TW201000547A - Active energy ray-curable resin composition, cured film, laminate, optical recording medium and process for producing cured film - Google Patents

Active energy ray-curable resin composition, cured film, laminate, optical recording medium and process for producing cured film Download PDF

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Publication number
TW201000547A
TW201000547A TW098113982A TW98113982A TW201000547A TW 201000547 A TW201000547 A TW 201000547A TW 098113982 A TW098113982 A TW 098113982A TW 98113982 A TW98113982 A TW 98113982A TW 201000547 A TW201000547 A TW 201000547A
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Taiwan
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group
active energy
energy ray
meth
weight
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TW098113982A
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Chinese (zh)
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TWI448503B (en
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Makoto Terauchi
Tomokazu Iwasaki
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Mitsubishi Chem Corp
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING 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
    • C09D4/00—Coating 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers 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 of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/24—Homopolymers or copolymers of amides or imides
    • C08L33/26—Homopolymers or copolymers of acrylamide or methacrylamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers 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 of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
    • G11B7/252—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers
    • G11B7/254—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of protective topcoat layers
    • G11B7/2542—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of protective topcoat layers consisting essentially of organic resins

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Optical Record Carriers And Manufacture Thereof (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
  • Epoxy Resins (AREA)
  • Paints Or Removers (AREA)
  • Manufacturing Optical Record Carriers (AREA)
  • Polymerisation Methods In General (AREA)
  • Laminated Bodies (AREA)

Abstract

This invention aims at providing an active energy ray-curable resin composition capable of forming a cured film superior in hardness, scratch resistance and antifouling property; a cured film, a laminate and an optical recording medium each obtained from the composition; and a process for producing a cured film. This invention relates to an active energy ray-curable resin composition obtained by mixing (A) a specific mono- to tetra-functional (meth) acrylate and/or (meth) acryl amide, (B) a multi-functional (meth) acrylate derivative having 3 or more (meth) acryloyl group per one molecule, other than (A), (C) a photopolymerization initiator, (D-1) an active energy ray-curable compound having at least one group selected from a polydimethylsiloxane group, a perfluoroalkyl group, and a perfluoroalkylene group within a specific composition range, the viscosity of which is 10-500mPa.s at 25 DEG C and which does not contain an organic solvent in an amount more than 5% by weight based on the composition.

Description

201000547 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種實質上不含溶劑之活性能量線硬化性 樹脂組成物、使該組成物硬化而成之硬化膜、積層體、光記 錄媒體及硬化膜之製造方法。 【先前技術】 塑膠製品例如聚碳酸酯、聚甲基丙烯酸曱酯、聚對苯二曱 酸乙二醇酯、聚對苯二曱酸丁二醇酯、丙烯腈-丁二烯-苯乙 稀共聚物（ABS，Acrylonitrile Butadiene Styrene)、曱基丙稀 酸曱酯-苯乙烯共聚物（MS 樹脂，Methyl[Technical Field] The present invention relates to an active energy ray-curable resin composition substantially free of a solvent, a cured film obtained by curing the composition, a laminated body, and an optical recording medium. And a method of producing a cured film. [Prior Art] Plastic products such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate, butylene terephthalate, acrylonitrile butadiene styrene Copolymer (ABS, Acrylonitrile Butadiene Styrene), mercapto acrylate-styrene copolymer (MS resin, Methyl

Methacrylate-Styrene resin)、丙烯腈-苯乙婦共聚物（as 樹 脂，Acrylonitrile Styrene resin)等苯乙烯系樹脂，氯乙烯系 樹脂，三乙醯纖維素等乙酸纖維素等之樹脂材料，因其輕量 性、易加工性、耐衝擊性等尤其優異’故可用於下列各種用 途：容器’汽車之儀錶板或外板或天窗，窗材料，屋頂材料， 太陽電池板，包裝材料，各種外殼材料，光碟基板，塑膠透 鏡，液晶顯示器或電漿顯示器、有機電激發光， deCtr〇luminescence)顯示器、投影電視等顯示設備之基材 等。 土 然而，該等塑膠製品因表面硬度較低故易劃傷，於如聚碳 酸酯或聚對苯二曱酸乙二醇酯之透明樹脂中，存在顯著損害 該樹脂原來所具有的透明性或外觀之缺點，而在需要耐磨^ 098113982 4 201000547 之領域t難以使用塑膠製品。 、因此’曰業者正在尋求勢該等塑膠製品的表㈣耐磨性之 活性能量線硬化性硬塗材料(被覆材料）。 」列如，i分子内具有3個以上丙煉酿基之多官能基丙婦酸 酯類、其衍生物（胺基甲酸乙酯丙烯酸酯、酯基丙烯萨酽 環氧丙烯酸酯等）被廣泛用作適於上述要求者。然而，2使 用此種化合物作為硬化成分之活性能量線硬化性硬汾材料 C 之硬化膜，因收縮較大、產生翹曲、產生剝離或者龜裂，故 難以較厚地塗佈，因而在可達成之硬度及耐劃傷性中存在著 限度。 又’除一部分化合物外’通常多官能丙烯酸酯類於室溫下 之黏度非常高（5000〜1000000 mPa · s)，因而對塗佈方法產 生限制’或者難以進行如均勻膜厚之塗佈、形成平滑表面之 塗佈’必須以溶劑進行稀釋或者使其形成水系乳液等藉此降 ϋ 低塗佈時之黏度。 另—方面，近年來，就降低環境負荷、提高生產性、溶液 再利用之容易性等各種觀點而言，儘量不使用溶劑而可於高 /辰度或無溶劑下使用活性能量線硬化性塗佈劑之必要性在 增加。 如上述之問題中，關於降低硬化收縮之方法，提出並實施 有各種方法。例如可舉出：使用1〜2官能之具有丙烯基之 化合物作為反應性稀釋劑之方法。 _113982 5 201000547 然而，該方法中，通常交聯密度會下降，因此存在原來的 硬度耐劃傷性下降之問題，從而在作為硬塗材料之使用中 存在著限度。 又，作為無溶劑之活性能量線硬化性樹脂組成物，限定於 特疋用适而提出其改良品，例如專利文獻丨中記載有聚酯薄 膜之線上硬塗用活性能量線硬化性樹脂組成物，專利文獻2 中6己載有用以貼合光碟之接著劑用活性能量線硬化性樹脂 組成物。 另方面，對最近開發之以藍色雷射進行寫入/刪除之次 世代型光碟而言，不僅要求賦予表面硬度及耐久性，而且亦 要求賦予高水準之耐污染性。 於次世代型光資訊媒體或觸控面板等光學物品中，近年來 心紋污㊉不僅對外觀*且對性能及安全造成影響已成為問 題，尤其於光貧訊媒體方面，在次世代型光資訊媒體中，記 錄/再生的誤差增大等作為對性能造成直接影響之問題逐漸 被視為嚴重之問題。不僅指紋污潰，視使用環境，塵、埃等 八他/亏木物貝亦會引起污染’該等亦成為記錄不良、再生不 良等誤差之主要原因。 其中’作為向密度之光資訊媒體，亦提出有藉由增大物鏡 的開口度（N/A)及/或使記錄/再生波長短波長化至· ，而減少光束聚光點徑，將每單位密度之記錄密度高密 度化為先則（數位多功能光碟①vd，卿㈤V賴仙以⑻) 098113982 201000547 的數倍以上之媒體’例如已出現Blu-Ray Disc(藍光光碟）或 HD-DVD(高解析DVD)等新的光資訊媒體。a styrene resin such as Methacrylate-Styrene resin, acrylonitrile-styrene resin (as-resin, Acrylonitrile Styrene resin), a vinyl chloride resin, or a cellulose resin such as cellulose acetate such as triacetyl cellulose. It is especially excellent in quantity, easy processing, impact resistance, etc. It can be used in the following various applications: container 'vehicle dashboard or outer panel or skylight, window material, roofing material, solar panel, packaging material, various outer casing materials, A substrate such as a disc substrate, a plastic lens, a liquid crystal display or a plasma display, an organic electroluminescence, a deCtr luminescence display, a projection television, or the like. However, these plastic products are easily scratched due to their low surface hardness. In transparent resins such as polycarbonate or polyethylene terephthalate, there is a significant impairment of the original transparency of the resin or The shortcomings of the appearance, and in the field where wear resistance is required 098113982 4 201000547, it is difficult to use plastic products. Therefore, the manufacturer is seeking an active energy ray-curable hard coating material (coating material) which is suitable for the wear of the plastic products (4). "For example, polyfunctional propyl acrylates having three or more propylene smelting groups in the i molecule, and derivatives thereof (amino acrylate acrylate, ester propylene oxime epoxy acrylate, etc.) are widely used. Used as a person suitable for the above requirements. However, 2 the cured film of the active energy ray-curable hard enamel material C using such a compound as a curing component has a large shrinkage, warpage, peeling or cracking, so that it is difficult to apply it thickly, and thus it is achievable. There are limits in hardness and scratch resistance. Also, 'except for some compounds', usually the polyfunctional acrylates have a very high viscosity at room temperature (5000~1000000 mPa·s), which limits the coating method' or makes it difficult to apply and form a uniform film thickness. The coating of the smooth surface must be diluted with a solvent or formed into an aqueous emulsion to lower the viscosity at the time of coating. On the other hand, in recent years, the active energy ray-curable coating can be used at high/instantness or without solvent, from the viewpoints of reducing environmental load, improving productivity, and ease of reusing the solution. The necessity of cloth is increasing. As described above, various methods have been proposed and implemented for the method of reducing the hardening shrinkage. For example, a method of using a compound having a propylene group of 1 to 2 functions as a reactive diluent can be mentioned. _113982 5 201000547 However, in this method, since the crosslinking density is usually lowered, there is a problem that the original hardness is scratch-resistant, and there is a limit in use as a hard coat material. In addition, the active energy ray-curable resin composition which is a solvent-free active energy ray-curable resin composition is limited to a special product, and an active energy ray-curable resin composition for on-line hard coating of a polyester film is described in the patent document. In Patent Document 2, 6 is an active energy ray-curable resin composition for an adhesive for bonding an optical disk. On the other hand, the next generation of optical discs that have been recently written/deleted with blue lasers are required to impart not only surface hardness and durability, but also high level of contamination resistance. In the next generation of optical information media or touch panels and other optical items, in recent years, the smudge of the heart has not only affected the appearance * and has an impact on performance and safety, especially in the light of the poor media, in the next generation of light In the information media, the problem of an increase in the error in recording/reproduction, etc., which is directly affected by performance, is gradually regarded as a serious problem. Not only the fingerprints are fouled, but also the environment, dust, ang, etc., and the loss of wood and shellfish can cause pollution. These have also become the main causes of errors such as poor recording and poor reproduction. Among them, as the information medium for density light, it is also proposed to reduce the aperture of the beam by increasing the aperture (N/A) of the objective lens and/or shortening the wavelength of the recording/reproducing wavelength to Recording Density of Unit Density is High-Precision (Digital Multi-Function Disc 1vd, Qing (5) V Lai Xian (8)) 098113982 201000547 More than a few times of media 'For example, Blu-Ray Disc or HD-DVD has appeared ( New optical information media such as high-resolution DVD).

若以上述方式提高記錄密度，則在媒體之記錄/再生光束 入射側表面上之記錄/再生光束之聚光點徑會變小，因此特 別是指紋或塵、埃等污染之影響會變大。特別是如指紋之含 有有機物之污潰，在污潰附著於媒體之雷射光入射側之表面 的情況下，可產生記錄/再生誤差等嚴重的影響，而且亦難 以將其去除’因此需要採取其對策。 專利文獻3及4中 W十、。ό q济性船1綠硬化性 基之石夕氧系化合物、氟系化合物之特定硬塗劑組成物，在次 世代光碟（高密度光記錄資訊媒體）的表面上形成硬塗被 膜，且記載有該等硬塗被膜顯示優異的耐指紋性。 於專利文獻5、專利文獻6中揭示有含有特定的聚秒 基=基之特定共聚物、或其(甲基)丙烯酸反 ^性賦Μ極為有效，本發明者們發現，含有此種耐污毕 予劑之居性能量線硬化性樹脂組成物作為次 碟用硬塗劑係極為優異者。 1光 [先行技術文獻] [專利文獻] 專利文獻1 ··日本專利特開麗_3_5鍊公報 專利文獻2:日本專職開薦·測88號公報 專利文獻3 :日本專利特開篇·〗524!8衆公報 098113982 7 201000547 專利文獻4 :曰本專利特開2005-112900號公報 專利文獻5 :曰本專利特開2006-160802號公報 專利文獻6 :國際公開第2006/059702號小冊子 【發明内容】 (發明所欲解決之問題） 然而’專利文獻1中記載之活性能量線硬化性樹脂組成物 係線上(in-line)硬塗用者，因此雖然在高於室溫的溫度下適 於塗佈製程，但此種組成物在室溫下的黏度較高，因此未必 適於通常之離線(〇ff4ine)之塗佈製程。 於專利文獻2中記載之活性能量線硬化性樹脂組成物 中，提出有在黏度、硬化性方面適於其塗佈製程者，但因係 接著劑用，故在作為硬塗材料使用時硬度不足，並不實用。 專利文獻3及4中記載之使驗㈣組成物而形成之被 膜，顯示如減小指紋附著徑之優異的拔水/拔油性，但指紋 之拭去性或其耐久性並非充分。其原因在於雖_塗層較薄 約為2 ’㈣性能量線硬化性基並非具有充分的薄膜硬 化性之基，或者耐污染性賦予劑之骨架本身健成為硬度相 對較低之結構。 士專利文獻5及6中呂己載之活性能量線硬化性樹脂組成物 之習知硬塗劑’含有有機溶劑，在考慮到降低對環境負荷的 影響/未反應㈣再利料之情況下，需要進行徹底的改良。 本毛月之目的在於解決上述問題，其目的在於提供一種如 098113982 201000547 下之活性能量線硬化性樹脂組成物：雖然實質上不含溶劑但 可進行對應於塗佈方法之寬廣範圍之黏度設定，並且因硬化 性優異故光聚合起始劑的用量較少，能夠於溫和條件下利用 活性能量線較硬化，進^轉硬化叙硬纽_傷性 (耐磨性）良好。 此外，本發明之目的在於亦提供一種使此種組成物硬化而 成之硬化収/絲面上具有由該硬化朗形紅硬塗層之 ί積層體’進而本發明亦提供—種如表面上具有高硬度、耐磨 !生優，、的耐/亏染性及耐污染性之耐久性之硬化膜及/或表 面上具有由該硬化膜所形成之硬塗層之積層體以及光記錄 媒體。 (解決問題之手段） 本發明者為達成上述目的而進行努力研究，結果發現：藉 由使用具有耐污染性之特定結構之活性能量線硬化性化合 (，物’並且選定特定之1或2官能之（甲基）丙烯酸酯或者（曱基） 丙烯醯胺、特定之多官能（曱基）丙烯酸酯衍生物、及以相對 較少的添加量即可硬化之光聚合起始劑的特定組合，而使得 5周配有該等之活性能量線硬化性樹脂組成物能夠設定成可 應對各種塗佈方法之黏度且塗佈性亦優異，進而由該組成物 所C彳于之硬化膜具有高於習知者的对污染性外而且具有高 硬化性、高硬度、耐劃傷性，並最終完成本發明。 即，本發明係有關於一種活性能量線硬化性樹脂組成物， 098113982 9 201000547 其係含有下述(A)、（B) ' (C)及(D-l) ’且於25。(：之黏度為10 〜500 mPa · s者，其特徵在於：在厚度為i mm之聚碳酸酯 薄膜上形成厚度為3 /im之由該活性能量線硬化性樹脂組 成物所構成之塗膜’於氧濃度為20%之條件下，利用於波長 254 nm下的放射照度為400 mW/cm2之高壓水銀燈，以累計 光量達到1000 mJ/cm2之方式照射紫外線時，硬化膜表面之 錯筆硬度為B以上，並且不含超過該組成物中之$重量％之 有機溶劑； (A) 1分子内具有1〜4個（曱基）丙烯醯基，且25。〇之黏度 為1〜500 mpa · s之1〜4官能之（甲基）丙烯酸酯、（甲基） 丙稀酿胺或者上述兩者之混合物：10〜70重量份； (B) l分子内具有3個以上（曱基;)丙烯醯基之由（A)以外的 多官能（甲基）丙烯酸酯及自其胺基甲酸乙酯改質體、酯改質 體以及碳酸酯改質體中選擇的一種以上所構成之多官能（曱 基）丙烯酸酯衍生物：30〜90重量份； (C) 光聚合起始劑：相對於(A)與(B)之合計量1〇〇重量份 為2〜6·5重量份； (D 1)¾有自I一曱基梦氧烧基、全氟烧基及全氟伸烧基 中選擇的一種以上基之活性能量線硬化性化合物：相對於(A) 與(B)之合計量100重量份為0_1〜15重量份。 又，本發明亦關於一種活性能量線硬化性樹脂組成物，其 係含有下述(A)、（B)及(D-3)者，其特徵在於：於25°C下之 098113982 10 201000547 黏度為10〜500 mPa · s，不含炉讲 之有機溶劑； 3超過⑹成物中之5重量％ (A) 1分子内具有1〜4個（甲基)丙_基，且於饥下之 黏度為1〜500 mPa · s之1〜4合A匕 簡丙稀醯胺:H)〜7。重量份^ (甲基)丙烯酸醋及/或 (B) l分子内具有3個以上Γ甲其α 夕^ (甲基)丙烯酿基之由(Α)以外的 多吕旎基（f基）丙烯酸酯及自兑美 質體、及碳酸_體中選擇:一：酸乙㈣體，改 (甲基)丙義副 人㈣具有相當於如下結構的結構之活絲量線硬化性聚 &物，該結構係使1分子内具有1個以上（甲基)丙烯酿義之 ㈣與如下單體混合物的自由基聚合物的至少一部 基反應而職，該賴混合物係含有具有自聚㈣ 基、全氟烧基及全氣伸烧基中選擇的一種以上基之二:: 有環氧基切轴細旨：彳目對於⑷與⑻之合計量、具 重量份為0.1〜15重量份。 00 進而，本發明係有關於-種硬化膜，其係向上述活性处旦 線硬化性樹脂組成物照射活性能⑽而成。 此里 上 又，本發明係有關於-種積層體，其係在表面上具有 述硬化膜所構成之硬塗層。 一 又’本發明係有關於一種光記錄媒體，其係由上述積 所構成’且硬塗層存在於光人射側之最表面上。 4 098113982 11 201000547 進而，本發明係有關於一種硬化膜之製造方法，其係藉由 旋塗法塗佈上述活性能量線硬化性樹脂組成物而形成塗 膜’在不經過使戎塗膜乾燥之步驟的情況下照射活性能量線 而形成硬化膜。 (發明效果） 本發明之活性能量線硬化性樹脂組成物雖然實質上不含 溶劑，但可根據塗佈方法進行寬廣範圍之黏度設定，並且因 硬化性優異故光聚合起始劑的用量較少，能夠於溫和條件下 利用活性能量線進行硬化，進而所得硬化膜之硬度及耐劃傷 性（耐磨性）良好。其結果，藉由將該活性能量線硬化性樹脂 組成物塗佈於光έ己錄媒體用之基板表面並使其硬化，而使今 光記錄媒體可具有優異的硬化性、耐劃傷性、透明性，進而 亦可提高該等性能之耐久性。特別是，本發明之活性能量線 硬化性樹脂組成物因硬化性良好，故可提供表面硬度較高之 硬塗層。 又’因實質上不含溶劑，故對未硬化之溶液之再利用亦容 易，而且因實質上不含易揮發的有機溶劑故環境負荷較小。 又，耐污染性（尤其是指纹污潰難以附著，即使萬一附著 亦可容易地拭去，其耐久性亦優異）非常優異，可提高製品 性能之耐久性。 因此，本發明可適用於光學物品（尤其是再生專用光碟、 光記錄光碟、磁光記錄光碟等光資訊媒體，或者如觸控面板 098113982 12 201000547 或液晶電視之光學顯示器用透明物品）、汽車相關零件（燈相 關、窗相關等物品（後窗、侧窗、天窗等））、生活相關物品（各 種電氣設備之殼體、裝飾板、傢具等）等廣泛物品之表面保 護，可作為各種物品之硬塗材料使用。 【實施方式】 以下’針對本發明之貫施形態加以詳細說明，但以下記載 之構成要件之說明係本發明實施態樣之代表例，本發明並不 f 限定於該等内容。 再者，於本說明書中，所謂（曱基）丙烯醯基，係指丙烯醯 基與曱基丙烯醯基之總稱。（甲基）丙烯酸、（曱基）丙烯酸酯 亦相同。 又，於本說明書中，所謂「〜」係以包括其前後所記載的 數值作為下限值及上限值之意義而使用。 [1 ]活性能量線硬化性樹脂組成物 G 本發明之活性能量線硬化性樹脂組成物係包含：分 子内具有1〜4個（甲基）丙烯醯基且25°C之黏度為1〜500 mPa.s之1〜4官能之（曱基）丙烯酸酯及/或（曱基）丙稀醯 胺、（B)特定之多官能（甲基）丙烯酸酯衍生物、（c)光聚合起 始劑、以及(D)具有特定結構之活性能量線硬化性化合物； 且25 C之黏度為10〜500 mPa · s，不含超過該組成物中之 5重量％之有機溶劑。 首先，就(A)〜（D)之各成分加以說明。 098113982 13 201000547 ⑷卜4個官能之（甲基)丙烯酸s旨及/或（曱基）丙稀酿胺 作為本發明活性能量線硬化性樹脂組成物中所含之成分 (A)即1〜4個官能之（甲基）丙婦酸 酯及/或（甲基）丙烯醯胺， 係1分子内具有1〜4個（甲基）肉馳基，且坑之黏度為 1〜50〇mPa.s之(曱基)丙浠酸酉旨及/或（甲基)丙稀酸胺。 關於成分(A)之黏度’為了將所得活性能量線硬化性樹脂 組成物_度調整為塗佈性優異之_定範圍，坑之黏度為 ImPa.s以上，較佳為以上，且為5〇〇mpa.s 以下，較佳為200 mPa · s以下。若為！ mPa · s以上，則不 會使活性能量線硬化性樹脂組成物的揮發性過高而浸入基 材’因而較佳，若為5〇〇 mPa · s以下，則可發揮如降低所 得組成物的黏度之效果’因而較佳。 作為成刀，只要為1分子内具有1〜4個（曱基）丙烯醯 土 之黏度為1〜5〇〇 mPa · s之（甲基）丙烯酸酯及/或 (甲基）丙烯醯胺，則並無特別限定，但就硬化性良好而言， 更仏為丙％酸|旨。 具體而言 可例示如以下者。 (1)單s %之（曱基）丙烯酸酯或（曱基）丙烯醯胺 作為單g能之（甲基）丙烯酸g旨或（曱基）丙烯醯胺，可舉出 ' C下為夜體且黏度為1〜500 mPa· s之1分子内具有1 個（曱基）丙歸酿基之（曱基）丙烯酸酯或（曱基）丙烯醯胺。具 體而言，例@ ^ 可舉出：（甲基）丙烯酸乙基己酯、（甲基）丙烯 098113982 14 201000547When the recording density is increased in the above manner, the spot diameter of the recording/reproducing light beam on the incident side surface of the recording/reproducing beam of the medium becomes small, so that the influence of fingerprints, dust, dust, and the like is particularly large. In particular, if the fingerprint contains organic matter, it may cause serious effects such as recording/reproduction errors and may be removed when the surface of the laser light incident on the incident side of the laser is contaminated. Therefore, it is necessary to take it. Countermeasures. Patent Documents 3 and 4, W. ό 济 济 济 济 济 济 济 济 济 济 济 济 济 济 济 济 济 济 济 济 济 济 济 济 济 济 济 济 济 济 济 济 济 济 济 济 济 济 济 济 济 济 济 济 济 济 济 济 济 济 济 济 济These hard coat films exhibit excellent fingerprint resistance. Patent Document 5 and Patent Document 6 disclose that a specific copolymer containing a specific polysecond group = group or a (meth)acrylic acid-reactive composition thereof is extremely effective, and the inventors have found that such a stain-resistant property is contained. The composition of the energy-curable resin of the bismuth agent is extremely excellent as a hard coat agent for a secondary dish. (1) Patent Document 1 Patent Document 1 Patent Document 1 Japanese Patent Publication No. _3_5 Chain Publication Patent Document 2: Japanese full-time publication and measurement No. 88 publication Patent Document 3: Japanese Patent Special Publication 〖524! 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 (Problems to be Solved by the Invention) However, the active energy ray-curable resin composition described in Patent Document 1 is in-line hard-coated, and therefore is suitable for coating at a temperature higher than room temperature. The process, but such a composition has a high viscosity at room temperature, and thus may not be suitable for a usual off-line (〇ff4ine) coating process. In the active energy ray-curable resin composition described in Patent Document 2, it is proposed to be suitable for the coating process in terms of viscosity and hardenability. However, since it is used as an adhesive, it is insufficient in hardness when used as a hard coat material. Not practical. The film formed by the composition (4) described in Patent Documents 3 and 4 exhibits excellent water extraction/oil extraction properties such as reduction in the fingerprint attachment diameter, but the fingerprint wiping property or durability is not sufficient. The reason for this is that although the coating layer is thin, it is about 2 ′. (IV) The energy ray-curable group does not have a sufficient film hardening property, or the skeleton of the stain resistance imparting agent itself has a relatively low hardness structure. In the conventional hard coat agent of the active energy ray-curable resin composition of the above-mentioned patent documents 5 and 6, the organic solvent contains an organic solvent, and in consideration of the effect of reducing the environmental load/unreacted (4), A thorough improvement is needed. The purpose of the present invention is to solve the above problems, and an object thereof is to provide an active energy ray-curable resin composition such as 098113982 201000547: although substantially free of a solvent, a viscosity setting corresponding to a wide range of coating methods can be performed. Moreover, since the photopolymerization initiator is used in a small amount because of its excellent hardenability, it can be hardened by the active energy ray under mild conditions, and the sclerosing (wear resistance) is good. In addition, it is an object of the present invention to provide a layered body having a hardened red hard coat layer on a hardened/silk surface which is formed by hardening such a composition, and further provided by the present invention. a cured film having high hardness, abrasion resistance, excellent durability, resistance to loss and stain resistance, and/or a laminate having a hard coat layer formed of the cured film on the surface, and an optical recording medium . (Means for Solving the Problem) The inventors of the present invention have made an effort to achieve the above object, and have found that by using an active energy ray-curable compound having a specific structure having stain resistance, it is selected and a specific one or two functions are selected. a specific combination of (meth) acrylate or (fluorenyl) acrylamide, a specific polyfunctional (fluorenyl) acrylate derivative, and a photopolymerization initiator which can be hardened with a relatively small amount of addition, Further, the active energy ray-curable resin composition having such an active energy ray-curable resin composition can be set to have a viscosity in accordance with various coating methods and is excellent in coatability, and the cured film of the composition is higher than that of the cured film. The present invention is highly polluting and has high hardenability, high hardness, and scratch resistance, and finally completes the present invention. That is, the present invention relates to an active energy ray-curable resin composition, 098113982 9 201000547 Containing the following (A), (B) '(C) and (Dl)' and at 25. (: viscosity of 10 to 500 mPa · s, characterized by: a polycarbonate film having a thickness of i mm Formed on a thickness of 3 / The coating film composed of the active energy ray-curable resin composition is used in a high-pressure mercury lamp having a illuminance of 400 mW/cm 2 at a wavelength of 254 nm under an oxygen concentration of 20%, and the cumulative light amount is reached. When the ultraviolet ray is irradiated in a manner of 1000 mJ/cm 2 , the blunt hardness of the surface of the cured film is B or more, and does not contain an organic solvent exceeding the weight % of the composition; (A) 1 to 4 molecules in one molecule (曱) Acryl fluorenyl group and having a viscosity of from 1 to 500 mpa · s of 1 to 4 functional (meth) acrylate, (meth) acrylamide or a mixture of the two: 10 to 70 (B) a polyfunctional (meth) acrylate other than (A) having 3 or more (fluorenyl) acryl fluorenyl groups in the molecule, and modified from a urethane modified ester or ester a polyfunctional (fluorenyl) acrylate derivative composed of one or more selected from the group consisting of a plastid and a carbonate modified body: 30 to 90 parts by weight; (C) Photopolymerization initiator: relative to (A) and (B) The total amount of 1 part by weight is 2 to 6 · 5 parts by weight; (D 1) 3⁄4 is from I-based oxycarbyl group, perfluoroalkyl group And an active energy ray-curable compound selected from the group consisting of one or more groups selected from the group consisting of a total amount of (0) to 15 parts by weight based on 100 parts by weight of the total of (A) and (B). Further, the present invention relates to an activity. An energy ray-curable resin composition containing the following (A), (B), and (D-3), characterized in that the viscosity at 098113982 10 201000547 at 25 ° C is 10 to 500 mPa · s, Excluding the organic solvent of the furnace; 3 more than 5% by weight of the (6) product (A) 1 to 4 (methyl) propyl groups in 1 molecule, and the viscosity under hunger is 1~500 mPa · s 1 to 4 in combination with A 匕 acrylamide: H) ~ 7. Parts by weight of (meth)acrylic acid vinegar and/or (B) l having more than 3 kinds of armor in the molecule, and the polypyridyl (f-) acrylate other than (Α) And self-reserving plastids, and carbonic acid _ body selection: one: acid B (four) body, change (methyl) propyl sense deputy (four) has a structure equivalent to the following structure of the live wire amount line hardening poly & This structure is one in which one or more (meth)acryloyl groups in one molecule are reacted with at least one group of a radical polymer of a monomer mixture containing a self-polymerized (tetra) group, Two or more bases selected from the group consisting of a fluoroalkyl group and an all-gas extension base: The epoxy group has the following principle: The total amount of (4) and (8) is 0.1 to 15 parts by weight. Further, the present invention relates to a cured film obtained by irradiating an active energy (10) onto the active site-hardening resin composition. Further, the present invention relates to a laminated body having a hard coat layer formed of a cured film on its surface. Further, the present invention relates to an optical recording medium which is constituted by the above-mentioned product and in which a hard coat layer is present on the outermost surface of the light incident side. Further, the present invention relates to a method for producing a cured film by applying the active energy ray-curable resin composition by a spin coating method to form a coating film 'without drying the ruthenium coating film. In the case of the step, the active energy ray is irradiated to form a cured film. (Effect of the Invention) The active energy ray-curable resin composition of the present invention contains substantially no solvent, but can be set in a wide range of viscosity according to the coating method, and the photopolymerization initiator is used in a small amount because of excellent curability. It can be hardened by an active energy ray under mild conditions, and the hardness and scratch resistance (wear resistance) of the obtained cured film are good. As a result, the active energy ray-curable resin composition is applied to the surface of the substrate for the optical recording medium and cured, whereby the optical recording medium can have excellent hardenability and scratch resistance. Transparency, in turn, can also improve the durability of these properties. In particular, since the active energy ray-curable resin composition of the present invention has good curability, it can provide a hard coat layer having a high surface hardness. Further, since the solvent is not substantially contained, it is easy to reuse the uncured solution, and the environmental load is small because it does not substantially contain a volatile organic solvent. Further, the stain resistance (especially, the fingerprint is hard to adhere, and it can be easily wiped off even if it is adhered, and the durability is excellent) is excellent, and the durability of the product can be improved. Therefore, the present invention can be applied to optical articles (especially optical information media such as a reproduction-only optical disk, an optical recording optical disk, a magneto-optical recording optical disk, or a transparent material such as a touch panel 098113982 12 201000547 or an optical display for a liquid crystal television), and an automobile related Surface protection of parts (lights, window related items (rear window, side window, sunroof, etc.)), life-related items (shells of various electrical equipment, decorative panels, furniture, etc.), etc., can be used as various items. Hard coating materials are used. [Embodiment] The following is a detailed description of the embodiments of the present invention, but the description of the constituent elements described below is a representative example of the embodiment of the present invention, and the present invention is not limited to the contents. Further, in the present specification, the term "fluorenyl" acrylonitrile refers to a general term for a fluorenyl group and a fluorenyl fluorenyl group. The same applies to (meth)acrylic acid or (mercapto) acrylate. In the present specification, the term "~" is used in the sense that the numerical values described before and after are used as the lower limit and the upper limit. [1] Active energy ray-curable resin composition G The active energy ray-curable resin composition of the present invention comprises: 1 to 4 (meth)acryl fluorenyl groups in the molecule and a viscosity of 1 to 500 at 25 ° C. 1 to 4 functional (mercapto) acrylate and/or (mercapto) acrylamide of mPa.s, (B) specific polyfunctional (meth) acrylate derivative, (c) photopolymerization initiation And (D) an active energy ray-curable compound having a specific structure; and a viscosity of 25 C of 10 to 500 mPa·s, and no organic solvent exceeding 5% by weight of the composition. First, each component of (A) to (D) will be described. 098113982 13 201000547 (4) Four functional (meth)acrylic acid s and / or (mercapto) acrylamide as a component (A) contained in the active energy ray-curable resin composition of the present invention, that is, 1 to 4 a functional (meth) propionate and / or (meth) acrylamide, having 1 to 4 (methyl) carcass in 1 molecule, and the viscosity of the pit is 1 to 50 〇 mPa. s (mercapto) propionate and/or (meth) acrylate. The viscosity of the component (A) is adjusted so that the obtained active energy ray-curable resin composition _ degree is excellent in coatability, and the viscosity of the pit is ImPa.s or more, preferably more than 5 Å. Preferably, 〇mpa.s is 200 mPa·s or less. If it is! When mPa · s or more, the volatility of the active energy ray-curable resin composition is not excessively apt to immerse in the substrate ′, which is preferable, and if it is 5 〇〇 mPa · s or less, the resultant composition can be reduced. The effect of viscosity is thus preferred. As the knives, (meth) acrylate and/or (meth) acrylamide having a viscosity of 1 to 5 〇〇mPa·s in 1 to 4 (fluorenyl) propylene bauxite in one molecule is used. Although it is not specifically limited, when it is good in hardenability, it is more preferable. Specifically, the following can be exemplified. (1) Single s % (mercapto) acrylate or (mercapto) acrylamide as a single g energy (meth)acrylic acid or (mercapto) acrylamide, which can be exemplified as 'C under night The compound having a viscosity of from 1 to 500 mPa·s has one (fluorenyl) acrylate (mercapto) acrylate or (fluorenyl) acrylamide. Specifically, the example @ ^ can be exemplified by ethyl (meth) acrylate and (meth) propylene 098113982 14 201000547

