TW201241553A - Photocurable resin composition for printing process - Google Patents

Photocurable resin composition for printing process Download PDF

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Publication number
TW201241553A
TW201241553A TW100146465A TW100146465A TW201241553A TW 201241553 A TW201241553 A TW 201241553A TW 100146465 A TW100146465 A TW 100146465A TW 100146465 A TW100146465 A TW 100146465A TW 201241553 A TW201241553 A TW 201241553A
Authority
TW
Taiwan
Prior art keywords
resin composition
photocurable resin
printing process
group
compound
Prior art date
Application number
TW100146465A
Other languages
Chinese (zh)
Inventor
Jun-Yong Song
Seung-Hyup Shin
Mi-Kyung Choi
Kwang-Young Lee
Original Assignee
Dongjin Semichem Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dongjin Semichem Co Ltd filed Critical Dongjin Semichem Co Ltd
Publication of TW201241553A publication Critical patent/TW201241553A/en

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Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/0275—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with dithiol or polysulfide compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • G03F7/0395—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having a backbone with alicyclic moieties
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/075—Silicon-containing compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/38—Treatment before imagewise removal, e.g. prebaking
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
    • H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
    • H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
    • H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
    • H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
    • H01L21/0274—Photolithographic processes

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Paints Or Removers (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

The present invention relates to a photo-curable resin composition for a printing process and more specifically to a photo-curable resin composition comprising a polysilazane compound. The composition according to the invention comprises the polysilazane compound, thereby ensuring an excellent adhesive force to a substrate, heat resistance, durability (against high temperature, high pressure, and high humidity) and lower layer protection property while maintaining high permeability even after high temperature treatment. Therefore, the photo-curable resin composition can be useful in the formation of a fine pattern and a protective layer.

