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TWI438235B - Curable composition for imprint, curing object using the same, manufacturing method thereof and member for liquid crystal display device - Google Patents

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

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TWI438235B
TWI438235B TW098122172A TW98122172A TWI438235B TW I438235 B TWI438235 B TW I438235B TW 098122172 A TW098122172 A TW 098122172A TW 98122172 A TW98122172 A TW 98122172A TW I438235 B TWI438235 B TW I438235B
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present
composition
antioxidant
imprint
acrylate
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TW098122172A
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TW201008996A (en
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Hiroyuki Yonezawa
Akinori Fujita
Takashi Takayanagi
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Fujifilm Corp
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    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/0045Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/0047Photosensitive materials characterised by additives for obtaining a metallic or ceramic pattern, e.g. by firing
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/027Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Liquid Crystal (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Shaping Of Tube Ends By Bending Or Straightening (AREA)
  • Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polymerisation Methods In General (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Description

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Curable composition for imprint, cured product using the same, method for producing the same, and member for liquid crystal display device

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。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.

壓印法方面,提議有使用熱可塑性樹脂作為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。In the embossing 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 (for example, refer to Non-Patent Document 2) 2 technologies. In the case of the hot stamping 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, application in various aspects is expected. For example, Patent Documents 1 and 2 below disclose a hot stamping method in which a nano pattern is inexpensively formed using a thermoplastic resin.

另一方面,透過透明模具或透明基材照射光線,使光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,尚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。On the other hand, a photoimprint method in which light is cured by a transparent mold or a transparent substrate to photoharden the photocurable composition does not require heating of the material of the transfer pattern when the mold is pressed, and can be imprinted at room temperature. Recently, there have been reports of new developments such as the nano-casting method and the reverse imprinting method of a three-dimensional laminated structure combining the advantages of both.

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為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(圖案)本身具有功能,可應用作為各種奈米技術之要素零件、或作為構造構件者,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,作為另外之其他技術,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μ-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為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。In this imprint method, the following application techniques on the nanometer scale have been proposed. The first technique is applied to the fabrication of a high-density semiconductor integrated circuit or the fabrication of a transistor for a liquid crystal display by high-precision position blending and high integration, instead of the prior lithography. The shape (pattern) formed by the second technique has its own function and can be applied as an elemental part of various nano technologies or as a structural member, and examples thereof include various micro-nano optical elements or high-density recording media, and opticals. Thin film, structural members in flat displays, and the like. Further, as another technique, it is applied to a μ-TAS (Micro-Total Analysis System) or a bio-wafer by integrally molding a micro-structure and a nanostructure at the same time, or by simply blending between layers to form a laminated structure. Production. The third technique utilizes high-precision position blending and high-combination, and is suitable for fabrication of a high-density semiconductor integrated circuit or a transistor for a liquid crystal display, instead of the prior lithography. Including the foregoing techniques, practical combinations of imprint methods for such applications are becoming increasingly active.

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,作為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,作為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為剛性打印頭(stamp)使用,藉由圖案轉印而形成25nm以下之微細構造的奈米壓印技術。隨著此趨勢,為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、圖案轉印精度等為始的性質的檢討。An application example of the fabrication of the high-density semiconductor integrated circuit in the first technique described above will be described. In recent years, the semiconductor integrated circuit has progressed in miniaturization and integration, 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 low cost, it has been proposed to use an imprint lithography technique, in particular, a nanoimprint lithography technique (photon nanoimprint method). For example, Patent Document 1 listed below discloses a nanoimprint technique in which a tantalum wafer is used as a rigid printhead to form a fine structure 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.

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為廉價之微影術,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,作為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蝕刻光阻相異,由於最終殘存於平面顯示器面板等之顯示器内,故稱為「永久光阻」或「永久膜」。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 size and high-definition of LCD substrates and PDP substrates, 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 for a cell gap of a liquid crystal display. The photoresist for such a structural member is different from the above-described etching resist, and is eventually referred to as a "permanent photoresist" or a "permanent film" because it eventually remains in a display such as a flat panel display panel.

作為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、或為了減低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)之形成中,由於要求塗布膜之均勻性、超過200℃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10μm~20μm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。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 various properties such as uniformity of the coating film, high light transmittance after heat treatment exceeding 200 ° C, and scratch resistance are required, it is required to perform imprinting for satisfying such characteristics. Development of a hardenable composition. 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 having a size of about 10 μm to 20 μm, and was further formed by post-baking heat hardening. In addition to hardness and pattern precision, the spacer used in the liquid crystal display device described above requires a high elastic recovery ratio, and development of a hardenable composition for imprint which satisfies these characteristics has been sought.

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。Further, in the imprint method, it is necessary to improve the fluidity of the curable composition for imprinting in the cavity in which the concave portion 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).

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。As noted above, the required characteristics of the materials used in embossing lithography vary widely depending on the application. However, there has been a description of the expectation of viscosity, for example, regarding the composition for imprint, but there have been no reports of design guidelines for materials suitable for each application.

因此,作為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為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)硬化性之賦予係為重要。Therefore, various problems such as pattern accuracy, heat resistance, and hardness have been cited as main technical problems of the permanent film. 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.

作為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,能夠承受作為永久膜使用之(4)高彈性回復率之賦予係為重要。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(較佳為5mPa.s以下)、與(6)為了作為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。As a problem specific to the curable composition for photoimprint, in addition to the properties (1) to (3) above, one of the mechanical properties can withstand the use of a high elastic recovery rate (4) which is used as a permanent film. . 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. The low viscosity (preferably 5 mPa.s or less) under the use of a solvent, and (6) must be improved in consideration of voltage characteristics for use as a structural member of an electric circuit, and the technical difficulty in designing the composition is further improved.

近年來,為了抑制退色,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,實際上現狀係尚未檢討將抗氧化劑用於壓印用硬化性組成物。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 actuality, the use of antioxidants for the hardening composition for imprinting has not been reviewed.

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,可舉例為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,組成物的黏度變為380mPa.s(25℃),非為可應用於專利文獻5所記載之謀求低黏度化組成物的壓印用硬化性組成物。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). An example in which less than 0.2% by mass of an antioxidant is used in the photocurable composition is described in the same document, but it is not suggested to satisfy imprintability, heat resistance, photocurability, high elastic recovery, low viscosity, voltage characteristics, and the like. Description of the characteristics required for the curable composition for imprint. In particular, in the case of using an antioxidant of less than 0.2% by mass, the viscosity of the composition is 380 mPa·s (25 ° C), and it is not applicable to the imprint of the low-viscosity composition described in Patent Document 5. Use a hardening composition.

又,以改善黏度為目的,已報告在活性光線硬化型噴墨用組成物中添加0.15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。Further, an example of adding 0.15 mass% of an antioxidant to the active light-curing inkjet composition has been reported for the purpose of improving the viscosity (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.

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為了防止空氣中的氧導致之氧化、或為了低黏度化,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獻的目的亦為抑制在加熱時氧化導致之樹脂變色。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, the purpose of the known literature in which an antioxidant is added to a thermosetting resin is to suppress discoloration of the resin caused by oxidation upon heating.

[先前技術文獻][Previous Technical Literature]

[專利文獻][Patent Literature]

[專利文獻1]美國專利第5,772,905號公報[Patent Document 1] U.S. Patent No. 5,772,905

[專利文獻2]美國專利第5,956,216號公報[Patent Document 2] U.S. Patent No. 5,956,216

[專利文獻3]特開2008-105414號公報[Patent Document 3] JP-A-2008-105414

[專利文獻4]特開2008-92099號公報[Patent Document 4] JP-A-2008-92099

[專利文獻5]特開2002-256228號公報[Patent Document 5] JP-A-2002-256228

[專利文獻6]特開2006-124636號公報[Patent Document 6] JP-A-2006-124636

[非專利文獻][Non-patent literature]

[非專利文獻1]S.Chou等人:Appl. Phys. Lett. Vol.67,3114(1995)[Non-Patent Document 1] S. Chou et al.: Appl. Phys. Lett. Vol. 67, 3114 (1995)

[非專利文獻2]M.Colbun等人:Proc.SPIE,Vol. 3676,379(1999)[Non-Patent Document 2] M. Colbun et al.: Proc. SPIE, Vol. 3676, 379 (1999)

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,為不良者。In view of the above-described problems, the composition described in Patent Document 6 is used as it is for imprinting, and it is understood that the heat resistance, the elastic recovery rate, and the voltage characteristics are poor.

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。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, an object of the present invention is to provide a curable composition for imprint which is particularly suitable for a permanent film such as a transparent protective film or a spacer of a flat panel display or the like.

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。Based on the above-mentioned problems, the inventors of the present invention conducted a drill collar investigation and found that a composition satisfying the above characteristics (1) to (6) can be designed by including a specific amount of an antioxidant in the curable composition for imprint. Among them, (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]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為80~99質量%,前述C)抗氧化劑之含量為0.3~7質量%,前述C)抗氧化劑係僅為受阻酚系抗氧化劑、僅為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、或僅為受阻胺系抗氧化劑中的任一者。[1] A curable composition for imprinting comprising: A) a photopolymerizable monomer, B) a photopolymerization initiator, and C) an optical imprint composition of an antioxidant, wherein the aforementioned A The content of the photopolymerizable monomer is from 80 to 99% by mass, the content of the above C) antioxidant is from 0.3 to 7% by mass, and the above-mentioned C) antioxidant is only a hindered phenol-based antioxidant, and only a semi-hindered phenolic resistance Any of an oxidizing agent, a mixture of a hindered phenol-based antioxidant and a semi-hindered phenol-based antioxidant, or only a hindered amine-based antioxidant.

[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。[2] The curable composition for imprint according to [1], wherein the antioxidant is composed only of a semi-hindered phenol-based antioxidant.

[3]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為80~99質量%,前述C)抗氧化劑之含量為0.3~7質量%,前述C)抗氧化劑為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。[3] A curable composition for embossing, comprising: A) a photopolymerizable monomer, B) a photopolymerization initiator, and C) an antioxidant photo-imprint composition, wherein the aforementioned A The content of the photopolymerizable monomer is 80 to 99% by mass, and the content of the C) antioxidant is 0.3 to 7% by mass, and the C) antioxidant is a mixture of a hindered phenol antioxidant and a thioether antioxidant, or A mixture of a semi-hindered phenolic antioxidant and a thioether antioxidant.

[4]如[3]所記載之壓印用硬化性組成物,其中前述抗氧化劑為半受阻酚系與硫醚系之混合物。[4] The curable composition for imprint according to [3], wherein the antioxidant is a mixture of a semi-hindered phenol system and a thioether system.

[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為0.5~5質量%。[5] The composition for imprint according to any one of [1] to [4] wherein the content of the antioxidant is from 0.5 to 5% by mass.

[6]如[1]~[5]中任一項所記載之壓印用組成物,其彈性回復率為70%以上。[6] The composition for imprint according to any one of [1] to [5], wherein the elastic recovery ratio is 70% or more.

[7]一種硬化物,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。[7] A cured product obtained by curing the curable composition for imprint according to any one of [1] to [6].

[8]一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。[8] A member for a liquid crystal display device, characterized by comprising the cured product according to [7].

[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。[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]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。[10] The method for producing a cured product according to [9], which further comprises the step of heating the pattern forming layer of the irradiated light.

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。According to the present invention, it is possible to provide a curable composition for imprint, 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 member for a liquid crystal display device.

[實施發明之形態][Formation of the Invention]

以下針對本發明之内容加以詳細說明。本案說明書中使用「~」,係指包括其前後所記載數值為下限值及上限值。The contents of the present invention are described in detail below. The use of "~" in the present specification means that the numerical values listed before and after are referred to as the lower limit and the upper limit.

又,在本說明書中,「(甲基)丙烯酸酯」係表示「丙烯酸酯」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,指重量平均分子量為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。In the present specification, "(meth)acrylate" means "acrylic acid ester" and "methacrylic acid ester", and "(meth)acrylic acid" means "acrylic acid" and "methacrylic acid", "( "Methyl) 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 means 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.

又,在本發明所說的壓印係可包括約數十nm~數十μm之尺寸的圖案轉印,亦包括奈米壓印,非為限定奈米等級者。Further, the imprinting system according to the present invention may comprise a pattern transfer of a size of about several tens of nanometers to several tens of micrometers, and also includes nanoimprinting, not limited to a nanoscale.

又,在本說明書中,「受阻酚系抗氧化劑」與「半受阻酚系」係不重複之概念,明確地區別。Further, in the present specification, the concept of "hindered phenolic antioxidant" and "semi-hindered phenolic" are not clearly distinguished.

[壓印用硬化性組成物][Sclerosing composition for imprint]

本發明之壓印用硬化性組成物(以下,簡稱為「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為80~99質量%,前述抗氧化劑之含量為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為受阻酚系抗氧化劑、僅為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、或僅為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。The curable composition for imprint of the present invention (hereinafter, simply referred to as "the composition of the present invention") is a photoimprint composition containing a photopolymerizable monomer, a photopolymerization initiator, and an antioxidant, and the photopolymerization is carried out. The content of the monomer is 80 to 99% by mass, and the content of the antioxidant is 0.3 to 7% by 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 A mixture of phenolic antioxidants or only one of 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. a mixture of antioxidants.

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,尚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為高水準。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。The composition of the present invention contains a specific range of amounts of the antioxidant in addition to a photopolymerizable monomer and a photopolymerization initiator in a specific range, thereby achieving high level of imprintability and photocurability at the same time. Heat resistance and voltage characteristics, in addition, can also make the elastic recovery rate a high level. Increasing the elastic recovery rate is a particularly surprising effect since the effect of increasing the elastic recovery rate cannot be expected from the function of the previous antioxidant.