酸月桂醋、其環氧乙烷改質體等於25〇c下為液體之（曱基） 丙烯酸烷基酯；（曱基）丙烯酸苄酯、（甲基）丙烯酸苯基乙酯 等之於25°c下為液體之（曱基）丙烯酸芳烷基酯；丙烯酸三環 癸醋、（曱基）丙烯酸異冰片酯、（曱基）丙烯酸環己酯、其環 氧乙烧改質體等之於25〇c下為液體之具有脂環結構之丙烯 酸酉θ ’丙稀酸四氫糠酯、其氧化乙烯改質體等之於25°C下 為液體之具有含雜原子的環結構之丙烯酸酯；N -丙烯醯基咮 啉等之於25°C下為液體之丙烯醯胺衍生物；苯基環氧丙基 謎之丙烯酸加成物、環氧環己燒之丙烯酸加成物等之環氧丙 烯1自曰，末端為〇H之聚乙二醇單丙烯酸酯、末端為曱氧基 之聚乙二醇單丙烯酸酯、末端為苯氧基之聚乙二醇單丙烯酸 酉旨、末端為苯氧基之聚丙二醇單丙烯酸I旨等之聚烷二醇單丙 烯p ’聚己内6旨單丙烯酸轉之聚g旨㈣酸醋等。 〜轉杆之容易性、所形成硬化膜之表面硬度及透明 之特料活雜銳硬化輯缝尤其重要 脂環結槿2方面而S，較佳為魏二醇單丙烯酸Sl、具有 曰义、口 之單丙烯酸酯、且有含雜眉早夕 醋、聚己内gt /、有“原子之環結構之丙烯酸 醋、丙烯丙稀酸醋等;具體而言，較佳為丙烯酸環己 乙二醇單㊉衫§旨、丙烯酸四氫糠_、末端為苯氛基之聚 m2官< 歸酸醋、聚己内醋單丙烯酸酿。 (2)2 g月匕< 作為2官^丙烯 或（曱基）丙烯醯胺 S犯之（曱基)丙烯酸酉旨或（曱基)丙烯醒胺 ，可舉出 098113982 15 201000547 、 ，-站又‘、、1〜500 mPa.s之1分子内具有2 個（曱基）丙烯醯基之（曱基）丙烯酸醋或（甲基）㈣酿胺。且 體而言，例如可舉出：丁二醇二（甲基）丙稀㉖崎、己二醇^ (甲基）丙烯酸酯、新戊二醇二（甲基）丙烯酸唪、癸二醇二（甲 基）丙烯酸醋、以及該等之環氧燒改質物等之於25口為液 體之烷二醇二(甲基)丙烯酸醋；聚乙二醇二(甲基)丙烯： 醋、聚丙二醇二（甲基)丙烯酸自旨、聚丁二醇二（甲基)丙稀酸 醋等之於25X：下為液體之聚燒二醇二（甲基w烯酸i三環 癸烧二曱醇二（甲基）丙烯酸g旨等之於坑下為液體之具有 脂環結構之二（曱基）丙烯酸酿；烧乙二醇二（甲基）丙稀 酸s旨(例如日本化藥公q製造之KAYARAD r.)等於坑 下為液體之具有含雜原子之環結構之二（甲基）丙烯酸醋；二 乙氧基化雙1^ A之—（甲基）丙稀酸§旨等之於25。(：下為液體 之含有芳錢之二（甲基）㈣經單末端胺基改質之聚 乙:醇^單（甲基)丙烯酸醋單（甲基)丙烯酿胺、經末端胺基 貝κ乙一醇之雙（甲基）丙烯醯胺、經末端胺基改質之聚 丙二醇之雙（甲基）丙烯醯胺等。 八 就彳乂彳于之谷易度、所形成硬化膜之表面硬度及透明 性、^i兄特性等作為活性能量線硬化性樹脂組成物尤其重要 為良好方面而言，較佳為聚烷二醇二丙烯酸酯、具有 署構之一丙烯酸酯等，具體而言，較佳為丁二醇二丙烯 西允西匕 「▲ '. 夂曰—醇二丙烯酸酯、新戊二醇二丙烯酸酯、以及該等 098113982 16 201000547 環癸烷二甲醇二丙烯 之環氧乙烷改質物、 酸酯 号烷乙 二醇二丙婦酸酯。 3官能或4官能 (3)3官能或4官能之（甲|、 基）丙烯酸酯、或者 之（甲基）丙烯酿胺 作為3官能或4官# 月匕之（甲基）丙烯酸酯、或 官能之(甲基)丙烯醯胺，可舉出於25 S能或4 〜500 mPa.s之1分子内 ’、、、，夜體且勘度為i (甲基）丙烯酸酯或（甲基）而 ^ 烯醯基之 三鮮基城：（甲㈣:邊。具體而言，如可舉出： 凡一IT基）丙烯酸酯、季戊四 物之三或四（甲基）丙烯酸酯.-其 烷加成 成物之三或四㈣)丙稀酸二 烧加成物之單（甲基）丙_胺二（甲基）丙烯酸料之料乙 其就獲得之容易度、所形成硬化膜之表面硬度及透明 性、％ i兄特料作為活性能量線硬化性樹脂組成物尤其重要 之特性為良好方面而言，較佳為聚H丙烯酸§旨或聚烧 二醇四丙烯酸酯，具體而言，較佳為三羥曱基丙烷三丙烯酸 酉曰其％氣乙烧加成物、季戊四醇三丙稀酸g旨或四丙稀酸酉旨 之環氧乙烷加成物、於25°C之黏度為1〜500 mPa · S之二 季戊四醇四丙烯酸酯之環氧乙烷加成物。 如上所述，作為可用於本發明活性能量線硬化性樹脂組成 物之尤佳之成分(A)，可舉出聚烷二醇之單丙烯酸酯、二丙 烯酸酯、三丙烯酸酯、四丙烯酸酯。該等係所得組成物之親 098113982 17 201000547 水/親油平衡控⑽面為優異，㈣在祕光⑽媒體之硬 塗層的情況下’有助於提升由於水所造成的光記錄媒體之記 錄膜的劣化及硬倾表面的耐污染性下降等光㈣之 環境财受性，因而較佳。又，該等成分(Α)容易獲得，從而 可廉價地獲躲性能量線硬化性觸組成物，因而較佳。 另-方面，在所得活性能量線硬化性樹脂組成物需要尤其 高之硬化性的情況下’於上述⑴及⑺之（甲基）丙烯酸醋或 (甲基）丙烯醯胺中，較佳為使用具有易受到奪氫之含有活性 氫原子等的結構、或者含有氮原子的結構之特定化學結構之 1或2官能之（曱基）丙烯酸酯或者丨或2官能之（曱基）丙烯 醯胺。作為此種（甲基）丙烯酸酯或者（甲基）丙烯醯胺，具體 可舉出下述(i)〜（iii)。 ⑴一種（甲基）丙烯酸酯，其係丨分子内具有丨個（曱基）丙 烯醯基者，且與該（曱基）丙烯醯基鍵結之氧原子上，直接鍵 結或者經由0；-位碳或β -位碳而鍵結有自（聚）環院基、（聚） 環烯基、羥烷基、環狀醚基、及（聚)環氧烷基中選擇之丨個； (i)係1分子内具有1個（曱基）丙烯醯基之（甲基）丙烯酸 酉曰，其具有如下結構：與該（曱基）丙烯醮基鍵結之氧原子 上，直接鍵結或者經由位碳或石-位碳而鍵結有自（聚）環 烷基、（聚)環烯基、羥烷基、環狀醚基、及（聚)環氧烷基中 遥擇之1個。具有該等結構之（曱基）丙烯酸酯的硬化性良 好，因而較佳，更佳為丙烯酸酯。 098113982 18 201000547 产说基、(聚)環婦基、經燒基、環狀_基、⑼ =有只_結或者經由—= 於⑴所具有之1個（甲 』硬、、，口 可。此處，當存在丨個二個^鍵結之氧原子上即 基的氧魏氧:祕 稱一，= ⑻„ 孝冉為經由α -位礙❹-位碳而鍵社。 :钱基或⑻環稀基只要為環狀之餘麵基則並^ 生i 2 ’碳數只要為3以上即可，但就與其他成分 =::::::::τ又，自㈣環 =以之結構相崎，尤佳㈣度地對環施加變 形之壞歧環、環己垸環# 5〜6 Μ環、以及三環癸燒产、 金剛烧環等5〜6員環進行縮環而成之結構。 ^ 在(丨)具有（聚)環烧基或（聚)環烯基的情況下，較佳為直接 鍵結或者經由α _位碳而鍵結於氧原子上之結構。 舰基只要為具有1似上隸之碳數為1以上之院基， 則並無特難^，減（f細馳自旨單赌訂的穩定性 及硬化性均良好方面而言，較佳為在氧原子與經燒基之間存 在1個或2個碳原子，更佳為1個。 作為羥基烷基，烷基之碳數較佳為1或2。即，較佳為羥 曱基或羥乙基。 又，在(i)具有羥烷基的情況下，較佳為直接鍵結或者經由 098113982 19 201000547 u碳而鏠結於氧原子上。 隶仏為石炭數1， 作為環狀心於氧原子上。 無特別限定，& , ‘，、、％狀且其裱内含有醚基之結構則並 佳為5以下。1佳為石反數為2以上’ ^較佳為以下，更 碳數為3之:二體而言’例如可舉出：碳數為2之環氧基、 碳數為5之四Γ坑基、兔數為4之四氫吱喃基、二概基、 喃基、二^^㈣基。其中’亦較佳為三号烧基、四氫吱 芡基、四氫哌喃基。 又’在(i)l右 由α·位^鍵_為直接鍵結或者經 作為(聚)料私/。衫 限定，但就（ΨΑ、/、要為八有乳原子之烧基則並無特別 VT I)丙烯酸酯單 良好方面w，純為在均 之間存在1〜3輪子1 子紙)W谢的氧原子 氧烧基的碳原子端鍵結於〜甲:本:：中，通常使用環 子、或者⑽、―ΙΓ合物咖'结的氧原 (聚)環氧烧基之妓較佳為碳數為卜6，更 或二即，.較佳為(聚)環氧乙絲、（聚)環氧丙烧基。 者經二況下，較佳為直接鍵結或 隶佳為碳數為2之（平彳& 上述（聚舰基、元基直接鍵結於氧原子上。 098113982 (糸基、羥烷基、環狀醚基及（聚) 20 201000547 環氧烷基均可具有取代基。作為取代基，並無特別限定，但 較佳為分子量為15〜350。又，取代基可為鏈狀亦可為環 狀，亦可含有氧原子、氮原子等。作為取代基之具體例，可 舉出：曱基、乙基、丁基、曱氧基、乙氧基、丁氧基、曱氧 基乙基、乙氧基乙基、丁氧基乙基、環己基、三環癸基、苯 基、苄基、二曱胺基乙基、二曱胺基丙基、四氫呋喃基、四 氫哌喃基等。尤佳為曱基、乙基、曱氧基、乙氧基、曱氧基 乙基。 作為（i)，只要具有如上述之結構則並無特別限定，具體而 言，例如可舉出：（曱基）丙烯酸環己酯、（曱基）丙烯酸環戊 酯、（曱基）丙烯酸環己基甲酯、三環癸烷單（曱基）丙烯酸酯、 (曱基）丙烯酸金剛烷基酯、環氧環己烷之（曱基）丙烯酸加成 物、三環癸烷曱醇（曱基）丙烯酸酯、（曱基）丙烯酸金剛烷曱 酯、（曱基）丙烯酸環己基乙酯、三環癸烷乙醇單（曱基）丙烯 酸酯、丙烯酸環氧環己烷基甲酯等之具有（聚）環烷基之（曱基) 丙烯酸酯；三環癸烯單（曱基）丙烯酸酯、三環癸烯曱醇（曱基） 丙烯酸酯、三環癸烯乙醇單（曱基）丙烯酸酯等之具有（聚）環 烯基之（曱基）丙烯酸酯；（曱基）丙烯酸羥乙酯、（曱基）丙烯 酸3-苯氧基-2-羥丙酯、（曱基）丙烯酸3-曱氧基-2-羥丙酯等 之具有羥烷基之（曱基）丙烯酸酯；（曱基）丙烯酸四氫糠酯、 (曱基）丙稀酸四氫吱喃酯、甘油醇縮丙酿l(solketal)單（曱基） 丙烯酸酯、4-(曱基）丙烯醯氧基乙基四氫哌喃等之具有環狀 098113982 21 201000547 醚基之（甲基）丙烯酸酯；（曱基）丙烯酸甲氧基甲酯、聚乙二 醇單⑶基）丙烯酸酯、聚丙二醇單（甲基）丙㈣請1及該 等之末端-甲氧化物、末端-笨氧化物、（甲基）丙稀酸曱氧基 乙醋、（曱基）丙烯酸乙氧基乙酯、（甲基）内歸酉楚丁氧基乙醋、 乙氧化三環魏曱醇單（甲基）丙烯酸能、數量平均分子量為 ⑼〜500之聚乙二醇單（曱基）丙烯酸_、以及其…末端之 烧基、苯基取代物等之具有⑻環氧燒基之（曱基）丙稀義 等。 其中，就硬化性及獲得之容易性方面而言，較佳為丙稀酸 環己醋、三環癸烯單丙烯賴、三環癸境單丙稀動旨、丙稀 酸3-苯氧基_2_經乙醋、聚乙二醇單丙稀酸酿、以及該等之 末端-甲氧化物、末端-苯氧化物、丙烯酸甲氧基乙醋、丙烯 酸四氫糠酯、丙職四氫㈣自旨，尤佳為三環魏單丙稀酸 醋、聚乙二醇單丙輪、以及該等之末端-甲氧化物、末 端苯氧化物、丙_甲氧基乙_、丙_四氯糖醋。 (")-種(甲基)丙稀酸S旨’其係i分子内具有2個(甲基)丙 烯醯基者，且在鍵結於至少任意—個（甲基)丙烯醯基上之氧 原子上，直接鍵結或者經由^位碳❹·位碳而鍵結有自（聚) 伸裱烷基、（聚)伸環烯基、羥基伸烷基、環狀醚基、（聚)環 氧烷基中選擇之1個； (II)係1分子内具有2個（曱基）丙烯醯基之（曱基）丙烯酸 S曰，且具有如下結構··在鍵結於至少任意一個（甲基）丙烯醯 098113982 22 201000547 基上之氧原子上，直接鍵結或者經由位碳或位碳而鍵 …有自（ΛΚ)伸環烧基、（聚）伸環稀基、經基伸烧基、環狀鍵 基及（聚）環氧烷基中選擇之1個。若為具有該等結構之（甲基) 丙烯酸酯，則硬化性良好因而較佳，更佳為丙烯酸酯。 關於（聚)伸環烷基、（聚）伸環烯基、羥基伸烷基、環狀醚 基（水）環氧烧基，只要直接鍵結或者經由α _位碳或石-位 碳而鍵結於與(I丨)所具有的2個（曱基）丙烯醯基中的至少任 {意一個鍵結之氧原子上即可，亦可直接鍵結或者經由α-位 碳或/3-位碳而鍵結於與2個（曱基）丙烯醯基鍵結之兩個氧 原子上。 作為（聚)伸環烷基或（聚）伸環烯基，只要為環狀之伸烷基 或伸烯基則並無特別限定，碳數只要為3以上即可，較佳為 5以上，更佳為6以上，且較佳為2〇以下，更佳為μ以下。 具體而言，例如可舉出：伸環己基、三伸環癸基、五伸環十 (,>五基等。 在00具有（聚)環烷基或（聚)伸環烯基的情況下，較佳為直 接鍵結或者經由位碳而鍵結於氧原子上之結構。 羥基伸烷基只要為具有丨個以上羥基之碳數為 1以上之伸 烧基則並無特別限定，但就（甲基)丙婦酸醋單獨情況下的穩 疋!·生及硬化均良好方面而言，較佳為在氧原子與經基伸烧 基之間存在1個或2個碳原子，更佳為1個。 作為絲伸燒基，較佳為伸燒基之碳數為工或2。又，在 098113982 23 201000547 ⑻具有經基伸燒基的情況下，較佳為直接鍵結或者經由『 位碳而鍵結於氧原子上。最佳為碳數為2之縣伸烧基直接 鍵結於氧原子上。 關於環狀醚基、（聚）環氧烷基，與上述(丨)之情形相同。 (聚）伸裱烷基、（聚）伸環烯基、羥基伸烷基、環狀醚基及（聚） 環氧烧基均可具有取代基。作為取代基，較佳情形與⑴相同。 作為（II) ’只要具有如上述之結構則並無特別限定，具體 而言，例如可舉出：三環癸烧二曱醇二（曱基）丙烯酸1 = 環癸烷二(曱基)丙烯酸酯、環己烷二曱醇二(曱基)丙烯酸 酉旨、環己烧二乙醇二（曱基）丙烯酸醋等之具有（聚)伸環烷基 之（曱基）丙烯酸酯，二（曱基）丙烯酸伸環己烯基酯、二（曱美） 丙稀酸三伸環癸稀基1旨、三環癸稀二甲醇二（甲基）丙稀酸土醋 等之具有（聚）伸環烯基之（曱基）丙烯酸酯；丨，^二環氧己二曰 之（曱基)丙稀酸加成物等之具有經基伸炫基之（曱基）兩稀= 酉旨；異山梨醇二（甲基)丙婦酸酉旨、2,6_二（曱基）丙歸酸氧基甲义 基四氫哌喃、3,5-二（曱基）丙烯醯氧基乙基四氫哌喃等呈 有環狀醚基之（曱基）丙烯酸酯；聚乙二醇二 之具 ^ , 一、〒基）丙烯酸 酯、乙氧化丁二酵一（曱基）丙烯酸酯、乙氧化己二醇二（曱 丙稀酸酉旨、6氧化三環癸烧二甲醇二（甲基）丙稀酸:基） 二曱氧基-1，6-己一醇二（甲基）丙烯酸酯、數量平均八子s ' 150〜500之聚乙二醇二（曱基）丙烯酸酯等之具有（^)=量為 基之（曱基）丙烯酸酯等。 A 1 长氧燒 098113982 24 201000547 L更化性及獲得之容易性等方面而言，較佳為三環 y f醇—丙婦酸自旨、聚乙二醇二丙烯酸醋、乙氧化丁二 和-丙稀酸g旨、乙氧化已二醇二丙婦酸自旨，尤佳為三環癸競 二’醇二丙烯酸酯、聚乙二醇二丙烯酸酯、乙氧化己二醇二 丙烯酸酯。 (i i ·) X 分子内具有1個或2個（甲基）丙烯醯基之（甲基） ㈣胺’且鍵結於（甲基）丙朗基上之胺基被2個 ¢-/U 厂贫士 、2個烧基可直接鍵結或者經由雜原子而鍵結）。 (1分子内具有丨個或2個（甲基）丙烯醯基之（曱基） 烯▲胺，且具有鍵結於（甲基）丙烯醯基上的胺基被2個烷 基取代之結構。其中，2個烷基可直接鍵結或者經由雜原子 °若為具有該等結構之（曱基）丙稀醯胺，則硬化性良 好因而較佳，更佳為丙烯醢胺。 被2個烷基取代之胺基中之烷基並無特別限定，在2個烷 V.基不相互鍵結的情況下，就硬化性優異方面而言，較佳為分 另J為兔數2以下之烧基。更佳為2個均為甲基。 又，在2個烷基相互鍵結的情況下，2個烷基之碳數總和 較佳為2以上，且較佳為10以下，更佳為6以下。進^， 作為經由雜原子而鍵結的情況下之雜原子，例如可舉出氧原 子、氮原子、硫原子；其中較佳為氧原子。 、 :為（iii) ’只要具有如上述之結構則並無特別限定，具體 而。例如可舉出：Ν,Ν-二甲基（曱基）丙烯醯胺、N，N-二乙 098113982 25 201000547 基（曱基）丙烯醯胺、亞曱基雙（甲基）丙烯醯胺之N,N，-二曱基 體、Ν-(甲基）丙烯醯基咮啉、Ν-(曱基）丙烯醯基吼咯啶、Ν-(甲 基）丙烯醯基哌啶等。其中，就硬化性及獲得之容易性等方 面而言’較佳為Ν，Ν-二甲基丙烯醯胺、Ν-丙烯醯基咮啉。 在使用上述⑴〜（iii)之（曱基）丙烯酸酯或（曱基）丙烯醯胺 作為成分(A)的情況下，硬化性尤其優異，進而所得硬化膜 之硬度及耐劃傷性（对磨性）為良好。其結果，由所得活性能 量線硬化性樹脂組成物所構成之硬塗層可具有優異的硬化 性、耐劃傷性、透明性，進而亦可提高該等性能之耐久性。 (B)多官能基（甲基）丙烯酸酯衍生物 本發明活性能量線硬化性樹脂組成物中所含之成分(B)即 多官能基（甲基）丙稀酸醋衍生物，係1分子内具有3個以上 (曱基）丙烯醯基之由（A)以外之多官能（曱基）丙烯酸酯衍生 物及自其胺基曱酸乙酯改質體、酯改質體及碳酸酯改質體中 選擇之一種以上所構成。 關於成分(B) ’就易於將所得活性能量線硬化性樹脂組成 物之黏度调整為塗佈性優異之一定範圍而言，較佳為2 5 之黏度為50 mPa · s以上、更佳為60 mPa · s以上，且較佳Acid laurel vinegar, its ethylene oxide modified body is equal to liquid (mercapto) alkyl acrylate at 25 〇c; benzyl (meth) acrylate, phenyl ethyl (meth) acrylate, etc. At °c, it is a liquid (fluorenyl) aralkyl acrylate; acrylic tricyclic vinegar, (mercapto) isopropyl isobornyl ester, (fluorenyl) hexyl hexyl acrylate, its epoxy ethene modified body, etc. Acrylic acid having an alicyclic structure of yttrium θ 'acrylic acid tetrahydrofurfuryl ester having an alicyclic structure at 25 ° C, an oxyethylene modified body thereof, etc., having a hetero atom-containing ring structure at 25 ° C An acrylamide derivative which is a liquid at 25 ° C, such as an N-acryloyl porphyrin; an acrylic acid addition product of a phenyl epoxy propyl group; an acrylic acid addition product of an epoxy ring hexane, etc. Epoxy propylene 1 self-twisting, polyethylene glycol monoacrylate with 末端H at the end, polyethylene glycol monoacrylate with a terminal methoxy group, polyethylene glycol monoacrylate with a terminal phenoxy group, and terminal Polypropylene glycol monoacrylic acid, which is a phenoxy group, a polyalkylene glycol monoacrylic acid, etc. Purpose (four) sour vinegar and so on. The ease of the rod, the surface hardness of the formed cured film, and the transparent special material, the hard-cured seam is particularly important in terms of the alicyclic crucible 2, preferably the Weidiol monoacrylic acid S1, which has a derogatory meaning. The mono-acrylate of the mouth, and the yoghurt containing miscellaneous eyebrows, polyglycol gt /, acryl vinegar having a ring structure of atoms, acrylic acetonic acid vinegar, etc.; specifically, preferably cyclohexyl acrylate Alcohol single ten shirt §, tetrahydroanthracene acrylate _, the end of the benzene group of poly m2 official < vinegar, poly propylene vinegar monoacrylic brewing. (2) 2 g 匕 匕 lt; Or (mercapto) acrylamide S (meth) acrylic acid or (mercapto) acrylamide, 098113982 15 201000547, , - station and ', 1 to 500 mPa.s of one molecule There are two (fluorenyl) acrylonitrile-based (fluorenyl) acrylate vinegars or (meth) acrylamides, and the body is, for example, butanediol di(methyl) propylene sulphate, Hexanediol^(meth)acrylate, neopentyl glycol di(meth)acrylate, decanediol di(meth)acrylic acid vinegar, and the epoxy modification of these The substance is equal to 25 liquid alkanediol di(meth)acrylic acid vinegar; polyethylene glycol di(meth) propylene: vinegar, polypropylene glycol di(meth)acrylic acid, polytetramethylene glycol Methyl)acrylic acid vinegar or the like at 25X: a liquid polyalkylene glycol diol (methyl keonic acid i tricyclic oxime bismuth diol di(meth) acrylate g is equivalent to a liquid under the pit The bis(indenyl)acrylic acid having an alicyclic structure; the burning of ethylene glycol di(meth)acrylic acid s (for example, KAYARAD r. manufactured by Nippon Kayaku K.) is equal to the liquid containing impurities in the pit. Atomic ring structure of the two (meth)acrylic acid vinegar; diethoxylated double 1 ^ A - (meth) acrylic acid § is equivalent to 25. (: the next liquid contains the second money ( Methyl) (iv) Poly(ethylene) modified by a single-end amine group: alcohol, mono (meth) acrylate acetonic (meth) acrylamide, bis(meth) acrylamide via terminal amine benzyl alcohol A bis(meth) acrylamide which is modified by a terminal amine group, such as propylene glycol, etc. VIII is easy to use, the surface hardness and transparency of the formed cured film, the characteristics of the brother, etc. It is particularly important that the active energy ray-curable resin composition is a polyalkylene glycol diacrylate, a acrylate having a constitution, etc., and particularly preferably a butanediol dipropylene propylene.允西匕 "▲ '. 夂曰-alcohol diacrylate, neopentyl glycol diacrylate, and 098113982 16 201000547 cyclodecane dimethanol dipropylene ethylene oxide modification, acid ester Alcohol dipropionate. A trifunctional or tetrafunctional (3) trifunctional or tetrafunctional (methyl) acrylate, or a (meth) acrylamide as a trifunctional or 4-member Methyl) acrylate, or functional (meth) acrylamide, which can be exemplified by 25 S energy or 4 to 500 mPa.s in 1 molecule, ',,, night body and degree i (methyl) ) Acrylate or (methyl) and ^ olefin based on the three fresh base city: (A (four): side. Specifically, for example, an IT-based acrylate, a tetrakis or a tetrakis (meth) acrylate of a pentaerythrine, a three or four (four) alkane addition product thereof, and a second acrylic acid The addition of the mono(methyl)propyl-amine di(meth)acrylic acid material of the adduct is easy to obtain, the surface hardness and transparency of the formed cured film, and the % i-species as the active energy ray hardening Particularly important characteristics of the resin composition are, in terms of good terms, poly-acrylic acid acrylate or polyalkylene glycol tetraacrylate, and specifically, trishydroxypropyl propane triacrylate is preferred. Ethylene burn adduct, pentaerythritol triacrylic acid g or tetrapropyl acid oxime ethylene oxide adduct, viscosity at 25 ° C is 1~500 mPa · S dipentaerythritol tetraacrylate ring Oxyethane adduct. As described above, as a component (A) which is particularly preferably used as the active energy ray-curable resin composition of the present invention, monoacrylate, diacrylate, triacrylate or tetraacrylate of polyalkylene glycol can be mentioned. The pro- 098113982 17 201000547 water/lipophile balance control (10) surface is excellent, and (4) in the case of the hard coating of the secret light (10) media, which helps to improve the recording of optical recording media caused by water. It is preferable that the film is deteriorated and the stain resistance of the hard-tilted surface is lowered, such as environmental benefits of light (4). Further, since these components (Α) are easily obtained, the energy ray-curable touch composition can be obtained at a low cost, which is preferable. On the other hand, in the case where the obtained active energy ray-curable resin composition requires particularly high hardenability, it is preferably used in (meth)acrylic acid vinegar or (meth)acrylamide in the above (1) and (7). A 1- or 2-functional (fluorenyl) acrylate or a fluorene- or 2-functional (fluorenyl) acrylamide having a specific chemical structure which is susceptible to hydrogen abstraction and contains a structure of an active hydrogen atom or the like, or a structure containing a nitrogen atom. Specific examples of the (meth) acrylate or (meth) acrylamide include the following (i) to (iii). (1) a (meth) acrylate having a fluorene (fluorenyl) propylene fluorenyl group in the molecule, and bonded directly to the oxygen atom bonded to the (fluorenyl) propylene sulfhydryl group or via 0; a carbon or a β-position carbon bonded to one selected from the group consisting of a (poly) ring, a (poly)cycloalkenyl group, a hydroxyalkyl group, a cyclic ether group, and a (poly)alkylene oxide group; (i) is a (meth)acrylic acid fluorene having one (fluorenyl) acrylonitrile group in one molecule, which has a structure in which a direct bond is bonded to an oxygen atom bonded to the (fluorenyl) acrylonitrile group. Or via a carbon or a rock-site carbon bonded to a (poly)cycloalkyl group, a (poly)cycloalkenyl group, a hydroxyalkyl group, a cyclic ether group, and a (poly)alkylene group. One. The (fluorenyl) acrylate having such a structure is preferably excellent in curability, and more preferably an acrylate. 098113982 18 201000547 Produced base, (poly) ring base, burnt base, ring base, (9) = only _ knot or via -= one of (1) (A) is hard, and can be used. Here, when there are two oxygen bonds on the oxygen atoms of the two bonds, the oxy-oxygen is called the first one, = (8) „ 冉 is the α-positional carbon via the α-position. (8) As long as the ring-like base is a ring-shaped base, and the number of carbon atoms is only 3 or more, it is equivalent to other components =::::::::τ, and (four) ring = The structure of Azaki, Yu Jia (four) degrees of deformation of the ring to the deformation of the ring, ring 垸 垸 ring # 5~6 Μ ring, and the three ring 癸 产, the diamond ring and other 5~6 member ring is condensed In the case where (丨) has a (poly)cycloalkyl group or a (poly)cycloalkenyl group, it is preferably a structure which is directly bonded or bonded to an oxygen atom via an α-position carbon. As long as it has a court base having a carbon number of 1 or more, it is not particularly difficult, and it is preferable that the stability and the hardenability are good. One or two carbons between the oxygen atom and the burned group More preferably, the number of carbon atoms of the alkyl group is preferably 1 or 2. That is, it is preferably a hydroxymethyl group or a hydroxyethyl group. Further, in the case of (i) having a hydroxyalkyl group Preferably, it is directly bonded or entangled on the oxygen atom via 098113982 19 201000547 u carbon. The enthalpy is a charcoal number 1, as a ring-shaped heart on the oxygen atom. No particular limitation, & , ',,, The structure having an ether form and having an ether group in the oxime is preferably 5 or less. 1 is preferably an inverse number of 2 or more '^ is preferably below, and the number of carbon atoms is 3: for the two bodies, for example, : an epoxy group having 2 carbon atoms, a 4 decyl group having a carbon number of 5, a tetrahydrofuranyl group having a rabbit number of 4, a dibasinyl group, a decyl group, and a bis(4) group. No. 3 alkyl, tetrahydroindenyl, tetrahydropyranyl. Also 'in (i) l right by α · position ^ bond _ for direct bonding or as (poly) material private / shirt limited, but (ΨΑ, /, to be a base with eight milk atoms, there is no special VT I) acrylate single good aspect w, purely between 1 to 3 wheels 1 sub-paper) W Xie oxygen atomic oxygen The carbon atom of the alkyl group is bonded to the armor: In the following, it is preferred to use a ring, or (10), a conjugate of an oxo (poly) epoxy group, preferably having a carbon number of 2.6, more or two, preferably ( Poly)ethylene oxide, (poly) epoxy propyl group. In the case of two conditions, it is preferably a direct bond or a good carbon number of 2 (flat 彳 & above (poly ship base, yuan base Directly bonded to an oxygen atom. 098113982 (fluorenyl group, hydroxyalkyl group, cyclic ether group, and (poly) 20 201000547 The alkylene oxide group may have a substituent. The substituent is not particularly limited, but is preferably The molecular weight is 15 to 350. Further, the substituent may be in the form of a chain or a ring, and may contain an oxygen atom, a nitrogen atom or the like. Specific examples of the substituent include a mercapto group, an ethyl group, a butyl group, a decyloxy group, an ethoxy group, a butoxy group, a decyloxyethyl group, an ethoxyethyl group, and a butoxyethyl group. Cyclohexyl, tricyclodecyl, phenyl, benzyl, dimethylaminoethyl, dimethylaminopropyl, tetrahydrofuranyl, tetrahydropyranyl and the like. More preferably, it is an anthracenyl group, an ethyl group, a decyloxy group, an ethoxy group or a decyloxyethyl group. (i) is not particularly limited as long as it has the above-described structure, and specific examples thereof include (cycloalkyl)cyclohexyl acrylate, cyclopentyl (meth) acrylate, and (fluorenyl) acrylate ring. Hexylmethyl ester, tricyclodecane mono(indenyl) acrylate, adamantyl (mercapto) acrylate, (cyclo)acrylic acid adduct of epoxycyclohexane, tricyclodecane decyl alcohol Acrylate, (adadenyl)adamantyl decyl acrylate, (decyl)cyclohexylethyl acrylate, tricyclodecaneethanol mono(indenyl) acrylate, epoxycyclohexyl methacrylate, etc. Poly(cycloalkyl) acrylate; tricyclodecene mono(indenyl) acrylate, tricyclic terpene sterol (fluorenyl) acrylate, tricyclodecene ethanol mono(indenyl) acrylate (()-(cyclo)acrylic acid ester of (poly)cycloalkenyl; hydroxyethyl (meth) acrylate, 3-phenoxy-2-hydroxypropyl (meth) acrylate, 3-(meth)acrylic acid (mercapto) acrylate having a hydroxyalkyl group such as decyloxy-2-hydroxypropyl ester; Hydroquinone ester, (mercapto) methic acid tetrahydrofurfuryl ester, glycerol solketal mono(indenyl) acrylate, 4-(indenyl) propylene oxiranyl ethyl tetrahydropyran Etc. with ring 098113982 21 201000547 ether-based (meth) acrylate; (mercapto) methoxy methacrylate, polyethylene glycol mono (3) acrylate, polypropylene glycol mono (methyl) propyl (four) 1 and the ends - such as methoxide, terminal - stupid oxide, (meth) acrylate methoxy acetate, (mercapto) ethoxyethyl acrylate, (methyl) guilty Ethyl acetoacetate, ethoxylated tricycloteranol mono(meth)acrylic acid, polyethylene glycol mono(indenyl)acrylic acid having a number average molecular weight of (9) to 500, and a phenyl group at the end of the phenyl group The substituent or the like has (8) an alkyl group of an epoxy group, and the like. Among them, in terms of hardenability and ease of availability, it is preferably cyclohexyl acrylate, tricyclodecene monopropene, tricyclic dimethicone, and 3-phenoxy acrylate. _2_ brewed with vinegar, polyethylene glycol monoacrylic acid, and the terminal-formaldehyde, terminal-phenoxide, methoxyethyl acrylate, tetrahydrofurfuryl acrylate, and tetrahydrogen (4) From the purpose, especially for the three-ring Wei single acrylic acid vinegar, polyethylene glycol single-propane wheel, and the terminal - methoxide, terminal phenoxide, propyl methoxy _, propyl _ four Chlorohydrate. (")-(Meth)acrylic acid S is intended to have two (meth) acrylonitrile groups in the molecule i, and is bonded to at least any one (meth) acrylonitrile group On the oxygen atom, directly bonded or via a carbon-position carbon, a (poly)alkylene group, a (poly)cycloalkenyl group, a hydroxyalkylene group, a cyclic ether group, (1) one selected from the group consisting of epoxyalkyl groups; (II) is a (fluorenyl)acrylic acid S曰 having two (fluorenyl) acrylonitrile groups in one molecule, and has the following structure: (Methyl) propylene 醯 113 113 113 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯One of the group, the cyclic bond group, and the (poly)alkylene oxide group. In the case of the (meth) acrylate having such a structure, the curability is good, and it is preferably an acrylate. Regarding (poly)cycloalkylene, (poly)cycloalkenyl, hydroxyalkylene, cyclic ether (water) epoxy alkyl, as long as it is directly bonded or via alpha _ carbon or stone carbon Bonding to at least one of the two (indenyl) acrylonitrile groups (I丨) may be bonded to an oxygen atom, or may be directly bonded or via an α-position carbon or /3 - Carbon is bonded to two oxygen atoms bonded to two (fluorenyl) acrylonitrile groups. The (poly)cycloalkylene group or the (poly)cycloalkenyl group is not particularly limited as long as it is a cyclic alkyl group or an alkenyl group, and the number of carbon atoms is preferably 3 or more, preferably 5 or more. More preferably, it is 6 or more, and is preferably 2 inches or less, more preferably μ or less. Specific examples include, for example, a cyclohexylene group, a tri-extended ring fluorenyl group, a penta-extension ring hexa group, a penta-5 group, etc., in the case where 00 has a (poly)cycloalkyl group or a (poly)cycloalkenyl group. In the following, it is preferably a structure in which a direct bond or a bond to an oxygen atom is bonded via a carbon. The hydroxyalkyl group is not particularly limited as long as it has a carbon number of 1 or more and has a carbon number of 1 or more. In the case of (meth) propyl acetoacetate alone, it is preferable that the raw material and the hardening are good, preferably one or two carbon atoms are present between the oxygen atom and the base-based alkyl group, and more preferably Preferably, the number of carbon atoms of the stretching base is 2 or 2, and in the case of having a base stretching base, it is preferably direct bonding or via "bit". Carbon is bonded to the oxygen atom. It is optimal that the carbonic acid number of the county is directly bonded to the oxygen atom. Regarding the cyclic ether group, the (poly)alkylene group, and the above (丨) The same may be substituted for the (poly)alkylene group, the (poly)cycloalkenyl group, the hydroxyalkylene group, the cyclic ether group, and the (poly)alkylene group. The substituent is preferably the same as (1). The (II) ' is not particularly limited as long as it has the structure as described above, and specific examples thereof include tricyclic anthracyl diacetate bis(indenyl)acrylic acid. 1 = cyclodecane bis(indenyl) acrylate, cyclohexanedimyl bis(indenyl) acrylate, cyclohexanyl diethanol bis(indenyl) acrylate, etc. (Mercapto) acrylate, bis(indenyl)acrylic acid cyclohexenyl ester, bis(combined) acrylic acid tri-extension ring 癸1, tricyclic hydrazine dimethanol di(methyl) propyl a (poly)cycloalkenyl (indenyl) acrylate such as dilute acid vinegar; or a fluorenyl hexamethylene acrylate derivative having a base group (曱基) two dilute = 酉 ;; isosorbide di(methyl) propyl benzoate, 2,6-di(indenyl)propanoic acid methoxymethylidene tetrahydropyran, 3,5- Di(indenyl) acryloxyethyltetrahydropyran or the like having a cyclic ether group (mercapto) acrylate; polyethylene glycol bis, ^, fluorenyl acrylate, ethoxylated Two leave one (Mercapto) acrylate, hexylene glycol ethoxylate di(anthracene acid, 6 oxidized tricycloanthracene dimethanol di(methyl)propionic acid: yl) dimethoxy-1,6-hexyl (Alkenyl) acrylate having a (^)= amount, such as a monohydric bis(meth) acrylate, a polyethylene bis(indenyl) acrylate having an average number of s' 150 to 500 Å. A 1 long-oxygen burning 098113982 24 201000547 L is more preferable in terms of beautification and ease of obtaining, etc., preferably tricyclic yf alcohol - propyl ketone, polyethylene glycol diacrylate vinegar, ethoxylated dibutyl and Acetic acid g, ethoxylated diol dipropylene acetoin from the purpose, especially preferably tricyclic 癸 二 二 'alcohol diacrylate, polyethylene glycol diacrylate, ethoxylated hexanediol diacrylate. (ii.) The (meth)(tetra)amine having one or two (meth)acrylonitrile groups in the X molecule and the amine group bonded to the (meth)alanyl group is 2 ¢-/U The factory is poor, two bases can be directly bonded or bonded via heteroatoms). (A structure in which one or two (meth)acrylonitrile-based (fluorenyl)-ene-amines have a structure in which an amine group bonded to a (meth)acryl fluorenyl group is substituted with two alkyl groups. Among them, two alkyl groups may be directly bonded or via a hetero atom, and if it is a (mercapto) acrylamide having such a structure, the hardenability is good, and it is more preferable, and it is more preferably acrylamide. The alkyl group in the alkyl group substituted with an alkyl group is not particularly limited, and when the two alkane groups are not bonded to each other, it is preferable that the number of rabbits is 2 or less in terms of excellent hardenability. More preferably, both of them are methyl groups. Further, when two alkyl groups are bonded to each other, the total number of carbon atoms of the two alkyl groups is preferably 2 or more, and preferably 10 or less, more preferably In the case of a hetero atom in the case of bonding via a hetero atom, for example, an oxygen atom, a nitrogen atom, or a sulfur atom may be mentioned; among them, an oxygen atom is preferred. . . : (iii) ' The structure as described above is not particularly limited, and specific examples thereof include ruthenium, osmium-dimethyl(fluorenyl) acrylamide, and N,N-diethyl 098,113,982. 25 201000547 base (fluorenyl) acrylamide, N,N,-dimercapto, fluorenyl-(methyl)propenyl porphyrin, fluorene-(fluorenyl) Acryl hydrazinyl pyrrolidine, fluorene-(meth) acrylonitrile piperidine, etc. Among them, hydrazine, dimethyl methacrylamide, hydrazine are preferred in terms of hardenability and ease of availability. - propylene decyl porphyrin. When the (meth) acrylate or (mercapto) acrylamide of the above (1) to (iii) is used as the component (A), the hardenability is particularly excellent, and the hardness of the obtained cured film is further obtained. And the scratch resistance (peelability) is good. As a result, the hard coat layer composed of the obtained active energy ray-curable resin composition can have excellent hardenability, scratch resistance, transparency, and further (B) Polyfunctional (meth) acrylate derivative The component (B) contained in the active energy ray-curable resin composition of the present invention is a polyfunctional (meth) propylene. The acid vinegar derivative is a polyfunctional (fluorenyl group) other than (A) having three or more (fluorenyl) acrylonitrile groups in one molecule. The acrylate derivative and one or more selected from the group consisting of an amino acid phthalate modified body, an ester modified body, and a carbonate modified body. The component (B) 'is easy to obtain the obtained active energy ray hardenability. In a certain range in which the viscosity of the resin composition is adjusted to be excellent in coatability, the viscosity of 25 is preferably 50 mPa·s or more, more preferably 60 mPa·s or more, and preferably.

