embossing] The composition of each of the examples and the comparative examples was measured and evaluated for the embossability, photocurability, heat resistance, elastic recovery ratio, and voltage characteristics in accordance with the following evaluation methods. The results are shown in Tables 2 to 6 below. <Imprinting> The pattern transferred to the photoresist is evaluated to what extent the shape of the mold can be reproduced. Specifically, each of the compositions was spin-coated on a glass substrate in a film thickness of 3.0; / m. The spin-coated base film was placed in an imprint apparatus made of a high-pressure mercury lamp (lamp power of 2000 mW/cm 2 ) made by 0RC, with a mold pressure of 0.8 kN and a vacuum of exposure of 10 Torr (about 1.33×10 04 Pa). The condition is that the mold is pressed, and the mold is made of a material having a line/pitch pattern of 10/zm and a groove depth of 4.0/m is a polydimethyl siloxane (made by Toray Dow Corning). SILPOT 184" is cured at 80 ° C for 60 minutes • 65 - 201008996) and then exposed from the surface of the mold at 240 nU/cm 2 . After the exposure, the mold was removed to obtain a photoresist pattern. Then, the obtained photoresist pattern was heated in an oven at 230 ° C for 30 minutes to completely harden. The shape of the pattern after the transfer was observed by a scanning electron microscope and an optical microscope, and the pattern shape was evaluated in accordance with the following criteria. 5: The transfer rate of the mold shape was 95% or more. 4: The transfer rate of the mold shape was 90% or more and less than 95%. 3: The transfer rate of the mold shape is 80% or more and less than 90%. ® 2 : The transfer rate of the mold shape is 70% or more and less than 80%. 1 : The transfer rate of the mold shape was less than 70% » <Evaluation of photocurability> Each composition was spin-coated on a glass substrate so that the film thickness was 3.0 # m, and the mold was not pressed, and nitrogen was applied. The exposure was carried out under the atmosphere of 10 mW and 300 m/cm2. Then, a plastic film was pressed on the surface of the film to evaluate the residual trace (adhesiveness) when the plastic film was peeled off, and the photocurability was measured. A 5: There are no traces at all. 4: Although there are residual marks, they disappear within a few seconds. 3: Although there are residual marks, they disappear within a few minutes. 2: Residual traces, and the passage of time has not disappeared. 