Description

201241553 六、發明說明： 【發明戶斤属之技術領域3 發明領域 本發明係有關於一種用於印刷製程之光硬化性樹脂組 成物，其製造在壓印微影術及輥印刷步驟所使用的微細圖 案及保護膜係有用的。 【先前技術3 發明背景 通常，形成應用在資訊保存、小型傳感器、光結晶及 光學元件、微細電子機械元件、顯示元件、顯示器及半導 體的微細圖案之步驟，係使用利用光線而形成微細圖案之 微影術(photolithography)之方法。 先前的微影術方法係依照在曝光步驟所使用之光線的 波長而決定電路線寬或圖案線寬。考慮目前的技術水準 時，微影術步驟係因為光線的干擾而難以在基板上形成 50nm以下的微細圖案之狀況。又，由於圖案的超微細化進 展，如曝光裝備之昂貴裝置造成初期投資費用增加且高解 像度的光罩之價格亦暴漲而且有效率性低落之缺點，必須 使用昂貴的裝備之問題點，其結果會以其他的重要原因之 方式起作用而造成成本上升。 不僅如此，因為每次形成圖案都必須進行曝光、曝光 後烘烤、顯像、顯像後烘烤、蝕刻步驟、洗淨步驟等，所 以需要長的步驟時間而且必須重數次的光步驟，有生產性 低落的問題點浮出。 201241553 作為能夠解決此種問題之方法，壓印微影術及輥印刷 技術興起。壓印微影術係美國Princeton大學的Stephen chou 等人為了刻奈米等級的記號而發明之方法，係預先在相對 強度較強的無機物或高分子表面製作必要的形狀，且將此 在其他物質的上面壓記號而形成微細圖案。具體上，係使 用預先形成有所需要的微細圖案之無機物或高分子模具 (Mold)，黏住已被塗佈在金屬膜或有機膜上之硬化性組成 物且使其熱或光硬化而形成圖案之技術，相較於原有的微 影術方法，有步驟單純化及形成微細圖案之有利的優點。 此種壓印技術係在美國專利第5，772,905號(專利文獻1)、美 國專利第5,259,926號（專利文獻2)、曰本專利公報第 2007-244984號(大韓民國公開專利公報第1〇_2〇〇9_〇〇31274號) (專利文獻3)有揭示技術。 又，大韓民國專利申請第2006-0005482號（公開專利公 報第10-2007-76292號）（專利文獻4)係揭示一種親印刷置及 使用其之顯示裝置之製造方法，該揭示係利用i或其以上的 親之報印刷技術，在FED(Field Emission Display ;場發射顯 示器）、OLED(Organic Light-Emitting Diode ;有機發光二極 體）、PDP(Plasma Display Panel;電漿顯示面板）等裝置均能 夠應用，有提及前述裝置的製造步驟係變為簡單且反復印 刷之後亦能夠確保圖案的精密度。 前述輥印刷技術係利用輥至板、輥與輥等而能夠形成微 細圖案’來代替原有之使用微影術形成圖案時所使用的高解 像度光罩。此種輥印刷技術係能夠藉由步驟的簡單化而使生 201241553 產性及作業效率提升。又，揭示能夠作為代替方案，來劃 時代性地減少在經過如微影術的曝光和顯像作業的各種步 驟之同時所附帶的複雜步驟以及因其而發生的步驟費用。 有關此種能夠以低費用完成之圖案形成用印刷技術， 在曰本公開專利公報第2005_197699號（專利文獻5)係揭示 一種半導體微影術用壓印組成物。又，作為LCD等的構件， 在曰本公開專利公報第2005-301289號(專利文獻6)，係針對 透明保護膜材料、間隙物等亦揭示應用光硬化型印刷微影 術。在日本公開專利公報第2〇〇5 3〇1289號所揭示之透明保 護膜材料、間隙物等的光阻，係與蝕刻光阻不同，因為材 料在最後係殘留，所以被稱為保護膜(永久膜）。 此種保濩膜（永久膜)係與蝕刻光阻不同，為殘留在TFT 顯不益之要素。在TFT基板時，係形成用以保護薄膜電晶體 之透明保護膜。先前的保護膜(永久膜)係大部分藉由使用光 阻材料之微影術步驟而形成。與此同樣地，lcd上板亦是 在形成衫色渡光狀後，形成保制(永久膜)時係在彩色 渡光片上塗佈級化性樹脂，且藉由微影術除去電極引出 部並且實施熱硬化步驟而形成保護膜（永久膜）。彩色渡光片 用保護膜(永久膜)係能夠減少彩色濾光片_段差且能夠 經得起形成透明電極(ΙΤ0)時對高溫步驟之耐性。 先引先色;慮光片用保遵膜(永久膜)係使用石夕氧烧聚合 物、石夕崎醯亞胺、環氣如旨、丙_樹料的光硬化性 樹脂和熱硬化性樹脂。 又’原有祕護膜（永久膜)係在金屬上面形成氣化石夕 201241553 (SiNx)，且在其上面形成保護膜（永久膜）。但是，為了完成 無氮化矽（SiNx free)步驟，因為必須在金屬上面直接形成光 硬化性樹脂組成物，保護膜的任務亦相應地變大，完成此 種步驟，能夠除去藉由蒸鍍而進行之氮化矽（SiNx)形成步 驟，藉此，具有許多實現低費用之優點。 在藉由壓印及輥印刷步驟來形成微細圖案及保護膜 (永久膜），在如Cu、SiNx、Mo等的無機物層及有機物層、 PET、PES專的薄膜層之各式各樣的材料之基板(substrate) 塗佈樹脂組成物而使其光硬化之後，所形成之塗膜對下部 基板的接著力係必要的。 又，在基板上形成光硬化性樹脂組成物時，在完成高 溫的熱步驟時’依照在基板被圖案化之金屬的種類，亦有 因金屬材料的氧化及擴散(diffusion)等而造成金屬材料變 性之情形。此種金屬材料之代表物有銅。利用壓印步驟而 在TFT電極之銅的上面形成保護膜（永久膜）時，實施高溫的 熱步驟時，因為銅層的氧化及擴散而在塗膜發生黑點及污 垢現象引起的不良。此種不良被指出係在銅層上面進行形 成有機機材料之步驟時最大的問題點。 作為保護膜（永久膜)之主要技術課題，係必須完成接著 力、高溫處理後的透射度、機械特性的優秀性、耐化學性、 減低脫氣(Outgas)等許多的課題。但是，有機物材料係顯示 溫度、壓力、水分、硬度等許多的界限性，由於此種界限 性，使用材料亦一部分有限制之緣故，能夠滿足前述條件 之樹脂組成物尚不容易提供。又，能夠應用在無氮化石夕 201241553 (SiNx free)用途之塗佈用樹脂組成物的情況，係基於下部膜 材料的變性及材料物性的界限性等之理由，現實上更無法 提供。 先前技術文獻 專利文獻 [專利文獻1]美國專利第5,772,9〇5號 [專利文獻2]美國專利第5 259 926號 [專利文獻3]日本專利公報第2〇〇7 244984號 [專利文獻4]大韓民國專利申請第2〇〇6 〇〇〇5482號 [專利文獻5]日本公開專利公報第2005-197699號 [專利文獻6]日本公開專利公報第2005-301289號 【明内】 發明概要 發明欲解決之課題 為了解決此種問題點，本發明之目的係提供一種用於 印刷製私之光硬化性樹脂紐成物，其接著性優良而能夠應 用在塑膠、金屬、麵等各_基材，JL對高溫、高濕及 局壓條件之耐久性、高溫處理後的透射度及耐熱性優良， 而且下部膜的變性程度少。 又，本發明之目的係提供一種用於印刷製程之保護膜 之製造方法、及藉由前述方法所製造之保護膜，該用於印 刷製程之保護膜侧用前迷光硬化性樹脂組·，能夠安 定且容易地形成在包含”體、顯示㈣各種電子元件產 業步驟所必要的微細圖案。 201241553 用以欲解決課題之手段 為了達成前述目的，本發明係提供一種用於印刷製程 之光硬化性樹脂組成物，其含有： (1) 聚矽氮烷化合物， (2) 乙烯系單體， (3) 具有至少2個以上的乙烯系雙鍵之交聯性單體， (4) 光聚合起始劑及 (5) 界面活性劑。 又，本發明係提供一種用於印刷製程之保護膜之製造 方法，其含有在基板塗佈前述用於印刷製程之光硬化性樹 脂組成物且使其曝光之階段。 而且，本發明係提供一種用於印刷製程之保護膜，其 係藉由前述製造方法所製成者。 發明效果 本發明之光硬化性樹脂組成物係藉由含有聚矽氮烷化 合物，在形成保護膜時，相較於利用在原有的壓印微影術 及輥印刷步驟所使用的樹脂組成物而成之塗膜，藉由同時 改善與基板的接著力、高溫處理後亦維持高的透射度、在 高溫、高濕等嚴酷的條件下之耐久性、耐熱性及防止高溫 步驟引起下部膜變性等，而顯示作為保護膜（永久膜）之優良 的性能。 圖式簡單說明 第1圖係對使保護膜熱硬化前的下部膜之電子顯微鏡 觀察照片，該保護膜係使用本發明之實施例1的組成物製 201241553 成。 第2圖係使用 部膜的變性裡後欠照、片·'" 製成。 微鏡觀察使保護膜熱硬化後之下 該保護膜係使用實施例1的組成物 第3圖係使用 片’該保護膜係使用實施例2的組成物 部膜的變性程度欠顯微鏡觀察使保護膜熱硬化後之下 製成。力 微鏡觀察使保護膜熱硬化後之下 該保護膜係使用實施例3的組成物 第4圖係使用雷 嚷子顯 部膜的變性程夜史照 製成。 、’ 第5圖係使用電子 部膜的變性程度文照、片 製成 顯微鏡觀察使保護膜熱硬化後之下 ’該保護膜係使用比較例1的組成物 【實施令吒】 較佳實施例之詳細說明 务之用於印刷製程之光硬化性樹脂組成物，其特 U在於，含有聚魏烧化合物用以提升前述組成物經硬 化後之高分子樹脂、亦即保護膜的接著性、耐久性、高溫 處理後的透射度及耐熱性，且防止下部膜的變性。 具體上，本發明之用於印刷製程之光硬化性樹脂組成 物係含有： (1) 1〜60重量％之聚矽氮烷化合物， (2) 1〇〜80重量％之乙烯系單體， (3) 1〇~8〇重量％之具有至少2個以上的乙烯系雙鍵之 201241553 交聯性單體， (4) 0.1~12重量％之光聚合起始劑，及 (5) 0.001 ~5重量％之界面活性劑。 以下，針對各成分進行說明。 (1)聚矽氮烷化合物 在本發明所使用 Λ 〇物係沒有特別限定， 只要不阻礙本發明的效果，能夠任意地選擇。該 ， 化合物或有機化合物的任一者均能夠提供。 本發明之聚矽氮烷化合物的使用量係丨〜如重量％， 佳是使用10~40重量％。 < 前述聚矽氮烷化合物的使用量小於1重量％時，防止所 得到之薄膜的下部膜變性及接著力等有低落的傾向大Ζ 60重里％時，由於黏度增加而有成為印刷性有變差的原因 之情形。 在本發明所使用之聚矽氮烷化合物，係以含有具有下 述化學式1的結構單位之直鏈狀結構’具有3〇〇~2 〇〇〇分子 量，且在i分子中具有3~10個Si%基’而且藉由化學分析所 得之各元素比率係：以重量％計，平均為& : 59〜62、N : 31〜34及H : 6.5~7.5之全氫化聚矽氮烷，及換算聚苯乙烯平 均分子量為2,000~20,000的範圍之全氫化聚矽氮烷為佳。 [化學式1] 201241553 在上述式中，η係整數。 上述全氫化聚矽氮烷係能夠藉由該領域通常的方法製 造，例如能夠藉由在日本專利公開昭63-16325號所記載之 方法來製造，基本上係在分子内含有鏈狀部分及環狀部分 且能夠以下述化學式2表示。 [化學式2]201241553 VI. Description of the Invention: [Technical Field of Invention] 3 Field of the Invention The present invention relates to a photocurable resin composition for use in a printing process, which is manufactured in the steps of imprint lithography and roll printing. Fine patterns and protective films are useful. [Prior Art 3] In general, the steps of forming a fine pattern applied to information preservation, small sensors, photocrystallization and optical elements, fine electromechanical elements, display elements, displays, and semiconductors are used to form fine patterns using light rays. The method of photolithography. Previous lithography methods determined the circuit line width or pattern line width in accordance with the wavelength of the light used in the exposure step. When the current technical level is considered, the lithography step is difficult to form a fine pattern of 50 nm or less on the substrate due to light interference. Moreover, due to the advancement of the ultra-fineness of the pattern, such as the expensive equipment of the exposure equipment, the initial investment cost is increased, and the price of the high-resolution photomask is also soaring and the efficiency is low, the problem of expensive equipment must be used, and the result is It will work in other important ways and cause costs to rise. Not only that, because each time a pattern is formed, it is necessary to perform exposure, post-exposure baking, development, post-image baking, etching step, cleaning step, etc., so that a long step time is required and the light step must be repeated several times. The problem of low productivity is floating. 201241553 As a method to solve this problem, imprint lithography and roll printing technology have emerged. Embossing lithography is a method invented by Stephen Chou et al. of Princeton University in the United States for the marking of the nanometer grade. It is preliminarily made into the necessary shape on the surface of a relatively strong inorganic or polymer, and this is in other substances. The upper surface is stamped to form a fine pattern. Specifically, an inorganic material or a polymer mold (Mold) in which a desired fine pattern is formed in advance is used, and a hardenable composition that has been coated on a metal film or an organic film is adhered and cured by heat or light. The technique of pattern has the advantage of simplification of steps and formation of fine patterns compared to the original lithography method. The embossing technique is disclosed in U.S. Patent No. 5,772,905 (Patent Document 1), U.S. Patent No. 5,259,926 (Patent Document 2), and Japanese Patent Publication No. 2007-244984 (Korea Publication No. 1/2) 〇〇9_〇〇31274) (Patent Document 3) discloses a technique. Further, the Korean Patent Application No. 2006-0005482 (Publication No. 10-2007-76292) (Patent Document 4) discloses a method of manufacturing a display device using the same and using the same, and the disclosure utilizes i or The above-mentioned pro-printing printing technology can be used in devices such as FED (Field Emission Display), OLED (Organic Light-Emitting Diode), PDP (Plasma Display Panel), and the like. In the application, it is mentioned that the manufacturing steps of the above-described apparatus are simple and the precision of the pattern can be ensured after repeated printing. The above-described roll printing technique can form a fine pattern ′ by using a roll-to-plate, a roll and a roll, etc., instead of the high-resolution reticle used in forming a pattern using lithography. This type of roll printing technology enables the productivity and productivity of the 201241553 to be improved by simplifying the steps. Further, it is disclosed that, as an alternative, it is possible to reduce the complexity of the steps involved in the various steps of exposure and development operations such as lithography, and the cost of the steps incurred therewith. A printing technique for pattern formation which can be completed at a low cost is disclosed in Japanese Laid-Open Patent Publication No. 2005_197699 (Patent Document 5). In the case of a transparent protective film material, a spacer, or the like, a photo-curable printing lithography is also disclosed in Japanese Laid-Open Patent Publication No. 2005-301289 (Patent Document 6). The photoresist of the transparent protective film material, the spacer, and the like disclosed in Japanese Laid-Open Patent Publication No. 2, No. 3, No. 1,289, is different from the etching resist, and is called a protective film because the material remains in the last stage ( Permanent film). Such a protective film (permanent film) is different from the etching resist, and is an element that remains unfavorable in the TFT. In the case of a TFT substrate, a transparent protective film for protecting a thin film transistor is formed. The previous protective film (permanent film) was mostly formed by the lithography step using a photoresist material. Similarly, the lcd upper plate is coated with a graded resin on a color light-receiving sheet after forming a protective color (permanent film), and the electrode lead-out portion is removed by lithography. And a thermosetting step is performed to form a protective film (permanent film). The color filter used for the protective film (permanent film) can reduce the color filter _ step and can withstand the high temperature step when forming the transparent electrode (ΙΤ0). The first color is used first; the light-shielding film is made of shizheng film (permanent film), and the photo-curing resin and heat-curing property of Shixia oxygenated polymer, Shi Xiqi yimide, ring gas, and propylene-tree are used. Resin. Further, the original secret film (permanent film) forms a gasified stone on the metal layer 201241553 (SiNx), and a protective film (permanent film) is formed thereon. However, in order to complete the SiNx free step, since the photocurable resin composition must be directly formed on the metal, the task of the protective film is correspondingly increased, and by performing such a step, the evaporation can be removed. A tantalum nitride (SiNx) forming step is performed, whereby there are many advantages of achieving low cost. A fine pattern and a protective film (permanent film) are formed by an imprinting and roll printing step, and various materials such as an inorganic layer and an organic layer such as Cu, SiNx, Mo, and a PET/PES-specific thin film layer are formed. Substrate After the resin composition is applied and photohardened, the formed coating film is necessary for the adhesion of the lower substrate. Further, when a photocurable resin composition is formed on a substrate, when a high-temperature thermal step is completed, 'the metal material is patterned according to the type of metal patterned on the substrate, and the metal material is oxidized and diffused. The case of transsexuality. A representative of such a metallic material is copper. When a protective film (permanent film) is formed on the upper surface of the copper of the TFT electrode by the imprinting step, when a high-temperature thermal step is performed, black spots and dirt are formed in the coating film due to oxidation and diffusion of the copper layer. This defect is pointed out to be the biggest problem when the step of forming the organic material on the copper layer. As a main technical subject of the protective film (permanent film), it is necessary to complete many problems such as adhesion after heat treatment, high-temperature treatment, excellent mechanical properties, chemical resistance, and reduction of outgas. However, organic materials exhibit many limitations such as temperature, pressure, moisture, hardness, and the like. Due to such limitations, some materials are limited, and resin compositions satisfying the above conditions are not easily provided. In addition, it is not possible to provide a coating resin composition for use in the application of the nitride film No. 201241553 (SiNx free), which is based on the degeneration of the lower film material and the limit of physical properties of the material. [Patent Document 1] U.S. Patent No. 5,772,9,5 [Patent Document 2] U.S. Patent No. 5,259,926 [Patent Document 3] Japanese Patent Publication No. 2 〇〇 244 984 [Patent Document 4 [Patent Document 5] Japanese Laid-Open Patent Publication No. 2005-197699 [Patent Document 6] Japanese Laid-Open Patent Publication No. 2005-301289 No. 2005-301289 In order to solve such a problem, an object of the present invention is to provide a photocurable resin composite for printing and printing, which is excellent in adhesiveness and can be applied to various substrates such as plastics, metals, and surfaces. JL is excellent in durability against high temperature, high humidity, and local pressure conditions, transmittance and heat resistance after high temperature treatment, and the degree of denaturation of the lower film is small. Moreover, an object of the present invention is to provide a method for producing a protective film for a printing process, and a protective film produced by the above method, which is used for a protective film side for a front side of a protective film. It is stable and easy to form a fine pattern necessary for industrial steps including various bodies and displays (4). 201241553 Means for Solving the Problems In order to achieve the above object, the present invention provides a photocurable resin for a printing process. a composition comprising: (1) a polyazide compound, (2) a vinyl monomer, (3) a crosslinkable monomer having at least two ethylene double bonds, and (4) photopolymerization initiation Further, the present invention provides a method for producing a protective film for a printing process, comprising coating and exposing a photocurable resin composition for a printing process to a substrate. Further, the present invention provides a protective film for a printing process which is produced by the above-described production method. Advantageous Effects of Invention The photocurable resin composition of the present invention By containing a polyazide compound, when the protective film is formed, the coating film formed by using the resin composition used in the original imprint lithography and roll printing steps is simultaneously improved by the substrate. After the force and high-temperature treatment, the high transmittance is maintained, the durability under the severe conditions such as high temperature and high humidity, the heat resistance, and the high temperature step are prevented from causing the lower film to be denatured, and the like is excellent as a protective film (permanent film). BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is an electron microscopic observation photograph of a lower film before thermosetting a protective film, which is made using the composition of the first embodiment of the present invention 201241553. Fig. 2 is used After the denaturation of the film, the film was made and the film was made. The film was thermally cured by microscopic observation, and the film of Example 1 was used. The degree of denaturation of the film of the composition portion of Example 2 was made by under-microscopic observation to thermally cure the protective film. The micro-mirror was used to thermally cure the protective film, and the protective film was used as the composition of Example 3. 4 The picture is made using the nighttime history of the degeneration of the Thunder film. [Fig. 5 shows the degree of denaturation of the electronic film, and the film is made into a microscope to make the protective film thermally hardened. Protective film using the composition of Comparative Example 1 [Detailed Description of the Preferred Embodiment] The detailed description of the preferred embodiment is directed to a photocurable resin composition for a printing process, which is characterized in that it contains a polywei compound to enhance the foregoing The polymer resin after curing, that is, the adhesion of the protective film, durability, transmittance after heat treatment, and heat resistance, and prevention of denaturation of the lower film. Specifically, the light for printing process of the present invention The curable resin composition contains: (1) 1 to 60% by weight of a polyazide compound, (2) 1 to 80% by weight of a vinyl monomer, and (3) 1 to 8% by weight of At least two or more ethylene double bonds of 201241553 crosslinkable monomer, (4) 0.1 to 12% by weight of a photopolymerization initiator, and (5) 0.001 to 5% by weight of a surfactant. Hereinafter, each component will be described. (1) Polyazide compound The hydrazine system to be used in the present invention is not particularly limited, and can be arbitrarily selected as long as the effects of the present invention are not inhibited. Any of the compounds or organic compounds can be provided. The polyazirane compound of the present invention is used in an amount of 丨 to % by weight, preferably 10 to 40% by weight. < When the amount of the polyazide compound to be used is less than 1% by weight, the lower film of the obtained film is prevented from being degraded, and the adhesion force tends to be low. When the weight is 60% by weight, the viscosity is increased and the printing property is improved. The cause of the deterioration. The polyazide compound used in the present invention has a linear structure having a structural unit of the following chemical formula 1 and has a molecular weight of 3 〇〇 2 2, and has 3 to 10 in the i molecule. Si% base' and the ratio of each element obtained by chemical analysis is: in terms of % by weight, the average is & : 59 to 62, N: 31 to 34, and H: 6.5 to 7.5 of perhydropolyazane, and It is preferred to convert the perhydropolyazane in the range of 2,000 to 20,000 in terms of polystyrene. [Chemical Formula 1] 201241553 In the above formula, η is an integer. The above-mentioned perhydropolyazane can be produced by a usual method in the field, and can be produced, for example, by the method described in Japanese Patent Laid-Open Publication No. SHO63-16325, which basically contains a chain portion and a ring in a molecule. The portion can be represented by the following Chemical Formula 2. [Chemical Formula 2]