為10000 mPa · s以下、更佳為8000 mPa · s以下。若25°C 之黏度為50 mPa · s以上，則不會因揮發性過高而浸入基 材’因而較佳’若25°C之黏度為i〇〇〇〇mpa · s以下，則所 得組成物之黏度易於調整為塗佈性良好之適當範圍因而較 098113982 26 201000547 佳。 作為成分(B)，只要為丨分子内具有3個以上（曱基)丙稀酿 基之由（A)以外之多官能（曱基）丙烯酸酯衍生物及自其胺基 曱酸乙_改質體、I旨改質體、及碳酸自旨改質體中選擇之一種 以上所構成，則並無特別限定，但就硬化性良好方面而言， 更佳為丙婦酸酉旨。 具體而S，可例示如以下者，但只要可獲得本申請案發明 ( 之樹脂組成物則並不限定於該等。 例如有·季戊四醇三丙烯酸酯、季戊四醇四丙烯酸酯、二 季戊四醇五丙稀酸酯、二季戊四醇六丙稀酸酯、二（三經曱 基丙烷）四丙烯酸酯、丁二酸酐之季戊四醇三丙烯酸酯加成 物、丁二酸軒之二季戊四醇五丙烯酸酯加成物等之多官能丙 烯酸酯類，在侧鏈或側鏈及末端上具有（甲基）丙烯醯基之聚 酯低聚物（具體而言，為東亞合成公司製造之M8030、M7100 ί ;等）等之聚酯（曱基）丙烯酸酯類；異佛爾酮二異氰酸酯 (IPDI ’ Isophorone Diisocyanate)之異三聚氰酸®旨體與聚丁·一 . 醇（PTMG，Polytetramethylene Glycol)及丙稀酸經乙西旨 . (HEA ’ Hydroxyethyl Acrylate)之反應物、六亞曱基一異氰酸 酯（HDI ’ Hexamethylene Diisocyanate)的異氰酸醋體與 PTMG的反應物與季戊四醇三丙烯酸酯之反應物等之多官 能基胺基曱酸乙酯（甲基）丙烯酸酯類；使用聚碳酸酯二醇之 低聚酯與季戊四醇三丙烯酸酯的反應物等之具有碳酸酯鍵 098113982 27 201000547 之聚醋（曱基）⑽酸_;IPDI與聚碳酸_ 腦的反㈣等之具有械_之聚絲甲酸⑽^與) 丙烯酸酯類m之丙烯酸加成物(具體而言，為新中村 化學公司製造之EA_聰）等之聚環氧（曱基）丙烯酸醋類；三 乙氧基異—聚氰酸二丙稀酸g旨、三乙氧基異三聚氰酸三两歸 酸酉1(具體而言’為東亞合成公司製造之ARONIX M315、 M3.13)等之具有異三聚氰酸醋環之三乙氧基（曱基）丙稀酸聘 類；以及該等之環氧烧改質物；聚己内S旨改質物等。A中' 上述例示純除成分(A)以外者，主要制旨饥之黏度超過 500 mPa.s者。又’該等可單獨使用，亦可併用以以上。 其中，就活性能量線硬化性樹脂組成物之黏度及硬化性、 所得硬化齡面之硬度等方面而言，尤料季細醇三丙歸 酸醋:季戊四醇四丙烯酸g|、二季戊四醇五丙烯酸酯、二季 戊四醇六丙烯酸酯、三羥甲基丙烷三丙烯酸酯、二(三羥曱 基丙烷)四兩烯酸醋，以及二季戊四醇三丙烯酸酯、季戊四 @子四丙烯酸_、二季戊四醇五丙烯酸§旨、二季戊四醇六 酸醋之環氧烧改質體、己内S旨改質體等。 本發明之活性能量線硬化性樹脂組成物中’將成分(八)斑 (B)之合計量設為i⑽重量份時，其中(a)i〜4個官能之岬 基）丙稀酸s旨及/或（曱基）丙稀醯胺為10〜70 f量份。若(A) 為10重里&以上’則活性能量線硬化性樹脂組成物之點产 不會過高，因而塗佈性及生產性優異，若(八)為70重量^ 098113982 28 201000547 γ ’則可獲得硬化性良好且硬度及耐劃傷性㈣之硬_ 〇 車父佳為（Α)為15重量份以上且50重量份以下。 在僅使用聚烷二醇之單丙烯酸酯、二丙烯酸酯、三丙烯酸 酉旨、四丙烯酸醋作為成分⑷的情況下，若成分⑷相對於成 分(Α)與⑼之合計量1〇〇重量份為5〇重量份以下，則硬度 及耐磨性良好因而較佳。更佳為15重量份以上且必重量$ 以下。 ( 另一方面，於欲獲得尤其是硬化性優異之活性能量線硬化 性樹脂組成物的情況下，較佳為成分(Α)之總重量的1/3以 上為上述(丨)〜（ih_)之化合物。進而較佳為35/100以上，更佳 為40/100以上，最佳為全部量為（i)〜（ii〇之化合物。 又’將成分(A)與(B)之合計量設為100重量份時，（則多 官能（曱基）丙烯酸酯衍生物為3〇〜9〇重量份。若(B)為30 重量份以上，則可獲得硬化性良好且硬度及耐劃傷性較高之 U 硬化膜；若（B)為90重量份以下，則所得活性能量線硬化性 樹脂組成物之黏度會變低，因而塗佈性優異。較佳為4〇重 量份以上且80重量份以下。 (C)光聚合起始劑 作為本發明活性能量線硬化性樹脂組成物中所含之成分 (C)即光聚合起始劑，可廣泛採用公知者，較佳為羥基苯 乙酮（α-羥基苯基酮）系、α_胺基苯乙酮系、苄基縮酮系等 之苯烷基酮型化合物；醯基膦氧化物型化合物；肟酯化合 098113982 29 201000547 物；乙酸氧基苯酯類；安息香醚類；芳香族酮類（二苯甲酮 類）：酮/胺化合物；苯甲醯基甲酸及其酯衍生物等。 具體而言’例如較佳為安息香甲醚、安息香乙醚、安息香 丙醚、安息香丁醚、二乙氧基笨乙酮、苄基二甲基縮酮、2_ 羥基-2-曱基苯丙酮、1-羥基環己基苯基酮、二苯曱酮、2,4,6· 三曱基笨偶姻二苯基膦氧化物、2-曱基_[4_(甲硫基）笨 基]-2-咮啉基-1-丙酮、2-苄基-2-二曱胺基-丨^私咮啉基苯基)· 丁烧-1-嗣、米其勒嗣（Michler’s Ketone)、Ν,Ν-二曱基胺基笨 曱酸異戊酯、2-氯-9-氧硫ρ山嗟、2,4-二乙基_9_氧硫ρ山嗟、 苯曱醯基甲酸、苯曱醯基曱酸甲酯、苯曱醯基曱酸乙酯。該 等光聚合起始劑亦可適當併用2種以上。 其中’就可將硬化性的下降抑制至最小限度、容易獲得、 難以引起著色等方面而言’較佳為使用2-羥基-2-曱基苯丙 酮、1-羥基環己基苯基酮等經基苯基酮類作為成分(c)的 至少一部分。 又’尤其是為了獲得硬化性良好之活性能量線硬化性樹脂 組成物’較佳為2-曱基-[4-(甲硫基）苯基]-2-咮啉基-1-丙酮、 2-苄基-2-二甲胺基-1-(4-咮啉基苯基)-丁烷-1-酮等之〇：-胺 基苯基酮類；二苯甲酮、米其勒酮、2-氯-9-氧硫岫嗟、異 丙基-9-氧硫p山嗟、2,4-二乙基-9-氧硫p山嗟等之二苯曱酮 類；苯甲醯基甲酸甲酯、苯甲醯基甲酸、苯甲醯甲酸乙酯等 之苯曱醯曱酸（酯）類；CGI242(Ciba製造）、OXE01(Ciba製 098113982 30 201000547 造）等之㈣類。進而，更佳為使用2_甲師_(曱硫基）苯 基]-2-咮琳基]侧、24基_2_二甲胺基邮』树基苯私 丁烧-1-酮、二笨甲酮、苯甲醯基甲酸曱酉旨等，尤佳為2·甲 基-[4-(甲硫基）苯基㈣琳基」·丙綱、2_节基_2•二甲胺基 小(4_味淋基笨基)-丁烧+酮、苯曱酸基甲酸甲酯。 在使用該等作為成分(c)的情況下，若含有上述⑴〜(晴 為成分⑷的至少-部分，射更顯著地看見硬化性之提 升’因而更佳。 將活性能量線硬化性樹·成物中之成分(A)與⑻之合 計量(總重量)設為100重量份時，（C)光聚合起始劑為2〜6 5 重里份，更佳為2·5重里份以上、5.5重量份以下。若（c)未 滿2重量份則所得活性能量線硬化性樹脂組成物之硬化性 差’右（C)為6.5重里伤以上則硬化膜之物性下降，因而欠 佳0 又，就硬化性方面而言，較佳為成分（C)之總重量的1/3 以上為自（2-致基本基綱類、（2 -胺基笨基嗣類、二苯甲酮 類、苯甲醯基甲酸(酯）類、及肟酯類中選擇之任意種、或者 該等之組合。進而較佳為1/2以上，更佳為3/5以上。 再者’向本發明活性能量線硬化性樹脂組成物照射活性能 量線而獲得硬化膜之時’在使用紫外線或軟X射線等作為 活性能量線的情況下，較佳為本發明之組成物中含有如上述 之成分(C) ’但在使用能量相對較高之電子束或硬X射線等 098113982 31 201000547 的情況下，亦可不含成分(c)。 (D)活性能量線硬化性化合物 作為本發明活性能量線硬化性樹脂組成物中所含之成分 ⑼即活性能量線硬化性化合物，為(叫)含有自聚二甲基石夕 氧院基、全氟&基及全氣伸絲_藝之-_上基之活性 能量線硬化性化合物。 於成分(D-1)中，就所得組成物之硬化性優異方面而言， 較佳為（D-3)具有相當於如下結構之結構之活性能量線硬化 性聚合物，該結構係使丨分子内具有丨個以上（曱基）丙烯醯 基之羧酸與如下單體混合物的自由基聚合物之環氧基的至 少一部進行反應而形成，該單體混合物含有具有自聚二甲基 矽氧烷基、全氟烷基以及全氟伸烷基中選擇之一種以上基之 單體與具有環氧基之（甲基）丙烯酸酯。進而，若為（D_2)含有 自t 一甲基梦乳炫基、全氟烧基以及全氟伸烧基中選擇之一 種以上基之活性能量線硬化性化合物，其具有相當於如下結 構之結構，該結構係使1分子内具有1個以上（甲基）丙烯醯 基之羧酸與含有二巯基聚矽氧烷和具有環氧基之（甲基）丙 烯酸酯的單體混合物之自由基聚合物之環氧基的至少一部 分進行反應而形成’則耐污染性尤其高且硬化膜之透明性及 耐污染性等性能之耐久性優異，因而較佳。 成分(D-1)之活性能量線硬化性化合物只要含有自聚二甲 基碎氧院基、全氟烧基及全氣伸烧基中選擇之一種以上基， 098113982 32 201000547 則並無特別限定，通常在側鏈或末端上含有至少1個（甲A) 丙烯酿基、或者環氧基等活性能量線硬化性基。 " 就所得組成物之硬純優異方㈣言，較偶成分(叫） 具有（甲基Μ騎基料硬化縣。輯得組絲之硬化性 尤其優異方面而言，成分(ΙΜ)中之（甲基）丙婦醒基之含量較 佳為6重量％以上’進而較佳為1〇重量％以上，更佳= 重量％以上。 ’ (《分(D-1)之數量平均分子量較佳為麵以上、進而較佳 為10000以上，且較佳為1〇〇〇〇〇以下、更佳為5〇〇⑼以下二 若成分(D-1)之數量平均分子量為1〇〇〇以上則所得硬化膜之 耐污染性較高’ ^為以下則存在組成物之黏度成為 適當範圍、而且與組成物中的其他成分之相容性變良好之傾 向’因而較佳。 進而，在欲挺兩所得組成物之硬化性的情況下，成分(D_i) I較佳為在其單個或兩個之末端具有（曱基）丙烯醯基。若在聚 合主鏈之末端具有（甲基）丙烯醯基，則成分(Dq)之反應性變 佳，因此硬化性變得良好因而較佳。更佳為在兩個之末端= 有（曱基）丙烯醯基。 八 再者，關於成分(D-1)中較佳之（曱基）丙烯醯基之含量、數 量平均分子量、或者（曱基）丙烯醯基之位置，於後述之 (D-2)、（D-3)中亦同樣地為較佳。 又，就耐污染性方面而言，較佳為含有數量平均分子量為 098113982 33 201000547 1000以上且10000 之全基、·為7之聚㈡甲基魏基、碳數為4以上 中之至少—個耐污染性^且碳數為12以下之全氟伸烧基 土夕氣烷基之數量平均分子量為1000以上，則 可充分發揮耐污毕柯处 乂上則 H Ρ ^ 、肊，右為10000以下，則硬化膜之透明 性會變良好，因而較佳。 ^ x 又，右全氟烷基之碳數為4以上， 則可充为發揮耐污染性， 右為12以下則溶解性良好且硬化 膜之透明性及外觀會變良好，因而較佳。 例如1聚—氧燒基，只要為可獲得本中請案之效果 者則並㈣卿d料含有數量平均好量為丨_以上 之聚2基錢烧基者，可舉出：在兩末端具有曱基丙稀酿 基之h Ψ基;^氧烧(例如信越化學製造之m64A)、在 衫端具有環氧基之聚二曱―氧垸、在兩末端及側鏈上具 有裒氧基之甲基#氧燒、日本專利特開平5] 17说號 公報中記載之聚二甲基錢烧；在側鏈上具有⑽基之聚二 曱基石夕氧烧衍生物(例如EV0NIK公司（原吻腿公司）製 造之Tego-Rad)、在側鏈上具有丙稀酿基之聚二甲基石夕氧烧 衍生物（例如Gelest公司製造之UMS182)、在兩末端具有丙 稀醢基之聚二曱基石夕氧烧（例如Gelest公司製造之 DMS-U22)、丙烯醯氧基丙基曱基矽氧烷均聚物（例如Gelest 公司製造之UMS992)、在主鏈或側鏈上具有聚二甲基石夕氧 炫且在側鏈及/或末端上具有丙稀酿基及/或環氧基之共聚 098113982 34 201000547 物等。 又，作為含有全氟烧基中較佳使用之碳數為4以上之全氟 烧基者’可例示：（甲基）丙埽酸全氟丁基乙醋、（甲基）丙稀 .酸全氟辛基乙酉旨、（曱基）丙埽酸全氟己基乙醋、或者使該等 -共聚合且在側鏈及/或末端上具有丙烯醯基及/或環氧基之 共聚物等。 又，作為含有全默伸烧基中較佳使用之碳數為2以上之全 Γ氟伸烧基者，可辦：在末端具有（曱基)丙稀酿基之全氣伸 烧基聚醚、全氟丁二醇二丙烯酸醋、全氟己二醇二丙稀酸 醋、或者使該等共聚合且在側鏈及/或末端1具有丙稀酿基 及/或環氧基之共聚物等。 再者，上述聚二曱基矽氧烷基、全氟烷基、及全氟伸烷基 等耐污染性基’亦可含有2種以上，例如可例示具有聚二甲 基石夕氧烧基及全IL辛基且在側鏈及/或末端上具有（曱基）丙It is 10000 mPa·s or less, more preferably 8000 mPa·s or less. If the viscosity at 25 ° C is 50 mPa · s or more, it will not be immersed in the substrate due to excessive volatility. Therefore, if the viscosity at 25 ° C is below i〇〇〇〇mpa · s, the composition is obtained. The viscosity of the material is easily adjusted to a suitable range of good coating properties and thus is better than 098113982 26 201000547. The component (B) is a polyfunctional (fluorenyl) acrylate derivative other than (A) having three or more (fluorenyl) propylene groups in the fluorene molecule, and is modified from its amino phthalic acid. The plastid, the modified body, and the carbonic acid are not particularly limited as long as they are selected from the above-mentioned modified substances. However, in terms of good curability, it is more preferably a glycerin. Specifically, S can be exemplified as follows. However, the resin composition of the present application is not limited to these. For example, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentapropan acid Ester, dipentaerythritol hexaacrylate, di(trimylpropanepropane) tetraacrylate, succinic anhydride pentaerythritol triacrylate adduct, succinic acid dipentaerythritol pentaacrylate adduct, etc. Functional acrylates, polyesters having a (meth) acrylonitrile-based polyester oligomer (specifically, M8030, M7100 ί; etc. manufactured by Toagosei Co., Ltd.) in a side chain or a side chain and a terminal (mercapto) acrylates; isophorone diisocyanate (IPDI ' Isophorone Diisocyanate) iso-cyanuric acid® and polybutanol (PTMG, Polytetramethylene Glycol) and acrylic acid (HEA 'Hydroxyethyl Acrylate) reactant, reaction of hexamethylene monoisocyanate (HDI ' Hexamethylene Diisocyanate) isocyanate with PTMG and pentaerythritol triacrylate a polyfunctional aminoethyl decanoate (meth) acrylate such as a compound; a polyester having a carbonate bond of 098113982 27 201000547 using a reaction of a oligoester of a polycarbonate diol with pentaerythritol triacrylate (曱) (10) acid _; IPDI and polycarbonate _ brain anti-(four) and so on _ the poly-methyl formic acid (10) ^ and) Acrylate m acrylic acid adduct (specifically, manufactured by Shin-Nakamura Chemical Co., Ltd. Poly(epoxy) acrylate vinegar such as EA_Cong); triethoxy oxy-polycyanate dipropylene acid g, triethoxy octa-cyanuric acid Specifically, 'ARONIX M315, M3.13 manufactured by East Asia Synthetic Co., Ltd.), etc., having a triacetocyanate ring of triethoxycyanate, and the like; Qualitative; In the above, the above-mentioned examples are purely in addition to the component (A), and the main purpose is to have a viscosity of more than 500 mPa.s. Further, these may be used alone or in combination. Among them, in terms of the viscosity and hardenability of the active energy ray-curable resin composition, the hardness of the obtained hardened age, and the like, especially the quaternary alcohol triglyceride: pentaerythritol tetraacrylic acid g|, dipentaerythritol pentaacrylate , dipentaerythritol hexaacrylate, trimethylolpropane triacrylate, bis(trihydroxydecylpropane) tetraenoic acid vinegar, and dipentaerythritol triacrylate, pentaerythritol tetra-acrylic acid _, dipentaerythritol pentaacrylate § The purpose is to modify the epoxy-modified plastid of dipentaerythritol hexahydrate and the modified body of S. In the active energy ray-curable resin composition of the present invention, when the total amount of the component (eight) spots (B) is i (10) parts by weight, (a) i to 4 functional thiol) acrylic acid s And/or (mercapto) acrylamide is in the range of 10 to 70 f. If (A) is 10 weights & above, the active energy ray-curable resin composition is not excessively high in yield, and therefore excellent in coatability and productivity, if (eight) is 70 weights ^ 098113982 28 201000547 γ ' In the case where the hardenability is good and the hardness and the scratch resistance (4) are obtained, the hardness is 15 parts by weight or more and 50 parts by weight or less. In the case where only a monoalkyl acrylate, a diacrylate, a triacrylate, or a tetraacrylate acrylate is used as the component (4), the component (4) is used in an amount of 1 part by weight based on the total of the components (Α) and (9). When it is 5 parts by weight or less, hardness and abrasion resistance are good, which is preferable. More preferably, it is 15 parts by weight or more and must be less than or equal to $. On the other hand, in the case of obtaining an active energy ray-curable resin composition which is excellent in curability, it is preferable that 1/3 or more of the total weight of the component (Α) is the above (丨) to (ih_). Further, it is preferably 35/100 or more, more preferably 40/100 or more, and most preferably the total amount is (i) to (ii) a compound. Further, the total amount of the components (A) and (B) When it is 100 parts by weight, (the polyfunctional (fluorenyl) acrylate derivative is from 3 to 9 parts by weight. When (B) is 30 parts by weight or more, the curing property is good, and the hardness and scratch resistance are obtained. When the (B) is 90 parts by weight or less, the viscosity of the obtained active energy ray-curable resin composition is lowered, so that the coating property is excellent, and it is preferably 4 parts by weight or more and 80%. (C) Photopolymerization initiator The photopolymerization initiator which is a component (C) contained in the active energy ray-curable resin composition of the present invention can be widely used, and is preferably hydroxybenzene. a keto ketone type compound such as a ketone (α-hydroxyphenyl ketone) system, an α-amino acetophenone system or a benzyl ketal system; Phosphine oxide type compound; oxime ester compound 098113982 29 201000547; oxyphenyl acetate; benzoin ether; aromatic ketone (benzophenone): ketone/amine compound; benzoic acid and its Ester derivatives, etc. Specifically, for example, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin butyl ether, diethoxy acetophenone, benzyl dimethyl ketal, 2 hydroxy hydroxy hydrazine Phenylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, diphenyl fluorenone, 2,4,6· tridecyl benzoate diphenylphosphine oxide, 2-mercapto _[4_(methylthio) stupid Methyl-2-phenyl-2-propanone, 2-benzyl-2-didecylamino-p-carbazyl phenyl), butyl ketone, Michler's Ketone , hydrazine, hydrazine-dimercaptoamine albendate, 2-chloro-9-oxosulfonate, 2,4-diethyl-9-oxosulfonate, phenylmercaptocarboxylic acid Benzyl phthalic acid methyl ester or phenyl decyl decanoic acid ethyl ester. These photopolymerization initiators may be used in combination of two or more kinds, in which 'the reduction in hardenability can be minimized and easily obtained. , it is difficult to cause coloring, etc. A phenyl ketone such as 2-hydroxy-2-mercaptopropiophenone or 1-hydroxycyclohexyl phenyl ketone is used as at least a part of the component (c). In particular, in order to obtain an active energy ray having good curability The curable resin composition 'preferably 2-mercapto-[4-(methylthio)phenyl]-2-indolyl-1-propanone, 2-benzyl-2-dimethylamino-1- (4-Purinylphenyl)-butan-1-one and the like: -aminophenones; benzophenone, mischoketone, 2-chloro-9-oxopurine, different Dibenzoquinones such as propyl-9-oxosulfonate, 2,4-diethyl-9-oxosulfonate, etc.; methyl benzylidenecarboxylate, benzhydrazinic acid, benzoic acid Benzoic acid (ester) such as ethyl formate; CGI242 (manufactured by Ciba); OXE01 (manufactured by Ciba 098113982 30 201000547) and the like (4). Further, it is more preferred to use 2_甲师_(曱thio)phenyl]-2-indolyl] side, 24-based _2-dimethylamino-based phenyl phenyl butyl ketone-1-one, Dimethylene ketone, benzhydrazide hydrazide, etc., especially preferably 2·methyl-[4-(methylthio)phenyl(tetra)-linyl··propyl, 2_knot 2·dimethyl The amine group is small (4-flavor base)-butylate + ketone, methyl benzoate. In the case of using the above-mentioned component (c), it is more preferable to contain the above (1) to (smooth is at least a part of the component (4), and it is more remarkable to see an increase in hardenability. When the total amount (total weight) of the components (A) and (8) in the product is 100 parts by weight, the photopolymerization initiator (C) is 2 to 6 parts by weight, more preferably 2 to 5 parts by weight or more. 5.5 parts by weight or less. If (c) is less than 2 parts by weight, the resulting active energy ray-curable resin composition has poor hardenability. When the right (C) is 6.5 or more, the physical properties of the cured film are lowered, and thus the result is less than 0. In terms of hardenability, it is preferred that more than 1/3 of the total weight of the component (C) is derived from (2-amino basic class, (2-aminophenyl), benzophenone, and benzoic acid. Any one selected from the group consisting of thioglycolic acid esters and oxime esters, or a combination thereof, further preferably 1/2 or more, more preferably 3/5 or more. Further to the active energy ray of the present invention When the curable resin composition is irradiated with an active energy ray to obtain a cured film, the use of ultraviolet rays or soft X-rays as an active energy ray is used. In the case where the composition of the present invention contains the component (C) as described above, but in the case of using an electron beam or a hard X-ray having a relatively high energy, 098113982 31 201000547, the component (c) may not be contained. (D) Active energy ray-curable compound as an active energy ray-curable compound as a component (9) contained in the active energy ray-curable resin composition of the present invention, which is called (self-polydimethyl oxalate) In the component (D-1), it is preferred that the composition of the composition (D-1) is excellent in the hardenability of the composition, and it is preferably a perfluoro-amp; (D-3) an active energy ray-curable polymer having a structure corresponding to a structure in which a carboxylic acid having at least one (fluorenyl) acrylonitrile group in a fluorene molecule and a radical of a monomer mixture as follows Forming at least a portion of an epoxy group of a polymer containing a monomer having one or more selected from the group consisting of polydimethyl methoxyalkyl groups, perfluoroalkyl groups, and perfluoroalkyl groups And (meth) acrylate having an epoxy group. Further, (D_2) an active energy ray-curable compound containing at least one selected from the group consisting of a t-methyl serotonyl group, a perfluoroalkyl group and a perfluoroalkylene group, and has a structure equivalent to the following structure This structure is a radical polymerization of a carboxylic acid having one or more (meth)acryl fluorenyl groups in one molecule and a monomer mixture containing a dimercapto polyoxyalkylene and a (meth) acrylate having an epoxy group. It is preferred that at least a part of the epoxy group of the substance is reacted to form 'the stain resistance is particularly high, and the durability of the cured film and the stain resistance are excellent. Therefore, the active energy ray of the component (D-1) is preferable. The curable compound is not particularly limited as long as it contains at least one selected from the group consisting of a polydimethyl oxalate group, a perfluoroalkyl group and a total gas stretching group, and usually contains at least a side chain or an end. One (AA) acryl-based or active energy ray-curable group such as an epoxy group. " In terms of hard and pure composition of the obtained composition (4), it is more than the even component (called) (methyl Μ riding base hardening county. In addition to the excellent hardenability of the composition silk, the composition (ΙΜ) The content of the (meth) propyl group is preferably 6% by weight or more, and more preferably 1% by weight or more, more preferably 5% by weight or more. ' (The number average molecular weight of the fraction (D-1) is preferably It is more than 10,000 or more, and more preferably 10,000 or more, and preferably 1 Torr or less, more preferably 5 Å (9) or less. If the number average molecular weight of the component (D-1) is 1 〇〇〇 or more, When the obtained cured film has a high stain resistance, the thickness of the composition is as follows, and the viscosity of the composition is in an appropriate range, and the compatibility with other components in the composition tends to be good, and thus it is preferable. In the case of the hardenability of the obtained composition, the component (D_i) I preferably has a (fluorenyl) acrylonitrile group at the terminal of one or both of them. If it has a (meth) acrylonitrile group at the terminal of the polymerization main chain Further, since the reactivity of the component (Dq) is improved, the curability is improved, which is preferable. To have a (fluorenyl) acrylonitrile group at the end of the two. VIII, the content of the preferred (fluorenyl) propylene fluorenyl group in the component (D-1), the number average molecular weight, or (mercapto) propylene The position of the sulfhydryl group is also preferably the same in (D-2) and (D-3) which will be described later. Further, in terms of stain resistance, it is preferred to contain a number average molecular weight of 098113982 33 201000547 1000 or more. And the total number of 10000, the number of poly(di)-terminated bases of 7-poly(di)methyl-Wiki, carbon number of 4 or more, and the number of carbon atoms of 12 or less When the average molecular weight is 1,000 or more, it is preferable that H Ρ ^ and 肊 are formed on the ruthenium-resistant ruthenium, and the right side is 10000 or less, and the transparency of the cured film is improved, so that it is preferable. When the number of carbon atoms of the alkyl group is 4 or more, it is sufficient to exhibit contamination resistance, and when it is 12 or less on the right, the solubility is good, and the transparency and appearance of the cured film are improved, which is preferable. For example, a polyoxyl group, As long as the effect of the case is obtained, and (4) the average amount of the material contains 丨_ 2 base money base, which can be exemplified by a sulfhydryl group having a mercapto propylene group at both ends; an oxygen burning (for example, m64A manufactured by Shin-Etsu Chemical Co., Ltd.) and a poly-2-anthracene having an epoxy group at the end of the shirt- Oxygen oxime, methyl oxyhydroxide having a decyloxy group at both ends and side chains, polydimethyl ketone described in Japanese Patent Laid-Open No. 5-17, and a group of (10) groups on the side chain Diterpenoid oxime derivative (such as Tego-Rad manufactured by EV0NIK (formerly Kiss Leg Company)), polydimethyl oxalate derivative with acrylonitrile on the side chain (for example, manufactured by Gelest) UMS182), polydimethyl fluorene oxalate with acrylonitrile at both ends (for example, DMS-U22 manufactured by Gelest), propylene methoxypropyl decyl decane homopolymer (for example, manufactured by Gelest) UMS992), copolymerized with dimethyl sulphur in the main chain or side chain and having propylene and/or epoxy groups on the side chains and/or ends, 098113982 34 201000547 and the like. Further, as a perfluoroalkyl group having a carbon number of 4 or more which is preferably used in the perfluoroalkyl group, '(methyl)propionic acid perfluorobutyl acetoacetate, (meth) acrylic acid is exemplified. Perfluorooctylethylene, (fluorenyl)propionic acid perfluorohexylacetic acid, or a copolymer having such a -copolymerization and having an acryloyl group and/or an epoxy group at a side chain and/or a terminal . Further, as a perylene fluorine-extension base having a carbon number of 2 or more which is preferably used in a fully-expanded base, it is possible to: a full-gas stretch-polyether having a (fluorenyl) propylene base at the end , perfluorobutanediol diacrylate vinegar, perfluorohexanediol diacrylic acid vinegar, or copolymers which copolymerize and have propylene and/or epoxy groups at the side chain and/or terminal 1 Wait. In addition, the pollution-resistant group ' such as a polydiindenyloxyalkyl group, a perfluoroalkyl group, and a perfluoroalkylene group may be contained in two or more types, and for example, it may be exemplified to have a polydimethyl oxalate group. And all-IL octyl groups with (fluorenyl) propyl groups on the side chains and/or ends