1: The film is not hardened. <Heat resistance> Each composition was spin-coated on a glass substrate so as to have a film thickness of 3.0, and was not pressed against a mold, and was subjected to a condition of -66 - .201008996 in a nitrogen atmosphere at a temperature of 300 μm/cm 2 . Exposure. Then, it was hardened by heating in an oven at 23 ° C for 15 minutes. The film thickness before and after baking in the oven was measured, and the reduction rate was determined. The film reduction rate (film reduction) due to heating was evaluated in accordance with the following criteria. The film reduction before and after baking at 5:230° (: -15 〇 111 丨 11 is 5% or less. 4: The film reduction before and after baking at 230 ° C - 150 min is 5% or more and less than 10%. 3 : 230 The film reduction before and after baking at °C -150min is 10% or more and less than 15%. Φ 2: The film reduction before and after baking at 230 °C-150min is 15% or more and less than 20%. 1 : 23 (TC -150 min before and after baking, the film reduction was 20% or more. <Evaluation of elastic recovery rate> Each composition was spin-coated on a glass substrate so as to have a film thickness of 3.0, and the mold was not pressed, and nitrogen gas was applied thereto. The film was exposed to light at a temperature of 230 ° C for 30 minutes in an oven, and the film obtained by curing the film was made into a column shape of 20 x 30 x 4 # m, and the elastic recovery rate was measured by DUH-W201 manufactured by Shimadzu Corporation. 5: The elastic recovery rate is 80% or more. 4: The elastic recovery rate is 75% or more and less than 80%. 3: The elastic recovery rate is 70% or more and less than 75%. 2: The elastic recovery rate is 60% or more and less than 75. %: 1: The elastic recovery rate is less than 60%. <Evaluation of voltage characteristics> -67- 201008996 Each composition is spin-coated on a glass substrate so that the film thickness becomes 3.0. The film was exposed to light at 10 mW to 200 mJ in a nitrogen atmosphere without pressing the mold, and then hardened by heating at 230 ° C for 30 minutes in an oven, and the volume resistance of the film obtained by the hardening was measured according to the concentric ring method, and the voltage characteristics were measured. The obtained voltage characteristics were evaluated in accordance with the following evaluation: 5: The volume resistance was 1 χ 10 Ε 15 Ω · πι or more. 4 : The volume resistance was 5 χ 10 Ε 14 Ω · m or more and less than 1 χ 1 〇Ε 15 Ω. m. 3: The volume resistance was 1 χ 10 Ε 14 Ω·m or more. Less than 5χ10Ε14Ω·m. ❹ 2: The volume resistance is 1×10E13 Ω·m or more, less than 1χ1〇Ε14Ω·m. 1 : The volume resistance is less than 1χ1〇Ε13Ω·ιη. Here, Examples 1 to 7 and Comparative Example 26 are used only. In the case of the hindered phenol-based antioxidant, the amount of the antioxidant added was changed. Examples 8 to 14 and Comparative Example 27 were only used in the form of a semi-hindered phenol-based antioxidant, and the amount of the antioxidant added was changed for comparison. Examples 15 to 21 and Comparative Example 28 were compared using only the semi-hindered phenol-based antioxidant, and the addition amount φ of the antioxidant was changed. Examples 22 to 28 