SiH2NH-- .a .b ——SiH?SiH2NH-- .a .b - SiH?

. J C (a+b十 c;l) 作為前述全氫化聚矽氮烷之較佳例子，可舉出具有下 述化學式3或4的結構之化合物。 [化學式3]J C (a + b dec c; l) A preferred example of the above-mentioned perhydropolyazane is a compound having a structure of the following Chemical Formula 3 or 4. [Chemical Formula 3]

h2 h2 /Si\H2 h2 /Si\

HN N NHN N N

I HI H

H2Si\H2Si\

HaSi [化學式4] Γ Ri ΊHaSi [Chemical Formula 4] Γ Ri Ί

I ^ «atsaa·—amMammr· -r2 r3 - n 在上述式中，R,、R2及R3係各自獨立地表示氫原子、 11 201241553 院基、烯基、環烷基'芳基、氟烷基等直接鍵結至矽之基 為碳之基、烷基矽烷基、烷胺基、及烷氧基，η係整數。（此 時，Ri ' R2及R3中的至少1者為氫原子）。 在本發明’係含有聚矽氮烷或其改性物，該聚矽氮烷 係具有由此種結構單元所構成之骨架且數量平均分子量為 約 100~50,000者。 作為含有前述化學式4的結構之化合物的例子，在Ri 及R·2具有虱原子及在R；j具有甲基之聚石夕氮烧的製造方法， 係在文獻[D. Seyferth等Polym. Prepr. Am. Chem· Soc. Div. Polym. Chem. 25.10 (1984年)]有報告。藉由該方法所得到之 聚矽氮烷係鏈狀聚合物及環狀聚合物，且雙方均無交聯結 構。 又，在前述化學式4中，在心及心具有氫原子、及在& 具有有機基之聚有機（虱化)石夕氮院時，係主要有具有聚合度 為3~5之環狀結構者、在分子内同時具有鏈狀結構及環狀結 構者。 而且，亦有在前述化學式4中，在Ri具有氫原子、及在 R2及R3具有有機基之聚矽氮烷，以及在心及心具有有機 基、及在R3具有氫原子之聚合度為3〜5左右的環狀結構之聚 矽氮烷。 在本發明，作為前述具有化學式4的結構之化合物以外 之有機聚矽氮烷，能夠含有在分子内具有下述化學式5的交 聯結構之聚有機（氫化)矽氮烷，及藉由R1SiX3(x :鹵素）的 氨分解而得到之具有交聯結構的聚矽氮烷、R1Si(NH)x、 12 201241553 或RlSiX3的共氨分解而得到之具有下述化學式6的結構之 聚矽氮烷（參照日本專利公開昭49-69717號公報）。 [化學式5]I ^ «atsaa·—amMammr· -r2 r3 - n In the above formula, R, R2 and R3 each independently represent a hydrogen atom, 11 201241553, an alkenyl group, a cycloalkyl 'aryl group, a fluoroalkyl group The base directly bonded to the oxime is a carbon group, an alkylalkyl group, an alkylamino group, and an alkoxy group, and an η-based integer. (At this time, at least one of Ri ' R2 and R3 is a hydrogen atom). The present invention contains a polyazide or a modified product thereof having a skeleton composed of such a structural unit and having a number average molecular weight of about 100 to 50,000. As an example of the compound containing the structure of the above Chemical Formula 4, a method for producing a polyfluorene having a ruthenium atom in Ri and R·2 and a polymethyl group having a methyl group in R; j is in the literature [D. Seyferth et al. Polym. Prepr Am. Chem. Soc. Div. Polym. Chem. 25.10 (1984)] Reported. The polyazane-based chain polymer and the cyclic polymer obtained by the method have no cross-linking structure. Further, in the above Chemical Formula 4, when the core and the heart have a hydrogen atom, and in the & organic group-containing polyorganic (deuterated) Shixia Yanyuan, the system mainly has a cyclic structure having a degree of polymerization of 3 to 5. A person having both a chain structure and a ring structure in a molecule. Further, in the above Chemical Formula 4, a polyazide having a hydrogen atom at Ri and an organic group at R2 and R3, and an organic group at the center of the heart and a hydrogen atom at R3 are also 3~ A polyazane having a cyclic structure of about 5. In the present invention, the organopolyazane other than the compound having the structure of the chemical formula 4 may contain a polyorgano(hydrogenated) decazane having a crosslinked structure of the following chemical formula 5 in the molecule, and R1SiX3 (by R1SiX3 ( x: a polyazide having a structure of the following chemical formula 6 obtained by decomposing a polyazide having a crosslinked structure, a polyazide having a crosslinked structure, R1Si(NH)x, 12201241553 or RlSiX3; Reference is made to Japanese Patent Laid-Open Publication No. SHO-49-69717. [Chemical Formula 5]

R=cm [化學式6]R=cm [Chemical Formula 6]

