TWI408498B - Photo-curing composition and producing method of pattern using the same - Google Patents

Photo-curing composition and producing method of pattern using the same Download PDF

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TWI408498B
TWI408498B TW096124852A TW96124852A TWI408498B TW I408498 B TWI408498 B TW I408498B TW 096124852 A TW096124852 A TW 096124852A TW 96124852 A TW96124852 A TW 96124852A TW I408498 B TWI408498 B TW I408498B
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composition
photocurable composition
acrylate
meth
mold
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TW200811597A (en
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Yasumasa Kawabe
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
    • G03F7/027Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C37/00Component parts, details, accessories or auxiliary operations, not covered by group B29C33/00 or B29C35/00
    • B29C37/0053Moulding articles characterised by the shape of the surface, e.g. ribs, high polish
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00Processes of polymerisation
    • C08F2/44Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10Esters
    • C08F220/20Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • 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
    • G03F7/0002Lithographic processes using patterning methods other than those involving the exposure to radiation, e.g. by stamping
    • 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
    • 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
    • G03F7/031Organic compounds not covered by group G03F7/029
    • 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
    • G03F7/038Macromolecular compounds which are rendered insoluble or differentially wettable
    • 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
    • G03F7/075Silicon-containing compounds
    • G03F7/0757Macromolecular compounds containing Si-O, Si-C or Si-N bonds

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
  • Polymerisation Methods In General (AREA)
  • Drying Of Semiconductors (AREA)
  • Shaping Of Tube Ends By Bending Or Straightening (AREA)

Abstract

A photocurable composition is provided to have excellent properties such as photocurability, adhesion, demoldability, pattern profiles, coating uniformity, and etching appropriateness. A photocurable composition includes (a) a polymerizable compound, (b) 0.1-15% by mass of a photopolymerization initiator and/or a photoacid generator, and (c) 0.001-5% by mass of at least one selected from fluorine-based surfactants, silicon-based surfactants, and fluorine-silicon-based surfactants, and has a viscosity of 3-18 mPa.s at 25 °C. The polymerizable compound(a) contains (e) a polymerizable unsaturated monomer having a primary irritation index of 4.0 or less and (f) a polymerizable unsaturated monomer having a viscosity of 30 mPa.s or less at 25 °C, wherein the respective monomers are contained in amounts of 50% by mass or more.

Description

光硬化性組成物及使用它之圖案形成方法Photocurable composition and pattern forming method using same

本發明係有關於一種光硬化性組成物及使用它之圖案形成方法。The present invention relates to a photocurable composition and a pattern forming method using the same.

奈米壓印法係一種發展在光碟製造被熟悉的壓紋技術,將形成有凹凸圖案之模具原型(通常稱為模具、衝壓模、模板)加壓在光阻上而使其產生力學性變形,來精密地轉印微細圖案之技術。因為一次製成模具時,奈米結構能夠簡單地重複成型,所以係一種除了經濟性以外,同時有害的廢棄、排出物較少之奈米加工技術,近年來被期待應用在各式各樣的領域。The nanoimprint method is a embossing technique developed in the manufacture of optical discs. The prototype of a mold (often called a mold, a stamping die, a template) formed with a concave-convex pattern is pressed against the photoresist to cause mechanical deformation. , the technology to precisely transfer fine patterns. Since the nanostructure can be simply reshaped when it is made into a mold at one time, it is a nano processing technology that is harmful in addition to economical waste and has a small amount of waste, and has been expected to be applied to various types in recent years. field.

奈米壓印法有二種提案,包含使用熱塑性樹脂作為被加工材料時(S.Chou等人,Appl.Phys.Lett.Vol.67,114,3314(1995年));及使用光硬化性樹脂時(M.Colbun等人,Proc.SPIE,Vol.676,78(1999年)。熱式奈米壓印時係將模具加壓於已加熱至玻璃轉移溫度以上之高分子樹脂,冷卻後藉由將模具脫模來將微細結構轉印至基板上的樹脂。因為亦能夠應用在多種樹脂材料或玻璃材料,所以被期待應用在各式各樣的應用。美國專利第5,772,905號公報、美國專利第5,956,216號公報揭示一種方法,係使用熱塑性樹脂來價廉地形成奈米圖案之奈米壓印方法。There are two proposals for nanoimprinting, including the use of thermoplastic resins as materials to be processed (S. Chou et al., Appl. Phys. Lett. Vol. 67, 114, 3314 (1995)); and when using photocurable resins. (M. Colbun et al., Proc. SPIE, Vol. 676, 78 (1999). Thermal nanoimprinting is the pressing of a mold onto a polymer resin that has been heated above the glass transition temperature, after cooling. The mold is demolded to transfer the fine structure to the resin on the substrate. Since it can be applied to various resin materials or glass materials, it is expected to be applied to various applications. US Patent No. 5,772,905, US Patent No. Japanese Patent Publication No. 5,956,216 discloses a method of forming a nanoprinting method using a thermoplastic resin to form a nano pattern at a low cost.

另一方面,透過透明模具照射光,來使光硬化性組成物光硬化之光奈米印刷方式,能夠在室溫進行壓印。最近亦有報告,揭示製造組合該兩者的優點而成之奈米鑄塑法或三維積層結構之逆壓印方法等新的展開。認為此種奈米壓印法係大致有三個階段的應用。第一階段係所成型的形狀本身具有功能,能夠應用作為各種奈米技術的主要零件之情況,可舉出各種微奈米光學主要元件或高密度的記錄媒體、光學薄膜。第二階段係藉由微結構及奈米結構之同時整體成型、或簡單的層間位置配合來構築積層結構,欲應用來製造μ-TAS或生物晶片之物。第三階段係藉由高精確度的位置配合及高積體化,欲應用於製造高密度半導體用代替先前的微影法、欲應用於製造液晶顯示器的電晶體等,正積極地致力於實用化。On the other hand, a light nano-printing method in which light is irradiated through a transparent mold to photoharden the photocurable composition can be imprinted at room temperature. Recently, there have also been reports on new developments such as the nano-casting method or the reverse embossing method of three-dimensional laminated structure, which combines the advantages of the two. It is believed that this nanoimprinting method has roughly three stages of application. In the first stage, the shape formed by itself has a function and can be applied as a main part of various nano technologies, and various micro-nano optical main elements or high-density recording media and optical films can be cited. In the second stage, the laminated structure is constructed by the simultaneous molding of the microstructure and the nanostructure, or a simple interlayer positional cooperation, and is applied to manufacture a μ-TAS or a biochip. The third stage is actively applied to the manufacture of high-density semiconductors in place of the previous lithography method, and is intended to be used in the manufacture of liquid crystal displays, etc., through high-precision position matching and high integration. Chemical.

說明製造高密度半導體積體電路的應用例,來作為奈米壓印法之應用例。近年來,半導體積體電路係朝向微細化、積體化進展,為了實現該微細加工,圖案轉印技術及光微影術裝置已朝高精確度化進展。但是,加工方法接近光曝光的光源波長時,微影技術亦已接近界限。因此,為了革新微細化、高精確度化,已使用電荷粒子線裝置的一種之電子射線描繪裝置來代替微影技術。使用電子射線形成圖案時係與使用i射線、準分子雷射等光源形成圖案時採用的總曝光方法不同,因為係採用描繪光罩圖案的方法,會有描繪圖案越多時越花費曝光(描繪)時間、形成圖案越花費時間之缺點。因此,隨著積體度以256Mega、1Giga、4Giga的方式飛躍性地提高,形成對應該程度的圖案之時間亦高飛躍性地增長,產量有顯著變差的可能性。因此,為了使電子射束描繪裝置高速化,組合各種形狀的光罩而將此等總括照射電子射束,來形成複雜形狀的電子射線之總括圖形照射法的開發正進展中。結果,雖然圖案的微細化一直進展,但是因為電子射線描繪裝置必須大型化、必須具有更高精確度地控制光罩位置等之機構等,會有裝置成本變高的缺點。An application example of manufacturing a high-density semiconductor integrated circuit will be described as an application example of the nanoimprint method. In recent years, the semiconductor integrated circuit has progressed toward miniaturization and integration, and in order to realize the microfabrication, the pattern transfer technique and the photolithography apparatus have progressed with high precision. However, when the processing method is close to the wavelength of the light source for light exposure, the lithography technique is also close to the limit. Therefore, in order to innovate the miniaturization and high precision, an electron beam drawing device of a charged particle beam device has been used instead of the lithography technique. When a pattern is formed using an electron beam, it is different from the total exposure method used when forming a pattern using a light source such as an i-ray or a quasi-molecular laser, because the method of drawing a mask pattern is used, and the more the pattern is drawn, the more exposure is required (depicting Time, the more time it takes to form a pattern. Therefore, as the degree of integration is dramatically increased by 256 Mega, 1 Giga, and 4 Giga, the time for forming the pattern corresponding to the degree is also drastically increased, and the yield is significantly deteriorated. Therefore, in order to speed up the electron beam drawing device, the development of the collective pattern irradiation method in which the photomasks of various shapes are combined and the electron beams are collectively irradiated to form an electron beam having a complicated shape is progressing. As a result, although the miniaturization of the pattern has progressed, there is a disadvantage that the cost of the device becomes high because the electron beam drawing device must be large in size, and it is necessary to have a mechanism for controlling the position of the mask or the like with higher accuracy.

相對地,有提案揭示一種奈米壓印微影法,作為以低成本的方式進行形成微細圖案之技術。例如美國專利第5,772,905號公報、美國專利第5,259,926號公報揭示一種奈米壓印技術,係使用矽晶圓作為衝壓模,藉由轉印來形成25奈米以下的微細結構。In contrast, there is a proposal to disclose a nanoimprint lithography method as a technique for forming a fine pattern in a low cost manner. For example, U.S. Patent No. 5,772,905 and U.S. Patent No. 5,259,926 disclose a nanoimprint technique using a tantalum wafer as a stamping die to form a fine structure of 25 nm or less by transfer.

又,特表2005-527110號公報揭示一種使用奈米壓印而成的複合物組成物,能夠應用在半導體微影法領域。另一方面,為了將奈米壓印微影法應用於製造半導體積體電路,微細模具製造技術、模具的耐久性、模具的製造成本、模具從樹脂之剝離性、壓印均勻性、或對準精確度、檢查技術等之研討,亦開始積極地進行中。Further, Japanese Laid-Open Patent Publication No. 2005-527110 discloses a composite composition using nanoimprinting, which can be applied to the field of semiconductor lithography. On the other hand, in order to apply the nanoimprint lithography method to the manufacture of a semiconductor integrated circuit, the micro-die manufacturing technique, the durability of the mold, the manufacturing cost of the mold, the peelability of the mold from the resin, the uniformity of the imprint, or Discussions on quasi-accuracy, inspection techniques, etc. have also begun to be actively pursued.

但是,在奈米壓印微影法所使用的光阻,儘管與先前的半導體微細加工用光阻同樣地,必須具有能夠適應各種基板之蝕刻適合性或蝕刻後的剝離適合性,但是尚未充分地研討。However, the photoresist used in the nanoimprint lithography method, although similar to the conventional photoresist for semiconductor micromachining, has to be adapted to the etching suitability of various substrates or the peeling suitability after etching, but it is not yet sufficient. Research.

接著,說明在液晶顯示器(LCD)或電漿顯示器(PDP)等平面顯示器之奈米壓印微影法的應用例。隨著LCD或PDP基板大型化或高精確度的動向,使用奈米壓印微影法作為廉價的微影法來代替製造薄膜電晶體(TFT)或電極板時所使用先前的光微影法,特別受到注意。因此,有必要開發光硬化性組成物來代替在先前的光微影法所使用的蝕刻光阻。先前的光微影法所使用的蝕刻光阻被要求以高敏感度、塗膜均勻性、省光阻化為重點、以及與各種基板之黏附性、蝕刻耐性、耐熱性等,代替其之光奈米壓印光阻亦必須有同樣的特性。Next, an application example of a nanoimprint lithography method for a flat panel display such as a liquid crystal display (LCD) or a plasma display (PDP) will be described. With the large-scale or high-precision movement of LCD or PDP substrates, the nano-imprint lithography method is used as an inexpensive lithography method instead of the previous photolithography method used to fabricate thin film transistors (TFTs) or electrode plates. Special attention is paid. Therefore, it is necessary to develop a photohardenable composition instead of the etching resist used in the previous photolithography method. The etching photoresist used in the previous photolithography method is required to be high-sensitivity, uniformity of coating film, light-resistance, and adhesion to various substrates, etching resistance, heat resistance, etc., instead of the light thereof. The nanoimprint resist must also have the same characteristics.

關於塗膜均勻性,隨著基板的大型化,對於基板的中央部與周邊部之塗布膜厚度均勻性、或隨著高解像度化之尺寸均勻性、膜厚度、形狀等在各式各樣部分的要求逐漸嚴格。先前,在使用小型玻璃基板之液晶顯示元件製造領域,光阻塗布方法係使用中央滴加後旋轉之方法(電子期刊(Electronic Journal)121-123 No.8(2002年))。雖然中央滴加後旋轉之塗布法能夠得到良好的塗布性,但是例如1公尺四方的玻璃大型基板時,在旋轉時被甩掉而廢棄的光阻量相當多,又,會有因高速旋轉造成基板破裂、或確保產出時間(tact time)之問題。而且,在中央滴加後旋轉之方法時,因為塗布性能係依存旋轉時的旋轉速度及光阻的塗布量,應用於更大型化之第5世代基板時,缺少能獲得必要加速度之泛用型馬達,若特別訂購此種馬達時,會有零件成本增加之問題。又,隨著基板尺寸或裝置尺寸大型化,因為例如塗布均勻性±3%、產出時間60~70秒/片等在塗布步驟要求性能係大致沒有改變,中央滴加後旋轉之方法時,對應塗布均勻性以外之要求亦變為困難。由於如此現狀,有提案揭示一種吐出噴嘴式之光阻塗布法,能夠應用於第4世代基板以後,特別是第5世代基板以後的大型基板作為新穎的光阻塗布方法。該吐出噴嘴式之光阻塗布法係藉由使吐出噴嘴與基板相對地移動,而在基板的塗布面全面塗布光阻組成物之方法,例如有提案揭示一種方法,係使用具有由複數個噴嘴孔列狀地配列而成的吐出口或狹縫狀的吐出口,能夠將光阻組成物帶狀地吐出之吐出噴嘴。又,亦有提案揭示一種方法,係以吐出噴嘴式將光阻組成物塗布在基板的塗布面全面後,使該基板旋轉來調整膜厚度的方法。因此,為了將先前的光微影法之光阻變更為奈米壓印組成物,而應用於此等液晶顯示元件製造領域,對基板之塗布均勻性係為重要的。Regarding the uniformity of the coating film, the uniformity of the thickness of the coating film at the center portion and the peripheral portion of the substrate, or the dimensional uniformity, film thickness, shape, and the like with high resolution are various in various parts as the size of the substrate is increased. The requirements are gradually stricter. Conventionally, in the field of manufacturing liquid crystal display elements using small glass substrates, the photoresist coating method uses a method of centrally dropping and rotating (Electronic Journal 121-123 No. 8 (2002)). Although a coating method in which the center is dripped and rotated can obtain good coatability, for example, when a large-sized glass substrate of 1 m square is used, the amount of photoresist that is thrown off during rotation is considerable, and there is a high-speed rotation. Causes the substrate to rupture or ensure a tact time. In addition, in the case of the method of rotating and squeezing in the center, the coating performance is dependent on the rotation speed at the time of rotation and the amount of photoresist applied, and when it is applied to the fifth-generation substrate of a larger size, there is a lack of a general-purpose type capable of obtaining the necessary acceleration. Motors, if you order such a motor, there will be an increase in the cost of parts. Further, as the size of the substrate or the size of the device is increased, for example, the coating uniformity is ±3%, the production time is 60 to 70 seconds/piece, and the like, and the performance is required to be substantially unchanged in the coating step, and the method of rotating after the center is added and then Requirements other than coating uniformity also become difficult. In view of the current situation, there is a proposal to disclose a discharge nozzle type photoresist coating method which can be applied to a fourth generation substrate, in particular, a large substrate after the fifth generation substrate, as a novel photoresist coating method. The discharge nozzle type photoresist coating method is a method in which a photoresist composition is entirely applied to a coated surface of a substrate by moving the discharge nozzle relative to the substrate. For example, it is proposed to disclose a method in which a plurality of nozzles are used. The discharge port or the slit-shaped discharge port which is arranged in the form of a row of holes can discharge the nozzle of the photoresist composition in a strip shape. Further, there has been proposed a method of coating a photoresist composition on a coating surface of a substrate by a discharge nozzle type, and rotating the substrate to adjust the film thickness. Therefore, in order to change the photoresist of the conventional photolithography method to a nanoimprint composition, it is applied to the field of manufacturing such liquid crystal display elements, and the uniformity of coating of the substrate is important.

在製造半導體積體電路或製造液晶顯示器所使用的正型光阻或製造彩色濾光片用顏料分散光阻等,添加氟系及/或矽系界面活性劑,來解決塗布性、具體而言如在基板上塗布時之條紋、或鱗狀的花紋(光阻膜的乾燥不均)等塗布不良的問題係眾所周知的(特開平7-230165號公報、特開2000-181055號公報、特開2004-94241號公報)。又,為了改良小型雷射唱片(CD,compact disk)、光磁碟等之保護膜的磨耗性或塗布性,有揭示在無溶劑系光硬化性組成物添加氟系界面活性劑或矽系界面活性劑(特開2004-94241號公報、特開平4-149280號公報、特開平7-62043號公報、特開2001-93192號公報)。同樣地,為了改良噴墨用組成物的印墨吐出性,已知在特開2005-8759號公報,係添加非離子系氟系界面活性劑。而且,在特開2003-165930號公報,使用全息照像加工用模具對使用毛刷、筆、棒塗布器等厚膜地塗布而成的塗料組成物進行紋加工時,添加1%以上含聚合性不飽和雙鍵之界面活性劑、較佳是3%以上,來改良硬化膜的水潤脹性之例子。如此,在正型光阻、彩色濾光片製造用顏料分散光阻、或光磁碟等的保護膜添加界面活性劑,來改良塗布性之技術係眾所周知的的技術。又,從上述噴墨、或塗料組成物的例子可以得知,為了在無溶劑系光硬化性樹脂添加界面活性劑,來改良在各自用途的特性,添加界面活性劑之技術亦是眾所周知的。但是,提高並非以顏料、染料、有機溶劑作為必要成分之低黏度的光硬化性奈米壓印光阻組成物的基板塗布性之方法,以往並未知悉。In the production of a semiconductor integrated circuit, a positive photoresist used in the manufacture of a liquid crystal display, or a pigment dispersion resist for color filters, and the like, a fluorine-based and/or a lanthanum-based surfactant is added to solve the coating property, specifically For example, the problem of coating defects such as streaks or scaly patterns (drying unevenness of the photoresist film) when applied on a substrate is known (Japanese Unexamined Patent Publication No. Hei No. Hei 7-230165, No. 2000-181055, No. Bulletin 2004-94241). Further, in order to improve the abrasion resistance or coating property of a protective film such as a compact compact disc (CD) or a magneto-optical disc, it is disclosed that a fluorine-based surfactant or a lanthanoid interface is added to the solvent-free photocurable composition. The active agent is disclosed in JP-A-2004-94241, JP-A-4-149280, JP-A-7-62043, and JP-A-2001-93192. In the same manner, in order to improve the ink discharge property of the composition for inkjet, it is known to add a nonionic fluorine-based surfactant to JP-A-2005-8759. In the holographic image processing die, when a paint composition coated with a thick film such as a brush, a pen, or a bar coater is subjected to embossing, a polymerization of 1% or more is added. The surfactant of the unsaturated double bond, preferably 3% or more, is an example of improving the water swellability of the cured film. As described above, a technique known as a technique for improving the coating property by adding a surfactant to a protective film such as a positive-type resist, a pigment dispersion resist for color filter production, or a magneto-optical disk is known. Further, from the examples of the above-described inkjet or coating composition, it is known that a technique of adding a surfactant to a solventless photocurable resin to improve the properties of each application is also known. However, a method of improving the substrate coating property of a low-viscosity photocurable nanoimprint resist composition which is not an essential component of a pigment, a dye or an organic solvent has not been known.

而且,在平面顯示器領域,在變更先前的光微影法為奈米壓印微影法之步驟時,在塗布、曝光、模具剝離、加熱(後烘焙)時,強烈地要求光硬化性組成物的構成成分不揮發。在光奈米壓印微影法的步驟通常使用的光硬化性組成物的光聚合性單體成分,與先前光微影法所使用的酚醛清漆樹脂或萘醌二疊氮感光劑比較時,分子量較小、容易揮發(蒸發)之物較多。光硬化性組成物的成分揮發時,會產生步驟污染,在製造顯示器時不僅使產率變差,而且,作業者吸入或接觸到揮發的蒸氣時,亦會影響到作業者皮膚發炎等作業者的安全性。由此觀點,應用於奈米壓印之光硬化性組成物的成分,必須選擇不容易揮發、且一次皮膚刺激性(PII值)盡可能較小的材料。Further, in the field of flat panel displays, when the previous photolithography method is changed to the step of the nanoimprint lithography method, the photocurable composition is strongly required during coating, exposure, mold peeling, and heating (post-baking). The constituents are not volatile. When the photopolymerizable monomer component of the photocurable composition generally used in the step of photon lithography is compared with the novolak resin or naphthoquinone diazide sensitizer used in the previous photolithography method, It has a small molecular weight and is more volatile (evaporated). When the components of the photocurable composition are volatilized, step contamination occurs, which not only deteriorates the yield when manufacturing the display, but also affects the operator's skin inflammation and the like when the operator inhales or contacts the volatilized vapor. Security. From this point of view, it is necessary to select a material which is applied to the photocurable composition of the nanoimprint, and it is necessary to select a material which is not easily volatilized and which has a primary skin irritation (PII value) as small as possible.

又,應用含有有機溶劑之光奈米壓印光阻時,塗布後,必須使溶劑揮發。使用含有此種考慮的有機溶劑之組成物時,因為吸入揮發的溶劑等對作業者的安全性、或對步驟工數的簡略化係不利的,強烈地要求開發未含有有機溶劑之組成物。Further, when a photon imprinting resist containing an organic solvent is used, it is necessary to volatilize the solvent after coating. When a composition containing an organic solvent having such a consideration is used, since the solvent which is volatilized by suction or the like is unfavorable to the safety of the operator or the simplification of the number of steps, it is strongly required to develop a composition which does not contain an organic solvent.

更詳細地說明本發明的應用範圍之光奈米壓印之先前技術。光奈米壓印微影法通常有在矽晶圓、石英、玻璃、薄膜、或其他材料、例如陶瓷材料、金屬或聚合物等的基板上滴加液狀的光硬化性組成物,以大約數十奈米~數微米的膜厚塗布,再將具有大約數十奈米~數十微米圖案尺寸的微細凹凸之模具壓住而加壓,在加壓狀態進行光照射來使組成物硬化後,使模具從塗膜脫模,來得到已轉印的圖案之方法。因此,光奈米壓印微影法時,為了進行光照之理由,基板或模具的至少一方必須透明。通常,一般的情況係從模具側進行光照射,模具材料多半係使用石英、藍寶石等透射UV光之無機材料或光透射性的樹脂等。The prior art of the light nanoimprint of the application range of the present invention is explained in more detail. The light nanoimprint lithography method generally has a liquid photocurable composition dripped on a substrate of ruthenium wafer, quartz, glass, film, or other material such as ceramic material, metal or polymer, to approximately A film thickness of several tens of nanometers to several micrometers is applied, and a mold having fine unevenness of a pattern size of about several tens of nanometers to several tens of micrometers is pressed and pressurized, and light is irradiated under pressure to harden the composition. A method of releasing a mold from a coating film to obtain a transferred pattern. Therefore, in the case of the photon imprint lithography method, at least one of the substrate or the mold must be transparent for the purpose of illumination. Usually, in general, light irradiation is performed from the mold side, and most of the mold material is an inorganic material that transmits UV light such as quartz or sapphire, or a light-transmitting resin.

光奈米壓印法與熱奈米壓印法比較時,可舉出以下的主要優點,(1)不須要加熱/冷卻步驟,預期產量較高,(2)因為使用液狀組成物,能夠使用低加壓來進行奈米壓印,(3)無因熱膨脹之尺寸變化,(4)模具透明,所以對準容易,(5)硬化後,能夠得到堅強的三維交聯體等。特別是適用於例如要求對準精確度半導體微細加工用途、或平面面板顯示器領域之微細加工用途。When comparing the nano-imprint method with the hot nano-imprint method, the following main advantages can be mentioned: (1) the heating/cooling step is not required, and the expected yield is high, and (2) because of the use of the liquid composition, Low pressurization is used for nanoimprinting, (3) no dimensional change due to thermal expansion, (4) the mold is transparent, so alignment is easy, and (5) after hardening, a strong three-dimensional crosslinked body can be obtained. In particular, it is suitable for use in, for example, microfabrication applications requiring alignment precision semiconductor microfabrication or in the field of flat panel displays.

又,光奈米壓印法之其他特徵係與通常的光微影法比較時因為解像度未依存光源波長,而具有即便奈米等級之微細加工亦不須要步進機或電子射線描繪裝置等高價的裝置之特徵。另一方面,光奈米壓印微影法必須等倍模具,因為模具與樹脂接觸,必須顧慮模具的耐久性或成本。而且,在光奈米壓印微影步驟容易產生殘膜(使模具凸部分壓住光硬化性組成物之位置)。該殘膜層越薄時,能夠使用奈米壓印形成的結構體越精密,乃是較佳,又,殘膜多時,在蝕刻時亦容易成為線寬度控制性或蝕刻殘渣。Moreover, the other characteristics of the photon imprinting method are compared with the conventional photolithography method because the resolution does not depend on the wavelength of the light source, and the microfabrication of the nanometer level does not require a high price such as a stepper or an electron beam drawing device. The characteristics of the device. On the other hand, the photon imprint lithography method must be equal to the mold, because the mold must be in contact with the resin, and the durability or cost of the mold must be considered. Further, in the photonic embossing lithography step, a residual film is easily generated (the position where the convex portion of the mold is pressed against the photocurable composition). The thinner the residual film layer is, the more precise the structure can be formed by nanoimprinting, and the more the residual film is, the more easily the wire width control property or the etching residue is at the time of etching.

如此,應用熱式及/或光奈米壓印法來將奈米尺寸的圖案大面積地壓印時,不僅是要求壓住壓力的均勻性或原版(模具)的平坦性,而且亦必須控制因被壓住而流出之光阻的舉動。因為先前的半導體技術能夠在晶圓上任意地設定不作為元件使用的區域,所以能夠使用小的原版在壓印部的外側設置光阻流出部。又,半導體時係將壓印不良部分作為不良元件而不使用即可,但是例如應用於硬碟等的情況,因為必須以整面作為元件的功能,所以必須特別地設法使印壓缺陷不產生。Thus, when applying thermal and/or photon imprinting to imprint a nano-sized pattern over a large area, it is not only required to suppress the uniformity of the pressure or the flatness of the original (mold), but also must be controlled. The action of the light resistance that flows out due to being pressed. Since the prior semiconductor technology can arbitrarily set a region that is not used as an element on a wafer, it is possible to provide a photoresist outflow portion outside the embossed portion using a small original plate. Further, in the semiconductor case, the defective portion is not used as a defective element. However, for example, when it is applied to a hard disk or the like, since it is necessary to use the entire surface as a function of the element, it is necessary to specifically seek to prevent the printing defect from occurring. .

光奈米壓印微影法所使用的模具,能夠由各式各樣的材料、例如金屬、半導體、陶瓷、SOG(旋塗式玻璃;Spin On Glass)、或規定的塑膠等製造。例如,國際公開WO99/22849號小冊子所記載之提案,揭示一種具有需要的微細結構之柔軟的聚二甲基矽氧烷的模具。為了在該模具的表面形成三維結構體,能夠按照相對於結構體的尺寸及其分解性能之規格,使用各式各樣的微影方法。電子射線及X射線的微影法通常能夠使用於小於300奈米的結構體尺寸。直接雷射曝光及UV微影法能夠使用於較大的結構體。The mold used in the photon lithography method can be manufactured from various materials such as metal, semiconductor, ceramic, SOG (Spin On Glass), or a prescribed plastic. For example, the proposal described in the pamphlet of International Publication WO99/22849 discloses a mold having a soft polydimethyl siloxane having a desired fine structure. In order to form a three-dimensional structure on the surface of the mold, various lithography methods can be used in accordance with the specifications of the size of the structure and its decomposition performance. The lithography of electron ray and X-ray can generally be used for structural sizes of less than 300 nm. Direct laser exposure and UV lithography can be used for larger structures.

關於光奈米壓印法,模具與光硬化性組成物之剝離性係重要的,模具或模具的表面處理,具體上,以往嘗試使用氫化倍半矽氧烷(HSQ:Hydrogen Silsequioxane)或氟化乙烯丙烯共聚物模具來解決黏附問題。Regarding the photon imprint method, the releasability of the mold and the photocurable composition is important, and the surface treatment of the mold or the mold, specifically, attempts to use hydrogenated silsesquioxane (HSQ: Hydrogen Silsequioxane) or fluorination. Ethylene propylene copolymer mold to solve the adhesion problem.

在此,說明光奈米壓印微影法所使用的光硬化性樹脂。能夠應用在奈米壓印之光硬化性樹脂,從反應機構的不同,可大致區分為自由基聚合型式及離子聚合型式、或是該等的混合型式。任一者之組成物都能夠壓印,通常係使用材料選擇範圍較廣闊的自由基聚合型(F.Xu等人,SPIE微影研討會(SPIE Microlithography Conference),5374,232(2004年))。自由基聚合型通常係使用具有能夠自由基聚合之乙烯基或(甲基)丙烯基之單體或低聚物與光聚合引發劑之組成物。光照射時,從光聚合引發劑產生的自由基會攻擊乙烯基而進行連鎖聚合,來形成聚合物。以2官能以上多官能基單體或低聚物作為成分使用時能夠得到交聯結構體。D.J.Resnick等人,J.Vac.Sci.Technol.B,第21卷,No.6,2624(第2003年)揭示一種組成物,藉由使用低黏度之能夠UV硬化的單體,能夠在低壓、室溫下進行壓印。Here, the photocurable resin used in the photo nanolithography method will be described. The photocurable resin which can be applied to nanoimprinting can be roughly classified into a radical polymerization type, an ion polymerization type, or a mixed type depending on the reaction mechanism. Any of the components can be embossed, usually using a radically polymerized type with a wide range of material selection (F.Xu et al., SPIE Microlithography Conference, 5374, 232 (2004)) . The radical polymerization type is usually a composition using a monomer or oligomer having a radically polymerizable vinyl group or a (meth) propylene group and a photopolymerization initiator. At the time of light irradiation, radicals generated from the photopolymerization initiator attack the vinyl group and undergo chain polymerization to form a polymer. When a bifunctional or higher polyfunctional monomer or oligomer is used as a component, a crosslinked structure can be obtained. DJ Resnick et al., J. Vac. Sci. Technol. B, Vol. 21, No. 6, 2624 (2003) discloses a composition that can be used at low pressure by using a low viscosity UV curable monomer. Imprint at room temperature.

詳細地說明在光奈米壓印微影法所使用材料的特性。材料的要求特性係依照應用用途而不同,但在步驟特性的要求係具有與用途無關的共同點。例如,在最新光阻材料手冊第1頁、第103~104頁(2005年、情報機構出版)所示之主要項目有塗布性、基板黏附性、低黏度(<5mPa.s)、脫模性、低硬化收縮率、速硬化性等。特別是在必須低壓壓印、降低殘膜率之用途,已知強烈地要求低黏度材料。另一方面,舉出因用途別而要求的特性時,例如光學構件有折射係數、光的透射性等、及蝕刻光阻之蝕刻耐性或殘膜厚度降低等。如何控制此等特性、如何取得各種特性的平衡,成為材料設計的關鍵。因為至少步驟材料與永久膜之要求特性不同,所以材料必須按照步驟或用途來開發。應用於此種光奈米壓印微影法用途之材料,最近光阻材料手冊,第1頁、第103~104頁(2005年、情報機構出版)所揭示之具有約60mPa.s(25℃)的黏度之光硬化性材料係眾所周知的。同樣地,CMC出版,奈米壓印的開發及應用,第159~160頁(2006)所揭示之含氟感光性樹脂(以丙烯酸單甲酯作為主成分、黏度為14.4mPa.s、已提高脫膜性)。The characteristics of the materials used in the photon lithography method will be described in detail. The required characteristics of the materials vary depending on the application, but the requirements of the step characteristics have in common with the use. For example, in the latest photoresist materials manual, page 1, page 103~104 (2005, published by the intelligence agency), the main items are coating properties, substrate adhesion, low viscosity (<5mPa.s), mold release. , low hardening shrinkage rate, quick hardenability, etc. In particular, in applications where low pressure imprinting is required and the residual film ratio is lowered, it is known that a low viscosity material is strongly required. On the other hand, when characteristics required for use are mentioned, for example, the optical member has a refractive index, light transmittance, and the like, and the etching resistance of the etching resist or the thickness of the residual film is lowered. How to control these characteristics and how to achieve a balance of various features becomes the key to material design. Because at least the material of the step differs from the desired properties of the permanent film, the material must be developed in accordance with the steps or uses. Materials used in such photon nanoimprint lithography methods, recently disclosed in the Handbook of Photoresist Materials, page 1, pages 103-104 (2005, published by the intelligence agencies) have about 60mPa. Photocurable materials of s (25 ° C) viscosity are well known. Similarly, CMC Publishing, Development and Application of Nanoimprint, 159-160 (2006) discloses a fluorine-containing photosensitive resin (with a monomethyl acrylate as a main component and a viscosity of 14.4 mPa·s, which has been improved). Release property).

關於在此種光奈米壓印使用組成物,雖然有記載關於黏度之要求,但是以往並沒有用以適合各用途之材料的設計方針的報告例。Regarding the composition for use in such a photon embossing, there is a description of the viscosity of the composition, but there is no report example of a design policy for materials suitable for each application.

說明以往應用於光奈米壓印微影法之光硬化性樹脂的例子。特開2004-59820號公報、特開2004-59822號公報揭示一種使用光硬化性樹脂,來進行壓紋加工,該光硬化性樹脂具有含異氰酸酯基用以製造浮凸型全息照像或繞射格子之聚合體。又,美國公開2004/110856號公報揭示一種含有聚合物、光聚合引發劑、及黏度調整劑之奈米壓印用光硬化性組成物。An example of a photocurable resin which has been conventionally applied to a photon lithography method will be described. JP-A-2004-59820 discloses an embossing process using a photocurable resin having an isocyanate group for producing an embossed hologram or diffraction. A polymer of lattices. Further, U.S. Patent Publication No. 2004/110856 discloses a photocurable composition for nanoimprinting containing a polymer, a photopolymerization initiator, and a viscosity modifier.

N.Sakai等人在J.Photopolymer Sci.Technol.第18卷,No.4,531(2005年),揭示將組合(1)官能性丙烯酸單體、(2)官能性丙烯酸單體、(3)官能性丙烯酸單體與光聚合引發劑而成之光硬化性自由基聚合性組成物、或含有光硬化性環氧化合物與光酸產生劑之光陽子聚合物組成物等應用於光奈米壓印微影法,來調整熱安定性或模具剝離性等之例子。N. Sakai et al., J. Photopolymer Sci. Technol. Vol. 18, No. 4, 531 (2005), discloses combining (1) functional acrylic monomers, (2) functional acrylic monomers, (3) functional groups. Photocurable radical polymerizable composition obtained by using an acrylic monomer and a photopolymerization initiator, or a photo-cationic polymer composition containing a photocurable epoxy compound and a photoacid generator, etc., is applied to photon imprinting The lithography method is used to adjust examples of thermal stability or mold peelability.

M.Stewart等人在MRS Bu1etin第30期,No.12,947(2005年),揭示一種光硬化性組成物,係含有(1)官能性丙烯酸單體、(2)含有官能丙烯酸單體、含矽之1官能丙烯酸單體、及光聚合引發劑,用以設法改良光硬化性樹脂與模具等的剝離性、硬化後的膜收縮性、在氧存在下因光聚合阻礙所產生的低敏感度化等問題。M. Stewart et al., MRS Bu1etin, No. 30, 947 (2005), discloses a photocurable composition comprising (1) a functional acrylic monomer, (2) a functional acrylic monomer, and a ruthenium containing The monofunctional acrylic monomer and the photopolymerization initiator are used to improve the peelability of the photocurable resin and the mold, the film shrinkage after curing, and the low sensitivity caused by photopolymerization inhibition in the presence of oxygen. And other issues.