and Comparative Example 29 were treated with hindered phenol-based antioxidants. The aspect of the mixture of the thioether-based antioxidants was changed by changing the amount of the antioxidant added. Examples 29 to 35 and Comparative Example 30 were changed using a mixture of a semi-hindered phenol-based antioxidant and a thioether-based antioxidant. The amount of antioxidant added was compared. In Examples 36 and 37 and Comparative Examples 17 to 2, in the case where only the semi-hindered phenol-based antioxidant was used, the addition amount of the non-polymerizable molecule C1 was further increased to increase the amount of addition. Example 3 8 to 44, Comparative Example 25, and Comparative Example 3 1 The photopolymerizable monomers M1 to M3 of Examples 8 to 14 were subjected to the use of only the semi-hindered phenol system-68-201008996 antioxidant. Change to photopolymerizable oxetane compounds M4 to M6 and change the addition amount. Further, Comparative Example 1 was compared when no antioxidant was added. Comparative Example 2 was a comparison when no photopolymerization initiator was added. In Comparative Examples 3 to 8, the amount of addition was changed using a phenol-based antioxidant, and compared with the effect of the specific antioxidant of the examples of the present invention. Comparative Examples 9 and 10 are comparative examples in which the amount of the photopolymerization initiator added is increased by using a phenol-based antioxidant. In Comparative Examples 11 to 16, the addition amount of the thioether-based antioxidant was used alone, and the effect of the specific antioxidant of the examples of the present invention was compared. Comparative Examples 22 to 24 in which the pigments of Νο·8, No. 9 and Νο·11 described in Table 18 of JP-A-2006-124636 were completely compared with Examples 1 to 44 of the present invention. ❹ -69- 201008996

24*β 33.7 d 5 3 « 臂 u> δ 24.8 33.7 3&6 〇 s 5 5 -r 对 U5 U» u> ο 24.8 33.7 3SJ 户 d S O s in u> U3 u> S 24.8 33.7 37.7 § *· e* 3 B Vi in U) 寸 U) 24.8 33.7 39.6 S »» d 5 S ψ» U) M ΙΟ S 24.8 SM 5 O u> m ΙΟ S 24.8 34w4 39.B S 5 5 2 8 u> w «0 PQ to ϊ 7Α& 33.7 S S 5 5 s S IA m •& in W 24.8 3X7 S 5 5 s s •r· IA 令 u> 10 u» Μ 24月 33.7 35.0 S 〇- 3 〇 I u> ie u> IO IA 24.β 33.7 37.7 S 5 5 5 100 $ IA m ΙΟ U> S 24^ 33.7 30.6 S w· S e] 100 to lt> 对 IO α 24J 丨 34<2 3M S 5 8 T-· U) U9 IP CO 24^ 34.4 39.S r«j 5 S s IA uy W U3 卜 24.8 33.7 S S 5 5 s o — irj rt V to « 24Λ 33.7 36J 3 5 s s — id eo ΙΟ (Ο U> ΙΟ 248 33.7 35Λ § 5 5 3 106 u> 吋 ΙΟ u> to 寸 248 | 33.7 S 5 8 IA U) Xf tfl eo 24名 33.7 30.6 Ui ο' 5 t-； 2 g U> 对臂 u> es} 24.8 34^ 39-8 g 5 5 3 too U) "tt IO Ζ4νβ | 34.4 3M s 5 3 a s t· u> fO «0 ko 資施例髮 a s 2 室 δ E CM Ξ： 5 u A01 A02 A03 A〇4 AOS m <n 壓印性光硬化性耐熱性彈性回復率 s担特性光聚合性單分子 1非聚合性分子1 I 連 a 4 e » l ϊ a 长 J 界面活性劑抗氧化劑 ο 20100899624*β 33.7 d 5 3 «arm u> δ 24.8 33.7 3&6 〇s 5 5 -r for U5 U» u> ο 24.8 33.7 3SJ household d SO s in u> U3 u> S 24.8 33.7 37.7 § *· e* 3 B Vi in U) Inch U) 24.8 33.7 39.6 S »» d 5 S ψ» U) M ΙΟ S 24.8 SM 5 O u> m ΙΟ S 24.8 34w4 39.BS 5 5 2 8 u> w «0 PQ to ϊ 7Α& 33.7 SS 5 5 s S IA m •& in W 24.8 3X7 S 5 5 ss •r· IA 令 u> 10 u» Μ 24 33.7 35.0 S 〇- 3 〇I u> ie u> IO IA 24.