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),可具有如下特徵。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)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,因為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。(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)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)。(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)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。(3) Because of uniform coating, it is suitable for coating of large substrates, fine processing, and the like.

(4)因為光硬化性、耐熱性、彈性回復率等機械特性高,因此適合作為永久膜。(4) Since it has high mechanical properties such as photocurability, heat resistance, and elastic recovery, it is suitable as a permanent film.

(5)由於電壓特性優異,故適合於電子電路用材料等。(5) Since it is excellent in voltage characteristics, it is suitable for materials for electronic circuits and the like.

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。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.

(光聚合性單體)(photopolymerizable monomer)

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」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。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" means a monomer which can initiate a polymerization reaction by light irradiation to form a high molecular weight body.

作為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。從組成物之黏度調整的觀點來看,較佳為使用低黏度之光聚合性單體。又,為了提升硬化物之圖案精度,組成物之黏度通常較佳為18mPa‧s以下,其目的係以使用盡可能低黏度之聚合性單體為佳。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。As the main function of the photopolymerizable monomer used in the present invention, the viscosity of the composition or the mechanical properties of the cured film can be appropriately selected depending on the purpose. From the viewpoint of viscosity adjustment of the composition, it is preferred to use a photopolymerizable monomer having a low viscosity. Further, in order to improve the pattern accuracy of the cured product, the viscosity of the composition is usually preferably 18 mPa ‧ or less, and the purpose is preferably to use a polymerizable monomer having a viscosity as low as possible. The viscosity of the photopolymerizable monomer is related to the molecular weight, the intermolecular interaction, and the like. Therefore, a single amount of low-viscosity of photoradical polymerization can be achieved by considering low molecular weight and low intermolecular interaction.

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,較佳為具有100mPa‧s以下的黏度之化合物、更佳為50mPa‧s以下、特佳為10mPa‧s以下。The photopolymerizable monomer used in the present invention is preferably a compound having a viscosity of 100 mPa·s or less, more preferably 50 mPa·s or less, and particularly preferably 10 mPa·s or less from the viewpoint of adjusting the viscosity of the composition.

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,較佳為500以下、更佳為100~400、特佳為100~300。The weight average molecular weight of the photopolymerizable monomer in the present invention is preferably 500 or less, more preferably 100 to 400, and particularly preferably 100 to 300, from the viewpoint of adjusting the viscosity of the composition.

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、烯丙基苯乙烯基為較佳。本發明之組成物所含的光聚合性單體可為1種,亦可為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)。In addition, the photoradical polymerizable functional group which the photopolymerizable monomer has in the present invention may, for example, be a functional group having an ethylenically unsaturated bond, and may be a (meth)acrylic group, a vinyl group or an allyl styrene. The base is preferred. The photopolymerizable monomer 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 a photopolymerizable monomer having a photoradical polymerizable functional group or a photopolymerizable monomer (for example, a polymerizable monomer having a cationic polymerizable group).

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為較佳。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。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 is inevitably increased in viscosity due to an increase in molecular weight, and the pattern viscosity is lowered due to high viscosity of the composition. Therefore, the polymerizable single system used in the present invention considers a combination of a low-viscosity single molecule for viscosity adjustment and a polyfunctional single molecule imparted to impart mechanical properties to the cured film, or an oxetane of the present invention (oxetane) A combination of a compound or a functional anhydride is selected in a comprehensive manner.

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%為較佳、以30~70質量%為更佳。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。In the curable composition for imprint of the present invention, the content of the photopolymerizable monomer in the total composition is preferably from 20 to 90% by mass, preferably from 30 to 70, from the viewpoint of pattern accuracy after light irradiation. The mass % is better. However, the content of the photopolymerizable monomer in the present invention is as described above, and is determined in consideration of the content of the compound having a radical polymerizable functional group in the composition of the present invention.

在本發明,可僅含1種之倍半矽氧烷(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%之比例為較佳、以含1~20質量%之比例為更佳。藉由成為此範圍,可兼具組成物黏度與硬化膜的機械特性。In the present invention, only one type of silsesquioxane compound may be contained, or two or more types may be contained. Further, in the composition of the present invention, the sesquioxane compound is preferably contained in an amount 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.

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、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(以下稱為「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(以下稱為「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。In the photopolymerizable monomer of the present invention, a polymerizable unsaturated monomer (monofunctional polymerizable unsaturated 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, butane diol mono (meth) acrylate, (methyl) Butyloxyethyl acrylate, butyl (meth) acrylate, hexadecyl (meth) acrylate, ethylene oxide modification (hereinafter referred to as "EO") cresyl (meth) acrylate, ( Dipropylene glycol (meth)acrylate, phenyl ethoxylate (meth)acrylate, ethyl (meth)acrylate, isoamyl (meth)acrylate, isobutyl (meth)acrylate, (methyl) Isooctyl acrylate, cyclohexyl (meth)acrylate, (meth) propyl Isobornyl enoate, dicyclopentanyl (meth)acrylate, dicyclopentyloxyethyl (meth)acrylate, isomyristyl (meth)acrylate, lauryl (meth)acrylate, (A) (meth) propylene dipropylene glycol acrylate, methoxy tripropylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, methoxy triethylene glycol (meth) acrylate, Methyl (meth) acrylate, neopentyl glycol benzoate (meth) acrylate, decyl phenoxy polyethylene glycol (meth) acrylate, decyl phenoxy poly(meth) acrylate Propylene glycol ester, octyl (meth) acrylate, p-cumyl phenoxy glycol (meth) acrylate, epichlorohydrin (hereinafter referred to as "ECH") modified phenoxy acrylate, (methyl Benzyl acrylate, phenoxy diethylene glycol (meth) acrylate, phenoxy hexaethylene glycol (meth) acrylate, phenoxytetraethylene glycol (meth) acrylate, Poly(ethylene glycol) (meth)acrylate, polyethylene glycol-polypropylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, stearyl (meth)acrylate, EO modified (methyl) Acetic acid succinic acid , tert-butyl (meth)acrylate, tribromophenyl (meth)acrylate, EO modified tribromophenyl (meth)acrylate, tri-dodecyl (meth)acrylate, p-isopropene Phenolic, styrene, α-methylstyrene, acrylonitrile, vinylcarbazole, ethyl oxetanemethyl acrylate.

再者,可例示乙烯基三氯矽烷、乙烯基參(β-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。Further, vinyl vinyl hydride, 3-methyl group such as vinyl trichloromethane, vinyl stilbene (β-methoxyethoxy) decane, vinyl triethoxy decane, vinyl trimethoxy decane, etc., may be exemplified. (Methyl) propylene oxime such as propylene methoxy propyl methyl dimethoxy decane, 3-methyl propylene methoxy propyl trimethoxy decane, 3- propylene methoxy propyl trimethoxy decane Base decane.

此等之中,本發明特別適合使用丙烯酸酯單分子。Among these, the present invention is particularly suitable for the use of acrylate single molecules.

又,作為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。作為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1,4-丁二醇酯、EO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、PO改質雙酚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(以後稱為「PO」。)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)丙烯酸酞酸酯、聚(乙二醇-丁二醇)二(甲基)丙烯酸酯、聚(丙二醇-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。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, 1,4-butanediol di(meth)acrylate, EO 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, PO modified bisphenol A di(meth) acrylate, modified bisphenol A di(meth) acrylate, EO modified bisphenol F II Methyl) acrylate, ECH modified hexahydrofurfurate diacrylate, hydroxytrimethyl acetic acid neopentyl glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, EO modified Neopentyl glycol acrylate, propylene oxide (hereinafter referred to as "PO".) modified neopentyl glycol diacrylate, caprolactone modified hydroxytrimethyl acetate neopentyl glycol, stearic acid Ethylene pentaerythritol (meth) acrylate, ECH modified di(meth)acrylic acid Phthalate, poly(ethylene glycol-butanediol) di(meth)acrylate, poly(propylene glycol-butanediol) di(meth)acrylate, polyester (di)acrylate, di(methyl) Polyethylene glycol acrylate, polypropylene glycol di(meth)acrylate, ECH modified propylene glycol di(meth)acrylate, fluorenone di(meth)acrylate, triethylene glycol di(meth)acrylate Ester, tetraethylene glycol di(meth)acrylate, (b) tricyclodecane dimethanol acetate, neopentyl glycol modified trimethylolpropane di(meth)acrylate, di(methyl) Tripropylene glycol acrylate, EO modified tripropylene glycol di(meth)acrylate, triglycerol di(meth)acrylate, dipropylene glycol di(meth)acrylate, divinylethylene urea, divinyl propylene Urea, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentyl di(meth)acrylate.

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)丙烯酸二環戊基酯等係特別適合用於本發明。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, dicyclopentyl di(meth)acrylate, and the like are particularly suitable for use in the present invention.

作為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。作為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、EO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)丙烯酸酯、EO改質三羥甲基丙烷三(甲基)丙烯酸酯、PO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。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). Glycerol acrylate, neopentyl glycol triacrylate, EO modified phosphoric acid triacrylate, trimethylolpropane tri(meth) acrylate, caprolactone modified trimethylolpropane tris Acrylate, EO modified trimethylolpropane tri(meth) acrylate, PO modified trimethylolpropane tri(meth) acrylate, ginseng (propylene oxyethyl) cyanuric acid Ester, dipentaerythritol hexa(meth)acrylate, caprolactone modified dipentaerythritol hexa(meth)acrylate, hydroxyp-pentaerythritol penta(meth)acrylate, alkyl modification R-pentaerythritol penta(meth)acrylate, di-n-pentyl glycol poly(meth)acrylate, alkyl-modified dipentaerythritol tris(meth)acrylate, di-trimethylol Propane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, and the like.

此等之中,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、三羥甲基丙烷三(甲基)丙烯酸酯、EO改質三羥甲基丙烷三(甲基)丙烯酸酯、PO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。Among these, EO modified tris(meth)acrylic acid glycerol ester, PO modified tris(meth)acrylic acid glycerol ester, trimethylolpropane tri(meth)acrylate, EO modified three Hydroxymethylpropane tri(meth)acrylate, PO modified trimethylolpropane tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, neopentyl tetra(meth)acrylate Alcohol ethoxylate, neopentyl tetra(meth)acrylate, and the like are particularly suitable for use in the present invention.

本發明所用之光聚合性單體,亦可使用乙烯基醚化合物。As the photopolymerizable monomer used in the present invention, a vinyl ether compound can also be used.

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、己二醇二乙烯基醚、四乙二醇二乙烯基醚、新戊四醇二乙烯基醚、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、乙二醇二乙烯乙烯基醚、三乙二醇二乙烯乙烯基醚、乙二醇二丙烯乙烯基醚、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、新戊四醇二乙烯乙烯基醚、新戊四醇三乙烯乙烯基醚、新戊四醇四乙烯乙烯基醚、1,1,1-參[4-(2-乙烯氧基乙氧基)苯基]乙烷、雙酚A二乙烯氧基乙基醚等。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, hexanediol divinyl ether, tetraethylene glycol divinyl ether, neopentyl alcohol divinyl ether, neopentyl alcohol trivinyl ether, neopentyl alcohol tetravinyl ether, sorbus Sugar alcohol tetravinyl ether, sorbitol pentavinyl ether, ethylene glycol divinyl vinyl ether, triethylene glycol divinyl vinyl ether, ethylene glycol dipropylene vinyl ether, triethylene glycol diethylene ethylene Ether, trimethylolpropane triethylene vinyl ether, trimethylolpropane divinyl vinyl ether, neopentyl alcohol divinyl vinyl ether, neopentyl alcohol triethylene glycol Ethyl ether, neopentyl alcohol tetravinyl vinyl ether, 1,1,1-gin[4-(2-vinyloxyethoxy)phenyl]ethane, bisphenol A divinyloxyethyl ether, etc. .

此等乙烯基醚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、或多元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。These vinyl ether compounds can be used, for example, by the method described in Stephen. C. Lapin, Polymers Paint Colour Journal. 179 (4237), 321 (1988), that is, by reaction of a polyhydric alcohol or a polyhydric phenol with acetylene, or The reaction of the polyol or the polyhydric phenol with the halogenated alkyl vinyl ether is carried out, and these may be used alone or in combination of two or more.

又,本發明所用之光聚合性單體亦可採用苯乙烯衍生物。作為苯乙烯衍生物,可舉出例如,p-甲氧基苯乙烯、p-甲氧基-β-甲基苯乙烯、p-羥基苯乙烯等。Further, the photopolymerizable monomer used in the present invention may also be a styrene derivative. Examples of the styrene derivative include p-methoxystyrene, p-methoxy-β-methylstyrene, and p-hydroxystyrene.

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、β-甲基苯乙烯、p-甲基-β-甲基苯乙烯、α-甲基苯乙烯、p-甲氧基-β-甲基苯乙烯、p-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、α-甲基-1-乙烯基萘、β-甲基-1-乙烯基萘、4-甲基-1-乙烯基萘、4-甲氧基-1-乙烯基萘等。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, β-methylstyrene, p-A. Base-β-methylstyrene, α-methylstyrene, p-methoxy-β-methylstyrene, p-hydroxystyrene, and the like. Further, in the present invention, a vinyl naphthalene derivative may be used, and examples thereof include 1-vinylnaphthalene, α-methyl-1-vinylnaphthalene, β-methyl-1-vinylnaphthalene, and 4- Methyl-1-vinylnaphthalene, 4-methoxy-1-vinylnaphthalene, and the like.