T.Beiley等人在J.Vac.Sci.Technol.B18(6),3572(2000年)揭示在矽基板上形成含有1官能丙烯酸單體、含1官能矽之單體、及光聚合引發劑之光硬化性組成物,能夠減少使用已表面處理過的模具藉由光奈米壓印微影法成型後的缺陷。T. Beiley et al., J. Vac. Sci. Technol. B18 (6), 3572 (2000) discloses the formation of a monofunctional acrylate monomer, a monofunctional fluorene containing monomer, and a photopolymerization initiator on a ruthenium substrate. The photocurable composition can reduce defects after molding using a surface-treated mold by a photo nano-imprint lithography method.

B.Vratzov等人在J.Vac.Sci.Technol.B21(6),2760(2003年)揭示在矽基板上形成含有矽單體、3官能丙烯酸單體、及光聚合引發劑之光硬化性組成物,藉由SiO2 模具,能夠得到高解像性、塗布均勻性優良的組成物。B. Vratzov et al., J. Vac. Sci. Technol. B21 (6), 2760 (2003), discloses the formation of photohardenability on a ruthenium substrate containing a ruthenium monomer, a trifunctional acrylate monomer, and a photopolymerization initiator. In the composition, a composition excellent in high resolution and uniform coating properties can be obtained by the SiO 2 mold.

E.K.Kim等人在J.Vac.Sci.Technol.B22(1),131(2004年)揭示使用組合特定的乙烯基醚化合物及光酸產生劑而成的陽離子聚合性組成物,來形成50奈米圖案大小的例子。雖然具有黏性低、且硬化速度快之特徵,但是亦敘述到有模板剝離性的問題。EKKim et al., J. Vac. Sci. Technol. B22(1), 131 (2004) disclose the use of a cationically polymerizable composition comprising a combination of a specific vinyl ether compound and a photoacid generator to form 50 Nai. An example of the size of a rice pattern. Although it has the characteristics of low viscosity and fast curing speed, it also describes the problem of template peelability.

但是,如N.Sakai等人在J.Photopolymer Sci.Technol.第18卷,No.4,531(2005年),M.Stewart等人在MRS Buletin第30期,No.12,947(2005年),T.Beiley等人在J.Vac.Sci.Technol.B18(6),3572(2000年),B.Vratzov等人在J.Vac.Sci.Technol.B21(6),2760(2003年),E.K.Kim等人在J.Vac.Sci.Technol.B22(1),131(2004年)所示,雖然將不同官能基之丙烯酸單體、丙烯酸聚合物、乙烯基醚化合物應用於光奈米壓印微影法之光硬化性組成物而有各式各樣的揭示,但是關於組成物之較佳種類、最佳單體物種、單體的組合、單體或光阻的最佳黏度、光阻之較佳溶液物性、光阻的塗布性改良等材料設計之方針,完全沒有揭示。因此,在光奈米壓印微影法用途,目前尚未知道有好的組成物能夠用以將該組成物廣泛地應用,絕對能夠滿足的光奈米壓印光阻組成物,實際上亦尚未有提案。However, as in N. Sakai et al., J. Photopolymer Sci. Technol. Vol. 18, No. 4, 531 (2005), M. Stewart et al., MRS Buletin, No. 30, 947 (2005), T. Beiley et al., J. Vac. Sci. Technol. B18 (6), 3572 (2000), B. Vratzov et al., J. Vac. Sci. Technol. B21 (6), 2760 (2003), EKKim Et al., J. Vac. Sci. Technol. B22(1), 131 (2004), although different functional acrylic monomers, acrylic polymers, vinyl ether compounds are applied to the photon imprinting micro There are various revelations of the light-curing composition of the photo method, but the best kind of composition, the best monomer species, the combination of monomers, the optimum viscosity of the monomer or photoresist, and the photoresist The material design guidelines for improving the physical properties of the solution and the improvement of the coating properties of the photoresist are not disclosed at all. Therefore, in the use of photon nanoimprint lithography, it is not known that a good composition can be widely used for the composition, and the photon imprinting resist composition which can be absolutely satisfied can not be actually There are proposals.

為了改良光聚合系組成物的PII值之化合物的設想,例如藉由在丙烯酸系單體加添環氧乙烷、環氧丙烷等、高分子量化、單體的環結構化、改變分枝等酯基的骨架,來嘗試進行降低皮膚刺激性(RadTech研究會編:新UV-EB硬化技術及應用展開、CMC(1997年)、美國專利第5,543,557號公報)。通常,甲基丙烯酸酯與丙烯酸酯比較,雖然有皮膚刺激性低之優點,但是亦已知反應性較低。又,上述乙烯基醚化合物與丙烯酸酯比較時,雖然有能夠改良PII值之優點,但是反應性較低。如此,雖然直至此時皮膚刺激性的改良已被檢討了,但是會有黏度上升、反應性下降等問題點。In order to improve the compound of the PII value of the photopolymerizable composition, for example, by adding ethylene oxide, propylene oxide, or the like to the acrylic monomer, high molecular weight, ring structure of the monomer, change of branching, etc. The backbone of the ester group is attempted to reduce skin irritation (RadTech Research Society: New UV-EB Hardening Technology and Application Development, CMC (1997), US Patent No. 5,543,557). In general, methacrylate has a lower reactivity than acrylate, but is also known to have low reactivity. Further, in comparison with the acrylate, the vinyl ether compound has an advantage of being able to improve the PII value, but has low reactivity. In this way, although the improvement of skin irritation has been reviewed until now, there are problems such as an increase in viscosity and a decrease in reactivity.

特開平4-149280號公報、特開2001-93192號公報、特開2003-165930號公報、特開平2-6562號公報、特開平7-70472號公報、特開平7-53895號公報揭示比較低黏度且低皮膚刺激性的光硬化性組成物,係將PII值低的(甲基)丙烯酸單體或丙烯醯胺應用於小型雷射唱片或光磁碟的保護膜、塗料、印墨。但是將該等組成物任一種的黏度都高,應用於奈米壓印組成物時,模具轉印後,殘膜多而難以應用作為基板加工用的光阻。又,作為小型雷射唱片或光磁碟的保護膜時,該等光硬化性組成物在微細的圖案形成性能、基板加工的蝕刻性有變差的傾向。Japanese Laid-Open Patent Publication No. Hei-4-149280, JP-A-2001-93192, JP-A-2003-165930, JP-A No. 2-6562, JP-A-7-70472, and JP-A No. 7-53895 disclose a relatively low disclosure. A photocurable composition having a low viscosity and a low skin irritation is a (meth)acrylic monomer or acrylamide having a low PII value applied to a protective film, a coating material, or an ink for a compact laser or a magneto-optical disk. However, any of these compositions has a high viscosity, and when applied to a nanoimprinting composition, after the transfer of the mold, there are many residual films, and it is difficult to apply a photoresist for substrate processing. Moreover, when it is a protective film of a small compact disc or a magneto-optical disk, these photocurable compositions tend to have poor pattern formation performance and etchability of substrate processing.

詳細地說明在基板加工用蝕刻光阻之應用。蝕刻光阻並不是直接留下之主要成分,只不過是用以複製半導體或電晶體電路的圖案。為了製造電路圖案,必須將含有該等光阻圖案之元件轉印至各種層。轉印圖案之方法能夠藉由選擇去除未被光阻被覆的部分之蝕刻步驟來進行。例如,製造TFT陣列基板及PDP的電極板,係藉由在玻璃或透明塑膠基板上之已濺鍍的導電性基材或絕緣性基材上,對各層薄膜施行塗布蝕刻光阻,並乾燥、圖案曝光、顯像、蝕刻、光阻剝離的步驟來進行。以往蝕刻光阻多半是使用正型光阻。特別是以鹼可溶性苯酚酚醛清漆樹脂及1,2-苯醌二疊氮化合物作為主要成分之光阻或以(聚)羥基苯乙烯作為聚合物之化學放大型光阻,因為具有高蝕刻耐性,且剝離亦容易,以往被廣泛地使用於半導體或TFT電晶體的蝕刻光阻,而累積了許多見識。蝕刻有使用各種液體蝕刻劑之濕式蝕刻法、及使用在減壓裝置內藉由電漿使氣體分解所產生的離子、或自由基(活性種,reactive species),來氣化除去基板上的膜之乾式蝕刻法。蝕刻係對元件的設計精確度、電晶體特性、產率、成本有重大影響之重要步驟,蝕刻光阻必須是在乾式蝕刻及濕式蝕刻任一者都能夠應用的材料、必須具有步驟適合性。將光奈米壓印微影法所使用的組成物,應用於使用以往的微影法之光阻領域時,必須與以往的光阻具有同樣的蝕刻性,因為未充分地檢討,在蝕刻步驟會產生各式各樣的問題。The application of the etching resist for substrate processing will be described in detail. Etching photoresist is not a major component left directly, but is a pattern used to replicate semiconductor or transistor circuits. In order to manufacture a circuit pattern, components containing the photoresist patterns must be transferred to various layers. The method of transferring the pattern can be performed by an etching step of selectively removing a portion not covered by the photoresist. For example, the electrode plate for manufacturing the TFT array substrate and the PDP is coated and etched on each layer of the thin film by a sputtered conductive substrate or an insulating substrate on a glass or transparent plastic substrate, and dried. The steps of pattern exposure, development, etching, and photoresist peeling are performed. In the past, most of the etching photoresist was a positive photoresist. In particular, a photoresist having a base-soluble phenol novolak resin and a 1,2-benzoquinonediazide compound as a main component or a chemically amplified photoresist having a (poly)hydroxystyrene as a polymer, because of high etching resistance, Moreover, peeling is also easy, and it has been widely used in the etching resist of a semiconductor or a TFT transistor, and has accumulated a lot of knowledge. Etching is performed by a wet etching method using various liquid etchants, and using ions or radicals generated by decomposing a gas by plasma in a decompression device to vaporize and remove the substrate. Dry etching of the film. The etching process is an important step that has a significant influence on the design accuracy, transistor characteristics, yield, and cost of the device. The etching photoresist must be a material that can be applied to either dry etching or wet etching, and must have step suitability. . When the composition used in the photon lithography method is applied to the field of photoresist using the conventional lithography method, it must have the same etching property as the conventional photoresist because it is not sufficiently reviewed in the etching step. There will be a wide variety of problems.

蝕刻光阻之主要的技術課題係圖案加工尺寸精確度的提高、錐角加工控制性的提升(凹陷(undercut)形狀的改善)、在大型基板之蝕刻均勻性提升、與下層之蝕刻選擇性的提升、蝕刻處理速度的提升、多層膜總括蝕刻性、廢液、廢氣等的安全性確保、蝕刻後的膜上缺陷(微粒、殘渣)的改良等許多課題。將光奈米壓印用光硬化性組成物應用作為蝕刻光阻時,與先前的正型光阻同樣地,(1)對於因膜種而選擇之蝕刻劑、蝕刻氣體的適合性,(2)為了不產生凹陷,而賦予圖案與蝕刻加工基板之黏附性,(3)為了改良蝕刻前之圖案尺寸的控制性,賦予蝕刻液與光阻之潤濕性係重要的。The main technical problems of etching photoresist are the improvement of the dimensional accuracy of the pattern processing, the improvement of the control of the taper angle processing (the improvement of the undercut shape), the improvement of the etching uniformity on the large substrate, and the selective etching with the lower layer. There are many problems such as improvement in lifting speed, improvement in etching processing speed, overall film etching resistance, waste liquid, exhaust gas, and the like, and improvement of defects (particles, residues) on the film after etching. When the photocurable composition for photon imprinting is applied as an etching resist, (1) the suitability of an etchant or an etching gas selected for the film type, similar to the previous positive resist (2) In order to improve the adhesion between the pattern and the etching substrate in order to prevent the occurrence of the depression, (3) it is important to impart wettability between the etching liquid and the photoresist in order to improve the controllability of the pattern size before etching.

但是,奈米壓印光硬化性組成物除了上述(1)~(3)以外,從以下所舉出的(4)(5)(6)的觀點,技術性難度更高。(4)為了提高與模具的剝離性,使光阻膜為疏水性時,蝕刻液與光阻的潤濕性變為更差,容易產生蝕刻殘渣。(5)因為光硬化性組成物係具有3維的網狀結構,與正型光阻比較時較難剝離,又,雖然藉由網狀結構變為堅固,能夠改善耐蝕刻性,但是剝離變為更難。(6)與先前的光微影法比較時,因為光奈米壓印微影法在模具剝離後,在欲蝕刻除去的部分容易產生殘渣,蝕刻亦容易產生殘渣等。However, in addition to the above (1) to (3), the nanoimprinted photocurable composition is more technically difficult from the viewpoints of (4), (5), and (6) described below. (4) In order to improve the peeling property with the mold and make the photoresist film hydrophobic, the wettability of the etching liquid and the photoresist is further deteriorated, and etching residue is likely to occur. (5) Since the photocurable composition has a three-dimensional network structure, it is difficult to peel off when compared with a positive photoresist, and although the mesh structure becomes strong, etching resistance can be improved, but peeling is changed. It is even harder. (6) When compared with the conventional photolithography method, the photon nanoimprint lithography method is likely to cause residue in the portion to be etched and removed after the mold is peeled off, and the residue is likely to be generated by etching.

關於奈米壓印用光硬化性組成物,雖然已揭示各種材料,但是目前尚未有能夠在奈米壓印的光微影步驟、蝕刻步驟、剝離步驟之任一步驟都適用之奈米壓印材料的揭示或材料的設計方針。又,以往在壓印用組成物或光磁碟用保護膜的用途已知的光硬化性組成物,雖然在光微影步驟的材料有共同的部分,但是因沒有蝕刻步驟或剝離步驟,所以與蝕刻光阻的差異大。因此,若將此等用途所應用的光硬化性樹脂直接應用作為蝕刻光阻時,在蝕刻步驟或剝離步驟多半會產生問題。Regarding the photocurable composition for nanoimprinting, although various materials have been disclosed, there is currently no nanoimprint which can be applied to any step of the photolithography step, the etching step, and the stripping step of the nanoimprinting. Material disclosure or material design guidelines. In addition, the photocurable composition known in the past for the use of the composition for imprint or the protective film for a magneto-optical disk has a common portion in the photolithography step, but there is no etching step or peeling step. The difference from the etching photoresist is large. Therefore, when the photocurable resin applied for such applications is directly applied as an etching photoresist, a problem often occurs in the etching step or the peeling step.

本發明係鑒於上述實情而完成,本發明之目的係提供一種光硬化性優良之新穎的組成物。本發明的目的特別是提供一種在光硬化性、黏附性、脫模性、殘膜性、圖案形狀、塗布性(I)、塗布性(II)、蝕刻適合性中任一者都優良的組成物The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a novel composition excellent in photocurability. In particular, the object of the present invention is to provide a composition excellent in any of photocurability, adhesion, mold release property, residual film property, pattern shape, coatability (I), coatability (II), and etching suitability. Object

基於上述課題,本發明者等專心研討之結果,發現藉由下以手段能夠解決上述課題。Based on the above-mentioned problems, the inventors of the present invention have found that the above problems can be solved by the following methods.

(1)一種光硬化性組成物,係含有(a)聚合性化合物、(b)0.1~15質量%光聚合引發劑及/或光酸產生劑、及(c)0.001~5質量%氟系界面活性劑、矽系界面活性劑及氟-矽系界面活性劑中之至少一種,且(d)於25℃之黏度在3~18mPa.s的範圍之光硬化性組成物,前述(a)聚合性化合物係含有分別為50質量%以上的(e)一次皮膚刺激性(PII值)為4.0以下之聚合性不飽和單體、及(f)於25℃之黏度在30mPa.s以下之聚合性不飽和單體(其中,前述(e)聚合性不飽和單體與前述(f)的聚合性不飽和單體之一部分或全部亦可以是相同的聚合性不飽和單體)。(1) A photocurable composition comprising (a) a polymerizable compound, (b) 0.1 to 15% by mass of a photopolymerization initiator and/or a photoacid generator, and (c) 0.001 to 5% by mass of a fluorine-based compound At least one of a surfactant, a lanthanide surfactant, and a fluorine-antimony surfactant, and (d) has a viscosity at 25 ° C of 3 to 18 mPa. In the photocurable composition of the range of s, the (a) polymerizable compound contains (e) a polymerizable unsaturated monomer having a primary skin irritation (PII value) of 4.0 or less and 50% by mass or more, respectively ( f) The viscosity at 25 ° C is 30mPa. a polymerizable unsaturated monomer of s or less (wherein part or all of the (e) polymerizable unsaturated monomer and the polymerizable unsaturated monomer of the above (f) may be the same polymerizable unsaturated monomer) .

(2)如(1)之光硬化性組成物,其中含有光自由基聚合性不飽和單體及/或光陽離子聚合性不飽和單體作為前述(a)聚合性化合物。(2) The photocurable composition according to (1), which comprises a photoradical polymerizable unsaturated monomer and/or a photocationic polymerizable unsaturated monomer as the above (a) polymerizable compound.

(3)如(1)之光硬化性組成物,其中含有具有乙烯性不飽和鍵含有基之單體作為前述(a)聚合性化合物。(3) The photocurable composition according to (1), which contains a monomer having an ethylenically unsaturated bond-containing group as the (a) polymerizable compound.

(4)如(1)之光硬化性組成物,其中前述含有具有環氧乙烷之化合物,作為前述(e)聚合性不飽和單體。(4) The photocurable composition according to (1), wherein the compound containing ethylene oxide is contained as the (e) polymerizable unsaturated monomer.

(5)如(1)之光硬化性組成物,其中前述含有具有氧雜環丁烷之化合物,作為前述(e)聚合性不飽和單體。(5) The photocurable composition according to (1), wherein the compound having an oxetane is contained as the (e) polymerizable unsaturated monomer.

(6)如(1)之光硬化性組成物,其中含有乙烯基醚作為前述(a)聚合性化合物。(6) A photocurable composition according to (1), which contains a vinyl ether as the above (a) polymerizable compound.

(7)如(1)之光硬化性組成物,其中含有苯乙烯衍生物作為前述(a)聚合性化合物。(7) The photocurable composition according to (1), which contains a styrene derivative as the above (a) polymerizable compound.

(8)如(1)~(7)項中任一項之光硬化性組成物,其係光奈米壓印微影法用。(8) The photocurable composition according to any one of (1) to (7), which is used in a photon lithography method.

(9)一種光阻,其係使用如(1)~(7)中任一項之光硬化性組成物而構成。(9) A photoresist comprising the photocurable composition according to any one of (1) to (7).

(10)一種圖案的形成方法,其係含有塗布如(1)~(7)中任一項之光硬化性組成物而使其硬化之步驟。(10) A method of forming a pattern, comprising the step of applying a photocurable composition according to any one of (1) to (7) and curing the pattern.

(11)一種光阻圖案的形成方法,其係包含以下步驟:塗布如(1)~(7)中任一項之光硬化性組成物之步驟;將光透射性模具加壓於基板上的光阻層,來使前述光硬化性組成物變形之步驟;從模具背面或基板背面照射光線使塗膜硬化,以形成嵌合所期望圖案的光阻圖案之步驟;將光透射性模具從塗膜脫附下來之步驟;以光硬化性組成物作為遮罩,來蝕刻基板之步驟;以及在蝕刻後剝離光硬化性組成物之步驟。(11) A method of forming a photoresist pattern, comprising the steps of: coating a photocurable composition according to any one of (1) to (7); and pressing the light transmissive mold onto the substrate a photoresist layer for deforming the photocurable composition; a step of irradiating light from the back surface of the mold or the back surface of the substrate to harden the coating film to form a photoresist pattern of a desired pattern; and coating the light transmissive mold a step of desorbing the film; a step of etching the substrate with the photocurable composition as a mask; and a step of peeling off the photocurable composition after etching.

藉由本發明能夠得到光硬化性、黏附性、塗布性中任一者都優良的組成物。According to the present invention, a composition excellent in any of photocurability, adhesion, and coating properties can be obtained.

以下,詳細地說明本發明的內容。又,在本說明書所使用的「~」係意指包含其前後所記載之數值作為下限值及上限值。Hereinafter, the contents of the present invention will be described in detail. In addition, the "~" used in the present specification means that the numerical values described before and after are included as the lower limit and the upper limit.

以下詳細地說明本發明。又,在本說明書中,(甲基)丙烯酸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。又,在本說明書中,單體與monomer係相同,在本發明之單體與低聚物及聚合物有區別,係指質量平均分子量為1,000以下之化合物。The present invention will be described in detail below. In the present specification, (meth)acrylic acid means acrylate and methacrylate, (meth)acrylic means acrylic acid and methacrylic acid, and (meth)acryloyl group means acrylonitrile group and (meth) Base) propylene fluorenyl. Further, in the present specification, the monomer is the same as the monomer, and the monomer of the present invention is different from the oligomer and the polymer, and means a compound having a mass average molecular weight of 1,000 or less.

又,在本發明所稱之奈米壓印係指轉印大約數微米至數十奈米大小的圖案。Further, the term "nano embossing" as used in the present invention means transferring a pattern having a size of about several micrometers to several tens of nanometers.

本發明的光硬化性組成物係能夠廣泛地使用於光奈米壓印微影法,能夠得到例如硬化前之光透射性高、微細凹凸圖案的形成性能、塗布適合性及其他的加工適合性、揮發性、及一次皮膚刺激性等生態安全性優良,同時在硬化後之敏感度(快速硬化性)、解像性、線邊緣粗糙性、塗膜強度、與模具之剝離性、殘膜特性、蝕刻耐性、低硬化收縮性、基板黏附性或其他各項優良的塗膜物性。The photocurable composition of the present invention can be widely used in a photonic lithography method, and can provide, for example, high light transmittance before curing, formation performance of fine concavo-convex patterns, coating suitability, and other processing suitability. , volatility, and skin irritation and other ecological safety, and sensitivity after hardening (rapid hardening), resolution, line edge roughness, film strength, peelability from the mold, residual film characteristics , etching resistance, low hardening shrinkage, substrate adhesion or other excellent coating properties.

亦即,本發明的光硬化性組成物使用於光奈米壓印微影法時,係具有以下的特徵之物,(1)因為在室溫之溶液流動性優良,該組成物能夠容易地流入模具凹部的槽內,因為不容易包容大氣所以不會產生氣泡缺陷,且無論在模具凸部、凹部在硬化後都不會產生殘渣。In other words, when the photocurable composition of the present invention is used in a photon lithography method, it has the following characteristics: (1) Since the solution has excellent fluidity at room temperature, the composition can be easily The flow into the groove of the mold recess does not cause air bubble defects because it is not easily contained in the air, and no residue is generated even after the convex portion and the concave portion of the mold are hardened.

(2)因為揮發性小、皮膚刺激性小,作業者的安全性優良。(2) Because the volatility is small and the skin irritation is small, the safety of the operator is excellent.

(3)因為硬化後的硬化膜之機械性質優良,塗膜與基板的黏附性優良、塗膜與模具的脫模性優良,在將模具剝離時,不會產生圖案崩潰或塗膜表面拉絲而引起表面粗糙,所以能夠形成良好的圖案。(3) Since the cured film is excellent in mechanical properties, the adhesion between the coating film and the substrate is excellent, and the release property of the coating film and the mold is excellent, and when the mold is peeled off, pattern collapse or brushing of the surface of the coating film is not caused. The surface is roughened, so that a good pattern can be formed.

(4)因為光硬化後的體積收縮小,且模具轉印特性優良,微細圖案能夠得到正確的賦型性。(4) Since the volume shrinkage after photohardening is small and the mold transfer characteristics are excellent, the fine pattern can obtain correct formability.

(5)因為塗布均勻性優良,能夠適合大型基板的塗布、微細加工領域等。(5) Since it is excellent in coating uniformity, it can be applied to the application of a large substrate, the field of microfabrication, and the like.

(6)因為膜的光硬化速度高,所以生產力高。(6) Since the film has a high photohardening speed, productivity is high.

(7)因為蝕刻加工精確度、蝕刻耐性等優良,能夠適合作為半導體元件或電晶體等基板加工用蝕刻光阻。(7) Since it is excellent in etching precision and etching resistance, it can be suitably used as an etching resist for substrate processing such as a semiconductor element or a transistor.

(8)因為蝕刻後之光阻剝離性優良,不會產生殘渣,適用作為蝕刻光阻。(8) Since the photoresist peeling property after etching is excellent, no residue is generated, and it is suitable as an etching photoresist.

首先,說明本發明的光硬化性組成物的黏度。在本發明若未特別提及時,係指在25℃時之黏度。First, the viscosity of the photocurable composition of the present invention will be described. In the present invention, unless otherwise specified, it means the viscosity at 25 °C.

本發明之光硬化性組成物在25℃時之黏度係在3~18mPa.s的範圍。The photocurable composition of the present invention has a viscosity of 3 to 18 mPa at 25 ° C. The scope of s.

藉由如此的黏度,能夠賦予硬化前之微細凹凸形成性能、塗布適合性及其他的加工適合性,及在硬化後解像性、線邊緣粗糙性、殘膜特性、基板黏附性或其他各項優良的塗膜物性。在此,最新光阻材料手冊第1頁、第103~104頁(2005年、情報機構出版),記載使黏度為5mPa.s以下為佳,但是本發明者等專心研討之結果,發現組成物的黏度並非單純地越低越佳,只有在特定黏度範圍,亦即具有3~18mPa.s的特定黏度範圍時,才能夠達成本發明的目的。By such a viscosity, it is possible to impart fine unevenness forming properties before curing, coating suitability, and other processing suitability, and resolution after hardening, line edge roughness, residual film characteristics, substrate adhesion, or the like. Excellent coating properties. Here, the latest photoresist material manual page 1, page 103~104 (2005, published by the intelligence agencies), recorded a viscosity of 5mPa. The following is preferable, but the inventors of the present invention have concentrated on the results of the study, and found that the viscosity of the composition is not simply lower, the better, only in the specific viscosity range, that is, has 3 to 18 mPa. The object of the invention can be achieved with a specific viscosity range of s.

亦即,本發明之光硬化性組成物的黏度小於3mPa.s時,會產生基板塗布適合性的問題或膜的機械強度低落。具體上,黏度太低時,因為組成物在塗布時會產生表面不均、塗布時組成物從基板流出,乃是不佳。但是,此種黏度對塗布性能之影響,以往完全沒有揭示。That is, the photocurable composition of the present invention has a viscosity of less than 3 mPa. In the case of s, there is a problem that the substrate coating suitability or the mechanical strength of the film is lowered. Specifically, when the viscosity is too low, it is not preferable because the composition causes surface unevenness at the time of coating and the composition flows out from the substrate at the time of coating. However, the effect of such viscosity on coating properties has not been disclosed at all.

另一方面,本發明之光硬化性組成物的黏度大於18mPa.s時,使具有微細凹凸圖案之模具黏附於光硬化性組成物時,組成物難以流入模具凹部的槽中、因為容易包容大氣而易於產生氣泡缺陷、光硬化後容易在模具凸部留下殘渣。又,最新光阻材料手冊第1頁、第103~104頁(2005年、情報機構出版)等以往所揭示的光奈米壓印組成物,因為黏度大約為50mPa.s,會有氣泡缺陷或光硬化後容易在模具凸部留下殘渣等問題,應用的用途受到限制。例如,在半導體積體電路或液晶顯示器的薄膜電晶體等微細加工用途難以展開。本發明的光硬化性組成物能夠適合應用於此等用途,亦能夠廣泛地應用於製造其他的用途,例如平面螢幕、微電機械系統(MEMS)、傳感器元件、光碟、高密度儲存碟等磁記錄媒體、繞射格子或浮凸型全息照像等的光學零件、奈米元件、光學元件、光學薄膜或偏光元件、有機電晶體、彩色濾光片、保護層、微透鏡陣列、免疫分析晶片、DNA分離晶片、微反應器、奈米生物元件、光波導器、濾光器、光子液晶等。In another aspect, the photocurable composition of the present invention has a viscosity greater than 18 mPa. In the case of s, when the mold having the fine concavo-convex pattern is adhered to the photocurable composition, it is difficult for the composition to flow into the groove of the concave portion of the mold, and it is easy to contain air bubbles due to easy inclusion of the atmosphere, and it is easy to leave residue in the convex portion of the mold after photohardening. . In addition, the light-sensitive nano-imprinting composition disclosed in the latest photo resist material manual page 1, page 103-104 (2005, information agency publication), because the viscosity is about 50mPa. s, there are problems such as bubble defects or photohardening, which tend to leave residue in the convex portion of the mold, and the application is limited. For example, it is difficult to develop microfabrication applications such as a semiconductor integrated circuit or a thin film transistor of a liquid crystal display. The photocurable composition of the present invention can be suitably used for such applications, and can be widely applied to other applications such as a flat screen, a micro electro mechanical system (MEMS), a sensor element, a compact disc, a high-density storage disc, and the like. Optical parts such as recording medium, diffraction lattice or embossed hologram, nano element, optical element, optical film or polarizing element, organic transistor, color filter, protective layer, microlens array, immunoassay wafer , DNA separation wafers, microreactors, nano-biocomponents, optical waveguides, filters, photonic liquid crystals, and the like.

又,在本發明的光硬化性組成物所含有的聚合性化合物必須在(a)總聚合性化合物的組成中,含有分別為50質量%以上的(e)一次皮膚刺激性(PII值)為4.0以下之聚合性不飽和單體、及(f)於25℃之黏度在30mPa.s以下之聚合性不飽和單體。在此前述(e)的聚合性不飽和單體、及前述(f)的聚合性不飽和單體,其一部分或全部亦可以是相同的聚合性不飽和單體。上述聚合性化合物比率以60%以上為佳,以75%以上為更佳。上限沒有特別限定,係與其他必要成分的合計為100質量%之數值。Further, in the composition of the (a) total polymerizable compound, the polymerizable compound contained in the photocurable composition of the present invention must contain 50% by mass or more of (e) primary skin irritation (PII value). The polymerizable unsaturated monomer below 4.0, and (f) the viscosity at 25 ° C is 30 mPa. Polymeric unsaturated monomers below s. Here, a part or all of the polymerizable unsaturated monomer of the above (e) and the polymerizable unsaturated monomer of the above (f) may be the same polymerizable unsaturated monomer. The ratio of the above polymerizable compound is preferably 60% or more, more preferably 75% or more. The upper limit is not particularly limited, and is a value of 100% by mass in total of other essential components.

通常,為了調整組成物的黏度,能夠混合不同黏度的各種單體、低聚物、聚合物,為了達成本發明的目的,必須含有50%以上黏度為30mPa.s以下的聚合性不飽和單體。亦即,在總組成分中,若30mPa.s以下的聚合性不飽和單體的比率,質量比小於50%時,在模具凹部容易包容大氣而產生氣泡缺陷,在光硬化後於模具凸部殘留有殘渣。留下大量的殘渣時,因為會對基板的蝕刻加工帶來障礙,以未留下殘渣為佳。以往,混合各種不同黏度的單體、低聚合、聚合物所產生的影響,在光奈米壓印用的組成物係完全未知道。Generally, in order to adjust the viscosity of the composition, various monomers, oligomers, and polymers of different viscosities can be mixed, and in order to achieve the object of the present invention, it is necessary to have a viscosity of 50% or more of 30 mPa. A polymerizable unsaturated monomer below s. That is, in the total composition, if 30mPa. When the mass ratio is less than 50%, the ratio of the polymerizable unsaturated monomer below s is likely to be contained in the concave portion of the mold to cause bubble defects, and the residue remains in the convex portion of the mold after photocuring. When a large amount of residue is left, it is preferable that the etching process of the substrate is hindered, and no residue is left. In the past, the effects of mixing monomers, oligomerization, and polymers of various different viscosities have not been known in the composition of photon imprinting.

在此,1次皮膚刺激性(PII值:皮膚刺激指數;Primary Irritation Index)係指對皮膚的刺激、皮膚發炎的指標。評價能夠依據例如ISO-10933或德崍茲(Draize)改良方法(J.H.Draize等人,“物質應用於局部皮膚及黏膜之刺激及毒性的研究方法;Method for the Study of Irritation and Toxicity of Subastance Applied Topically to the Skin and Mucous Membrance”藥理學及實驗治療學期刊(Journal of the Pharmacology and Experimental Therapcutics),82,377,1984)來進行評價,美國消費者產品安全委員會(The Consumer Product Safety Commision ofthe U.S.A.)之美國聯邦法規規範(The Code of Federal Regulations),第16篇,段落1500.41的規定測定。通常分類為6階段,PII值為0~0.03時無皮膚刺激性,0.04~0.99時有稍微的皮膚刺激性,1.0~1.99時有輕的皮膚刺激性,2.0~2.99時有不強的皮膚刺激性,3.0~5.99時有皮膚刺激性,6.0~8.0時有強的皮膚刺激性。Here, the skin irritation once (PII value: Primary Irritation Index) refers to an index of irritation to the skin and inflammation of the skin. Evaluation can be based on, for example, ISO-10933 or Draize's improved method (JHDraize et al., "Methods for the application of substances to local skin and mucous membrane irritation and toxicity; Method for the Study of Irritation and Toxicity of Subastance Applied Topically To the Skin and Mucous Membrance, Journal of the Pharmacology and Experimental Therapcutics, 82, 377, 1984, for evaluation, US Consumer of the Consumer Product Safety Commision of the USA The Code of Federal Regulations, Section 16, paragraph 1500.41. Usually classified as 6 stages, no skin irritation when PII value is 0~0.03, slight skin irritation from 0.04 to 0.99, mild skin irritation from 1.0 to 1.99, and weak skin irritation from 2.0 to 2.99 Sexuality, skin irritation from 3.0 to 5.99, strong skin irritation from 6.0 to 8.0.

在本發明的光硬化性組成物含有皮膚刺激性高的化合物時,會有威脅到作業者的生態安全性之危險。在本發明的光硬化性組成物以採用PII值為3以下的聚合性不飽和單體為佳,PII值為2以下為特佳。When the photocurable composition of the present invention contains a compound having high skin irritation, there is a risk of threatening the ecological safety of the operator. In the photocurable composition of the present invention, a polymerizable unsaturated monomer having a PII value of 3 or less is preferably used, and a PII value of 2 or less is particularly preferable.

亦即,本發明之光硬化性組成物的特定成分中,藉由選擇低黏度的聚合性不飽和單體及一次皮膚刺激性較低的聚合性不飽和單體,將其使用作為反應性稀釋劑,能夠以不會提高黏度的方式將組成物的各成分溶解,且能夠適合使用作為基板加工的蝕刻光阻。That is, in the specific component of the photocurable composition of the present invention, a low-viscosity polymerizable unsaturated monomer and a polymerizable unsaturated monomer having a low skin irritation are selected and used as a reactive dilution. The agent can dissolve the components of the composition so as not to increase the viscosity, and can suitably use an etching resist which is processed as a substrate.

本發明的聚合性化合物以含有光自由基聚合性不飽和單體/或光陽離子聚合性不飽和單體為佳。The polymerizable compound of the present invention preferably contains a photoradical polymerizable unsaturated monomer or a photocationic polymerizable unsaturated monomer.

在本發明能夠使用之自由基聚合性不飽和單體的具體例,以使用具有乙烯性聚合性不飽和鍵含有基之單體為佳。In the specific example of the radically polymerizable unsaturated monomer which can be used in the present invention, it is preferred to use a monomer having an ethylenically polymerizable unsaturated bond-containing group.