β 33.7 37.7 S 5 5 5 100 $ IA m ΙΟ U> S 24^ 33.7 30.6 S w· S e] 100 to lt> IO α 24J 丨34<2 3M S 5 8 T-· U) U9 IP CO 24^ 34.4 39.S r«j 5 S s IA uy W U3 Bu 24.8 33.7 SS 5 5 so — irj rt V to « 24Λ 33.7 36J 3 5 ss — id eo ΙΟ (Ο U> 248 248 33.7 35Λ § 5 5 3 106 u> 吋ΙΟ u> to inch 248 | 33.7 S 5 8 IA U ) Xf tfl eo 24 33.7 30.6 Ui ο' 5 t-; 2 g U> Pair arm u> es} 24.8 34^ 39-8 g 5 5 3 too U) "tt IO Ζ4νβ | 34.4 3M s 5 3 ast · u> fO «0 ko Example as 2 room δ E CM Ξ: 5 u A01 A02 A03 A〇4 AOS m <n embossing photocuring heat-resistant elastic recovery rate s-bearing characteristic photopolymerization single Molecular 1 non-polymerizable molecule 1 I 连 a 4 e » l ϊ a long J surfactant active antioxidant ο 201008996

201008996201008996

I II I

S 5 § d 〇 «· « csi N u> 0» S 5 in d d 〇 *«» IO CM υ» 00 f* S I tn S 5 5 ;· s IO W M u> 1 i S d O* o IO m CM eU ΙΑ <0 P w to 绔 § 5 CO tri s Y· 1C» CM CM U> K> 2 i5 «·> s Ρ» S 5 5 3 s m W CM ir> CO r* n in o' •Μ» Ξ 5 8 Β» CO CM CM U9 2 s 笤 s ϋ 5 M g u> « N (A «4 CO 豸 GO 异 s d 5 n S n T· f— in 1 S «» IO 5 5 n o s Κ» •I» U9 〇 00 CM δ ¢5 g 5 5 8 IO eg M to 9) S C9 P »· *· ώ — to 8 — u> « 97 tn ce eo 15 C9 IO 5 5 «〇 ΙΓ» S u> 严 IO IO to 卜 «0 55 IO «*ϊ S d 5 〇» V 8 ψ— u> «> IO V» <D I 5 CO 卜· R § 〇- 5 ra B r· u> Csi » u> IP § s Γ0 S 5 5 CM· 〇 u> 寸 tf> i 3 «〇英 u» o' d 5 tn d g 产 in est «0 o to n I s' «Ϊ s o' o' 3 s u> «Μ IO n «β Ο) « 5 g 产 u> 璲擊鹿阵 mm 璀鹿壤痣 t— 〇0 t 5 s eo s IO •r· o IA IO - - v> 比较例 »4 s w ΙΑ s δ s g i g Csl 5 s S < w 合 tfjft _1 壓印性光硬化性耐热性彈性回後率電腔特性光聚合性單分子 I非聚合性分子1 光聚合起始劑界面活性爾抗氣化剷 4201008996 [續表4] ΟS 5 § d 〇 «· « csi N u> 0» S 5 in dd 〇*«» IO CM υ» 00 f* SI tn S 5 5 ;· s IO WM u> 1 i S d O* o IO m CM eU ΙΑ <0 P w to 绔§ 5 CO tri s Y· 1C» CM CM U>K> 2 i5 «·> s Ρ» S 5 5 3 sm W CM ir> CO r* n in o' •Μ» Ξ 5 8 Β» CO CM CM U9 2 s 笤s ϋ 5 M g u> « N (A «4 CO 豸GO sd 5 n S n T· f— in 1 S «» IO 5 5 nos Κ» •I» U9 〇00 CM δ ¢5 g 5 5 8 IO eg M to 9) S C9 P »· *· ώ — to 8 — u> « 97 tn ce eo 15 C9 IO 5 5 «〇ΙΓ» S u> strict IO IO to 卜 «0 55 IO «*ϊ S d 5 〇» V 8 ψ- u>«> IO V» <DI 5 CO 卜·R § 〇- 5 ra B r· u> Csi » u> IP § s Γ0 S 5 5 CM· 〇u> inch tf> i 3 «〇英u» o' d 5 tn dg 产 in est «0 o to n I s' «Ϊ so' o' 3 s u> Μ IO n «β Ο) « 5 g production u> sniper deer mm mm 璀痣痣 — t t t t t t t t t t t t t t t t t t t t t t t t t t t t t t t t t t t t t t t t » » » » » » » » » » » » » Sgig Csl 5 s S < w combined with tfjft _1 embossing photocuring heat-resistant elastic back-return rate electric cavity characteristics photopolymerization single molecule I non-polymerizable molecule 1 photopolymerization initiator interface active anti-gas shovel 4201008996 [Continued from Table 4] Ο