又,為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為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。Further, in order to improve the peeling property and the coating property 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.

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。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.

本發明之壓印用硬化性組成物中,作為本發明所用之光聚合性單體,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,簡稱為「氧雜環丁烷化合物」或「氧雜環丁烷單分子」)作為光聚合性單體。本發明之組成物為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。In the curable composition for imprint of the present invention, the photopolymerizable 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 obtain excellent hardness by heating.

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為較佳、以1~3為更佳。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 viewpoint of the curing rate and the physical properties of the cured film. Preferably, it is preferably from 1 to 3.

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為較佳、以5~20為更佳。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.

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為較佳、以100~400為更佳。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.

又,作為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。作為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、苯乙烯基為較佳。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觀點來看,以1~4為較佳、以1~2為更佳。本發明之組成物中所含的具有氧雜環丁烷環之化合物可為1種、亦可為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(x)、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,基準為x)以1/2~5/1為較佳、以1/1~2/1為更佳。Moreover, the oxetane compound which is a photopolymerizable monomer in the present invention has a photoradical polymerizable functional group. The photoradical 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 precision at the time of light irradiation and the adhesion between the substrates. 1 to 2 is better. 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 polymerizable functional group and an oxetane compound not containing the same. When the compound (x) having a photoradical polymerizable functional group and the oxetane compound (y) having no photo-polymerizable functional group are used, the pattern precision after light irradiation and the suppression of suppression of volatilization of unreacted components during heating are suppressed. In view of the above, the content ratio (x:y, reference x) is preferably 1/2 to 5/1, more preferably 1/1 to 2/1.

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,除了作為光聚合性單體以外,亦可含具有氧雜環丁烷環之化合物。Further, the curable composition for imprint of the present invention may contain a compound having an oxetane ring in addition to the photopolymerizable monomer, as long as it does not deviate from the gist of the present invention.

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%為較佳、以10~30質量%為更佳。惟,本發明中具有氧雜環丁烷環之化合物為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。In the curable composition for imprint of the present invention, the content of the oxetane compound in the total composition is preferably from 5 to 50% by mass, preferably from 10%, from the viewpoint of pattern accuracy after light irradiation. 30% by mass is more preferred. 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 related to the content of the compound having another radical polymerizable functional group or the photoradical polymerizable functional group. The relationship between the content of the oxetane compound is appropriately determined.

作為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)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:OXT-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。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, manufactured by Toagosei Co., Ltd.), bis[1-ethyl(3-oxetanyl)]methyl ether (trade name: OXT-221, manufactured by East Asia Synthetic Co., Ltd.), 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane (trade name: OXT-212, East Asian Synthesis ( (4)-bis[3-ethyl-(3-oxetanyl)methoxymethyl]biphenyl (trade name: ETERNACOLLOXBP, Ube Industries, Ltd.) Sesquiterpene oxide modified oxetane (trade name: OX-SQ, manufactured by Toagosei Co., Ltd.), oxetane (meth) acrylate (trade name: OXE-10, 30, Osaka Organic Chemicals Co., Ltd.).

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為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高表面硬度而較佳。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 because a high surface hardness can be obtained after heat curing.

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。In the present invention, the "functional acid anhydride" is a compound obtained by dehydrating and condensing two molecules of keto acid, and is chemically bonded to other functional groups by heating or the like.

作為前述官能性酸酐酐,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、馬來酸酐類為較佳。Examples of the functional anhydride anhydride include phthalic anhydride, citraconic anhydride, succinic anhydride, propionic anhydride, maleic anhydride, and acetic anhydride, and the viscosity is lowered and the stability of the composition is considered. It is preferred to use phthalic anhydride or maleic anhydride.

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為較佳、以10~50為更佳。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.

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為較佳、以100~500為更佳。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.

又,前述官能性酸酐,從使光聚合性單體為前述範圍之觀點來看,以具有光自由基聚合性官能基為較佳。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、苯乙烯基為較佳。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為較佳、以1~2為更佳。本發明之組成物中所含的官能性酸酐可為1種、亦可為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,基準為q)以1/2~5/1為較佳、以1/1~2/1為更佳。Further, the functional acid anhydride is preferably a photoradical polymerizable functional group from the viewpoint that the photopolymerizable monomer is in the above range. The photoradical 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. 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 acid anhydride having a photoradical polymerizable functional group or a functional acid anhydride having no such functionality. When the compound (q) having a photoradical polymerizable functional group and the functional acid anhydride (w) having no functional group are used, the pattern precision 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 2/1.

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%為較佳、以10~30質量%為更佳。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。In the curable composition for imprint of the present invention, the content of the functional acid anhydride in the total composition is preferably from 5 to 50% by mass, preferably from 10 to 30% by mass, from the viewpoint of pattern accuracy after light irradiation. For better. However, when the functional acid anhydride of 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.

又,在本發明之壓印用硬化性組成物,本發明之氧雜環丁烷化合物(a)與官能性酸酐(b)之含有比(a:b,基準為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為較佳、以2/1~1/2為更佳。Further, in the curable composition for imprint of the present invention, the content ratio (a: b, reference a) of the oxetane compound (a) of the present invention to the functional acid anhydride (b) 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.

作為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:EPICLON B650、大日本油墨化學工業(股)製)、甲基-3,6-內亞甲基-1,2,3,6-四氫酞酸酐(商品名:MHAC-P、日立化成工業(股)製)、4-甲基六氫酞酸酐(商品名:RIKACID M H-700、新日本理化(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、新日本理化(股)製)、日本Zeon(股)製之Quinhard-200(商品名)、日本環氧樹脂(股)製之EPICURE YH-306(商品名)、Aldrich試藥(P25205、294152,B9750、B4600、412287、N818、N1607、330736)等。The functional anhydride in the present invention may, for example, be methyl-1,2,3,6-tetrahydrophthalic anhydride (trade name: EPICLON B570, manufactured by Dainippon Ink Chemicals Co., Ltd.), methyl-hexahydrogen Anthraquinone anhydride (trade name: EPICLON B650, manufactured by Dainippon Ink Chemical Industry Co., Ltd.), methyl-3,6-endomethyl-1,2,3,6-tetrahydrophthalic anhydride (trade name: MHAC- P, Hitachi Chemical Co., Ltd.), 4-methylhexahydrophthalic anhydride (trade name: RIKACID M H-700, manufactured by Nippon Chemical and Chemical Co., Ltd.), anhydrous citraconic acid, dodecene succinic anhydride (commercial product) Name: RIKACID DDSA, New Japan Physical and Chemical Co., Ltd.), glycerol bis(benzenetricarboxylic anhydride) monoacetate (trade name: RIKACID MTA-10, New Japan Physical and Chemical Co., Ltd.), Japan Zeon (share) It is manufactured by Quinhard-200 (trade name), EPICURE YH-306 (trade name) manufactured by Nippon Epoxy Resin Co., Ltd., Aldrich reagent (P25205, 294152, B9750, B4600, 412287, N818, N1607, 330736).

接著,針對本發明中之光聚合性單體的較佳調合形態加以說明。Next, a preferred blending form of the photopolymerizable monomer in the present invention will be described.

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為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)丙烯酸基為自由基聚合性官能基,故符合前述光聚合性單體。The total content of the photopolymerizable monomer in the curable composition for imprint of the present invention is from 80 to 99% by mass. The "photopolymerizable monomer" means a compound having a radical polymerizable functional group having an ethylenically unsaturated bond such as a (meth)acrylic group, a vinyl group or an allyl group. For example, the oxetane (meth) acrylate having a compound having an oxetane ring is a photopolymerizable monomer because the (meth)acrylic group is a radical polymerizable functional group.

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%為較佳、以80~98質量%為更佳。When the total content of the photopolymerizable monomer in the composition of the present invention is less than 80% by mass, the film can not be sufficiently cured even by light irradiation, and the mold pattern cannot be transferred accurately, and the physical properties such as the hardness of the cured film are not improved. full. 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, an additive such as a photoradical polymerization initiator or a surfactant is not sufficiently effective, pattern precision, physical properties of the cured film deterioration. The total content of the compound having a radical polymerizable functional group in the composition of the present invention is preferably from 60 to 99% by mass, more preferably from 80 to 98% by mass, from the viewpoint of pattern accuracy and physical properties of the cured film.

前述單官能之聚合性不飽和單體通常係作為反應性稀釋劑使用,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。較佳為添加20~80質量%、更佳為25~70質量%、特佳為30~60質量%之範圍。The monofunctional polymerizable unsaturated monomer is usually used as a reactive diluent, and the viscosity of the composition of the present invention is effectively lowered, and usually 10% by mass or more of the total polymerizable unsaturated monomer is added. It is preferably added in an amount of from 20 to 80% by mass, more preferably from 25 to 70% by mass, even more preferably from 30 to 60% by mass.

前述單官能之聚合性不飽和單體由於作為反應性稀釋劑更為,故以添加總聚合性不飽和單體之10質量%以上為較佳。Since the monofunctional polymerizable unsaturated monomer is more preferably a reactive diluent, it is preferably 10% by mass or more of the total polymerizable unsaturated monomer.

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)較佳為以總聚合性不飽和單體的90質量%以下、更佳為80質量%以下、特佳為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為以總聚合性不飽和單體之1~95質量%、更佳為3~95質量%、特佳為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為以總聚合性不飽和單體之80質量%以下、更佳為70質量%以下、特佳為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為80質量%以下,因可降低組成物之黏度而較佳。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 from 1 to 95% by mass, more preferably from 3 to 95% by mass, even more preferably from 5 to 90% by mass based on the total of the polymerizable unsaturated monomers. Add it. 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.

(光自由基聚合起始劑)(Photoradical polymerization initiator)

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為良好。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%為較佳、更佳為0.2~12質量%、特佳為0.3~10質量%。使用2種以上之光聚合起始劑時,其合計量係為前述範圍。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 content of the photoradical polymerization initiator used in the present invention is, for example, 0.1 to 15% by mass, more preferably 0.2 to 12% by mass, particularly preferably 0.3, based on the total composition. ~10% by mass. When two or more types of photopolymerization initiators are used, the total amount thereof is in the above range.

前述光自由基聚合起始劑之比例為0.1質量%以上時,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為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/或顏料之系統中,此等係具有作為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。When the ratio of the photoradical polymerization initiator is 0.1% by mass or more, sensitivity (speed hardenability), resolution, line edge roughness, and coating film strength tend to be improved. On the other hand, when the ratio of the photoradical polymerization initiator is 15% by mass or less, light permeability, colorability, 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 amount of the preferred photopolymerization initiator and/or photoacid generator added to the curable composition for photoimprint lithography for imprinting or the like is not 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.

本發明所用之光自由基聚合起始劑係摻合對所使用之光源的波長具有活性且使用產生適當活性種者。The photoradical polymerization initiator used in the present invention is blended to be active at the wavelength of the light source used and used to produce an appropriate active species.