具有1個乙烯性聚合性不飽和鍵含有基之單體的例子可舉出酞酸2-丙烯醯氧基乙酯、酞酸2-丙烯醯氧基2-羥基乙酯、六氫酞酸2-丙烯醯氧基乙酯、酞酸2-丙烯醯氧基丙酯、2-乙基-2-丁基丙二醇丙烯酸酯、(甲基)丙烯酸2-乙基己酯、2-乙基己基卡必醇(甲基)丙烯酸酯、(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、丙烯酸二聚物、脂肪族環氧(甲基)丙烯酸酯、(甲基)丙烯酸苄酯、丁二醇(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)丙烯酸己內酯、(甲基)丙烯酸十六烷酯、環氧乙烷改性(以下稱為「EO」)甲酚(甲基)丙烯酸酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸二環戊酯、(甲基)丙烯酸二環戊烯酯、(甲基)丙烯酸二環戊烯氧基乙酯、雙丙甘醇(甲基)丙烯酸酯、(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)丙烯酸異莰酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸異十四烷酯、(甲基)丙烯酸月桂酯、甲氧基雙丙甘醇(甲基)丙烯酸酯、甲氧基三伸丙二醇(甲基)丙烯酸酯、甲氧基聚乙二醇(甲基)丙烯酸酯、甲氧基三甘醇(甲基)丙烯酸酯、(甲基)丙烯酸甲酯、新戊二醇苯甲酸(甲基)丙烯酸酯、壬基苯氧基聚乙二醇(甲基)丙烯酸酯、壬基苯氧基聚丙二醇(甲基)丙烯酸酯、(甲基)丙烯酸酯辛酯、對異丙苯基苯氧基乙二醇(甲基)丙烯酸酯、表氯醇(以下稱為「ECH」)改性苯氧基丙烯酸酯、苯氧基(甲基)丙烯酸乙酯、苯氧基二甘醇(甲基)丙烯酸酯、苯氧基六甘醇(甲基)丙烯酸酯、苯氧基四甘醇(甲基)丙烯酸酯、聚乙二醇(甲基)丙烯酸酯、聚乙二醇-聚丙二醇(甲基)丙烯酸酯、聚丙二醇(甲基)丙烯酸、(甲基)丙烯酸硬脂酸酯、EO改性琥珀酸(甲基)丙烯酸酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸第三丁基環己酯、(甲基)丙烯酸四氫糠酯、(甲基)丙烯酸己內酯改性四氫糠酯、(甲基)丙烯酸三溴苯酯、(甲基)丙烯酸EO改性三溴苯酯、(甲基)丙烯酸十三烷酯、(甲基)丙烯酸三氟乙酯、一(甲基)丙烯酸胺基甲酸酯、(甲基)丙烯酸金剛烷酯、(甲基)丙烯酸3-羥基金剛烷酯、對異丙烯基苯酚、4-乙烯基吡啶、N-甲基丙烯醯胺、N,N-二甲基丙烯醯胺、N,N-二乙基丙烯醯胺、N-羥基乙基丙烯醯胺、(甲基)丙烯酸N,N-二甲胺基乙酯、(甲基)丙烯酸二乙胺基乙酯、苯乙烯、α-甲基苯乙烯、丙烯腈、乙烯基己內醯胺、乙烯基咔唑、1-乙烯基咪唑、2-甲基-1-乙烯基咪唑、亞胺基丙烯酸酯、乙烯基唑啉等。Examples of the monomer having one ethylenic polymerizable unsaturated bond-containing group include 2-propenyloxyethyl citrate, 2-propenyloxy 2-hydroxyethyl phthalate, and hexahydrofurfuric acid 2. - propylene methoxyethyl ester, 2-propenyl methoxy propyl phthalate, 2-ethyl-2-butyl propylene glycol acrylate, 2-ethylhexyl (meth) acrylate, 2-ethylhexyl card Alcohol (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-methyl (meth) acrylate Oxyethyl ester, 3-methoxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, dimer of acrylic acid, aliphatic epoxy (meth) acrylate, (meth)acrylic acid Benzyl ester, butanediol (meth) acrylate, butoxyethyl (meth) acrylate, butyl (meth) acrylate, caprolactone (meth) acrylate, cetyl (meth) acrylate Ethylene oxide modified (hereinafter referred to as "EO") cresol (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, bicyclo (meth) acrylate Pentene ester, (meth) propylene Dicyclopentenyloxyethyl ester, dipropylene glycol (meth) acrylate, ethoxylated phenyl (meth) acrylate, ethyl (meth) acrylate, isoamyl (meth) acrylate, ( Isodecyl methacrylate, isobutyl (meth)acrylate, isooctyl (meth)acrylate, isotetradecyl (meth)acrylate, lauryl (meth)acrylate, methoxybispropane Glycol (meth) acrylate, methoxy tripropylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, methoxy triethylene glycol (meth) acrylate, ( Methyl)methyl acrylate, neopentyl glycol benzoic acid (meth) acrylate, nonyl phenoxy polyethylene glycol (meth) acrylate, nonyl phenoxy polypropylene glycol (meth) acrylate, (Meth) acrylate octyl ester, p-cumylphenoxyethylene glycol (meth) acrylate, epichlorohydrin (hereinafter referred to as "ECH") modified phenoxy acrylate, phenoxy ( Ethyl methyl acrylate, phenoxy diglycol (meth) acrylate, phenoxy hexaethylene glycol (meth) acrylate, phenoxy tetraethylene glycol (meth) acrylate, polyethylene glycol (meth) acrylate, polyethyl b Glycol-polypropylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, (meth) acrylate stearate, EO modified succinic acid (meth) acrylate, (meth) acrylate third Ester, tert-butylcyclohexyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, caprolactone (meth)acrylate modified tetrahydrofurfuryl ester, tribromophenyl (meth)acrylate, (meth)acrylic acid EO modified tribromophenyl ester, tridecyl (meth)acrylate, trifluoroethyl (meth)acrylate, mono(meth)acrylate, (meth)acrylic acid Adamantyl ester, 3-hydroxyadamantyl (meth)acrylate, p-isopropenylphenol, 4-vinylpyridine, N-methylpropenylamine, N,N-dimethylpropenamide, N,N - diethyl acrylamide, N-hydroxyethyl acrylamide, N,N-dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, styrene, α- Methylstyrene, acrylonitrile, vinyl caprolactam, vinyl carbazole, 1-vinylimidazole, 2-methyl-1-vinylimidazole, imidoacrylate, vinyl Oxazoline and the like.

此等之中,(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸乙氧化苯酯、(甲基)丙烯酸異莰酯、苯氧基(甲基)丙烯酸乙酯、苯氧基四甘醇(甲基)丙烯酸酯、N-乙烯基-2-吡咯啶酮、N-丙烯醯基啉等因為一次皮膚刺激性低、揮發性優良,特別適用於本發明。Among these, 2-hydroxyethyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, isodecyl (meth)acrylate, phenoxy (methyl) Ethyl acrylate, phenoxytetraethylene glycol (meth) acrylate, N-vinyl-2-pyrrolidone, N-propylene fluorenyl Porphyrins and the like are particularly suitable for use in the present invention because of low skin irritation and excellent volatility.

又,為了提升與模具之脫模性或與基板之黏附性或塗布性之目的,亦能夠使用(甲基)丙烯醯基改性矽、乙烯基改性矽、矽酮六丙烯酸酯等矽化合物、市售之矽酮丙烯酸酯(商品名:DESOLAIT Z7500(JSR製)、SHC200、SHC900、UVHC85XX系列、UVHC11XX系列(任一者都是GE-東芝SILICONE公司製)、二甲基矽氧烷單甲基丙烯酸酯(FM0711、FM0721、FM0725(任一者都是CHISSO(股)公司製)、二甲基矽氧烷二甲基丙烯酸酯(DMS-V2(CHISSO(股)公司製))、Ebercryl-1360(DAICEL化學工業製))。同樣地,亦能夠使用(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)丙烯酸四氟丙酯等含有氟原子之化合物。Further, in order to improve the mold release property to the mold or the adhesion to the substrate or the coating property, a ruthenium compound such as a (meth) acrylonitrile-modified oxime, a vinyl-modified oxime or an anthrone hexaacrylate can also be used. Commercially available anthrone acrylate (trade name: DESOLAIT Z7500 (JSR), SHC200, SHC900, UVHC85XX series, UVHC11XX series (any one is manufactured by GE-Toshiba SILICONE Co., Ltd.), dimethyloxane mono Acrylate (FM0711, FM0721, FM0725 (any one is manufactured by CHISSO), dimethyloxane dimethacrylate (DMS-V2 (manufactured by CHISSO)), Ebercryl- 1360 (manufactured by DAICEL Chemical Industry Co., Ltd.). Similarly, trifluoroethyl (meth)acrylate, pentafluoroethyl (meth)acrylate, (perfluorobutyl)ethyl (meth)acrylate, ( Perfluorobutyl hydroxypropyl methacrylate, (perfluorohexyl) ethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctyl (meth) acrylate, (methyl) A compound containing a fluorine atom such as tetrafluoropropyl acrylate.

而且,為了提高與基板的黏附性,可在本發明使用例如酸性磷酸(甲基)丙烯酸乙酯、(甲基)丙烯酸3-氯-2-酸性磷氧基丙酯、酸性磷酸聚乙二醇(甲基)丙烯酸酯、酸性磷酸(甲基)丙烯酸2-羥基乙酯、酸性磷酸2-(甲基)丙烯醯氧基乙基己酸酯等含有磷酸之(甲基)丙烯酸單體。Further, in order to improve the adhesion to the substrate, for example, acid ethyl (meth) acrylate, 3-chloro-2-acid phosphopropyl (meth) acrylate, or acid polyethylene PEG can be used in the present invention. A (meth)acrylic acid monomer containing phosphoric acid such as (meth) acrylate, 2-hydroxyethyl (meth) acrylate, or 2-(meth) propylene methoxyethyl hexanoate.

為提高本發明之光硬化性組成物的基板黏附性或膜的機械特性,亦可在本發明的光硬化性組成物含有異氰酸酯系的(甲基)丙烯酸酯化合物。The photocurable composition of the present invention may contain an isocyanate-based (meth) acrylate compound in order to improve the substrate adhesion of the photocurable composition of the present invention or the mechanical properties of the film.

異氰酸酯系的(甲基)丙烯酸酯化合物之具體例,可例示的有異氰酸(甲基)丙烯酸甲酯、異氰酸(甲基)丙烯酸乙酯、異氰酸(甲基)丙烯酸正丙酯、異氰酸(甲基)丙烯酸異丙酯、異氰酸(甲基)丙烯酸正丁酯、異氰酸(甲基)丙烯酸異丁酯、異氰酸(甲基)丙烯酸第二丁酯、異氰酸(甲基)丙烯酸第三丁酯等的異氰酸(甲基)丙烯酸烷酯;及(甲基)丙烯醯基異氰酸甲酯、(甲基)丙烯醯基異氰酸乙酯、(甲基)丙烯醯基異氰酸正丙酯、(甲基)丙烯醯基異氰酸異丙酯、(甲基)丙烯醯基異氰酸正丁酯、(甲基)丙烯醯基異氰酸異丁酯、(甲基)丙烯醯基異氰酸第二丁酯、(甲基)丙烯醯基異氰酸第三丁酯等的(甲基)丙烯醯基異氰酸烷酯。Specific examples of the isocyanate-based (meth) acrylate compound include methyl (meth) acrylate, ethyl (meth) acrylate, and n-propyl isocyanate (meth) acrylate. Ester, isopropyl isocyanate (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, dibutyl methacrylate (meth) acrylate And alkyl isocyanate (meth)acrylate such as isocyanate (meth)acrylate; and (meth) propylene decyl isocyanate, (meth) propylene decyl isocyanate Ethyl ester, n-propyl (meth) propylene decyl isocyanate, isopropyl (meth) propylene sulfonate, n-butyl (meth) propylene phthalate, (meth) propylene (Meth)acrylonitrile isocyanate such as isobutyl phthalocyanate, second butyl (meth) propylene phthalocyanate, and tert-butyl (meth) propylene phthalocyanine Alkyl ester.

又,二氧雜戊環骨架的(甲基)丙烯酸亦可使用於本發明的光硬化性組成物。Further, a (meth)acrylic acid having a dioxalane skeleton can also be used in the photocurable composition of the present invention.

二氧雜戊環骨架的(甲基)丙烯酸的具體例可舉出4-丙烯醯氧基甲基-2-甲基-2-乙基-1,3-二氧雜戊環、4-丙烯醯氧基甲基-2-甲基-2-異丁基-1,3-二氧雜戊環、4-丙烯醯氧基甲基-2-甲基-2-環己基-1,3-二氧雜戊環、4-甲基丙烯醯氧基甲基-2,2-二甲基-1,3-二氧雜戊環、4-甲基丙烯醯氧基甲基-2-甲基-2-乙基-1,3-二氧雜戊環、4-甲基丙烯醯氧基甲基-2-甲基-2-異丁基-1,3-二氧雜戊環、4-甲基丙烯醯氧基甲基-2-環己基-1,3-二氧雜戊環等。Specific examples of the (meth)acrylic acid of the dioxalane skeleton include 4-propenyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane and 4-propene.醯oxymethyl-2-methyl-2-isobutyl-1,3-dioxolane, 4-propenyloxymethyl-2-methyl-2-cyclohexyl-1,3- Dioxapentane, 4-methylpropenyloxymethyl-2,2-dimethyl-1,3-dioxolane, 4-methylpropenyloxymethyl-2-methyl -2-ethyl-1,3-dioxolane, 4-methylpropenyloxymethyl-2-methyl-2-isobutyl-1,3-dioxolane, 4- Methyl propylene methoxymethyl-2-cyclohexyl-1,3-dioxolane and the like.

其中,較佳之物可舉出4-丙烯醯氧基甲基-2-甲基-2-乙基-1,3-二氧雜戊環、4-丙烯醯氧基甲基-2-甲基-2-異丁基-1,3-二氧雜戊環等。Among them, preferred are 4-propenyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane and 4-propenyloxymethyl-2-methyl. 2-isobutyl-1,3-dioxolane and the like.

在本發明可使用之具有2個乙烯性聚合性不飽和鍵含有基之單體的例子可舉出二甘醇一乙基醚(甲基)丙烯酸酯、二羥甲基二環戊烷二(甲基)丙烯酸酯、二(甲基)丙烯酸化三聚異氰酸酯、1,3-丁二醇二(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯、EO改性1,6-己二醇二(甲基)丙烯酸酯、ECH改性1,6己二醇二(甲基)丙烯酸酯、丙烯醯氧基聚乙二醇丙烯酸酯、1.9-壬二醇二(甲基)丙烯酸酯、EO改性雙酚A二(甲基)丙烯酸酯、PO改性雙酚A二(甲基)丙烯酸酯、改性雙酚A二(甲基)丙烯酸酯、EO改性雙酚F二(甲基)丙烯酸酯、ECH改性六氫酞酸二丙烯酸酯、羥基三甲基乙酸新戊二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、EO改性新戊二醇二丙烯酸酯、環氧丙烷(以後稱為「PO」)改性新戊二醇二丙烯酸酯、新戊二醇己內酯改性羥基三甲基乙酸酯、硬脂酸改性新戊四醇二(甲基)丙烯酸酯、ECH改性酞酸二(甲基)丙烯酸酯、聚(乙二醇-伸丁二醇)二(甲基)丙烯酸酯、聚(丙二醇-伸丁二醇)二(甲基)丙烯酸酯、聚酯型(二)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、聚丙二醇二(甲基)丙烯酸酯、ECH改性丙二醇二(甲基)丙烯酸酯、矽酮二(甲基)丙烯酸酯、三甘醇二(甲基)丙烯酸酯、四甘醇二(甲基)丙烯酸酯、三環癸烷二甲醇(二)丙烯酸酯、新戊二醇改性三羧甲基丙烷二(甲基)丙烯酸酯、三伸丙二醇二(甲基)丙烯酸酯、EO改性三伸丙二醇二(甲基)丙烯酸酯、三甘油二(甲基)丙烯酸酯、二丙二醇二(甲基)丙烯酸酯、二乙烯基伸乙脲、二乙烯基伸丙脲。Examples of the monomer having two ethylenic polymerizable unsaturated bond-containing groups which can be used in the present invention include diethylene glycol monoethyl ether (meth) acrylate and dimethylol dicyclopentane di ( Methyl)acrylate, di(meth)acrylated trimer isocyanate, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, EO modification 1,6-hexanediol di(meth)acrylate, ECH modified 1,6-hexanediol di(meth)acrylate, propyleneoxypolyethylene glycol acrylate, 1.9-nonanediol II Methyl) acrylate, EO modified bisphenol A di(meth) acrylate, PO modified bisphenol A di(meth) acrylate, modified bisphenol A di(meth) acrylate, EO modification Bisphenol F di(meth)acrylate, ECH modified hexahydrophthalic acid diacrylate, hydroxytrimethylacetic acid neopentyl glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate EO modified neopentyl glycol diacrylate, propylene oxide (hereinafter referred to as "PO") modified neopentyl glycol diacrylate, neopentyl glycol caprolactone modified hydroxy trimethyl acetate, Stearic acid modified neopentyl alcohol di(methyl) propyl Ether ester, ECH modified di(meth)acrylate, poly(ethylene glycol-butanediol) di(meth)acrylate, poly(propylene glycol-butanediol) di(methyl) Acrylate, polyester (di) acrylate, polyethylene glycol di(meth) acrylate, polypropylene glycol di(meth) acrylate, ECH modified propylene glycol di(meth) acrylate, fluorenone bis ( Methyl) acrylate, triethylene glycol di(meth) acrylate, tetraethylene glycol di(meth) acrylate, tricyclodecane dimethanol (di) acrylate, neopentyl glycol modified tricarboxymethyl Propane di(meth)acrylate, tripropylene glycol di(meth)acrylate, EO modified tripropylene glycol di(meth)acrylate, triglycerin di(meth)acrylate, dipropylene glycol di(methyl) ) acrylate, divinyl acetal, divinyl acetal.

而且,為了提高與基板的黏附性,亦可在本發明使用EO改性磷酸二(甲基)丙烯酸酯等含有磷酸之二(甲基)丙烯酸單體。Further, in order to improve the adhesion to the substrate, a bis(meth)acrylic acid monomer containing phosphoric acid such as EO-modified di(meth)acrylate may be used in the present invention.

此等之中,1.9-壬二醇二(甲基)丙烯酸酯、三伸丙二醇二(甲基)丙烯酸酯、四甘醇二(甲基)丙烯酸酯、羥基三甲基乙酸新戊二醇二(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯等在2官能單體中係低黏度、低皮膚刺激性,特別適用於本發明。Among these, 1.9-nonanediol di(meth)acrylate, tri-propylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, hydroxytrimethylacetate neopentyl glycol (Meth) acrylate, polyethylene glycol di(meth) acrylate, etc. are low viscosity and low skin irritation among bifunctional monomers, and are particularly suitable for use in the present invention.

在本發明可使用之具有3個以上乙烯性聚合性不飽和鍵含有基之多官能單體的例子可舉出ECH改性甘油三(甲基)丙烯酸酯、EO改性甘油三(甲基)丙烯酸酯、PO改性甘油三(甲基)丙烯酸酯、新戊四醇三丙烯酸酯、EO改性磷酸三丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、己內酯改性三羥甲基丙烷三(甲基)丙烯酸酯、EO改性三羥甲基丙烷三(甲基)丙烯酸酯、PO改性三羥甲基丙烷三(甲基)丙烯酸酯、參(丙烯醯氧基乙基)三聚異氰酸酯、二新戊四醇六(甲基)丙烯酸酯、己內酯改性二新戊四醇六(甲基)丙烯酸酯、二新戊四醇羥基五(甲基)丙烯酸酯、烷基改性二新戊四醇羥基五(甲基)丙烯酸酯、二新戊四醇聚(甲基)丙烯酸酯、烷基改性二新戊四醇參(甲基)丙烯酸酯、雙三羥甲基丙烷四(甲基)丙烯酸酯、新戊四醇乙氧基四(甲基)丙烯酸酯、新戊四醇四(甲基)丙烯酸酯等。Examples of the polyfunctional monomer having three or more ethylenic polymerizable unsaturated bond-containing groups which can be used in the present invention include ECH-modified glycerol tris(meth)acrylate and EO-modified glycerol tris(methyl). Acrylate, PO modified glycerol tri(meth) acrylate, neopentyl alcohol triacrylate, EO modified phosphoric acid triacrylate, trimethylolpropane tri (meth) acrylate, caprolactone modified three Hydroxymethylpropane tri(meth)acrylate, EO modified trimethylolpropane tri(meth)acrylate, PO modified trimethylolpropane tri(meth)acrylate, ginseng (propylene oxy group) Ethyl)trimeric isocyanate, dipentaerythritol hexa(meth)acrylate, caprolactone modified dipentaerythritol hexa(meth)acrylate, dipentaerythritol hydroxypenta(meth)acrylic acid Esters, alkyl-modified dipentaerythritol hydroxypenta(meth) acrylate, dipentaerythritol poly(meth) acrylate, alkyl-modified dipentaerythritol ginseng (meth) acrylate, Bis-trimethylolpropane tetra(meth)acrylate, pentaerythritol ethoxytetra(meth)acrylate, neopentyltetrakis(meth)acrylate, and the like.

此等之中,EO改性甘油三(甲基)丙烯酸酯、PO改性甘油三(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、EO改性三羥甲基丙烷三(甲基)丙烯酸酯、PO改性三羥甲基丙烷三(甲基)丙烯酸酯、二新戊四醇六(甲基)丙烯酸酯、新戊四醇乙氧基四(甲基)丙烯酸酯、新戊四醇四(甲基)丙烯酸酯等3官能以上單體中係低黏度、低皮膚刺激性,特別適用於本發明。Among these, EO-modified glycerol (meth) acrylate, PO-modified glycerol tri(meth) acrylate, trimethylolpropane tri(meth) acrylate, EO-modified trimethylolpropane Tris(meth)acrylate, PO modified trimethylolpropane tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, pentaerythritol ethoxytetra(meth)acrylic acid A trifunctional or higher monomer such as an ester or neopentyltetrakis(meth)acrylate is low in viscosity and low in skin irritation, and is particularly suitable for use in the present invention.

使用在一分子內具有2個以上光聚合性官能基之物時,因為如上述,能夠在組成物導入多量的光聚合性官能基,所以組成物的交聯密度變為非常大,提升硬化後的各種物性的效果高。硬化後的各種物性之中,特別是藉由增大交聯密度,能夠提升耐熱性及耐久性(耐磨耗性、耐藥品性、耐水性),即便曝露於高熱、磨擦或溶劑時,亦不容易產生微細凹凸圖案變形、消失、損傷。When a material having two or more photopolymerizable functional groups in one molecule is used, since a large amount of photopolymerizable functional groups can be introduced into the composition as described above, the crosslinking density of the composition becomes extremely large, and after the hardening is cured The effect of various physical properties is high. Among various physical properties after hardening, in particular, by increasing the crosslinking density, heat resistance and durability (abrasion resistance, chemical resistance, and water resistance) can be improved, and even when exposed to high heat, friction, or solvent, It is not easy to cause deformation, disappearance, and damage of the fine concavo-convex pattern.

為了更提高交聯密度,本發明的光硬化性組成物能夠在達成本發明的目的之範圍調配分子量比上述多官能體更大的多官能低聚物或聚合物。具有光自由基聚合物之多官能低聚物可舉出聚酯型丙烯酸酯、聚丙烯酸胺基甲酸酯、聚醚型丙烯酸酯、聚環氧丙烯酸酯等各種丙烯酸酯低聚物、磷肌酸骨架、金剛烷骨架、卡爾多(Cardo)骨架、降烯骨架等具有高體積結構之低聚物或聚合物等。In order to further increase the crosslinking density, the photocurable composition of the present invention can be formulated with a polyfunctional oligomer or polymer having a molecular weight larger than that of the above polyfunctional body within the scope of achieving the object of the present invention. Examples of the polyfunctional oligomer having a photo-radical polymer include various acrylate oligomers such as polyester acrylate, polyacrylic acid urethane, polyether acrylate, and polyepoxy acrylate, and phosphorus muscle. Acid skeleton, adamantane skeleton, Cardo skeleton, descending An oligomer or a polymer having a high volume structure such as an olefin skeleton.

本發明所使用之聚合性不飽和單體亦可採用具有環氧乙烷環之化合物。具有環氧乙烷環之化合物可舉出例如脂環族聚環氧化物類、多元酸之聚環氧丙基酯類、多元醇之聚環丙基醚類、聚氧乙烯二醇之聚環氧丙基醚類、芳香族多元醇之聚環氧丙基醚類、芳香族多元醇之聚環氧丙基醚類的加氫化合物類、胺基甲酸酯聚環氧化合物及環氧化聚丁二烯類等。此等化合物可單獨使用一種,亦可混合使用2種以上。The polymerizable unsaturated monomer used in the present invention may also be a compound having an oxirane ring. The compound having an oxirane ring may, for example, be an alicyclic polyepoxide, a polyepoxypropyl ester of a polybasic acid, a polycyclopropyl ether of a polyhydric alcohol, or a polycycloethylene polyoxyethylene diol. Hydroxypropyl ethers, polyepoxypropyl ethers of aromatic polyols, hydrogenated compounds of polyepoxypropyl ethers of aromatic polyols, urethane polyepoxides and epoxidized poly Butadiene and the like. These compounds may be used alone or in combination of two or more.

含環氧丙基之化合物其適用之市售品,可舉出UVR-6216(Uniion Carbide公司製)、GLYCIDOL、AOEX24、CYCROMER-A200(以上,Daicel化學工業(股)製)、EPICOAT 828、EPICOAT 812、EPICOAT 1031、EPICOAT 872、EPICOAT CT 508(以上,油化SHELL(股)製)、KRM-2400、KRM-2410、KRM-2408、KRM-2490、KRM-2720、KRM-2750(以上,旭電化工業(股)製)等。此等可單獨使用1種,亦可組合使用2種以上。Commercially available products of the epoxy group-containing compound include UVR-6216 (manufactured by Uniion Carbide Co., Ltd.), GLYCIDOL, AOEX24, CYCROMER-A200 (above, manufactured by Daicel Chemical Industry Co., Ltd.), EPICOAT 828, and EPICOAT. 812, EPICOAT 1031, EPICOAT 872, EPICOAT CT 508 (above, oiled SHELL (share) system), KRM-2400, KRM-2410, KRM-2408, KRM-2490, KRM-2720, KRM-2750 (above, Asahi Electrochemical industry (shares) system, etc. These may be used alone or in combination of two or more.

又,此等具有環氧乙烷環之化合物不限其製法,例如能夠參考丸善KK出版、第四版實驗化學講座20有機合成II、213~、平成4年,Alfred Hasfner編輯,雜環化合物之化學-小環雜環、第3篇環氧乙烷(The chemistry of heterocyclic compounds-Small Ring Heterocycles part3 Oxiranes)、John & Wiley and Sons,An Interscience Pulication,New York,1985年、吉村、接著、29卷12號、32、1985年、吉村、接著、30卷5號、42、1986年、吉村、接著、30卷7號、42、1986年、特開平11-100378號公報、特許第2906245號公報、特許第2926262號公報等之文獻來合成。Moreover, such compounds having an oxirane ring are not limited to the preparation method thereof, for example, refer to Maruzen KK Publishing, Fourth Edition Experimental Chemistry Lecture 20 Organic Synthesis II, 213~, Heisei 4, edited by Alfred Hasfner, Heterocyclic Compounds The chemistry of heterocyclic compounds-Small Ring Heterocycles part3 Oxiranes, John & Wiley and Sons, An Interscience Pulication, New York, 1985, Yoshimura, Next, 29 No. 12, 32, 1985, Yoshimura, vol., No. 30, No. 5, No. 42, 1986, Yoshimura, et al., Vol. 30, No. 7, No. 42, 1986, Japanese Patent Laid-Open No. 11-100378, and No. 2906245. It is synthesized by a document such as Japanese Patent No. 2926262.

本發明所使用的聚合性不飽和化合物可舉出氧雜環丁烷化合物。氧雜環丁烷化合物係例如特開平8-143806號公報、特開2001-220526號公報、特開2001-310937號公報所記載之氧雜環丁烷化合可適用。此外,為了改良耐熱性或膜硬度、脫模性,亦可使用具有氧雜環丁烷基之矽酸鹽類化合物或具有氧雜環丁烷基之氟化合物。The polymerizable unsaturated compound used in the present invention may, for example, be an oxetane compound. The oxetane compound can be suitably used, for example, in the oxetane compound described in JP-A-2001-310937, JP-A-2001-210526, and JP-A-2001-310937. Further, in order to improve heat resistance, film hardness, and mold release property, a phthalate compound having an oxetanyl group or a fluorine compound having an oxetanyl group may also be used.

在分子內具有1個氧雜環丁烷環之化合物,可舉出例如3-乙基-3-羥基甲基氧雜環丁烷、3-(甲基)烯丙氧基甲基-2-乙基氧雜環丁烷、(3-乙基-3-氧雜環丁烷基甲氧基)甲基苯、4-氟-[1-(3-乙基-3-氧雜環丁烷基甲氧基)甲基]苯、4-甲氧基-[1-(3-乙基-3-氧雜環丁烷基甲氧基)甲基]苯、[1-(3-乙基-3-氧雜環丁烷基甲氧基)乙基]苯基醚、異丁氧基甲基(3-乙基-3-氧雜環丁烷基甲基)醚、異莰氧基乙基(3-乙基-3-氧雜環丁烷基甲基)醚、異莰基(3-乙基-3-氧雜環丁烷基甲基)醚、2-乙基己基(3-乙基-3-氧雜環丁烷基甲基)醚、乙基二甘醇(3-乙基-3-氧雜環丁烷甲基)醚、二環戊二烯(3-乙基-3-氧雜環丁烷基甲基)醚、二環戊烯氧基乙基(3-乙基-3-氧雜環丁烷甲基)醚、二環戊烯(3-乙基-3-氧雜環丁烷基甲基)醚、四氫糠基(3-乙基-3-氧雜環丁烷基甲基)醚、四溴苯基(3-乙基-3-氧雜環丁烷基甲基)醚、2-四溴苯氧基乙基(3-乙基-3-氧雜環丁烷甲基)醚、三溴苯基(3-乙基-3-氧雜環丁烷基甲基)醚、2-三溴苯氧基乙基(3-乙基-3-氧雜環丁烷基甲基)醚、2-羥基乙基(3-乙基-3-氧雜環丁烷基甲基)醚、2-羥基丙基(3-乙基-3-氧雜環丁烷基甲基)醚、丁氧基乙基(3-乙基-3-氧雜環丁烷甲基)醚、五氯苯基(3-乙基-3-氧雜環丁烷基甲基)醚、五溴苯基(3-乙基-3-氧雜環丁烷基甲基)醚、基(3-乙基-3-氧雜環丁烷基甲基)醚、3-(4-溴丁氧基甲基)-3-甲基氧雜環丁烷、(3-甲基氧雜環丁烷-3-基)甲基苯甲酸酯等。The compound having one oxetane ring in the molecule may, for example, be 3-ethyl-3-hydroxymethyloxetane or 3-(methyl)allyloxymethyl-2- Ethyloxetane, (3-ethyl-3-oxetanylmethoxy)methylbenzene, 4-fluoro-[1-(3-ethyl-3-oxetane) Methoxy)methyl]benzene, 4-methoxy-[1-(3-ethyl-3-oxetanylmethoxy)methyl]benzene, [1-(3-ethyl) 3-oxetanylmethoxy)ethyl]phenyl ether, isobutoxymethyl (3-ethyl-3-oxetanylmethyl)ether, isodecyloxy B (3-ethyl-3-oxetanylmethyl)ether, isodecyl (3-ethyl-3-oxetanylmethyl)ether, 2-ethylhexyl (3- Ethyl-3-oxetanylmethyl)ether, ethyldiglycol (3-ethyl-3-oxetanylmethyl)ether, dicyclopentadiene (3-ethyl-) 3-oxetanylmethyl)ether, dicyclopentenyloxyethyl (3-ethyl-3-oxetanylmethyl)ether, dicyclopentene (3-ethyl-3) -oxetanylmethyl)ether, tetrahydroindenyl (3-ethyl-3) -oxetanylmethyl)ether, tetrabromophenyl(3-ethyl-3-oxetanylmethyl)ether, 2-tetrabromophenoxyethyl (3-ethyl- 3-oxetanylmethyl)ether, tribromophenyl(3-ethyl-3-oxetanylmethyl)ether, 2-tribromophenoxyethyl (3-ethyl- 3-oxetanylmethyl)ether, 2-hydroxyethyl(3-ethyl-3-oxetanylmethyl)ether, 2-hydroxypropyl (3-ethyl-3- Oxetanemethyl)ether, butoxyethyl (3-ethyl-3-oxetanyl)ether, pentachlorophenyl (3-ethyl-3-oxetane) Alkylmethyl)ether, pentabromophenyl (3-ethyl-3-oxetanylmethyl)ether, (3-ethyl-3-oxetanylmethyl)ether, 3-(4-bromobutoxymethyl)-3-methyloxetane, (3-methyloxa) Cyclobutane-3-yl)methylbenzoate or the like.

在分子內具有2個以上氧雜環丁烷環之化合物,可舉出例如3,7-雙(3-氧雜環丁烷基)-5-壬烷、3,3’-(1,3-(2-亞甲基)丙烷二基雙(羥亞甲基))雙(3-乙基氧雜環丁烷)、1,4-雙[(3-乙基-3-氧雜環丁烷基甲氧基)甲基]苯、1,4-雙[(3-乙基-3-氧雜環丁烷基甲氧基)甲基]聯苯、1,2-雙[(3-乙基-3-氧雜環丁烷基甲氧基)甲基]乙烷、1,3-雙[(3-乙基-3-氧雜環丁烷基甲氧基)甲基]丙烷、乙二醇雙(3-乙基-3-氧雜環丁烷基甲基)醚、二環戊烯雙(3-乙基-3-氧雜環丁烷基甲基)醚、三甘醇雙(3-乙基-3-氧雜環丁烷基甲基)醚、四甘醇雙(3-乙基-3-氧雜環丁烷基甲基)醚、三環癸烷二基二亞甲基(3-乙基-3-氧雜環丁烷基甲基)醚、三羥甲基丙烷參(3-乙基-3-氧雜環丁烷基甲基)醚、1,4-雙(3-乙基-3-氧雜環丁烷基甲氧基)丁烷、1,6-雙(3-乙基-3-氧雜環丁烷基甲氧基)己烷、新戊四醇參(3-乙基-3-氧雜環丁烷基甲基)醚、新戊四醇肆(3-乙基-3-氧雜環丁烷基甲基)醚、聚乙二醇雙(3-乙基-3-氧雜環丁烷基甲基)醚、二新戊四醇六(3-乙基-3-氧雜環丁烷基甲基)醚、二新戊四醇五(3-乙基-3-氧雜環丁烷基甲基)醚、二新戊四醇四(3-乙基-3-氧雜環丁烷基甲基)醚、己內酯改性二新戊四醇六(3-乙基-3-氧雜環丁烷基甲基)醚、己內酯改性二新戊四醇五(3-乙基-3-氧雜環丁烷基甲基)醚、雙三羥甲基丙烷肆(3-乙基-3-氧雜環丁烷基甲基)醚、EO改性雙酚A雙(3-乙基-3-氧雜環丁烷基甲基)醚、PO改性雙酚A雙(3-乙基-3-氧雜環丁烷基甲基)醚、EO改性加氫雙酚A雙(3-乙基-3-氧雜環丁烷基甲基)醚、PO改性加氫雙酚A雙(3-乙基-3-氧雜環丁烷基甲基)醚、EO改性雙酚F雙(3-乙基-3-氧雜環丁烷基甲基)醚、聚(3-(4-溴丁氧基甲基)-3-甲基氧雜環丁烷)、N-氧雜環丁烷-2-基甲氧基甲基丙烯醯胺、3,5-雙(3-乙基-氧雜環丁烷基甲氧基)苯甲酸、3,5-雙(3-乙基-氧雜環丁烷基甲氧基)苯甲酸甲酯、5-(3-乙基-3-氧雜環丁烷基)異酞酸、1,1,1-參[4(3-乙基-3-氧雜環丁烷基甲氧基)苯基]乙烷等。此等可單獨使用1種,亦可組合使用2種以上。The compound having two or more oxetane rings in the molecule may, for example, be 3,7-bis(3-oxetanyl)-5- Decane, 3,3'-(1,3-(2-methylene)propanediylbis(hydroxymethylene))bis(3-ethyloxetane), 1,4-double [ (3-ethyl-3-oxetanylmethoxy)methyl]benzene, 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl] Biphenyl, 1,2-bis[(3-ethyl-3-oxetanylmethoxy)methyl]ethane, 1,3-bis[(3-ethyl-3-oxocyclo) Butyryl methoxy)methyl]propane, ethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, dicyclopentene bis(3-ethyl-3-oxa Cyclobutanemethyl)ether, triethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, tetraethylene glycol bis(3-ethyl-3-oxetanyl) Methyl)ether, tricyclodecanediyldimethylene (3-ethyl-3-oxetanylmethyl)ether, trimethylolpropane ginseng (3-ethyl-3-oxo) Cyclobutanemethyl)ether, 1,4-bis(3-ethyl-3-oxetanylmethoxy)butane, 1,6-bis(3-ethyl-3-oxa Cyclobutane methoxy)hexane, neopentyl alcohol ginseng (3-ethyl-3-oxetanylmethyl)ether, neopentyl sterol oxime (3-ethyl 3-oxetanylmethyl)ether, polyethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, dipentaerythritol hexa(3-ethyl- 3-oxetanylmethyl)ether, dipentaerythritol penta(3-ethyl-3-oxetanylmethyl)ether, dipentaerythritol tetrakis(3-ethyl- 3-oxetanylmethyl)ether, caprolactone modified dineopentalol hexa(3-ethyl-3-oxetanylmethyl)ether, caprolactone modified two new Pentaerythritol penta(3-ethyl-3-oxetanylmethyl)ether, bistrimethylolpropane oxime (3-ethyl-3-oxetanylmethyl)ether, EO Modified bisphenol A bis(3-ethyl-3-oxetanylmethyl)ether, PO modified bisphenol A bis(3-ethyl-3-oxetanylmethyl)ether , EO modified hydrogenated bisphenol A bis(3-ethyl-3-oxetanylmethyl)ether, PO modified hydrogenated bisphenol A bis(3-ethyl-3-oxetane Alkylmethyl)ether, EO-modified bisphenol F bis(3-ethyl-3-oxetanylmethyl)ether, poly(3-(4-bromobutoxymethyl)-3- Methyloxetane), N-oxetan-2-ylmethoxymethylpropane Indoleamine, 3,5-bis(3-ethyl-oxetanylmethoxy)benzoic acid, 3,5-bis(3-ethyl-oxetanylmethoxy)benzoic acid Methyl ester, 5-(3-ethyl-3-oxetanyl)isodecanoic acid, 1,1,1-gin[4(3-ethyl-3-oxetanylmethoxy) Phenyl]ethane and the like. These may be used alone or in combination of two or more.