r Ri卜 I 4 r R1 j I c Η ΙΊ 111111"〇! 1 j m .1 r2 NH 在上述式中，心及!^係各自獨立地表示氫原子、烷基、 稀基或芳基，m及η係各自獨立地為整數。 又，除了前述化合物以外，亦可以含有增加分子量、 或提升财水解性而成之無機碎氮炫共聚物和改性聚石夕氣烧 (參照日本專利公開平1-138108號、平1-138107號、平 1-203429號及平1-203430號），亦可以含有在聚矽氮烷導入 有機成分而成之對厚膜化有利的共聚合矽氮烷（參照曰本 專利公開平2-175726號、平5-86200號、平5-331293號及平 3-31326號）等。 在前述所提出之聚矽氮烷化合物，係可單獨或混合2種 13 201241553 以上而使用。 (2) 乙烯系單體 在本發明之光硬化性樹脂組成物，乙稀系單體的使用 量係以使用10〜80重量％為佳，更佳是使用20〜60重量％。 前述乙烯系單體的使用量小於10重量％時，所得到的 溝膜分子置係不充分’強度有低落之傾向，大於重量％ 時，未反應物變多而有成為收縮的原因之情形。 作為前述乙烯系單體的具體例，可舉出丙稀酸異丁 酯、丙烯酸第三丁酯、丙烯酸月桂酯、曱基丙烯酸甲酯、 丙烯酸烷酯、丙烯酸環己酯、丙烯酸異莰酯、甲基丙稀酸 苄醋、丙稀酸苄醋' 2-經基丙稀酸g旨、丙烤酸三曱氧基丁 酯、丙缚酸乙基卡必醇酯、丙烯酸苯氧基乙酯、丙稀酸4_ 經基丁醋、苯氧基聚乙二醇丙稀酸醋、丙烯酸2-經基乙酯、 丙烯酸2-經基丙g旨、駄酸2-丙稀醯氧基乙基-2-經基丙g旨、 丙烯酸2-羥基-3-苯氧基丙酯及該等的曱基丙烯酸酯類；如 丙烯酸3-氟乙酯、丙稀酸4-氟丙酯之含_素化合物之丙稀酸 酯及該等的曱基丙烯酸酯類；如丙烯酸三乙基曱石夕烧氧基 乙酯之含矽氧烷基之丙烯酸酯及該等的甲基丙烯酸酯類； 如苯乙烯及4-甲氧基苯乙烯之具有芳香族的烯烴類等，但 是不被此限定，可單獨或混合2種以上而使用。 (3) 具有至少2個以上的乙烯系雙鍵之交聯性單體 又’在本發明之光硬化性樹脂組成物，具有至少2個以 上的乙烯系雙鍵之交聯性單體的使用量係以1〇~80重量％ 為佳，更佳是使用20~60重量％。 14 201241553 前述交聯性單體的使用量小於ίο重量％時’係硬化度 不足，對於形成圖案不利，大於80重量％時’硬化度增加 致使硬度過度升高、不如說是未反應物變多而成為收縮的 原因。 作為前述交聯性單體的具體例，可舉出二伸乙甘醇一 乙基醚、二羥曱基二環戊烷二丙烯酸酯、1,4-丁二醇二丙烯 酸酯、1,3-丁二醇二丙烯酸酯、1,6-己二醇二丙烯酸酯、烯 丙氡基聚乙二醇丙浠酸酯、丙烯酸二環戊稀酯、經基三曱 基乙酸新戊二醇二丙烯酸酯、新戊二醇二丙烯酸酯、1,9- 壬二醇二丙烯酸酯、聚乙二醇二丙烯酸酯、山梨糖醇三丙 烯酸酯、雙酚A二丙稀酸酯衍生物、三曱基丙烷三丙烯酸 醋、及該等的曱基丙烯酸類等。 又’作為具有3個以上的官能基之多官能交聯性單體， 可舉出EO改性甘油丙烯酸酯、p〇改性甘油丙烯酸酯、三羥 曱基丙烷三丙烯酸酯、新戊四醇乙氧基丙烯酸酯、二新戊 四醇六丙烯酸酯、EO三羥甲基丙烷三丙烯酸酯及該等的甲 基丙烯酸酯類等，但是不被此限定，可單獨或混合2種以上 而使用該等。 (4)光聚合起始齊,丨 在本發明之光硬化性樹脂組成物，光聚合起始劑的使 用量係以0·1〜12重量％為佳，更佳是以0.5~8重量％使用。 則述光聚合起始劑的使用量小於0.1重量％時，光硬化 係變慢或U難，大於12重量％時，產生抑制反應效果而膜 特性歸、或透射度低落，而有硬化餘裕度低落之傾向。 15 201241553 作為前述光聚合起始劑的具體例，可舉出Irgacure 369、Igacure 907、Igacure 184、Igacure 651、Igacure 819、 Igacure 2959 ' Igacure 1800 ' Darocur 1173 ' Darocur 1116 及Darocur 1020 ; 2,2’-二乙氧基苯乙酮' 2,2，-二丁氧基苯 乙酮、2-羥基-2-甲基苯丙酮、對第三丁基三氣苯乙酮、對 第三丁基二氣苯乙酮、二苯基酮、4-氣苯乙酮、4,4’-二甲 胺基二苯基酮、4,4’-二氣二苯基酮、3,3’-二曱基-2-甲氧基 二苯基酮、2,2’-二氣-2-苯氧基二苯基酮、2-甲基-1-(4-甲硫 基）苯基)-2-咪啉丙烧-1-酮、2-(4-甲苄基)-2-二甲胺基-1-(4-咮啉苯基)-丁烷-1-酮及2-苄基-2-二曱胺基-1-(4-咮啉苯基)-丁烷-1-酮等的苯乙酮系化合物；二苯基酮、苯甲醯基苯甲 酸、苯甲醯基苯甲酸甲酯、4-苯基二苯基酮、羥基二苯基 酮、丙烯酸化二苯基酮、4、4’-雙(二曱胺基)二苯基_及4,4，-雙(二乙胺基)二苯基酮等的二苯基酮系化合物；9_氧硫。山^星 (thioxanthone)、2-氣9-氧硫。山。星、2-曱基9-氧硫咄。星、異丙 基9-氧硫。山嚜、2,4-二乙基9-氧硫汕嚜、2,4-二異丙基9-氧 硫汕噔及2-氣9-氧硫》山嚜等的9-氧硫。山嚜系化合物；苯偶 姻、苯偶姻甲基醚、苯偶姻乙基醚、苯偶姻丙基醚、苯偶 姻丁基醚及节基二曱基縮酮等的苯偶姻系化合物；及2,4,6_ 二氣-s-二啡、二苯基4,6-雙（三氣曱基)_s_三畊、2_(3，，4，_二 甲氧基苯乙烯基)-4,6-雙(三氣甲基)_s_三畊、2_(4，_甲氧基萘 基)-4,6-雙（三氣甲基)_s_三畊、2_(對曱氧基苯基)_4,6-雙（三 氣甲基)-s-三畊、2-(對甲苯基)_4,6_雙（三氣甲基)+三0丼、 2-苯基4,6-雙（三氣曱基)_s_三畊、雙（三氣曱基)6苯乙烯基 16 201241553 井、2-(萘并，卜雙(三氯曱基)s三畊、2(4甲氧 基奈并1-基)-4,6-雙(三氯甲基)_s三π井、2_心三氣曱基(胡椒 基）6 —井及2-4-二氯甲基(4,甲氧基苯乙烯基)6-三讲等 的二讲系化合物等’但是不被此限定 ，可單獨或混合2種以 上而使用該等。 佳是苯乙_ ’對於確保硬化餘裕度係有利的。 (5)界面活性劑 本發明之光硬化性樹脂組成物係可以含有界面活性 诗J。/、要旎夠改善光硬化性樹脂組成物的塗佈性，前述界 面活性劑係任一者均能夠使用，在本發明所使用之界面活 性劑的使用量’係相對於整體組成物，以0.00卜5重量％為 佳，更佳是以0.01〜2重量％使用。混合使用2種以上的界面 活性劑時’整體含量係與前述所提出者相同。 前述界面活性劑的含量0.001重量％以下時，進行均勻 的塗佈係有限制的，5重量％以上時，模具轉印特性及在後 面步驟之形成追加材料有造成問題點之情形。 别述界面活性劑係以含有矽系及氟系界面活性劑中 的至少1種為佳，亦可混合2種以上而使用。 作為前述界面活性劑的具體例，可舉出大曰本XNK化學 工業、3M及信越化學工業公司的氟系界面活性劑、及 DOW、B YK及EVONIK公司的石夕系界面活性劑，但是不被 此限定。 又，本發明之光硬化性樹脂組成物係能夠追加性地含 有溶劑。 17 201241553 通常，用於印刷製程之光硬化性樹脂組成物之情況係 不使用溶液，但是在本發明，為了聚矽氮烷的溶解或與光 硬化性樹脂組成物的相溶性，亦可以添加溶劑。前述溶劑 的使用量係以0〜70重量％為佳，更佳是以0~50重量％使用。 作為前述溶劑的具體例，可舉出乙腈、甘油、二曱基 亞砜、硝基曱烷、二曱基甲醯胺、苯酚、N-甲基吡咯啶酮、 吡啶全氟三丁胺、全氟十氫萘、2-丁酮、碳酸亞曱酯、甲 醇、乙醇、乙二醇、三伸乙甘醇、四伸乙甘醇、丙二醇、 伸丙基伸乙基二醇、二伸乙甘醇、丁二醇、苄醇及己醇等 的醇類；碳酸伸丙酯、四氫呋喃、1,4-二哼烷、1-曱氧基-2-丙醇、曱氧基苯、二丁基醚及二苯酚醚等的醚類；乙酸乙 酯、乙酸丙酯、乙酸丁酯、丙酸乙酯、乙酯、丁酯、甲基 -2-羥基異丁酸酯、2-曱氧基-1-曱基乙基醚、2-曱氧基乙醇 乙酸酯及2-乙氧基乙醇乙酸酯等的酯類；乙二醇甲基醚乙 酸酯及乙二醇乙基醚乙酸酯等的乙二醇烷基醚乙酸酯類； 乙二醇甲基醚丙酸酯及乙二醇乙基醚丙酸酯等的乙二醇烷 基醚丙酸酯類；乙二醇甲基醚及乙二醇乙基醚等的乙二醇 單烷基醚類；二伸乙甘醇一甲基醚、二伸乙甘醇一乙基醚、 二伸乙甘醇二甲基醚及二乙二醇甲基醚等的二伸乙甘醇烷 基醚類；丙二醇甲基醚乙酸酯、丙二醇乙基醚乙酸酯及丙 二醇丙基醚乙酸酯等的丙二醇烷基醚乙酸酯類；丙二醇曱 基醚丙酸酯、丙二醇乙基醚丙酸酯及丙二醇丙基醚丙酸酯 等的丙二醇烷基醚丙酸酯類；丙二醇甲基醚、丙二醇乙基 醚、丙二醇丙基醚及丙二醇丁基醚等的丙二醇單烷基醚 18 201241553 類，二伸丙甘醇二曱基醚及二伸丙甘醇二乙基醚等的二伸 丙甘醇烷基醚類；丁二醇—曱基醚及丁二醇一乙基醚等的 丁二醇單甲基醚類；及二伸丁二醇二曱基醚及二伸丁二醇 二乙基醚等的二伸丁二醇烷基醚類等，但是不被此限定， 可單獨或混合2種以上而使用該等。 本發明之組成物的黏度係在25。〇為21111^ • s至25mPa · s， 較佳是3mPa . s至20mPa . s，更佳是5mPa . s至 15mPa . s。 此時’本發明的組成物之黏度為2mPa . s以下時，形成 所需要的塗膜厚度係有限制，25mpa. s以上時，依照塗佈 方法亦有難以在基板塗佈材料之情形。 又’本發明係提供一種利用前述的光硬化性樹脂組成 物之用於印刷製程之保護膜及微細圖案之製造方法、以及 藉由前述方法所製造之保護膜及微細圖案。 具體上，本發明之用於印刷製程之保護膜之製造方 法’係含有將本發明的光硬化組成物塗佈在基板且進行曝 光之階段。 又，依照本發明，將前述組成物塗佈在基板之後，利 用壓印微影術或輥印刷步驟而形成塗膜且曝光，能夠安定 且容易地形成在包含半導體、顯示器之各種電子元件產業 步驟之必要的微細圖案。 此時，前述組成物係以在基板（例如矽基板、陶瓷基 板、金屬層 '高分子層等）的上面，使用旋轉塗佈、輥塗佈、 狹縫塗佈、噴墨塗佈等適當的方法塗佈0.5〜ΙΟμπι的厚度為 佳0 19 201241553 作為曝光所使用的光源’例如能夠使用19〇〜45〇nm、 較佳是200〜40〇nm區域的UV，而且亦可以照射電子射線。 又’在以後為了提升膜的用途及特性，亦可實施高溫熱處 理步驟。 依照本發明所製造之保s蒦臈及微細圖案，因為對基板 的接著力、對高溫、高濕及高壓的條件之耐久性、高溫處 理後的透射率及耐熱性優良’而且下部膜的變性程度少， 能夠有用地使用作為包含半導體、顯示器之各種電子元件 產業步驟之必要的冑細圖案，使用本發明的組成物之壓印 微影術及輥印刷步驟，藉由代替先前用以形成微細圖案之 微影術步驟，不僅能夠使原有的微影術步驟之曝光、顯像、 洗淨等各式各樣的階段簡單化’而且能夠縮短製造步驟時 間（tact time)而節省製造成本而且使生產性提升。 以下，提出用以理解本發明之較佳實施例，但是下述 的實施例只不過是例示本發明，本發明的範圍係不被下述 的實施例限定。 [實施例1] 將5重量份之具有前述化學式i的結構且分子量為5〇〇 之聚矽氮烷SN-1、作為乙烯系單體之3〇重量份丙烯酸4_羥 基丁酯及30重量份丙烯酸苯氧基乙酯、具有乙烯系雙鍵之 父聯性單體之30重量份1，4-丁二醇二丙烯酸酯、作為光聚合 起始劑之3重量份Igacure 369 (CIB A製品）、及作為界面活性 劑之0.1重量份BYK公司的矽系界面活性劑，在常溫均勻地 混合6小時以上而製造本發明之光硬化組成物。 20 201241553 又，在經脫脂洗淨之金屬基板上’將前述所製造之光 硬化組成物各自塗佈〇·5~5μιη的厚度，且與高分子模具黏在 一起，而且使用具有365nm波長的燈進行曝光之後，將所形 成之薄膜與高分子模具脫模而形成保護膜。 [實施例2] 除了使用10重量份之具有前述化學式1的結構且分子 量為500之聚矽氡烧SN-1以外，藉由與前述實施例i同樣的 方法製造本發明之光硬化組成物及保護膜。 [實施例3 ] 除了使用10重量份之具有前述化學式1的結構且分子 量為1，500之聚矽氮烷SN-2代替聚矽氮烷SN-1以外，藉由與 前述實施例1同樣的方法製造本發明之光硬化組成物及保 護膜。 [比較例1] 除了不使用聚石夕氮院而使用40重量份丙烯酸4-經基丁 酯以外，藉由與前述實施例1同樣的方法製造光硬化組成物 及保護膜。 [實驗] 對前述實施例1~3 '及比較例丨所製造之保護膜，藉由 如下述的方法測定與基板的接著力、耐久性、透射度、耐 熱性及防止下部膜變性程度，並將其結果顯示在下述表【。 I)接著力（基板密著性） 製作橫、縱100個的格子(cell)且使用3Μ公司的010接著 膠帶，使其密著在如前述形成有保護膜的基板之後，將膠 21 201241553 帶慢慢地剝下時，將基板上殘留的格子數目每i個指定為 1%而且依’、、、如下述的鱗來實施接著性及密著性的評 價。 A在基板上殘留格子的數目為腦％~臟時 B .在基板上殘留格子的數目為8〇%~5〇%時 c .在基板上殘留格子的數目為5〇%~15%時 D在基板上殘留格子的數目為〜⑽時 II)而ί久性（尚溫、局濕、高墨） 將如則㈣成有保護膜的基板於2抓在烘箱使其熱 硬化30分鐘’且藉由與麵)同樣的方法相接著力而確認 100%接著狀態。 將則述基板在能夠高溫、高濕、高壓的裝備 以 120°c、 濕度100%、2氣壓、放置24小時的條件進行處理之後，再 次確認基㈣表面狀態及接著狀態，並將其結果與前述 同樣的基準進行評價。 此時，因為確認投入裝備前為接著1〇〇%狀態，所以接 著狀態差時，係意味著水分侵入塗膜内部致使與下部基板 產生浮起現象。 ΠΙ)透射度 將如前述形成有保護膜之基板，於23〇〇c在烘箱使其熱 硬化150分鐘，且將形成有塗膜的基板利用透射率裝備以 400nm測定透射率，並且如下述的基準進行評價。 A :透射度為98%以上時 B :透射度為97%以上時 22 201241553 C :透射度為96%以上時 D :透射度為95%以上時 IV) 耐熱性 將如前述形成有保護膜之基板，於23(TC在烘箱邊使其 熱硬化30分鐘邊使用熱重量分析器（TGA)測定重量減少且 如下述的基準進行評價。 A :重量減少為小於1%時 B :重量減少為小於1%以上、小於3%時 c :重量減少為小於3%以上、小於5%時 D :重量減少為5%以上時 V) 防止下部膜變性 將如前述形成有保護膜之基板，於23(TC在烘箱使其熱 硬化30分鐘，並且將形成有保護膜之基板使用肉眼確認污 垢及藉由SEM(磁氣掃描顯微鏡)確認，而且如下述的基準進 行評價。 A :表面污垢為20%以下、 B :表面污垢為20%以上、40%以下、 c :表面污垢為40%以上、60%以下、 D :表面污垢為60%以上 [表1]r Ri Bu I 4 r R1 j I c Η ΙΊ 111111"〇! 1 jm .1 r2 NH In the above formula, the heart and the !^ each independently represent a hydrogen atom, an alkyl group, a dilute group or an aryl group, m and The η series are each independently an integer. Further, in addition to the above-mentioned compounds, an inorganic nitrous oxide copolymer and a modified polysulfide smectite which are obtained by increasing the molecular weight or enhancing the hydrolysis property may be contained (refer to Japanese Patent Laid-Open No. Hei No. 1-138108, No. 1-138107). No., No.1-203429, and No.1-203430), may also contain a copolymerized decazane which is advantageous for thick film formation by introducing an organic component into polyazide (refer to Japanese Patent Laid-Open No. 2-157726 No., No. 5-86200, No. 5-331293 and No. 3-31326). The polyaziridine compound proposed above may be used alone or in combination of two kinds of 13 201241553 or more. (2) Vinyl monomer In the photocurable resin composition of the present invention, the amount of the ethylene monomer used is preferably 10 to 80% by weight, more preferably 20 to 60% by weight. When the amount of the vinyl monomer used is less than 10% by weight, the obtained grooved film molecules are insufficiently set, and the strength tends to be low. When the amount is more than % by weight, the amount of unreacted materials increases, which may cause shrinkage. Specific examples of the vinyl monomer include isobutyl acrylate, tributyl acrylate, lauryl acrylate, methyl methacrylate, alkyl acrylate, cyclohexyl acrylate, isodecyl acrylate, and the like. Benzyl methacrylate, benzyl acetate bromo 2- 2- propyl acrylate, tridecyl butyl acrylate, ethyl carbitol, phenoxyethyl acrylate ,acrylic acid 4_ butyl vinegar, phenoxy polyethylene glycol acrylate vinegar, 2-ethylidene acrylate, 2-acrylic acid acrylate, 2-acrylic acid ethyl phthalate 2-Benzyl propyl, 2-hydroxy-3-phenoxypropyl acrylate and such decyl acrylates; such as 3-fluoroethyl acrylate and 4-fluoropropyl acrylate Acrylates of the compound and the mercapto acrylates; such as decyloxyalkyl acrylates of triethyl phthalocyanine acrylate and such methacrylates; Although the aromatic olefins of styrene and 4-methoxy styrene are not limited to these, they may be used alone or in combination of two or more. (3) A crosslinkable monomer having at least two or more ethylene double bonds, and a use of a crosslinkable monomer having at least two or more ethylene double bonds in the photocurable resin composition of the present invention The amount is preferably from 1 to 80% by weight, more preferably from 20 to 60% by weight. 