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-丙烷-1-酮、Irgacure(註冊商標)184:(1-羥基環己基苯基酮)、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)1800:(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)1800:(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-酮)、Irgacure(註冊商標)OXE01:(1,2-辛烷二酮,1-[4-(苯基硫)苯基]-2-(O-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-(O-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 TPO-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ESACURE1001M:(1-[4-苯甲醯基苯基巰基]苯基]-2-甲基-2-(4-甲基苯基碸基)丙烷-1-酮、可由N-1414旭電化公司取得之Adeka Optomer(註冊商標)N-1414:(咔唑‧苯酮系)、Adeka Optomer(註冊商標)N-1717:(吖啶系)、Adeka Optomer(註冊商標)N-1606:(三系);三和化學製之TFE-三:(2-[2-(呋喃-2-基)乙烯基]-4,6-雙(三氯甲基)-1,3,5-三)、三和化學製之TME-三:(2-[2-(5-甲基呋喃-2-基)乙烯基]-4,6-雙(三氯甲基)-1,3,5-三)、三和化學製之MP-三:(2-(4-甲氧基苯基)-4,6-雙(三氯甲基)-1,3,5-三)、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)、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)、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、1,1,1-三氯苯乙酮、二乙氧基苯乙酮及二苯并環庚酮、o-苯甲醯基安息香酸甲酯、2-苯甲醯基萘、4-苯甲醯基聯苯、4-苯甲醯基二苯基醚、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-氯苯基)4,5,4’,5’-肆(3,4,5-三甲氧基苯基)1,2’-聯咪唑、2,2-雙(o-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。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-propane-1- Ketone, Irgacure (registered trademark) 184: (1-hydroxycyclohexyl 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-1-(4) - morpholinyl phenyl) butanone-1), Irgacure (registered trademark) 907: (2-methyl-1[4-methylthiophenyl]-2- morpholinopropan-1-one, Irgacure ( Registered trademark) 819: (bis(2,4,6-trimethylbenzylidene)-phenylphosphine, Irgacure (registered trademark) 1800: (bis(2,6-dimethoxybenzylidene) -2,4,4-trimethyl-pentylphosphine, 1-hydroxy-cyclohexyl-phenyl-one), Irgacure (registered trademark) 1800: (bis(2,6-dimethoxybenzamide) )-2,4,4-trimethyl-pentylphosphine, 2-hydroxy-2-methyl-1-phenyl-1-propan-1-one), Irgacure (registered trademark) OXE01: (1, 2 - Octanedione, 1-[4-(phenylthio)phenyl]-2-(O-benzylidenehydrazine), Darocur (registered trademark) 1173: (2-hydroxy-2- 1-phenyl-1-propan-1-one), Darocur (registered trademark) 1116, 1398, 1174 and 1020, CGI242: (ethanone, 1-[9-ethyl-6-(2-methyl) Benzyl hydrazino)-9H-carbazol-3-yl]-1-(O-ethenyl hydrazine); Lucirin TPO available from BASF: (2,4,6-trimethylbenzoguanidinyl) Phenylphosphine), Lucirin TPO-L: (2,4,6-trimethyl benzhydrylethoxyphenylphosphine); ESACURE can be obtained by Siber Hegner, Japan, ESACURE 1001M: (1-[4-benzamide] Aphenyl fluorenyl]phenyl]-2-methyl-2-(4-methylphenylindenyl)propan-1-one, Adeka Optomer (registered trademark) N-1414 available from N-1414 Asahi Chemical Co., Ltd. : (carbazole benzophenone), Adeka Optomer (registered trademark) N-1717: (acridine), Adeka Optomer (registered trademark) N-1606: (three Department); Sanhe Chemical TFE-three :(2-[2-(furan-2-yl)vinyl]-4,6-bis(trichloromethyl)-1,3,5-three ), three and chemical TME-three :(2-[2-(5-methylfuran-2-yl)vinyl]-4,6-bis(trichloromethyl)-1,3,5-three ), Sanhe Chemical MP-III :(2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-three ), MIDORI Chemical TAZ-113: (2-[2-(3,4-Dimethoxyphenyl)vinyl]-4,6-bis(trichloromethyl)-1,3,5-three ), MIDORI Chemical TAZ-108 (2-(3,4-dimethoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-three ), benzophenone, 4,4'-bisdiethylaminobenzophenone, methyl-2-benzophenone, 4-benzylidene-4'-methyldiphenyl sulfide , 4-phenylbenzophenone, ethyl acesulfame, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-Diethylthioxanthone, 1-chloro-4-propoxythioxanthone, 2-methylthioxanthone, thioxanthone ammonium salt, benzoin, 4,4'-dimethoxy Benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, 1,1,1-three Chloroacetophenone, diethoxyacetophenone and dibenzocycloheptanone, methyl o-benzylidene benzoate, 2-benzylidene naphthalene, 4-benzylidenebiphenyl, 4- Benzyl decyl diphenyl ether, 1,4-benzylidene benzene, benzyl, 10-butyl-2-chloroacridone, [4-(methylphenylthio)phenyl]phenylmethane ), 2-ethyl hydrazine, 2,2-bis(2-chlorophenyl) 4,5,4',5'-fluorene (3,4,5-trimethoxyphenyl) 1,2'- Biimidazole, 2,2-bis(o-chlorophenyl)4,5,4',5'-tetraphenyl-1,2'-biimidazole, ginseng (4-dimethylaminophenyl)methane Ethyl-4-(dimethylamino)benzoate 2- (dimethylamino) ethyl benzoate, butoxyethyl 4- (dimethylamino) benzoate and the like.

(抗氧化劑)(Antioxidants)

本發明之壓印用硬化性組成物亦可含抗氧化劑。The curable composition for imprint of the present invention may also contain an antioxidant.

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為受阻酚系抗氧化劑、僅為半受阻酚系抗氧化劑、為受阻酚系抗氧化劑與半受阻酚系抗氧化劑之混合物、或僅為受阻胺系抗氧化劑中之任一者。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.

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為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。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.

本發明之特徵係藉由使用在上述本發明之2種態樣的抗氧化劑,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。The present invention is characterized in that the antioxidants used in the above-described two aspects of the present invention are used to enhance 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.

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。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.

本發明之壓印用硬化性組成物所用之抗氧化劑的含量為全組成物中的0.3~7質量%、較佳為0.5~5質量%、更佳為1.5~5質量%。使用2種以上之抗氧化劑時,使其合計量為前述範圍。若前述抗氧化劑之含量為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為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,若為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為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,因此特佳為1.5~5質量%。The content of the antioxidant used in the curable composition for imprint of the present invention is 0.3 to 7% by mass, preferably 0.5 to 5% by mass, and more preferably 1.5 to 5% by mass based on the total composition. When two or more types of antioxidants are used, the total amount thereof is in the above range. When the content of the antioxidant is 0.3% by mass or more, the heat resistance and the elastic recovery ratio are preferably improved, and when the content is 7% by mass or less, the photocurability is improved. In addition, when the content of the antioxidant is 0.5% by mass or more, the heat resistance and the elastic recovery ratio are further improved, and when the content is 5% by mass or less, the photocurability is further improved. In addition, when the content of the antioxidant is 1.5% by mass or more, the heat resistance and the elastic recovery ratio can be further improved, and therefore it is particularly preferably 1.5 to 5% by mass.

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。The hindered phenol-based antioxidant of the present invention has a structure represented by the following general formula (1).

一般式(1)中、R1 及R2 係各自獨立地表示tert-丁基或-C(R4 R5 )-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。In the general formula (1), R 1 and R 2 each independently represent tert-butyl or -C(R 4 R 5 )-R 6 , and R 3 represents a hydrogen atom or a branch having a carbon number of 1 to 6 or A linear alkyl group which may have a substituent, and L 1 represents a monovalent substituent. R 4 and R 5 each independently represent a hydrogen atom or a methyl group, and R 6 represents a substituent of the structure represented by the following general formula (2).

一般式(2)中、X1 表示氫原子、烷基、羥基、(甲基)丙烯酸酯基、羧基,X1 為羥基時R7 表示tert-丁基,X1 為羥基以外時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。In the general formula (2), X 1 represents a hydrogen atom, an alkyl group, a hydroxyl group, a (meth) acrylate group or a carboxyl group, and when X 1 is a hydroxyl group, R 7 represents a tert-butyl group, and when X 1 is a hydroxyl group, R 7 represents a hydrogen atom, a branched or straight-chain alkyl group having 1 to 6 carbon atoms, and R 8 represents a hydrogen atom or a branched or linear alkyl group having 1 to 6 carbon atoms, which may have a substituent. L 2 represents a monovalent substituent, and * represents a bonding site.

在一般式(1),前述R1 及前述R2 較佳為tert-丁基。In the general formula (1), the above R 1 and the above R 2 are preferably tert-butyl.

前述R3 較佳為氫原子。The above R 3 is preferably a hydrogen atom.

前述R4 及R5 較佳為氫原子。The above R 4 and R 5 are preferably a hydrogen atom.

前述L1 較佳為氫原子、或碳數1~6之分枝或直鏈的可具有取代基之烷基、烷氧基。更佳為具有甲基、烷氧基或胺基作為取代基之碳數1~4的烷基。The above L 1 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.

前述R6 為複數時,複數個R6 係可彼此不同或相同。When the above R 6 is a complex number, the plurality of R 6 systems may be different from each other or the same.

在一般式(2),前述X1 較佳為氫原子、烷基、羥基、(甲基)丙烯酸酯基、羧基,更佳為羥基。In the general formula (2), the above X 1 is preferably a hydrogen atom, an alkyl group, a hydroxyl group, a (meth) acrylate group or a carboxyl group, and more preferably a hydroxyl group.

前述X1 為羥基以外時,前述R7 較佳為氫原子、甲基、tert-丁基,更佳為tert-丁基。When X 1 is other than a hydroxyl group, R 7 is preferably a hydrogen atom, a methyl group or a tert-butyl group, more preferably a tert-butyl group.

前述R8 較佳為氫原子。The above R 8 is preferably a hydrogen atom.

前述L2 係與前述L1 之較佳範圍相同。The aforementioned L 2 system is the same as the preferred range of the above L 1 .

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。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.

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。The semi-hindered phenol-based antioxidant of the present invention has a structure represented by the following general formula (3).

一般式(3)中,R11 表示氫原子或甲基,R12 表示tert-丁基或-C(R14 R15 )-R16 ,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R15 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。In the general formula (3), R 11 represents a hydrogen atom or a methyl group, R 12 represents tert-butyl or -C(R 14 R 15 )-R 16 , and R 13 represents a hydrogen atom or a carbon number of 1 to 6 A branched or straight chain alkyl group which may have a substituent, and L 11 represents a monovalent substituent. R 14 and R 15 each independently represent a hydrogen atom or a methyl group, and R 16 represents a substituent of the structure represented by the following general formula (4).

一般式(4)中,X11 表示氫原子、烷基、羥基、(甲基)丙烯酸酯基、羧基,X11 為羥基時,R17 表示氫原子或甲基,X11 為羥基以外時,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。In the general formula (4), X 11 represents a hydrogen atom, an alkyl group, a hydroxyl group, a (meth) acrylate group or a carboxyl group, and when X 11 is a hydroxyl group, R 17 represents a hydrogen atom or a methyl group, and when X 11 is a hydroxyl group, R 17 represents a hydrogen atom, a branched group having 1 to 6 carbon atoms or a linear alkyl group which may have a substituent, and R 18 represents a hydrogen atom, or a branched or straight chain having a carbon number of 1 to 6 may have a substituent. Alkyl groups, L 12 represents a monovalent substituent, and * represents a bond site.

在一般式(3),前述R11 較佳為甲基。In the general formula (3), the above R 11 is preferably a methyl group.

前述R12 較佳為tert-丁基。The aforementioned R 12 is preferably a tert-butyl group.

前述R13 較佳為氫原子。The above R 13 is preferably a hydrogen atom.

前述R14 及R15 較佳為氫原子。The above R 14 and R 15 are preferably a hydrogen atom.

前述L11 係與前述L1 之較佳範圍相同。The aforementioned L 11 system is the same as the preferred range of the above L 1 .

在一般式(4),前述X11 較佳為氫原子、烷基、羥基、(甲基)丙烯酸酯基、羧基、更佳為羥基。In the general formula (4), the above X 11 is preferably a hydrogen atom, an alkyl group, a hydroxyl group, a (meth) acrylate group, a carboxyl group, or more preferably a hydroxyl group.

前述X11 為羥基時,前述R17 較佳為tert-丁基。When X 11 is a hydroxyl group, R 17 is preferably a tert-butyl group.

前述X11 為羥基以外時,前述R17 較佳為氫原子、甲基、tert-丁基,更佳為甲基。When X 11 is other than a hydroxyl group, R 17 is preferably a hydrogen atom, a methyl group or a tert-butyl group, more preferably a methyl group.

前述R8 較佳為氫原子。The above R 8 is preferably a hydrogen atom.

前述L2 係與前述L1 之較佳範圍相同。The aforementioned L 2 system is the same as the preferred range of the above L 1 .

作為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示。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. Further, the present invention is not limited to the examples of the specific examples.

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)所示之構造作為部分構造之化合物。The hindered amine-based antioxidant of the present invention is not particularly limited, and a compound having a structure represented by the following general formula (5) as a partial structure can be exemplified.

一般式(5)中、R21 表示一價取代基、L21 表示一價取代基。In the general formula (5), R 21 represents a monovalent substituent, and L 21 represents a monovalent substituent.

前述R21 以表示氫原子、或碳數1~6之分枝或直鏈的可具有取代基之烷基、烷氧基為較佳,以氫原子或烷氧基為更佳。R 21 is preferably a hydrogen atom or a branched or straight-chain alkyl group or alkoxy group having 1 to 6 carbon atoms, more preferably a hydrogen atom or an alkoxy group.

前述L21 之較佳範圍係與前述L1 之較佳範圍相同。The preferred range of the aforementioned L 21 is the same as the preferred range of the aforementioned L 1 .

作為受阻胺系抗氧化劑之具體例,可舉出雙(2,2,6,6-四甲基-4-哌啶基)癸二酸酯、雙(N-甲基-2,2,6,6-四甲基-4-哌啶基)癸二酸酯、N,N’-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-N-(2,2,6,6-四甲基-4-哌啶基)丙醯胺、肆(2,2,6,6-四甲基-4-哌啶基)(1,2,3,4-丁烷四羧酸酯、聚[{6-(1,1,3,3-四甲基丁基)亞胺基-1,3,5-三-2,4-二基}{(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}]、聚[(6-味啉基-1,3,5-三-2,4-二基){(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}]、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-N-(1,2,2,6,6-五甲基-4-哌啶基)胺基}-1,3,5-三-2-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。Specific examples of the hindered amine-based antioxidant include bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate and bis(N-methyl-2,2,6). ,6-tetramethyl-4-piperidinyl) sebacate, N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-1,6-hexa Methyldiamine, 2-methyl-2-(2,2,6,6-tetramethyl-4-piperidyl)amino-N-(2,2,6,6-tetramethyl-4 - piperidinyl) propylamine, hydrazine (2,2,6,6-tetramethyl-4-piperidinyl) (1,2,3,4-butane tetracarboxylate, poly[{6- (1,1,3,3-tetramethylbutyl)imido-1,3,5-three -2,4-diyl}{(2,2,6,6-tetramethyl-4-piperidinyl)imido}hexamethyl{(2,2,6,6-tetramethyl-4) -piperidinyl)imido}], poly[(6-morpholinyl-1,3,5-three -2,4-diyl){(2,2,6,6-tetramethyl-4-piperidinyl)imide}}hexamethine{(2,2,6,6-tetramethyl-4- Piperidinyl)imine}], dimethyl succinate and 1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate, N, N '-4,7-肆[4,6-bis{N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino}-1,3, 5-three -2-yl]-4,7-diazadecane-1,10-diamine, and the like. Further, the present invention is not limited to the examples of the specific examples.

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’係分別為烷基或烷基酯基,以烷基酯基為較佳。The thioether-based antioxidant of the present invention is a compound represented by the general formula R-S-R'. Here, R and R' are each an alkyl group or an alkyl ester group, and an alkyl ester group is preferred.