上述具有氧雜環丁烷環之各化合物的製法沒有特別限定,可依照先前已知的方法,例如Pattison(D.B.Pattison,J.Am.Chem.Soc.,3455,79(1957年)所揭示之從二醇合成氧雜環丁烷環之方法等。The method for producing each of the above compounds having an oxetane ring is not particularly limited and can be carried out according to a previously known method, for example, by Pattison (DB Patticon, J. Am. Chem. Soc., 3455, 79 (1957). A method of synthesizing an oxetane ring from a diol, and the like.

又,此外,亦可舉出具有分子量1000~5000左右的高分子量之含有1~4個氧雜環丁烷環之化合物。Further, a compound having a high molecular weight of about 1 to 4 oxetane rings having a molecular weight of about 1,000 to 5,000 is also mentioned.

氧雜環丁烷化合物的市售品可使用例如東亞合成公司製OXT101(3-乙基-3-羥基氧雜環丁烷、東亞合成公司製OXT221(二[1-乙基(3-氧雜環丁烷基)甲基醚]、東亞合成公司製1,4-雙[(3-乙基-3-氧雜環丁烷基)甲氧基甲基]苯、東亞合成公司製OXT211(3-乙基-3-(苯氧基甲基)氧雜環丁烷)、東亞合成公司製MPO(3,3-二甲基-2-(對甲氧基苯基)氧雜環丁烷)、宇部興業製ETERNACOLL OXBP。As a commercial product of the oxetane compound, for example, OXT101 (3-ethyl-3-hydroxyoxetane, manufactured by Toagosei Co., Ltd., OXT221 (two [1-ethyl (3-oxa)) can be used. Cyclobutane) methyl ether], 1,4-bis[(3-ethyl-3-oxetanyl)methoxymethyl]benzene manufactured by Toagosei Co., Ltd., OXT211 (3) manufactured by Toagosei Co., Ltd. -ethyl-3-(phenoxymethyl)oxetane), MPO (3,3-dimethyl-2-(p-methoxyphenyl)oxetane) manufactured by Toagosei Co., Ltd. Ube Industries Co., Ltd. ETERNACOLL OXBP.

此等之中,能夠適用作為本發明的光硬化性組成物的構成成分之氧雜環丁烷化合物,較佳是分子內的氧雜環丁烷環數目為1~10,以1~4為更佳。具體上可舉出(3-乙基-3-氧雜環丁烷基甲氧基)甲基苯、1,4-雙[(3-乙基-2-氧雜環丁烷基甲氧基)甲基]苯、1,2-雙(3-乙基-3-氧雜環丁烷基甲氧基)乙烷三羥甲基丙烷參(3-乙基-3-氧雜環丁烷基甲基)醚、3-乙基-3-氧雜環丁烷基甲氧基苯等。Among these, an oxetane compound which is a constituent component of the photocurable composition of the present invention can be suitably used, and the number of oxetane rings in the molecule is preferably from 1 to 10, and is from 1 to 4 Better. Specifically, (3-ethyl-3-oxetanylmethoxy)methylbenzene, 1,4-bis[(3-ethyl-2-oxetanylmethoxy) )methyl]benzene, 1,2-bis(3-ethyl-3-oxetanylmethoxy)ethane trimethylolpropane (3-ethyl-3-oxetane) Methyl)ether, 3-ethyl-3-oxetanylmethoxybenzene, and the like.

本發明所使用聚合性化合物可舉出乙烯基醚化合物、乙烯基醚化合物可適當地選擇,可舉出例如2-乙基己基乙烯基醚、丁二醇-1,4-二乙烯基醚、環己烷二甲醇一乙烯基醚、二甘醇一乙烯基醚、乙二醇二乙烯基醚、三甘醇二乙烯基醚、1,2-丙二醇二乙烯基醚、1,3-丙二醇乙烯基醚、1,3-丁二醇乙烯基醚、1,4-丁二醇二乙烯基醚、伸丁二醇二乙烯基醚、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、1,4-環己二醇二乙烯基醚、四甘醇二乙烯基醚、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、乙二醇二伸乙基乙烯基醚、三甘醇二伸乙基乙烯基醚、乙二醇二伸丙基乙烯基醚、三甘醇二伸乙基乙烯基醚、三羥甲基丙烷三伸乙基乙烯基醚、三羥甲基丙烷二伸乙基乙烯基醚、新戊四醇二伸乙基乙烯基醚、新戊四醇三伸乙基乙烯基醚、新戊四醇四伸乙基乙烯基醚、異莰基乙烯基醚、基乙烯基醚、環戊基乙烯基醚、1,1,1-參[4-(2-羥基乙氧基)苯基]乙烷、雙酚A二羥基乙基醚等。The polymerizable compound to be used in the invention may be appropriately selected from the group consisting of a vinyl ether compound and a vinyl ether compound, and examples thereof include 2-ethylhexyl vinyl ether and butanediol-1,4-divinyl ether. Cyclohexane dimethanol monovinyl ether, diethylene glycol monovinyl ether, ethylene glycol divinyl ether, triethylene glycol divinyl ether, 1,2-propylene glycol divinyl ether, 1,3-propanediol ethylene Ether, 1,3-butanediol vinyl ether, 1,4-butanediol divinyl ether, butanediol divinyl ether, neopentyl glycol divinyl ether, trimethylolpropane three Vinyl ether, trimethylolethane trivinyl ether, hexanediol divinyl ether, 1,4-cyclohexanediol divinyl ether, tetraethylene glycol divinyl ether, neopentyl alcohol divinyl Ethyl ether, neopentyl alcohol trivinyl ether, neopentyl alcohol tetravinyl ether, sorbitol tetravinyl ether, sorbitol penta vinyl ether, ethylene glycol diethyl vinyl ether, triglyceride Alcohol diethyl ether, ethylene glycol dipropyl vinyl ether, triethylene glycol diethyl vinyl ether, trimethylolpropane triethyl ether, three Hydroxymethylpropane di-ethyl vinyl ether, neopentyl alcohol di-ethyl vinyl ether, neopentyl alcohol tri-ethyl vinyl ether, neopentyl alcohol tetraethyl vinyl ether, isoindole Vinyl ether, Vinyl ether, cyclopentyl vinyl ether, 1,1,1-gin[4-(2-hydroxyethoxy)phenyl]ethane, bisphenol A dihydroxyethyl ether, and the like.

此等乙烯基醚系化合物具有低黏度、低臭味、低皮膚刺激性之特徵,在自由基聚合,或在陽離子聚合係有用的。These vinyl ether-based compounds are characterized by low viscosity, low odor, and low skin irritation, and are useful in radical polymerization or in cationic polymerization.

此等乙烯基醚例如能夠藉由Stephen.C.Lapin,Polymers Paint Colour Journal.179(4237)、321(1988年)所記載之方法,亦即能夠藉由使多元醇或多元酚與乙炔反應,或是使多元醇或多元酚與鹵化烷基乙烯基醚反應來合成,此等可單獨使用1種,亦可組合使用2種以上。Such vinyl ethers can be, for example, by the method described in Stephen. C. Lapin, Polymers Paint Colour Journal. 179 (4237), 321 (1988), that is, by reacting a polyhydric alcohol or a polyhydric phenol with acetylene. Alternatively, the polyol or the polyhydric phenol may be used in combination with a halogenated alkyl vinyl ether. These may be used alone or in combination of two or more.

本發明所使用的聚合性化合物,可舉出苯乙烯衍生物。苯乙烯衍生物可舉出例如苯乙烯、對甲基苯乙烯、對甲氧基苯乙烯、β-甲基苯乙烯、對甲基-β-甲基苯乙烯、α-甲基苯乙烯、對甲氧基-β-甲基苯乙烯、對羥基苯乙烯等,乙烯基萘衍生物例如有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,N-乙烯基化合物類可舉出例如N-乙烯基咔唑、N-乙烯基吡咯啶酮、N-乙烯基吲哚、N-乙烯基吡咯、N-乙烯基啡噻、N-乙烯基乙醯苯胺、N-乙烯基乙基乙醯胺、N-乙烯基琥珀醯亞胺、N-乙烯基酞醯亞胺、N-乙烯基己內醯胺、N-乙烯基咪唑等。The polymerizable compound used in the present invention may, for example, be a styrene derivative. The styrene derivative may, for example, be styrene, p-methylstyrene, p-methoxystyrene, β-methylstyrene, p-methyl-β-methylstyrene, α-methylstyrene, or the like. Methoxy-β-methylstyrene, p-hydroxystyrene, etc., vinylnaphthalene derivatives such as 1-vinylnaphthalene, α-methyl-1-vinylnaphthalene, β-methyl-1-vinyl Naphthalene, 4-methyl-1-vinylnaphthalene, 4-methoxy-1-vinylnaphthalene, etc., and examples of the N-vinyl compound include N-vinylcarbazole and N-vinylpyrrolidone. , N-vinyl anthracene, N-vinylpyrrole, N-vinylmorphophene , N-vinylacetanilide, N-vinylethylacetamide, N-vinyl succinimide, N-vinyl quinone imine, N-vinyl caprolactam, N-vinyl Imidazole and the like.

能夠調配丙烯基醚及丁烯基醚作為本發明所使用的聚合性化合物。例如1-十二烷基-丙烯基醚、1-十二烷基-1-丁烯基醚、1-丁烯氧基甲基-2-降烯、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、二甘醇二(1-丁烯基)醚、1,2,3-三(1-丁烯氧基)丙烷、丙烯基醚碳酸丙烯酯等係適用。A propenyl ether and a butenyl ether can be formulated as the polymerizable compound used in the present invention. For example, 1-dodecyl-propenyl ether, 1-dodecyl-1-butenyl ether, 1-butenoxymethyl-2-nor Alkene, 1-4-bis(1-butoxy)butane, 1,10-bis(1-butoxy)decane, 1,4-bis(1-butoxymethyl) ring Hexane, diethylene glycol bis(1-butenyl)ether, 1,2,3-tris(1-butoxy)propane, propylene ether propylene carbonate, and the like are suitable.

在本發明的光硬化性組成物亦可按照必要調配各種多元醇化合物。能夠適用多元醇係例如乙二醇、甘油、新戊四醇、二新戊四醇、三羥基丙烷、雙三羥基丙烷、新戊二醇、螺乙二醇、各種聚醚多元醇、各種聚酯多元醇、各種己內酯多元醇可以適用。藉由添加如此各種多元醇,能夠提高硬化速度。此等多元醇之中,因為羥基當量小、與光陽離子硬化性組成物之主要成分之環氧化合物及/或氧雜環丁烷化合物之相溶性優良,且添加所產生的黏度上升小,以應用乙二醇、三羥基丙烷於本發明為佳。In the photocurable composition of the present invention, various polyol compounds may be formulated as necessary. It is applicable to polyols such as ethylene glycol, glycerin, neopentyl alcohol, dipentaerythritol, trihydroxypropane, ditrihydroxypropane, neopentyl glycol, spiroethylene glycol, various polyether polyols, various kinds of poly Ester polyols and various caprolactone polyols can be used. By adding such various polyols, the hardening speed can be increased. Among these polyols, since the hydroxyl group equivalent is small, the compatibility with the epoxy compound and/or the oxetane compound which is a main component of the photocationic curable composition is excellent, and the viscosity increase due to the addition is small, The use of ethylene glycol or trihydroxypropane is preferred in the present invention.

上述多元醇可單獨使用1種,亦可組合使用2種以上。所使用之多元醇的分子量以100~50,000為佳,以160~20,000為更佳。藉由使用分子量在該範圍之多元醇,能夠得到形狀安定性及物性安定性良好的光硬化性組成物,同時具有能夠抑制所得到光硬化性組成物的黏度過大、彈性模數降低之傾向。These polyols may be used alone or in combination of two or more. The molecular weight of the polyol used is preferably from 100 to 50,000, more preferably from 160 to 20,000. By using a polyol having a molecular weight in this range, a photocurable composition having good shape stability and physical stability can be obtained, and the viscosity of the obtained photocurable composition can be suppressed from being excessively large and the modulus of elasticity tends to be lowered.

在本發明使用作為聚合性不飽和化合物之光陽離子聚合性的反應成分,不僅是一分子內有環氧基、氧雜環丁烷基、乙烯基等陽離子反應性的單一官能基之上述化合物,而且在同一分子內具有複數種類的官能基之化合物亦能夠適用。In the present invention, a photocationic polymerizable reaction component as a polymerizable unsaturated compound is used, and not only a compound having a cationically reactive single functional group such as an epoxy group, an oxetane group or a vinyl group in one molecule, Further, a compound having a plurality of types of functional groups in the same molecule can also be applied.

例如,能夠在同一分子內含有乙烯基醚基與環氧基之化合物、或是含有丙烯基醚基與環氧基之反應性化合物。For example, a compound containing a vinyl ether group and an epoxy group in the same molecule or a reactive compound containing a propenyl ether group and an epoxy group can be used.

又,光陽離子聚合性及光自由基聚合性的反應性成分能夠使用3-甲基-3-氧雜環丁烷基丙烯酸甲酯(大阪有機化學工業公司製、OXE-10)、3-甲基-3-氧雜環丁烷基丙烯酸甲酯(大阪有機化學工業公司製、OXE-30)、一氧化乙烯基環己烯1,2-乙氧基-4-乙烯基環己烷(DAICEL化學工業製、CELOXIDE 2000)、具有氧雜環丁烷環之(甲基)丙烯酸酯化合物(宇部興業製ETERNACOLL OXMA等)等化合物。Further, as the reactive component of the photocationic polymerizability and the photoradical polymerizability, methyl 3-methyl-3-oxetanyl acrylate (OXE-10, manufactured by Osaka Organic Chemical Industry Co., Ltd.), 3-A can be used. Methyl 3-oxetanyl acrylate (OXE-30, manufactured by Osaka Organic Chemical Industry Co., Ltd.), vinylcyclohexene oxide 1,2-ethoxy-4-vinylcyclohexane (DAICEL) Chemical industry, CELOXIDE 2000), a compound having a oxetane ring (meth) acrylate compound (ETERNACOLL OXMA, etc.).

本發明的光硬化性組成物亦可按照必要含有與具有自由基硬化機構之反應性成分混合化而成之物。混合化係藉由例如在含有以環氧化合物、氧雜環丁烷化合物、乙烯基化合物等作為反應性化合物之陽離子硬化性成分中混合含有丙烯醯基之化合物等自由基硬化型成分及按照必要之自由基硬化引發劑而得到。較佳之含有丙烯醯基之化合物,可舉出例如(甲基)丙烯酸-(乙烯氧基)乙酯等在同一分子中具有陽離子聚合性的乙烯基醚及自由基聚合性的丙烯醯基之化合物等。The photocurable composition of the present invention may contain a mixture of a reactive component having a radical scavenging mechanism as necessary. In the case of the cation-curable component containing an epoxy compound, an oxetane compound, a vinyl compound or the like as a reactive compound, a radical-curable component such as a compound containing an acryl-based group, and The free radical hardening initiator is obtained. The compound containing a propylene fluorenyl group is preferably a compound having a cationically polymerizable vinyl ether and a radically polymerizable acryl oxime group in the same molecule, such as (meth)acrylic acid-(vinyloxy)ethyl ester. Wait.

混合系化合物之市售品可舉出例如3-甲基-3-氧雜環丁烷基丙烯酸甲酯(大阪有機化學工業公司製、OXE-10)、3-甲基-3-氧雜環丁烷基丙烯酸甲酯(大阪有機化學工業公司製、OXE-30)、具有氧雜環丁烷環之(甲基)丙烯酸酯化合物(宇部興業製ETERNACOLL OXMA等)、丙烯酸-2-(2-乙烯氧基乙氧基)乙酯或甲基丙烯酸-2-(2-乙烯氧基乙氧基)乙酯(日本觸媒公司製、VEEA)、3,4-乙氧基環己基(甲基)丙烯酸酯(Daicel化學工業製、CYCROMER-A400、A100)等。The commercially available product of the mixed compound is, for example, methyl 3-methyl-3-oxetanyl acrylate (OXE-10, manufactured by Osaka Organic Chemical Industry Co., Ltd.), 3-methyl-3-oxacyclohexane. Methyl butane acrylate (OXE-30, manufactured by Osaka Organic Chemical Industry Co., Ltd.), (meth) acrylate compound having oxetane ring (ETERNACOLL OXMA, etc.), Acrylic acid-2-(2- Ethoxyethoxyethyl)ethyl ester or 2-(2-vinyloxyethoxy)ethyl methacrylate (VEEA, VEEA), 3,4-ethoxycyclohexyl (methyl) Acrylate (made by Daicel Chemical Industry Co., Ltd., CYCROMER-A400, A100).

接著,說明本發明的光硬化性組成物之光自由基聚合性單體之較佳混合形態。本發明的光硬化性組成物係以含有50質量%以上黏度為30mPa.s以下的聚合性不飽和單體(較佳是含有具有1個乙烯性不飽和鍵含有基之單體、具有2個乙烯性不飽和鍵含有基之單體、及具有3個乙烯性不飽和鍵含有基之單體中任一種以上)的方式混合而使用。Next, a preferred mixed form of the photoradical polymerizable monomer of the photocurable composition of the present invention will be described. The photocurable composition of the present invention contains 50% by mass or more and a viscosity of 30 mPa. a polymerizable unsaturated monomer of s or less (preferably a monomer having one ethylenically unsaturated bond-containing group, a monomer having two ethylenically unsaturated bond-containing groups, and having three ethylenic unsaturations) The bond is mixed and used in such a manner that one or more of the monomers are contained.

在本發明,具有1個不飽和鍵含有基之光自由基聚合性單體通常能夠使用作為反應性稀釋劑,對於降低本發明的光硬化性組成物的黏度係有效的,以佔總聚合性化合物的80質量%以下為佳,以70質量%以下為更佳,以60質量%以下的範圍添加為特佳。藉由使具有1個不飽和鍵含有基之單體的比率為80質量%以下,將本發明的光硬化性組成物硬化而成的硬化膜之機械強度、耐蝕刻性、耐熱性有更良好的傾向,使用作為光奈米壓印的模具材時,能夠抑制因模具潤脹而導致模具劣化之傾向,乃是較佳。另一方面,因為使用具有1個及/或2個不飽和鍵含有基之單體作為反應性稀釋劑更為良好,因此以添加具有1個及/或2個不飽和鍵含有基之單體為佳。In the present invention, a photoradical polymerizable monomer having one unsaturated bond-containing group can be generally used as a reactive diluent, and is effective for lowering the viscosity of the photocurable composition of the present invention to account for total polymerizability. 80% by mass or less of the compound is preferable, 70% by mass or less is more preferable, and addition in a range of 60% by mass or less is particularly preferable. The cured film obtained by curing the photocurable composition of the present invention has better mechanical strength, etching resistance, and heat resistance by setting the ratio of the monomer having one unsaturated bond-containing group to 80% by mass or less. In the case of using a mold material which is a photon imprint, it is preferable to suppress the tendency of the mold to deteriorate due to swelling of the mold. On the other hand, since it is more preferable to use a monomer having one and/or two unsaturated bond-containing groups as a reactive diluent, a monomer having one and/or two unsaturated bond-containing groups is added. It is better.

具有2個不飽和鍵含有基之單體,以佔總聚合性化合物的90質量%以下為佳,以80質量%以下為更佳,以70質量%以下的範圍添加為特佳。具有1個及/或2個不飽和鍵含有基之單體的比率,以佔總聚合性化合物的1~95質量%為佳,以3~95質量%為更佳,以5~90質量%的範圍添加為特佳。具有3個不飽和鍵含有基之單體的比率,以佔總聚合性化合物的80質量%以下為佳,以70質量%以下為更佳,以60質量%以下的範圍添加為特佳。藉由使具有3個以上不飽和鍵含有基之單體的比率為80質量%以下,能夠更容易地將組成物的黏度調整在本發明的黏度範圍,乃是較佳。The monomer having two unsaturated bond-containing groups is preferably 90% by mass or less based on the total polymerizable compound, more preferably 80% by mass or less, and particularly preferably 70% by mass or less. The ratio of the monomer having one and/or two unsaturated bond-containing groups is preferably from 1 to 95% by mass based on the total polymerizable compound, more preferably from 3 to 95% by mass, and from 5 to 90% by mass. The range is added as a special one. The ratio of the monomer having three unsaturated bond-containing groups is preferably 80% by mass or less based on the total polymerizable compound, more preferably 70% by mass or less, and particularly preferably 60% by mass or less. By setting the ratio of the monomer having three or more unsaturated bond-containing groups to 80% by mass or less, it is possible to more easily adjust the viscosity of the composition to the viscosity range of the present invention.

而且,敘述在本發明之光硬化性組成物,光陽離子聚合性單體之較佳混合形態。光陽離子性單體的混合範圍係只要未脫離本發明的黏度條件及PII值的範圍時,未特別限定於該等。Further, a preferred form of mixing of the photocurable polymerizable monomer in the photocurable composition of the present invention will be described. The mixing range of the photocationic monomer is not particularly limited as long as it does not deviate from the viscosity condition and the PII value of the present invention.

在本發明,具有一個陽離子聚合性基之陽離子聚合性單體通常能夠使用作為反應性稀釋劑,對於降低本發明的光硬化性組成物的黏度係有效的,以佔總單體的95質量%以下為佳,以90質量%以下為更佳,以85質量%以下的範圍添加為特佳。藉由使具有1個陽離子聚合性基之單體的比率為95質量%以下,硬化膜之機械強度、耐蝕刻性、耐熱性有更良好的傾向,乃是較佳,又,使用有機聚合物作為光奈米壓印的模具材時,能夠抑制因模具潤脹。降低模具劣化之傾向。另一方面,因為具有1個及/或2個陽離子聚合性基之單體係作為反應性稀釋劑使用,必須添加具有1個及/或2個陽離子聚合性基之單體,以佔總單體的1質量%以上為佳,以3質量%以上為較佳,以5質量%以上比率調配為更佳。In the present invention, a cationically polymerizable monomer having one cationically polymerizable group can be generally used as a reactive diluent, and is effective for lowering the viscosity of the photocurable composition of the present invention, and accounts for 95% by mass of the total monomer. The following is preferable, and it is more preferably 90% by mass or less, and particularly preferably 85% by mass or less. When the ratio of the monomer having one cationically polymerizable group is 95% by mass or less, the mechanical strength, etching resistance, and heat resistance of the cured film tend to be more excellent, and it is preferable to use an organic polymer. When it is a mold material for photon imprinting, it is possible to suppress swelling due to the mold. Reduce the tendency of the mold to deteriorate. On the other hand, since a single system having one and/or two cationically polymerizable groups is used as a reactive diluent, it is necessary to add a monomer having one and/or two cationically polymerizable groups to account for the total amount. The content is preferably 1% by mass or more, more preferably 3% by mass or more, and more preferably 5% by mass or more.

又,本發明的光硬化性組成物在調製時之水分量以2.0質量%以下為佳,以1.5質量%以下為較佳,以1.0質量%以下為更佳。藉由使調製時之水分量為2.0質量%以下,能夠使本發明的光硬化性組成物的保存安定性更安定。In the photocurable composition of the present invention, the water content at the time of preparation is preferably 2.0% by mass or less, more preferably 1.5% by mass or less, and still more preferably 1.0% by mass or less. By setting the water content at the time of preparation to 2.0% by mass or less, the storage stability of the photocurable composition of the present invention can be made more stable.

又,本發明之光硬化性組成物的有機溶劑含量在總組成物中以3.0質量%以下為佳。亦即,因為本發明的光硬化性組成物較佳是含有特定的1官能及/或2官能的單體作為反應性稀釋劑,所以並不一定需要用以溶解本發明之光硬化性組成物的成分之有機溶劑。又,因為若未含有有機溶劑時,不需要以使溶劑揮發為目的之烘焙步驟,具有能夠有效地將步驟簡略化等之優點。因此,本發明之光硬化性組成物的有機溶劑含量以3.0質量%以下為佳,以2.0質量%以下為更佳,以未含有為特佳。雖然本發明之光硬化性組成物並不一定需要有機溶劑,但是將反應性稀釋劑無法溶解的化合物溶解製成本發明的光硬化性組成物時,或是微調整黏度時,能夠任意地添加。在本發明的光硬化性組成物能夠使用之較佳溶劑,係通常使用作為光硬化性組成物或光阻之溶劑,若能夠將本發明所使用的化合物溶解及均勻分散之物、且不會與該等成分反應之物時即可,沒有特別限定。Moreover, the organic solvent content of the photocurable composition of the present invention is preferably 3.0% by mass or less based on the total composition. That is, since the photocurable composition of the present invention preferably contains a specific monofunctional and/or bifunctional monomer as a reactive diluent, it is not necessarily required to dissolve the photocurable composition of the present invention. The organic solvent of the ingredients. In addition, when the organic solvent is not contained, a baking step for the purpose of volatilizing the solvent is not required, and there is an advantage that the steps can be simplified in an efficient manner. Therefore, the organic solvent content of the photocurable composition of the present invention is preferably 3.0% by mass or less, more preferably 2.0% by mass or less, and particularly preferably not contained. Although the photocurable composition of the present invention does not necessarily require an organic solvent, when a compound in which the reactive diluent is insoluble is dissolved to form the photocurable composition of the present invention, or when the viscosity is finely adjusted, it can be arbitrarily added. In the preferred solvent which can be used for the photocurable composition of the present invention, a solvent which is a photocurable composition or a photoresist is usually used, and if the compound used in the present invention can be dissolved and uniformly dispersed, it does not The substance to be reacted with these components is not particularly limited.

前述有機溶劑可舉出例如甲醇、乙醇等醇類;四氫呋喃等醚類;乙二醇一甲基醚、乙二醇二甲基醚、乙二醇甲基醚、乙二醇一乙基醚等二醇醚類;甲基賽路蘇乙酸酯、乙基賽路蘇乙酸酯等乙二醇烷基醚乙酸酯類;二甘醇一甲基醚、二甘醇二乙基醚、二甘醇二甲基醚、二甘醇乙基甲基醚、二甘醇一乙基醚、二甘醇一丁基醚等二甘醇類、丙二醇甲基醚乙酸酯、丙二醇乙基醚乙酸酯等丙二醇烷基醚乙酸酯類;甲苯、二甲苯等芳香族烴類;丙酮、甲基乙基酮、環己酮、4-羥基-4-甲基-2-戊酮、2-庚酮等酮類;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、乙氧基乙酸乙酯、羥基乙酸乙酯、2-羥基-2-甲基酞酸甲酯、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、乙酸乙酯、乙酸丁酯、乳酸甲酯、乳酸乙酯等乳酸酯類等酯類等。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 ether, and ethylene glycol monoethyl ether. Glycol ethers; ethylene glycol alkyl ether acetates such as methyl sarbuta acetate and ethyl sarbuta acetate; diethylene glycol monomethyl ether, diethylene glycol diethyl ether, two Diethylene glycol such as glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether Propylene glycol alkyl ether acetates such as acid esters; aromatic hydrocarbons such as toluene and xylene; acetone, methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, 2-glycol Ketones such as ketones; ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropanoate, ethyl 2-hydroxy-2-methylpropanoate, ethyl ethoxyacetate, ethyl hydroxyacetate , methyl 2-hydroxy-2-methyl decanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxypropane Ethyl acetate, ethyl acetate, butyl acetate, Methyl lactate, ethyl lactate esters, esters, etc. and the like.

而且,能夠添加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-甲基吡咯啶酮、二甲亞碸、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、乙酸乙酯、苯甲酸乙酯、草酸二乙酯、順丁烯二酸二乙酯、γ-丁內酯、碳酸乙烯酯、碳酸丙烯酯、苯基賽路蘇乙酸酯等高沸點溶劑。此等可單獨使用1種,亦可組合使用2種以上。Furthermore, N-methylformamide, N,N-dimethylformamide, N-methylformamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl hydrazine, benzyl ethyl ether, dihexyl ether, acetone acetone, isophorone, hexanoic acid, octanoic acid, 1-octanol, 1-nonanol, benzyl alcohol High-boiling solvent such as ethyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, and phenyl racelus acetate . These may be used alone or in combination of two or more.

此等之中,以甲氧基丙二醇乙酸酯、2-羥基丙酸乙酯、3-甲氧基丙酸甲酯、3-乙氧基丙酸甲酯、乳酸乙酯、環己酮、甲基異丁基酮、2-庚酮等為特佳。Among these, methoxypropylene glycol acetate, ethyl 2-hydroxypropionate, methyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl lactate, cyclohexanone, Methyl isobutyl ketone, 2-heptanone and the like are particularly preferred.

本發明之光硬化性組成物可使用光聚合引發劑及/或光酸產生劑。在本發明所使用的光聚合引發劑及/或光酸產生劑,在總組成物中之質量比係含有0.1~15質量%,以0.2~12質量%為佳,以0.3~10質量%為更佳。其中,並用其他的光聚合引發劑及光酸產生劑時,其等的合計量係在上述範圍。A photopolymerization initiator and/or a photoacid generator can be used as the photocurable composition of the present invention. The photopolymerization initiator and/or photoacid generator used in the present invention has a mass ratio of 0.1 to 15% by mass in the total composition, preferably 0.2 to 12% by mass, and 0.3 to 10% by mass. Better. In the case where other photopolymerization initiators and photoacid generators are used in combination, the total amount of these is in the above range.

因此,本發明的光硬化性組成物係含有能夠藉由自由基聚合及/或陽離子聚合進行光硬化之物、及光硬化而成之物之雙方。Therefore, the photocurable composition of the present invention contains both a material which can be photocured by radical polymerization and/or cationic polymerization, and a product which is photocured.

光聚合引發劑及/或光酸產生劑的比率小於0.1質量%時,敏感度(快速硬化性)、解像度、線邊緣粗糙性、塗膜強度變差,乃是不佳。另一方面光聚合引發劑及/或光酸產生劑的比率大於15質量%時,光透射性、著色性、處理性等變差,乃是不佳。以往,在含有染料及/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,雖然對較佳光聚合引發劑及/或光酸產生劑的添加量進行了各種研討,但是對於奈米壓印用等的光硬化性組成物之較佳光聚合引發劑及/或光酸產生劑的添加量尚沒有報告。亦即,在含有染料及/或顏料之體系時,此等具有自由基偶合劑之作用,而影響光聚合性、敏感度。考慮此點,此等的用途係藉由光聚合引發劑的添加量來加以最適合化。另一方面,在本發明的光硬化性組成物,染料及/或顏料並非必要成分,光聚合引發劑的最佳範圍會有與噴墨用組成物或液晶顯示器彩色濾光片用組成物等領域之物有不同的情況。When the ratio of the photopolymerization initiator and/or the photoacid generator is less than 0.1% by mass, the sensitivity (rapid hardenability), the resolution, the line edge roughness, and the coating film strength are deteriorated, which is not preferable. On the other hand, when the ratio of the photopolymerization initiator and/or the photoacid generator is more than 15% by mass, light transmittance, coloring property, handleability, and the like are deteriorated, which is not preferable. Conventionally, in the inkjet composition containing a dye and/or a pigment, or the liquid crystal display color filter composition, although the amount of the photopolymerization initiator and/or the photoacid generator to be added is variously studied, various studies have been made. The amount of the photopolymerization initiator and/or photoacid generator added to the photocurable composition for nanoimprinting or the like has not been reported. That is, in the case of a system containing a dye and/or a pigment, these have a function as a radical coupling agent, which affects photopolymerization and sensitivity. In consideration of this point, these uses are most suitably determined by the addition amount of the photopolymerization initiator. On the other hand, in the photocurable 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 a composition for an inkjet or a composition for a color filter of a liquid crystal display. There are different situations in the field.

在本發明所使用的光聚合引發劑,係調配對所使用光源的波長具有活性之物,係按照反應形式的不同(例如自由基聚合或陽離子聚合等)而使用能夠產生適當的活性種之物。又,光聚合引發劑可以只使用1種,亦可使用2種以上。The photopolymerization initiator used in the present invention is a substance which is active at a wavelength of a light source to be used, and is a substance which can produce an appropriate active species depending on the reaction form (for example, radical polymerization or cationic polymerization). . Further, the photopolymerization initiator may be used alone or in combination of two or more.