烯醯基及/或環氧基之共聚物等。 在成分(D-1)含有全氟烷基的情況下’就所得組成物之起 泡性難以變高方面而言，較佳為減少碳數為8以上之直鍵全 氟烧基的含量。 較佳為將成分(D-1)中所含之全氟烧基中的碳數為8以上 之直鏈全氟烷基的比例設為50重量％以下，更佳為設為45 重量％以下。作為碳數為8以上之直鏈全氟烷基，例如可舉 出：全氟辛基乙基、全氟癸基乙基、源自全氟辛基環氧丙基 098113982 35 201000547 醚之基等中之1種或2種以上。 相對於此，作為以超過50重量％之範圍而較佳使用之全 氟烧基’可舉出以下者作為較佳例。 •碳數為4〜7之直鏈全氟烷基，例如全氟己基乙基、源 自全氟己基環氧丙基醚之基、源自全氟庚基環氧丙基醚之基 等； 1 •碳數為6以上且末端為二氟曱基之全氟烷基，例如 1H，1H，7H-十二氟庚基、1H,1h，9h_+六氟壬基等； •石反數為8以上且具有支鏈之全氟烷基，例如全氟々_ 曱基辛基）乙基等； •礙數為8以上且具有内部稀烴結構之全氟絲，例如十 七氟壬烯基等。 戎等之中，尤佳為碳數為6之直鏈/飽和全說燒基，例如 全氟己基乙基、源自全氟己基環氧丙基謎之基。 該等全氟絲，可單獨含有丨種，亦可混合含有2種以上。 又’在成分(D-1)含有全氟伸烷基的情況下，亦存在與含 有全氟絲之情況相同之傾向，較佳樣態亦與上述相同。 將活性能量線硬化性樹脂組成物中之成分(A)與（B)之總 重量設為100 f量份時，（IM)活性能量線硬化性化合物為 〇·1〜15重量份，較佳為0.2重量份以上、12重量份以下。 若未滿0.1重量份’則難以賦予充分的耐污染性，另一方面， 右超過15重量份，則有時表面硬度會下降、或者硬化性會 098113982 36 201000547 下降^或者透明性會下降，因而欠佳。 ()為具有相當於如下結構的結構之活性能量線硬a copolymer of an oxime group and/or an epoxy group, and the like. In the case where the component (D-1) contains a perfluoroalkyl group, it is preferable to reduce the content of the direct bond perfluoroalkyl group having a carbon number of 8 or more in terms of difficulty in increasing the foaming property of the obtained composition. The ratio of the linear perfluoroalkyl group having 8 or more carbon atoms in the perfluoroalkyl group contained in the component (D-1) is preferably 50% by weight or less, more preferably 45% by weight or less. . Examples of the linear perfluoroalkyl group having 8 or more carbon atoms include perfluorooctylethyl group, perfluorodecylethyl group, and perfluorooctyl epoxypropyl group 098113982 35 201000547 ether group. One or two or more of them. On the other hand, as the perfluoroalkyl group which is preferably used in the range of more than 50% by weight, the following are preferred examples. • a linear perfluoroalkyl group having a carbon number of 4 to 7, such as perfluorohexylethyl, a group derived from perfluorohexylepoxypropyl ether, a group derived from perfluoroheptyl epoxypropyl ether, and the like; 1 • a perfluoroalkyl group having a carbon number of 6 or more and having a terminal difluoroindolyl group, such as 1H, 1H, 7H-dodecylheptyl, 1H, 1h, 9h_+hexafluoroanthryl, etc.; a perfluoroalkyl group having 8 or more and having a branch, such as a perfluoroindole-nonyloctyl)ethyl group; and a perfluoro-filament having a hindrance of 8 or more and having an internal dilute hydrocarbon structure, such as heptadecafluorodecenyl group Wait. Among them, a linear/saturated all-burning group having a carbon number of 6, for example, a perfluorohexylethyl group derived from a perfluorohexyl epoxypropyl group is preferred. These perfluoro-filaments may be contained alone or in combination of two or more. Further, in the case where the component (D-1) contains a perfluoroalkylene group, the same tendency as in the case of containing a perfluoromethyl group is also observed, and the preferred embodiment is also the same as described above. When the total weight of the components (A) and (B) in the active energy ray-curable resin composition is 100 parts by weight, the (IM) active energy ray-curable compound is preferably 1 to 15 parts by weight, preferably It is 0.2 part by weight or more and 12 parts by weight or less. If it is less than 0.1 part by weight, it is difficult to provide sufficient stain resistance. On the other hand, if the right side exceeds 15 parts by weight, the surface hardness may decrease, or the hardenability may fall 098113982 36 201000547 or the transparency may decrease. Poor. () is an active energy line hard having a structure equivalent to the following structure

化陡聚口物，讀結構係使1分子内具有1個以上（曱基）丙烯 醯基之羧酸與如T "口 Μ ^ A I 下早體k合物的自由基聚合物之環氧基的 ^ °卩刀進行反應而形成，該單體混合物含有具有自聚二 甲基石夕氧燒基、全氟絲、及全氣伸減中選擇之-種以上 基之單^財縣基之(甲基）丙稀酸脂。 2為3有自聚二甲基發氧燒基、全氟烧基、及全氟伸絲 擇之種以上基之單體，只要含有如上述之聚二甲基石夕 戰烧基王氟垸基、及全氣伸燒基則並無特別限定，例如作 、聚甲基矽氧烷基之單體的具體例，可舉出：在末端 或_上具有1個（甲基)丙_基之聚二甲絲氧炫 末端上具有縣之聚二甲基錄炫、在末端或側鏈 應:成的y场氧基^'具有使該環氧基與（甲基)丙烯酸反 :及全聚二曱基料烧等；又，作為含有自全氣燒 =:在。。:基中選擇之一種以上基之單體的具體例，可舉 化八物早在=側鏈上具有1個（甲基)㈣醯基之全氟貌基 全㈣燒二人 1 或具有疏基之全氣烧基化合物或 呈右料》 端或側鏈上具有1個以上環氧基且 ” 4氧基與（甲基）丙烯酸反應而成的結構之全氣燒A steep agglomerate, the read structure is an epoxy having a free radical polymer of one or more (mercapto)acrylonitrile groups in one molecule and a free radical polymer such as T " The base is formed by a reaction, and the monomer mixture contains a single-capacity base having a self-polydimethyl oxalate group, a perfluorofilament, and an all-gas extension. (Meth) acrylate. 2 is a monomer having 3 or more kinds of polydimethyloxy oxo group, perfluoroalkyl group, and perfluoroextension type, as long as it contains a polydimethyl sulphate as described above. The base and the total gas stretching base are not particularly limited, and specific examples of the monomer of the polymethyl siloxane are exemplified by having one (meth) propyl group at the terminal or _. The polydimethyl oxime end has a polydimethyl group in the county, and the terminal or side chain should be: the y field oxy group has the opposite of the epoxy group and the (meth) acrylate: The polyfluorene base material is burned, etc.; . A specific example of a monomer selected from the group consisting of one or more bases, which may have a perfluoromorphic group having a (meth) (tetra) fluorenyl group as early as the side chain; An all-gas-burning compound or a gas-fired structure having a structure in which one or more epoxy groups are present on the terminal or side chain and the "oxy group is reacted with (meth)acrylic acid.