14 201241553 When the amount of the crosslinkable monomer used is less than ίο重量%, the degree of hardening is insufficient, and it is disadvantageous for forming a pattern. When the amount is more than 80% by weight, the increase in the degree of hardening causes the hardness to rise excessively, as is the case where the amount of unreacted matter increases. And it becomes the cause of contraction. Specific examples of the crosslinkable monomer include diethylene glycol monoethyl ether, dihydroxyindenyl dicyclopentane diacrylate, 1,4-butanediol diacrylate, and 1,3. - Butanediol diacrylate, 1,6-hexanediol diacrylate, allyl mercapto polyethylene glycol propionate, dicyclopentyl acrylate, trans-tris-mercaptoacetic acid neopentyl glycol Acrylate, neopentyl glycol diacrylate, 1,9-nonanediol diacrylate, polyethylene glycol diacrylate, sorbitol triacrylate, bisphenol A diacrylate derivative, triterpene Propane triacrylate vinegar, and such mercapto acrylates. Further, examples of the polyfunctional crosslinkable monomer having three or more functional groups include EO-modified glycerin acrylate, p-modified glycerin acrylate, trishydroxypropyl propane triacrylate, and neopentyl alcohol. Ethoxy acrylate, dipentaerythritol hexaacrylate, EO trimethylolpropane triacrylate, and the like, but not limited thereto, and may be used alone or in combination of two or more. These are the same. (4) Photopolymerization is started, and the photocurable resin composition of the present invention, the photopolymerization initiator is preferably used in an amount of from 0.1 to 12% by weight, more preferably from 0.5 to 8% by weight. use. When the amount of the photopolymerization initiator used is less than 0.1% by weight, the photocuring system becomes slow or U is difficult, and when it is more than 12% by weight, the reaction effect is suppressed and the film property is lowered or the transmittance is lowered, and the curing margin is obtained. The tendency to be low. 15 201241553 Specific examples of the photopolymerization initiator include Irgacure 369, Igacure 907, Igacure 184, Igacure 651, Igacure 819, Igacure 2959 'Igacure 1800 'Darocur 1173 'Darocur 1116 and Darocur 1020; 2, 2' -diethoxyacetophenone '2,2,-dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone, p-tert-butyltrisacetophenone, p-tert-butyldi Gas acetophenone, diphenyl ketone, 4-epoxyacetophenone, 4,4'-dimethylaminodiphenyl ketone, 4,4'-dioxadiphenyl ketone, 3,3'-dioxene Benzyl-2-methoxydiphenyl ketone, 2,2'-dioxa-2-phenoxydiphenyl ketone, 2-methyl-1-(4-methylthio)phenyl)-2- Phenylpropan-1-one, 2-(4-methylbenzyl)-2-dimethylamino-1-(4-pyridylphenyl)-butan-1-one and 2-benzyl-2 - an acetophenone-based compound such as diammonium-1-(4-porphyrinphenyl)-butan-1-one; diphenyl ketone, benzhydryl benzoic acid, benzhydryl benzoic acid Ester, 4-phenyldiphenyl ketone, hydroxydiphenyl ketone, acrylated diphenyl ketone, 4,4'-bis(diguanidino)diphenyl _ and 4,4,-bis (diethyl Diphenyl ketones such as amino)diphenyl ketone Thereof; 9_ oxygen sulfur. Thioxanthone, 2-gas 9-oxosulfur. mountain. Star, 2-mercapto 9-oxopurine. Star, isopropyl 9-oxo sulfur. 9-oxosulfuric acid such as hawthorn, 2,4-diethyl 9-oxosulfonium, 2,4-diisopropyl 9-oxopurine and 2-gas 9-oxosulfide. Hawthorn compound; benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin butyl ether, and benzyl ketone ketone a compound; and 2,4,6_diqi-s-dimorphine, diphenyl 4,6-bis(triseodecyl)_s_three tillage, 2_(3,4,4-dimethoxystyryl )-4,6-bis(trioxanemethyl)_s_three tillage, 2_(4,_methoxynaphthyl)-4,6-bis(trismethyl)_s_three tillage, 2_(pair Oxyphenyl) 4,6-bis(trimethyl)-s-trin, 2-(p-tolyl)_4,6-bis(trimethyl)+trimethyl, 2-phenyl-4 ,6-double (three gas sulfhydryl)_s_three tillage, double (triplemethane)6 styryl 16 201241553 well, 2-(naphtho, bis(trichloroindenyl)s three tillage, 2 ( 4 methoxynazepine-1-yl)-4,6-bis(trichloromethyl)_s three π well, 2_heart trigassulfonyl (piperidinyl) 6 - well and 2-4-dichloromethyl (4, methoxystyryl) 6-triple, etc., but not limited thereto, and may be used alone or in combination of two or more. It is preferably phenylethyl _ 'to ensure a hardening margin The degree is advantageous. (5) Surfactant The photocurable resin composition of the present invention It is possible to contain an interface activity poem J./, and to improve the coatability of the photocurable resin composition, any of the above-mentioned surfactants can be used, and the amount of the surfactant used in the present invention is ' It is preferably 0.00 5% by weight, more preferably 0.01 to 2% by weight, based on the total composition. When two or more kinds of surfactants are used in combination, the overall content is the same as that described above. When the content of the agent is 0.001% by weight or less, uniform coating is limited, and when it is 5% by weight or more, mold transfer characteristics and formation of additional materials in subsequent steps may cause problems. It is preferable to use at least one of a lanthanide-based and a fluorine-based surfactant, and two or more types may be used in combination. Specific examples of the surfactant may include Otsuka XNK Chemical Industry, 3M, and Shin-Etsu Chemical Co., Ltd. The fluorine-based surfactant of the industrial company, and the Shih-shi surfactant of DOW, B YK, and EVONIK Co., Ltd. are not limited thereto. Moreover, the photocurable resin composition of the present invention can Additively, the solvent is contained. 17 201241553 In general, the photocurable resin composition used in the printing process does not use a solution, but in the present invention, in order to dissolve the polyazane or the phase of the photocurable resin composition The solvent may be added in an amount of 0 to 70% by weight, more preferably 0 to 50% by weight. Specific examples of the solvent include acetonitrile, glycerin and dimercapto. Sulfoxide, nitrodecane, dimethylformamide, phenol, N-methylpyrrolidone, pyridine perfluorotributylamine, perfluorodecalin, 2-butanone, decyl carbonate, methanol, Alcohols such as ethanol, ethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, ethyl propylene glycol, diethylene glycol, butanediol, benzyl alcohol and hexanol; An ether such as propyl ester, tetrahydrofuran, 1,4-dioxane, 1-decyloxy-2-propanol, nonyloxybenzene, dibutyl ether or diphenol ether; ethyl acetate, propyl acetate, Butyl acetate, ethyl propionate, ethyl ester, butyl ester, methyl-2-hydroxyisobutyrate, 2-decyloxy-1-mercaptoethyl ether, 2- Esters such as oxyethanol acetate and 2-ethoxyethanol acetate; ethylene glycol alkyl ether acetates such as ethylene glycol methyl ether acetate and ethylene glycol ethyl ether acetate Ethylene glycol alkyl ether propionates such as ethylene glycol methyl ether propionate and ethylene glycol ethyl ether propionate; B such as ethylene glycol methyl ether and ethylene glycol ethyl ether Diethylene glycol monoalkyl ethers; diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether and diethylene glycol methyl ether Glycol alkyl ethers; propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, and propylene glycol propyl ether acetate; propylene glycol decyl ether propionate, propylene glycol B Propylene glycol alkyl ether propionates such as propyl ether propionate and propylene glycol propyl ether propionate; propylene glycol monoalkyl ethers such as propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether and propylene glycol butyl ether 18 201241553, diethylene glycol ethers such as diethylene glycol diethylene ether and diethylene glycol diethylene ether; butanediol-mercapto ether and butanediol Butanediol monomethyl ethers such as ethers; dibutylene glycol alkyl ethers such as dibutylene glycol dimercapto ether and dibutylene glycol diethyl ether, but not These may be used alone or in combination of two or more. The composition of the present invention has a viscosity of 25. 