本發明所使用的自由基光聚合引發劑例如能夠使用市售的引發劑。此等可舉出例如能夠從Ciba公司購得之Irgacure(註冊商標)2959(1-[4-(2-羥基甲氧基)苯基]-2-羥基-2-甲基-1-丙-1-酮、Irgacure(註冊商標)184(1-羥基環己基苯基酮)、Irgacure(註冊商標)500(1-羥基環己基苯基酮、二苯基酮)、Irgacure(註冊商標)651(2,2-二甲氧基-1,2-二苯基乙-1-酮)、Irgacure(註冊商標)369(2-苄基-2-二甲基胺基-1-(4-啉苯基)丁酮-1)、Irgacure(註冊商標)907(2-甲基-1[4-甲硫基苯基]-2-啉丙-1-酮、Irgacure(註冊商標)819(雙(2,4,6-三甲基苯甲醯基)-苯基氧化膦、Irgacure(註冊商標)1800(雙(2,6-二甲氧基苯甲醯基)-2,4,4-三甲基-戊基氧化膦,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-戊基氧化膦,2-羥基-2-甲基-1-苯基-1-丙-1-酮)、Irgacure(註冊商標)OXE01(1,2-辛烷二酮,1-[4-(苯硫基)苯基]-2-(O-苯甲醯肟)、Darocur(註冊商標)1173(1-羥基-2-甲基-1-苯基-1-丙-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-乙醯肟)、能夠從BASF公司購得之Lucirin TPO(2,4,6-三甲基苯甲醯基二苯基氧化膦)、Lucirin TPO-L(2,4,6-三甲基苯甲醯基苯基乙氧基氧化膦)、能夠從ESACURE日本SiberHegner(NSH)公司購得之ESACURE 1001M(1-[4-苯甲醯基苯基磺醯基]苯基)-2-甲基-2-(4-甲基苯基磺醯基)丙-1-酮、能夠從N-1414旭電化公司購得之ADEKAOPTOMER(註冊商標)N-1414(咔唑-苯酚系)、ADEKAOPTOMER(註冊商標)N-1717(吖啶系)、ADEKAOPTOMER(註冊商標)N-1606(三系)、三和CHEMICAL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CHEMICAL製之TME-三(2-[2-(5-甲基呋喃基-2-基)乙烯基]-4,6-雙(三氯甲基)-1,3,5-三)、三和CHEMICAL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-(3,4-二甲氧苯基)-4,6-雙(三氯甲基)-1,3,5-三)、二苯基酮、4,4’-雙(二乙胺基)二苯基酮、甲基-2-二苯基酮、4-苯甲醯基-4’-甲基二苯基硫醚、4-苯基二苯基酮、乙基米其勒酮、2-氯噻噸酮、2-甲基噻噸酮、2-異丙基噻噸酮、4-異丙基噻噸酮、2,4-二乙基噻噸酮、1-氯-4-丙氧基噻噸酮、2-甲基噻噸酮、噻噸酮銨鹽、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、苯偶姻丁基醚、苄基二甲基縮酮、1,1,1-三氯乙醯苯、二乙氧基乙醯苯及二苯并環庚酮、鄰苯甲醯苯甲酸甲酯、2-苯甲醯萘、4-苯甲醯聯苯、4-苯甲醯二苯基醚、1,4-苯甲醯苯、苯偶醯、10-丁基-2-氯吖啶酮、[4-(甲基苯硫基)苯基]苯基甲烷)、2-乙基蒽、2,2-雙(2-氯苯基)4,5,4’,5’-肆(3,4,5-三甲氧基苯基)1,2’-二咪唑、2,2-雙(鄰-氯苯基)4,5,4’,5’-四苯基-1,2’-二咪唑、參(4-二甲胺基苯基)甲烷、乙基-4-(二甲胺基)苯甲酸酯、2-(二甲胺基)乙基苯甲酸酯、丁氧基乙基-4-(二甲胺基)苯甲酸酯等。As the radical photopolymerization initiator used in the present invention, for example, a commercially available initiator can be used. These may, for example, be Irgacure (registered trademark) 2959 (1-[4-(2-hydroxymethoxy)phenyl]-2-hydroxy-2-methyl-1-propene-) commercially available from Ciba Corporation. 1-ketone, Irgacure (registered trademark) 184 (1-hydroxycyclohexyl phenyl ketone), Irgacure (registered trademark) 500 (1-hydroxycyclohexyl phenyl ketone, diphenyl ketone), Irgacure (registered trademark) 651 ( 2,2-dimethoxy-1,2-diphenylethan-1-one), Irgacure (registered trademark) 369 (2-benzyl-2-dimethylamino-1-(4-) Phenanylphenyl)butanone-1), Irgacure (registered trademark) 907 (2-methyl-1[4-methylthiophenyl]-2- Phenylpropan-1-one, Irgacure (registered trademark) 819 (bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide, Irgacure (registered trademark) 1800 (double (2,6-two) Methoxybenzylidene)-2,4,4-trimethyl-pentylphosphine oxide, 1-hydroxy-cyclohexyl-phenyl-one), Irgacure (registered trademark) 1800 (double (2,6-) Dimethoxybenzylidene)-2,4,4-trimethyl-pentylphosphine oxide, 2-hydroxy-2-methyl-1-phenyl-1-propan-1-one), Irgacure ( Registered trademark) OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl]-2-(O-benzamide), Darocur (registered trademark) 1173 (1-hydroxy- 2-methyl-1-phenyl-1-propan-1-one), Darocur (registered trademark) 1116, 1398, 1174 and 1020, CGI242 (ethanone, 1-[9-ethyl-6-(2- Methyl benzhydryl)-9H-indazol-3-yl]1-(O-acetamidine), Lucirin TPO (2,4,6-trimethylbenzylidene) available from BASF Diphenylphosphine oxide), Lucirin TPO-L (2,4,6-trimethylbenzhydrylphenylethoxyphosphine oxide), ESACURE 1001M (1) available from ESACURE Japan SiberHegner (NSH) -[4-Benzyl fluorenyl Alkylsulfonyl]phenyl)-2-methyl-2-(4-methylphenylsulfonyl)propan-1-one, ADEKAOPTOMER (registered trademark) N which can be purchased from N-1414 Asahi Chemical Co., Ltd. -1414 (carbazole-phenol system), ADEKAOPTOMER (registered trademark) N-1717 (acridine system), ADEKAOPTOMER (registered trademark) N-1606 (three Department), three and 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-methylfuryl-2-yl)vinyl]-4,6-bis(trichloromethyl)-1,3,5-three ), three and CHEMICAL made MP-three (2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-three ), MIDORI chemical system TAZ-113 (2-[2-(3,4-dimethoxyphenyl)vinyl]-4,6-bis(trichloromethyl)-1,3,5-three ), MIDORI chemical system TAZ-108 (2-(3,4-dimethoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-three ), diphenyl ketone, 4,4'-bis(diethylamino)diphenyl ketone, methyl-2-diphenyl ketone, 4-benzylidene-4'-methyldiphenyl sulphide Ether, 4-phenyldiphenyl ketone, ethyl melamine, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone 2,4-Diethylthioxanthone, 1-chloro-4-propoxythioxanthone, 2-methylthioxanthone, thioxanthone ammonium salt, benzoin, 4,4'-dimethyl Oxybenzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin butyl ether, benzyl dimethyl ketal, 1,1,1-three Chlorophene benzene, diethoxy acetophenone and dibenzocycloheptanone, methyl phthalic acid benzoate, 2-benzylidene naphthalene, 4-benzylidene biphenyl, 4-benzyl hydrazine Phenyl ether, 1,4-benzylidene benzene, benzoin, 10-butyl-2-chloroacridone, [4-(methylphenylthio)phenyl]phenylmethane), 2-B Base, 2,2-bis(2-chlorophenyl)4,5,4',5'-fluorene (3,4,5-trimethoxyphenyl) 1,2'-diimidazole, 2,2 - bis(o-chlorophenyl) 4,5,4',5'-tetraphenyl-1,2'-diimidazole, ginseng (4-dimethylamino group) Methane, ethyl-4-(dimethylamino)benzoate, 2-(dimethylamino)ethyl benzoate, butoxyethyl-4-(dimethylamino)benzene Formate and so on.

能夠適用於本發明的光硬化性組成物之光陽離子聚合引發劑,係若能夠藉由接受紫外線等的能量線而產生能夠引發光陽離子聚合的物質之化合物時即可,以鎓鹽之芳基鋶鹽或芳基碘鎓鹽等為佳。The photocationic polymerization initiator which can be used in the photocurable composition of the present invention is a compound which can form a substance capable of initiating photocationic polymerization by receiving an energy ray such as ultraviolet rays. A phosphonium salt or an aryl iodide salt is preferred.

而且,在本發明的光硬化性組成物,除了光聚合引發劑及/或光酸產生劑以外,亦可添加光敏化劑,來調整UV區域的波長。在本發明能夠使用之典型的敏化劑可舉出Crivello[J.V.Crivello,Adv.in Polymer Sci,62,1(1984年)]所揭示之物,具體上可舉出芘、苝、吖啶橙、噻噸酮、2-氯噻噸酮、苯并黃素、N-乙烯基咔唑、9,10-二丁氧基蒽、蒽醌、香豆素、氧代香豆素、菲、樟腦醌、啡噻衍生物等。Further, in the photocurable composition of the present invention, in addition to the photopolymerization initiator and/or the photoacid generator, a photosensitizer may be added to adjust the wavelength of the UV region. Typical sensitizers which can be used in the present invention include those disclosed by Crivello [JVCrivello, Adv. in Polymer Sci, 62, 1 (1984)], and specifically, ruthenium, osmium, acridine orange, Thioxanthone, 2-chlorothioxanthone, benzoxanthin, N-vinylcarbazole, 9,10-dibutoxyanthracene, anthraquinone, coumarin, oxocoumarin, phenanthrene, camphor Thiophene Derivatives, etc.

為了引發本發明之聚合的光,不只是紫外光、近紫外光、遠紫外光、可見光、紅外光等區域之波長的光或電磁波,亦包含放射線,放射線係例如包含微波、電子射線、EUV、X射線。又,亦可用248奈米準分子雷射、193奈米準分子雷射、172奈米準分子雷射等雷射光。此等光可以是透過濾光器之單色光(單一波長光),亦可以是複數不同波長的光(複合光)。曝光可以是多次曝光,為了提高膜強度、蝕刻耐性之目的,亦可以在形成圖案後,更進行整面曝光。In order to induce the light of the polymerization of the present invention, not only ultraviolet light, near ultraviolet light, far ultraviolet light, visible light, infrared light or the like, but also light or electromagnetic waves, the radiation system includes, for example, microwave, electron beam, EUV, X-rays. Further, laser light such as a 248 nm excimer laser, a 193 nm excimer laser, or a 172 nm excimer laser can be used. Such light may be monochromatic light (single wavelength light) transmitted through the filter, or multiple light of different wavelengths (composite light). The exposure may be multiple exposures, and for the purpose of improving film strength and etching resistance, it is also possible to perform full-surface exposure after patterning.

本發明所使用之光聚合引發劑,必須按照所使用光源的波長而適當地選擇,以在模具加壓、曝光中,不會產生氣體之物為佳。不會產生氣體之物時從不會污染模具、能降低洗滌模具的頻率、因為光硬化性組成物不容易在模具內變形而不會使轉印圖案精確度變差等觀點,乃是較佳。The photopolymerization initiator used in the present invention must be appropriately selected in accordance with the wavelength of the light source to be used, and it is preferred that the gas is not generated during pressurization or exposure of the mold. It is preferable that the gas is not generated, the mold is not contaminated, the frequency of the washing mold can be lowered, and the photocurable composition is not easily deformed in the mold without deteriorating the accuracy of the transfer pattern. .

本發明的光硬化性組成物含有0.001~5質量%氟系界面活性劑、矽系界面活性劑及氟-矽系界面活性劑中之至少1種。組成物中之上述界面活性劑比率以0.002~4質量%為佳,以0.005~3質量%為特佳。The photocurable composition of the present invention contains at least one of 0.001 to 5% by mass of a fluorine-based surfactant, a lanthanoid surfactant, and a fluorine-antimony surfactant. The ratio of the above surfactant in the composition is preferably 0.002 to 4% by mass, particularly preferably 0.005 to 3% by mass.

在此,氟-矽系界面活性劑係指同時具有氟系界面活性劑及矽系界面活性劑雙方的必要條件之物。Here, the fluorine-rhodium-based surfactant refers to a material having both a fluorine-based surfactant and a lanthanoid surfactant.

藉由使用此種界面活性劑,能夠降低組成物的黏度,其目的係用以解決將本發明的光硬化性組成物塗布於半導體元件製造用矽晶圓、液晶元件製造用的玻璃四方基板、形成有鉻膜、鉬模、鉬合金膜、鉭膜、鉭合金膜、氮矽膜、非晶矽膜、摻合氧化錫而成的氧化銦(ITO)膜或氧化錫膜等各種膜等之基板上時所產生的條紋或鱗狀的花樣(光阻膜的乾燥不均)等塗布不良的問題、改良組成物往模具凹部的槽內流動、改良模具與光阻劑間的脫膜性、改良光阻劑與基板間的粘附性。特別是,在本發明的光硬化性組成物,藉由添加上述界面活性劑,能夠大幅度地改良塗布均勻性,在使用旋轉塗布或狹縫塗布之塗布,不管基板尺寸都能夠得到良好的塗布適合性。By using such a surfactant, the viscosity of the composition can be reduced, and the purpose of the present invention is to solve the problem of applying the photocurable composition of the present invention to a silicon wafer for manufacturing a semiconductor device or a glass square substrate for manufacturing a liquid crystal device. A chromium film, a molybdenum mold, a molybdenum alloy film, a ruthenium film, a ruthenium alloy film, a nitrogen ruthenium film, an amorphous ruthenium film, an indium oxide (ITO) film in which tin oxide is doped, or a film such as a tin oxide film are formed. Problems such as coating defects such as streaks or scaly patterns (drying unevenness of the photoresist film) generated on the substrate, improvement of the flow of the composition into the grooves of the mold recess, improvement of the release property between the mold and the photoresist, Improve the adhesion between the photoresist and the substrate. In particular, in the photocurable composition of the present invention, coating uniformity can be greatly improved by adding the above-mentioned surfactant, and coating by spin coating or slit coating can be applied regardless of the substrate size. Suitability.

在本發明所使用之非離子氟系界面活性劑的例子,可舉出商品名FRORAD FC-430、FC431(住友3M公司製)、商品名SARFRON「S-382」(旭硝子製)、EFTOP「EF-122A、122B、l22C、EF-121、EF-126、EF-127、MF-100」(TOHKEM PRODUCT公司製)、商品名PF-636、PF-6320、PF-656、PF-6520(任一者都是OMNOVA公司製)、商品名FTAGENT FT250、FT251、DFX18(任一者都是NEOS(股)製)、商品名YUNIDAIN DS-401、DS-403、DS-451(任一者都是DAIKIN工業(股)製)、商品名MEGAFAC 171、172、173、178K、178A(任一者都是大日本油墨化學工業(股)製),非離子性矽系界面活性劑的例子可舉出例如商品名SI-10系列(竹本油脂公司製)、MEGAFACPENTAD31(大日本油墨化學工業(股)製)、KP-341(信越化學工業製)。Examples of the nonionic fluorine-based surfactant to be used in the present invention include FRORAD FC-430 and FC431 (manufactured by Sumitomo 3M Co., Ltd.), SARFRON "S-382" (made by Asahi Glass Co., Ltd.), and EFTOP "EF". -122A, 122B, l22C, EF-121, EF-126, EF-127, MF-100" (manufactured by TOHKEM PRODUCT Co., Ltd.), trade name PF-636, PF-6320, PF-656, PF-6520 (any All are manufactured by OMNOVA), trade names FTAGENT FT250, FT251, DFX18 (any one is NEOS (share) system), trade names YUNIDAIN DS-401, DS-403, DS-451 (any one is DAIKIN) Industrial Co., Ltd., and trade names MEGAFAC 171, 172, 173, 178K, and 178A (all of which are manufactured by Dainippon Ink Chemical Industry Co., Ltd.), and examples of the nonionic lanthanum surfactant are exemplified by Product name: SI-10 series (made by Takemoto Oil Co., Ltd.), MEGAFACPENTAD31 (made by Dainippon Ink Chemical Industry Co., Ltd.), KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.).

本發明所使用的氟-矽系界面活性劑可舉出例如商品名X-70-090、X-70-091、X-70-092、X-70-093(任一者都是信越化學工業製)、商品名MEGAFAC R-08、XRB-4(任一者都是大日本油墨化學工業(股)製)。The fluorine-antimony surfactant used in the present invention may, for example, be trade names X-70-090, X-70-091, X-70-092, X-70-093 (any one is Shin-Etsu Chemical Industry) (product) MEGAFAC R-08, XRB-4 (any one is manufactured by Dainippon Ink Chemical Industry Co., Ltd.).

氟系界面活性劑、矽系界面活性劑、及氟-矽系界面活性劑的調配量係此等之界面活性劑的合計量,在組成物中調配0.001~5質量%的範圍,以在0.01~3質量%的範圍添加為佳。氟系界面活性劑、矽系界面活性劑、及氟-矽系界面活性劑在組成物中調配小於0.001質量%時,塗布的均勻性效果不充分,另一方面,大於5質量%時,因為會使模具轉印特性變差,乃是不佳。本發明所使用的氟系界面活性劑、矽系界面活性劑、及氟-矽系界面活性劑可單獨使用,亦可組合使用2種類以上。在本發明,以含有氟系界面活性劑及矽系界面活性劑的雙方、或氟-矽系界面活性劑為佳,以含有氟-矽系界面活性劑為最佳。The blending amount of the fluorine-based surfactant, the rhodium-based surfactant, and the fluorine-fluorene-based surfactant is a total amount of these surfactants, and is adjusted in the range of 0.001 to 5% by mass in the composition to be 0.01. A range of ~3 mass% is preferably added. When the fluorine-based surfactant, the lanthanoid surfactant, and the fluorine-ruthenium-based surfactant are blended in the composition to be less than 0.001% by mass, the effect of uniformity of coating is insufficient. On the other hand, when it is more than 5% by mass, It will make the transfer characteristics of the mold worse, which is not good. The fluorine-based surfactant, the lanthanoid surfactant, and the fluorine-antimony surfactant used in the present invention may be used singly or in combination of two or more. In the present invention, it is preferable to contain both a fluorine-based surfactant and a lanthanoid surfactant, or a fluorine-ruthenium-based surfactant, and it is preferable to contain a fluorine-ruthenium-based surfactant.

為了改良光硬化性組成物的柔軟性等目的,亦可在本發明的光硬化性組成物並用其他的非離子系界面活性劑。非離子系界面活性劑的市販品能夠例示的有竹本油脂(股)製之PIONINE系列的D-3110、D-3120、D-3412、D-3440、D-3510、D-3605等的聚氧乙烯烷基胺、竹本油脂(股)製之PIONINE系列的D-1305、D-1315、D-1405、D-1420、D-1504、D-1508、D-1518等的聚氧乙烯烷基醚、竹本油脂(股)製之PIONINE系列的D-2112-A、D-2112-C、D-2123-C等的聚氧乙烯一脂肪酸酯、竹本油脂(股)製之PIONINE系列的D-2405-A、D-2410-D、D-2110-D等的聚氧乙烯二脂肪酸酯、竹本油脂(股)製之PIONINE系列的D-406、D-410、D-414、D-418等的聚氧乙烯烷基苯基醚、日信化學工業(股)製的SAFINOL系列的104S、420、440、465、485等的聚氧乙烯四甲基癸炔二醇二醚等。又具有聚合性不飽和基之反應性界面活性劑亦能與本發明所使用的界面活性劑並用。可舉出例如烯丙氧基聚乙二醇單甲基丙烯酸酯(日本油脂(股)商品名:BLENMER PKE系列)、壬基苯氧基聚乙二醇單甲基丙烯酸酯(日本油脂(股)商品名:BLENMER PNE系列)、壬基苯氧基聚丙二醇單甲基丙烯酸酯(日本油脂(股)商品名:BLENMER PNP系列)、壬基苯氧基聚(乙二醇-丙二醇)單甲基丙烯酸酯(日本油脂(股)商品名:BLENMER PNEP-600)、AKUARON RN-10、RN-20、RN-30、RN-50、RN-2025、HS-05、HS-10、HS-20(第一工業製藥(股)製)等。For the purpose of improving the flexibility of the photocurable composition, etc., other nonionic surfactants may be used in combination with the photocurable composition of the present invention. A commercially available product of a non-ionic surfactant is exemplified by polyoxane such as D-3110, D-3120, D-3412, D-3440, D-3510, and D-3605 of PIONINE series manufactured by Takemoto Oil Co., Ltd. Polyoxyethylene alkyl ethers of D-1305, D-1315, D-1405, D-1420, D-1504, D-1508, D-1518, etc. of PIONINE series manufactured by ethylene alkylamine and Zhuben Oil Co., Ltd. PIONINE series of D-2112-A, D-2112-C, D-2123-C and other polyoxyethylene mono-fatty acid esters of the PIONINE series, and the PIONINE series of D-made by the bamboo oils and fats. Polyoxyethylene difatty acid esters such as 2405-A, D-2410-D, and D-2110-D, D-406, D-410, D-414, and D-418 of PIONINE series manufactured by Takeshi Oil Co., Ltd. Polyoxyethylene alkyl phenyl ether, etc., polyoxyethylene tetramethyl decyne diol diether such as 104S, 420, 440, 465, and 485 of the SAFINOL series manufactured by Nissin Chemical Industry Co., Ltd., and the like. Further, a reactive surfactant having a polymerizable unsaturated group can also be used in combination with the surfactant used in the present invention. For example, allyloxy polyethylene glycol monomethacrylate (Japanese fat (stock) trade name: BLENMER PKE series), nonylphenoxy polyethylene glycol monomethacrylate (Japanese fats and oils) ): BLENMER PNE series), mercaptophenoxy polypropylene glycol monomethacrylate (Japanese fat (stock) trade name: BLENMER PNP series), nonylphenoxy poly(ethylene glycol-propylene glycol) monomethyl Acrylate (Japanese oil (stock) trade name: BLENMER PNEP-600), AKUARON RN-10, RN-20, RN-30, RN-50, RN-2025, HS-05, HS-10, HS-20 (First Industrial Pharmaceutical Co., Ltd.) and the like.

本發明的光硬化性組成物除了上述成分以外,亦可按照必要添加脫模劑、矽烷偶合劑、聚合抑制劑、抗氧化劑、紫外線吸收劑、光安定劑、防老劑、可塑劑、黏附促進劑、熱聚合引發劑、著色劑、無機粒子、彈性體粒子、抗氧化劑、光酸增殖劑、光鹼產生劑、鹼性化合物、流動調整劑、消泡劑、分散劑等。In addition to the above components, the photocurable composition of the present invention may further contain a release agent, a decane coupling agent, a polymerization inhibitor, an antioxidant, an ultraviolet absorber, a photostabilizer, an antioxidant, a plasticizer, and an adhesion promoter, as necessary. , a thermal polymerization initiator, a colorant, inorganic particles, elastomer particles, an antioxidant, a photoacid proliferation agent, a photobase generator, a basic compound, a flow regulator, an antifoaming agent, a dispersant, and the like.

為了提高有微細凹凸圖案之表面結構的耐熱性、強度、或與金屬蒸鍍層之黏附性,在本發明的光硬化性組成物亦可調配有機金屬偶合劑。又,有機金屬偶合劑具有促進行熱硬化反應之效果。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、錫偶合劑等各種偶合劑。In order to improve the heat resistance, the strength, or the adhesion to the metal deposition layer of the surface structure having the fine concavo-convex pattern, the photocurable composition of the present invention may be formulated with an organic metal coupling agent. Further, the organic metal coupling agent has an effect of promoting a heat hardening 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.

在光硬化性組成物的固體成分總量中,上述有機金屬偶合劑可任意地調配0.001~10質量%的比率。藉由使有機金屬偶合劑的比率為0.001質量%以上,在改良耐熱性、強度、或賦予與金屬蒸鍍層的黏附性方面,具有效果更大的傾向。另一方面,藉由使有機金屬偶合劑的比率為10質量%以下,具有抑制組成物的安定性、成膜性的缺損之傾向,乃是較佳。The organometallic coupling agent may be optionally blended at a ratio of 0.001 to 10% by mass based on the total amount of the solid components of the photocurable composition. When the ratio of the organic metal coupling agent is 0.001% by mass or more, the effect is improved in terms of improving heat resistance, strength, or adhesion to the metal deposition layer. On the other hand, when the ratio of the organic metal coupling agent is 10% by mass or less, it tends to suppress the stability of the composition and the defect of film formability.

抗氧化劑之市售品,可舉出Irganox1010、1035、1076、1222(以上,CIBA-GEIGY(股)製、Antigene P、3C、FR、SUMILIZER(住友化學工業製)等。相對於組成物的總量,抗氧化劑以0.01~10質量%的比率調配為佳。The commercially available products of the antioxidants include Irganox 1010, 1035, 1076, and 1222 (above, CIBA-GEIGY Co., Ltd., Antigene P, 3C, FR, SUMILIZER (manufactured by Sumitomo Chemical Industries, Ltd.), etc. The amount of the antioxidant is preferably 0.01 to 10% by mass.

紫外線吸收劑的市售品可舉出例如Tinuvin P、234、320、326、327、328、213(以上,CIBA-GEIGY(股)製、Sumisorb 110、130、140、220、250、300、320、340、350、400(以上,住友化學工業(股)製)等。相對於光硬化性組成物的總量,紫外線吸收劑以任意地調配0.01~10質量%為佳。Commercial products of the ultraviolet absorber include, for example, Tinuvin P, 234, 320, 326, 327, 328, and 213 (above, CIBA-GEIGY Co., Ltd., Sumisorb 110, 130, 140, 220, 250, 300, 320). 340, 350, 400 (above, Sumitomo Chemical Co., Ltd.), etc. The ultraviolet absorber is preferably arbitrarily blended in an amount of 0.01 to 10% by mass based on the total amount of the photocurable composition.

光安定劑的市售品可舉出例如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。相對於組成物的總量,光安定劑以調配0.01~10質量%的比率為佳。Commercial products of the light stabilizers include, for example, Tinuvin 292, 144, and 622 LD (above, CIBA-GEIGY Co., Ltd., SANOL LS-770, 765, 292, 2626, 1114, 744 (above, Sankyo Chemical Industry Co., Ltd.) The system is preferably a ratio of 0.01 to 10% by mass based on the total amount of the composition.

防老劑之市售品可舉出Antigene W、S、P、3C、6C、RD-G、FR、AW(以上,住友化學工業(股)製)等。相對於組成物的總量,防老劑以調配0.01~10質量%的比率為佳。Commercial products of the anti-aging agent include Antigene W, S, P, 3C, 6C, RD-G, FR, AW (above, Sumitomo Chemical Industries Co., Ltd.). The ratio of the antioxidant to the total amount of the composition is preferably 0.01 to 10% by mass.

為了調整本發明的光硬化性組成物與基板之黏附性或膜的柔軟性、硬度等,可在本發明的光硬化性組成物添加可塑劑。較佳之可塑劑之具體例,有例如酞酸二辛酯、酞酸二月桂酯、三甘醇二辛酸酯、二甲基乙醇酞酸酯、磷酸三甲苯酯、己二酸二辛酯、癸二酸二丁酯、三乙醯基甘油、己二酸二甲酯、己二酸二乙酯、己二酸二正丁酯、辛二酸二甲酯、辛二酸二乙酯、辛二酸二正丁酯等,在組成物中可塑劑能夠以30質量%以下任意添加。以20質量%以下為佳,以10質量%以下為更佳。為了得到可塑劑的添加效果,以0.1質量%以上為佳。A plasticizer may be added to the photocurable composition of the present invention in order to adjust the adhesion between the photocurable composition of the present invention and the substrate, or the flexibility, hardness, and the like of the film. Specific examples of preferred plasticizers include, for example, dioctyl phthalate, dilauryl citrate, triethylene glycol dicaprylate, dimethylethanol phthalate, tricresyl phosphate, dioctyl adipate, Dibutyl sebacate, triethyl decyl glycerol, dimethyl adipate, diethyl adipate, di-n-butyl adipate, dimethyl suberate, diethyl suberate, octyl In the composition, the plasticizer can be arbitrarily added in an amount of 30% by mass or less. 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.

使本發明的光硬化性組成物硬化時,亦能夠按照必要添加熱聚合引發劑。較佳之熱聚合引發劑可舉出例如過氧化物、偶氮化合物。具體上可舉出過氧化苯甲醯、過氧化苯甲酸第三丁酯、偶氮雙異丁腈等。When the photocurable composition of the present invention is cured, a thermal polymerization initiator can be added as necessary. Preferred examples of the thermal polymerization initiator include a peroxide and an azo compound. Specific examples thereof include benzamidine peroxide, tert-butyl peroxybenzoate, azobisisobutyronitrile, and the like.

為了調整圖案形狀、感度等之目的,亦可按照必要在本發明的光硬化性組成物添加光鹼產生劑。可舉出的較佳之物有例如2-硝基苄基環己基胺基甲酸酯、三苯基甲醇、O-胺基甲醯羥基醯胺、O-胺基甲醯肟、[[(2,6-二硝基苄基)氧基]羰基]環己胺、雙[[(2-硝基苄基)氧基]羰基]己烷1,6-二胺、4-(甲硫基苯甲醯基)-1-甲基-1-啉乙烷、(4-啉苯甲醯基)-1-苄基-1-二甲胺基丙烷、N-(2-硝基苄氧基羰基)吡咯啶、參(三苯基甲基硼酸)六氨鈷(III)、2-苄基-2-二甲胺基-1-(4-啉苯基)-丁烷、2,6-二甲基-3,5-二乙醯-4-(2’-硝基苯基)-1,4-二吡咯吡啶、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。For the purpose of adjusting the shape, sensitivity, and the like, a photobase generator may be added to the photocurable composition of the present invention as necessary. Preferred examples include, for example, 2-nitrobenzylcyclohexylcarbamate, triphenylmethanol, O-aminoformamidine hydroxyguanamine, O-aminoformamidine, [[(2) ,6-dinitrobenzyl)oxy]carbonyl]cyclohexylamine, bis[[(2-nitrobenzyl)oxy]carbonyl]hexane 1,6-diamine, 4-(methylthiobenzene) Methotyl)-1-methyl-1- Chlorinated ethane, (4- Phenylbenzylidene)-1-benzyl-1-dimethylaminopropane, N-(2-nitrobenzyloxycarbonyl)pyrrolidine, ginseng(triphenylmethylborate)hexa-cobalt(III) 2-benzyl-2-dimethylamino-1-(4- Phenylphenyl)-butane, 2,6-dimethyl-3,5-diethylindole-4-(2'-nitrophenyl)-1,4-dipyrrolidine, 2,6-dimethyl 3-3,5-Diethylinden-4-(2',4'-dinitrophenyl)-1,4-dihydropyridine or the like.

為了提高塗膜的可見性之目的,本發明的光硬化性組成物亦可任意地添加著色劑。在不損害本發明的目的之範圍,著色劑可使用UV噴墨組成物、彩色濾光片用組成物及CCD影像傳感器用組成物等之顏料或染料。本發明可使用的顏料可使用先前眾所周知的各種無機顏料或有機顏料。無機顏料有金屬氧化物、金屬錯鹽等所示之金屬化合物,具體上可舉出鐵、鈷、鋁、鎘、鉛、銅、鈦、鎂、鉻、鋅、銻等金屬氧化物、金屬複合氧化物。有機顏料可例示的有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。In order to improve the visibility of the coating film, the photocurable composition of the present invention may optionally be added with a coloring agent. In the range which does not impair the object of the present invention, a pigment or a dye such as a composition for a UV inkjet composition, a composition for a color filter, and a composition for a CCD image sensor can be used as the colorant. As the pigment which can be used in the present invention, various inorganic pigments or organic pigments which are well known in the past can be used. Examples of the inorganic pigment include a metal compound such as a metal oxide or a metal salt, and specific examples thereof include metal oxides such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, and antimony, and metal composites. Oxide. The organic pigments can be exemplified by 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, 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.

無機微粒子在光硬化性組成物的固體成分總量中,以調配1~70質量%的比率為佳,以調配1~50質量%的比率為特佳。藉由使無機微粒子的比率為1質量%以上,能夠充分地提升本發明之光硬化性組成物的賦型性、形狀維持性及脫模性,使無機微粒子的比率為70質量%以下時,從曝光硬後的強度及表面硬度而言,乃是較佳。The inorganic fine particles are preferably a ratio of 1 to 70% by mass in the total solid content of the photocurable composition, and a ratio of 1 to 50% by mass is particularly preferable. When the ratio of the inorganic fine particles is 1% by mass or more, the formability, the shape retainability, and the mold release property of the photocurable composition of the present invention can be sufficiently increased, and when the ratio of the inorganic fine particles is 70% by mass or less, It is preferable from the viewpoint of the strength after the exposure and the surface hardness.

又,為了提升機械強度、柔軟性等之目的,可在本發明的光硬化性組成物任意地添加彈性體粒子。Moreover, in order to improve mechanical strength, flexibility, and the like, the elastomer particles may be arbitrarily added to the photocurable composition of the present invention.

能夠在本發明的光硬化性組成物添加作為任意成分之彈性體粒子的平均粒子大小以10奈米~700奈米為佳,以30奈米~300奈米為更佳。例如有聚丁二烯、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/多烯共聚物、丙烯酸橡膠、丁二烯/(甲基)丙烯酸酯共聚物、苯乙烯/丁二烯嵌段共聚物、苯乙烯/異丙烯嵌段共聚物等彈性體的粒子。又,可使用將此等彈性體粒子使用甲基丙烯酸甲酯聚合物、甲基丙烯酸甲酯/甲基丙烯酸環氧丙酯共聚物等被覆而成的芯/殼型粒子。彈性體粒子亦可以是交聯結構。The average particle size of the elastomer particles which can be added as an optional component to the photocurable composition of the present invention is preferably from 10 nm to 700 nm, more preferably from 30 nm 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/isopropylene A particle of an elastomer such as a segment 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 be crosslinked structures.

此等彈性體粒子可單獨使用,亦可組合使用2種以上。在本發明的光硬化性組成物之彈性體成分的含有比率以1~35質量%為佳,以2~30質量%為更佳,以3~20質量%為特佳。These elastomer particles may be used singly or in combination of two or more. The content ratio of the elastomer component of the photocurable composition of the present invention is preferably 1 to 35% by mass, more preferably 2 to 30% by mass, and particularly preferably 3 to 20% by mass.

在本發明的光硬化性組成物,能夠含有眾所周知的抗氧化劑。抗氧化劑係用以抑制因光照射所引起的褪色及因臭氧、活性氧、NOx 、SOx (X為整數)等各種氧化性氣體所引起的褪色之物。此等抗氧化劑可舉出肼類、受阻胺系抗氧化劑、含氮雜環氫硫系化合物、硫醚系抗氧化劑、受阻酚系抗氧化劑、抗壞血酸類、硫酸鋅、硫氰酸鹽類、硫脲衍生物、糖類、亞硝酸鹽、亞硫酸鹽、硫代硫酸鹽、羥基胺衍生物等。The photocurable composition of the present invention can contain a well-known antioxidant. Based antioxidant to inhibit discoloration caused by light irradiation and by ozone, active oxygen, NO x, SO x (X is an integer), and other oxidizing gases of fading was caused. Examples of such antioxidants include anthraquinones, hindered amine-based antioxidants, nitrogen-containing heterocyclic hydrogen sulfide-based compounds, thioether-based antioxidants, hindered phenol-based antioxidants, ascorbic acid, zinc sulfate, thiocyanate, and sulfur. Urea derivatives, sugars, nitrites, sulfites, thiosulfates, hydroxylamine derivatives, and the like.

為了抑制硬化收縮、提高熱安定性等之目的,在本發明的光硬化性組成物亦可任意地添加鹼性化合物。鹼性化合物可舉出例如胺和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。其中,從與光聚合單體之相溶性方面,以胺為佳,可舉出例如辛胺、萘胺、苯二甲胺、二苄基胺、二苯胺、二丁胺、二辛胺、二甲基苯胺、奎寧環、三丁胺、二辛胺、四甲基伸乙二胺、四甲基-1,6-六亞甲二胺、六亞甲四胺及三乙醇胺等。The basic compound may be arbitrarily added to the photocurable composition of the present invention for the purpose of suppressing the curing shrinkage and improving the thermal stability. The basic compound may, for example, be an amine and a quinoline and a quinolin. A nitrogen-containing heterocyclic compound, a basic alkali metal compound, a basic alkaline earth metal compound, or the like. Among them, an amine is preferred from the viewpoint of compatibility with a photopolymerizable monomer, and examples thereof include octylamine, naphthylamine, xylylenediamine, dibenzylamine, diphenylamine, dibutylamine, dioctylamine, and Methylaniline, quinuclidine, tributylamine, dioctylamine, tetramethylethylenediamine, tetramethyl-1,6-hexamethylenediamine, hexamethylenetetramine and triethanolamine.

在本發明,亦可在藉由能量線產生酸之陽離子聚合引發劑中,組合藉由所產生的酸之作用來產生新的自觸媒性酸之物質(以下稱為酸增殖劑),來提高硬化速度。作為酸增殖劑,例如特開平08-248561號公報、特開平10-1508號公報、特許第3102640號公報所示之化合物,具體上可舉出1,4-雙(對甲苯磺醯氧基)環己烷、順-3-(對甲苯磺醯氧基)-2-蒎烷醇、順-3-(對辛烷磺醯氧基)-2-蒎烷醇等。市售的化合物可舉出AKPREX11M(日本CHEMIX公司製)等。In the present invention, in the cationic polymerization initiator which generates an acid by an energy ray, a substance which generates a new self-catalytic acid (hereinafter referred to as an acid proliferator) by the action of the generated acid may be combined. Improve the hardening speed. Specific examples of the compound shown in JP-A-H08-248561, JP-A No. 10-1508, and No. 3102640 include 1,4-bis(p-toluenesulfonyloxy). Cyclohexane, cis-3-(p-toluenesulfonyloxy)-2-nonanol, cis-3-(p-octanesulfonyloxy)-2-nonanol, and the like. Commercially available compounds include AKPREX 11M (manufactured by CHEMIX Co., Ltd.) and the like.