基化合物或全氟伸絲化合物等。 I 3有王氟燒基之（甲基）丙烯酸g|作為成分①_3)中 098113982 37 201000547 之含有全氟烷基之單體的情況下’就所得組成物之起泡性難 以變高方面而言’較佳為減少含有碳數為8以上的直鏈全氟 烧基之（甲基）丙烯酸酯的使用量。 杈佳為將成分(D-3)中之含有全氟烷基之（曱基）丙烯酸酯 中’含有碳數為8以上之直鏈全氟烷基之（甲基）丙烯酸酯的 比例設為50重量％以下’更佳為設為45重量％以下。作為 含有碳數為8以上之直鏈全氟烷基之（曱基）丙烯酸酯，例如 可舉出：（甲基）丙烯酸全氟辛基乙酯、（甲基）丙烯酸全氟癸 基乙酯、全氟辛基環氧丙基醚之（曱基）丙烯酸加成物等中之 1種或2種以上。 相對於此，作為以超過5〇重量％之範圍而較佳使用之含 有全氟烷基之（甲基）丙浠酸酯，可舉出以下者作為較佳例。 •含有碳數為4〜7之直鏈全氟烧基之（甲基）丙烯酸酯， 例如（曱基）丙烯酸全氟己基乙酯、全氟己基環氧丙基醚之（甲 基）丙烯酸加成物、全氟庚基環氧丙基醚之（曱基）丙烯酸加成 物等； •含有碳數為6以上且末端為二氟曱基的全氟烷基之（甲 基）丙烯酸酯’例如（甲基）丙烯酸_1h,ih，7H-十二氟庚酯、（甲 基）丙烯酸1H,1H，9H-十六氟壬酯等； •含有碳數為8以上且具有支鏈的全氟炫基之（甲基）丙稀 酸酯，例如（曱基）丙烯酸2-(全氟_7_甲基辛基）乙酯等； •含有碳數為8以上且具有内部烯烴結構的全氟烷基之 098113982 38 201000547 (曱基）丙烯酸酯，例如（曱基）丙烯酸十七氟壬烯基酯等。 名等之中，尤佳為含有碳數為6的直鏈/飽和全氟烷基之 (曱基）丙烯酸酯，例如（甲基）丙烯酸全氟己基乙酯、全氟己 基環氧丙基醚之（曱基）丙烯酸加成物。 該等含有全氟烷基之（曱基）丙烯酸酯，可單獨使用丨種， 亦可將2種以上混合使用。 成分(D-2)之活性能量線硬化性化合物為含有自聚二曱基 Γ 矽氧烷基、全氟烷基及全氟伸烷基中選擇的一種以上基之活 性能量線硬化性化合物，其係具有相當於如下結構的結構之 聚合物，該結構係使1分子内具有2個以上（甲基）丙烯醯基 之羧酸與含有二巯基聚矽氧烷及具有環氧基之（曱基）丙烯 酸酯之單體混合物之自由基聚合物之環氧基的至少一部分 進行反應而形成。 成分(D-2)之較佳數量平均分子量之範圍，在成分(D_2)中 I;含有20重量％以上之矽原子的情況下為1〇〇〇〜3000，在成 分(D-2)中之矽原子含量未滿2〇重量％的情況下為3〇〇〇〜 30000 〇 成分(D-3)及成分(D-2)均具有使1分子内具有1個以上（曱 基）丙稀醯基之羧酸與環氧基上反應而成之結構，因此含有 其之組成物之硬化性變得良好，因而較佳。其可認為係在使 叛酸與環氧基進行反應而成之結構中，於源自羧基而形成之 醋鍵之氧原子上所連結的々位碳具有源自環氧基而形成的 098113982 39 201000547 羥基，該Θ位碳之C-Η鍵易被切斷’因而容易產生自由基， 並且該自由基相對容易地移動至（甲基）丙烯酿基，因此易發 生聚合/硬化。目此’含有具有如下結構之成分(D_3)及成分 (D-2)之組成物的硬化性變得良好，因而較佳，該結構係使1 分子内具有1個以上（甲基）丙烯醯基之羧酸與環氧基上進行 反應而形成。 以下記載成分(D-2)之較佳製造方法之例。此處，記載成 分(D-2)之製造方法作為代表例，在將下述(al)二巯基聚矽氧 烧替換成含有自聚二甲基@氧燒基、全氟烧基、及全氟伸院 基中選擇的-種以上基之單體的情況下，成分(D_3)亦可以 同樣之方式製造。 再者，以下有時將作為成分(D_2)的製造原料之單體混合 物100重量份中之各成分之量（重量份)稱為「使用量」。 又，成分(D-2)只要具有與以下述方法獲得之聚合物相當 的結構即可，並不限定於以下述製造法而獲得者。 <(a!)二巯基聚矽氧烷〉 本發明活性能量線硬化性樹脂組成物中所使用之(al)二 酼基聚矽氧烷，係具有將2個以上下述式（1)的重複結構單 位加以連結之聚矽氧烷結構。 _(SiRiR2-0)- (1) 式（1)中’心及R2分別獨立表示亦可具有取代基之烷基或 者亦可具有取代基之苯基，較佳為亦可被羥基或烷氧基取代 098113982 201000547 (更it為燒氧基及烧基之碳數為1〜3)’更佳為不具有 取代基之喊數為1〜3之烷基，最佳為曱基。 作為此種化合物，例如可舉出：α,ω-二巯基聚二曱基矽 二巯基聚二乙基矽氧烷、二巯基聚曱基 乙基石夕氧燒、α，ω-二酼基聚二羥曱基矽氧烷、α，ω-二酼 基水一甲氣基甲基矽氧烷等，其中，較佳為在α，ω-二毓基 聚一甲基石夕氧烷中，該巯基可直接與聚矽氧基連結，亦可經 由伸烧基與聚矽氧基連結。更佳為巯基經由伸丙基與聚矽氧 基連結之聚矽氡烷（α，ω-二髄基丙基聚二曱基矽氧烷）。其 中’只要係獲得本申請案發明之效果者，則並不限定於該等。 為了平衡性良好地達成耐污染性與硬度，（al)二巯基聚矽 氧烧之數量平均分子量較佳為1〇〇〇〜5〇〇〇左右。 此種(al)二巯基聚矽氧烷，可單獨使用1種，亦可將2種 以上混合使用。 製造成分(D-2)時之(ai)二酼基聚矽氧烷之使用量，較佳為 〇.〇1重ΐ份以上、15重量份以下。^⑽二魏基聚魏燒之 使用量為G.(H重量份以上，則可充分發揮耐污染性賦予性 能，若為15重量份以下’麟得成分Φ.2)與其他成分之相 容性（聚合反應時“之均勻相容性、以及製成組成物時成 分(D-2)與其他成分之相容性）良好，所得硬化膜之硬度變 高，因而較佳。 (&1)二疏基料魏之使用量更佳為丨重量份以上。又， 098113982 41 201000547 (a 1)二魏基聚石夕氧烧之使用量更佳為12重量份以下。 <(a2)具有環氧基之（甲基）丙烯酸酯> 若揭示（a2)具有環氧基之（曱基）丙烯酸酯之若干代表性的 具體例，可舉出：丙烯酸環氧丙酯、甲基丙烯酸環氧丙酯等 之具有環氧丙基之（甲基）丙烯酸酯；丙烯酸3,4-環氧基環己 酯、曱基丙烯酸3,4-環氧基環己酯、丙烯酸3,4-環氧基環己 基曱酯、曱基丙烯酸3,4-環氧基環己基曱酯等之環氧基與脂 環結構直接鍵結之（曱基）丙烯酸酯，但只要係獲得本申請案 發明之效果者則並不限定於該等。 該等之中，就獲得之容易性、利用（甲基）丙烯酸進行改質 之容易性方面而言，尤佳為曱基丙烯酸環氧丙酯、丙烯酸 3.4- 環氧基環己酯、甲基丙烯酸3,4-環氧基環己酯、丙烯酸 3.4- 環氧基環己基曱酯、曱基丙烯酸3,4-環氧基環己基曱酯 等。 此種（a2)具有環氧基之（曱基）丙烯酸酯，可單獨使用1 種，亦可將2種以上混合使用。 製造成分（D-2)時之（a2)具有環氧基之（曱基）丙烯酸酯之 使用量，較佳為5重量份以上、60重量份以下。若（a2)具有 環氧基之（甲基）丙烯酸酯之使用量為5重量份以上，則可充 分發揮由於藉由具有（曱基）丙烯醯基的羧酸改質而導入的 (甲基）丙烯醯基之光自由基聚合所導致之高硬化性或高硬 度化效果、表面硬化性之提升效果，若為60重量份以下， 098113982 42 201000547 則含有成分(D-2)之聚合物溶液之黏度及溶液穩定性變良 好，而且看見由於光自由基聚合所產生的更高的硬化性或硬 度化，因而較佳。 (a2)具有環氧基之（曱基）丙烯酸酯之使用量更佳為15重 量份以上。又，（a2)具有環氧基之（甲基）丙烯酸酯之使用量 更佳為55重量份以下。 <(a3)分子量為1〇〇〜300之單官能基硫醇> Γ) 作為製造成分(D-2)時之原料，以藉由分子量控制而表現 出較優異的與其他成分之親和性更優異的消泡性為目的，亦 可含有（a3)分子量為1〇〇〜300之單官能基硫醇。又，於如 成分(D-2)般具有Μ基並且具有易與其反應的官能基(例如 環氧基、異氰酸醋基、烧氧基石夕院基等）之自由基聚合性單 體中，在聚合時有時會產生以下問題：疏基與環氧基等如上 述的反應基發生副反應’歸生交聯/不溶化/凝膠化丨但藉 G由使用（a3)分子量為1〇〇〜3〇〇之單官能硫醇，如下所述， 可控制副反應且抑制交聯/不溶化/凝膠化，從而可製造良好 的成分(D-2)。 作為（a3)分子量為1〇〇〜3〇〇 <早官能硫醇，例如可例示· 己基硫醇、癸基硫醇、十二絲硫醇、十城基硫醇、十八 烧基硫醇等之烧基硫醇；環己基硫醇等之環絲硫醇；苯硫 紛、氯苯雜、難料之㈣麵醇等，但只要係可獲得 本申凊錄日狀效果相並不較於料。其卜財慮到 098113982 43 201000547 反應性、反應選擇性、臭氣等，則最佳為癸基硫醇、十二烷 基硫醇等碳數為9〜15之烷基硫醇。 若本發明活性能量線硬化性樹脂組成物中所使用之單官 能硫醇的分子量為100以上，則揮發性低，因此在進行聚合 反應時不會自反應系統中逃逸’從而易於表現效果。又，若 單官能硫醇之分子量為300以下，則與其他單體之相容性提 升，難以發生相分離，因而較佳。單官能硫醇之更佳分子量 為150以上、且250以下。 此種(a3)單官能基硫醇’可單獨使用1種，亦可將2種以 上混合使用。 在製造成分(D-2)時使用（a3)分子量為1〇〇〜3〇〇之單官能 硫醇的情況下，其使用量為〇.01重量份以上、尤佳為〇j 重量份以上，為5重量份以下、尤佳為4重量份以下。若（a3) 單吕能硫醇之使用量為〇·〇 1重量份以上，則（a3)單官能基硫 酵之濃度變為適當，反應性充分，且可控制反應而不引起(al) 二巯基聚矽氧烷與(a2)具有環氧基之（曱基）丙烯酸酯間的副 反應。另一方面，若（a3)單官能硫醇之使用量為5重量份以 下’則未反應之單體難以殘冑’所得成分(D_2)之分子量變 為適當’因而較佳。 又，在使用（a3)分子量為1〇〇〜3〇〇之單官能硫醇的情況 下較it為以（al)一疏基聚石夕氧垸之魏基（以下記作「M(ai)」） 與⑷)分子4為⑽〜之單官能硫醇之減（以下記作 098113982 44 201000547 「M(a3)」）的莫耳比M(al)/M(a3)通常為〇 〇1以上、較佳為 〇.〇5以上、更佳為（U以上，且為2〇以下、較佳為15以下、 更佳為10以下之量加以使用。若M(al)/M(a3)g 〇 〇1以上， 則可控制反應而實質上不引起由於(al)二疏基聚石夕氧烧之 巯基與(a2)具有環氧基之（曱基）丙埤酸酯之環氧基的反應所 導致之交聯、分散液之黏度上升、溶解性下降等；若為 以下，則未反應之單體難以殘留，所獲得成分(D_2)之分子 ( 量變為較佳，因而較佳。 <(a4)其他含有乙烯基之單體> 除上述(al)〜（a3)以外，可含有（a4)其他含有乙烯基之單體 作為製造成分(D-2)時之原料。作為_其他纟有乙稀基之單 體’只要為可獲得本申請案發明之效果者則並無制限定， 較佳為使用與環氧基的反應性較低且不會使生成之聚合物 的穩定性降低者、或者骨架為剛性且不降低硬度者、可進— ί 步提高耐污染性者等。 若舉出此種(a4)其他含有乙稀基之單體的若干具體例，則 可例示：苯乙稀、或其低級(碳數為卜4之成基、稀基取 代衍生物、碳數為K20之（甲基）丙烯酸烧基酯、烧基（甲基） 丙烯酿胺、具有碳數$ 5〜2〇之(聚)環烧基側鍵之（甲基）丙 烯酸钱基酯、（甲基）丙烯醒胺類等之自由基聚合性單體 等。 作為該等㈣其齡有乙縣之單體，可單獨使用^種， 098113982 45 201000547 亦可將2種以上混合使用。 製造成分(D-2)時㈣其他含有乙烯基之單體之使用旦 佳為】重量份以上、50重量份以下。若㈣其他含有乙里= 之單體的使料為丨重量份以上，則溶解性及透明性優/ 另一方面，若為50重量份以下，則所得硬化膜之 "， 劃傷性及鉛筆硬度變得良好，因而較甘又面的耐 基之單體的使用量更佳為5重編上。(又=含有乙稀 〇〇 丄人，（a4)其他含有 乙烯基之單體的使用量更佳為4〇重量份以下。 <溶劑> 在進打含有上述(al)〜_成分 < 單體混合物的自由基聚 合日寸’為了提两均勻性，亦可加入溶劑。 作為此種溶劑之較佳例，可舉出：丙酮、曱基乙基酉同⑽跋) 等之酮系溶劑；乙醇、甲醇、異丙醇(IpA)、異丁醇等之醇 系mu甲醚、丙二醇單甲醚等之峻系溶劑；乙酸 乙酯、丙二醇單甲醚乙酸醋、乙酸2_乙氧基乙醋等之^ 溶劑；甲笨等之芳香族烴系溶劑；以及水。 ' 該等溶劑可單獨使用1種，亦可將2種以上混合使用。在 使用2種w上的情況下’較佳為不成為2層而形成 溶劑。 θ <自由基聚合起始劑> 含有上述（al)〜（a4)成分之單體混合物之自由基聚合中 較佳為使用自由基聚合起始劑。 098113982 46 201000547 作為該自由基聚合起始劑並無特別限定，通常可使用一般 用於自由基聚合之公知之起始劑；作為較佳例，可舉出：過 氧化苯甲醯、過氧化二第三丁基等之有機過氧化物；2,2’-偶氮雙丁腈、2,2’-偶氮雙(2,4-二曱基戊腈）、2,2'-偶氮雙(4-曱氧基-2,4-二曱基戊腈）等之偶氮化合物。 該等自由基聚合起始劑，可單獨使用1種，亦可將2種以 上混合使用。 <自由基聚合方法及條件> 對於進而視需要在含有上述(al)〜（a2)成分之單體混合物 中使用（a3)成分、（a4)成分、溶劑以及自由基聚合起始劑進 行自由基聚合時之、單體成分與溶劑之混合/溶解方法等， 並無特別限制，例如較佳為將單體成分與溶劑混合後，於一 定時間以内較佳為3小時以内添加自由基聚合起始劑，而開 始聚合。 供於自由基聚合之反應液中的單體成分之總濃度，較佳為 10重量％以上、60重量％以下；自由基聚合起始劑之使用 量，較佳為相對於單體成分之總計較佳為0.1重量％以上、 更佳為0.2重量％以上且較佳為10重量％以下、更佳為2重 量％以下。 又，較佳之聚合條件則視所使用之自由基聚合起始劑而不 同，但聚合溫度通常為20〜150°C，聚合時間通常為1〜72 小時。 098113982 47 201000547 <具有（甲基）丙浠醯基之羧酸〉 於成分(D-2)之製造中，通常使1分子内具有】個以上（甲 基）丙烯醯基之羧酸、較佳為1分子内具有丨〜5個（〒基）丙 烯醯基之羧酸加成至以上述方式獲得之自由基聚合物之環 氧基的至少一部分上。 作為此處所使用之具有（甲基）丙烯醯基之羧酸，例如可舉 出：基）丙烯酸；2-(f基）丙烯醯氧基乙基丁二酸；2_(甲 基）丙烯醯氧基乙基六氫鄰苯二甲酸；末端為羧酸之聚己内 酯丙浠酸酯，季戊四醇三（甲基）丙烯酸酯與丁二酸酐、鄰苯 二甲酸酐、六氫鄰苯二曱酸酐等酸酐之加成物；二季戊四醇 五（甲基）丙烯酸酯與丁二酸酐、鄰苯二甲酸酐、六氫鄰苯二 甲酸酐荨酸酐之加成物等。該等可單獨使用1種，亦可將2 種以上混合使用。 <加成反應之方法及條件> 於上述加成反應之例中，自由基聚合物所具有的環氧基與 具有（甲基）丙烯醯基之羧酸的羧基發生反應。 自由基聚合物與具有（甲基）丙烯醯基之羧酸，較佳為以自 由基聚合物的環氧基與具有（甲基）丙烯醯基之羧酸的羧基 之個數比（以下有時僅稱為「環氧基/叛基」）為！以上之比例 加以使用。又，環氧基增基q，較佳為iq以下，進而較 佳為5以下，更佳為2以下。 若環氧基/羧基之比係在上 %卞限值以上 ，則可防止由於 098113982 48 201000547 未反應而殘留之具有（甲基）丙烯醯基之it酸所導致的穩定 f生下降若為上述上限值，則可防止由於殘留之環氧基所導 致的穩定性下降，因而較佳。 又，較佳為自由基聚合物所具有的環氧基中有5〇〜99% 與具有（甲基）兩烯醯基之羧酸的羧基發生反應。 該加成反應，較佳為於50〜11(TC下進行3〜50小時。 又於本反應中’為了促進反應，例如可使用三乙胺、三 f 丁胺、二乙二胺、N，N-二曱基苄胺、氯化苄基三曱基銨、及 一笨基科4中之1種或2種以上作為觸媒。其使用量，相對 於反應混合物（即，自由基聚合物與具有（曱基）丙烯醯基之羧 酉欠之總δ十）較佳為〇 〇 1重量％以上，進而較佳為〇 〇5重量％ 以上。又’較佳為2重量％以下，進而較佳為1重量％以下。 又，於本反應中，為了防止由於具有（曱基）丙烯醯基之羧 酸的（甲基）丙烯醯基所導致之自由基聚合，例如較佳為使用 〇 對苯二酚、對苯二酚單曱醚、鄰苯二酚、對第三丁基鄰苯二 酚、吩噻讲(phenothiazine)等聚合抑制劑中之1種或2種以 上。聚合抑制劑之使用量，相對於反應混合物較佳為0.01 重量％以上’進而較佳為〇.〇5重量％以上。又，較佳為1重 量％以下，進而較佳為5重量％以下。 依照如上述之例，可獲得用於本發明之成分(D-2)。 在本發明活性能量線硬化性樹脂組成物含有具有環氧基 之化合物作為成分(D-1)的情況下，若進一步含有（E)光陽離 098113982 49 201000547 子硬化起始劑，則表面硬化性會進—步提升，因而較佳。作 =成分⑹，只要為陽離子聚合性之光起始劑則並無特別限 定通吊較佳地使用公知之光酸產生劑，進而較佳為二芳基 鎭a型或者二芳基銃鹽型；作為對離子，可例示pF6、Sbp5、 Ash、BPh4、CF3〇S〇2等。再者，若僅使用該成分，在硬化 性較低地情況下，有時較佳為併用胺類(三乙醇胺等）、麟類 (二丁基膦等）、9-氧硫咄嗟進行增感。該等為可用作(E)光陽 離子硬化起始劑之代表例，而並不限於以上所揭示者。 本發明之活性能量線硬化性樹脂組成物，以賦予各種功能 性為目的，較佳為調配入抗靜電劑、潤滑性賦予劑、防霧賦 予劑、剝離性賦予劑中之至少1種。 該等分別只要不損及本發明之效果則並無特別限定，例如 右為抗靜電劑，尤佳為如日本專利特開2〇〇3_2〇1444號公報 中δ己載之抗靜電劑（含有四級錢驗之聚合物、或者含有四級 銨鹼之矽烷偶合劑等）。 又，作為潤滑性賦予劑，可例示如具有聚二曱基矽氧烷基 之聚合物。 另一方面，作為防霧賦予劑，可例示：親水基改質膠體二 氧化矽、矽酸鹽改質膠體二氧化矽、在侧鏈上具有聚烷二醇 基專親水基之聚合物或低聚物類。 進而，作為剝離性賦予劑，可例示：公知之矽g同系、氟系、 長鏈丙烯酸系之自低聚物至聚合物型、該等中含有硬化性基 098113982 50 201000547 者等。 若以賦予除上述外之各種功能性為目的而於本發明活性 能量線硬化性樹脂組成物中調配人紫外線吸收劑、受阻胺系 光穩定劑’财時耐候性會進-步_著提升，因而較佳。 作為紫外線吸收劑，只要不損及本發明之效果則並無特別 限定，作為較佳例，可舉出：苯并三唑系、二苯甲§同系、水 揚酸系、氰基丙稀酸酯系、三讲系紫外線吸收劑等。 (作為受阻胺系光穩定劑，並無特別限定，作為較佳化合 物’例如可舉出Ciba Specialty Chemicals公司製造之 TINUVIN 765等之N-甲基體’亦可使用Ciba Specialty Chemicals公司製造之TINUVIN 770等通常之N-H體。 以改良硬化膜物性為目的，亦可於本發明活性能量線硬化 性樹脂組成物中調配入抗氧化劑（例如’受阻酚系、硫系、 磷系抗氧化劑等）、抗結塊劑、助滑劑、調平劑等通常於此 I; 種耐污染性賦予劑中所調配之各種添加劑。作為此情況下之 調配量，較佳為調配入組成物整體之〇.〇1〜2重量％。 本發明活性能量線硬化性樹脂組成物之25。(：下之黏度為 10〜50〇mpa . s。若為1〇mPa · s以上，則可避免塗佈時的 揮發或者引起溶液的不利的流動而不變為均勻膜厚之現 象，因而較佳’若為500 mPa · s以下，則濕潤性佳且涂佈 時/谷液均勻擴散，從而可確保均勻的膜厚，因而較佳。_佳 為15 mPa · s以上、進而較佳為2〇 mPa · s以上，且較佳為 098113982 51 201000547 450 mPa · s以下、進而較佳為4〇〇 mpa · s以下。 又，本發明之活性能量線硬化性樹脂組成物，不含超過該 、’且成物中之5重量。/。之有機溶劑，因而可作為實質上不含有 機溶劑者進行操作。#此，可避免伴隨有機溶_發之環境 污染’從而可降低環境負荷。又’不會產生伴隨有機溶劑揮 發之溶液濃度的變動，從而濃度為固定，因而溶液之再利用 變得容易。作為結果，導致環境負荷降低、生產性提高，因 而較佳。 具體而言，若有機溶劑之量為該組成物中的5重量％以 下，較佳為沸點為10〇1以下之有機溶劑（例如，乙醇、異 丙醇、丙_、甲基乙基酮等）為2重量％以下，則可充分發 揮如上述之效果。為了使環境負荷成為零，更佳為該組成: 中完全不含有機溶劑。 關於除有機溶劑以外之溶劑中之水，較佳為不含超過該組 成物中的1重量％之水。對於水，控制為完全不含水係非常 困難，若將水設為1重量％以下’則不會引起由於溶液的分 離所導致之混濁，硬化性變得良好，因而較佳。 本發明之活性能量線硬化性樹脂組成物，可提供硬度高且 耐劃傷性及耐污染性優異之硬化膜，因此尤其適宜用作光記 錄媒體硬塗用。 [η]硬化獏、及具有由該硬化瞑所構成的硬塗層之積層體、 以及光記錄媒體 °98113982 52 201000547 向本發明活性能量線硬化性樹脂組成物照射活性能量線 以使其聚合而成之硬化膜、及具有由該硬化膜所形成的硬塗 層之積層體、以及光記錄媒體，係硬度、耐劃傷性等特性為 優異者。 本發明之硬化膜係硬度、耐劃傷性等特性為優異者，因此 適合在物品表面上用作硬塗層。作為形成該硬塗層之方法， 可將組成物塗佈於物品表面，然後照射活性能量線而使其聚 合；亦可先另外製作照射活性能量線使其聚合之膜’然後再 積層於物品上。 本發明之硬化膜可適用於各種物品，可適用於光學物品 (尤其是再生專用光碟、光記錄光碟、磁光記錄光碟等光資 訊媒體、或者如觸控面板或液晶電視之光學顯示器用透明物 «口）、π車相關零件(燈相關、窗相關等物品(後窗、侧窗、天 自等)）、生活相關物品(各種電氣設備之殼體、裝御板、傢具 等）等廣泛物cm之表面保護，且可用作各種物品之硬塗材 料作為可應用之物品，具體而言，例如可舉出：光學透鏡、 光干稜鏡/夂鏡片、α車之窗材料、眼鏡透鏡、太陽電池之 表面保護薄膜、農業用湖挪 眉膠、/里室之透明薄膜、反光標識表面 保護用透明薄膜等。 田 本發明之積層體，係扣户々 在各種基材的表面上具有硬塗層之 積層體，該硬塗層係由自+ 1層之 . 本發明活性能量線硬化性樹脂士 物所獲得之硬化膜所槿占^ Μ日組成 098113982 战。基材之種類並無特別限定，就接 53 201000547 著性之南低等方面而言’較佳為由樹脂所構成之基材。樹脂 基材可為板狀、>1狀、薄膜狀之中任意者，亦可為任意形狀 之成形品。又’基材可為積層體的一部分，亦可再基材與硬 化膜之間介隔其他層。 樹脂基材可為熱塑性樹脂，亦可為藉由熱或活性能量線而 硬化之硬化樹脂。 作為熱塑性樹脂，例如可舉出：聚對苯二甲酸乙二醇酯 (PET)或聚萘二甲酸乙二醇酯等之聚酯、聚曱基丙烯酸甲酯 (PMMA)、含有曱基丙烯酸甲酯（MMA)之共聚物（甲基丙烯 酸曱酯-苯乙烯共聚合樹脂(MS樹脂））、聚碳酸酯（PC)、三乙 醯纖維素、丙烯腈-丁二烯-苯乙烯共聚物(ABS樹脂）、改質 聚烯烴樹脂、氫化聚苯乙烯樹脂、環烯烴系樹脂(例如 製造之ARTON，日本ΖΕΟΝ製造之ZEONEX、ZEONOR， 三井化學製造之APEL)等。 作為硬化樹脂，例如可舉出：環氧樹脂、胺基甲酸乙酯樹 脂、熱硬化性或光硬化性之丙烯酸系樹脂之硬化物、熱硬化 性或光硬化性之有機無機混成樹脂等之硬化物等。 該等基材’例如可為其本身塗佈而形成之膜，亦可為利用 各種成形法之成形品。 本發明之硬化膜係透明性優異且硬度、耐劃傷性優異者， 因此可應用於要求高透明性之光學物品。此時，在基材亦必 須透明的情況下，較理想的是基材係以塗佈法、炫融擠出成 098113982 54 201000547 形法、溶誠鑄法巾之任意方法㈣者。又，在基材含有可 利用活性能量線或熱而發生硬化之官能基的情況下，更佳為 利用活性能量線騎或加紐其硬化。又，該等基材可為成 形品(物品)之雜者’亦可為在基材與本發明組成物的塗佈 面之間介隔其他層。再者’所謂透明，—般係指目標波長之 光的穿透率為80%以上。 由本發明活性能量線硬化性樹脂組成物所獲得之硬化 膜，尤其可適宜用作光記錄媒體之耐污染性硬塗層。因此， 在表面上具有該硬塗層之積層體，較佳為用作光記錄媒體， 尤佳為將該硬塗層製成存在於光入射側的最表面之光記錄 媒體。於此種光記錄媒體中，在硬塗層與記錄膜面之間可具 有至少一層透光層。 作為光記錄媒體具代表性者為光碟，種類可為相變型、色 素型、磁光型、再生專用型等中之任意者。其中，較佳為 I DVD或HD DVD、Blu-Ray Disc等高密度記錄用光碟。為 了提高記錄密度’記錄標記與記錄/再生用雷射光的光束徑 均變小，因此對污潰及刮傷敏感且抖動易變高或者記錄/再 生誤差易增加’從而需要对污染性及硬度優異之硬塗層。 較佳構成係在基板上具有至少含有記錄層或反射層的多 層膜之光記錄媒體’係至少在該光記錄媒體之光入射側的最 表面具有本發明之硬化膜之構成。若光入射側的最表面存在 污潰及刮傷，則會遮擋記錄/再生光束而產生誤差，因此較 098113982 55 201000547 么為在光入射側的最表面設置本發明之硬化膜作為耐污染 生更塗層。例如存在：（1)如Blu-Ray Disc等般相對於記錄 層或反射層在基板側相反側為光入射面者；（2)如DVD等般 相對於記錄層或反射層在基板側為光入射面者。在此情況 下，硬塗層必須具有透光性。所謂透光性，通常係指對於記 錄/再生光的波長之光而言穿透度為80%以上之狀態。亦可 在與光入射側相反側的最表面上設置本發明之硬化膜。 以下’就光記錄媒體之較佳層構成加以說明。 (1)將多層膜侧表面作為記錄/再生光束入射側表面之光記錄 媒體 Λ 此種光記錄媒體之較佳層構成係在基板上依序具有（反射 層、）記錄層、硬塗層（硬化膜)者。進而較佳為在記錄層等與 硬塗層之間具有透光層。藉由設置透光層，而使得光記錄媒 體的光入射侧最表面與記錄層（反射層）之間隔增加，從而記 錄/再生光束難以受到媒體表面之污潰或刮傷的影響，因而 較佳。透光層之膜厚較佳為30 Am以上，更佳為7〇 以上。又’透光層之厚度較佳為2〇〇 #爪以下，更佳為15〇 # m以下。 根據目的亦可在各層間設置任意之層。例如，亦可在記錄 層的上下設置由介電體等所構成之無機保護層。或者，為了 提高記錄容量’亦可以透光間隔層為介隔而設置複數層記錄 層或反射層。設置透光間隔層係用以防止在複數層記錄層間 098113982 56 201000547 信號混雜，膜厚較佳為與透光層同等程产。 作為尤佳之層麟之例，可較佳地舉出：基板/反射層/無 機保護層/記錄層/無機保護層/透光層/硬塗層、基板/反射層/ 透光層/硬塗層之構成，或基板/反射層/無機保護層/記錄^ 無機保護層/透光間隔層/反射層/無機保護層/記錄層/無機保 護層/透光層/硬塗層、基板/無機保護層/記錄層/無機保護層/ 透光層/硬塗層等之構成，但並不限定於該等。 ( 基板、圮錄層、反射層、热機保護層之材質並無特別限定， 亦可使用光記錄媒體中所使用之公知之任咅者。 作為基板，可使用聚碳酸酯、聚丙烯酸酯、聚烯烴等樹脂， 或者玻璃等。在自基板侧入射記錄再生光的情況下，基板必 須對於記錄/再生光為透明。基板之厚度通常為〇3〜12 # m。大多在基板上形成有槽（溝）或凹坑。 記錄層有相變型、色素型、磁光型等。在再生專用型的情 V.,,况下’有時亦不具有記錄層。相變型記錄層中常使用氧族元 素系合金，例如可舉出：GeSbTe系合金、InSbTe系合金、 • GeSnTe系合金、AglnSbTe系合金。相變型記錄層之厚度通 • 常為3 nm〜50 nm。色素型記錄層中可使用偶氣系色素、花 青（cyanme)系色素、酞菁（phthal〇cyanine)系色素、紫質 (porphyrin)系色素等，但並不限定於該等。色素型記錄層之 厚度通常為5 0 nm〜1 m。 無機保護層之材料係考慮折射率、熱導率、化學穩定性、 098113982 57 201000547 機械強度、密著性等而決定，通常使用介電體。無機保護層 之材料，一般而言係使用透明性較高且為高熔點之金屬或半 體的氧化物、硫化物、乳硫化物、氮化物，或Ca、jy[g、 Li等的氟化物。無機保護層之厚度通常為5〜2〇〇nm左右。 反射層較佳為由反射率及熱導度較大之材料所構成。作為 反射率及熱導度較大之反射層材料，可舉出以Ag、Au、A卜 Cu等作為主成分之金屬。其中，Ag與Au、Al、Cu相比， 反射率、熱導度較大。該等中亦可含有最多為5原子％左右 之 Cr、Mo、Mg、Zr、V、Ag、In、Ga、Zn、Sn、Si、Cu、a base compound or a perfluoroextension compound or the like. In the case of a monomer containing a perfluoroalkyl group of 098113982 37 201000547 in the component 1_3), in the case where the foaming property of the obtained composition is difficult to be high, It is preferred to reduce the amount of (meth) acrylate containing a linear perfluoroalkyl group having a carbon number of 8 or more. It is preferable to set the ratio of the (meth) acrylate having a linear perfluoroalkyl group having a carbon number of 8 or more in the perfluoroalkyl group-containing (fluorenyl) acrylate in the component (D-3). 50% by weight or less is more preferably set to 45% by weight or less. Examples of the (fluorenyl) acrylate having a linear perfluoroalkyl group having 8 or more carbon atoms include perfluorooctyl ethyl (meth)acrylate and perfluorodecyl ethyl (meth)acrylate. And one or more of the (fluorenyl) acrylate addition products of perfluorooctyl epoxypropyl ether. On the other hand, as the (meth)propionate containing a perfluoroalkyl group which is preferably used in the range of more than 5% by weight, the following are preferred examples. • (Meth) acrylate containing a linear perfluoroalkyl group having a carbon number of 4 to 7, such as (fluorenyl) perfluorohexyl acrylate, perfluorohexyl epoxypropyl ether (meth) acrylate a product, a perfluoroheptylepoxypropyl ether (mercapto)acrylic acid adduct, etc.; • a (meth)acrylate containing a perfluoroalkyl group having a carbon number of 6 or more and a terminal difluoroindenyl group For example, (meth)acrylic acid_1h, ih, 7H-dodecafluoroheptyl ester, (meth)acrylic acid 1H, 1H, 9H-hexadecafluorodecyl ester, etc.; • contains a carbon number of 8 or more and has a branched chain a (meth) acrylate of fluorone, such as 2-(perfluoro_7-methyloctyl)ethyl (meth) acrylate; • a whole having a carbon number of 8 or more and having an internal olefin structure Fluoroalkyl 098113982 38 201000547 (fluorenyl) acrylate, such as heptafluorodecenyl (meth) acrylate. Among the names, it is particularly preferred to have a linear/saturated perfluoroalkyl (indenyl) acrylate having a carbon number of 6, such as perfluorohexylethyl (meth)acrylate, perfluorohexylepoxypropyl ether. (曱-based) acrylic acid adduct. These (fluorenyl) acrylates containing a perfluoroalkyl group may be used singly or in combination of two or more. The active energy ray-curable compound of the component (D-2) is an active energy ray-curable compound containing one or more selected from the group consisting of polydidecylsulfonyloxyalkyl, perfluoroalkyl and perfluoroalkylene. It is a polymer having a structure corresponding to a structure in which a carboxylic acid having two or more (meth)acryl fluorenyl groups in one molecule and a dimercapto polysiloxane and having an epoxy group are present. The at least a portion of the epoxy group of the radical polymer of the acrylate monomer mixture is reacted to form. The preferred number average molecular weight of the component (D-2) is in the range of the component (D_2) I; in the case of containing 20% by weight or more of the ruthenium atom, it is 1 〇〇〇 to 3,000, and in the component (D-2) In the case where the atomic content is less than 2% by weight, it is 3 〇〇〇 to 30000. The 〇 component (D-3) and the component (D-2) each have one or more (fluorenyl) propylene in one molecule. Since the carboxylic acid of the mercapto group has a structure in which it reacts with an epoxy group, the composition containing the mercapto group has a good hardenability, which is preferable. It is considered that in the structure in which the oxic acid and the epoxy group are reacted, the ninth carbon bonded to the oxygen atom of the vinegar bond formed by the carboxyl group has 098113982 which is derived from the epoxy group. 201000547 Hydroxyl group, the C-Η bond of the carbon of the position is easily cut off' thus easily generating a radical, and the radical is relatively easily moved to the (meth)acrylic group, and thus polymerization/hardening easily occurs. Therefore, it is preferable that the composition containing the component (D_3) and the component (D-2) having the following structure has good curability, and the structure is such that one or more (meth) acrylonitriles are contained in one molecule. The carboxylic acid of the group is formed by reacting with an epoxy group. An example of a preferred production method of the component (D-2) will be described below. Here, as a representative example, the production method of the component (D-2) is replaced by the following (al) dimercaptopolyoxyl combustion to contain self-polydimethyl@oxyalkyl, perfluoroalkyl, and In the case of a monomer having more than one selected group selected from the group, the component (D_3) can also be produced in the same manner. In the following, the amount (parts by weight) of each component in 100 parts by weight of the monomer mixture as a raw material for the component (D_2) is referred to as "amount of use". Further, the component (D-2) is not limited to the one obtained by the following production method as long as it has a structure corresponding to the polymer obtained by the following method. <(a!) Dimercaptopolyoxyalkylene> The (al) dimercaptopolyoxyalkylene used in the active energy ray-curable resin composition of the present invention has two or more of the following formula (1) The repeating structural unit is linked to a polyoxyalkylene structure. _(SiRiR2-0)- (1) In the formula (1), the core and R2 each independently represent an alkyl group which may have a substituent or a phenyl group which may have a substituent, and preferably may also be a hydroxyl group or an alkoxy group. The base is substituted by 098113982 201000547 (more it is an alkoxy group and the carbon number of the alkyl group is 1 to 3). More preferably, it is an alkyl group having 1 to 3 substituents without a substituent, and is preferably a mercapto group. As such a compound, for example, α,ω-dimercaptopolydidecylfluorenyldifluorenyldiethyloxane, dimercaptopolydecylethylcarbazide, α,ω-dimercapto group can be mentioned. Dihydroxyindenyl oxane, α, ω-dimercapto-hydryl-methyl-methyl oxane, etc., among which, preferably, in α,ω-dimercaptopolymethyl oxalate, The thiol group may be directly bonded to the polyoxyalkylene group or may be bonded to the polyoxyalkylene group via a stretching group. More preferably, the sulfhydryl group is a polydecane (α,ω-dimercaptopropylpolydidecyloxane) bonded to the polyfluorene group via a propyl group. Here, 'as long as the effect of the invention of the present application is obtained, it is not limited to these. In order to achieve good stain resistance and hardness in a well-balanced manner, the number average molecular weight of the (al) dimercapto-polyoxyl combustion is preferably about 1 〇〇〇 to 5 Torr. The (al) dimercapto polyoxyalkylene may be used singly or in combination of two or more. The amount of the (ai) dimercaptopolyoxyalkylene used in the production of the component (D-2) is preferably 〇.〇1 or more and 15 parts by weight or less. ^(10) The amount of use of diWei-based poly-Wei-burn is G. (H parts by weight or more, the anti-pollution property can be sufficiently exerted, and if it is 15 parts by weight or less, the compatibility of the components of Φ.2) with other components ( In the polymerization reaction, "the uniform compatibility and the compatibility of the component (D-2) with other components when the composition is formed) are good, and the hardness of the obtained cured film is high, which is preferable. (&1) The use amount of the base material Wei is more preferably 丨 by weight or more. Further, 098113982 41 201000547 (a 1) The use amount of the diWei-based polysulfide is preferably 12 parts by weight or less. <(a2) (Meth)acrylate having an epoxy group> When a specific representative example of (a2) (fluorenyl) acrylate having an epoxy group is disclosed, an acrylic propylene acrylate is exemplified. Ethoxypropyl (meth) acrylate such as ester, glycidyl methacrylate, etc.; 3,4-epoxycyclohexyl acrylate, 3,4-epoxycyclohexyl methacrylate, a (fluorenyl) acrylate in which an epoxy group such as 3,4-epoxycyclohexyl decyl acrylate or 3,4-epoxycyclohexyl decyl acrylate is directly bonded to an alicyclic structure, but The effect of obtaining the invention of the present application is not limited to these. Among these, in terms of easiness of obtaining and ease of upgrading by (meth)acrylic acid, it is particularly preferred to be a glycidyl methacrylate, a 3.4-epoxycyclohexyl acrylate, or a methyl group. 3,4-epoxycyclohexyl acrylate, 3.4-epoxycyclohexyl decyl acrylate, 3,4-epoxycyclohexyl decyl methacrylate, and the like. (a2) The (fluorenyl) acrylate having an epoxy group may be used singly or in combination of two or more kinds. In the case of producing the component (D-2), (a2) the amount of the (fluorenyl) acrylate having an epoxy group is preferably 5 parts by weight or more and 60 parts by weight or less. When (a2) the (meth) acrylate having an epoxy group is used in an amount of 5 parts by weight or more, it can be sufficiently introduced by a modification of a carboxylic acid having a (fluorenyl) acrylonitrile group (methyl group). a high-hardening property or a high-hardnessing effect by the radical polymerization of an acrylonitrile group, and an effect of improving surface hardenability, if it is 60 parts by weight or less, 098113982 42 201000547 contains a polymer solution of the component (D-2) The viscosity and solution stability become good, and it is preferable to see higher hardenability or hardness due to photoradical polymerization. (a2) The amount of the (fluorenyl) acrylate having an epoxy group is more preferably 15 parts by weight or more. Further, the amount of (a2) (meth) acrylate having an epoxy group is more preferably 55 parts by weight or less. <(a3) Monofunctional mercaptan having a molecular weight of from 1 to 300; Γ) As a raw material for producing component (D-2), it exhibits superior affinity with other components by molecular weight control For the purpose of more excellent defoaming property, it may also contain (a3) a monofunctional mercaptan having a molecular weight of from 1 〇〇 to 300. Further, in the radical polymerizable monomer having a mercapto group as in the component (D-2) and having a functional group which is easily reacted therewith (for example, an epoxy group, an isocyanato group, an alkoxy group, etc.) In the polymerization, the following problems may occur: a side reaction such as a sulfhydryl group and an epoxy group, such as the above-mentioned reaction group, a reductive cross-linking/insolubilization/gelation, but a molecular weight of 1 by using (a3). The monofunctional thiol of 〇~3〇〇 can control the side reaction and suppress the crosslinking/insolubilization/gelation as described below, thereby producing a good component (D-2). As (a3) molecular weight is 1〇〇~3〇〇 <Early-functional thiol, for example, a mercapto thiol such as hexyl mercaptan, mercapto mercaptan, dodecyl mercaptan, decyl mercaptan or octadecyl mercaptan; cyclohexyl mercaptan; Cyclosyl mercaptan; benzene sulfide, chlorobenzene, unpredictable (four) surface alcohol, etc., but as long as the system can obtain the date of the application is not compared with the material. It is considered to be 098113982 43 201000547 reactivity, reaction selectivity, odor, etc., and it is preferably an alkylthiol having 9 to 15 carbon atoms such as mercapto mercaptan or dodecyl mercaptan. When the molecular weight of the monofunctional thiol used in the active energy ray-curable resin composition of the present invention is 100 or more, the volatility is low, so that it does not escape from the reaction system during the polymerization reaction, and the effect is easily exhibited. Further, when the molecular weight of the monofunctional thiol is 300 or less, the compatibility with other monomers is improved, and phase separation is less likely to occur, which is preferable. The more preferable molecular weight of the monofunctional thiol is 150 or more and 250 or less. The (a3) monofunctional thiol can be used singly or in combination of two or more. When (a3) a monofunctional thiol having a molecular weight of 1 〇〇 to 3 Å is used in the production of the component (D-2), the amount thereof is 0.001 parts by weight or more, particularly preferably 〇j by weight or more. It is 5 parts by weight or less, and particularly preferably 4 parts by weight or less. When the amount of (a3) uni-energy thiol is 〇·〇1 part by weight or more, the concentration of the (a3) monofunctional thiol is appropriate, the reactivity is sufficient, and the reaction can be controlled without causing (al) A side reaction between a dimercapto polyoxyalkylene and (a2) an epoxy group-containing (fluorenyl) acrylate. On the other hand, when the amount of the (a3) monofunctional thiol used is 5 parts by weight or less, the unreacted monomer is less likely to be ruined, and the molecular weight of the component (D_2) obtained is appropriately changed. Further, in the case of using (a3) a monofunctional thiol having a molecular weight of 1 〇〇 to 3 Torr, it is a wei group of (al) sulphide sulphate (hereinafter referred to as "M (ai)" ))) and (4)) the molar ratio of (4) to the monofunctional thiol of (10)~ (hereinafter referred to as 098113982 44 201000547 "M(a3)"), the molar ratio M(al)/M(a3) is usually 〇〇1 The above is preferably 〇. 5 or more, more preferably (U or more, and is 2 Å or less, preferably 15 or less, more preferably 10 or less. If M (al) / M (a3) g 〇〇1 or more, the reaction can be controlled without substantially causing an epoxy group of (al) bismuth-based polyoxo-oxygen group and (a2) (epoxy)-propionate having an epoxy group. In the case of the reaction, the viscosity of the dispersion increases, the solubility decreases, and the like, and if it is as follows, the unreacted monomer is hard to remain, and the molecular weight of the obtained component (D_2) is preferable, which is preferable. <(a4) Other vinyl group-containing monomer> In addition to the above (al) to (a3), (a4) another vinyl group-containing monomer may be contained as a raw material in the case of producing the component (D-2). The monomer as the other ethylene group is not limited as long as the effect of the invention of the present application can be obtained, and it is preferred to use a polymer having low reactivity with an epoxy group and not to form a polymer. Those with reduced stability, or those whose skeleton is rigid and do not reduce the hardness, can be improved by increasing the pollution resistance. Specific examples of such (a4) other ethylidene-containing monomers can be exemplified by styrene, or a lower order thereof (carbon number is a group of 4, a halogen-substituted derivative, carbon number) Is a (meth)acrylic acid alkyl ester of K20, a pyridyl (meth)acrylic amine, a (meth)acrylic acid ketone ester having a (poly)cycloalkyl side bond having a carbon number of 5 to 2 Å, ( A radically polymerizable monomer such as a methyl methacrylate or the like may be used alone or as a monomer of the same age, and may be used alone or in combination of two or more. (D-2) (4) The use of other vinyl-containing monomers is preferably 5% by weight or more and 50 parts by weight or less. If (4) other monomers containing Bili = are more than 丨 by weight, dissolve On the other hand, when the amount is 50 parts by weight or less, the resulting cured film has a good scratch resistance and pencil hardness, and thus the amount of the base which is more resistant to the base is more used. Jia is 5 re-edited. (also = contains Ethylene, (a4) other vinyl-containing monomers are used more preferably 4 Parts by weight or less. <Solvent> Including the above (al)~_ ingredients < Free radical polymerization of the monomer mixture. In order to improve the uniformity, a solvent may also be added. Preferable examples of such a solvent include a ketone solvent such as acetone or decylethyl hydrazine (10) hydrazine; and an alcoholic mu 甲 such as ethanol, methanol, isopropanol (IpA) or isobutanol. a solvent such as ether or propylene glycol monomethyl ether; a solvent such as ethyl acetate, propylene glycol monomethyl ether acetate vinegar or acetic acid 2-ethoxyethoxy ketone; an aromatic hydrocarbon solvent such as acetaminophen; and water. 'These solvents may be used alone or in combination of two or more. In the case of using two kinds of w, it is preferred to form a solvent without forming two layers. θ <Radical Polymerization Initiator> In the radical polymerization of the monomer mixture containing the above (al) to (a4) components, a radical polymerization initiator is preferably used. 098113982 46 201000547 The radical polymerization initiator is not particularly limited, and generally known initiators generally used for radical polymerization can be used. Preferred examples include benzamidine peroxide and peroxide peroxide. Organic peroxide such as third butyl; 2,2'-azobisbutyronitrile, 2,2'-azobis(2,4-dimercaptophthalonitrile), 2,2'-azo double An azo compound such as (4-nonyloxy-2,4-dicinyl valeronitrile). These radical polymerization initiators may be used singly or in combination of two or more. <Free Radical Polymerization Method and Conditions> Further, if necessary, the component (a3), the component (a4), the solvent, and the radical polymerization initiator are used in the monomer mixture containing the components (a1) to (a2). The method of mixing/dissolving the monomer component and the solvent in the case of radical polymerization is not particularly limited. For example, it is preferred to add a radical polymerization after mixing the monomer component and the solvent within a certain period of time, preferably within 3 hours. Start the polymerization and start the polymerization. The total concentration of the monomer components in the reaction solution for radical polymerization is preferably 10% by weight or more and 60% by weight or less; and the amount of the radical polymerization initiator used is preferably the total amount with respect to the monomer components. It is preferably 0.1% by weight or more, more preferably 0.2% by weight or more, and most preferably 10% by weight or less, more preferably 2% by weight or less. Further, preferred polymerization conditions are different depending on the radical polymerization initiator to be used, but the polymerization temperature is usually from 20 to 150 ° C, and the polymerization time is usually from 1 to 72 hours. 098113982 47 201000547 <Carboxylic acid having a (meth)propenyl group. In the production of the component (D-2), a carboxylic acid having one or more (meth)acrylonyl groups in one molecule is usually used, and preferably 1 is used. A carboxylic acid having 丨~5 (fluorenyl) acrylonitrile groups in the molecule is added to at least a portion of the epoxy group of the radical polymer obtained in the above manner. Examples of the carboxylic acid having a (meth) acrylonitrile group used herein include, for example, acryl; 2-(f-) acryloxyethyl succinic acid; 2-(methyl) propylene oxime Ethyl hexahydrophthalic acid; polycaprolactone propionate at the end of carboxylic acid, pentaerythritol tri(meth) acrylate with succinic anhydride, phthalic anhydride, hexahydrophthalic anhydride An adduct of an acid anhydride; an adduct of dipentaerythritol penta (meth) acrylate with succinic anhydride, phthalic anhydride, hexahydrophthalic anhydride phthalic anhydride, and the like. These may be used alone or in combination of two or more. <Method and Condition of Addition Reaction> In the above-described addition reaction example, the epoxy group of the radical polymer reacts with the carboxyl group of the carboxylic acid having a (meth) acrylonitrile group. a radical polymer and a carboxylic acid having a (meth) acrylonitrile group, preferably a ratio of an epoxy group of a radical polymer to a carboxyl group of a carboxylic acid having a (meth) acrylonitrile group (hereinafter, It is only called "epoxy/rebel")! The above ratios are used. Further, the epoxy group-enhancing q is preferably iq or less, more preferably 5 or less, still more preferably 2 or less. If the ratio of the epoxy group to the carboxyl group is above the upper % limit, it is possible to prevent a stable f-life drop caused by the (meth) acrylonitrile-based it acid remaining due to 098113982 48 201000547 unreacted. The upper limit value is preferable because it can prevent a decrease in stability due to residual epoxy groups. Further, it is preferred that 5 to 99% of the epoxy groups of the radical polymer react with the carboxyl group of the carboxylic acid having a (meth)dienyl group. The addition reaction is preferably carried out at 50 to 11 (TC for 3 to 50 hours. In the present reaction, 'in order to promote the reaction, for example, triethylamine, tri-f-butylamine, diethylenediamine, N, One or more of N-dimercaptobenzylamine, benzyltrimethylammonium chloride, and one of the stupid bases 4 as a catalyst. The amount used is relative to the reaction mixture (ie, free radical polymer) The total δ of the carboxy group having a (fluorenyl) acrylonitrile group is preferably 〇〇1% by weight or more, more preferably 5% by weight or more, and further preferably 5% by weight or less. It is preferably 1% by weight or less. Further, in the present reaction, in order to prevent radical polymerization due to a (meth) acrylonitrile group of a carboxylic acid having a (fluorenyl) acrylonitrile group, for example, ruthenium is preferably used. One or more of polymerization inhibitors such as hydroquinone, hydroquinone monoterpene ether, catechol, p-tert-butyl catechol, and phenothiazine. The amount used is preferably 0.01% by weight or more with respect to the reaction mixture, and further preferably 5% by weight or more. It is 1% by weight or less, and more preferably 5% by weight or less. According to the above examples, the component (D-2) used in the present invention can be obtained. The active energy ray-curable resin composition of the present invention contains an epoxy resin. When the compound of the group is used as the component (D-1), if the (E) photo-cationic 098113982 49 201000547 sub-hardening initiator is further contained, the surface hardenability is further improved, so that it is preferable to be the component (6). The photopolymerizable photoinitiator is not particularly limited as long as it is preferably a known photoacid generator, and more preferably a diarylsulfonium type or a diarylsulfonium salt; as a counter ion, PF6, Sbp5, Ash, BPh4, CF3〇S〇2, etc. may be exemplified. Further, when only the component is used, in the case where the curability is low, it is preferred to use an amine (triethanolamine or the like) in combination. The sensitization of the class (dibutylphosphine, etc.) and 9-oxopurine is used as a representative example of the (E) photocationic curing initiator, and is not limited to the above. An energy ray-curable resin composition for the purpose of imparting various functionalities, At least one of an antistatic agent, a lubricity imparting agent, an antifogging agent, and a peelability imparting agent is preferably blended. These are not particularly limited as long as the effects of the present invention are not impaired, for example, antistatic to the right. The agent is, in particular, an antistatic agent (a polymer containing a four-stage acid test or a decane coupling agent containing a quaternary ammonium base), which is contained in the Japanese Patent Publication No. 2〇〇3_2〇1444. As a lubricity imparting agent, a polymer having a polydiindenyl oxoalkyl group can be exemplified. On the other hand, as an antifogging agent, a hydrophilic group modified colloidal cerium oxide or bismuth citrate can be exemplified. Colloidal cerium oxide, a polymer or oligomer having a polyalkylene glycol-based hydrophilic group in the side chain. Further, as the releasability-imparting agent, a known fluorene-based, fluorine-based, long-chain acrylic acid can be exemplified. From oligomers to polymers, such as those containing curable groups 098113982 50 201000547. When a human ultraviolet absorber or a hindered amine light stabilizer is blended in the active energy ray-curable resin composition of the present invention for the purpose of imparting various functionalities other than the above, the weather resistance is improved. Therefore, it is preferred. The ultraviolet absorber is not particularly limited as long as it does not impair the effects of the present invention, and preferred examples thereof include a benzotriazole system, a diphenyl phthalate, a salicylic acid, and a cyanoacrylic acid. Ester system, three lectures are UV absorbers, etc. (The hindered amine-based light stabilizer is not particularly limited, and as the preferred compound, for example, an N-methyl group such as TINUVIN 765 manufactured by Ciba Specialty Chemicals Co., Ltd. may be used. TINUVIN 770 manufactured by Ciba Specialty Chemicals Co., Ltd. may also be used. For the purpose of improving the physical properties of the cured film, an antioxidant (for example, a hindered phenol, a sulfur, a phosphorus antioxidant, or the like) may be formulated in the active energy ray-curable resin composition of the present invention. An agglomerating agent, a slip aid, a leveling agent, and the like are usually various additives formulated in the antifouling imparting agent. The blending amount in this case is preferably blended into the entire composition. 1 to 2% by weight. The active energy ray-curable resin composition of the present invention is 25. (The viscosity is 10 to 50 〇 mpa. s. If it is 1 〇 mPa · s or more, the volatilization during coating can be avoided. Or it may cause an unfavorable flow of the solution without becoming a uniform film thickness, and therefore it is preferable that if it is 500 mPa·s or less, the wettability is good and the coating/valley liquid is uniformly diffused, thereby ensuring a uniform film thickness. And thus Preferably, it is 15 mPa · s or more, more preferably 2 〇 mPa · s or more, and more preferably 098113982 51 201000547 450 mPa · s or less, further preferably 4 〇〇 mpa · s or less. The active energy ray-curable resin composition of the present invention does not contain an organic solvent exceeding 5 parts by weight of the product, and thus can be handled as a substantially organic solvent-free one. The environmental pollution of the organic solvent can reduce the environmental load. In addition, the concentration of the solution accompanying the volatilization of the organic solvent does not change, and the concentration is fixed, so that the reuse of the solution becomes easy. As a result, the environmental load is lowered. Specifically, if the amount of the organic solvent is 5% by weight or less of the composition, an organic solvent having a boiling point of 10 〇 1 or less (for example, ethanol, isopropyl alcohol, or the like) is preferable. When the amount of C- or methyl ethyl ketone is 2% by weight or less, the above effects can be sufficiently exhibited. In order to reduce the environmental load to zero, it is more preferable that the composition contains no organic solvent at all. The water in the solvent other than the agent preferably contains no more than 1% by weight of water in the composition. It is very difficult to control the water to be completely free of water, and if the water is set to 1% by weight or less, The active energy ray-curable resin composition of the present invention can provide a cured film having high hardness, excellent scratch resistance and stain resistance, and is excellent in the turbidity due to the separation of the solution. Therefore, it is particularly suitably used for hard coating of an optical recording medium. [η] hardened enamel, and a laminated body having a hard coat layer composed of the hardened yttrium, and an optical recording medium. 98113982 52 201000547 The active energy ray hardenability of the present invention A cured film obtained by irradiating an active energy ray with a resin composition, a laminate having a hard coat layer formed of the cured film, and an optical recording medium are excellent in properties such as hardness and scratch resistance. . The cured film of the present invention is excellent in properties such as hardness and scratch resistance, and therefore is suitable for use as a hard coat layer on the surface of an article. As a method of forming the hard coat layer, the composition may be applied to the surface of the article and then irradiated with an active energy ray to polymerize it; or a film which is irradiated with an active energy ray to be polymerized may be separately prepared and then laminated on the article. . The cured film of the invention can be applied to various articles, and can be applied to optical articles (especially optical information media such as reproduced optical discs, optical recording discs, magneto-optical recording discs, or transparent materials such as touch panels or liquid crystal televisions). «口口", π car related parts (light related, window related items (rear window, side window, Tianzi, etc.)), life related items (various electrical equipment shells, mounting boards, furniture, etc.) The surface protection of cm can be used as a hard coating material for various articles as an applicable article, and specific examples thereof include an optical lens, a light dry/夂 lens, an alpha vehicle window material, and a spectacle lens. The surface protection film of the solar cell, the agricultural eyebrow gel, the transparent film of the inner chamber, and the transparent film for the surface protection of the reflective mark. The laminate of the invention of the present invention is a laminate of a hard coat layer on the surface of various substrates, which is obtained from the layer of + 1 layer. The active energy ray-curable resin material of the present invention is obtained. The hardened film occupies the ^ 098 组成 098 098 098 098 098 098 098 098 098 The type of the substrate is not particularly limited, and it is preferably a substrate composed of a resin. The resin substrate may be any of a plate shape, a shape of 1 and a film, and may be a molded article of any shape. Further, the substrate may be a part of the laminate, and another layer may be interposed between the substrate and the hardened film. The resin substrate may be a thermoplastic resin or a hardened resin which is hardened by heat or active energy rays. Examples of the thermoplastic resin include polyesters such as polyethylene terephthalate (PET) or polyethylene naphthalate, and polymethyl methacrylate (PMMA), which contains thioglycolic acid. Copolymer (MMA) copolymer (decyl methacrylate-styrene copolymer resin (MS resin)), polycarbonate (PC), triethylene phthalate cellulose, acrylonitrile-butadiene-styrene copolymer ( ABS resin), modified polyolefin resin, hydrogenated polystyrene resin, cycloolefin resin (for example, manufactured by ARTON, ZEONEX manufactured by Nippon Kasei, ZEONOR, APEL manufactured by Mitsui Chemicals Co., Ltd.). Examples of the cured resin include hardening of an epoxy resin, a urethane resin, a thermosetting or photocurable acrylic resin, and an organic-inorganic hybrid resin such as thermosetting or photocurable. Things and so on. These base materials 'for example, may be formed by coating them themselves, or may be molded articles by various molding methods. Since the cured film of the present invention is excellent in transparency and excellent in hardness and scratch resistance, it can be applied to an optical article requiring high transparency. In this case, in the case where the substrate must be transparent, it is preferred that the substrate be extruded by any of the methods (4) of the method of coating, squeezing and melting into a 098113982 54 201000547 method or a melt casting method. Further, in the case where the substrate contains a functional group which can be hardened by an active energy ray or heat, it is more preferably cured by active energy ray riding or addition. Further, the substrates may be those of the molded article (article), or may be another layer interposed between the substrate and the coated surface of the composition of the present invention. Further, the term "transparent" means that the transmittance of light of a target wavelength is 80% or more. The cured film obtained from the active energy ray-curable resin composition of the present invention is particularly suitably used as a stain-resistant hard coat layer of an optical recording medium. Therefore, a laminate having the hard coat layer on the surface is preferably used as an optical recording medium, and it is particularly preferable to form the hard coat layer as an optical recording medium which is present on the outermost surface of the light incident side. In such an optical recording medium, at least one light-transmitting layer may be provided between the hard coat layer and the recording film surface. The optical recording medium is typically a disc, and the type may be any of a phase change type, a color type, a magneto-optical type, and a reproduction-only type. Among them, high-density recording optical discs such as I DVD, HD DVD, and Blu-Ray Disc are preferable. In order to increase the recording density, the beam diameter of the recording mark and the recording/reproducing laser light becomes smaller, so it is sensitive to stains and scratches, and the jitter is liable to become high or the recording/reproduction error is easily increased, which requires excellent contamination and hardness. Hard coating. Preferably, the optical recording medium having a multi-layer film including at least a recording layer or a reflective layer on the substrate has a structure of the cured film of the present invention at least on the outermost surface of the light-receiving side of the optical recording medium. If there is a stain or scratch on the outermost surface of the light incident side, the recording/reproducing beam will be blocked and an error will occur. Therefore, the cured film of the present invention is provided on the outermost surface of the light incident side as a pollution-resistant one more than 098113982 55 201000547. coating. For example, there is: (1) a light incident surface on the opposite side of the substrate side with respect to the recording layer or the reflective layer as in the case of a Blu-Ray Disc or the like; (2) light on the substrate side with respect to the recording layer or the reflective layer as in a DVD or the like The person who entered the face. In this case, the hard coat layer must have light transmissivity. The term "transparency" generally refers to a state in which the transmittance is 80% or more for light of a wavelength of recording/reproducing light. The cured film of the present invention may also be provided on the outermost surface on the side opposite to the light incident side. The following is a description of the preferred layer configuration of the optical recording medium. (1) An optical recording medium having a side surface of a multilayer film as an incident side surface of a recording/reproducing light beam. A preferred layer structure of such an optical recording medium has a (reflective layer,) recording layer and a hard coat layer on the substrate. Hardened film). Further preferably, a light transmitting layer is provided between the recording layer and the like and the hard coat layer. By providing the light transmitting layer, the interval between the light incident side most surface and the recording layer (reflecting layer) of the optical recording medium is increased, so that the recording/reproducing light beam is hardly affected by the stain or scratch of the media surface, and thus it is preferable. . The film thickness of the light transmitting layer is preferably 30 Am or more, more preferably 7 Å or more. Further, the thickness of the light transmitting layer is preferably 2 〇〇 #爪以下, more preferably 15 〇 #m or less. Any layer may be provided between the layers depending on the purpose. For example, an inorganic protective layer made of a dielectric or the like may be provided on the upper and lower sides of the recording layer. Alternatively, in order to increase the recording capacity, a plurality of recording layers or reflective layers may be provided with the light-transmissive spacer layer interposed therebetween. The light-transmissive spacer layer is provided to prevent signal mixing between the plurality of recording layers 098113982 56 201000547, and the film thickness is preferably the same as that of the light-transmitting layer. As an example of a preferred layer, a substrate/reflective layer/inorganic protective layer/recording layer/inorganic protective layer/light transmitting layer/hard coating layer, substrate/reflecting layer/light transmitting layer/hard can be preferably cited. Composition of coating, or substrate/reflective layer/inorganic protective layer/recording^ Inorganic protective layer/transparent spacer layer/reflective layer/inorganic protective layer/recording layer/inorganic protective layer/transparent layer/hard coating layer, substrate/ The inorganic protective layer/recording layer/inorganic protective layer/transmissive layer/hard coat layer or the like is constituted, but is not limited thereto. (The material of the substrate, the recording layer, the reflective layer, and the heat-protecting layer is not particularly limited, and any known ones used in an optical recording medium can be used. As the substrate, polycarbonate, polyacrylate, or the like can be used. Resin such as polyolefin, glass, etc. When recording and reproducing light is incident from the substrate side, the substrate must be transparent to the recording/reproducing light. The thickness of the substrate is usually 〇3 to 12 # m. Most of the grooves are formed on the substrate. (ditch) or pit. The recording layer has a phase change type, a pigment type, a magneto-optical type, etc. In the case of a reproduction-only type, V., sometimes there is no recording layer. Oxygen is often used in the phase change type recording layer. Examples of the elemental alloy include a GeSbTe alloy, an InSbTe alloy, a GeSnTe alloy, and an AglnSbTe alloy. The thickness of the phase change recording layer is usually 3 nm to 50 nm. a gas pigment, a cyanme dye, a phthalphthalein pigment, or a porphyrin dye, but is not limited thereto. The thickness of the dye recording layer is usually 50 nm. ~1 m. Inorganic protection The material is determined by considering the refractive index, thermal conductivity, chemical stability, mechanical strength, adhesion, etc., and dielectric materials are generally used. The material of the inorganic protective layer is generally transparent and has high transparency. It is a high melting point metal or a half of an oxide, a sulfide, a milk sulfide, a nitride, or a fluoride of Ca, jy [g, Li, etc. The thickness of the inorganic protective layer is usually about 5 to 2 nm. The reflective layer is preferably made of a material having a large reflectance and thermal conductivity. As a material of the reflective layer having a large reflectance and thermal conductivity, a metal containing Ag, Au, A, Cu or the like as a main component is exemplified. Among them, Ag has a higher reflectance and thermal conductivity than Au, Al, and Cu. These may also contain Cr, Mo, Mg, Zr, V, Ag, In, Ga up to about 5 atom%. , Zn, Sn, Si, Cu,