〇 is 21111^ • s to 25 mPa · s, preferably 3 mPa. s to 20 mPa. s, more preferably 5 mPa. s to 15 mPa. s. In this case, when the viscosity of the composition of the present invention is 2 mPa·s or less, the thickness of the coating film to be formed is limited. When it is 25 mPa·s or more, it is difficult to apply a material to the substrate according to the coating method. Further, the present invention provides a method for producing a protective film and a fine pattern for a printing process using the above-described photocurable resin composition, and a protective film and a fine pattern produced by the above method. Specifically, the method for producing a protective film for a printing process of the present invention includes a step of applying the photohardenable composition of the present invention to a substrate and performing exposure. Further, according to the present invention, after the composition is applied to a substrate, a coating film is formed by an embossing lithography or a roll printing step and exposed, and it can be stably and easily formed in various electronic component industrial steps including a semiconductor and a display. The necessary fine pattern. In this case, the composition is suitably applied to the upper surface of a substrate (for example, a tantalum substrate, a ceramic substrate, or a metal layer 'polymer layer, etc.) by spin coating, roll coating, slit coating, inkjet coating, or the like. The thickness of the coating of 0.5 to ΙΟμπι is preferably 0 19 201241553. As the light source used for the exposure, for example, UV in the region of 19 〇 to 45 〇 nm, preferably 200 to 40 〇 nm, can be used, and electron beams can also be irradiated. Further, in order to enhance the use and characteristics of the film, a high-temperature heat treatment step can be carried out. The 保 蒦臈 and the fine pattern manufactured according to the present invention are excellent in adhesion to the substrate, durability against high temperature, high humidity and high pressure conditions, transmittance after heat treatment, and heat resistance 'and denaturation of the lower film To a lesser extent, it is possible to usefully use a fine pattern which is necessary for industrial steps of various electronic components including semiconductors and displays, and use the imprint lithography and roll printing steps of the composition of the present invention instead of forming a fine The lithography step of the pattern not only simplifies the various stages of exposure, development, cleaning, etc. of the original lithography step, but also shortens the manufacturing time (tact time) and saves manufacturing costs. Improve productivity. The preferred embodiments of the present invention are set forth below, but the following examples are merely illustrative of the present invention, and the scope of the present invention is not limited by the following examples. [Example 1] 5 parts by weight of polydecazane SN-1 having a structure of the above chemical formula i and having a molecular weight of 5 Å, 3 parts by weight of a vinyl monomer, 4 hydroxybutyl acrylate, and 30 parts by weight 30 parts by weight of 1,4-butanediol diacrylate of phenoxyethyl acrylate, a parent monomer having a vinyl double bond, and 3 parts by weight of Igacure 369 (CIB A product as a photopolymerization initiator) And 0.1 part by weight of a fluorene-based surfactant of BYK Co., Ltd. as a surfactant, and uniformly mixed at room temperature for 6 hours or more to produce the photohardenable composition of the present invention. 20 201241553 Further, each of the photocurable compositions produced by the above-described degreased metal substrate is coated with a thickness of 〇5 to 5 μm, and adhered to a polymer mold, and a lamp having a wavelength of 365 nm is used. After the exposure, the formed film is released from the polymer mold to form a protective film. [Example 2] The photohardenable composition of the present invention was produced by the same method as the above Example i, except that 10 parts by weight of the polyfluorene SN-1 having the structure of the above Chemical Formula 1 and having a molecular weight of 500 was used. Protective film. [Example 3] The same procedure as in Example 1 except that 10 parts by weight of the polyazoxide SN-2 having the structure of the above Chemical Formula 1 and having a molecular weight of 1,500 was used instead of the polyazane SN-1 The photohardenable composition and protective film of the present invention are produced. [Comparative Example 1] A photocurable composition and a protective film were produced in the same manner as in Example 1 except that 40 parts by weight of 4-butylidene acrylate was used without using a polylithium. [Experiment] The protective film produced in the above Examples 1 to 3' and Comparative Example was measured for adhesion to the substrate, durability, transmittance, heat resistance, and degree of denaturation of the lower film by the following method, and The results are shown in the table below. I) Adhesive force (substrate adhesion) A cell having a width of 100 and a vertical length is produced, and a 010 adhesive tape of a 3 Μ company is used to adhere the substrate to the substrate having the protective film as described above, and the adhesive 21 201241553 is brought. When peeling off slowly, the number of lattices remaining on the substrate was specified to be 1%, and the adhesion and adhesion were evaluated according to the following scales. A The number of residual lattices on the substrate is brain %~ dirty B. When the number of residual lattices on the substrate is 8〇%~5〇% c. When the number of residual lattices on the substrate is 5〇%~15%, D When the number of remaining lattices on the substrate is ~(10), II) and the longness (still temperature, wetness, high ink), then (4) the substrate with the protective film is rubbed in the oven for 2 minutes and is thermally hardened for 30 minutes' The 100% subsequent state was confirmed by the same method as the surface. After the substrate is treated at 120 ° C, humidity 100%, and 2 atmospheres for 24 hours under conditions of high temperature, high humidity, and high pressure, the surface state and the subsequent state of the substrate are again confirmed, and the results are compared with the results. The same criteria as described above were evaluated. At this time, since it is confirmed that the state is 1%% before the equipment is placed, when the state is inferior, it means that moisture intrudes into the inside of the coating film to cause a floating phenomenon with the lower substrate. ΠΙ) Transmittance The substrate on which the protective film was formed as described above was thermally hardened in an oven at 23 ° C for 150 minutes, and the substrate on which the coating film was formed was measured by transmittance to measure transmittance at 400 nm, and as described below. Benchmarks are evaluated. A: When the transmittance is 98% or more, B: When the transmittance is 97% or more, 22 201241553 C: When the transmittance is 96% or more, D: When the transmittance is 95% or more, IV) Heat resistance is formed as described above with a protective film. The substrate was evaluated for weight loss using a thermogravimetric analyzer (TGA) at 23 (the TC was thermally hardened for 30 minutes in an oven and evaluated according to the following criteria. A: When the weight loss was less than 1%, B: the weight loss was less than 1% or more and less than 3% c: weight reduction is less than 3% or more, less than 5%, D: weight reduction is 5% or more, V) prevention of lower film denaturation, the substrate having the protective film formed as described above, at 23 ( The TC was heat-hardened in an oven for 30 minutes, and the substrate on which the protective film was formed was visually confirmed with dirt and confirmed by SEM (Magnetic Gas Scanning Microscope), and evaluated according to the following criteria: A: Surface fouling was 20% or less. B: Surface fouling is 20% or more, 40% or less, c: Surface fouling is 40% or more, 60% or less, D: Surface fouling is 60% or more [Table 1]