诚例 21 22 23 24 25 26 27 28 29 30 31 光聚合性單分子 Μ1 特開2006-124636的表18 Νο·8(除去顔料）特開2006-124636的表18 Νο·9(除去顔料）特開2006-124636的表18 No.ll(除去顏料） 24.8 24.8 2.ΛΛ 24』 24.8 M2 33.7 33.7 33.7 33.7 33.7 M3 79.8 33.7 33.7 33.7 33.7 33.7 Μ4 52.4 45.7 Μ5 7.5 7.5 Μβ 24.3 24,1 非聚合性分子 C1 16.4 15 14.9 光聚合起始劑 ΡΙ1 0.5 0.5 0.5 0.5 0.5 0.5 ΡΙ2 0.5 0.5 界面活性劑 W1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 W2 0.1 0.1 0.1 0.1 0.1 0,1 0.1 0.1 抗氧化劑 Α01 7.1 4.7 Α02 3.1 0.15 7.1 4.7 7.1 Α03 Α04 7.1 Α05 2.4 2.4 合1« 100 100 100 100 100 100 too 100 壓印性 2 5 5 5 5 5 5 5 5 5 S 光硬化性 5 5 5 5 5 2 2 2 2 a 2 耐熱性 2 1 2 2 2 4 4 4 4 4 4 彈性回復率 2 1 2 2 2 4 4 . 4 4 4 3 電壓特性 5 3 3 3 3 5 5 5 5 5 3 上述表4中、比較例2之耐熱性、彈性回復率及電壓特性係無法測定。 -73- 201008996Example 21 22 23 24 25 26 27 28 29 30 31 Photopolymerizable single molecule Μ1 Table 18 of 2006-124636 Νο·8 (removal of pigment) Table 18 of 20062006-124636 Νο·9 (removal of pigment) Table 18 No. 11 of 2006-124636 (removal of pigment) 24.8 24.8 2.ΛΛ 24』 24.8 M2 33.7 33.7 33.7 33.7 33.7 M3 79.8 33.7 33.7 33.7 33.7 33.7 Μ4 52.4 45.7 Μ5 7.5 7.5 Μβ 24.3 24,1 Non-polymerizable molecule C1 16.4 15 14.9 Photopolymerization initiator ΡΙ1 0.5 0.5 0.5 0.5 0.5 0.5 ΡΙ2 0.5 0.5 Surfactant W1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 W2 0.1 0.1 0.1 0.1 0.1 0,1 0.1 0.1 Antioxidant Α01 7.1 4.7 Α02 3.1 0.15 7.1 4.7 7.1 Α03 Α04 7.1 Α05 2.4 2.4 in 1« 100 100 100 100 100 100 too 100 Imprint 2 5 5 5 5 5 5 5 5 5 S Photocurability 5 5 5 5 5 2 2 2 2 a 2 Heat resistance 2 1 2 2 2 4 4 4 4 4 4 Elastic recovery ratio 2 1 2 2 2 4 4 . 4 4 4 3 Voltage characteristics 5 3 3 3 3 5 5 5 5 5 3 Heat resistance of the above Table 4 and Comparative Example 2 , elastic recovery rate and voltage characteristics are not determined-73- 201008996

ο CD 53.2 10.0 11.7 20.1 S· ρ q U> ΙΟ ο 〇 to to ΙΑ 寸 ιο U> CO 43.2 10.0 21.7 20.1 3 Ρ 。· u> ΙΟ o to Ui u> ΙΟ S 33.2 10.0 31.7 20.1 S ο ρ 户 to ιτ> ο o u> U> ΙΟ ΙΟ CO CD 53.2 10.0 12.3 20.1 S ο ρ CSJ cj s IO U) eo ΙΟ ιη CNT <〇 43.2 10.0 22.3 i 3 ο ρ OJ o CSJ o IT) ID «0 ΙΟ ΙΑ z 33.2 10.0 32.3 20.1 3 Ο. τ~ ρ C4 〇· Μ c> o *— ir> u> η ιο ΙΟ S 53.2 o o. 12.3 20.1 S Ο »-· ρ csl OJ o IO IO co u> ιη <n l〇 43.2 10.0 22.3 20.1 S Ο Ο τ·· CVI CM d o IO If) eo If) ιο CO m 33.2 10.0 32.3 20.1 S ρ ρ Cn| CM 〇· s U3 u> ο ΙΟ ιη !〇 53.2 12.3 20.t S ρ ρ Csl OJ o in u> 兮 u> ιη (O u> 43.2 to.o 22.3 20.1 3 ο ρ τ· eg o 〇 o to u> 寸 ΙΟ ίο to u> 33.2 10,0 32.3 20.1 S ρ Ο τ» «sj CM 〇· o IO u> 寸 to ΙΟ IO 53.2 i 10.0 I 12.3 20,1 S ρ Ο CSI o IA u» 寸 ΙΟ ΙΟ CO IO 43.2 10.0 22*3 20.1 s ρ ο oi o ej o in to 寸 1C U3 CM If) 33.2 10.0 j 32.3 20.1 s ο ρ CSI CSl O o IA ID ΙΟ ΙΟ IO 43.2 20,0 12.3 20.1 s ρ ρ 严 Ol CM d o 1» in 寸 U) ΙΟ δ 33.2 40.0 eo 20.1 s ρ ο CSI eg 〇 o in to ιτ> ν> 33.2 30.0 12.3 20.1 s 〇· ρ 严 €S| CSI o to ID 寸 U9 ΙΟ § 33.2 20.0 22.3 i s 〇. ο C4 o IO to 寸 u> ιη 53.2 10.0 12.3 i s ρ ρ CM o M 〇· 100 to » ιο tr> o 43.2 10.0 22.3 20.1 s ρ q CM 〇 csl o s IO ια 寸 ιη ιο l〇 33.2 10.0 32.3 20.1 s Ρ ο 〇l d CSJ o IO to ιη ίο 實施例 s M10 2 室 Mil 沄 § SCI i A02 Aoe 合肝量 .