Au、A1、Pd、Pt、Pb、Ta、Ni、Co、O、Se、V、Nb、Ti、 〇、N等元素。反射層之厚度通常為3〇〜2〇〇nm。又，反射 層亦可為所謂半反射層。 透光層及透光間隔層只要具有透光性且具有規定厚度即 可，對材質及形成方法並無特別限定，通常使用樹脂組成 物，代表性的是利用以下2種方法來形成。第一種方法，係 以旋塗法等將硬化性樹脂組成物塗佈後，利用光或熱使其硬 化而形成臈之方法。此時，若含有胺基曱酸乙酯丙烯酸酯， 則可抑制由於硬化收縮所造成的翹曲並且可提高表面的硬 度及耐劃傷性，因而較佳。又，在不損害透光性之範圍内含 有膠體二氧化矽等無機氧化物微粒，亦可提高表面之硬度及 耐劃傷性，因而較佳。第二種方法，係將以溶劑澆鑄法或熔 融擠出成形法等而製作之薄膜直接進行贴附或者經由黏著 098113982 58 201000547 劑而進行貼附之方法。此時，為了進—牛 芡扠问表面的硬度及 耐劃傷性，較佳為在不損害透光性之範圍内含有膠體二氧化 石夕等無魏化物齡。有時亦錢細隔層均成有 或凹坑。 以下，就由自本發明之組成物所獲得的硬化膜所構成之硬 塗層的形成方法力口以說明。通常為如下方法：以旋塗法等在 / 如上述之層上將本發明之域物崎塗職，_活性能量 線照射使其聚合而形成硬化膜。或者，亦較佳為如下方法. 在剝離性薄膜上將本發明之組成物進行塗佈並利用活性能 量線照射使其聚合硬化而形成膜後，將膜側直接或者經由黏 著劑貼附於光記錄媒體上，剝離薄膜，而形成硬塗層。進而， 亦較佳為如下方法：在以溶織鑄法姐融擠出成形法等所 製作之薄膜上將本發明之組成物進行塗佈後，利用活性能量 線照射使其聚合而成為硬化膜，將形成有硬化膜之薄膜直接 k.,. 或者經由黏著劑貼附於光記錄媒體上，藉此同時形成透光層 與硬塗層。 乍為八有此種層構成之光記錄媒體，則有d以 等。 於用以形成硬塗層之方法之任意方法中，為了進一步提高 表面的硬度/耐劃傷性，均可在不損害透明性等其他性能之 範圍内調配人無機氧化物微粒。 、、疋在以旋塗法形成後使其硬化、膜化的情況下， 098113982 59 201000547 若使用如提高膜硬度之組成物’則通常產生由於硬化收縮所 導致之Μ曲。為了避免此情形’尤佳為調配人無機氧化物微 粒及/或含有胺基甲酸乙酯丙烯酸酯。 (2)將基板側表面作為記錄/再生光束入射側表面之光記錄媒 體 此種光記錄媒體之較佳層構成，係在基板上依序具有記錄 層（、反射層），且在基板的另一面上具有硬塗層者。記錄/ 再生光通過硬塗層、基板而入射至記錄層或反射層。亦可在 基板與硬塗層之間設置透光層。 亦可根據目的’在各層間設置任意之層。例如，亦可在記 錄層的上下設置由介電體等所構成之無機保護層。又，為了 提尚記錄容量，亦可以透光間隔層為介隔而設置複數層記錄 層或反射層。 作為尤佳之層構成之例，可較佳地舉出：硬塗層/基板/無 機保護層/記錄層/無機保護層/反射層、硬塗層/基板/反射層 之構成，或硬塗層/基板/無機保護層/記錄層/無機保護層/反 射層/透光間隔層/無機保護層/記錄層/無機保護層/反射層、 硬塗層/透光層/基板/無機保護層/記錄層/無機保護層/反射 層等之構成，但並不限定於該等。 各層之材質及厚度較佳為與（1)相同。 作為具有此種層構成之光記錄媒體，則有DVD±R、DVD 土RW、DVD-ROM等各種DVD(亦包括具有複數層記錄層之 098113982 60 201000547 DVD)或 HD DVD。 本構成中之硬塗層之形成方法通常為以下方法：以旋塗法 等將本發明之組成物塗佈於基板等上，然後利用活性能量線 照射使其聚合硬化而成為膜。 作為用以形成由本發明之硬化膜所構成之硬塗層之通常 的塗佈方法，作為例子，可舉出：旋塗法、浸塗法、流塗法、 喷塗法、棒塗法、凹印塗佈法、輥塗法、刮刀塗佈法、氣刀 塗佈法等’尤佳輕塗法。在將本發明活性能量線硬化性樹 脂，成物進行㈣㈣成塗膜的情況下，若為-面使被塗佈 物高速旋轉一面塗佈塗佈液之方法，則能夠於短時間内均勻 地，佈’而且即使殘留少量的揮發性有機溶劑或水，但在塗 佈日守其大部分揮發’因而亦可省略乾燥步驟。因此，就生產 效率/品質穩定/生產設備成本之降低等各方面而言，作為光 記錄媒體用途中之塗佈方法，域塗法最為合適。Au, A1, Pd, Pt, Pb, Ta, Ni, Co, O, Se, V, Nb, Ti, 〇, N and the like. The thickness of the reflective layer is usually from 3 〇 to 2 〇〇 nm. Further, the reflective layer may also be a so-called semi-reflective layer. The light-transmitting layer and the light-transmitting spacer layer are not particularly limited as long as they have a light-transmissive property and have a predetermined thickness. The resin composition is usually used, and is typically formed by the following two methods. The first method is a method in which a curable resin composition is applied by a spin coating method or the like, and then hardened by light or heat to form a crucible. In this case, if the amino phthalic acid acrylate is contained, the warpage due to the hardening shrinkage can be suppressed, and the hardness and scratch resistance of the surface can be improved, which is preferable. Further, it is preferable to contain inorganic oxide fine particles such as colloidal ceria in the range which does not impair the light transmittance, and to improve the hardness and scratch resistance of the surface. In the second method, a film produced by a solvent casting method, a melt extrusion molding method, or the like is directly attached or adhered by adhesion of 098113982 58 201000547. In this case, in order to improve the hardness and scratch resistance of the surface of the burr, it is preferable to contain colloidal silica, such as colloidal silica, in the range which does not impair the light transmittance. Sometimes the fine compartments are formed with pits or pits. Hereinafter, a method of forming a hard coat layer composed of a cured film obtained from the composition of the present invention will be described. In general, the method of the present invention is carried out by spin coating or the like on the layer as described above, and the active energy ray is irradiated to polymerize to form a cured film. Alternatively, it is also preferably a method in which the composition of the present invention is applied onto a release film and is cured by polymerization with an active energy ray to form a film, and then the film side is attached to the light directly or via an adhesive. On the recording medium, the film was peeled off to form a hard coat layer. Furthermore, it is also preferable to apply the composition of the present invention to a film produced by a melt-kneading method such as extrusion molding, and then polymerize it by active energy ray irradiation to form a cured film. The film formed with the cured film is directly k., or attached to the optical recording medium via an adhesive, thereby simultaneously forming the light-transmitting layer and the hard coat layer. For an optical recording medium having such a layer, there are d and so on. In any of the methods for forming a hard coat layer, in order to further improve the hardness/scratch resistance of the surface, the human inorganic oxide fine particles can be blended in a range that does not impair the other properties such as transparency. In the case where the crucible is formed by spin coating and then hardened and filmed, 098113982 59 201000547, if a composition such as a film hardness is used, distortion due to hardening shrinkage usually occurs. In order to avoid this, it is preferred to formulate the inorganic oxide particles and/or the ethyl urethane acrylate. (2) an optical recording medium having a substrate side surface as an optical recording medium for recording/reproducing a light incident side surface, preferably having a recording layer (reflecting layer) on the substrate, and another substrate A hard coating on one side. The recording/reproducing light is incident on the recording layer or the reflective layer through the hard coat layer or the substrate. A light transmissive layer may also be provided between the substrate and the hard coat layer. Any layer may be provided between the layers depending on the purpose. For example, an inorganic protective layer made of a dielectric or the like may be provided on the upper and lower sides of the recording layer. Further, in order to increase the recording capacity, a plurality of recording layers or reflective layers may be provided as a spacer for the light-transmitting spacer layer. As an example of a particularly preferable layer constitution, a hard coat layer/substrate/inorganic protective layer/recording layer/inorganic protective layer/reflective layer, a hard coat layer/substrate/reflective layer, or a hard coat layer may be preferably exemplified. Layer/substrate/inorganic protective layer/recording layer/inorganic protective layer/reflective layer/transparent spacer layer/inorganic protective layer/recording layer/inorganic protective layer/reflective layer, hard coating/transparent layer/substrate/inorganic protective layer The composition of the recording layer, the inorganic protective layer, the reflective layer, and the like is not limited thereto. The material and thickness of each layer are preferably the same as (1). Examples of the optical recording medium having such a layer structure include various DVDs such as DVD±R, DVD RW, and DVD-ROM (including 098113982 60 201000547 DVD having a plurality of recording layers) or HD DVD. The method for forming the hard coat layer in the present embodiment is generally a method in which the composition of the present invention is applied onto a substrate or the like by a spin coating method or the like, and then polymerized and cured by irradiation with an active energy ray to form a film. Examples of a usual coating method for forming a hard coat layer composed of the cured film of the present invention include a spin coating method, a dip coating method, a flow coating method, a spray coating method, a bar coating method, and a concave coating method. Printing method, roll coating method, knife coating method, air knife coating method, etc. 'Easy light coating method. When the active energy ray-curable resin of the present invention is formed into a coating film by (4) (4), if the coating liquid is applied to the surface of the object to be coated at a high speed, the coating liquid can be uniformly applied in a short time. , cloth 'and even if a small amount of volatile organic solvent or water remains, but it is mostly volatilized on the coating day' and thus the drying step can be omitted. Therefore, in terms of production efficiency, quality stabilization, and reduction in production equipment cost, the domain coating method is most suitable as a coating method in optical recording media applications.