區分 接著力 财久性 透射度 耐熱性 防止下部 膜變性 B 實施例1 B B A B 實施例2 A A A A —--- A 實施例3 A A A B 比較例1 D D C C D 23 201241553 如前述表1所表示，不含有聚矽氮烷化合物之比較例1 的組成物的情況，接著力、财久性、透射度、财熱性及防 止下部膜變性係顯著地低落，相反地，含有聚矽氮烷化合 物之實施例1〜3的組成物，係在接著力、耐久性、透射度、 耐熱性及防止下部膜變性方面顯示全部優良之效果。特別 是含有10重量％以上的聚矽氮烷化合物之實施例2及3的情 況，係在接著力、耐久性、透射度、耐熱性及防止下部膜 變性方面顯示更優良的效果。 【圖式簡單說明3 第1圖係對使保護膜熱硬化前的下部膜之電子顯微鏡 觀察照片，該保護膜係使用本發明之實施例1的組成物製 成。 第2圖係使用電子顯微鏡觀察使保護膜熱硬化後之下 部膜的變性程度之照片，該保護膜係使用實施例1的組成物 製成。 第3圖係使用電子顯微鏡觀察使保護膜熱硬化後之下 部膜的變性程度之照片，該保護膜係使用實施例2的組成物 製成。 第4圖係使用電子顯微鏡觀察使保護膜熱硬化後之下 部膜的變性程度之照片，該保護膜係使用實施例3的組成物 製成。 第5圖係使用電子顯微鏡觀察使保護膜熱硬化後之下 部膜的變性程度之照片，該保護膜係使用比較例1的組成物 製成。 24 201241553 【主要元件符號說明】 (無） 25Distinguishing the strength of the long-term transmittance, heat resistance, prevention of the lower film denaturation B Example 1 BBAB Example 2 AAAA —--- A Example 3 AAAB Comparative Example 1 DDCCD 23 201241553 As shown in Table 1 above, no polyfluorene nitrogen In the case of the composition of Comparative Example 1 of the alkane compound, the force, the long-lasting property, the transmittance, the heat-generating property, and the prevention of the lower film denaturation system were remarkably lowered. Conversely, Examples 1 to 3 containing the polyazide compound were used. The composition showed all excellent effects in terms of adhesion, durability, transmittance, heat resistance, and prevention of degeneration of the lower film. In particular, in the cases of Examples 2 and 3 containing 10% by weight or more of the polyazide compound, it exhibited a more excellent effect in terms of adhesion, durability, transmittance, heat resistance, and prevention of lower film denaturation. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is an electron microscopic observation photograph of a lower film before thermosetting a protective film, which is produced using the composition of Example 1 of the present invention. Fig. 2 is a photograph showing the degree of denaturation of the lower film after thermosetting the protective film by an electron microscope, and the protective film was produced using the composition of Example 1. Fig. 3 is a photograph showing the degree of denaturation of the lower film after thermosetting the protective film using an electron microscope, and the protective film was produced using the composition of Example 2. Fig. 4 is a photograph showing the degree of denaturation of the lower film after thermosetting the protective film using an electron microscope, and the protective film was produced using the composition of Example 3. Fig. 5 is a photograph showing the degree of denaturation of the lower film after thermosetting the protective film using an electron microscope, and the protective film was produced using the composition of Comparative Example 1. 24 201241553 [Explanation of main component symbols] (None) 25