接著,說明使用本發明的光硬化性組成物之圖案(特別是微細凹凸圖案)的形成方法。本發明係塗布硬化性組成物並使其硬化來形成圖案。具體上,係在基板或支撐體上至少塗布由本發明的光硬化性組成物所構成的圖案形成層,按照必要使其乾燥而形成由光硬化性組成物所構成的層(圖案形成層)來製造圖案收受體,並使模具對該圖案收受體的圖案形成層表面進行加壓熔接,來進行模具圖案的轉印加工,然後將微細凹凸圖案形成層曝光而使硬化。依照本發明的圖案形成方法之光壓印微影法亦能夠積層化或多重圖案化,亦能夠組合通常的熱壓印法而使用。Next, a method of forming a pattern (particularly, a fine concavo-convex pattern) using the photocurable composition of the present invention will be described. In the present invention, a curable composition is applied and hardened to form a pattern. Specifically, at least a pattern forming layer composed of the photocurable composition of the present invention is applied onto a substrate or a support, and dried as necessary to form a layer (pattern forming layer) composed of a photocurable composition. The pattern is received and received by the mold, and the surface of the pattern forming layer of the pattern acceptor is pressure-welded to transfer the mold pattern, and then the fine uneven pattern forming layer is exposed and cured. The photoimprint lithography method according to the pattern forming method of the present invention can also be laminated or multi-patterned, and can also be used in combination with a usual hot stamping method.

又,應用本發明之光硬化性組成物,在基板或支撐體上塗布本發明的光硬化性組成物,藉由使由該組成物所構成的層曝光、硬化、按照必要使其乾燥(烘焙),亦能夠製造保護膜層或絕緣膜等永久膜。Further, by applying the photocurable composition of the present invention, the photocurable composition of the present invention is applied onto a substrate or a support, and the layer composed of the composition is exposed, cured, and dried as necessary (baking) ), it is also possible to manufacture a permanent film such as a protective film layer or an insulating film.

以下,使用敘述本發明的光硬化性組成物之圖案的形成方法、圖案轉印方法。Hereinafter, a method of forming a pattern of the photocurable composition of the present invention and a pattern transfer method will be described.

本發明的光硬化性組成物能夠藉由通常已知的塗布方法例如浸漬法、氣動刮塗法、簾流塗布法、棒材塗布法、凹版塗布法、擠壓塗布法、旋轉塗布法、狹縫塗布法進行塗布來形成。由本發明的光硬化性組成物所構成的層之膜厚度係依照使用用途而異,為0.05微米~30微米。又,本發明的光硬化性組成物亦能夠進行多重塗布。The photocurable composition of the present invention can be applied by a generally known coating method such as a dipping method, a pneumatic blade coating method, a curtain coating method, a bar coating method, a gravure coating method, an extrusion coating method, a spin coating method, or a narrow coating method. The slit coating method is applied by coating. The film thickness of the layer composed of the photocurable composition of the present invention varies from 0.05 μm to 30 μm depending on the intended use. Further, the photocurable composition of the present invention can also be subjected to multiple coating.

為塗布本發明光硬化性組成物之基板或支撐體係石英、玻璃、光學薄膜、陶瓷材料、蒸鍍膜、磁性膜、反射膜、Ni、Cu、Cr、Fe等的金屬基板、紙、SOG、聚酯薄膜、聚碳酸酯薄膜、聚醯亞胺薄膜等的聚合物基板、TFT陣列基板、PDP的電極板、玻璃或透明塑膠基板、ITO或金屬等的導電性基材、絕緣性基材、矽、氮化矽、多晶矽、氧化矽、非晶矽等的半導體製造基板等,沒有特別限定。基板的形狀可以是板狀、亦可以是輥狀。A substrate, a supporting system of the photocurable composition of the present invention, a quartz, a glass, an optical film, a ceramic material, a vapor deposited film, a magnetic film, a reflective film, a metal substrate of Ni, Cu, Cr, Fe, etc., paper, SOG, poly A polymer substrate such as an ester film, a polycarbonate film or a polyimide film, a TFT array substrate, an electrode plate of a PDP, a glass or a transparent plastic substrate, a conductive substrate such as ITO or metal, an insulating substrate, or a crucible A semiconductor-made substrate such as tantalum nitride, polycrystalline germanium, cerium oxide, or amorphous germanium is not particularly limited. The shape of the substrate may be a plate shape or a roll shape.

使本發明的光硬化性組成物硬化之光沒有特別限定,可舉出例如高能量電離放射線、近紫外、遠紫外、可見、紅外等區域波長的光或放射線。高能量電離放射線源係例如藉由科克羅夫特型加速器、范德格拉夫型加速器、線性加速器、電子回旋加速器、回旋加速器等加速器加速而成的電子射線,在工業上便利且能夠經濟地使用,此外,亦可使用從放射性同位元素或原子爐等所放射的γ射線、X射線、α射線、中子射線、質子射線等放射線。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、水銀燈等。放射線包含例如微波、EUV。又,在本發明,LED、半導體雷射光、或是248奈米的KrF準分子雷射光或193奈米ArF準分子雷射等半導體微細加工所使用的雷射光亦適合使用。此等光可以是單色光,亦可以是複數不同波長的光(混合光)。The light for curing the photocurable composition of the present invention is not particularly limited, and examples thereof include light or radiation having a wavelength of a region such as high energy ionizing radiation, near ultraviolet light, far ultraviolet light, visible light, or infrared light. The high-energy ionizing radiation source is an electron beam accelerated by an accelerator such as a Cockcroft type accelerator, a Vandergrave type accelerator, a linear accelerator, an electron cyclotron, a cyclotron, etc., which is industrially convenient and economical. Further, it is also possible to use radiation such as gamma rays, X rays, alpha rays, neutron rays, or proton rays emitted from a radioactive isotope element 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 mercury lamp. Radiation includes, for example, microwaves, EUV. Further, in the present invention, laser light used for semiconductor microfabrication such as LED, semiconductor laser light, or 248 nm KrF excimer laser light or 193 nm ArF excimer laser is also suitable. These lights may be monochromatic light or multiple light of different wavelengths (mixed light).

說明在本發明能夠使用的模具材。使用本發明的光硬化性組成物之光奈米壓印微影法,在模具材及/或基板之至少一方,必須選擇光透射性材料。應用於本發明之光奈米壓印微影法,係在基板上塗布光硬化性組成物,然後將光透射性模具壓住,並從模具的背面照射光,來使光硬化性組成物硬化。又,亦可在光透射性基板上塗布光硬化性組成物,然後壓住模具,從模具的背面照射光,來使光硬化性組成物硬化。A mold material that can be used in the present invention will be described. The light-transmitting lithography method of the photocurable composition of the present invention requires selection of a light-transmitting material in at least one of the mold material and/or the substrate. The photon nanoimprint lithography method applied to the present invention is characterized in that a photocurable composition is coated on a substrate, and then the light transmissive mold is pressed, and light is irradiated from the back surface of the mold to harden the photocurable composition. . Further, the photocurable composition may be applied to the light-transmitting substrate, and then the mold may be pressed to irradiate light from the back surface of the mold to cure the photocurable composition.

光照射可以在黏附著模具的狀態下進行,亦可在模具剝離後進行,在本發明,以在黏附著模具的狀態下進行為佳。The light irradiation may be carried out in a state in which the mold is adhered, or may be performed after the mold is peeled off, and in the present invention, it is preferably carried out in a state in which the mold is adhered.

本發明能夠使用的模具,可使用具有應轉印圖案之模具。模具能夠藉由例如光微影法或電子射線描繪法,按照需要的加工精確度來形成圖案,在本發明,模具圖案形成方法沒有特別限制。For the mold that can be used in the present invention, a mold having a pattern to be transferred can be used. The mold can be patterned in accordance with a desired processing precision by, for example, photolithography or electron beam drawing. In the present invention, the mold pattern forming method is not particularly limited.

在本發明能夠使用的光透射性模具材沒有特別限定,若具有規定強度、耐久性之物即可。具體上,可例示的有玻璃、石英、PMMA、聚碳酸酯樹脂等光透明性樹脂、透明金屬蒸鍍膜、聚二甲基矽氧烷等的柔軟膜、光硬化膜、金屬膜等。The light-transmitting mold material which can be used in the present invention is not particularly limited, and may have a predetermined strength and durability. Specifically, a light-transparent resin such as glass, quartz, PMMA or polycarbonate resin, a transparent metal vapor-deposited film, a soft film such as polydimethyl siloxane or a photocured film or a metal film can be exemplified.

使用本發明的透明基板時,能夠使用之非光透射型模具材沒有特別限定,若具有規定強度即可。具體上,可例示的有陶瓷材料、蒸鍍膜、磁性膜、反射膜、Ni、Cu、Cr、Fe等的金屬基板、SiC、矽、氮化矽、多晶矽、氧化矽、非晶矽等的基板等,沒有特別限制。形狀可以是板狀模具、輥狀模具中任一者,輥狀模具特別是能應用在必須連續地轉印生產之情況。When the transparent substrate of the present invention is used, the non-light-transmitting mold material that can be used is not particularly limited, and may have a predetermined strength. Specifically, a ceramic material, a vapor deposited film, a magnetic film, a reflective film, a metal substrate such as Ni, Cu, Cr, or Fe, or a substrate such as SiC, tantalum, tantalum nitride, polycrystalline germanium, germanium oxide, or amorphous germanium may be exemplified. Etc., there are no special restrictions. The shape may be any one of a plate-shaped mold and a roll-shaped mold, and the roll-shaped mold can be applied particularly in a case where it is necessary to continuously transfer the production.

上述本發明所使用的模具亦可使用進行過脫模處理之物,用以提升光硬化性組成物與模具的剝離性。藉由矽系或氟系等的矽烷偶合劑進行處理過之物,例如DAIKIN工業製:商品名OPTOOL DSX或住友3M製:商品名Novec EGC-1720等市售的脫模劑亦適合使用。The mold used in the above invention may also be subjected to a release treatment to improve the peelability of the photocurable composition from the mold. A commercially available release agent such as DAIKIN Industrial Co., Ltd., trade name: OPTOOL DSX or Sumitomo 3M: trade name Novec EGC-1720 is also suitable for use as a treatment with a decane coupling agent such as a fluorene or a fluorine-based compound.

使用本發明進行光壓印微影時,通常,以在模具的壓力為10氣壓以下進行為佳。藉由模具的壓力為10氣壓以下,模具或基板不容易變形,且圖案精確度有提升的傾向,又,因為加壓較低,所以有能夠縮小裝置的傾向,乃是較佳。模具壓力以在模具凸部之光硬化性組成物的殘膜變少的範圍、且能夠確保模具轉印的均勻性之區域選擇為佳。When photoimprint lithography is carried out using the present invention, it is usually preferred to carry out the pressure at the mold to be 10 or less. When the pressure of the mold is 10 or less, the mold or the substrate is not easily deformed, and the pattern accuracy tends to be improved. Further, since the pressurization is low, there is a tendency that the apparatus can be reduced, which is preferable. The mold pressure is preferably selected in a region where the residual film of the photocurable composition of the mold convex portion is small and the uniformity of the transfer of the mold can be ensured.

在本發明,若光壓印微影時之光照射若比硬化所必要的照射量大相當多時即可。硬化所必須的照射量係調查光硬化性組成物之不飽和鍵的消耗量或硬化膜的膠黏性來決定。In the present invention, it is sufficient that the light irradiation at the time of photoimprint lithography is considerably larger than the amount of irradiation necessary for hardening. The amount of irradiation necessary for hardening is determined by investigating the consumption of the unsaturated bond of the photocurable composition or the adhesiveness of the cured film.

又,能夠應用本發明之光壓印微影法,光照射時之基板溫度通常係在室溫進行,但是為了提高反應性,亦可邊加熱邊光照射。光照射的前階段若在真空狀態時,因為能夠防止氣泡混入,抑制因氧混入所造成的反應性下降,且具有提升模具與光硬化性組成物的黏附性之效果,所以亦可以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至常壓的範圍進行。Further, the photoimprint lithography method of the present invention can be applied, and the substrate temperature at the time of light irradiation is usually performed at room temperature, but in order to improve the reactivity, light irradiation may be performed while heating. When the light is in the vacuum stage, it is possible to prevent the bubbles from entering, suppress the decrease in reactivity due to oxygen incorporation, and improve the adhesion between the mold and the photocurable composition. Light irradiation is performed. In the present invention, it is preferred that the degree of vacuum is in the range of from 10 -1 Pa to atmospheric pressure.

本發明的光硬化性組成物在混合上述各成分後,例如藉由孔徑0.05微米~5.0微米的過濾器來調製作為溶液。光硬化性組成物的混合、溶解,通常係在0℃~100℃的範圍進行。過濾亦可以多階段進行,亦可重複進行多次。又,亦可將已過濾的液體再過濾。過濾所使用的材質可使用聚乙烯樹脂、聚丙烯樹脂、氟樹脂、耐綸樹脂等,沒有特別限定。The photocurable composition of the present invention is prepared as a solution by mixing the above components, for example, by a filter having a pore diameter of 0.05 μm to 5.0 μm. The mixing and dissolution of the photocurable composition are usually carried out in the range of 0 ° C to 100 ° C. Filtration can also be carried out in multiple stages or repeated several times. Alternatively, the filtered liquid can be filtered again. The material used for the filtration may be, for example, a polyethylene resin, a polypropylene resin, a fluororesin, or a nylon resin, and is not particularly limited.

說明將本發明的光硬化性組成物應用在蝕刻光阻之情況。蝕刻步驟能夠藉由適當地選自眾所周知的蝕刻處理方法來進行,用以除去未被光阻圖案覆蓋的下層部分,而得到薄膜的圖案。藉由蝕刻液處理(濕式蝕刻)、或藉由在減壓下使用電漿放電來使反應性氣體活性化處理(乾式蝕刻)之任一者來進行。The case where the photocurable composition of the present invention is applied to an etching photoresist will be described. The etching step can be performed by suitably selecting a well-known etching treatment method for removing the underlying portion not covered by the photoresist pattern to obtain a pattern of the thin film. The reactive gas activation treatment (dry etching) is performed by etching liquid treatment (wet etching) or by using plasma discharge under reduced pressure.

進行前述濕式蝕刻時之蝕刻液,能夠使用由氯化鐵/鹽酸系、鹽酸/硝酸系、溴化氫系等為代表之已被開發的許多蝕刻液。Cr用係硝酸鈰銨溶液、或硝酸鈰-過氧化氫水的混合液、Ti用係稀釋氟酸、氟酸-硝酸混合液、Ta用係銨溶液與過氧化氫水的混合液、Mo用係過氧化氫水、氨水-過氧化氫水的混合物、磷酸-硝酸的混合液、MoW、Al用係磷酸-硝酸混合液、氟酸-硝酸的混合液、磷酸-硝酸-乙酸的混合液、ITO用係稀釋王水、氯化鐵溶液、碘化氫水、SiNx或SiO2 用係緩衝氟酸、氟酸-氟化銨混合液、Si、多晶矽用係氟酸-硝酸-乙酸的混合液、W用係氨水-過氧化氫水的混合物、PSG用係硝酸-氟酸的混合液、BSG用係氟酸-氟化銨混合液等各自係如上述使用。A plurality of etching liquids which have been developed, such as ferric chloride/hydrochloric acid, hydrochloric acid/nitric acid, and hydrogen bromide, can be used as the etching liquid in the wet etching. For the Cr, a mixed solution of ammonium cerium nitrate solution or cerium nitrate-hydrogen peroxide water, a mixed solution of hydrofluoric acid, a hydrofluoric acid-nitric acid mixed solution for Ti, a mixed solution of ammonium ammonium hydroxide solution and hydrogen peroxide, and Mo a mixture of hydrogen peroxide water, ammonia water-hydrogen peroxide water, a mixture of phosphoric acid and nitric acid, a mixture of MoW, a phosphoric acid-nitric acid mixture for Al, a mixture of hydrofluoric acid and nitric acid, and a mixture of phosphoric acid and nitric acid-acetic acid. ITO is used to dilute aqua regia, ferric chloride solution, hydrogen iodide water, SiNx or SiO 2 buffered hydrofluoric acid, hydrofluoric acid-ammonium fluoride mixed solution, Si, polycrystalline fluorene-fluoric acid-nitric acid-acetic acid mixture The mixture of a mixture of ammonia-hydrogen peroxide water, a mixture of nitric acid and hydrofluoric acid for PSG, and a mixture of hydrofluoric acid and ammonium fluoride for BSG are used as described above.

濕式蝕刻亦可以沖淋方式,亦可以是浸漬方式,因為蝕刻速度、面內均勻性、及配線寬度的精確度非常地依存處理溫度,所以條件必須按照基板種類、用途、線寬度來加以最適化。又,進行前述濕式蝕刻時,為了防止蝕刻液的滲透造成凹陷,以進行後烘焙為佳。通常,此等後烘焙係在90℃~140℃左右進行,但未必限定於此。Wet etching can also be a shower method or an immersion method. Since the etching speed, in-plane uniformity, and wiring width accuracy depend very much on the processing temperature, the conditions must be optimized according to the substrate type, application, and line width. Chemical. Further, in the case of the above-described wet etching, it is preferable to perform post-baking in order to prevent the depression of the etching liquid. Usually, such post-baking is carried out at about 90 ° C to 140 ° C, but is not necessarily limited thereto.

乾式蝕刻可使用平行平板型的乾式蝕刻裝置,該蝕刻裝置基本上在真空裝置內設置有一對平行配置的電極、且在另一方的電極上設置基板。藉由使高頻電源連接設置基板側的電極、或連接於相反的電極用以產生電漿,能夠分類成以離子為主要參與之反應性離子蝕刻(RIE)模式、及以自由基為主要參與之電漿蝕刻(PE)模式。The dry etching may use a parallel plate type dry etching apparatus which basically has a pair of electrodes arranged in parallel in the vacuum apparatus and a substrate on the other electrode. By connecting a high-frequency power source to the electrode on the substrate side or to the opposite electrode to generate plasma, it can be classified into a reactive ion etching (RIE) mode in which ions are mainly involved, and free radicals are mainly involved. Plasma etching (PE) mode.

在前述乾式蝕刻所使用的蝕刻氣體,能夠使用各自的膜種之蝕刻氣體。可舉出a-Si/n 或s-Si用係四氟化碳(氯)+氧、四氟化碳(六氟化硫)+氯化氫(氯)、a-SiNx用係四氟化碳+氧、a-SiOx用係四氟化碳+氧、三氟化碳+氧、Ta用係四氟化碳(六氟化硫)+氧、MoTa/MoW用係四氟化碳+氧、Cr用係氯+氧、A l用係三氯化硼+氯、溴化氫、溴化氫+氯、碘化氫等。在乾式蝕刻的步驟,藉由離子衝擊或熱會使光阻的結構產生重大變質,且亦影響剝離性。In the etching gas used for the dry etching described above, an etching gas of each film type can be used. Examples of a-Si/n + or s-Si are carbon tetrafluoride (chlorine) + oxygen, carbon tetrafluoride (sulfur hexafluoride) + hydrogen chloride (chlorine), and a-SiNx for carbon tetrafluoride. + oxygen, a-SiOx with carbon tetrafluoride + oxygen, carbon trifluoride + oxygen, Ta with carbon tetrafluoride (sulfur hexafluoride) + oxygen, MoTa / MoW with carbon tetrafluoride + oxygen, For Cr, it is chlorine + oxygen, and A l is boron trichloride + chlorine, hydrogen bromide, hydrogen bromide + chlorine, hydrogen iodide, and the like. In the dry etching step, the structure of the photoresist is greatly deteriorated by ion impact or heat, and the peeling property is also affected.

敘述蝕刻後,剝離將圖案轉印至下層基板之光阻的方法。剝離係使用液體來除去(濕式剝離)、或在減壓下藉由氧氣的電漿放電使其氧化成為氣體狀而除去(乾式剝離/灰化),或是藉由臭氧及UV光使其氧化成為氣體狀而除去(乾式剝離/UV灰化)等,能夠藉由若干方法來除去光阻。剝離液通常已知有如氫氧化鈉水溶液、氫氧化鉀水溶液、臭氧溶解水之水溶液系、及如胺與二甲亞碸或N-甲基吡咯啶酮之有機溶劑。後者的例子已知有一乙醇胺/二甲亞碸混合物(質量混合比=7/3)。After the etching, the method of transferring the pattern to the photoresist of the underlying substrate is peeled off. The peeling is removed by using a liquid (wet peeling) or by plasma discharge of oxygen under reduced pressure to be oxidized to a gas state (dry peeling/ashing), or by ozone and UV light. The oxidation is removed into a gas form (dry peeling/UV ashing) or the like, and the photoresist can be removed by a number of methods. As the stripping liquid, an aqueous solution such as an aqueous solution of sodium hydroxide, an aqueous solution of potassium hydroxide, an aqueous solution of ozone, and an organic solvent such as an amine and dimethyl hydrazine or N-methylpyrrolidone are generally known. An example of the latter is known to have an ethanolamine/dimethyl hydrazine mixture (mass mixing ratio = 7/3).

光阻剝離速度與溫度、液量、時間、壓力等相當有關,能夠按照基板種類、用途而最適化。可舉出例如以在室溫~100℃左右的溫度範圍浸漬基板(數分鐘~數十分鐘),來進行乙酸丁酯等溶劑沖洗、水洗為佳。從提升剝離液本身的沖洗性、微粒除去性、及耐腐蝕性的觀點,亦可只使用水沖洗。可舉出的較佳例子係水洗為純水沖洗、乾燥為氣體刮除乾燥。在基板上,非結晶質矽露出時,因為在水與空氣的存在下會形成氧化膜,所以將空氣隔離為佳。又,並用藉由灰化及藥液剝離之方法亦佳。灰化可舉出電漿灰化、向下吹風灰化、使用臭氧之灰化、及UV/臭氧灰化。例如使用乾式蝕刻加工Al基板之情況,通常係使用氯系的氣體,但是氯與Al的生成物之氯化鋁等會有腐蝕Al之情形。為了防止此等情形,亦可使用添加有防腐劑之剝離液。The photoresist peeling speed is equivalent to temperature, liquid amount, time, pressure, etc., and can be optimized according to the type and use of the substrate. For example, it is preferable to immerse the substrate (minutes to several tens of minutes) at a temperature ranging from room temperature to about 100 ° C to perform solvent washing such as butyl acetate or water washing. From the viewpoint of improving the rinsing property, the particle removability, and the corrosion resistance of the peeling liquid itself, it is also possible to rinse only with water. A preferred example which can be mentioned is that the water is washed with pure water and dried for gas scraping and drying. On the substrate, when the amorphous material is exposed, since an oxide film is formed in the presence of water and air, it is preferable to isolate the air. Moreover, it is also preferable to use a method of ashing and chemical separation. Ashing may include plasma ashing, downward blowing ashing, ozone ashing, and UV/ozone ashing. For example, in the case of processing an Al substrate by dry etching, a chlorine-based gas is usually used, but aluminum chloride or the like which is a product of chlorine and Al may corrode Al. In order to prevent such a situation, a peeling liquid to which a preservative is added may also be used.

前述蝕刻步驟、剝離步驟、沖洗步驟、水洗以外的其他步驟,沒有特別限定,可舉出適當地選自眾所周知的圖案形成步驟。可舉出例如硬化處理步驟等。此等可單獨使用1種,亦可組合使用2種以上。硬化處理步驟沒有特別限制,能夠按照目的而適當地選擇,例如適合舉出的有全面加熱處理或全面曝光處理等。The steps other than the etching step, the peeling step, the rinsing step, and the water washing are not particularly limited, and may be appropriately selected from a well-known pattern forming step. For example, a hardening treatment step or the like can be given. These may be used alone or in combination of two or more. The hardening treatment step is not particularly limited, and can be appropriately selected according to the purpose, and for example, a comprehensive heat treatment or a full exposure treatment, which is suitably mentioned, is exemplified.

前述全面曝光處理之方法,可舉出例如使形成有圖案的全面曝光之方法。因為藉由全面曝光,能夠促進形成前述感光層之組成物中的硬化,來使前述圖案的表面硬化,能夠提高蝕刻耐性。進行前述全面曝光之裝置沒有特別限制,能夠按照目的而適當地選擇,例如適合舉出的有超高壓水銀燈等的UV曝光機。The method of the above comprehensive exposure treatment may, for example, be a method of forming a full exposure by forming a pattern. Since the curing in the composition of the photosensitive layer can be promoted by the full exposure, the surface of the pattern can be hardened, and the etching resistance can be improved. The apparatus for performing the above-described overall exposure is not particularly limited, and can be appropriately selected according to the purpose, and for example, a UV exposure machine such as an ultrahigh pressure mercury lamp which is suitably used.

實施例Example

以下舉出實施例來具體地說明本發明。在以下的實施例所示材料、使用量、比率、處理內容、處理順序只要未脫離本發明的宗旨時,能夠適當地進行變更。因此,本發明的範圍未限定於以下所示的具體例。The invention will be specifically described below by way of examples. The materials, the amounts used, the ratios, the contents of the treatment, and the treatment procedures in the following examples can be appropriately changed as long as they do not deviate from the gist of the invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

本發明的實施例及比較例所使用各單體的略號如下。The abbreviations of the respective monomers used in the examples and comparative examples of the present invention are as follows.

<單體>R-01:丙烯酸苄酯(BISCOAT#160大阪有機化學公司製)R-02:環氧丙烯酸乙酯(LIGHTACRYLATE PO-A:共榮社油脂公司製)R-03:丙烯酸異莰酯(ARONIX M-156:東亞合成公司製)R-04:N-乙烯基-2-吡咯吡酮(ARONIX M-150:東亞合成公司製)R-05:N-丙烯醯基啉(ACMO:興人公司製)R-06:苯氧基己二醇乙酸酯(AMP-60G:新中村化學公司製)R-07:苯氧基二甘醇丙烯酸酯(ARONIX M-101:東亞合成公司製)R-08:乙氧基二甘醇丙烯酸酯(LIGHTACRYLATE EC-A:共榮社化學公司製)R-09:羥基三甲基乙酸新戊二醇二丙烯酸酯(KARAYAD MANDA:日本化藥公司製)R-10:聚乙二醇二丙烯酸酯(NEWFRONTIA PE-300:第一工業製藥製)R-11:三伸丙二醇二丙烯酸酯(KARAYAD TPGDA:日本化藥公司製)R-12:環氧乙烷改性三羥甲基丙烷三丙烯酸酯(SR-454:SATOMER KAYAKU公司製)R-13:環氧丙烷改性三羥甲基丙烷三丙烯酸酯(NEWFRONTIA TMP-3P:第一工業製藥製)R-14:新戊四醇乙氧基四丙烯酸酯(Ebercryl 40:DAICEL-UCB公司製)R-15:二新戊四醇六丙烯酸酯(KARAYAD DPHA:日本化藥公司製)R-16:環氧乙烷改性磷酸二甲基丙烯酸酯(KAYAMA-PM-21:日本化藥公司製)R-17:環氧乙烷改性新戊二醇二丙烯酸酯(PHTOMER 4160:SANNOPCO公司製)R-18:丙烯酸四氫糠酯(BISCOAT#150大阪有機化學公司製)R-19:三羥基丙烷三丙烯酸酯(ARONIX M-309:東亞合成公司製)R-20:1,6-己二醇二丙烯酸酯(FRONTIA HDDA:第一工業製藥製)R-21:環氧乙烷改性雙酚A二丙烯酸酯(SR-602:SATOMER KAYAKU公司製)R-22:新戊二醇二丙烯酸酯(SR-351:SATOMER KAYAKU公司製)R-23:雙酚系環氧丙烯酸酯(RIPOXY SP1509:昭和高分子公司製)R-24:丙烯酸胺基甲酸酯(BEAMSET 551B:荒川化學工業公司製)R-25:環氧丙烯酸酯(Ebercryl 3701:DAICEL-UCB公司製)R-26:N-羥基乙基丙烯醯胺(HEAA:興人公司製)R-27:環氧乙烷改性雙酚A二丙烯酸酯(ARONIX M-211B東亞合成公司製)R-28:ACARON RN-20:第一工業製藥製)R-29:苯基環氧丙基醚環氧丙烯酸酯R-30:4-丙烯醯氧基甲基-2-甲基-2-乙基-1,3-二氧雜戊環(MEDOL10:大阪有機工業公司製)C-1:3,4-環氧環己基甲基-3’,4’-環氧環己烷羧酸酯(Cyracure-6105:UNION CARBIDE公司製)C-2:1.2:8,9二環氧薴烯(CEROKISAID 3000:DAICAL化學工業製)C-3:3-乙基-3-(苯氧基甲基)氧雜環丁烷(OXT211:東亞合成公司製)C-4:3-乙基-3-羥基乙基氧雜環丁烷(OXT101:東亞合成公司製)C-5:二[1-乙基(3-氧雜環丁烷基)甲基醚(OXT221:東亞合成公司製)C-6:主成分1,4-雙[(3-乙基-3-氧雜環丁烷基甲氧基)甲基]苯(OXT121:東亞合成公司製)C-7:3-乙基-3-(2-乙基己醯氧基甲基)氧雜環丁烷(OXT212:東亞合成公司製)C-8:羥基丁基乙烯基醚(HBVE:丸善石油化學公司製)C-9:一氧化乙烯基環己烯1,2-環氧-4-乙烯基環己烯(CEROKISAID 2000:DAICEL化學工業製)C-10:三甘醇二乙烯基醚(RAPI-CURE DVE-3:ISP JAPAN公司製)C-11:環氧化亞麻仁油(Vikoflex9040:ATOFINA公司製)<Monomer> R-01: benzyl acrylate (BISCOAT #160 Osaka Organic Chemical Co., Ltd.) R-02: Epoxy acrylate (LIGHTACRYLATE PO-A: manufactured by Kyoeisha Oil Co., Ltd.) R-03: Acrylic isophthalic acid Ester (ARONIX M-156: manufactured by Toagosei Co., Ltd.) R-04: N-vinyl-2-pyrrolidone (ARONIX M-150: manufactured by Toagosei Co., Ltd.) R-05: N-acrylonitrile Porphyrin (ACMO: manufactured by Xingren Co., Ltd.) R-06: phenoxyhexanediol acetate (AMP-60G: manufactured by Shin-Nakamura Chemical Co., Ltd.) R-07: phenoxy diglycol acrylate (ARONIX M-101) :East Asia Synthetic Co., Ltd.) R-08: Ethoxydiethylene glycol acrylate (LIGHTACRYLATE EC-A: manufactured by Kyoeisha Chemical Co., Ltd.) R-09: Hydroxytrimethylacetic acid neopentyl glycol diacrylate (KARAYAD MANDA) :Nippon Chemical Co., Ltd.) R-10: Polyethylene glycol diacrylate (NEWFRONTIA PE-300: manufactured by Daiichi Kogyo Co., Ltd.) R-11: Tri-propylene glycol diacrylate (KARAYAD TPGDA: manufactured by Nippon Kayaku Co., Ltd.) R-12: Ethylene oxide modified trimethylolpropane triacrylate (SR-454: manufactured by SATOMER KAYAKU) R-13: propylene oxide modified trimethylolpropane triacrylate (NEWFRONTIA TMP-3P :First Industrial Pharmaceuticals, Ltd.) R-14: Pentaerythritol ethoxytetraacrylate (Ebercryl 40: manufactured by DAICEL-UCB) R-15: dipentaerythritol hexaacrylate (KARAYAD DPHA: Nippon Chemical Company-made) R-16: Ethylene oxide modified phosphodimethacrylate (KAYAMA-PM-21: manufactured by Nippon Kayaku Co., Ltd.) R-17: Ethylene oxide Modified neopentyl glycol diacrylate (PHTOMER 4160: manufactured by SANNOPCO Co., Ltd.) R-18: tetrahydrofurfuryl acrylate (BISCOAT #150 Osaka Organic Chemical Co., Ltd.) R-19: trihydroxypropane triacrylate (ARONIX M- 309: manufactured by Toagosei Co., Ltd.) R-20: 1,6-hexanediol diacrylate (FRONTIA HDDA: manufactured by Daiichi Kogyo Co., Ltd.) R-21: Ethylene oxide modified bisphenol A diacrylate (SR- 602: manufactured by SATOMER KAYAKU Co., Ltd.) R-22: neopentyl glycol diacrylate (SR-351: manufactured by SATOMER KAYAKU Co., Ltd.) R-23: bisphenol epoxy acrylate (RIPOXY SP1509: manufactured by Showa Polymer Co., Ltd.) R -24: Acrylic urethane (BEAMSET 551B: manufactured by Arakawa Chemical Industries, Ltd.) R-25: Epoxy acrylate (Ebercryl 3701: manufactured by DAICEL-UCB) R-26: N-hydroxyethyl acrylamide ( HEAA: manufactured by Xingren Co., Ltd.) R-27: Ethylene oxide modified bisphenol A diacrylate (ARONIX M-211B manufactured by Toagosei Co., Ltd.) R-28: ACARON RN-20: First Industrial Pharmaceutical Co., Ltd.) R- 29: phenylepoxypropyl ether epoxy acrylate R-30: 4-propenyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane ( MEDOL 10: manufactured by Osaka Organic Industries Co., Ltd.) C-1: 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate (Cyracure-6105: manufactured by UNION CARBIDE Co., Ltd.) C-2 : 1.2:8,9 Diepylene Terpene (CEROKISAID 3000: manufactured by DAICAL Chemical Industry Co., Ltd.) C-3: 3-ethyl-3-(phenoxymethyl)oxetane (OXT211: manufactured by Toagosei Co., Ltd.) C-4: 3-ethyl-3-hydroxyethyloxetane (OXT101: manufactured by Toagosei Co., Ltd.) C-5: bis[1-ethyl(3-oxetanyl)methyl Ether (OXT221: manufactured by Toagosei Co., Ltd.) C-6: main component 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene (OXT121: manufactured by Toagosei Co., Ltd.) C-7: 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane (OXT212: manufactured by Toagosei Co., Ltd.) C-8: hydroxybutyl vinyl ether (HBVE: Maruzen Petrochemical Co., Ltd.) C-9: Vinylcyclohexene oxide 1,2-epoxy-4-vinylcyclohexene (CEROKISAID 2000: manufactured by DAICEL Chemical Industry Co., Ltd.) C-10: Triethylene glycol divinyl Ether (RAPI-CURE DVE-3: manufactured by ISP JAPAN) C-11: epoxidized linseed oil (Vikoflex 9040) ATOFINA Inc.)

本發明實施例及比較例所使用的光聚合引發劑、光酸產生劑的略號係如下述。The abbreviations of the photopolymerization initiator and the photoacid generator used in the examples and comparative examples of the present invention are as follows.

<光聚合引發劑>P-1:2,4,6-三甲基苯甲醯基-乙氧基苯基-氧化膦(Lucirin TPO-L:BASF公司製)P-2:2,2-二甲氧基-1,2-二苯基乙-1-酮(Irgacure 651:CIBA SPECIALTY CHEMICALS公司製)P-3:2-羥基-2-甲基-1-苯基-丙-1-酮(Darocure 1173:CIBA SPECIALTY CHEMICALS公司製)P-4:2,4,6-三甲基苯甲醯基-二苯基氧化膦與2-羥基-2-甲基-1-苯基-丙-1-酮之混合物(Darocure 4265:CIBA SPECIALTY CHEMICALS公司製)P-5:2-苄基-2-二甲胺基-1-(4-啉苯基)-丁酮-1與2,2-二甲氧基-1,2-二苯基乙-1-酮之混合物(Irgacure 1300:CIBA SPECIALTY CHEMICALS公司製)P-6:1-[4-苯甲醯苯基磺醯基]苯基]-2-甲基-2-(4-甲基苯基磺醯基)丙-1-酮(ESACUR1001M:日本SiberHegner公司製)2,4,6-三甲基苯甲醯基-乙氧基苯基-氧化膦(Lucirin TPO-L:BASF公司製)P-7:2-甲基-1[4-甲硫基苯基]=2=啉丙-1-酮(Irgacure-907:CIBA SPECIALTY CHEMICALS公司製)P-8:羥基環己基苯基酮(CIBA SPECIALTY CHEMICALS公司製:Irgacure-184)<Photopolymerization initiator> P-1: 2,4,6-trimethylbenzylidene-ethoxyphenyl-phosphine oxide (Lucirin TPO-L: manufactured by BASF Corporation) P-2: 2,2- Dimethoxy-1,2-diphenylethan-1-one (Irgacure 651: manufactured by CIBA SPECIALTY CHEMICALS) P-3: 2-hydroxy-2-methyl-1-phenyl-propan-1-one (Darocure 1173: manufactured by CIBA SPECIALTY CHEMICALS) P-4: 2,4,6-trimethylbenzimidyl-diphenylphosphine oxide and 2-hydroxy-2-methyl-1-phenyl-propyl- 1-ketone mixture (Darocure 4265: manufactured by CIBA SPECIALTY CHEMICALS) P-5: 2-benzyl-2-dimethylamino-1-(4- Mixture of phenyl phenyl)-butanone-1 and 2,2-dimethoxy-1,2-diphenylethan-1-one (Irgacure 1300: manufactured by CIBA SPECIALTY CHEMICALS) P-6: 1-[ 4-benzylidene phenylsulfonyl]phenyl]-2-methyl-2-(4-methylphenylsulfonyl)propan-1-one (ESACUR1001M: manufactured by Siber Hegner, Japan) 2, 4, 6-trimethylbenzimidyl-ethoxyphenyl-phosphine oxide (Lucirin TPO-L: manufactured by BASF Corporation) P-7: 2-methyl-1[4-methylthiophenyl]=2= Phenylpropan-1-one (Irgacure-907: manufactured by CIBA SPECIALTY CHEMICALS) P-8: hydroxycyclohexyl phenyl ketone (manufactured by CIBA SPECIALTY CHEMICALS: Irgacure-184)

<光酸產生劑>U-1:DOW CHEMICAL公司製:SAIRACURE-UVI 6990 U-2:MIDORI化學公司製:DTS-102<Photoacid generator> U-1: manufactured by DOW CHEMICAL Co., Ltd.: SAIRACURE-UVI 6990 U-2: manufactured by MIDORI Chemical Co., Ltd.: DTS-102

本發明的實施例及比較例所使用的界面活性劑、添加劑的略號係如下述。The abbreviations of the surfactants and additives used in the examples and comparative examples of the present invention are as follows.