作為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。Examples of the thioether-based antioxidant include di-tridecyl thiodipropionate and the like. Further, the present invention is not limited to the examples of the specific examples.

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。Further, the phenol-based antioxidant other than the range of the present invention has a structure represented by the following general formula (6).

一般式(6)中、R31 及R32 表示氫原子或甲基,R33 及L31 表示一價取代基。In the general formula (6), R 31 and R 32 represent a hydrogen atom or a methyl group, and R 33 and L 31 represent a monovalent substituent.

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為更佳。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.

又,在本發明之壓印用硬化性組成物第二態樣,前述抗氧化劑為半受阻酚系與硫醚系之混合物,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為更佳。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 system and a thioether system, and the viewpoint of further improving oxidation resistance, reducing polymerization inhibition, and improving photocurability Look at it better.

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為整數)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。The antioxidant can suppress discoloration due to heat or light irradiation, and various oxidizing gases such as ozone, active oxygen, NOx, SOx (x is an integer), and the like to discoloration. In particular, the present invention has an advantage of preventing the coloration of the cured film and reducing the film thickness due to decomposition by adding an antioxidant.

作為前述抗氧化劑之市售品,可列舉商品名Irganox 1010、1035、1076、1222(以上Ciba Geigy(股)製)、商品名AntigeneP、3C、FR、Sumilizer S、Sumilizer GA80(住友化學工業(股)製)、商品名ADK STAB AO7O、AO80、AO503((股)ADEKA製)等。此等可單獨使用,亦可混合使用。Commercial products of the above-mentioned antioxidants include Irganox 1010, 1035, 1076, and 1222 (manufactured by Ciba Geigy Co., Ltd.), trade names Antigene P, 3C, FR, Sumilizer S, and Sumilizer GA80 (Sumitomo Chemical Industries Co., Ltd.) )), the product name is ADK STAB AO7O, AO80, AO503 (made by Adeka). These may be used alone or in combination.

又,前述抗氧化劑係可藉由公知之方法來合成。Further, the antioxidant can be synthesized by a known method.

(界面活性劑)(surfactant)

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,0.001~5質量%、較佳為0.002~4質量%、更佳為0.005~3質量%。使用2種以上之界面活性劑時,係使其合計量為前述範圍。界面活性劑若佔組成物中0.001~5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。The curable composition for imprint of the present invention may also contain a surfactant. The total surfactant composition used in the present invention contains, for example, 0.001 to 5% by mass, preferably 0.002 to 4% by mass, more preferably 0.005 to 3% by mass. When two or more types of surfactants are used, the total amount thereof is in the above range. When the surfactant is in the range of 0.001 to 5% by mass of 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.

作為前述界面活性劑,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種為較佳,以含氟系界面活性劑與矽酮系界面活性劑兩找或含氟‧矽酮系界面活性劑為更佳,以含氟‧矽酮系界面活性劑為最佳。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為較佳。As the surfactant, at least one of a fluorine-containing surfactant, an anthrone-based surfactant, and a fluoro-ketone-based surfactant is preferable, and a surfactant of a fluorine-containing surfactant and an anthrone is used. It is more preferable to use a two-component or fluorine-containing ketone-based surfactant, and a fluorine-containing ketone-based surfactant is preferred. Further, the fluorine-based surfactant and the anthrone-based surfactant are preferably a nonionic surfactant.

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。Here, the "fluoro-ketone-based surfactant" means a component having both a fluorine-based surfactant and an anthrone-based surfactant.

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、鉭膜、鉭合金膜、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。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 crepe film, a bismuth 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). Moreover, 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-430、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(TOCHEM PRODUCTS(股)製)、商品名PF-636、PF-6320、PF-656、PF-6520(均為OMNOVA Solutions,Inc.)、商品名FUTAGENT FT250、FT251、DFX18(均為NEOS(股)製)、商品名UNIDAIN DS-401、DS-403、DS-451(均為DAIKIN工業(股)製)、商品名MEGAFAC 171、172、173、178K、178A、(均為大日本油墨化學工業(股)製)。Examples of the nonionic fluorine-based surfactant which can be used in the present invention include the trade names Fluorad FC-430, 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), trade name PF-636, PF-6320, PF-656, PF -6520 (both OMNOVA Solutions, Inc.), trade names FUTAGENT FT250, FT251, DFX18 (both NEOS), trade names UNIDAIN DS-401, DS-403, DS-451 (both DAIKIN Industries) Co., Ltd.), trade names MEGAFAC 171, 172, 173, 178K, 178A, (all manufactured by Dainippon Ink Chemical Industry Co., Ltd.).

又,作為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)。In addition, examples of the nonionic ketone-based surfactants include the product name SI-10 series (made by Takeshi Oil Co., Ltd.), MEGAFAC PEINTAD 31 (made by Dainippon Ink Chemical Industry Co., Ltd.), KP-341 (Shin-Etsu Chemical Industry Co., Ltd.).

又,作為前述氟‧矽酮系界面活性劑的實例,可舉出商品名X-70-090、X-70-091、X-70-092、X-70-093(均為信越化學工業(股)製)、商品名MEGAFAC R-08、XRB-4(均為大日本油墨化學工業(股)製)。Moreover, examples of the fluorine fluorenone-based surfactant include trade names X-70-090, X-70-091, X-70-092, and X-70-093 (all of Shin-Etsu Chemical Industries ( Co., Ltd.), trade name MEGAFAC R-08, XRB-4 (both manufactured by Dainippon Ink Chemical Industry Co., Ltd.).

(其他成分)(other ingredients)

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、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。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 photo-stabilizer, an anti-aging agent, and a plasticizer. , adhesion promoter, thermal polymerization initiator, photobase generator, colorant, elastomer particles, photosensitizer, basic compound, and other flow regulators, antifoaming agents, dispersants, and the like.

本發明之組成物,為了密接性之賦予、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。作為此種非聚合性分子,可舉出例如如癸二酸二辛酯之烷酯、(硫)尿素化合物、有機微粒子、無機微粒子等。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 an alkyl ester such as dioctyl sebacate, a (sulfur) urea compound, organic fine particles, and inorganic fine particles.

在本發明之組成物,為了更提高交聯密度,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。作為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%為較佳、更佳為0~20質量%、進一步較佳為0~10質量%、最佳為0~5質量%。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-mentioned polyfunctional other polymerizable monomer may 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%.

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為較佳。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為較佳、以5000~50000為更佳。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%為較佳、更佳為0~20質量%、進一步較佳為0~10質量%、最佳為2質量%以下。又,從圖案形成性的觀點來看,樹脂成分以盡可能少為較佳,較佳為除了界面活性劑、微量添加劑外,不含樹脂成分。The curable composition for imprint of the present invention may further contain a polymer component from the viewpoint of improving the embossability and the curability. The polymer component is preferably a polymer having a polymerizable functional group in a side chain. The weight average molecular weight of the 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, even 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. 2% by mass or less. Further, from the viewpoint of pattern formability, 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.

為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(特弗龍為註冊商標)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。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 without causing surface cracking or residue 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 may be attached to the mold.

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為基本構造之脫膜劑,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。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 the residual phenomenon is less likely to occur. The above-mentioned anthrone-based release agent is a release agent having a basic structure of an organic polyoxymethane, for example, a polyoxane or an anthrone having an unmodified or modified eucalyptus oil, trimethylphosphonium decanoic acid. It is compatible with an acrylic resin or the like, and an anthrone-based leveling agent which is usually used for a composition for a hard coat layer is also applicable.

前述改質矽油係將聚矽氧烷之側鏈及/或末端改質而成者,可分為反應性矽油與非反應性矽油。作為反應性矽油,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、巰基改質、苯酚改質、單末端反應性、異種官能基改質等。作為非反應性矽油,可舉出聚醚改質、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。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 heterogeneous functional group modification. Quality and so on. Examples of the non-reactive eucalyptus oil include polyether modification, methylstyryl modification, alkyl modification, higher fatty ester modification, hydrophilic special modification, higher alkoxy modification, and higher fatty acid modification. Fluorine modification.

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。It is also possible to carry out two or more modification methods as described above for one polyoxyalkylene molecule.

前述改質矽油較佳為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。The modified eucalyptus oil preferably has a moderate compatibility with the composition component. 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 The adhesion of the cured film is hindered, contaminated, deteriorated, and the like. 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.

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為較佳。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.

前述脫膜劑可僅添加1種或組合2種以上。The above-mentioned release agent may be added alone or in combination of two or more.

在本發明之壓印用硬化性組成物添加脫膜劑時,較佳為在組成物總量中摻合0.001~10質量%之比例、更佳為添加0.01~5質量%之範圍。當脫膜劑之含量為0.01~5質量%之範圍内時,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)。When the release agent is added to the curable composition for imprint of the present invention, it is preferably blended in a ratio 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 surface. The surface cracking problem occurs, and the adhesion of the vapor deposition layer, the destruction of the film at the time of transfer, and the like (the film strength becomes too weak) occurs in the substrate itself or in the adjacent layer.

本發明之組成物為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。作為前述有機金屬偶合劑,例如可使用矽烷偶合劑、鈦偶合劑、鋯偶合劑、鋁偶合劑、錫偶合劑等之各種偶合劑。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 organic metal coupling agent is effective because it also has an effect of promoting a thermosetting reaction. As the organic metal coupling agent, for example, various coupling agents such as a decane coupling agent, a titanium coupling agent, a zirconium coupling agent, an aluminum coupling agent, and a tin coupling agent can be used.

可用於本發明之組成物的矽烷偶合劑,可列舉例如,β-(3,4-環氧基環己基)乙基三甲氧基矽烷、γ-環氧丙氧基丙基三甲氧基矽烷、γ-環氧丙氧基丙基甲基二乙氧基矽烷等之環氧基矽烷;N-β-(胺基乙基)-γ-胺基丙基三甲氧基矽烷、N-β-(胺基乙基)-γ-胺基丙基甲基二甲氧基矽烷、γ-胺基丙基三甲氧基矽烷、N-苯基-γ-胺基丙基三甲氧基矽烷等之胺基矽烷;及作為其他矽烷偶合劑,可舉出γ-巰基丙基三甲氧基矽烷、γ-氯丙基甲基二甲氧基矽烷、γ-氯丙基甲基二乙氧基矽烷等。The decane coupling agent which can be used in the composition of the present invention may, for example, be β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane or γ-glycidoxypropyltrimethoxydecane. An epoxy decane such as γ-glycidoxypropylmethyldiethoxy decane; N-β-(aminoethyl)-γ-aminopropyltrimethoxydecane, N-β-( Amino group such as aminoethyl)-γ-aminopropylmethyldimethoxydecane, γ-aminopropyltrimethoxydecane, N-phenyl-γ-aminopropyltrimethoxydecane The decane; and other decane coupling agents may, for example, be γ-mercaptopropyltrimethoxydecane, γ-chloropropylmethyldimethoxydecane, or γ-chloropropylmethyldiethoxydecane.

作為前述鈦偶合劑,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碸基鈦酸酯、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。The titanium coupling agent may, for example, be isopropyl triisostearate titanate, isopropyl tri-dodecylphenylphosphonium titanate or isopropyl sulfonate (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, diisopropyl phenyl phenyl Oxyacetate titanate, diisostearate vinyl titanate, and the like.

作為前述鋯偶合劑,可舉出例如,四-n-丙氧基鋯、四-丁氧基鋯、四乙醯基丙酮酸鋯、二丁氧基雙(乙醯基丙酮酸)鋯、三丁氧基乙基乙醯乙酸鋯、丁氧基乙醯基丙酮酸酯雙(乙基乙醯乙酸)鋯等。The zirconium coupling agent may, for example, be tetra-n-propoxy zirconium, tetra-butoxy zirconium, zirconium tetraethanopyruvate, zirconium dibutoxy bis(ethylmercaptopyruvate), or the like. Zirconium butoxide, zirconium butoxide, bis(ethylacetonitrile acetate), zirconium, and the like.

作為前述鋁偶合劑,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。Examples of the aluminum coupling agent include aluminum isopropylate, aluminum sec-butoxydiisopropylate, aluminum sec-butyrate, aluminum acetate, and ethyl acetoacetate aluminum diisopropylate. Refractory (ethyl acetoacetate) aluminum, alkyl acetoacetate aluminum diisopropylate, acetoacetate bis(ethyl acetonitrile) aluminum, ginseng (ethylene acetonitrile) aluminum Wait.

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為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為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。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 defect of the film formability.

本發明之壓印用硬化性組成物為了提升儲存安定性等,亦可摻合聚合抑制劑。作為前述聚合抑制劑,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為0.001~10質量%之比例任意地摻合為較佳。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; Class; 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.

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)、Sumisorb110、130、140、220、250、300、320、340、350、400(以上,住友化學工業(股)製)等。紫外線吸收劑較佳為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。An ultraviolet absorber can also be used for the curable composition for imprint of the present invention. Commercial products of the ultraviolet absorber include Tinuvin P, 234, 320, 326, 327, 328, 213 (above, manufactured by Ciba Geigy Co., Ltd.), Sumisorb 110, 130, 140, 220, 250, 300, 320, 340, 350, 400 (above, Sumitomo Chemical Industry Co., Ltd.) and so on. 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.