壓印性光硬化性耐熱性彈性回復率電壓特性光聚合性單分子光聚合起始劑界面活性劑矽烷偶合劑筘氧化劑 201008996 [表6] 比較例 32 33 34 35 36 37 光聚合性單分子 M3 33.2 43*2 53.2 33^ 43.2 53*2 M9 10.0 10.0 10.0 10.0 10.0 10.0 M10 M1 M7 32.5 22.5 12.5 3Z7 22.7 12.7 M8 M11 20.1 20.1 20.1 20.1 20.1 20.1 光聚合起始劑 PI1 2.0 2.0 2.0 2.0 2.0 2.0 界面活性劑 W3 1.0 1.0 1.0 1.0 1.0 1.0 矽烷偶合劑 set 1.0 1.0 1.0 1.0 1.0 1.0 抗氧化劑 A02 0.1 0.1 αι A06 0.1 0.1 0.1 合計置 100 100 100 100 100 100 壓印性 5 5 5 5 5 5 光硬化性 5 5 5 5 5 5 耐熱性 2 2 2 1 1 1 弹性回復率 5 5 5 5 5 5 電壓特性 5 5 5 5 5 5 由上述表2〜表4可知，相對於把特開2006-12463 6號公報的表18所記載之No.8、No.9及No.11之中的顏料除去之比較例22〜24而言，實施例之各組成物均爲壓印性、光硬化性、耐熱性、彈性回復率及電壓特性良好。又，使用〇氧雜環丁烷化合物的實施例38〜44與其他實施例相比，電壓特性的改善效果低。另一方面，由於比較例1不含抗氧化劑，故耐熱性及彈性回復率爲低評價。比較例2因不含光聚合起始劑，故評價非常低。由比較例3〜10可知僅使用苯酚系抗氧化劑的情形，光硬化性之評價明顯降低，即使是犧牲耐熱性及彈性回復率而增加光聚合劑的添加量之比較例9及10亦無法得到本發明所求性質之硬化膜。由比較例丨丨〜丨6可知， -75- 201008996 僅使用硫醚系抗氧化劑的情況’耐熱性與彈性回爲低評價。由實施例36、37及比較例17〜21的解，即使是例如僅使用半受阻酣系抗氧化劑之態聚合性單體的添加量在本發明之範圍内（80質量（量％)時，可同時改善光硬化性、耐熱性及彈性回係顯著的效果。又’在微調整單官能、二官能及分子之摻合量的比較例19〜21中，耐熱性或彈性無法提升，因此可知光聚合性單體的添加量爲：參素。由實施例3 8〜44、比較例25及比較例3 1之比若抗氧化劑之添加量在本案發明之範圍内（0.3 %)，可顯著改善耐熱性及彈性回復率。又，由表5及表6亦可明白，抗氧化劑含量明之實施例與抗氧化劑含量少的比較例相比，耐性回復率係顯著地改善。【圖式簡單說明】無。 ❹ 【主要元件符號說明】無。復率明顯比較可瞭樣，當光给〜9 9質復率，其三官能單回復率亦重要之要較可知，〜7質量高的本發熱性及彈 -76-ο CD 53.2 10.0 11.7 20.1 S· ρ q U> ο ο 〇 to to 寸 inch ιο U> CO 43.2 10.0 21.7 20.1 3 Ρ . · u> ΙΟ o to Ui u> ΙΟ S 33.2 10.0 31.7 20.1 S ο ρ 到 to ιτ> ο o u> U> ΙΟ ΙΟ CO CD 53.2 10.0 12.3 20.1 S ο ρ CSJ cj s IO U) eo ΙΟ ιη CNT &lt ;〇43.2 10.0 22.3 i 3 ο ρ OJ o CSJ o IT) ID «0 ΙΟ ΙΑ z 33.2 10.0 32.3 20.1 3 Ο. τ~ ρ C4 〇· Μ c> o *- ir> u> η ιο ΙΟ S 53.2 o o. 12.3 20.1 S Ο »-· ρ csl OJ o IO IO co u> ιη <nl〇43.2 10.0 22.3 20.1 S Ο Ο τ·· CVI CM do IO If) eo If) ιο CO m 33.2 10.0 32.3 20.1 S ρ ρ Cn| CM 〇· s U3 u> ο ΙΟ ιη !〇53.2 12.3 20.t S ρ ρ Csl OJ o in u>兮u> ιη (O u> 43.2 to.o 22.3 20.1 3 ο ρ τ· eg o too to u> inch ΙΟ ίο to u> 33.2 10,0 32.3 20.1 S ρ Ο τ» «sj CM 〇· o IO u> inch to ΙΟ IO 53.2 i 10.0 I 12.3 20,1 S ρ Ο CSI o IA u» inchΙΟ ΙΟ CO IO 43.2 10.0 22*3 20.1 s ρ ο oi o ej o in to inch 1C U3 CM If) 33.2 10.0 j 32.3 20.1 s ο ρ CSI CSl O o IA ID ΙΟ ΙΟ IO 43 .2 20,0 12.3 20.1 s ρ ρ 严Ol CM do 1» in inch U) ΙΟ δ 33.2 40.0 eo 20.1 s ρ ο CSI eg 〇o in to ιτ>ν> 33.2 30.0 12.3 20.1 s 〇· ρ 严€S CSI o to ID inch U9 ΙΟ § 33.2 20.0 22.3 is 〇. ο C4 o IO to inch u> ιη 53.2 10.0 12.3 is ρ ρ CM o M 〇· 100 to » ιο tr> o 43.2 10.0 22.3 20.1 s ρ q CM 〇csl os IO ια inch ιη ιο l〇33.2 10.0 32.3 20.1 s Ρ ο 〇ld CSJ o IO to ιη ίο Example s M10 2 Room Mil 沄§ SCI i A02 Aoe Hepatic volume. Imprinted photohardening heat resistance Elastic recovery rate voltage characteristics Photopolymerizable single molecule photopolymerization initiator Surfactant decane coupling agent oxime oxidant 201008996 [Table 6] Comparative Example 32 33 34 35 36 37 Photopolymerizable single molecule M3 33.2 43*2 53.2 33^ 43.2 53*2 M9 10.0 10.0 10.0 10.0 10.0 10.0 M10 M1 M7 32.5 22.5 12.5 3Z7 22.7 12.7 M8 M11 20.1 20.1 20.1 20.1 20.1 20.1 Photopolymerization initiator PI1 2.0 2.0 2.0 2.0 2.0 2.0 Surfactant W3 1.0 1.0 1.0 1.0 1.0 1. 