<界面活性劑>W-1:氟系界面活性劑(TOHKEM-PRODUCTS公司製:氟界面活性劑)W-2:矽系界面活性劑(大日本油墨化學工業公司製:MEGAFACPENTAD31)W-3:氟-矽系界面活性劑(大日本油墨化學工業公司製:MEGAFAC R-08)W-4:氟-矽系界面活性劑(大日本油墨化學工業公司製:MEGAFAC XRB-4)W-5:炔二醇系非離子界面活性劑(信越化學工業公司製:SAFINOL 465)W-6:聚氧乙烯聚氧丙烯縮合物(竹本油脂公司製:PIONINE P-1525)W-7:氟系界面活性劑(大日本油墨化學工業公司製:F-173)W-8:氟系界面活性劑(住友3M公司製:FC-430)W-9:氟系界面活性劑(大日本油墨化學工業公司製:MEGAFAC 470)W-10:氟系界面活性劑(大日本油墨化學工業公司製:MEGAFAC EXP.TF907)<Interacting Agent> W-1: Fluorine-based surfactant (manufactured by TOHKEM-PRODUCTS: Fluoride surfactant) W-2: Lanthanide surfactant (manufactured by Dainippon Ink and Chemicals, Inc.: MEGAFACPENTAD31) W-3: Fluorine-ruthenium-based surfactant (manufactured by Dainippon Ink and Chemicals, Inc.: MEGAFAC R-08) W-4: Fluorine-antimony surfactant (manufactured by Dainippon Ink and Chemicals, Inc.: MEGAFAC XRB-4) W-5: Alkynediol-based nonionic surfactant (manufactured by Shin-Etsu Chemical Co., Ltd.: SAFINOL 465) W-6: Polyoxyethylene polyoxypropylene condensate (manufactured by Takemoto Oil Co., Ltd.: PIONINE P-1525) W-7: Fluoride-based interfacial activity Agent (made by Dainippon Ink Chemical Industry Co., Ltd.: F-173) W-8: Fluorine-based surfactant (produced by Sumitomo 3M Co., Ltd.: FC-430) W-9: Fluorine-based surfactant (manufactured by Dainippon Ink Chemical Industry Co., Ltd.) :MEGAFAC 470)W-10: Fluorine-based surfactant (manufactured by Dainippon Ink and Chemicals, Inc.: MEGAFAC EXP.TF907)

<添加劑>A-01:2-氯噻噸酮A-02:9,10-二丁氧基蒽(川崎化成工業公司製)A-03:矽烷偶合劑(乙烯基三乙氧基矽烷)(信越SILICONE製)A-04:矽油(NIPPON UNICAR公司製:L-7001)A-05:苯甲酸2-二甲胺基乙酯A-06:二苯基酮A-07:4-二甲胺基苯甲酸酯A-08:改性二甲基聚矽氧烷(Big Chemie Japan公司製:BYK-307)A-09:紅色225號(蘇丹III)A-10:N-乙基二乙醇胺A-11:碳酸丙烯酯(關東化學製)A-12:分散劑(AJINOMOTO FINETECHNO公司製:PB822)A-13:CI顏料黑7(CLARIANT JAPAN製)<Additive> A-01: 2-chlorothioxanthone A-02: 9,10-dibutoxyanthracene (manufactured by Kawasaki Kasei Kogyo Co., Ltd.) A-03: decane coupling agent (vinyl triethoxy decane) ( Shin-Etsu SILICONE system) A-04: Oyster sauce (NIPPON UNICAR company: L-7001) A-05: 2-dimethylaminoethyl benzoate A-06: Diphenyl ketone A-07: 4-dimethylamine Benzoic acid ester A-08: Modified dimethyl polyoxyalkylene (Big Chemie Japan company: BYK-307) A-09: Red No. 225 (Sudan III) A-10: N-ethyldiethanolamine A-11: propylene carbonate (manufactured by Kanto Chemical Co., Ltd.) A-12: dispersant (manufactured by AJINOMOTO FINETECHNO Co., Ltd.: PB822) A-13: CI Pigment Black 7 (manufactured by CLARIANT JAPAN)

<光硬化性組成物的評價>依照下述的評價方法,評價藉由實施例1~25及比較例1~20所得到之各自的組成物。<Evaluation of Photocurable Composition> The respective compositions obtained in Examples 1 to 25 and Comparative Examples 1 to 20 were evaluated in accordance with the following evaluation methods.

表1、表2係各自表示組成物所使用的聚合性不飽和單體(實施例、比較例)。Tables 1 and 2 each show a polymerizable unsaturated monomer used in the composition (Examples, Comparative Examples).

表3、表4、表7係各自表示組成物所使用的聚合性不飽和單體的調配比(實施例)。Table 3, Table 4, and Table 7 each show the mixing ratio of the polymerizable unsaturated monomer used for a composition (Example).

表5、表8係各自表示組成物所使用單體、光聚合引發劑、界面活性劑、及添加劑的調配比(實施例、比較例)。Tables 5 and 8 show the blending ratios of the monomers, photopolymerization initiators, surfactants, and additives used in the composition (Examples, Comparative Examples).

表6、表9係各自表示本發明的結果(實施例、比較例)。Tables 6 and 9 show the results (Examples and Comparative Examples) of the present invention.

<黏度測定>黏度的測定係用東機產業(股)製之RE-80L型旋轉黏度計,在25±0.2℃測定。<Viscosity measurement> The viscosity was measured at 25 ± 0.2 ° C using a RE-80L rotary viscometer manufactured by Toki Sangyo Co., Ltd.

測定時之旋轉速度係各自如下述進行,在0.5mPa.s以上小於5mPa.s係100rpm,5mPa.s以上小於10mPa.s係50rpm,10mPa.s以上小於30mPa.s係20rpm,30mPa.s以上小於60mPa.s係10rpm,60mPa.s以上小於120mPa.s係5rpm,120mPa.s以上係1rpm或0.5rpm。The rotation speeds at the time of measurement were each as follows, at 0.5 mPa. Above s is less than 5mPa. s series 100rpm, 5mPa. Above s is less than 10mPa. s system 50rpm, 10mPa. Above s is less than 30mPa. s series 20rpm, 30mPa. Above s is less than 60mPa. s series 10rpm, 60mPa. Above s is less than 120mPa. s is 5 rpm, 120 mPa. The above is 1 rpm or 0.5 rpm.

<光硬化速度的測定>光硬化速度的測定係使用高壓水銀燈作為光源,使用傅立葉變換型紅外分光裝置(FT-IR)測定單體在810cm-1 的吸收變化,實時進行計算硬化反應速度(單體消耗率)。A係表示硬化反應速度為0.2/秒以上時,B係表示硬化反應速度為小於0.2/秒的情況。<Measurement of Light Curing Rate> The photohardening speed was measured by using a high-pressure mercury lamp as a light source, and the absorption change of the monomer at 810 cm -1 was measured using a Fourier transform infrared spectrometer (FT-IR), and the hardening reaction rate was calculated in real time (single) Body consumption rate). When the A system indicates that the curing reaction rate is 0.2/sec or more, the B system indicates that the curing reaction rate is less than 0.2/sec.

<黏附性>黏附性係在已光硬化之光硬化性光阻圖案表面貼上膠帶,在剝除後,藉由目視觀察判斷在膠帶是否附著有已光硬化之光硬化性光阻圖案,並如下進行評價。<Adhesiveness> Adhesive tape is attached to the surface of the photocurable photoresist pattern which has been photohardened, and after peeling, it is visually observed whether or not the photohardenable photocurable photoresist pattern is adhered to the tape. Evaluation was performed as follows.

A:膠帶側未附著圖案B:認定在膠帶側極薄地附著圖案C:認定在膠帶側顯著地附著圖案A: The tape side is not attached to the pattern B: It is confirmed that the pattern C is extremely thinly attached to the tape side: it is confirmed that the pattern is remarkably attached to the tape side.

<剝離性>剝離性係光硬化後,將模具剝離時,使用光學顯微鏡觀察在模具上是否有殘留未硬化物,並如下進行評價。A:無殘留物B:有殘留物<Removability> After peeling-off photohardening, when the mold was peeled off, whether or not the unhardened material remained on the mold was observed using an optical microscope, and the evaluation was performed as follows. A: no residue B: there is residue

<殘膜性及圖案形狀的觀察>藉由掃描型電子顯微鏡觀察轉印之圖案形狀,及轉印圖案的殘渣,並如下進行評價殘膜性及圖案形狀。<Observation of Residual Film Property and Pattern Shape> The pattern shape of the transfer and the residue of the transfer pattern were observed by a scanning electron microscope, and the residual film property and the pattern shape were evaluated as follows.

(殘膜性)A:未觀察到殘渣B:觀察到有少許殘渣C:觀察到有大量殘渣(residual film property) A: No residue was observed B: A small amount of residue was observed C: A large amount of residue was observed

(圖案形狀)A:圖案形狀與來源之模具的原版圖案形狀大致相同B:圖案形狀與來源之模具的原版圖案形狀在一部分有差異(pattern shape) A: The pattern shape is substantially the same as the original pattern shape of the source mold B: the pattern shape and the original pattern shape of the source mold are different in part

(與原版的圖案在小於20%範圍)C:圖案形狀與來源之模具的原版圖案形狀有明顯不同、或是圖案的膜厚度與原版的圖案差異為20%以上(with the original pattern in the range of less than 20%) C: The pattern shape is significantly different from the original pattern shape of the source mold, or the difference between the pattern thickness of the pattern and the original pattern is 20% or more.

<旋轉塗布適合性>塗布性(I)在形成有膜厚4000的鋁(Al)被膜之4英吋、0.7毫米厚的玻璃基板上,以成為厚度6.0微米的方式旋轉塗布本發明的光硬化性組成物後,使該玻璃基板靜置1分鐘後,進行面狀觀察,並如下進行評價。<Rotary coating suitability> Coating property (I) is formed with a film thickness of 4000 On the glass substrate of 4 mm and 0.7 mm thick of the aluminum (Al) film, the photocurable composition of the present invention was spin-coated so as to have a thickness of 6.0 μm, and then the glass substrate was allowed to stand for 1 minute, and then the surface was surfaced. Observe and evaluate as follows.

A:未觀察到收縮斑及塗布線條(條紋)B:觀察到少許的塗布線條C:觀察到顯著的收縮斑及塗布線條A: No shrinkage spots and coating lines (streaks) were observed B: A few coated lines were observed C: Significant shrinkage spots and coated lines were observed

<狹縫塗布適合性>塗布性(II)使用大型基板塗布用之狹縫光阻塗布裝置(平田機工(股)製模頭塗布系統),在形成有膜厚度4000的鋁(Al)被膜之4英吋、0.7毫米厚的玻璃基板(550毫米×650毫米)上,塗布本發明的光硬化性組成物,來形成膜厚度2.0微米的光阻被膜,觀察在縱橫向是否有出現線條狀不均,並如下進行評價。<Slit coating suitability> Coating property (II) Using a slit photoresist coating apparatus for a large-substrate coating (Pingda Machining Co., Ltd.), a film thickness of 4000 is formed. The photocurable composition of the present invention was coated on a 4 inch-thick, 0.7 mm-thick glass substrate (550 mm × 650 mm) of an aluminum (Al) film to form a photoresist film having a film thickness of 2.0 μm, and observed in the cross direction. Whether there is a line-like unevenness or not is evaluated as follows.

A:未觀察到線條狀不均B:觀察到微弱的線條狀不均C:觀察到顯著的線條狀不均A: No line-like unevenness was observed. B: Weak line-like unevenness was observed. C: Significant line-like unevenness was observed.

<蝕刻性>在形成於玻璃基板上之前述鋁(Al)上,圖案狀地形成本發明的光硬化性組成物,在硬化後,藉由磷硝酸蝕刻液對鋁薄膜進行蝕刻,目視及顯微鏡觀察10微米線/間距,並如下進行評價。<Etching property> The photocurable composition of the invention is patterned on the aluminum (Al) formed on the glass substrate, and after curing, the aluminum thin film is etched by a phosphorus nitric acid etching solution, visually and microscopically observed. 10 micron lines/pitch and evaluated as follows.

A:能夠得到線寬度10±2.0微米的鋁線B:成為線的線寬偏差大於±2.0微米的線C:線存在有缺損部分、或是線之間未連接A: It is possible to obtain an aluminum wire B having a line width of 10 ± 2.0 μm: a line having a line width deviation greater than ± 2.0 μm of the line C: a defective portion exists in the line, or the line is not connected

實施例1Example 1

精稱9.799克作為聚合性不飽和單體之丙烯酸苄酯單體(R-01)、78.392克三伸丙二醇二丙烯酸酯單體(R-11)、9.799克環氧乙烷改性三羥甲基丙烷三丙烯酸酯(R-12)、2.00克作為光聚合引發劑之2,4,6-三甲基苯甲醯基-乙氧基苯基-氧化膦(BASF公司製、Lucirin TPO-L)(P-1)、及0.01克作為界面活性劑之EFTOP、EF-122A(氟系、W-1),在室溫混合24小時,成為均勻溶液。在此所使用的聚合性不飽和單體的官能基數、黏度、一次皮膚刺激性(PII值)係如表1所示,聚合性不飽和單體的組成比係如表3所示,組成物的調配係如表5所示。實施例1所得到的組成物(塗布性)係黏度為30mPa.s以下之聚合性不飽和單體的比率為90質量%,組成物的黏度為18mPa.s。9.799 g of benzyl acrylate monomer (R-01) as polymerizable unsaturated monomer, 78.392 g of tripropylene glycol diacrylate monomer (R-11), 9.799 g of ethylene oxide modified trishydroxyl Propane triacrylate (R-12), 2.00 g of 2,4,6-trimethylbenzylidene-ethoxyphenyl-phosphine oxide as a photopolymerization initiator (manufactured by BASF Corporation, Lucirin TPO-L) (P-1) and 0.01 g of EFTOP and EF-122A (fluorine-based, W-1) as surfactants were mixed at room temperature for 24 hours to obtain a homogeneous solution. The number of functional groups, viscosity, and primary skin irritation (PII value) of the polymerizable unsaturated monomer used herein are shown in Table 1, and the composition ratio of the polymerizable unsaturated monomer is shown in Table 3. The matching system is shown in Table 5. The composition (coating property) obtained in Example 1 had a viscosity of 30 mPa. The ratio of the polymerizable unsaturated monomer below s is 90% by mass, and the viscosity of the composition is 18 mPa. s.

在形成有膜厚4000的鋁(Al)被膜之4英吋、0.7毫米厚的玻璃基板上,以成為厚度6.0微米的方式旋轉塗布如此調整後的組成物。將旋轉塗布後塗布基膜安裝在使用ORC公司製的高壓水銀燈(燈輸出功率為2000mW/平方公分)作為光源之奈米壓印裝置,以模具加壓力為0.8kN、曝光中的真空度為10托、從以具有10微米的線/間距圖案、溝深度為5.0微米之聚二甲基矽氧烷(TORAY-DOWCORNING公司製、將SILPOT184在80℃硬化60分而成之物)作為材質之模具的背面,以100mJ/平方公分的條件進行曝光,曝光後,將模具卸下,得到光阻圖案。隨後,使用磷硝酸蝕刻液除去未被覆光阻之鋁(Al)部,來形成鋁(Al)製的電極圖案。而且使用一乙醇胺/二甲亞碸混合剝離液在80℃浸漬處理3分鐘來進行剝離光阻。結果如表6所示。依照表6結果,本發明的組成物係光硬化性、黏附性、脫模性、殘模性、圖案形狀、塗布性(旋轉塗布性、狹縫塗布性)、蝕刻性中任一者都能夠滿足之物。Formed with a film thickness of 4000 The thus-adjusted composition was spin-coated on a glass substrate of 4 mm and 0.7 mm thick on an aluminum (Al) film so as to have a thickness of 6.0 μm. The spin-coated base film was mounted on a nano-imprinting apparatus using a high-pressure mercury lamp (light output of 2000 mW/cm 2 ) manufactured by ORC Co., Ltd. as a light source, with a mold pressing pressure of 0.8 kN and an exposure vacuum of 10 A mold made of polydimethyl methoxyoxane (manufactured by TORAY-DOWCORNING Co., Ltd., which has a SILPOT 184 hardened at 80 ° C for 60 minutes) having a line/pitch pattern of 10 μm and a groove depth of 5.0 μm. The back surface was exposed to 100 mJ/cm 2 , and after exposure, the mold was removed to obtain a photoresist pattern. Subsequently, an aluminum (Al) portion which is not coated with a photoresist is removed using a phosphorus nitric acid etching solution to form an electrode pattern made of aluminum (Al). Further, the peeling resist was performed by immersion treatment at 80 ° C for 3 minutes using a monoethanolamine / dimethyl hydrazine mixed stripping solution. The results are shown in Table 6. According to the results of Table 6, the composition of the present invention can be any of photocurability, adhesion, mold release property, mold resilience, pattern shape, coatability (spin coating property, slit coating property), and etching property. Satisfied with things.

實施例2Example 2

精稱29.39克作為聚合性不飽和單體之環氧丙烯酸乙酯單體(R-02)、48.98克羥基三甲基乙酸新戊二醇二丙烯酸酯單體(R-09)、9.795克三伸丙二醇二丙烯酸酯(R-11)、9.795克環氧丙烷改性三羥甲基丙烷三丙烯酸酯(R-13)、2.0克作為光聚合引發劑之2,4,6-三甲基苯甲醯基-乙氧基苯基-氧化膦(BASF公司製、Lucirin TPO-L)(P-1)、及0.05克作為界面活性劑之MEGAFACPENTAD 31(矽系、W-2),在室溫混合24小時,成為均勻溶液。在此所使用的聚合性不飽和單體的官能基數、黏度、一次皮膚刺激性(PII值)係如表1所示,聚合性不飽和單體的組成比係如表3所示,組成物的調配係如表5所示。實施例2的組成物係黏度為30mPa.s以下之聚合性不飽和單體的比率為90質量%,組成物的黏度為18mPa.s。將該組成物與實施例1同樣地進行曝光、圖案化,並調查組成物的特性。結果如表6所示。依照表6結果,本發明的組成物係光硬化性、黏附性、脫模性、殘模性、圖案形狀、塗布性(旋轉塗布性、狹縫塗布性)、蝕刻性中任一者都能夠滿足之物。29.39 g of epoxy ethyl acrylate monomer (R-02) as a polymerizable unsaturated monomer, 48.98 g of hydroxytrimethylacetic acid neopentyl glycol diacrylate monomer (R-09), 9.795 g of three Propylene glycol diacrylate (R-11), 9.795 g of propylene oxide modified trimethylolpropane triacrylate (R-13), 2.0 g of 2,4,6-trimethylbenzene as a photopolymerization initiator Methylmercapto-ethoxyphenyl-phosphine oxide (manufactured by BASF Corporation, Lucirin TPO-L) (P-1), and 0.05 g of MEGAFACPENTAD 31 (lanthanide, W-2) as a surfactant, at room temperature Mix for 24 hours to become a homogeneous solution. The number of functional groups, viscosity, and primary skin irritation (PII value) of the polymerizable unsaturated monomer used herein are shown in Table 1, and the composition ratio of the polymerizable unsaturated monomer is shown in Table 3. The matching system is shown in Table 5. The composition of Example 2 has a viscosity of 30 mPa. The ratio of the polymerizable unsaturated monomer below s is 90% by mass, and the viscosity of the composition is 18 mPa. s. This composition was exposed and patterned in the same manner as in Example 1, and the characteristics of the composition were examined. The results are shown in Table 6. According to the results of Table 6, the composition of the present invention can be any of photocurability, adhesion, mold release property, mold resilience, pattern shape, coatability (spin coating property, slit coating property), and etching property. Satisfied with things.

實施例3~實施例18Embodiment 3 to Embodiment 18

與實施例1同樣地進行,以表3所示比率混合表1所示之聚合性不飽和單體,來調製表5所記載之組成物。將該調製後的組成物與實施例1同樣地進行而圖案化,並調查組成物的特性。結果如表6所示。依照表6結果,實施例3~18中任一者的組成物係光硬化性、黏附性、脫模性、殘模性、圖案形狀、塗布性(旋轉塗布性、狹縫塗布性)、蝕刻性中任一者都能夠滿足之物。In the same manner as in Example 1, the polymerizable unsaturated monomers shown in Table 1 were mixed at the ratios shown in Table 3 to prepare the compositions described in Table 5. The composition after the preparation was patterned in the same manner as in Example 1, and the characteristics of the composition were examined. The results are shown in Table 6. According to the results of Table 6, the composition of any of Examples 3 to 18 was photocurability, adhesion, mold release property, mold resilience, pattern shape, applicability (spin coating property, slit coating property), and etching. Any one of the sexes can satisfy.

實施例19Example 19

精稱18.86克作為聚合性不飽和單體之3,4-環氧環己基甲基-3’,4’-環氧環己烷羧酸酯單體(C-1)、56.58克二[1-乙基(3-氧雜環丁烷基)甲基醚(C-5)、18.86克三甘醇二乙烯基醚(C-10)、3.0克作為光聚合引發劑之鋶鹽系的UVI 6990(DOW-CHEMICAL公司製)、0.2克作為矽系界面活性劑之MEGAFAC XRB-4(大日本油墨化學工業公司製)、0.50克作為敏化劑之2-氯噻噸酮,在室溫混合24小時,成為均勻溶液。與實施例1同樣地測定組成物的黏度時,為18mPa.s。在4英吋的玻璃基板上,以成為厚度6.0微米的方式旋轉塗布該調整後的組成物。將旋轉塗布後塗布基膜安裝在使用ORC公司製的高壓水銀燈(燈輸出功率為2000mW/平方公分)作為光源之奈米壓印裝置,以模具加壓力為50Kn/平方公分、曝光中的真空度為0.2托、從以具有10微米的線/間距圖案、溝深度為5.0微米之聚二甲基矽氧烷(TORAY-DOWCORNING公司製、將SILPOT184在80℃硬化60分而成之物)作為材質之模具的背面,以170mJ/平方公分的條件進行曝光,曝光後,將模具卸下,與實施例1同樣地進行調查組成物的特性。結果係光硬化性、黏附性、脫模性、殘模性、圖案形狀、塗布性(旋轉塗布性、狹縫塗布性)、蝕刻性中任一者都能夠滿足之物。18.86 g of 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate monomer (C-1) as a polymerizable unsaturated monomer, 56.58 g of two [1] -Ethyl (3-oxetanyl)methyl ether (C-5), 18.86 g of triethylene glycol divinyl ether (C-10), 3.0 g of UVI as a photopolymerization initiator 6990 (manufactured by DOW-CHEMICAL Co., Ltd.), 0.2 g of MEGAFAC XRB-4 (manufactured by Dainippon Ink and Chemicals Co., Ltd.) as a lanthanide surfactant, and 0.50 g of 2-chlorothioxanthone as a sensitizer, mixed at room temperature After 24 hours, it became a homogeneous solution. When the viscosity of the composition was measured in the same manner as in Example 1, it was 18 mPa. s. The adjusted composition was spin-coated on a 4 inch glass substrate so as to have a thickness of 6.0 μm. The spin-coated base film was mounted on a nano-imprinting apparatus using a high-pressure mercury lamp (light output of 2000 mW/cm 2 ) manufactured by ORC Co., Ltd. as a light source, and the pressure was 50 Kn/cm 2 and the degree of vacuum in the exposure. As a material of 0.2 Torr, a polydimethyl methoxy oxane having a line/pitch pattern of 10 μm and a groove depth of 5.0 μm (manufactured by TORAY-DOWCORNING Co., Ltd., which is obtained by hardening SILPOT 184 at 80 ° C for 60 minutes) The back surface of the mold was exposed to 170 mJ/cm 2 , and after the exposure, the mold was removed, and the characteristics of the composition were investigated in the same manner as in Example 1. As a result, any of photocurability, adhesion, mold release property, mold resilience, pattern shape, applicability (spin coating property, slit coating property), and etching property can be satisfied.

實施例20~25Example 20~25

與實施例19同樣地進行,以表2所示比率混合表4所示之聚合性不飽和單體,來調製表5所記載之組成物。將該調製後的組成物與實施例19同樣地進行圖案化,並調查組成物的特性。結果如表6所示。實施例20~25中任一者的組成物係光硬化性、黏附性、脫模性、殘模性、圖案形狀、塗布性(旋轉塗布性、狹縫塗布性)、蝕刻性中任一者都能夠滿足之物。In the same manner as in Example 19, the polymerizable unsaturated monomers shown in Table 4 were mixed at the ratios shown in Table 2 to prepare the compositions described in Table 5. The composition after the preparation was patterned in the same manner as in Example 19, and the characteristics of the composition were examined. The results are shown in Table 6. The composition of any of Examples 20 to 25 is any of photocurability, adhesion, mold release property, mold resilience, pattern shape, coatability (spin coating property, slit coating property), and etching property. All can satisfy things.

比較例1、比較例2Comparative Example 1 and Comparative Example 2

將在特開平7-70472號公報所揭示之光碟保護膜用紫外線硬化塗料的實施例4、實施例5所記載之組成物,與本發明的實施例1同樣地進行,將表1所示之聚合性不飽和單體以表7所示的比率混合,來調製表8所記載之組成物。將該調製的組成物與實施例1同樣地進行而圖案化,並調查組成物的特性。結果如表9所示。The composition described in the fourth embodiment and the fifth embodiment of the ultraviolet curable coating material for a disc protective film disclosed in Japanese Laid-Open Patent Publication No. Hei 7-70472 is the same as that of the first embodiment of the present invention, and is shown in Table 1. The polymerizable unsaturated monomers were mixed at a ratio shown in Table 7 to prepare the compositions described in Table 8. The composition to be prepared was patterned in the same manner as in Example 1, and the characteristics of the composition were examined. The results are shown in Table 9.

比較例1的組成物係PII值為4.0以下,且黏度為30mPa.s以下之聚合性不飽和單體的比率為60質量%,組成物的黏度為22mPa.s。The composition of Comparative Example 1 had a PII value of 4.0 or less and a viscosity of 30 mPa. The ratio of the polymerizable unsaturated monomer below s is 60% by mass, and the viscosity of the composition is 22 mPa. s.

比較例2的組成物係PII值為4.0以下,且黏度為30mPa.s以下之聚合性不飽和單體的比率為70質量%,組成物的黏度為23mPa.s。The composition of Comparative Example 2 had a PII value of 4.0 or less and a viscosity of 30 mPa. The ratio of the polymerizable unsaturated monomer below s is 70% by mass, and the viscosity of the composition is 23 mPa. s.

而且,如表9所示,比較例1的組成物係脫模性、及塗布性(旋轉塗布性、狹縫塗布性)無法滿足之物。比較例2的組成物係、黏附性、塗布性(旋轉塗布性、狹縫塗布性)、及蝕刻性無法滿足之物。Further, as shown in Table 9, the composition of Comparative Example 1 was unsatisfactory in mold release property and coatability (spin coating property, slit coatability). The composition of the comparative example 2, the adhesiveness, the coating property (spin coating property, slit coating property), and the etching property were not satisfied.

比較例3、比較例4Comparative Example 3, Comparative Example 4

將在特開平7-70472號公報所揭示之光碟保護膜用紫外線硬化塗料的比較例4、比較例5所記載之組成物,與本發明的實施例1同樣地進行,將表1所示之聚合性不飽和單體以表7所示的比率混合,來調製表8所記載之組成物。將該調製的組成物與實施例1同樣地進行而圖案化,並調查組成物的特性。結果如表9所示。比較例3的組成物係PII值為4.0以下,且黏度為30mPa.s以下之聚合性不飽和單體的比率為50質量%,組成物的黏度為21mPa.s。比較例4的組成物係PII值為4.0以下,且黏度為30mPa.s以下之聚合性不飽和單體的比率為90質量%,組成物的黏度為20mPa.s。依照如表9的結果,比較例3、比較例4的組成物係脫模性、及塗布性(旋轉塗布性、狹縫塗布性)無法滿足之物。The composition described in Comparative Example 4 and Comparative Example 5 of the ultraviolet curable coating material for a disc protective film disclosed in Japanese Laid-Open Patent Publication No. Hei 7-70472 is carried out in the same manner as in the first embodiment of the present invention, and is shown in Table 1. The polymerizable unsaturated monomers were mixed at a ratio shown in Table 7 to prepare the compositions described in Table 8. The composition to be prepared was patterned in the same manner as in Example 1, and the characteristics of the composition were examined. The results are shown in Table 9. The composition of Comparative Example 3 had a PII value of 4.0 or less and a viscosity of 30 mPa. The ratio of the polymerizable unsaturated monomer below s is 50% by mass, and the viscosity of the composition is 21 mPa. s. The composition of Comparative Example 4 had a PII value of 4.0 or less and a viscosity of 30 mPa. The ratio of the polymerizable unsaturated monomer below s is 90% by mass, and the viscosity of the composition is 20 mPa. s. According to the results of Table 9, the compositions of Comparative Example 3 and Comparative Example 4 were unsatisfactory in mold release property and coatability (spin coating property, slit coatability).

比較例5、比較例6Comparative Example 5, Comparative Example 6

將在特開平4-149280號公報所揭示之光碟保護膜組成物的實施例、比較例1所記載之組成物,與本發明的實施例1同樣地進行,將表1所示之聚合性不飽和單體以表7所示的比率混合,來調製表8所記載之組成物。將該調製的組成物與實施例1同樣地進行而圖案化,並調查組成物的特性。結果如表9所示。比較例5的組成物係PII值為4.0以下,且黏度為30mPa.s以下之聚合性不飽和單體的比率為43質量%,組成物的黏度為29mPa.s。比較例6的組成物係PII值為4.0以下,且黏度為30mPa.s以下之聚合性不飽和單體的比率為0質量%,組成物的黏度為24mPa.s。依照如表9的結果,比較例5的組成物係黏附性、殘膜性、塗布性(旋轉塗布性、狹縫塗布性)、及蝕刻性無法滿足之物。比較例6的組成物係脫模性、及塗布性(旋轉塗布性、狹縫塗布性)、蝕刻性無法滿足之物。The composition of the optical disk protective film composition disclosed in Japanese Laid-Open Patent Publication No. Hei-4-149280, and the composition described in Comparative Example 1 were carried out in the same manner as in Example 1 of the present invention, and the polymerizability shown in Table 1 was not observed. The saturated monomers were mixed at a ratio shown in Table 7 to prepare the compositions described in Table 8. The composition to be prepared was patterned in the same manner as in Example 1, and the characteristics of the composition were examined. The results are shown in Table 9. The composition of Comparative Example 5 had a PII value of 4.0 or less and a viscosity of 30 mPa. The ratio of the polymerizable unsaturated monomer below s is 43% by mass, and the viscosity of the composition is 29 mPa. s. The composition of Comparative Example 6 had a PII value of 4.0 or less and a viscosity of 30 mPa. The ratio of the polymerizable unsaturated monomer below s is 0% by mass, and the viscosity of the composition is 24 mPa. s. According to the results of Table 9, the composition of Comparative Example 5 was incapable of satisfying adhesion, residual film property, applicability (spin coating property, slit coating property), and etching property. The composition of Comparative Example 6 was unsatisfactory in mold release property, coating property (spin coating property, slit coating property), and etching property.

比較例7Comparative Example 7

將在特開平7-62043號公報所揭示之保護塗層組成物的實施例1所記載之組成物,與本發明的實施例1同樣地進行,將表1所示之聚合性不飽和單體以表7所示的比率混合,來調製表8所記載之組成物。將該調製的組成物與實施例1同樣地進行而圖案化,並調查組成物的特性。結果如表9所示。比較例7的組成物係PII值為4.0以下,且黏度為30mPa.s以下之聚合性不飽和單體的比率為16.5質量%,組成物的黏度為65mPa.s。依照如表9的結果,比較例7的組成物係殘膜性、圖案形狀、塗布性(旋轉塗布性、狹縫塗布性)、及蝕刻性無法滿足之物。The composition described in Example 1 of the protective coating composition disclosed in Japanese Laid-Open Patent Publication No. Hei 7-62043 was carried out in the same manner as in Example 1 of the present invention, and the polymerizable unsaturated monomer shown in Table 1 was used. The compositions described in Table 8 were prepared by mixing at the ratios shown in Table 7. The composition to be prepared was patterned in the same manner as in Example 1, and the characteristics of the composition were examined. The results are shown in Table 9. The composition of Comparative Example 7 had a PII value of 4.0 or less and a viscosity of 30 mPa. The ratio of the polymerizable unsaturated monomer below s is 16.5% by mass, and the viscosity of the composition is 65 mPa. s. According to the results of Table 9, the composition of Comparative Example 7 was not satisfactory in terms of residual film properties, pattern shape, applicability (spin coating property, slit coating property), and etching property.

比較例8、比較例9Comparative Example 8 and Comparative Example 9

將在特開2001-93192號公報所揭示之保護塗層組成物的實施例1、比較例2所記載之組成物,與本發明的實施例1同樣地進行,將表1所示之聚合性不飽和單體以表7所示的比率混合,來調製表8所記載之組成物。將該調製的組成物與實施例1同樣地進行而圖案化,並調查組成物的特性。結果如表9所示。比較例8的組成物係PII值為4.0以下,且黏度為30mPa.s以下之聚合性不飽和單體的比率為30質量%,組成物的黏度為33mPa.s。比較例9的組成物係PII值為4.0以下,且黏度為30mPa.s以下之聚合性不飽和單體的比率為40質量%,組成物的黏度為31mPa.s。依照如表9的結果,比較例8的組成物係脫模性、及蝕刻性無法滿足之物。比較例9的組成物係黏附性、及蝕刻性無法滿足之物。The composition described in Example 1 and Comparative Example 2 of the protective coating composition disclosed in JP-A-2001-93192 was carried out in the same manner as in Example 1 of the present invention, and the polymerizability shown in Table 1 was carried out. The unsaturated monomers were mixed at a ratio shown in Table 7 to prepare the compositions described in Table 8. The composition to be prepared was patterned in the same manner as in Example 1, and the characteristics of the composition were examined. The results are shown in Table 9. The composition of Comparative Example 8 had a PII value of 4.0 or less and a viscosity of 30 mPa. The ratio of the polymerizable unsaturated monomer below s is 30% by mass, and the viscosity of the composition is 33 mPa. s. The composition of Comparative Example 9 had a PII value of 4.0 or less and a viscosity of 30 mPa. The ratio of the polymerizable unsaturated monomer below s is 40% by mass, and the viscosity of the composition is 31 mPa. s. According to the results as shown in Table 9, the composition of Comparative Example 8 was unsatisfactory in mold release property and etching property. The composition of Comparative Example 9 was incapable of satisfying adhesion and etching properties.