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,Ciba Geigy(股)製)、Sanol LS-770、765、292、2626、1114、744(以上,三共化成工業(股)製)等。光安定劑較佳為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。A light stabilizer can also be used for the curable composition for imprint of the present invention. Commercial products of the above-mentioned light stabilizers include Tinuvin 292, 144, 622LD (above, manufactured by Ciba Geigy Co., Ltd.), Sanol LS-770, 765, 292, 2626, 1114, and 744 (above, Sankyo Chemical Industry Co., Ltd. ( Stock system) and so on. The light stabilizer is preferably blended at a ratio of 0.01 to 10% by mass based on the total amount of the curable composition for imprint.

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。抗老化劑較佳為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。An anti-aging agent can also be used for the curable composition for imprint of the present invention. The commercial product of the anti-aging agent may, for example, be Antigene W, S, P, 3C, 6C, RD-G, FR, 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.

在本發明之壓印用硬化性組成物中,為了調整與基板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(n-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。較佳為20質量%以下、更佳為10質量%以下。為得可塑劑之添加效果,以0.1質量%以上為較佳。In the curable composition for imprint of the present invention, a plasticizer may be added in order to adjust the adhesion to the substrate, the flexibility of the film, the hardness, and the like. 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(n-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. In order to obtain the effect of adding a plasticizer, it is preferably 0.1% by mass or more.

在本發明之壓印用硬化性組成物為了調整與基板之接著性等,亦可添加密接促進劑。作為前述密接促進劑,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-乙基二乙醇胺、N-乙基乙醇胺及衍生物、苯并噻唑衍生物等。密接促進劑在組成物中較佳為20質量%以下、更佳為10質量%以下、進一步較佳為5質量%以下。為得密接促進劑之添加效果,以0.1質量%以上為較佳。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-ethyldiethanolamine, N-ethylethanolamine and derivatives, benzothiazole 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.

使本發明之組成物硬化時,亦可視需要添加熱聚合起始劑。作為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-過氧化苯甲酸酯、偶氮雙異丁腈等。熱聚合起始劑較佳為組成物中之8.0質量%以下、更佳為6.0質量%以下、進一步較佳為4.0質量%以下。為得熱聚合起始劑之添加效果,以3.0質量%以上為較佳。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-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.

本發明之壓印用硬化性組成物為了調整圖案形狀、感度等之目的,亦可視需要添加光鹼產生劑。作為光鹼產生劑,可舉出例如,2-硝基苄基環己基胺基甲酸酯、三苯基甲醇、O-胺甲醯基羥基醯胺、O-胺甲醯基肟、[[(2,6-二硝基苄基)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-1-味啉基乙烷、(4-味啉基苯甲醯基)-1-苄基-1-二甲基胺基丙烷、N-(2-硝基苄基氧基羰基)吡咯烷、六氨合鈷(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)-1,4-二氫吡啶等。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, O-amine formazan hydroxyguanamine, O-amine formazan, [[ (2,6-Dinitrobenzyl)oxy]carbonyl]cyclohexylamine, bis[[(2-nitrobenzyl)oxy]carbonyl]hexane 1,6-diamine, 4-(methyl Thiobenzylidene)-1-methyl-1-tyrosolinylethane, (4-morpholinylbenzylidene)-1-benzyl-1-dimethylaminopropane, N-(2 -Nitrobenzyloxycarbonyl)pyrrolidine, hexaammine cobalt(III) ginseng (triphenylmethylborate), 2-benzyl-2-dimethylamino-1-(4-morpholine Phenylphenyl)-butanone, 2,6-dimethyl-3,5-diethylindol-4-(2'-nitrophenyl)-1,4-dihydropyridine, 2,6-di Methyl-3,5-diethylinden-4-(2',4'-dinitrophenyl)-1,4-dihydropyridine or the like.

在本發明之壓印用硬化性組成物,為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。作為無機顏料,可舉出金屬氧化物、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。作為有機顏料,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.顏料紅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.顏料黑1,7及碳黑。著色劑相對於組成物之總量,較佳為摻合0.001~2質量%之比例。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. In the range which does not impair the object of the present invention, a pigment or a dye used for a UV inkjet composition, a color filter composition, a CCD image sensing application composition, or the like can be used as the colorant. 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 metal oxide or a metal salt, and specific examples thereof include iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, lanthanum, and the like. Metal oxide, metal composite oxide. 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, CI Pigment Red 105, 122, 149, 150, 155, 171, 175, 176, 177, 209, CI Pigment Violet 19, 23, 32, 39, CI Pigment Blue 1 can be exemplified. , 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.

又,在本發明之壓印用硬化性組成物,為了提升機械強度、柔軟性等目的,亦可添加作為任意成分之彈性體粒子。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.

在本發明之組成物可添加作為任意成分之彈性體粒子的平均粒子尺寸較佳為10nm~700nm、更佳為30~300nm。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。彈性體粒子亦可為交聯構造。The average particle size of the elastomer particles to 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 may also have a crosslinked structure.

作為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。For example, Resinous Bond RKB (manufactured by Resinous Chemical Co., Ltd.), Techno MBS-61, MBS-69 (manufactured by Techno Polymer Co., Ltd.), and the like are mentioned.

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為1~35質量%、更佳為2~30質量%、特佳為3~20質量%。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, even more preferably from 3 to 20% by mass.

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Crivello[J. V. Crivello,Adv. in Polymer Sci,62,1(1984)]者、具體而言,芘、苝、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、樟腦醌、啡噻衍生物等。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 Crivello [JV Crivello, Adv. in Polymer Sci, 62, 1 (1984)], specifically, hydrazine, hydrazine, acridine orange, thioxanthone. , 2-chlorothioxanthone, benzoxanthin, N-vinylcarbazole, 9,10-dibutoxyanthracene, anthraquinone, coumarin, ketocoumarin, phenanthrene, camphorquinone, thiophene Derivatives, etc.

在本發明之組成物為了硬化收縮之抑制、提升熱安定性等目的,亦可任意地添加鹼性化合物。作為鹼性化合物,可舉出胺與喹啉及喹等含氮雜環化合物、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,以胺為較佳,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。In the composition of the present invention, a basic compound may be arbitrarily added for the purpose of suppressing the curing shrinkage and improving the thermal stability. As a basic compound, an amine, a quinoline, and a quinine are mentioned. A nitrogen-containing heterocyclic compound, a basic alkali metal compound, a basic alkaline earth metal compound, or the like. 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.

本發明之組成物為了提升光硬化性,亦可添加鏈移動劑。作為前述鏈移動劑,具體而言可舉出4-雙(3-巰基丁基氧基)丁烷、1,3,5-參(3-巰基丁基氧基乙基)1,3,5-三-2,4,6(1H,3H,5H)-三酮、新戊四醇肆(3-巰基丁酸酯)。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. -three -2,4,6(1H,3H,5H)-trione, pentaerythritol bismuth (3-mercaptobutyrate).

又,本發明之壓印用硬化性組成物在調製時之水分量較佳為2.0質量%以下、更佳為1.5質量%、進一步較佳為1.0質量%以下。藉由使調製時之水分量為2.0質量%以下,可使本發明之組成物之保存性更安定。Moreover, the moisture content at the time of preparation 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.

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%以下為較佳。亦即,本發明之組成物較佳為含有如前述之單官能及/或二官能之其他單體作為反應性稀釋劑,故並非一定要含有用以溶解本發明之組成物之成分的有機溶劑。本發明之組成物中,有機溶劑的含量較佳為3質量%以下、更佳為2質量%以下,特佳為未含有。如此,本發明之組成物未必是不含有機溶劑者,在反應性稀釋劑將不溶解之化合物等溶解成本發明之組成物的情況、或微調整黏度時,亦可任意地添加。本發明之組成物中可較佳使用的有機溶劑之種類為在光壓印用硬化性組成物或光阻通常所用的溶劑,只要能將本發明所用之化合物溶解及均勻分散,且不與此等成分反應,即無特別限定。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. That is, the composition of the present invention preferably contains, as a reactive diluent, a monofunctional and/or difunctional monomer as described above, and therefore does not necessarily contain an organic solvent for dissolving the components of the composition of the present invention. . In the composition of the present invention, the content of the organic solvent is preferably 3% by mass or less, more preferably 2% by mass or less, and particularly preferably not contained. As described above, the composition of the present invention is not necessarily an organic solvent-free one, and may be arbitrarily added when the compound in which the reactive diluent is dissolved or the like is dissolved in the composition of the invention or when the viscosity is finely adjusted. The type of the organic solvent which can be preferably used in the composition of the present invention is a solvent which is usually used for a photocurable hardenable composition or a photoresist, as long as the compound used in the present invention can be dissolved and uniformly dispersed, and does not The component reaction is not particularly limited.

作為前述有機溶劑,可舉例如,甲醇、乙醇等之醇類;四氫呋喃等之醚類;乙二醇單甲基醚、乙二醇二甲基醚、乙二醇甲基乙基醚、乙二醇單乙基醚等之二醇醚類;甲基賽路蘇乙酸酯、乙基賽路蘇乙酸酯等之乙二醇烷基醚乙酸酯類;二乙二醇單甲基醚、二乙二醇二乙基醚、二乙二醇二甲基醚、二乙二醇乙基甲基醚、二乙二醇單乙基醚、二乙二醇單丁基醚等之二乙二醇類;丙二醇甲基醚乙酸酯、丙二醇乙基醚乙酸酯等之丙二醇烷基醚乙酸酯類;甲苯、二甲苯等之芳香族烴類;丙酮、甲基乙基酮、甲基異丁酮、環己酮、4-羥基-4-甲基-2-戊酮、2-庚酮等之酮類;2-羥基丙酸乙酯、2-羥基-2-甲基丙酸甲酯、2-羥基-2-甲基丙酸乙酯、乙氧基醋酸乙酯、羥基醋酸乙酯、2-羥基-2-甲基丁烷酸甲酯、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。Examples of the organic solvent include alcohols such as methanol and ethanol; ethers such as tetrahydrofuran; ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol methyl ethyl ether, and ethylene a glycol ether such as an alcohol monoethyl ether; a glycol alkyl ether acetate such as methyl stilbene acetate or ethyl stilbene acetate; diethylene glycol monomethyl ether; Diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, etc. Alcohols; propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate and propylene glycol ethyl ether acetate; aromatic hydrocarbons such as toluene and xylene; acetone, methyl ethyl ketone, methyl Ketones such as butanone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, 2-heptanone, etc.; ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate , 2-hydroxy-2-methylpropionic acid ethyl ester, ethoxyethyl acetate, ethyl hydroxyacetate, methyl 2-hydroxy-2-methylbutanoate, methyl 3-methoxypropionate, Ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxypropane Ethyl, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate esters, etc., etc. esters.

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、二甲基亞碸、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、γ-丁內酯、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。Further, N-methylformamide, N,N-dimethylformamide, N-methylformamide, N-methylacetamide, N,N-dimethylacetamide, N -methylpyrrolidone, dimethyl hydrazine, benzyl ethyl ether, dihexyl ether, acetonyl 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, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl racelus acetate. These may be used alone or in combination of two or more.

此等之中,特佳為甲氧基丙二醇乙酸酯、2-羥基丙炔酸乙酯、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。Among them, particularly preferred are methoxypropylene glycol acetate, ethyl 2-hydroxypropynoate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl lactate, and a ring. Hexanone, methyl isobutyl ketone, 2-heptanone, and the like.

本發明之壓印用硬化性組成物之表面張力以在18~30mN/m的範圍為較佳、以在20~28mN/m之範圍為更佳。藉由成為如此範圍,可得提升表面平滑性之效果。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 becoming such a range, the effect of improving surface smoothness can be obtained.

又,本發明之壓印用硬化性組成物在調製時之水分量較佳為2.0質量%以下、更佳為1.5質量%、進一步較佳為1.0質量%以下。藉由使調製時之水分量為2.0質量%以下,可使本發明之組成物之保存性更為安定。Moreover, the moisture content at the time of preparation 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.

針對本發明之壓印用硬化性組成物之黏度加以說明。本發明中的黏度只要沒有特別限定,即是指25℃之黏度。本發明之壓印用硬化性組成物在25℃之黏度以3~18mPa‧s為較佳、進一步較佳為5~15mPa‧s、特佳為7~12mPa‧s。藉由使本發明之組成物之黏度成為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,藉由使黏度為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,黏度為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為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為18mPa‧s以下時,於微細圖案的形成上黏度不造成影響。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 18 mPa ‧ s, more preferably 5 to 15 mPa ‧ s, and 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 substrate coating suitability is less likely to occur or the mechanical strength of the film tends to decrease. Specifically, by setting the viscosity to 3 mPa ‧ s or more, it is possible to suppress surface unevenness during coating of the composition or to flow out of the substrate from the substrate during coating. Further, the composition having a viscosity of 3 mPa ‧ or more is also easily modulated than the 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·s or less, the viscosity does not affect the formation of the fine pattern.

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。為了將本發明之壓印用硬化性組成物之黏度在前述範圍内設計,較佳為添加單分子黏度在5.0mPa‧s以下之組成物以調整黏度。Generally, the viscosity of the composition can be adjusted by doping various monomers, oligomers, and polymers having different viscosities. In order to design the viscosity of the curable composition for imprint 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.

[硬化物之製造方法][Method for producing cured product]

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)之形成方法加以說明。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組成物硬化,藉此可形成微細的凹凸圖案。尤其在本發明中,為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為較佳。即,較佳為本發明之壓印用硬化性組成物係以光及熱來硬化。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 can form a fine concavo-convex pattern. 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 light irradiation. That is, it is preferable that the curable composition for imprint of the present invention is cured by light and heat.

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。The cured product obtained by the method for producing a cured product of the present invention is excellent in pattern precision, curability, 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.

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。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.

又,作為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。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.