0 decane coupling agent set 1.0 1.0 1.0 1.0 1.0 1.0 Antioxidant A02 0.1 0.1 αι A06 0.1 0.1 0.1 Total 100 100 100 100 100 100 Imprint 5 5 5 5 5 5 Photocurability 5 5 5 5 5 5 Heat resistance 2 2 2 1 1 1 Elastic recovery rate 5 5 5 5 5 5 Voltage characteristics 5 5 5 5 5 5 As shown in Table 2 to Table 4 above, the No. is shown in Table 18 of JP-A-2006-12463. 8. Comparative Examples 22 to 24 in which the pigments were removed in No. 9 and No. 11, all of the compositions of the examples were excellent in embossability, photocurability, heat resistance, elastic recovery, and voltage characteristics. Further, in Examples 38 to 44 using the oxirane compound, the effect of improving the voltage characteristics was lower than that of the other examples. On the other hand, since Comparative Example 1 contained no antioxidant, the heat resistance and the elastic recovery ratio were low. Comparative Example 2 was very low in evaluation because it did not contain a photopolymerization initiator. In Comparative Examples 3 to 10, it was found that when only a phenol-based antioxidant was used, the evaluation of photocurability was remarkably lowered, and Comparative Examples 9 and 10 in which the amount of the photopolymerization agent was increased at the expense of heat resistance and elastic recovery were not obtained. A cured film of the nature sought for by the present invention. From the comparative examples 丨 to 丨6, it is understood that -75-201008996 is only a case where a thioether-based antioxidant is used, and heat resistance and elasticity are low. From the solutions of Examples 36 and 37 and Comparative Examples 17 to 21, even if the amount of the polymerizable monomer in the state of using only the semi-hindered lanthanide antioxidant is within the range of the present invention (80 mass%) It is possible to simultaneously improve the photocurability, heat resistance, and elastic remarks. In the comparative examples 19 to 21 in which the amount of monofunctional, difunctional, and molecular blending is finely adjusted, heat resistance or elasticity cannot be improved, so that it is known The amount of the photopolymerizable monomer to be added is: Mn. The ratio of the antioxidants in Examples 38 to 44, Comparative Example 25, and Comparative Example 3 is within the range of the present invention (0.3%), which is remarkable. The heat resistance and the elastic recovery rate were improved. Further, as can be seen from Tables 5 and 6, the examples in which the antioxidant content is clear have a marked improvement in the resistance recovery rate as compared with the comparative example in which the antioxidant content is small. 】 No. ❹ 【Main component symbol description】 None. The complex rate is obviously comparable. When the light gives ~9 9 mass recovery rate, its trifunctional single recovery rate is also important. It is better to know that the quality is higher than ~7. Sex and bullet-76-