Claims (1)

201241553 七、申請專利範圍： 1. 一種用於印刷製程之光硬化性樹脂組成物，其特徵在於 含有： (1) 聚矽氮烷化合物， (2) 乙烯系單體， (3) 具有至少2個以上的乙烯系雙鍵之交聯性單體， (4) 光聚合起始劑，及 (5) 界面活性劑。 2. 如申請專利範圍第1項之用於印刷製程之光硬化性樹脂 組成物，其中前述光硬化性樹脂組成物係含有： (1) 1〜60重量％之聚矽氮烷化合物， (2) 10~80重量％之乙烯系單體， (3) 10~80重量％之具有至少2個以上的乙烯系雙鍵 之交聯性單體， (4) 0.1~12重量％之光聚合起始劑，及 (5) 0.001~5重量％之界面活性劑。 3. 如申請專利範圍第1項之用於印刷製程之光硬化性樹脂 組成物，其中前述聚$夕氮烧化合物，係含有具有下述化 學式1的結構單位之直鏈狀結構，且具有300~2,000分子 量，而且在1分子中具有3~10個SiH3基，並且，藉由化 學分析所得之各元素比率係：以重量％計，平均為Si : 59〜62、N : 31〜34及Η : 6.5~7.5之全氫化聚矽氮烷， [化學式1] 26 201241553 Η ---Si-Ν-- Γ I ΐΤη Η Η 在上述式中，η係整數。 4·如申請專利範圍第3項之用於印刷製程之光硬化性樹脂 組成物，其中前述聚矽氮烷化合物係在分子内具有下述 化學式2的結構且含有鏈狀或環狀部分， [化學式2] 卜] L J • —SiHj a b ^ J C (a+b十c=1) 〇 5 ·如申請專利範圍第4項之用於印刷製程之光硬化性樹脂 組成物，其中前述聚矽氮烷化合物係具有下述化學式3 或4的結構且數量平均分子量為1000~50,000之化合物， [化學式3]201241553 VII. Patent application scope: 1. A photocurable resin composition for a printing process, characterized by comprising: (1) a polyazide compound, (2) a vinyl monomer, and (3) having at least 2 More than one crosslinkable monomer of a vinyl double bond, (4) a photopolymerization initiator, and (5) a surfactant. 2. The photocurable resin composition for a printing process according to the first aspect of the invention, wherein the photocurable resin composition contains: (1) 1 to 60% by weight of a polyazane compound, (2) 10 to 80% by weight of a vinyl monomer, (3) 10 to 80% by weight of a crosslinkable monomer having at least two or more ethylene double bonds, (4) 0.1 to 12% by weight of photopolymerization The starting agent, and (5) 0.001 to 5% by weight of the surfactant. 3. The photocurable resin composition for a printing process according to the first aspect of the invention, wherein the polyfluorene compound is a linear structure having a structural unit of the following chemical formula 1, and has 300 ~ 2,000 molecular weight, and having 3 to 10 SiH 3 groups in one molecule, and the ratio of each element obtained by chemical analysis is: in terms of % by weight, Si: 59 to 62, N: 31 to 34, and Η : a fully hydrogenated polyazane of 6.5 to 7.5, [Chemical Formula 1] 26 201241553 Η ---Si-Ν-- Γ I ΐΤη Η Η In the above formula, η is an integer. 4. The photocurable resin composition for a printing process according to the third aspect of the invention, wherein the polyazide compound has a structure of the following chemical formula 2 in a molecule and contains a chain or a cyclic moiety, [ Chemical formula 2] 卜] LJ • —SiHj ab ^ JC (a+b 十c=1) 〇5. The photocurable resin composition for printing process according to item 4 of the patent application, wherein the polypyridazane The compound is a compound having the structure of the following Chemical Formula 3 or 4 and having a number average molecular weight of from 1,000 to 50,000, [Chemical Formula 3] [化學式4] 27 201241553 Ν-—R311 2 R-S-R· Λ 在上述式中，Ri、R2及R·3係各自獨立地表示氫原 子、烧基、稀基、環炫基、芳基、直接鍵結至石夕之基為 碳之基、烷基矽烷基、烷胺基、及烷氧基，η係整數，（此 時，心、R2及R3中的至少1者為氫原子）。 6_如申請專利範圍第5項之用於印刷製程之光硬化性樹脂 組成物，其中前述聚矽氮烷化合物係數量平均分子量為 100〜50,000之聚矽氮烷或其改性物。 7. 如申請專利範圍第5項之用於印刷製程之光硬化性樹脂 組成物，其中前述化學式4的化合物係在心及化具有氫 原子、及在R3具有甲基之聚矽氮烷。 8. 如申請專利範圍第5項之用於印刷製程之光硬化性樹脂 組成物，其中前述化學式4的化合物係在心及化具有氫 原子、及在&具有有機基之聚有機（氫化)矽氮烷。 9. 如申請專利範圍第8項之用於印刷製程之光硬化性樹脂 組成物’其巾前述化學式4的化合物係具有聚合度為3〜5 之環狀結構者或是在分子内同時具有鏈狀結構與環狀 結構者。 0 士申μ專利範圍第5項之用於印刷製程之光硬化性樹脂 組成物，其中前述化學式4的化合物係在心具有氫原 子、及在R2及&具有有機基之聚矽氮烷。 申。s專利範gj第5項之用於印刷製程之光硬化性樹脂 28 201241553 組成物，其中前述化學式4的化合物係在比及112具有有 機基、及在R3具有氫原子之聚合度為3~5左右的環狀結 構之聚石夕氮烧。 12.如申請專利範圍第1項之用於印刷製程之光硬化性樹脂 組成物，其中前述聚矽氮烷化合物作為有機聚矽氮烷者 係在分子内具有下述化學式5的交聯結構之聚有機（氫 化)矽氮烷，及具有藉由RlSiX3(X :鹵素）的氨分解而得 到之交聯結構的聚矽氮烷、RlSi(NH)X、或具有藉由 RlSiX3的共氨分解而得到之下述化學式6的結構之聚矽 氮烷， [化學式5]27 201241553 Ν-—R311 2 RSR· Λ In the above formula, Ri, R 2 and R·3 each independently represent a hydrogen atom, an alkyl group, a dilute group, a cyclodextrin group, an aryl group, and a direct bond. The group to the group is a carbon group, an alkylalkyl group, an alkylamino group, and an alkoxy group, and an η-based integer (in this case, at least one of the core, R2 and R3 is a hydrogen atom). The photocurable resin composition for a printing process according to the fifth aspect of the invention, wherein the polyazirane compound has a polyazazane having a coefficient average molecular weight of from 100 to 50,000 or a modified product thereof. 7. The photocurable resin composition for a printing process according to the fifth aspect of the invention, wherein the compound of the above Chemical Formula 4 is a polyazane having a hydrogen atom and a methyl group at R3. 8. The photocurable resin composition for a printing process according to claim 5, wherein the compound of the above Chemical Formula 4 is a polyorgano(hydrogenated) ruthenium having a hydrogen atom and having an organic group. Azane. 9. The photocurable resin composition for a printing process according to claim 8 of the patent application, wherein the compound of the above chemical formula 4 has a cyclic structure having a degree of polymerization of 3 to 5 or has a chain in the molecule. Shaped structure and ring structure. A photocurable resin composition for use in a printing process according to the fifth aspect of the invention, wherein the compound of the above chemical formula 4 has a hydrogen atom in the center and a polyazane having an organic group in R2 and & Shen. s Patent No. 5, the photocurable resin for printing process 28 201241553, wherein the compound of the above Chemical Formula 4 has an organic group at a ratio of 112 and a degree of polymerization of a hydrogen atom at R3 of 3 to 5 The left and right ring-shaped structure is agglomerated with nitrogen. 12. The photocurable resin composition for a printing process according to the first aspect of the invention, wherein the polyazide compound has a crosslinked structure of the following chemical formula 5 in the molecule as an organopolyazane. a polyorgano(hydrogenated) decazane, and a polyazide having a crosslinked structure obtained by decomposition of ammonia of RlSiX3 (X: halogen), RlSi(NH)X, or having a co-ammonia decomposition by R1SiX3 A polyazane having the structure of the following chemical formula 6 is obtained, [Chemical Formula 5] R=CH3 [化學式6] R1 H R1 Η II i I Si——N--—Si——N .m . | R2 NH 在上述式中，心及尺2係各自獨立地表示氫原子、烷 基、烯基或芳基，m及η係各自獨立地為整數。 29 201241553 13.如申請專利範圍 組成物，其中前 物、改性聚矽氮烷、 第1項之用於印刷製程之光硬化性樹脂 述聚矽氮烷化合物係無機矽氮烷共聚 共聚合矽氮炫1。 或在聚石夕氮烧導入有機成分而成之 μ申#專利i&nn項之用於印刷製程之光硬化性樹脂 、且成物其中則述乙稀系單體係選自於由丙稀酸異丁R=CH3 [Chemical Formula 6] R1 H R1 Η II i I Si——N---Si——N .m . | R 2 NH In the above formula, the core and the rule 2 each independently represent a hydrogen atom or an alkyl group. Alkenyl or aryl, m and η are each independently an integer. 29 201241553 13. The composition of the patent scope, wherein the precursor, the modified polyazane, the photocurable resin used in the printing process of the first item, the polyazane compound, the inorganic sulfonium copolymerization copolymerization Nitrogen Hyun 1. Or a photo-curable resin used in the printing process of the patent application i & nn, which is formed by the introduction of an organic component in a polylithic zephyr, and wherein the ethylene system is selected from the group consisting of propylene Acid diced …％ u巫下％哔陥、丙烯毆本軋基乙酯、丙 稀酸4_經基丁醋、笨氧基聚乙二醇丙烯酸醋、丙烯酸2_ 羥基乙酯、丙烯酸2-羥基丙酯、酞酸2_丙烯醯氧基乙基 -2-羥基丙酯、丙烯酸2_羥基_3_苯氧基丙酯及該等的曱基 丙烯酸酯類；如丙烯酸3-氟乙酯、丙烯酸4_氟丙酯之含 齒素化合物之丙烯酸酯及該等的甲基丙烯酸酯類；如丙 烯酸三乙基甲矽烷氧基乙酯之含矽氧烷基之丙烯酸酯 及該等的甲基丙烯酸酯類；如苯乙烯及4甲氧基苯乙烯 之具有芳香族的烯烴類；及該等的混合物所構成群組。 15.如申請專利範圍第1項之用於印刷製程之光硬化性樹脂 組成物，其中前述具有至少2個以上的乙烯系雙鍵之交 聯性單體係選自於由二伸乙甘醇一乙基醚、二羥甲基二 環戊烷二丙烯酸酯、1，4-丁二醇二丙烯酸酯、丨，3_丁二醇 一丙稀fee g曰、ι，6-己一醇二丙稀酸醋、稀丙氧基聚乙二 醇丙烯酸酯、丙烯酸二環戊烯酯、羥基三甲基乙酸新戊 30 201241553 二醇二丙烯酸醋、新戍二醇二丙烯酸@旨、1，9_壬二醇二 丙稀酸醋、聚乙二醇二丙稀酸醋、山梨糖醇三丙稀酸 西旨、雙盼A二丙稀酸醋衍生物、三曱基丙燒三丙晞酸醋、 該等的曱基丙烯酸酯類及該等的混合物所構成群組。 16. 如申请專利範圍第1項之用於印刷製程之光硬化性樹脂 組成物，其中前述光聚合起始劑係選自於*Irgacure 369、Igacure 907、Igacure 184、Igacure 651、lgacure 819、 Igacure 2959、Igacure 1800、Darocur 1173、Darocur 1116 及Darocur 1020、苯乙酮系化合物、二苯基酮系化合物、 9-氧石爪0山0星系化合物、苯偶姻系化合物、三啡系化合物 及該等的混合物所構成群組。 17. 如申μ專利範圍第丨項之用於印刷製程之光硬化性樹脂 組成物’其中前述界面活性劑係選自於切系界面活性 劑、氟系界面活性劑及該等的混合物所構成群組。 18. 如申„月專利範圍第i項之用於印刷製程之光硬化性档十脂 組成物，其中前述光硬化性樹脂組成物係追加性地含有 溶劑。 19. 如申請專利範圍第18項之用於印刷製程之光硬化性樹 脂組成物，其中前述溶難選自於由乙腈、甘油、二甲 基亞砜硝基甲燒、二曱基甲醯胺、苯紛、N-甲基吼略 定酮^疋全敗二丁胺、全氟十氫萘、2_丁_、碳㈣ 甲酉:石厌酉夂伸丙醋、醇類、越類；酿類、乙二醇烧基鍵 乙S欠西曰類、乙_醇烧基㈣酸醋類、乙二醇單烧基峻 類、二伸乙甘軌基_、力二軌細乙酸㈣、兩 31 201241553 二醇烷基醚丙酸酯類、丙二醇單烷基醚類、二伸丙甘醇 烧基鍵類、丁二醇單甲基醚類、二伸丁二醇烷基醚類及 該等的混合物所構成群組。 2 0 ·如申請專利範圍第1項之用於印刷製程之光硬化性樹脂 組成物，其中前述光硬化性樹脂組成物係在25t具有 2mPa . s至25mPa . s的黏度。 21. —種用於印刷製程之保護膜之製造方法，係含有將如申 請專利範圍第1項之用於印刷製程之光硬化性樹脂組成 物塗佈在基板且進行曝光之階段。 22. -種微細圖案之製造方法，係含有將如巾料利範圍第 1項之用於印刷製程之光硬化性樹脂組成物塗佈在基 板’且利用壓印微影術或輥印刷步卿成塗膜之後進 行曝光之階段。 23. -種保護膜或微細圖案，係藉由如申請專利範圍第^及 22項之製造方法製成者。 32%% 哔陥, 殴 殴 轧 轧 轧 轧 轧 殴 殴 殴 、 、 、 、 、 、 轧 轧 轧 轧 轧 轧 轧 轧 轧 轧 轧 轧 轧 轧 哔陥 哔陥 哔陥 哔陥 哔陥 哔陥 哔陥 哔陥 哔陥 哔陥 哔陥 哔陥Capric acid 2_propylene oxiranyl ethyl-2-hydroxypropyl ester, 2-hydroxy-3-phenylphenoxypropyl acrylate and these methacrylates; such as 3-fluoroethyl acrylate, acrylic acid 4_ Acrylates of dentate-containing compounds of fluoropropyl esters and such methacrylates; oxyalkylene-containing acrylates such as triethylmethane alkoxyethyl acrylate and such methacrylates An aromatic olefin such as styrene and 4-methoxystyrene; and a mixture of such mixtures. 15. The photocurable resin composition for a printing process according to the first aspect of the invention, wherein the crosslinkable single system having at least two or more ethylene double bonds is selected from the group consisting of diethylene glycol Monoethyl ether, dimethylol dicyclopentane diacrylate, 1,4-butanediol diacrylate, hydrazine, 3-butanediol-propylene fee g曰, ι,6-hexanol Acrylic vinegar, dilute propoxy polyethylene glycol acrylate, dicyclopentenyl acrylate, hydroxytrimethyl acetic acid, neopentane 30 201241553 diol diacrylate vinegar, neodecanediol diacrylic acid @,, 9,9 _ diol diol diacrylic acid vinegar, polyethylene glycol diacetic acid vinegar, sorbitol tripropylene acid ketone, shuangyi A diacetic acid vinegar derivative, tridecyl propyl propyl tripropionate A group of vinegar, such thiol acrylates, and mixtures thereof. 16. The photocurable resin composition for a printing process according to the first aspect of the invention, wherein the photopolymerization initiator is selected from the group consisting of *Irgacure 369, Igacure 907, Igacure 184, Igacure 651, lgacure 819, Igacure. 2959, Igacure 1800, Darocur 1173, Darocur 1116 and Darocur 1020, an acetophenone-based compound, a diphenylketone-based compound, a 9-oxo-claw, a samarium compound, a benzoin-based compound, a trimorphine compound, and A mixture of equal parts constitutes a group. 17. The photocurable resin composition for a printing process according to the invention of claim 3, wherein the surfactant is selected from the group consisting of a cleavage surfactant, a fluorine-based surfactant, and the like. Group. 18. The photocurable resin composition for use in a printing process according to the item of the invention, wherein the photocurable resin composition additionally contains a solvent. The photocurable resin composition for use in a printing process, wherein the aforementioned dissolution is selected from the group consisting of acetonitrile, glycerin, dimethyl sulfoxide, fluoromethane, dimethyl carbamide, benzophenone, and N-methyl hydrazine. Slightly ketone ^ 疋 疋 二 二 二 dibutylamine, perfluoro decahydronaphthalene, 2 _ _, carbon (four) thyroid: stone 酉夂 酉夂 丙 丙 丙 醇 醇 醇 、 、 、 、 、 ; ; ; ; S owe oxime, B-alcohol-based (four) vinegar, ethylene glycol monoalkyl base, diethylene glycolate _, force two-rail fine acetic acid (four), two 31 201241553 glycol alkyl ether propionic acid a group consisting of esters, propylene glycol monoalkyl ethers, dipropylene glycol bases, butanediol monomethyl ethers, dibutylene glycol alkyl ethers, and mixtures thereof. The photocurable resin composition for a printing process according to the first aspect of the invention, wherein the photocurable resin composition has 2 mPa.s to 25 at 25t. The viscosity of mPa. s. 21. A method for producing a protective film for a printing process, comprising applying a photocurable resin composition for a printing process as disclosed in claim 1 to a substrate and performing exposure 22. A method for producing a fine pattern, comprising coating a photocurable resin composition for a printing process on a substrate as in the first item of the towel, and using an embossing lithography or a roll The step of exposure is carried out after the film is applied to the film. 23. A protective film or a fine pattern is produced by the manufacturing method as claimed in the claims of the first and second paragraphs.
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