在液晶顯示器(LCD)等所用之永久膜(構造構件用之光阻)中,為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,其濃度為1000ppm以下、宜為100ppm以下。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 ionic impurities of metal or organic substances from being mixed into the photoresist, and the concentration thereof is preferably 1000 ppm or less. It is 100 ppm or less.

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。Hereinafter, a method of producing a cured product (pattern forming method (pattern transfer method)) using the curable composition for imprint of the present invention will be specifically described.

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。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.

作為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,約為0.05μm~30μm。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。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 μm to 30 μm. 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.

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、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,可為板狀亦可為圓筒狀。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。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, fluorenone, fluorenone, amorphous fluorenone, etc. There is no particular limitation on the production of a substrate or the like. 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.

接著,在本發明之硬化物之製造方法,為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。Next, in the method for producing a cured product of the present invention, in order to transfer the pattern to 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.

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,從基材內面照射光,以使壓印用硬化性組成物硬化。Photoimprint lithography using the curable composition for imprint of the present invention requires selection of a light transmissive material in at least one of a mold material and/or a substrate. 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 light from the inner surface of the substrate to cure the curable composition for imprint.

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,較佳為以密接模具之狀態進行。The light irradiation may be performed 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.

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。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 according to a desired processing precision by, for example, photolithography or electron beam drawing. However, in the present invention, the mold pattern forming method is not particularly limited.

在本發明所用之光透過性模具材係無特別限定,只要為具有預定強度、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。The light-transmitting mold material used in the present invention is not particularly limited as long as it has predetermined strength and durability. Specifically, a light-transparent resin such as glass, quartz, PMMA or polycarbonate resin, a transparent metal deposition film, a soft film such as polydimethyl siloxane or a photocured film, a metal film, or the like can be exemplified.

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,只要為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。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. Specific examples thereof include a ceramic material, a vapor deposited film, a magnetic film, a reflective film, a metal substrate such as Ni, Cu, Cr, and Fe, SiC, anthrone, fluorenone, fluorenone, fluorenone, and amorphous. 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.

在本發明之硬化物之製造方法所用的模具,為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。作為此種模具,可為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。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.

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為10大氣壓以下來進行。藉由使模具壓力為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,從此點而言亦為較佳。模具壓力較佳為選擇在模具凸部的壓印用硬化性組成物之殘膜變少之範圍,可確保模具轉印之均勻性。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 this is also preferable. The mold pressure is preferably selected in a range in which the residual film of the curable composition for imprinting of the mold is reduced, and the uniformity of transfer of the mold can be ensured.

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,只要為比硬化所需之照射量為足夠大即可。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。In the method for producing a cured product of the present invention, the amount of irradiation of the light in the step of irradiating the pattern forming layer with light may be sufficiently larger than the amount of irradiation required for curing. The amount of irradiation required for the hardening is appropriately determined depending on the consumption of the unsaturated bond of the curable composition for imprint or the adhesiveness of the cured film.

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,惟為提高反應性亦可邊加熱邊進行光照射。在光照射的前階段,若控制為真空狀態,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為10-1 Pa~常壓之範圍。Further, in the photoimprint lithography which is applied to 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 perform light irradiation while heating in order 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 10 -1 Pa to normal pressure.

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、遠紫外、可視、紅外等範圍之波長的光或放射線。作為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,係工業上使用最為便利且經濟,亦可使用其他由放射性同位素或原子爐等所放射之γ線、X線、α線、中子線、質子線等之放射線。作為紫外線源,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)。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 ultraviolet light, visible light, and infrared light. 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 most convenient for industrial use. Further, it is also economical to use other radiation such as gamma rays, X-rays, alpha rays, neutron rays, proton wires, or the like which are emitted by a radioisotope or an atomic furnace. Examples of the ultraviolet light source include an ultraviolet fluorescent lamp, a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, a carbon arc lamp, and a sun lamp. Radiation includes, for example, microwaves, 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) can be used.

於曝光時,宜使曝光照度為1mW/cm2 ~50mW/cm2 之範圍。藉由為1mW/cm2 以上,因可縮短曝光時間而可提高生產性,藉由成為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。曝光量宜為5mJ/cm2 ~1000mJ/cm2 之範圍。若為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,曝光量若為1000mJ/cm2 以下,可抑制因組成物之分解導致永久膜劣化。At the time of exposure, the exposure illuminance is preferably in the range of 1 mW/cm 2 to 50 mW/cm 2 . When the thickness is 1 mW/cm 2 or more, the productivity can be improved by shortening the exposure time, and when it is 50 mW/cm 2 or less, it is preferable to suppress deterioration of permanent film characteristics due to side reactions. Exposure amount is suitably 5mJ / cm range of 2 ~ 1000mJ / cm 2 of. When it is 5 mJ/cm 2 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. Moreover, when the exposure amount is 1000 mJ/cm 2 or less, deterioration of the permanent film due to decomposition of the composition can be suppressed.

再者,於曝光時,為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,控制氧濃度為小於100mg/L。Further, at the time of exposure, in order to prevent the oxygen from causing the inhibition of radical polymerization, an inert gas such as nitrogen or argon may be passed to control the oxygen concentration to be less than 100 mg/L.

在本發明之硬化物之製造方法中,藉由光照射使圖案形成層硬化後,較佳為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為較佳。於光照射後加熱硬化本發明之組成物的熱,以150~280℃為較佳、以200~250℃為更佳。又,賦予熱之時間,以5~60分鐘為較佳、以15~45分鐘為更佳。In the method for producing a cured product of the present invention, after the pattern forming layer is cured 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 light after the light is irradiated, 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 after heating and hardening after light irradiation is preferably 150 to 280 ° C, more preferably 200 to 250 ° C. Further, the time for applying heat is preferably 5 to 60 minutes, more preferably 15 to 45 minutes.

在本發明,光壓印微影術之光照射只要比硬化所需要之照射量為夠大即可。硬化所需要之照射量係依照壓印微影術用硬化性組成物之不飽和鍵之消耗量或硬化膜之膠黏性加以決定。In the present invention, the light irradiation by photoimprint lithography may be sufficiently larger than the amount of irradiation required for hardening. The amount of irradiation required for hardening is determined in accordance with the consumption of the unsaturated bond of the hardenable composition by imprint lithography or the adhesiveness of the cured film.

又,適用於本發明之光壓印微影術中,光照射時之基板溫度通常係以室溫進行,惟為提高反應性亦可邊加熱邊進行光照射。在光照射的前階段,若控制為真空狀態,則可防止氣泡混入、抑制氧混入所致之反應性降低,因具有提升模具與壓印微影術用硬化性組成物之密接性之效果,故宜在真空狀態進行光照射。在本發明,較佳之真空度係在10-1 Pa~常壓之範圍進行。Further, in the photoimprint lithography used in the present invention, the substrate temperature at the time of light irradiation is usually performed at room temperature, but it is also possible to perform light irradiation while heating in order to improve the reactivity. In the pre-stage of light irradiation, 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 imprint lithography. Therefore, it is preferable to perform light irradiation in a vacuum state. In the present invention, it is preferred that the degree of vacuum is in the range of from 10 -1 Pa to atmospheric pressure.

本發明之壓印用硬化性組成物係混合上述各成分後,藉由以例如,孔徑0.05μm~5.0μm之過濾器進行過濾,而可調製為溶液。壓印用硬化性組成物之混合‧溶解通常係在0℃~100℃之範圍進行。過濾可為多階段進行,亦可重複多數次。又,亦可將經過濾的液體進行再過濾。過濾所使用之材質可使用聚乙烯樹脂、聚丙烯樹脂、氟樹脂、耐綸樹脂等,並無特別限定。The curable composition for imprint of the present invention is prepared by mixing the above components, and then filtering by, for example, a filter having a pore diameter of 0.05 μm to 5.0 μm to prepare a solution. The mixing of the curable composition for imprinting and the dissolution are usually carried out in the range of 0 °C to 100 °C. Filtration can be done in multiple stages or repeated many times. Alternatively, the filtered liquid can be refiltered. A polyethylene resin, a polypropylene resin, a fluororesin, a nylon resin, or the like can be used as the material used for the filtration, and is not particularly limited.

[硬化物][hardened material]

藉由上述本發明之硬化物之製造方法所形成的本發明硬化物係可作為用於液晶顯示器(LCD)等之永久膜(構造構件用光阻)或蝕刻光阻來使用。又,前述永久膜係在製造後裝瓶於加侖瓶或夸脫瓶等之容器,進行運輸、保管,此時,為了防止劣化,亦可將容器内以惰性氮或氬等取代。又,於運輸、保管時,可為常溫,為了更防止永久膜之變質,亦可溫度控制於-20℃~0℃之範圍。當然,以遮光至不進行反應的程度為較佳。The cured product of the present invention formed by the above-described method for producing a cured product of the present invention can be used as a permanent film (photoresist for a structural member) or an etching photoresist for a liquid crystal display (LCD) or the like. Further, the permanent film is bottled in a container such as a gallon bottle or a quart bottle after being manufactured, and transported and stored. In this case, in order to prevent deterioration, the inside of the container may be replaced with inert nitrogen or argon. Further, in transportation and storage, the temperature may be normal temperature, and in order to prevent deterioration of the permanent film, the temperature may be controlled within a range of -20 ° C to 0 ° C. Of course, it is preferred to be light-shielded to the extent that no reaction is carried out.

本發明之硬化物的彈性回復率從適合用來作為液晶顯示裝置用構件之觀點來看,以70%以上為較佳、以75%以上為更佳、80%以上為特佳。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.

[液晶顯示裝置用構件][Member for liquid crystal display device]

又,本發明之壓印用硬化性組成物可適用來作為半導體積體電路、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為較佳,以作為平面顯示器等之蝕刻光阻為更佳。Further, the curable composition for imprint of the present invention can be suitably used as a semiconductor integrated circuit, a recording material, and a member for a liquid crystal display device. Among them, a member for a liquid crystal display device is preferably used as an etching resist for a flat display or the like. For better.

利用本發明之壓印用組成物作為蝕刻光阻時,首先使用形成有例如SiO2 等薄膜的矽晶圓等作為基材,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、乾蝕刻時使用CF4 等蝕刻氣體進行蝕刻,藉此可在基材上形成希望的圖案。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 SiO 2 is formed is used as a substrate, and a nanoscale is formed on the substrate by the method for producing a cured product of the present invention. Fine pattern. Then, hydrogen etching or the like is used for wet etching, and etching is performed using an etching gas such as CF 4 during dry etching, whereby a desired pattern can be formed on the substrate.

[實施例][Examples]

以下舉出實施例更具體地說明本發明。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。The invention will be more specifically described below by way of examples. The materials, the amounts, the ratios, the treatment contents, the treatment procedures, and the like shown in the following examples can be appropriately changed without departing from the spirit of the invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

[實施例1][Example 1]

在下述表2所示之組成加入下述表1記載之光聚合性單體M1~M3、下述光自由基聚合起始劑P-1、下述界面活性劑W-1及W-2、下述抗氧化劑AO1,調製實施例1之壓印用硬化性組成物。又,表2中的數值為質量%。The photopolymerizable monomers M1 to M3 described in the following Table 1 and the following photoradical polymerization initiator P-1 and the following surfactants W-1 and W-2 were added to the composition shown in the following Table 2. The curable composition for imprint of Example 1 was prepared by the following antioxidant AO1. Further, the numerical values in Table 2 are mass%.

[實施例2~66、比較例1~21及25~37][Examples 2 to 66, Comparative Examples 1 to 21, and 25 to 37]

除了改為下述表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。These compositions were obtained in the same manner as the product of Example 1 except that they were changed to the compositions of the following Tables 2 to 6.

[比較例22~24][Comparative Examples 22 to 24]

將特開2006-124636號公報之表18所記載的No.8、No.9及No.11之中除去顏料,調製為比較例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)作為受阻酚系抗氧化劑,前述No.11係含有0.15質量%之Hostavin N-24(Clariant公司製)作為受阻胺系抗氧化劑。The pigments were removed from No. 8, No. 9, and No. 11 described in Table 18 of JP-A-2006-124636, and the compositions of Comparative Examples 22 to 24 were prepared. The No. 8 contains no antioxidant, and the No. 9 contains 0.15% by mass of Sumilizer MDP-S (manufactured by Sumitomo Chemical Co., Ltd.) as a hindered phenol-based antioxidant, and the No. 11 contains 0.15% by mass of Hostavin N- 24 (manufactured by Clariant Co., Ltd.) as a hindered amine-based antioxidant.

[壓印用硬化性組成物之評價][Evaluation of hardenable composition for imprint]

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。With respect to the compositions of the respective examples and comparative examples, the embossability, photocurability, heat resistance, elastic recovery ratio, and voltage characteristics were measured and evaluated according to the following evaluation methods. The results are shown in Tables 2 to 6 below.

<壓印性><embossing>

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,以膜厚成為3.0μm的方式旋塗於玻璃基板上。將經旋塗之塗布基膜安置在ORC公司製之以高壓水銀燈(燈具功率2000mW/cm2 )為光源的壓印裝置,以模具加壓力0.8kN、曝光中的真空度為10Torr(約1.33×104 Pa)之條件,以模具按壓,模具係使用具有10μm之線/間距圖案且溝槽深度為4.0μm的材質為聚二甲基矽氧烷(將東麗‧道康寧(股)製之「SILPOT184」以80℃ 60分鐘硬化而成)之物,然後,從模具表面以240mJ/cm2 的條件進行曝光。曝光後去除模具,得到光阻圖案。The pattern transferred to the photoresist evaluates to what extent the shape of the mold can be reproduced. Specifically, each of the compositions was spin-coated on a glass substrate so as to have a film thickness of 3.0 μm. The spin-coated base film was placed in an imprinting apparatus made of a high-pressure mercury lamp (lamp power of 2000 mW/cm 2 ) made by ORC, with a mold pressing pressure of 0.8 kN and an exposure vacuum of 10 Torr (about 1.33×). The condition of 10 4 Pa) was pressed by a mold, and the mold was made of a material having a line/space pattern of 10 μm and a groove depth of 4.0 μm as a polydimethyl siloxane (made by Toray ‧ Dow Corning Co., Ltd.) SILPOT 184" was cured at 80 ° C for 60 minutes, and then exposed from the surface of the mold at 240 mJ/cm 2 . After the exposure, the mold was removed to obtain a photoresist pattern.