比較例10Comparative Example 10

將在特開平2-6562號公報所揭示之光碟保護膜組成物的實施例1所記載之組成物,與本發明的實施例1同樣地進行,將表1所示之聚合性不飽和單體以表7所示的比率混合,來調製表8所記載之組成物。將該調製的組成物與實施例1同樣地進行而圖案化,並調查組成物的特性。結果如表9所示。比較例10的組成物係PII值為4.0以下,且黏度為30mPa.s以下之聚合性不飽和單體的比率為31.7質量%,組成物的黏度為56mPa.s。依照如表9的結果,比較例10的組成物係殘膜性、圖案形狀、塗布性(旋轉塗布性、狹縫塗布性)、及蝕刻性無法滿足之物。The composition described in Example 1 of the optical disk protective film composition disclosed in JP-A No. 2-6562 was carried out in the same manner as in Example 1 of the present invention, and the polymerizable unsaturated monomer shown in Table 1 was used. The compositions described in Table 8 were prepared by mixing at the ratios shown in Table 7. The composition to be prepared was patterned in the same manner as in Example 1, and the characteristics of the composition were examined. The results are shown in Table 9. The composition of Comparative Example 10 had a PII value of 4.0 or less and a viscosity of 30 mPa. The ratio of the polymerizable unsaturated monomer below s is 31.7% by mass, and the viscosity of the composition is 56 mPa. s. According to the results of Table 9, the composition of Comparative Example 10 was not satisfactory in terms of residual film properties, pattern shape, applicability (spin coating property, slit coating property), and etching property.

比較例11、比較例12Comparative Example 11 and Comparative Example 12

將在特開2001-270973號公報所揭示之紫外線及電子射線硬化性組成物的實施例1、實施例2所記載之組成物,與本發明的實施例1同樣地進行,將表1所示之聚合性不飽和單體以表7所示的比率混合,來調製表8所記載之組成物。將該調製的組成物與實施例1同樣地進行而圖案化,並調查組成物的特性。結果如表9所示。比較例11的組成物係PII值為4.0以下,且黏度為30mPa.s以下之聚合性不飽和單體的比率為0質量%,組成物的黏度為1600mPa.s。比較例12的組成物係PII值為4.0以下,且黏度為30mPa.s以下之聚合性不飽和單體的比率為0質量%,組成物的黏度為920mPa.s。依照如表9的結果,比較例11、12的組成物係光硬化性、殘膜性、圖案形狀、塗布性(旋轉塗布性、狹縫塗布性)、及蝕刻性無法滿足之物。The composition described in Example 1 and Example 2 of the ultraviolet-ray and electron beam-curable composition disclosed in JP-A-2001-270973 is carried out in the same manner as in the first embodiment of the present invention, and is shown in Table 1. The polymerizable unsaturated monomers were mixed at a ratio shown in Table 7 to prepare the compositions described in Table 8. The composition to be prepared was patterned in the same manner as in Example 1, and the characteristics of the composition were examined. The results are shown in Table 9. The composition of Comparative Example 11 had a PII value of 4.0 or less and a viscosity of 30 mPa. The ratio of the polymerizable unsaturated monomer below s is 0% by mass, and the viscosity of the composition is 1600 mPa. s. The composition of Comparative Example 12 had a PII value of 4.0 or less and a viscosity of 30 mPa. The ratio of the polymerizable unsaturated monomer below s is 0% by mass, and the viscosity of the composition is 920 mPa. s. According to the results of Table 9, the compositions of Comparative Examples 11 and 12 were incapable of satisfying photocurability, residual film properties, pattern shape, applicability (spin coating property, slit coating property), and etching property.

比較例13、比較例14Comparative Example 13, Comparative Example 14

將在特開7-53895號公報所揭示之保護塗層組成物的實施例1、比較例1所記載之組成物,與本發明的實施例1同樣地進行,將表1所示之聚合性不飽和單體以表7所示的比率混合,來調製表8所記載之組成物。將該調製的組成物與實施例1同樣地進行而圖案化,並調查組成物的特性。結果如表9所示。比較例13的組成物係PII值為4.0以下,且黏度為30mPa.s以下之聚合性不飽和單體的比率為70質量%,組成物的黏度為25mPa.s。比較例14的組成物係PII值為4.0以下,且黏度為30mPa.s以下之聚合性不飽和單體的比率為60質量%,組成物的黏度為28mPa.s。依照如表9的結果,比較例13、14的組成物係脫模性、塗布性(狹縫塗布性)、及蝕刻性無法滿足之物。The composition described in Example 1 and Comparative Example 1 of the protective coating composition disclosed in JP-A-H07-53895 was carried out in the same manner as in Example 1 of the present invention, and the polymerizability shown in Table 1 was carried out. The unsaturated monomers were mixed at a ratio shown in Table 7 to prepare the compositions described in Table 8. The composition to be prepared was patterned in the same manner as in Example 1, and the characteristics of the composition were examined. The results are shown in Table 9. The composition of Comparative Example 13 had a PII value of 4.0 or less and a viscosity of 30 mPa. The ratio of the polymerizable unsaturated monomer below s is 70% by mass, and the viscosity of the composition is 25 mPa. s. The composition of Comparative Example 14 had a PII value of 4.0 or less and a viscosity of 30 mPa. The ratio of the polymerizable unsaturated monomer below s is 60% by mass, and the viscosity of the composition is 28 mPa. s. According to the results of Table 9, the compositions of Comparative Examples 13 and 14 were unsatisfactory in mold release property, coatability (slit coatability), and etching property.

比較例15Comparative Example 15

將在特開2003-165930號公報所揭示之塗料組成物的實施例1所記載之組成物,與本發明的實施例1同樣地進行,將表1所示之聚合性不飽和單體以表7所示的比率混合,來調製表8所記載之組成物。將該調製的組成物與實施例1同樣地進行而圖案化,並調查組成物的特性。結果如表9所示。比較例15的組成物係PII值為4.0以下,且黏度為30mPa.s以下之聚合性不飽和單體的比率為35質量%,組成物的黏度為130mPa.s。依照如表9的結果,比較例15的組成物係黏附性、殘膜性、圖案形狀、塗布性(旋轉塗布性)、及蝕刻性無法滿足之物。The composition described in Example 1 of the coating composition disclosed in JP-A-2003-165930 was carried out in the same manner as in Example 1 of the present invention, and the polymerizable unsaturated monomer shown in Table 1 was used. The ratios shown in Table 7 were mixed to prepare the compositions described in Table 8. The composition to be prepared was patterned in the same manner as in Example 1, and the characteristics of the composition were examined. The results are shown in Table 9. The composition of Comparative Example 15 had a PII value of 4.0 or less and a viscosity of 30 mPa. The ratio of the polymerizable unsaturated monomer below s is 35% by mass, and the viscosity of the composition is 130 mPa. s. According to the results of Table 9, the composition of Comparative Example 15 was incapable of satisfying the adhesiveness, residual film property, pattern shape, applicability (spin coating property), and etching property.

比較例16Comparative Example 16

將在特開2005-8759號公報所揭示之噴墨組成物的實施例(印墨組成3)所記載之組成物,與本發明的實施例1同樣地進行,將表1所示之聚合性不飽和單體以表4所示的比率混合,來調製表8所記載之組成物。將該調製的組成物與實施例1同樣地進行而圖案化,並調查組成物的特性。結果如表9所示。比較例16的組成物係PII值為4.0以下,且黏度為30mPa.s以下之聚合性不飽和單體的比率為57.9質量%,組成物的黏度為30mPa.s。依照如表9的結果,比較例16的組成物係光硬化性、脫模性、圖案形狀、及蝕刻性無法滿足之物。The composition described in the example (ink composition 3) of the inkjet composition disclosed in JP-A-2005-8759 was carried out in the same manner as in Example 1 of the present invention, and the polymerizability shown in Table 1 was carried out. The unsaturated monomers were mixed at a ratio shown in Table 4 to prepare the compositions described in Table 8. The composition to be prepared was patterned in the same manner as in Example 1, and the characteristics of the composition were examined. The results are shown in Table 9. The composition of Comparative Example 16 had a PII value of 4.0 or less and a viscosity of 30 mPa. The ratio of the polymerizable unsaturated monomer below s is 57.9 mass%, and the viscosity of the composition is 30 mPa. s. According to the results of Table 9, the composition of Comparative Example 16 was incapable of satisfying photocurability, mold release property, pattern shape, and etching property.

比較例17Comparative Example 17

在比較例16的組成物,將著色劑(A-13)、分散劑(A-12)從組成物除去,其他的成分係使用與比較例16同樣的成分,與本發明的實施例1同樣地進行,將表1所示之聚合性不飽和單體以表4所示的比率混合,來調製表8所記載之組成物。將該調製的組成物與實施例1同樣地進行而圖案化,並調查組成物的特性。結果如表9所示。比較例16的組成物係PII值為4.0以下,且黏度為30mPa.s以下之聚合性不飽和單體的比率為57.9質量%,組成物的黏度為6mPa.s。依照如表9的結果,比較例17的組成物係光硬化性、脫模性、圖案形狀、及蝕刻性無法滿足之物。In the composition of Comparative Example 16, the coloring agent (A-13) and the dispersing agent (A-12) were removed from the composition, and the other components were the same as those of Comparative Example 16, and the same components as in Example 1 of the present invention were used. The polymerizable unsaturated monomers shown in Table 1 were mixed at a ratio shown in Table 4 to prepare the compositions described in Table 8. The composition to be prepared was patterned in the same manner as in Example 1, and the characteristics of the composition were examined. The results are shown in Table 9. The composition of Comparative Example 16 had a PII value of 4.0 or less and a viscosity of 30 mPa. The ratio of the polymerizable unsaturated monomer below s is 57.9 mass%, and the viscosity of the composition is 6 mPa. s. According to the results of Table 9, the composition of Comparative Example 17 was incapable of satisfying photocurability, mold release property, pattern shape, and etching property.

比較例18Comparative Example 18

在本發明之實施例1的組成物,除了將氟系界面活性劑(W-1)變更為炔二醇系非離子界面活性劑(W-5)以外,與本發明的實施例1同樣地進行並評價。結果如表9所示。依照如表9的結果,比較例18的組成物係黏附性、塗布性(旋轉塗布性、狹縫塗布性)、及蝕刻性無法滿足之物。The composition of the first embodiment of the present invention is the same as the first embodiment of the present invention except that the fluorine-based surfactant (W-1) is changed to the acetylene glycol-based nonionic surfactant (W-5). Conduct and evaluate. The results are shown in Table 9. According to the results of Table 9, the composition of Comparative Example 18 was inferior in adhesion, coating property (spin coating property, slit coating property), and etching property.

比較例19Comparative Example 19

在本發明之實施例2的組成物,除了將矽系界面活性劑(W-2)變更為聚氧乙烯聚氧丙烯縮合物(W-6)以外,與本發明的實施例2同樣地進行並評價。結果如表9所示。依照如表9的結果,比較例19的組成物係黏附性、塗布性(狹縫塗布性)、及蝕刻性無法滿足之物。The composition of the second embodiment of the present invention was carried out in the same manner as in the second embodiment of the present invention except that the lanthanoid surfactant (W-2) was changed to the polyoxyethylene polyoxypropylene condensate (W-6). And evaluation. The results are shown in Table 9. According to the results of Table 9, the composition of Comparative Example 19 was incapable of satisfying adhesion, coating properties (slit coating properties), and etching properties.

比較例20Comparative Example 20

將本發明之實施例12所使用之聚合性不飽和單體的混合比變更,並且為了降低黏度之目的,添加碳酸丙烯酯。更添加氟系界面活性劑(W-9)、光聚合引發劑(P-1),以表7所示比率混合,來調製表8所記載之組成物。將該調製的組成物與實施例1同樣地進行而圖案化,並調查組成物的特性。結果如表9所示。比較例20的組成物係PII值為4.0以下,且黏度為30mPa.s以下之聚合性不飽和單體的比率為100%,組成物的黏度為2mPa.s。依照如表9的結果,比較例20的組成物係光硬化性、脫模性、塗布性(狹縫塗布性)、及蝕刻性無法滿足之物。The mixing ratio of the polymerizable unsaturated monomer used in Example 12 of the present invention was changed, and propylene carbonate was added for the purpose of lowering the viscosity. Further, a fluorine-based surfactant (W-9) and a photopolymerization initiator (P-1) were added, and the compositions shown in Table 8 were prepared by mixing at the ratios shown in Table 7. The composition to be prepared was patterned in the same manner as in Example 1, and the characteristics of the composition were examined. The results are shown in Table 9. The composition of Comparative Example 20 had a PII value of 4.0 or less and a viscosity of 30 mPa. The ratio of the polymerizable unsaturated monomer below s is 100%, and the viscosity of the composition is 2 mPa. s. According to the results of Table 9, the composition of Comparative Example 20 was incapable of satisfying photocurability, mold release property, coatability (slit coatability), and etching property.

產業上之利用可能性Industrial use possibility

本發明之光硬化性組成物,能使用作為光奈米壓印光阻組成物,用以在製造半導體積體電路、平面螢幕、微電機械系統(MEMS)、傳感器元件、光碟、高密度儲存碟等磁記錄媒體、繞射格子或浮凸型全息照像等的光學零件、奈米元件、光學元件、為製造平面顯示器之光學薄膜或偏光元件、液晶顯示器之薄膜電晶體、有機電晶體、彩色濾光片、保護層、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、奈米生物元件、光波導器、濾光器、光子液晶等時形成微細圖案。The photocurable composition of the present invention can be used as a photo-nanoimprinting photoresist composition for manufacturing a semiconductor integrated circuit, a flat screen, a micro electro mechanical system (MEMS), a sensor element, a compact disc, and a high-density storage. Optical recording medium such as a disk, an optical component such as a diffraction grating or an embossed hologram, a nano component, an optical component, an optical film or a polarizing element for manufacturing a flat panel display, a thin film transistor for a liquid crystal display, an organic transistor, Color filter, protective layer, column, liquid crystal alignment rib, microlens array, immunoassay wafer, DNA separation wafer, microreactor, nano biocomponent, optical waveguide, filter, photonic liquid crystal, etc. A fine pattern is formed.

特別是本發明係適合使用於藉由光透射奈米衝壓法來形成微細圖案,在該光透射奈米壓印法(亦稱為光奈米壓印微影法)包含以下步驟:在基板上塗布液狀之未硬化光硬化性組成物之步驟;將光透射性模具加壓於基板上的塗膜層,來使塗膜變形之步驟;從模具背面或基板背面照射光線使光硬化物層硬化,以形成嵌合所期望圖案的光阻圖案之步驟;及將光透射性模具從塗膜脫附下來之步驟。In particular, the present invention is suitable for use in forming a fine pattern by a light transmission nano-stamping method, and the light-transmitting nanoimprint method (also referred to as a photon lithography method) comprises the following steps: on a substrate a step of applying a liquid uncured photocurable composition; a step of applying a light transmissive mold to a coating layer on the substrate to deform the coating film; and irradiating light from the back surface of the mold or the back surface of the substrate to form a photohardenable layer a step of hardening to form a photoresist pattern in which a desired pattern is fitted; and a step of desorbing the light-transmitting mold from the coating film.

特別是藉由本發明的光硬化性組成物,能夠能造實質上比先前的光微影法更經濟之電子零件的微細結構。而且,本發明的光硬化性組成物係具有以下特徵之物,(1)因為在室溫之溶液流動性優良,該組成物能夠容易地流入模具凹部的槽內,因為不容易包容大氣所以不會產生氣泡缺陷,且無論在模具凸部、凹部在硬化後都不會產生殘渣。又,因為本發明的光硬化性組成物揮發性小、皮膚刺激性小,作業者的安全性優良。In particular, the photocurable composition of the present invention can produce a fine structure of an electronic component which is substantially more economical than the conventional photolithography method. Further, the photocurable composition of the present invention has the following characteristics: (1) Since the solution has excellent fluidity at room temperature, the composition can easily flow into the groove of the mold recess, since it is not easy to contain the atmosphere, so Bubble defects are generated, and no residue is generated even after the convex portion and the concave portion of the mold are hardened. Moreover, since the photocurable composition of the present invention has low volatility and small skin irritation, the safety of the operator is excellent.

(2)因為由本發明的光硬化性組成物而成的硬化膜之機械性質優良,塗膜與基板的黏附性優良、在將模具剝離時,不會產生圖案崩潰或塗膜表面拉絲而引起表面粗糙,所以能夠形成良好的圖案。(2) Since the cured film obtained from the photocurable composition of the present invention is excellent in mechanical properties, the adhesion between the coating film and the substrate is excellent, and when the mold is peeled off, the pattern is not broken or the surface of the coating film is drawn to cause surface damage. Rough, so it can form a good pattern.

(3)因為本發明的光硬化性組成物在光硬化後的體積收縮小,且模具轉印特性優良,微細圖案能夠得到正確的賦型性。(3) Since the photocurable composition of the present invention has a small volume shrinkage after photocuring and excellent mold transfer characteristics, the fine pattern can obtain correct formability.

(4)因為本發明的光硬化性組成物之塗布均勻性優良,能夠適合大型基板的塗布、微細加工領域等。(4) Since the photocurable composition of the present invention is excellent in coating uniformity, it can be suitably used in the field of coating, microfabrication, and the like of a large substrate.

(5)因為本發明的光硬化性組成物之膜的光硬化速度高,所以生產力高。(5) Since the film of the photocurable composition of the present invention has a high photocuring rate, productivity is high.

(6)因為蝕刻加工精確度、蝕刻耐性等優良,能夠適合作為半導體元件或電晶體等基板加工用蝕刻光阻。(6) Since it is excellent in etching processing precision, etching resistance, and the like, it can be suitably used as an etching resistor for substrate processing such as a semiconductor element or a transistor.

(7)因為蝕刻後之光阻剝離性優良,不會產生殘渣,適用作為蝕刻光阻。(7) Since the photoresist peeling property after etching is excellent, no residue is generated, and it is suitable as an etching photoresist.

Claims (12)

一種光硬化性組成物,其係含有(a)聚合性化合物、(b)0.1~15質量%光聚合引發劑及/或光酸產生劑、及(c)0.001~5質量%氟系界面活性劑、矽系界面活性劑及氟-矽系界面活性劑中之至少一種,且(d)於25℃之黏度在3~18mPa‧s的範圍之光硬化性組成物,該(a)聚合性化合物係含有分別為50質量%以上的(e)一次皮膚刺激性(PII值)為4.0以下之聚合性不飽和單體,及(f)於25℃之黏度在30mPa‧s以下之聚合性不飽和單體(其中,該(e)的聚合性不飽和單體與該(f)的聚合性不飽和單體之一部分或全部亦可以是相同的聚合性不飽和單體)。 A photocurable composition comprising (a) a polymerizable compound, (b) 0.1 to 15% by mass of a photopolymerization initiator and/or a photoacid generator, and (c) 0.001 to 5% by mass of a fluorine-based interface activity At least one of a agent, a lanthanide surfactant, and a fluorine-antimony surfactant, and (d) a photocurable composition having a viscosity at 25 ° C of 3 to 18 mPa ‧ , (a) polymerizability The compound contains 50% by mass or more of (e) a polymerizable unsaturated monomer having a primary skin irritation (PII value) of 4.0 or less, and (f) a polymerizable property at a viscosity of 25 mPa·s or less at 25 ° C. A saturated monomer (wherein part or all of the polymerizable unsaturated monomer of (e) and one or more of the polymerizable unsaturated monomer of (f) may be the same polymerizable unsaturated monomer). 如申請專利範圍第1項之光硬化性組成物,其中含有光自由基聚合性不飽和單體及/或光陽離子聚合性不飽和單體作為該(a)聚合性化合物。 The photocurable composition according to claim 1, which comprises a photoradical polymerizable unsaturated monomer and/or a photocationic polymerizable unsaturated monomer as the (a) polymerizable compound. 如申請專利範圍第1項之光硬化性組成物,其中含有具有乙烯性不飽和鍵含有基之單體作為該(a)聚合性化合物。 The photocurable composition according to claim 1, wherein a monomer having an ethylenically unsaturated bond-containing group is contained as the (a) polymerizable compound. 如申請專利範圍第1項之光硬化性組成物,其中含有具有環氧乙烷之化合物作為該(e)聚合性不飽和單體。 A photocurable composition according to claim 1 which contains a compound having ethylene oxide as the (e) polymerizable unsaturated monomer. 如申請專利範圍第1項之光硬化性組成物,其中含有具有氧雜環丁烷之化合物作為該(e)聚合性不飽和單體。 A photocurable composition according to claim 1 which contains a compound having an oxetane as the (e) polymerizable unsaturated monomer. 如申請專利範圍第1項之光硬化性組成物,其中含有乙烯基醚作為該(a)聚合性化合物。 A photocurable composition according to claim 1 which contains a vinyl ether as the (a) polymerizable compound. 如申請專利範圍第1項之光硬化性組成物,其中含有苯乙烯衍生物作為該(a)聚合性化合物。 A photocurable composition according to claim 1 which contains a styrene derivative as the (a) polymerizable compound. 如申請專利範圍第1項之光硬化性組成物,該光硬化性組成物中有機溶劑的含量為2質量%以下。 The photocurable composition of the first aspect of the invention is characterized in that the content of the organic solvent in the photocurable composition is 2% by mass or less. 如申請專利範圍第1至8項中任一項之光硬化性組成物,其係光奈米壓印微影法用。 The photocurable composition according to any one of claims 1 to 8, which is used in a photon lithography method. 一種光阻,其係使用如申請專利範圍第1至8項中任一項之光硬化性組成物而構成。 A photoresist comprising the photocurable composition according to any one of claims 1 to 8. 一種圖案之形成方法,其係含有塗布如申請專利範圍第1至8項中任一項之光硬化性組成物而使其硬化之步驟。 A method of forming a pattern comprising the step of applying a photocurable composition according to any one of claims 1 to 8 to harden it. 一種光阻圖案之形成方法,其係包含以下步驟:塗布如申請專利範圍第1至8項中任一項之光硬化性組成物之步驟;將光透射性模具加壓於基板上的光阻層,來使該光硬化性組成物變形之步驟;從模具背面或基板背面照射光線使塗膜硬化,以形成嵌合所期望圖案的光阻圖案之步驟;將光透射性模具從塗膜脫附下來之步驟;以光硬化性組成物作為遮罩,來蝕刻基板之步驟;以及在蝕刻後剝離光硬化性組成物之步驟。 A method for forming a photoresist pattern, comprising the steps of: coating a photocurable composition according to any one of claims 1 to 8; and pressing a light transmissive mold on a substrate a step of deforming the photocurable composition; a step of irradiating light from the back surface of the mold or the back surface of the substrate to harden the coating film to form a photoresist pattern of a desired pattern; and removing the light transmissive mold from the coating film a step of attaching; a step of etching the substrate with the photocurable composition as a mask; and a step of peeling off the photocurable composition after etching.
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Families Citing this family (87)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008189821A (en) * 2007-02-05 2008-08-21 Fujifilm Corp Photocurable composition
JP5269449B2 (en) * 2007-03-24 2013-08-21 株式会社ダイセル Curable resin composition for nanoimprint
JP5264113B2 (en) * 2007-07-13 2013-08-14 旭化成イーマテリアルズ株式会社 Photocurable resin composition, molded article, and method for producing molded article
CN101809046A (en) * 2007-09-28 2010-08-18 旭硝子株式会社 Photocurable composition, method for producing fine patterned body, and optical device
JP5243887B2 (en) 2008-02-12 2013-07-24 富士フイルム株式会社 Curable composition for nanoimprint and pattern forming method
JP5435879B2 (en) * 2008-02-14 2014-03-05 株式会社ダイセル Curable resin composition for nanoimprint
JP2009208239A (en) * 2008-02-29 2009-09-17 Fujifilm Corp Pattern forming method
JP5130082B2 (en) * 2008-03-03 2013-01-30 株式会社ブリヂストン Composition for imprint molding and molded product using the same
JP5101343B2 (en) * 2008-03-03 2012-12-19 株式会社ダイセル Manufacturing method of fine structure
JP5065101B2 (en) * 2008-03-05 2012-10-31 東洋合成工業株式会社 Pattern formation method
JP2009209337A (en) * 2008-03-06 2009-09-17 Fujifilm Corp Curable composition for nanoimprint, cured material made using the same, method for producing the material, and member for liquid crystal display
JP2009215179A (en) * 2008-03-07 2009-09-24 Fujifilm Corp (meth)acrylate compound, curable composition using the same, composition for optical nano imprinting, and cured products of these curable compositions and its manufacturing method
JP2009214419A (en) * 2008-03-11 2009-09-24 Fujifilm Corp Image forming method and cured matter made by using the same
JP2009222792A (en) * 2008-03-13 2009-10-01 Fujifilm Corp Photosensitive resin composition, and method for forming light-shielding image
WO2009113615A1 (en) * 2008-03-13 2009-09-17 富士フイルム株式会社 Photosensitive resin composition, photosensitive resin hardened film, and method for forming light-shielding image
JP2009252319A (en) 2008-04-09 2009-10-29 Fujitsu Ltd Magnetic recording medium and magnetic recording and reproducing device
JP5306903B2 (en) * 2008-07-02 2013-10-02 富士フイルム株式会社 Curable composition for imprint, cured product using the same, method for producing the same, and member for liquid crystal display device
JP2010016149A (en) * 2008-07-03 2010-01-21 Fujifilm Corp Curable composition for nanoimprint, cured product and method of manufacturing the same, and member for liquid-crystal dispplay apparatus
JP2010018666A (en) * 2008-07-09 2010-01-28 Fujifilm Corp Composition for nano imprint, pattern and patterning method
KR101634804B1 (en) * 2008-07-10 2016-06-29 후지필름 가부시키가이샤 Curable composition for nanoimprint and cured material
JP5411518B2 (en) * 2008-07-10 2014-02-12 富士フイルム株式会社 Curable composition for nanoimprint and cured product
JP2010037541A (en) * 2008-07-10 2010-02-18 Fujifilm Corp Curable composition for imprint, pattern forming method, and pattern
JP5394707B2 (en) * 2008-11-26 2014-01-22 富士フイルム株式会社 Photosensitive composition and process for producing processed substrate
JP5481861B2 (en) * 2009-01-09 2014-04-23 日立化成株式会社 Photocurable resin composition, pattern forming method using the same, and fine structure
KR101669085B1 (en) * 2009-01-28 2016-10-25 제이에스알 가부시끼가이샤 Radiation sensitive resin composition, and interlayer insulating film and forming method thereof
JP2010218605A (en) 2009-03-13 2010-09-30 Toshiba Corp Ultraviolet-curable resin material for pattern transfer and method for manufacturing magnetic recording medium using the same
JP4543117B1 (en) 2009-03-13 2010-09-15 株式会社東芝 Ultraviolet curable resin material for pattern transfer and method for producing magnetic recording medium using the same
JP4729114B2 (en) 2009-03-18 2011-07-20 株式会社東芝 Method for manufacturing magnetic recording medium
JP4892026B2 (en) * 2009-03-19 2012-03-07 株式会社東芝 Pattern formation method
KR101762969B1 (en) 2009-03-24 2017-07-28 주식회사 다이셀 Curable composition for nanoimprinting and cured object
JP5604054B2 (en) * 2009-05-12 2014-10-08 日東電工株式会社 Method for manufacturing optical lens or optical waveguide or optical fiber core
JP5566639B2 (en) * 2009-07-16 2014-08-06 富士フイルム株式会社 Curable composition for imprint, cured product, and pattern forming method
JP2011060818A (en) * 2009-09-07 2011-03-24 Fujifilm Corp Curable composition for imprint, cured product and method of manufacturing the same
KR101759929B1 (en) 2009-11-20 2017-07-20 코오롱인더스트리 주식회사 Photosensitive resin composition
WO2011132616A1 (en) * 2010-04-19 2011-10-27 日産化学工業株式会社 Highly abrasion-resistant imprint material
US20110305787A1 (en) * 2010-06-11 2011-12-15 Satoshi Ishii Stamper for transfer of microscopic structure and transfer apparatus of microscopic structure
JP5753749B2 (en) 2010-09-27 2015-07-22 富士フイルム株式会社 Method for producing curable composition for imprint
CN103119691B (en) 2010-10-20 2016-01-13 株式会社德山 Photo-curable nano impression composition, use the formation method of the pattern of said composition and there is the nano impression copy mold of firming body of said composition
JP5697407B2 (en) * 2010-11-11 2015-04-08 旭化成株式会社 Photosensitive resin laminate
JP5790234B2 (en) 2010-12-13 2015-10-07 セイコーエプソン株式会社 UV-curable ink composition for inkjet, inkjet recording apparatus using the same, inkjet recording method using the same, and ink set
CN103261238B (en) 2011-01-13 2015-08-26 丸善石油化学株式会社 Optical pressure print resin combination, pattern formation method and etching mask
CN102757693B (en) 2011-04-28 2015-11-18 精工爱普生株式会社 Light curable type ink composition, recording method and device, light-cured type composition for ink jet recording and ink jet recording method
ITMI20111011A1 (en) * 2011-06-06 2012-12-07 Telecom Italia Spa INKJET PRINT HEAD INCLUDING A LAYER MADE WITH A RETICULAR RESIN COMPOSITION
JP5679445B2 (en) * 2011-06-14 2015-03-04 信越化学工業株式会社 Concave and convex pattern forming method
EP2543707B2 (en) 2011-07-08 2020-09-02 Seiko Epson Corporation Photocurable ink composition for ink jet recording and ink jet recording method
JP5807776B2 (en) 2011-09-12 2015-11-10 セイコーエプソン株式会社 Photocurable ink composition for inkjet recording
JP5696017B2 (en) 2011-09-27 2015-04-08 富士フイルム株式会社 Curable composition for imprint, pattern forming method and pattern
JP5788759B2 (en) * 2011-10-18 2015-10-07 富士フイルム株式会社 Curable composition for imprint and storage method thereof
JP6024150B2 (en) 2012-03-28 2016-11-09 セイコーエプソン株式会社 Ultraviolet curable clear ink composition and recording method
KR20150003158A (en) * 2012-04-09 2015-01-08 아사히 가라스 가부시키가이샤 Method for manufacturing article having fine pattern on surface thereof
JP6071255B2 (en) * 2012-06-04 2017-02-01 キヤノン株式会社 Photocured material
JP5932501B2 (en) * 2012-06-06 2016-06-08 キヤノン株式会社 Curable composition and pattern forming method using the same
JP6379458B2 (en) * 2012-09-13 2018-08-29 日立化成株式会社 Method for producing resin layer having pattern, and resin composition used therefor
JP5975814B2 (en) * 2012-09-14 2016-08-23 株式会社トクヤマ Photocurable nanoimprint composition and pattern formation method
JP6176937B2 (en) 2012-09-19 2017-08-09 キヤノン株式会社 Photo-curable composition for imprint and method for producing film
JP6278645B2 (en) * 2012-09-24 2018-02-14 キヤノン株式会社 Photocurable composition and method for producing film using the same
EP2911184B1 (en) * 2012-10-22 2019-07-24 Soken Chemical & Engineering Co., Ltd. Photocurable resin composition for imprinting, method for producing mold for imprinting, and mold for imprinting
US20150298365A1 (en) * 2012-11-27 2015-10-22 Daicel Corporation Method for producing microstructure and photocurable composition for nanoimprinting
KR20160002707A (en) * 2013-04-18 2016-01-08 닛산 가가쿠 고교 가부시키 가이샤 Imprint material
JP2013219366A (en) * 2013-05-16 2013-10-24 Toyo Gosei Kogyo Kk Composition, method of manufacturing composite body, and method of manufacturing optical member
KR101757573B1 (en) 2013-06-06 2017-07-12 디아이씨 가부시끼가이샤 Curable composition for imprinting
US9201305B2 (en) * 2013-06-28 2015-12-01 Az Electronic Materials (Luxembourg) S.A.R.L. Spin-on compositions of soluble metal oxide carboxylates and methods of their use
JP6286950B2 (en) * 2013-09-02 2018-03-07 大日本印刷株式会社 Curable resin composition and pattern forming method using the same
JP6460672B2 (en) * 2013-09-18 2019-01-30 キヤノン株式会社 Film manufacturing method, optical component manufacturing method, circuit board manufacturing method, and electronic component manufacturing method
JP5695726B1 (en) * 2013-12-18 2015-04-08 日新製鋼株式会社 Printing material
JP5763796B2 (en) * 2014-02-05 2015-08-12 富士フイルム株式会社 Fine pattern manufacturing method
JP6066960B2 (en) * 2014-05-30 2017-01-25 富士フイルム株式会社 Actinic ray curable ink composition for molding process, ink set, inkjet recording method, decorative sheet for molding process, decorative sheet molded product, and method for producing in-mold molded product
US10259957B2 (en) * 2014-09-26 2019-04-16 Lg Chem, Ltd. UV-curable ink composition, method for producing bezel pattern of display substrate using same, and bezel pattern produced thereby
KR101813338B1 (en) * 2014-12-11 2017-12-28 주식회사 엘지화학 photosensitive color ink composition for bezel, bezel pattern formed by using the same, and display panel comprising the pattern
JP2015144278A (en) * 2015-01-26 2015-08-06 東洋合成工業株式会社 Composition and method for producing composite material
JP2016162863A (en) * 2015-02-27 2016-09-05 キヤノン株式会社 Pattern formation method, manufacturing method for processed substrate, manufacturing method for optical component, manufacturing method for circuit board, and manufacturing method for electronic component
WO2016143740A1 (en) * 2015-03-11 2016-09-15 東レ株式会社 Organic el display device and method for manufacturing same
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JP6602062B2 (en) * 2015-06-17 2019-11-06 東京応化工業株式会社 Curable composition, method for producing cured product, and hard coat material
CN105242493A (en) * 2015-10-07 2016-01-13 南京鹏派新材料科技有限公司 Ultraviolet-cured nano-imprinting lithography glue and preparation method thereof
JP2017115073A (en) * 2015-12-25 2017-06-29 株式会社ダイセル Curable composition for three-dimensional molding
JP6732174B2 (en) * 2016-07-14 2020-07-29 協立化学産業株式会社 Photocurable resin composition for imprint molding
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5958648A (en) * 1997-05-22 1999-09-28 Jsr Corporation Radiation sensitive resin composition
US20040115558A1 (en) * 2002-10-04 2004-06-17 Seok-Yoon Yang Photosensitive resin composition controlling solubility and pattern formation method of double-layer structure using the same
TW200522806A (en) * 2003-10-30 2005-07-01 Fuji Photo Film Co Ltd Method for producing printed wiring board

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05105732A (en) * 1991-10-14 1993-04-27 Osaka Organic Chem Ind Ltd Photo-setting composition
JPH0718042A (en) * 1993-06-30 1995-01-20 Nippon Oil & Fats Co Ltd Diluent for photopolymerizable resin and photopolymerizable resin composition
JPH0741508A (en) * 1993-07-30 1995-02-10 Tosoh Corp Production of dispersion of optically active species
JP2004182933A (en) * 2002-12-05 2004-07-02 Riso Kagaku Corp Ultraviolet light-curing type inkjet ink
TWI313397B (en) * 2003-03-28 2009-08-11 Sumitomo Chemical Co Colored photosensitive resin composition
TWI342983B (en) * 2003-07-16 2011-06-01 Sumitomo Chemical Co Coloring photosensitive resin composition
JP2006110997A (en) * 2004-09-16 2006-04-27 Asahi Glass Co Ltd Manufacturing method for transfer body, photocurable composition, and manufacturing method for fine structure
WO2006046411A1 (en) * 2004-10-26 2006-05-04 Konica Minolta Medical & Graphic, Inc. Actinic-light-curable composition, actinic-light-curable inkjet ink, method of forming image with the actinic-light-curable inkjet ink, and inkjet recording apparatus
CN1797196A (en) * 2004-12-01 2006-07-05 Jsr株式会社 Photosensitive resin composites, spacer for display panel and display panel
JP4770354B2 (en) * 2005-09-20 2011-09-14 日立化成工業株式会社 Photocurable resin composition and pattern forming method using the same
JP4929722B2 (en) * 2006-01-12 2012-05-09 日立化成工業株式会社 Photo-curable nanoprint resist material and pattern formation method

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5958648A (en) * 1997-05-22 1999-09-28 Jsr Corporation Radiation sensitive resin composition
US20040115558A1 (en) * 2002-10-04 2004-06-17 Seok-Yoon Yang Photosensitive resin composition controlling solubility and pattern formation method of double-layer structure using the same
TW200522806A (en) * 2003-10-30 2005-07-01 Fuji Photo Film Co Ltd Method for producing printed wiring board

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