以上述塗佈方法形成塗膜後，藉由照射活性能量線而獲得 硬匕膜對於所獲得硬化膜之厚度並無制限定，例如可為 5二以上1可為2㈣以下。各自的較佳之膜厚之範 ，1根據光記錄媒體的種類及層構成而任意地決定。 厘t明之领能量線硬化性樹脂組成物在可進行薄膜化/ 、兩方面極有意義。經塗佈而成之塗膜之厚度，較佳 為 0·01 〜2Π it ^ , “坩’在重視硬度的情況下，尤佳為2〜1〇 在重視抑制氺#々立 以m ’ 先5己錄媒體之翹曲且相對不重視硬度的情況 098113982 61 201000547 下，尤佳為0.01〜2 //m。 作為活性能量線之照射法，例如可舉出：照射自気氣燈、 氙氣閃光燈、低壓水銀燈、高壓水銀燈、超高壓水銀p、 且 金" 屬鹵素燈、碳弧燈、鎢燈等光源發出之紫外線，或者自通常 為20〜2000 kV之粒子加速器中取出之電子束、α線、 β 線、7線或者軟X射線或硬X射線等X射線等活性能量、後 之方法。 利用此種活性能量線使其硬化之硬化膜係生產性/物性之 平衡為優異者，因而尤佳。 使本發明組成物硬化而成之硬化膜、以及由該硬化膜所_ 成之硬塗層，較佳為滿足下述物性。 1)鉛筆硬度 在厚度1mm之聚碳酸酯薄膜上’形成厚度為3 之由 本發明組成物所構成之塗膜，於氧濃度為2〇〇/。之條件下，使 用於波長254 nm下的放射照度為4〇〇 mw/cm2之高壓水銀 燈’以成為1000 mJ/cm2的累計光量之方式照射紫外線而獲 得硬化膜，該硬化膜表面之鉛筆硬度較佳為B以上。進而 較佳為HB以上。再者’此時之放射照度，係依據JIS(Japanese Industrial Standard，日本工業標準）(JIS_C Mo、！ 2〇〇6) ’使 用具有波長254 nm用感測器之照度計進行測定。 此處，鉛筆硬度自柔軟者起依序為6B、5B、…、B、HB、 F、Η、2H、3H、"·9Η。 098113982 62 201000547 2)接觸角 在厚度為1 mm之聚碳酸酯薄膜上，形成厚度為3以瓜之 由本發明組成物所構成之塗膜，於氧濃度為2〇%之條件下， 使用於波長254 nm下的放射照度為400 mW/cm2之高壓水 銀燈，以達到1000 mj/cm2的累計光量之方式照射紫外線而 獲得硬化膜，該硬化膜表面之水的接觸角為8〇度以上，較 佳為針對十六烷的接觸角為25度以上。 f: 3)ESCA(XPS) 在厚度為100 /zm之易接著之聚對苯二曱酸乙二醇酉旨 (PET)薄膜上，形成厚度為3 // m之由本發明組成物所構成 之塗膜，於氧漢度為20%之條件下，使用於波長254 nm下 的放射照度為400 mW/cm2之高壓水銀燈，以達到5〇〇 mJ/cm2的累計光量之方式照射紫外線時，自硬化膜的膜表 面起厚度為3 nm之位置之耐污染性賦予基的含量，較佳為 ( 該硬化膜整體之耐污染性賦予基的平均含量之3倍以上，尤 佳為3.2〜1〇〇倍。即，根據本發明之組成物，較佳為耐污 染性賦予基特異性且高濃度地存在於硬化膜的表面。可使硬 化膜成為此種構成係本發明組成物之特徵之一，其結果組成 物中之耐污染性賦予基的含量即使較低例如為組成物整體 之1重量％，塗膜表面之耐污染性賦予基的量亦會變多，結 果硬化膜之耐污染性變得優異。 於本說明書中，所謂耐污染性賦予基，係指聚二曱基矽氧 098113982 63 201000547 烷基、全氟烷基、全氟伸烷基等可賦予耐污染性之美。 該耐污染性賦予基之含量，例如可藉由使用χ射^°光電 子光譜分析裝置（以下稱為ESCA或XPS^、日丨+ 1 〜 4入Fb)之測定而求得。 即，利用ESCA(XPS)求出自表面起3 _之範圍的原子數 比，與該組成物的平均組成比進行比較，藉此可求出。此處， 例如在使用氟系耐污染性賦予基的情況下，求出F/c比&在 使用矽氧系耐污染性賦予基的情況下，求出Si/C比，箱^ 可進行比較。 胃 4)耐磨性After the coating film is formed by the above coating method, the hard enamel film is obtained by irradiating the active energy ray, and the thickness of the obtained cured film is not limited, and may be, for example, 5 or more and 1 or 2 or less. The preferred film thickness of each of them is arbitrarily determined depending on the type of the optical recording medium and the layer configuration. The energy-line curable resin composition of PCT T-Ming is extremely meaningful in terms of thinning and/or both. The thickness of the coated coating film is preferably 0·01 〜2Π it ^ , "坩" in the case of emphasis on hardness, especially preferably 2~1〇 in the emphasis on suppression 氺#々立以m ' first 5 The warpage of the recorded media and the relatively inferior importance of hardness 098113982 61 201000547, especially preferably 0.01~2 //m. As the active energy line irradiation method, for example, irradiation from xenon lamp, xenon flash lamp , low-pressure mercury lamp, high-pressure mercury lamp, ultra-high pressure mercury p, and gold " ultraviolet light emitted by a light source such as a halogen lamp, a carbon arc lamp, a tungsten lamp, or an electron beam taken from a particle accelerator of usually 20 to 2000 kV, α Active energy such as X-rays such as rays, β-rays, and 7-rays, or soft X-rays or hard X-rays, etc. The balance of productivity/physical properties of the cured film which is hardened by such active energy rays is excellent. More preferably, the cured film obtained by hardening the composition of the present invention and the hard coat layer formed from the cured film preferably satisfy the following physical properties: 1) Pencil hardness on a polycarbonate film having a thickness of 1 mm Forming a composition of the present invention having a thickness of 3 The coating film is irradiated in such a manner that the high-pressure mercury lamp having a irradiance of 4 〇〇mw/cm 2 at a wavelength of 254 nm is irradiated at a concentration of 1000 mJ/cm 2 at an oxygen concentration of 2 〇〇 /. The cured film is obtained by ultraviolet rays, and the pencil hardness of the surface of the cured film is preferably B or more. Further preferably HB or more. Further, the illuminance at this time is based on JIS (Japanese Industrial Standard) (JIS_C Mo). 2!6) 'Measurement using a illuminometer with a wavelength of 254 nm using a sensor. Here, the pencil hardness is 6B, 5B, ..., B, HB, F, Η, 2H from the softer. 3H, "·9Η. 098113982 62 201000547 2) Contact angle On a polycarbonate film having a thickness of 1 mm, a coating film composed of the composition of the present invention having a thickness of 3 to a melon is formed at an oxygen concentration of 2 〇. Under the condition of %, a high-pressure mercury lamp with a illuminance of 400 mW/cm2 at a wavelength of 254 nm is irradiated with ultraviolet rays to achieve a cumulative light amount of 1000 mj/cm2 to obtain a cured film, and a contact angle of water on the surface of the cured film More than 8 degrees, preferably The contact angle to hexadecane is 25 degrees or more. f: 3) ESCA (XPS) The thickness is formed on a polyethylene film of polyethylene terephthalate (PET) having a thickness of 100 / zm. 3 / m of the coating film composed of the composition of the present invention, under the condition of 20% oxygen, using a high-pressure mercury lamp having a radiance of 400 mW/cm 2 at a wavelength of 254 nm to reach 5 〇〇 mJ When the ultraviolet light is applied to the film surface of the cured film at a thickness of 3 cm from the film surface of the cured film, the content of the contamination imparting group is preferably (the average content of the stain resistant layer of the cured film as a whole) More than 3 times, especially preferably 3.2 to 1 times. That is, the composition according to the present invention is preferably present on the surface of the cured film with a specificity against the stain imparting group and a high concentration. The cured film can be one of the characteristics of the composition of the present invention, and as a result, the content of the stain resistance imparting group in the composition is as low as, for example, 1% by weight of the entire composition, and the surface of the coating film is resistant to contamination. The amount of the imparting group is also increased, and as a result, the stain resistance of the cured film becomes excellent. In the present specification, the term "concentration resistance" refers to a polydidecyloxy group 098113982 63 201000547 alkyl group, a perfluoroalkyl group, a perfluoroalkylene group or the like which imparts stain resistance. The content of the stain resistance imparting group can be determined, for example, by measurement using a krypton photoelectron spectrometer (hereinafter referred to as ESCA or XPS^, 丨+1 to 4 into Fb). In other words, the ratio of the number of atoms in the range of 3 _ from the surface by ESCA (XPS) can be obtained by comparing the average composition ratio of the composition. Here, for example, when a fluorine-based antifouling imparting group is used, the F/c ratio & when a xenon-based antifouling imparting group is used, the Si/C ratio is obtained, and the box can be obtained. Comparison. Stomach 4) wear resistance