Claims

201008996 VII. Patent application scope: 1. A hardenable composition for imprinting, which is characterized in that it contains eight) photopolymerizable monomer, B) photopolymerization initiator, and C) antioxidant for photoimprinting. In the composition, the content of the A) photopolymerizable monomer is ～99% by mass, and the content of the C) antioxidant is 〇3 to 7% by mass, and the C) antioxidant is only a hindered phenol-based antioxidant. It is only a semi-hindered phenolic antioxidant, a mixture of a hindered phenolic antioxidant and a semi-hindered phenolic antioxidant, or only a hindered amine antioxidant. 2. The curable composition for imprint of claim 1, wherein the antioxidant is composed only of a semi-hindered phenol antioxidant. 3. A curable composition for imprinting comprising: A) a photopolymerizable monomer, B) a photopolymerization initiator, and C) an optical imprint composition for an antioxidant, wherein the aforementioned A The content of the photopolymerizable monomer is 80 to 99% by mass, and the content of the above-mentioned C) antioxidant is 0.3 to 7% by mass, and the above-mentioned C) antioxidant is a mixture of a hindered phenol-based antioxidant and a thioether-based antioxidant, or A mixture of a semi-hindered phenolic antioxidant and a thioether antioxidant. 4. The hardenable composition for imprint of claim 3, wherein the antioxidant is a mixture of a semi-hindered phenol system and a thioether system. The composition for imprint according to any one of claims 1 to 4, wherein the content of the antioxidant is from 0.5 to 5% by mass. 6. The imprinting group -77-201008996 according to any one of claims 1 to 4, which has an elastic recovery rate of 70% or more. 7. A cured product obtained by curing the curable composition for imprint according to any one of claims 1 to 6. A member for a liquid crystal display device, characterized by comprising a cured product as in item 7 of the patent application. A method of producing a cured product, comprising the step of applying a curable composition for imprint according to any one of claims 1 to 6 to a substrate to form a pattern forming layer. And a step of pressing the mold against the surface of the pattern forming layer and a step of irradiating the pattern forming layer with light. 10. The method of producing a cured product according to claim 9 which further comprises the step of heating the pattern forming layer of the irradiated light. 〇 .201008996 IV. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: and. /\\\ Ref. 5. If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: 〇 /»w ❹