然後,將所得光阻圖案在烘箱以230℃、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。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:模具形狀的轉印率為95%以上。5: The transfer rate of the mold shape was 95% or more.

4:模具形狀的轉印率為90%以上、小於95%。4: The transfer rate of the mold shape was 90% or more and less than 95%.

3:模具形狀的轉印率為80%以上、小於90%。3: The transfer rate of the mold shape is 80% or more and less than 90%.

2:模具形狀的轉印率為70%以上、小於80%。2: The transfer rate of the mold shape was 70% or more and less than 80%.

1:模具形狀的轉印率為小於70%。1: The transfer rate of the mold shape is less than 70%.

<光硬化性之評價><Evaluation of light hardenability>

將各組成物以膜厚成為3.0μm的方式旋塗於玻璃基板上,不壓著模具,在氮氛圍氣下以10mW、300mJ/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。Each of the compositions was spin-coated on a glass substrate so that the film thickness was 3.0 μm, and the film was exposed to a condition of 10 mW and 300 mJ/cm 2 under a nitrogen atmosphere without pressing the mold. Then, the plastic film was pressed on the surface of the film, and the residual trace (adhesiveness) at the time of peeling off the plastic film was evaluated, and the photocurability was measured.

5:完全沒有殘留痕跡。5: There are no traces at all.

4:雖有殘留痕跡,但數秒內消失。4: Although there are residual marks, they disappear within a few seconds.

3:雖有殘留痕跡,但數分內消失。3: Although there are residual marks, they disappear within a few minutes.

2:殘留痕跡,時間經過也亦未消失。2: Residual traces, and the passage of time has not disappeared.

1:膜未硬化。1: The film is not hardened.

<耐熱性><heat resistance>

將各組成物以膜厚成為3.0μm的方式旋塗於玻璃基板上,不壓著模具,在氮氛圍氣下以10mW、300mJ/cm2 的條件進行曝光。然後,在烘箱以230℃、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)。Each of the compositions was spin-coated on a glass substrate so that the film thickness was 3.0 μm, and the film was exposed to a condition of 10 mW and 300 mJ/cm 2 under a nitrogen atmosphere without pressing the mold. Then, it was hardened by heating in an oven at 230 ° C for 15 minutes. The film thickness before and after baking in the oven was measured, and the rate of reduction was determined, and the film reduction rate (film reduction) by heating was evaluated according to the following criteria.

5:230℃-150min之烘烤前後的膜減少為5%以下。The film reduction before and after baking at 5:230 ° C - 150 min was 5% or less.

4:230℃-150min之烘烤前後的膜減少為5%以上、小於10%。The film reduction before and after baking at 4:230 ° C - 150 min is 5% or more and less than 10%.

3:230℃-150min之烘烤前後的膜減少為10%以上、小於15%。The film reduction before and after baking at 3:230 ° C - 150 min is 10% or more and less than 15%.

2:230℃-150min之烘烤前後的膜減少為15%以上、小於20%。2: The film reduction before and after baking at 230 ° C - 150 min is 15% or more and less than 20%.

1:230℃-150min之烘烤前後的膜減少為20%以上。The film reduction before and after baking at 1:230 ° C - 150 min is 20% or more.

<彈性回復率之評價><Evaluation of elastic recovery rate>

將各組成物以膜厚成為3.0μm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℃、30分鐘加熱使硬化,將硬化所得的膜做成20x30x4μm的柱狀,以島津製作所製DUH-W201測定彈性回復率。Each of the compositions was spin-coated on a glass substrate so as to have a film thickness of 3.0 μm, and was exposed to light at 10 mW to 200 mJ in a nitrogen atmosphere without pressing the mold. Thereafter, the film was cured by heating in an oven at 230 ° C for 30 minutes, and the film obtained by hardening was formed into a column shape of 20 x 30 x 4 μm, and the elastic recovery ratio was measured by DUH-W201 manufactured by Shimadzu Corporation.

5:彈性回復率為80%以上。5: The elastic recovery rate is 80% or more.

4:彈性回復率為75%以上、小於80%。4: The elastic recovery rate is 75% or more and less than 80%.

3:彈性回復率為70%以上、小於75%。3: The elastic recovery rate is 70% or more and less than 75%.

2:彈性回復率為60%以上、小於75%。2: The elastic recovery rate is 60% or more and less than 75%.

1:彈性回復率為小於60%。1: The elastic recovery rate is less than 60%.

<電壓特性之評價><Evaluation of voltage characteristics>

將各組成物以膜厚成為3.0μm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℃、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。Each of the compositions was spin-coated on a glass substrate so as to have a film thickness of 3.0 μm, and was exposed to light at 10 mW to 200 mJ in a nitrogen atmosphere without pressing the mold. Thereafter, the film was cured by heating in an oven at 230 ° C for 30 minutes, 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:體積電阻為1×10E15Ω‧m以上。5: The volume resistance is 1 × 10E15 Ω or more.

4:體積電阻為5×10E14Ω‧m以上、小於1×10E15Ω‧m。4: The volume resistance is 5 × 10 E14 Ω ‧ m or more and less than 1 × 10 E15 Ω ‧ m.

3:體積電阻為1×10E14Ω‧m以上、小於5×10E14Ω‧m。3: The volume resistance is 1×10E14 Ω··m or more and less than 5×10E14 Ω·m.

2:體積電阻為1×10E13Ω‧m以上、小於1×10E14Ω‧m。2: The volume resistance is 1 × 10 E13 Ω ‧ m or more and less than 1 × 10 E14 Ω ‧ m.

1:體積電阻小於1×10E13Ω‧m。1: Volume resistance is less than 1 × 10E13 Ω ‧ m.

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8~14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17~21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38~44、比較例25及比較例31係進行在僅使用半受阻酚系抗氧化劑之態樣中,將實施例8~14的光聚合性單體M1~M3變更為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10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No.8、No.9及No.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。Here, in Examples 1 to 7 and Comparative Example 26, only the hindered phenol-based antioxidant was used, and the amount of the antioxidant added was changed. In Examples 8 to 14 and Comparative Example 27, only the semi-hindered phenol-based antioxidant was used, and the amount of the antioxidant added was changed for comparison. In Examples 15 to 21 and Comparative Example 28, only the semi-hindered phenol-based antioxidant was used, and the amount of the antioxidant added was changed for comparison. Examples 22 to 28 and Comparative Example 29 were compared using a mixture of a hindered phenol-based antioxidant and a thioether-based antioxidant, and the amount of the antioxidant added was changed. In Examples 29 to 35 and Comparative Example 30, a mixture of a semi-hindered phenol-based antioxidant and a thioether-based antioxidant was used, and the amount of the antioxidant added was changed for comparison. In Examples 36 and 37 and Comparative Examples 17 to 21, 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. In Examples 38 to 44, Comparative Example 25, and Comparative Example 31, the photopolymerizable monomers M1 to M3 of Examples 8 to 14 were changed to photopolymerizable oxygen in the case of using only the semi-hindered phenol-based antioxidant. The heterocyclic butane compounds M4 to M6 were compared and the amount of addition was changed. 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 was changed by using only the thioether-based antioxidant alone, and compared with the effect of the specific antioxidant of the examples of the present invention. Comparative Examples 22 to 24 in which the pigments in No. 8, No. 9, and No. 11 described in Table 18 of JP-A-2006-124636 were completely compared with Examples 1 to 44 of the present invention.

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。The heat resistance, the elastic recovery ratio, and the voltage characteristics of the above Table 4 and Comparative Example 2 were not measured.

由上述表2~表4可知,相對於把特開2006-124636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為壓印性、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。From the above-mentioned Tables 2 to 4, the comparative examples 22 to 24 in which the pigments in No. 8, No. 9, and No. 11 described in Table 18 of JP-A-2006-124636 are removed are described. Each of the compositions of the examples was excellent in embossability, photocurability, heat resistance, elastic recovery, and voltage characteristics. Further, in Examples 38 to 44 in which the oxetane compound was used, the effect of improving the voltage characteristics was lower than that of the other examples.

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為低評價。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11~16可知,僅使用硫醚系抗氧化劑的情況,耐熱性與彈性回復率明顯為低評價。由實施例36、37及比較例17~21的比較可瞭解,即使是例如僅使用半受阻酚系抗氧化劑之態樣,當光聚合性單體的添加量在本發明之範圍内(80質量%~99質量%)時,可同時改善光硬化性、耐熱性及彈性回復率,其係顯著的效果。又,在微調整單官能、二官能及三官能單分子之摻合量的比較例19~21中,耐熱性或彈性回復率亦無法提升,因此可知光聚合性單體的添加量為重要之要素。由實施例38~44、比較例25及比較例31之比較可知,若抗氧化劑之添加量在本案發明之範圍内(0.3~7質量%),可顯著改善耐熱性及彈性回復率。On the other hand, since Comparative Example 1 does not contain an antioxidant, heat resistance and elastic recovery rate were low. In Comparative Example 2, since the photopolymerization initiator was not contained, the evaluation was extremely low. 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. As is apparent from Comparative Examples 11 to 16, when only the thioether-based antioxidant was used, the heat resistance and the elastic recovery ratio were remarkably low. From the comparison of Examples 36 and 37 and Comparative Examples 17 to 21, it is understood that even when only a semi-hindered phenol-based antioxidant is used, the amount of the photopolymerizable monomer added is within the range of the present invention (80 mass) When the amount is from % to 99% by mass, the photocurability, heat resistance and elastic recovery ratio can be simultaneously improved, which is a remarkable effect. Further, in Comparative Examples 19 to 21 in which the blending amount of the monofunctional, difunctional, and trifunctional single molecules was finely adjusted, the heat resistance and the elastic recovery ratio could not be improved. Therefore, it was found that the amount of the photopolymerizable monomer added was important. Elements. As is clear from the comparison of Examples 38 to 44, Comparative Example 25, and Comparative Example 31, when the amount of the antioxidant added is within the range of the present invention (0.3 to 7 mass%), the heat resistance and the elastic recovery ratio can be remarkably improved.

又,由表5及表6亦可明白,抗氧化劑含量高的本發明之實施例與抗氧化劑含量少的比較例相比,耐熱性及彈性回復率係顯著地改善。Further, as can be understood from Tables 5 and 6, the examples of the present invention having a high antioxidant content are remarkably improved in heat resistance and elastic recovery ratio as compared with the comparative examples having a small antioxidant content.

Claims (10)

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為80~99質量%,前述C)抗氧化劑之含量為0.3~7質量%,前述C)抗氧化劑係受阻酚系抗氧化劑與半受阻酚系抗氧化劑之混合物。 A curable composition for embossing, comprising: A) a photopolymerizable monomer, B) a photopolymerization initiator, and C) an optical imprint composition of an antioxidant, wherein A) photopolymerization The content of the monomer is 80 to 99% by mass, and the content of the above C) antioxidant is 0.3 to 7% by mass, and the above C) is a mixture of a hindered phenol-based antioxidant and a semi-hindered phenol-based antioxidant. 如申請專利範圍第1項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。 The curable composition for imprint of claim 1, wherein the antioxidant is composed only of a semi-hindered phenol-based antioxidant. 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為80~99質量%,前述C)抗氧化劑之含量為0.3~7質量%,前述C)抗氧化劑為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。 A curable composition for embossing, comprising: A) a photopolymerizable monomer, B) a photopolymerization initiator, and C) an optical imprint composition of an antioxidant, wherein A) photopolymerization The content of the 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 semi-hindered phenol. It is a mixture of an antioxidant and a thioether antioxidant. 如申請專利範圍第3項之壓印用硬化性組成物,其中前述抗氧化劑為半受阻酚系與硫醚系之混合物。 The curable composition for imprint of claim 3, wherein the antioxidant is a mixture of a semi-hindered phenol system and a thioether system. 如申請專利範圍第1至4項中任一項所記載之壓印用硬化性組成物,其中前述抗氧化劑之含量為0.5~5質量%。 The curable 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. 如申請專利範圍第1至4項中任一項所記載之壓印用硬化性組成物,其彈性回復率為70%以上。 The curable composition for imprint according to any one of claims 1 to 4, which has an elastic recovery ratio of 70% or more. 一種硬化物,其特徵係使如申請專利範圍第1至6項中任一項所記載之壓印用硬化性組成物硬化而成。 A cured product obtained by curing the curable composition for imprint according to any one of claims 1 to 6. 一種液晶顯示裝置用構件,其特徵係包括如申請專利範圍第7項之硬化物。 A member for a liquid crystal display device, characterized by comprising a cured product as in claim 7 of the patent application. 一種硬化物之製造方法,其特徵係包括:將如申請專利範圍第1至6項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。 A method for 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. 如申請專利範圍第9項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。 The method for producing a cured product according to claim 9, which further comprises the step of heating the pattern forming layer of the irradiated light.
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