在厚度為100 //m之易接著之聚對苯二甲酸乙二醇自旨 (PET)薄膜上，形成厚度為3 _之由本發明組成物所構= 之塗膜，於氧濃度為20%之條件下，使用於波長254下 的放射照度為400 mW/cm2之高壓水銀燈，以達到5〇〇 mJ/cm2的累計光量之方式照射紫外線時，所得硬化膜之耐 磨性較佳為25.0以下。再者，該耐磨性之測定方法記載於 下述之實施例項中。此時之放射照度，係依據JIS(JIS_C 1609-1 2006)，使用具有波長254nm用感測器之照度計進行 測定。 5)耐指紋性 可獲得如下之耐指紋去除性極佳之表面物性：在使指紋或 人工指紋液附著於藉由使用本發明活性能量線硬化性樹脂 組成物所獲得之硬化臈或硬塗層的表面上，然後於200 g負 098113982 64 201000547 重下以彳时纟峨去的情況τ，以3姉返以内之拭去操作、 進而較佳為2個往返以内之操作可完全除去指紋。再者，人 工才曰紋液，為以甘油三油酸酯/JIS試驗用粉體卜Η種（關東 ^日本氣體工業技術協會製造）/曱氧基丙醇= 1/0.4/10(重量比）之混合物，且為次世代光碟之财指紋性評 價中所採用之溶液。 作為DVD或次世代光碟用之耐指紋性賦予劑或光學顯示 器用途之耐指紋性賦予劑而開發出之許多耐污染性賦予 d例如大多係即使附著量或附著徑較小，但在拭去時潤滑 性(光滑性)過高或者硬度不足，因此易於在面上擴散，即使 拭去亦需要3個往返以上者；但本發明之硬化膜及硬塗層具 有如下特徵：因硬倾的硬度較高並且無過度_滑性，故 能夠以較少的拭去次數拭去。 一紗卜之更大特徵：即使附著指紋或人工指紋液’ =___進行3個往返的擦拭，重複2〇次 拭去刼作，但指紋去除性仍不會下降。 即使使用以較少的拭去次數可拭去之 因習知者係硬度不足 於將_ 7染性賦予劑自身並不會固定 ,,,A4 覆進仃附著、拭去操作，則以數次 〜十數次㈣會對表面造成 紋嫩進入其間隙中，或者耐的㈣，而指紋(或人工指 失，因而指紋去除性之耐久性/錄賦予劑自身自表面流 差’但本發明之硬化膜及硬塗 098113982 65 201000547 層具有如下特徵’具有如下極高的性能耐久性：因硬化後之 硬度較高並且將具有财污染性賦予基之化合物固定於膜表 面上’故即使重複進行20次以上、較佳為4〇次以上操作， 指紋（或人工指紋液）之去除性仍不會下降。 6)硬化性 較佳為獲得如下之硬化膜.於厚度為1 mm的聚碳酸|旨薄 膜上形成厚度為3 /zm之由本發明活性能量線硬化性樹脂 組成物所構成之塗膜，於氧濃度為20%之條件下，使用於波 長254 nm下的放射照度為400 mW/cm2之高壓水銀燈，以 達到500 mJ/cm2的累計光量之方式照射紫外線時，硬化進 行至完全不黏著為止之硬化膜。再者，此時之放射照度，係 依據JISQIS-C 1609-1 2006) ’使用具有波長254 nm用感測 器之照度計進行測定。 [實施例] 以下’舉出實施例更具體地說明本發明。以下實施例中所 揭示之材料、使用量、比例、處理内容、處理順序等，只要 不脫離本發明之主旨則可加以適當變更。因此，本發明之範 圍並不限定於以下所揭示之具體例。 再者’實施例中之「份」及「％」分別表示「重量份」及 「重量％」。 於實施例等中所獲得之活性能量線硬化性樹脂組成物以 及由該組成物所構成之硬化膜的物性，係藉由下述方法進行 098113982 66 201000547 評價。 (1) 黏度 對於組成物使用Brookfield型黏度計（Brookfield公司之 DV-1型），以25°C、30〜60rpm之條件進行測定（單位：mPa· s)。 (2) 外觀 以目測對組成物之外觀進行如下評價。 f 〇：以目測無法確認異物，均勻。 X :以目測可確認異物，不均勻。 (3) 硬化性 在厚度為1 mm之聚碳酸酯薄膜上，利用旋塗法形成厚度 為3 /zm之由活性能量線硬化性樹脂組成物所構成之塗 膜’於氧濃度為20%之條件下，使用於波長254 nm下的放 射照度為400 mW/cm2之高壓水銀燈照射紫外線，以如下方 式來評價此時之硬化性。再者，此時之放射照度，係依據 JIS(JIS-C 1609-1 2006) ’使用具有波長254 nm用感測器之 照度計EYE UV TESTER UV-PFA1受光部PD-254(岩崎電 氣公司製造）進行測定。 〇：累計光量S500 mJ/cm2下硬化膜表面變得不黏著。 △ : 500 mJ/cm2〈累計光量$ 1000 mJ/cm2下硬化祺表面 變得不黏著。 X :累計光量=1 〇〇〇 mJ/cm2下硬化膜表面並不變得不黏 098113982 67 201000547 著。 (4) -1透明性（霧值） 對於硬化膜基於JIS K-7105之條件測定並評價霧值。（4)-2 透明性（目測） 對於硬化膜以目測進行如下評價。 〇：塗佈膜上完全未見模糊、混濁、白化。 △:塗佈膜均勻地稍微地模糊。 X :塗佈膜不均勻地模糊、或者部分或整體混濁、或者看 見白化。 (5) 鉛筆硬度 對於硬化膜使用JIS標準鉛筆硬度計（太佑機材公司製 造），基於JIS K-5400之條件來進行測定，以不帶損傷之最 硬的鉛筆之支進行評價。 (6) 耐劃傷性 對於硬化膜使用鋼絲絨#〇〇〇〇,於200 g負重下進行摩擦， 進行如下評價。 ◎:進行10個往返，以目測完全無法確認損傷。 〇：進行5個往返，以目測無法確認損傷，進行10個往 返，以目測可確認損傷。 X :進行5個往返，以目測可確認顯著的損傷。 (7) 水之接觸角 將0.002 ml純水滴加至硬化膜上，測定1分鐘後之接觸 098113982 68 201000547 角。再者，接觸角之測定中係使用接觸角計（協和界面科學 公司製造之DropMaster 500)(單位：度）。 (8) 十六烧之接觸角 將0.002 ml十六烷滴加至硬化膜上，測定1分鐘後之接 觸角。再者，接觸角之測定中係使用接觸角計（協和界面科 學公司製造之DropMaster 500)(單位：度）。 (9) 指紋附著性 f 在射出成形為光碟形狀之厚度為1.1 mm之聚碳酸醋基板 上，以3000 rpm旋塗人工指紋液，於60°C下乾燥3分鐘’ 而製成人工指紋液母盤。再者，人工 指紋液為甘油三油酸酯 /JIS試驗用粉體Ml種（關東土壌，日本粉體工業技術協會 製造)/甲氧基丙醇==1/0.4/10(重量比）之混合物’且為次世代 光碟之耐指紋性評價中所採用之溶液。 準備以#240砂紙將No. 1之矽酮橡膠之較小一方的端面粗 ί , 化成一樣之轉印材料，以4.9 Ν之固定負重將粗化的端面擠 壓於該母盤上1〇秒種，繼而以4.9 Ν之固定負重將上述端 面擠壓於進行評價之硬化膜表面上(操作L1)。 進而，連續重複進行η次以4.9 Ν之固定負重將粗化的端 面擠壓於母盤上10秒之操作，增加人工指紋液之附著量 後’繼而以4.9 Ν之固定負重將上述端面擠壓於進行評價之 硬化膜表面上(操作Ln)。 以倍率為1 〇〇倍之附有標度之顯微鏡目視觀察由於該操 098113982 69 201000547 作所附上之人工指紋液之附著徑，在將最大附著徑保持於 20 /zm以下之範圍内，將η成為最大之操作Ln作為人工 指紋液附著性。 η成為最大之Ln較佳為L3或L4 ’進而較佳為L4。 (10) 指紋拭去性 以鼻脂來代替皮脂，將鼻脂附著於拇指上，將該拇指擠壓 於硬化膜上3秒鐘，將指紋附著於硬化膜上。將以衛生紙 (Crecia公司製造）輕拭表面，於間隔15 cm之狀態下，以目 測無法看見該指紋為止之往返次數作為指紋拭去性進行評 價。 (11) 指紋拭去耐久性 以鼻脂來代替皮脂，將鼻脂附著於拇指上，將該拇指擠壓 於硬化膜上3秒鐘，將指紋附著於硬化膜上。進行3個往返 以捲繞在200 g砝碼上之衛生紙(Crecia公司製造)擦拭該指 紋之操作。進行該操作直至重複次數為第20次為止。在該 第20次操作後，於間隔15 cm之狀態下，若以目測無法看 見指紋則評價為〇，若以目測看見指紋則評價為X。 (12) 耐麥克筆油墨附著性 以油性麥克筆（Zebra公司製造之Mackee Care極細（黑）之 細）描繪線’若在3 0秒後排斥線則評價為若不排斥線則 評價為X。 (13) 耐麥克筆油墨拭去性 098113982 70 201000547 以油性麥克筆(Zebra公司製造之Mackee Care極細（黑）之 細）描繪線，30秒後以衛生紙(Crecia公司製造)擦拭表面， 於3個往返以内，若拭去則評價為〇，若未拭去則評價為X。 〈製造例1〉活性能量線硬化性化合物(d_丨）之合成 於1000 ml之可分離式圓底燒瓶中加入曱基丙烯酸全氟辛 基乙酯50g、曱基丙烯酸月桂酯10g、α,ω_二巯基丙基聚 二甲基矽氧烷(數量平均分子量為1600)10 g、曱基丙烯酸環 ρ 氧丙Ss 30 g、十一垸基硫醇2 g(十二院基硫醇之基數/ α，ω-二巯基丙基聚二甲基矽氧烷之sH基數=^78，基 /環氧基=0.106)、1-甲氧基_1_丙醇(1&gt;(}^/[)2〇〇§，於氮氣流下 使内溫升溫至約60°C。之後’分2次添加總計1.5 g之2,2'_ 偶氮雙(2,4-二甲基戊腈)(V65) ’於65°C下繼續攪拌6小時。 之後，將内溫提高至80°C，使V65完全失活後，恢復至室 溫。數量平均分子量為15000，固形份濃度約為34%。 I， 再者，數量平均分子量係藉由凝膠滲透層析（Gpc，Gel Permeation Chromat0graphy)法，以 THF 作為溶劑進行測 疋。刀子里為聚本乙稀換算分子量。 接著，於空氣環境下加熱至卯^後，加入對曱氧基苯酚 0.1 g、二笨基膦0.5 g。5分鐘後，將丙烯酸丨5 3 g溶解於 PGM 50g中’用3〇分鐘滴加至圓底燒瓶中。其間，將液溫 保持於90〜1〇5ΐ。之後，使液溫上升至u〇t，於此溫度 下維持8小時後，恢復至室溫。固形份濃度為33(^04)。 098113982 71 201000547 此處’固形份濃度，係量取反應液1 g置於鋁杯中，於80 °C下真空乾燥3小時後，測定殘留固形物量（3點之平均值） 作為固形份濃度。 &lt;製造例2&gt;活性能量線硬化性化合物（d_2)之合成 於1000 ml之可分離式圓底燒瓶中加入曱基丙烯酸曱酯 35 g、二巯基丙基聚二曱基矽氧烷(數量平均分子量為 1600)15 g、甲基丙烯酸環氧丙酯50 g、十二烷基硫醇2 g(十 二烷基硫醇之SH基數/α ,ω-二酼基丙基聚二曱基矽氧烷之 SH 基數= 0.52，SH 基/環氧基= 0.081)、pgm 200 g，於氮 氣流下使内溫升溫至約60〇C。之後，分2次添加總計1.5 g 之V65，於65°C下連續攪拌6小時。之後，使内溫上升至 80°C，使V65完全失活，然後恢復至室溫。數量平均分子 量為16000，固形份濃度約為34〇/0。 接著，於空氣環境下加熱至9(TC後’加入對曱氧基苯酚 0.1 g、三苯基膦0.5 g。5分鐘後，將丙烯酸25 5 g溶解於 PGM50g t，用30分鐘滴加至圓底燒瓶中。其，將液溫 保持於90〜105°C。之後，使 使液溫上升至11Qt：，於此溫度On a polybutylene terephthalate (PET) film having a thickness of 100 //m, a coating film having a thickness of 3 Å and consisting of the composition of the present invention is formed at an oxygen concentration of 20%. Under the condition that the high-pressure mercury lamp having a irradiance of 400 mW/cm 2 at a wavelength of 254 is irradiated with ultraviolet rays so as to reach an integrated light amount of 5 〇〇 mJ/cm 2 , the abrasion resistance of the obtained cured film is preferably 25.0 or less. . Further, the method for measuring the abrasion resistance is described in the following examples. The illuminance at this time was measured by an illuminometer having a sensor having a wavelength of 254 nm in accordance with JIS (JIS_C 1609-1 2006). 5) Fingerprint resistance The following surface physical properties excellent in fingerprint removal resistance can be obtained by attaching a fingerprint or an artificial fingerprint liquid to a hardened crucible or a hard coat layer obtained by using the active energy ray-curable resin composition of the present invention. On the surface, then, in the case of 200 g minus 098113982 64 201000547, the τ is removed, and the fingerprint is removed by the operation of 3 姊 or less, and preferably within 2 round trips. In addition, the artificial crepe liquid is a triglyceride/JIS powder for the test (manufactured by Kanto^Japan Gas Industry Technology Association) / methoxypropanol = 1/0.4/10 (weight ratio) A mixture of the solutions used in the fingerprinting evaluation of the next generation of optical discs. Many of the antifouling properties d developed as a fingerprint-resistant imparting agent for a DVD or a next-generation optical disc or an anti-fingerprinting imparting agent for optical display use are, for example, mostly small in adhesion amount or adhesion diameter, but are wiped off. If the lubricity (smoothness) is too high or the hardness is insufficient, it is easy to spread on the surface, and even if it is wiped off, it is necessary to carry out three or more round trips. However, the cured film and the hard coat layer of the present invention have the following characteristics: hardness due to hard inclination High and without excessive _slip, so it can be wiped off with fewer wipes. A larger feature of a gauze: even if the fingerprint or artificial fingerprint liquid '=___ is applied for 3 round-trip wipes, the wipe is repeated 2 times, but the fingerprint removal property is not lowered. Even if the use of a small number of wiping times can be wiped out due to the fact that the hardness of the conventional person is not sufficient to fix the _ 7 dyeing agent itself, the A4 is applied to the 仃 adhesion and wiping operation, and then several times ~ Ten times (four) will cause the surface to appear in the gap, or resistance (4), and the fingerprint (or manual loss, thus the durability of the fingerprint removal / record the agent itself from the surface flow difference 'but the hardening of the present invention Film and hard coat 098113982 65 201000547 The layer has the following characteristics: It has the following extremely high performance durability: the hardness after hardening is high and the compound having a toxic contamination imparting base is fixed on the surface of the film, so even if it is repeated 20 times Above, preferably 4 times or more, the fingerprint (or artificial fingerprint liquid) is not degraded. 6) The hardenability is preferably obtained as follows: a polycarbonate having a thickness of 1 mm A coating film composed of the active energy ray-curable resin composition of the present invention having a thickness of 3 /zm is formed, and the illuminance at a wavelength of 254 nm is 400 mW/cm 2 at an oxygen concentration of 20%. Mercury lamp to When the integrated quantity of light of 500 mJ / cm2 of ultraviolet rays irradiated, hardened to proceed until the completely cured film of the adhesive. Further, the illuminance at this time was measured by using an illuminometer having a sensor having a wavelength of 254 nm in accordance with JISQIS-C 1609-1 2006). [Examples] Hereinafter, the present invention will be more specifically described by way of examples. The materials, the amounts, the ratios, the processing contents, the processing procedures, and the like disclosed in the following examples can be appropriately changed without departing from the gist of the invention. Therefore, the scope of the present invention is not limited to the specific examples disclosed below. Further, "parts" and "%" in the examples represent "parts by weight" and "% by weight", respectively. The physical energy ray-curable resin composition obtained in the examples and the like and the physical properties of the cured film composed of the composition were evaluated by the following method: 098113982 66 201000547. (1) Viscosity The composition was measured using a Brookfield type viscometer (Model DV-1 of Brookfield) at 25 ° C and 30 to 60 rpm (unit: mPa·s). (2) Appearance The appearance of the composition was visually evaluated as follows. f 〇: Foreign objects cannot be confirmed by visual inspection. X: Foreign matter was confirmed by visual inspection, and it was uneven. (3) Hardenability On a polycarbonate film having a thickness of 1 mm, a coating film composed of an active energy ray-curable resin composition having a thickness of 3 /zm is formed by spin coating at an oxygen concentration of 20%. Under the conditions, ultraviolet rays were irradiated with a high-pressure mercury lamp having a illuminance of 400 mW/cm 2 at a wavelength of 254 nm, and the hardenability at this time was evaluated in the following manner. In addition, the illuminance at this time is based on JIS (JIS-C 1609-1 2006) 'U.S. illuminance unit EYE UV TESTER UV-PFA1 light-receiving unit PD-254 (manufactured by Iwasaki Electric Co., Ltd.) using a sensor with a wavelength of 254 nm ) Perform the measurement. 〇: The surface of the cured film becomes non-adhesive at a cumulative light amount of S500 mJ/cm2. △ : 500 mJ/cm2 <The accumulated light amount is 1000 kJ/cm2 and the surface of the hardened crucible becomes non-adhesive. X: The cumulative light amount = 〇〇〇 mJ/cm2 The surface of the cured film does not become non-sticky 098113982 67 201000547. (4) -1 Transparency (haze value) The haze value was measured and evaluated on the cured film based on the conditions of JIS K-7105. (4)-2 Transparency (visual inspection) The cured film was visually evaluated as follows. 〇: No blur, turbidity or whitening was observed on the coating film. △: The coating film was uniformly slightly blurred. X: The coating film is unevenly blurred, or partially or wholly turbid, or whitened. (5) Pencil hardness The cured film was measured using a JIS standard pencil hardness tester (manufactured by Taisho Machinery Co., Ltd.) based on the conditions of JIS K-5400, and evaluated as the hardest pencil without damage. (6) Scratch resistance The steel was rubbed with a steel wool #〇〇〇〇, and rubbed under a load of 200 g, and the following evaluation was performed. ◎: 10 round trips were performed, and it was impossible to visually confirm the damage. 〇: Five round trips were performed to visually confirm that the damage could not be confirmed, and 10 returns were made to visually confirm the damage. X: Five round trips were performed to confirm significant damage by visual inspection. (7) Contact angle of water 0.002 ml of pure water was added to the cured film, and the contact of 098113982 68 201000547 was measured after 1 minute. Further, in the measurement of the contact angle, a contact angle meter (DropMaster 500 manufactured by Kyowa Interface Science Co., Ltd.) (unit: degree) was used. (8) Contact angle of hexadecacin. 0.002 ml of hexadecane was added dropwise to the cured film, and the contact angle after 1 minute was measured. Further, in the measurement of the contact angle, a contact angle meter (DropMaster 500 manufactured by Kyowa Interface Science Co., Ltd.) (unit: degree) was used. (9) Fingerprint adhesion f An artificial fingerprint liquid master is prepared by spin-coating an artificial fingerprint liquid at 3000 rpm on a polycarbonate substrate having a thickness of 1.1 mm which is formed into a disc shape and drying at 60 ° C for 3 minutes. plate. Further, the artificial fingerprint liquid is a triglyceride/JIS test powder M1 (Kanto Shoji, manufactured by Japan Powder Industrial Technology Association) / methoxypropanol = 1/0.4/10 (weight ratio) The mixture 'is the solution used in the fingerprint resistance evaluation of the next generation disc. Prepare the end face of the smaller one of the ketone rubber of No. 1 to be the same transfer material with #240 sandpaper, and press the roughened end face to the master for 1 〇 second with a fixed load of 4.9 Ν. Then, the above end faces were pressed against the surface of the cured film to be evaluated with a fixed load of 4.9 Torr (operation L1). Further, the operation of pressing the roughened end face to the master disk for 10 seconds with a fixed load of 4.9 Ν was repeated for n times, and the amount of the artificial fingerprint liquid was increased, and then the end face was pressed with a fixed load of 4.9 Ν. On the surface of the cured film to be evaluated (operation Ln). Visually observe the attachment diameter of the artificial fingerprint liquid attached to the 098113982 69 201000547 with a magnification of 1 〇〇 times, and keep the maximum attachment diameter within the range of 20 /zm or less. η becomes the maximum operation Ln as the artificial fingerprint liquid adhesion. The Ln at which η becomes the largest is preferably L3 or L4' and further preferably L4. (10) Fingerprint wipeability The sebum was used instead of the sebum, the nasal fat was attached to the thumb, and the thumb was pressed against the cured film for 3 seconds to attach the fingerprint to the cured film. The surface was lightly wiped with a toilet paper (manufactured by Crecia), and the number of round trips until the fingerprint was not visible was evaluated as a fingerprint wiping property at intervals of 15 cm. (11) Fingerprint wiping durability The sebum was used instead of sebum, the nasal fat was attached to the thumb, and the thumb was pressed against the cured film for 3 seconds to attach the fingerprint to the cured film. Three round trips were performed to wipe the fingerprint by the toilet paper (made by Crecia) wound on a 200 g weight. This operation is performed until the number of repetitions is 20th. After the 20th operation, in the state of 15 cm apart, if the fingerprint is not visible by visual inspection, it is evaluated as 〇, and if the fingerprint is visually observed, it is evaluated as X. (12) Resistance to Mace ink adhesion The oil line was drawn with an oily microphone pen (Mackee Care (fine) made by Zebra). If the line is rejected after 30 seconds, it is evaluated as X if it is not excluded. (13) Resistance to the ink of the Marker ink 098113982 70 201000547 The line was drawn with an oily mic pen (Mackee Care (fine) made by Zebra), and the surface was wiped with toilet paper (Crecia) after 30 seconds. Within the round trip, if it is wiped out, it is evaluated as 〇, and if it is not wiped, it is evaluated as X. <Production Example 1> Synthesis of active energy ray-curable compound (d_丨) In a 1000 ml separable round bottom flask, 50 g of perfluorooctyl methacrylate, 10 g of lauryl methacrylate, and α were added. ω_Dimercaptopropylpolydimethyloxane (quantitative average molecular weight 1600) 10 g, methacrylic acid ring cycline Ss 30 g, undecyl thiol 2 g (twelfth thiol) Cardinality / sH base of α,ω-dimercaptopropylpolydimethyloxane = ^78, benzyl/epoxy=0.106), 1-methoxy-1-propanol (1&gt;(}^/ [) 2〇〇§, the internal temperature is raised to about 60 ° C under a nitrogen stream. After that, a total of 1.5 g of 2,2'_ azobis(2,4-dimethylvaleronitrile) is added in two portions ( V65) 'Stirring was continued for 6 hours at 65 ° C. Thereafter, the internal temperature was raised to 80 ° C, and after completely deactivating V65, it was returned to room temperature. The number average molecular weight was 15,000, and the solid content concentration was about 34%. I, in addition, the number average molecular weight is measured by gel permeation chromatography (Gpc, Gel Permeation Chromatography) using THF as a solvent. The molecular weight in the knife is converted into a polyethylene. Next, heating in an air atmosphere After 卯^, 0.1 g of p-methoxyphenol and 0.5 g of diphenylphosphine were added. After 5 minutes, 5 3 g of ruthenium acrylate was dissolved in 50 g of PGM', and added dropwise to the round bottom flask over 3 minutes. The liquid temperature was maintained at 90 〇 1 〇 5 ΐ. Thereafter, the liquid temperature was raised to u 〇 t, and after maintaining at this temperature for 8 hours, the temperature was returned to room temperature. The solid content concentration was 33 (^04). 098113982 71 201000547 Here, 'solid content concentration, 1 g of the reaction solution was placed in an aluminum cup, and dried under vacuum at 80 ° C for 3 hours, and the amount of residual solid matter (average of 3 points) was measured as a solid content concentration. Example 2 &gt; Synthesis of active energy ray-curable compound (d_2) In a 1000 ml separable round bottom flask, 35 g of decyl methacrylate and dimethyl decyl polydecyl decane were added (the number average molecular weight was 1600) 15 g, glycidyl methacrylate 50 g, dodecyl mercaptan 2 g (SH base of dodecyl mercaptan / α, ω-dimercaptopropyl polydioxanoxane The SH base = 0.52, SH group / epoxy group = 0.081), pgm 200 g, and the internal temperature was raised to about 60 ° C under a nitrogen stream. 1.5 g of V65 was continuously stirred at 65 ° C for 6 hours. Thereafter, the internal temperature was raised to 80 ° C, the V65 was completely deactivated, and then returned to room temperature. The number average molecular weight was 16,000, and the solid concentration was about 34. 〇 / 0. Next, it was heated to 9 (after TC) to add 0.1 g of p-methoxyphenol and 0.5 g of triphenylphosphine. After 5 minutes, 25 5 g of acrylic acid was dissolved in 50 g of PGM, and added dropwise to the round bottom flask over 30 minutes. This maintains the liquid temperature at 90 to 105 °C. After that, the liquid temperature is raised to 11Qt: at this temperature.

矽氧烷(X-22-167B(信越化學公司製作）； 098113982 二毓基丙基聚二甲基 ;數量平均分子量為 72 201000547 1600)20 g、甲基乙基酮200 g，於氮氣流下使内溫升溫至約 60°C。接著，分2次添加總計丨.5 g之V65，於65°C下連續 攪拌6小時。之後，使内溫上升至80。(：，使V65完全失活 後，恢復至室溫。數量平均分子量為15000，固形份濃度約 為34%。之後，加入丙烯酸異氰酸酯基乙酯（Karenz AOI(昭 和電工公司製造))5.4 g、二月桂酸二辛基錫〇.〇5 g、對曱氧 基苯酚0.05 g’於空氣環境下於70°C下反應4小時，從而將 ， 丙烯基導入侧鏈’然後恢復至室溫。數量平均分子量為 % 16000，固形份濃度為35%(d-3)。 &lt;製造例4&gt;活性能量線硬化性化合物(d-4)之合成 於1000 ml之可分離式圓底燒瓶中加入甲基丙烯酸全氟己 基乙酯50 g、α，ω-二髓基丙基聚二甲基矽氧烷(數量平均分 子量為1600)15 g、甲基丙烯酸環氧丙酯3〇 g、十二烷基硫 醇2 g(十二烷基硫醇之SH基數/α，ω_二毓基丙基聚二甲基 i ：矽氧烷之SH基數= 0.52 ’ SH基/環氧基=0136)、PGM2〇〇 g，於氮氣流下使内溫升溫至約60°C。之後，分2次添加總 計1.5 g之V65，於65°C下連續攪拌6小時。之後，使内溫 上升至80°C，使V65完全失活’然後恢復至室溫。數量平 均分子量為15000 ’固形份濃度約為34〇/〇。 接著’於空氣環境下加熱至90。(：後，加入對甲氧基苯齡 0.1 g、三苯基膦0.5 g。5分鐘後’將丙烯酸25·5 g溶解於 PGM 50g中，用30分鐘滴加至圓底燒瓶中。其間，將液溫 098113982 73 201000547 保持於90〜105°C。之後，使液溫上升至ll〇t，於此溫度 下維持8小時後，恢復至室溫。固形份濃度為35%(d-4)。 &lt;實施例1〜17&gt; 以表1所示之組成調配成分(A)、（B)、（C)、（D-1)，獲得 作為透明液體之活性能量線硬化性樹脂組成物。該組成物之 物性如表1所示，硬化性之評價結果如表2所示。再者，在 使用（d-1)、（d-2)、（d-4)作為(D-1)成分的情況下，於調配後， 一面吹入氧氣一面將殘留溶劑減壓除去直至未滿組成物中 之5重量％。又，於實施例4〜6、10及17中，作為成分(B)， 係分別使用20重量份及50重量份、10重量份及45重量份、 15重量份及30重量份、20重量份及50重量、20重量份及 50重量份之KAYARAD DPHA(DPHA)及季戊四醇三丙烯酸 酯與季戊四醇四丙烯酸酯之混合物（PETA)。進而，於實施 例14中，作為成分(C)，係使用2重量份之IRGACURE9〇7 與2重量份之IRGACURE 184。上述實施例中，活性能量線 硬化性樹脂組成物於25°C下之黏度皆在較佳範圍内，塗佈 性優異。 接著’在厚度為i mm之聚碳酸g|薄膜上，藉由旋塗法形 成厚度為3，之由活性能量線硬純樹脂組成物所構成 之塗膜’於氧濃度為罵之條件下，使用於波長…細下 的放射照度為40。mWW之高壓水銀燈，以達到議 嫌爪、累計光量之方式照射紫料而獲得硬化膜，將該 098113982 74 201000547 硬化膜之物性示於表2。再者，此時之放射照度，係依據 JIS(JIS-C i 609-! 2006) ’利用具有波長254 用感測器之 照度計EYE UV TESTER UV-PFA1受光部PD-254(岩崎電 氣公司製造）進行測定。上述實施例中，活性能量線硬化性 樹脂組成物之鉛筆硬度皆為B以上’並且透明性、耐劃傷 性等其他物性亦優異。 又，將進行硬化膜之水及十六烧之接觸角、各種耐污染性 之評價的結果示於表3。上述實施例中，表面之水之接觸角 為80度以上，十六烷之接觸角為25度以上’並且耐污染性 優異。 098113982 75 外觀 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 黏度(mPa · s) r—&lt; 00 00 Γ—^ o 380 00 00 170 120 1—^ un 00 r-H τ—H 360 in (N 組成比(A/B/C/D-l)(重量份） 40/60/4/3 55/45/4/3 33/67/4/3 30/(20 + 50)/4/4 45/(10 + 45)/4/4 1 51/(15 + 30)/4/4 33/67/4/3 40/60/4/3 33/67/4/3 30/(20 + 50)/4/4 33/67/4/3 33/67/4/3 55/45/4/3 40/60/(2 + 2)/3 33/67/4/2 40/60/3/1 30/(20 + 50)/3/4 成分(D-l) (d-l) 1 (d-l) ! (d-l) ㈣ (d-l) (d-l) (d-2) 1 (d-2) | (d-2) (d-2) (d-2) (d-2) (d-2) UMS992 X-22-164A (d-4) 成分(c) 1907 1907 1907 1907 1907 1907 1907 1907 1907 1907 1907 1 1907 1184 MBF 1907 1907 1 成分(B) DPHA DPHA DPHA DPHA PETA DPHA PETA DPHA PETA PETA DPHA DPHA DPHA PETA PETA AD-TMP AD-TMP DPHA PETA PETA DPHA PETA 成分(A) THFA THFA CHA NPGDA NPGDA NPGDA A-DCP THFA CHA HPGDA ACMO A200 A200 ! 1 THFA HDDA-2E 702A NPGDA 實施例1 實施例2 實施例3 實施例4 實施例5 實施例6 實施例7 實施例8 實施例9 實施例10 實施例11 實施例12 實施例13 1 實施例14 實施例15 實施例16 實施例17 9L S6altso60 201000547 THFA :丙烯酸四氫糠酯（黏度：4〜7 mPa · s) CHA :丙烯酸環己酯（黏度：5〜8 mPa · s) NPGDA :新戍二酵二丙稀酸酉旨(黏度：8〜12 mPa · s) A-DCP :三環癸烷二甲醇二丙烯酸酯（黏度：100〜130 mPa · s) ACMO : N-丙烯醯基咮啉(黏度：6〜1〇 mpa · s) A200 :聚乙二醇#200之二丙烯酸酯（黏度：20 mPa · s) / . HDDA-2E :己二醉之2莫耳ί衣氧乙燒加成物之二丙稀酸 酉旨（黏度：20 mPa · s) 702A :笨基環氧丙基鍵之丙烯酸加成物（黏度：160 mPa · s) DPHA : KAYARAD DPHA(黏度：5000〜7000 mPa · s) (曰本化藥；二季戊四醇六丙烯酸酯與二季戊四醇五丙烯 酸酯之混合物） (； PETA :季戊四醇三丙烯酸酯與季戊四醇四丙烯酸酯之混 合物(黏度：700〜lOOOmPa· s) AD-TMP :二（三羥曱基丙烧）四丙烯酸醋（黏度：5〇〇〜700 mPa · s) I%7 : IRGACURE 9〇7(2·甲基-[4_(曱硫基）苯基]_2_咮啉基 -1 -丙酮） BP :二苯曱酮 1184 : IRGACURE 184(環己基苯基酮） 098113982 77 201000547 MBF : DAROCUR MBF(苯甲醯基甲酸甲酉^ UMS992 :丙烯醯氧基丙基甲基錢燒均:物公司 製造） X-22-164A.兩末端甲基丙烯基之聚二甲基矽氧炫(信越化 學公司製造） *各成分於25°C之黏度為目錄參照值 [表2]Oxane (X-22-167B (manufactured by Shin-Etsu Chemical Co., Ltd.); 098113982 dimercaptopropyl polydimethyl; number average molecular weight: 72 201000547 1600) 20 g, methyl ethyl ketone 200 g, under nitrogen flow The internal temperature is raised to about 60 °C. Next, a total of 丨.5 g of V65 was added in two portions, and stirring was continued at 65 ° C for 6 hours. After that, the internal temperature is raised to 80. (:, after completely inactivating V65, it was returned to room temperature. The number average molecular weight was 15,000, and the solid content concentration was about 34%. Then, isopropyl acrylate acrylate (Karenz AOI (manufactured by Showa Denko)) 5.4 g was added. Dioctyltin ruthenium dilaurate. 5 g, p-methoxyphenol 0.05 g' was reacted at 70 ° C for 4 hours in an air atmosphere, thereby introducing the propylene group into the side chain and then returning to room temperature. The average molecular weight was %16000, and the solid content concentration was 35% (d-3). <Production Example 4> Synthesis of active energy ray-curable compound (d-4) A 1000 ml separable round bottom flask was charged with a Perfluorohexyl acrylate 50 g, α, ω-dimylopropyl polydimethyl methoxy oxane (number average molecular weight 1600) 15 g, glycidyl methacrylate 3 〇 g, dodecane 2 g of thiol (the SH number of dodecyl mercaptan / α, ω - dimercaptopropyl polydimethyl i : SH base number of decane = 0.52 'SH group / epoxy group = 0136), PGM2〇〇g, the internal temperature was raised to about 60 ° C under a nitrogen stream. Thereafter, a total of 1.5 g of V65 was added in two portions, and stirring was continued for 6 hours at 65 ° C. The internal temperature is raised to 80 ° C, the V65 is completely deactivated' and then returned to room temperature. The number average molecular weight is 15000 'solids concentration is about 34 〇 / 〇. Then 'heated to 90 in air. (: Thereafter, 0.1 g of p-methoxybenzene and 0.5 g of triphenylphosphine were added. After 5 minutes, 25. 5 g of acrylic acid was dissolved in 50 g of PGM, and added dropwise to the round bottom flask over 30 minutes. Temperature 098113982 73 201000547 was maintained at 90~105 ° C. Thereafter, the liquid temperature was raised to ll 〇 t, and after maintaining at this temperature for 8 hours, it was returned to room temperature. The solid content concentration was 35% (d-4). (Examples 1 to 17) The components (A), (B), (C), and (D-1) were blended in the composition shown in Table 1, and an active energy ray-curable resin composition as a transparent liquid was obtained. The physical properties of the materials are shown in Table 1, and the evaluation results of the hardenability are shown in Table 2. Further, (d-1), (d-2), and (d-4) were used as the component (D-1). In the case, after the preparation, the residual solvent was removed under reduced pressure while blowing oxygen until it was less than 5% by weight of the composition. Further, in Examples 4 to 6, 10 and 17, (B), respectively, using 20 parts by weight and 50 parts by weight, 10 parts by weight, and 45 parts by weight, 15 parts by weight, and 30 parts by weight, 20 parts by weight, and 50 parts by weight, 20 parts by weight, and 50 parts by weight of KAYARAD DPHA (DPHA) And a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (PETA). Further, in Example 14, as component (C), 2 parts by weight of IRGACURE 9〇7 and 2 parts by weight of IRGACURE 184 were used. In the above examples, the active energy ray-curable resin composition has a viscosity in a preferred range at 25 ° C, and is excellent in coatability. Then, on the poly-g-g] film having a thickness of i mm, a coating film having a thickness of 3 and a composition of an active energy-line hard-pure resin is formed by spin coating, and the oxygen concentration is 骂. The irradiance used for the wavelength... is 40. The mWW high-pressure mercury lamp was irradiated with a purple material to obtain a cured film in such a manner that the amount of the claws and the cumulative amount of light were obtained, and the physical properties of the cured film of 098113982 74 201000547 are shown in Table 2. In addition, the illuminance at this time is based on JIS (JIS-C i 609-! 2006) 'E. illuminator PD-254 (made by Iwasaki Electric Co., Ltd.) using an illuminance meter with a wavelength of 254 sensor EYE UV TESTER UV-PFA1 ) Perform the measurement. In the above examples, the active energy ray-curable resin composition has a pencil hardness of B or more and is excellent in other physical properties such as transparency and scratch resistance. Further, the results of evaluation of the contact angle of the water of the cured film and the sixteen burns and various stain resistances are shown in Table 3. In the above embodiment, the contact angle of water on the surface is 80 degrees or more, the contact angle of hexadecane is 25 degrees or more', and the stain resistance is excellent. 098113982 75 Appearance 〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇 Viscosity (mPa · s) r—&lt; 00 00 Γ—^ o 380 00 00 170 120 1—^ un 00 rH τ—H 360 in (N composition ratio (A/B/C/Dl) (parts by weight) 40/60/4/3 55/45/4/3 33/67/4/3 30/(20 + 50)/4/ 4 45/(10 + 45)/4/4 1 51/(15 + 30)/4/4 33/67/4/3 40/60/4/3 33/67/4/3 30/(20 + 50)/4/4 33/67/4/3 33/67/4/3 55/45/4/3 40/60/(2 + 2)/3 33/67/4/2 40/60/3 /1 30/(20 + 50)/3/4 Component (Dl) (dl) 1 (dl) ! (dl) (iv) (dl) (dl) (d-2) 1 (d-2) | (d- 2) (d-2) (d-2) (d-2) (d-2) UMS992 X-22-164A (d-4) Component (c) 1907 1907 1907 1907 1907 1907 1907 1907 1907 1907 1907 1 1907 1184 MBF 1907 1907 1 Ingredient (B) DPHA DPHA DPHA DPHA PETA DPHA PETA DPHA PETA PETA DPHA DPHA DPHA PETA PETA AD-TMP AD-TMP DPHA PETA PETA DPHA PETA Ingredients (A) THFA THFA CHA NPGDA NPGDA NPGDA A-DCP THFA CHA HPGDA ACMO A200 A200 ! 1 THFA HDDA-2E 702A NPGDA Embodiment 1 Embodiment 2 Example 3 Embodiment 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Implementation 11 Example 12 Example 13 1 Example 14 Example 15 Example 16 Example 17 9L S6altso60 201000547 THFA: tetrahydrofurfuryl acrylate (viscosity: 4 to 7 mPa · s) CHA: cyclohexyl acrylate (viscosity: 5 ~8 mPa · s) NPGDA : New bismuth diacetate bismuth (viscosity: 8~12 mPa · s) A-DCP: tricyclodecane dimethanol diacrylate (viscosity: 100~130 mPa · s ACMO : N-propylene decyl porphyrin (viscosity: 6~1〇mpa · s) A200 : polyethylene glycol #200 diacrylate (viscosity: 20 mPa · s) / . HDDA-2E : 2 摩尔 乙 乙 乙 乙 乙 乙 乙 乙 ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( : KAYARAD DPHA (viscosity: 5000~7000 mPa · s) (Sakamoto Chemical; a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate) (; PETA: a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (viscosity) :700~lOOOOmPa·s) AD-TMP: Di(trihydroxymethyl propyl) acrylic acid vinegar (viscosity: 5〇〇~700 mPa · s) I%7 : IRGACUR E 9〇7(2·methyl-[4_(indenylthio)phenyl]_2_indolyl-1 -propanone) BP:dibenzophenone 1184 : IRGACURE 184 (cyclohexyl phenyl ketone) 098113982 77 201000547 MBF : DAROCUR MBF (benzhydryl carbazate ^ UMS992 : propylene methoxy propyl methyl ketone burn: manufactured by the company) X-22-164A. Both ends of methacrylic polydimethyl oxime Hyun (manufactured by Shin-Etsu Chemical Co., Ltd.) *The viscosity of each component at 25 °C is the catalog reference value [Table 2]

PC .聚碳酸酯薄膜（三菱工程塑膠公司製造之lup Sheet(厚度為1 mm，霧值為〇 1〇/〇)) im 098113982 78 201000547 [表3] 水之接 觸角 (度） 十六烷之 接觸角 (度） 指紋附 著性 指紋拭 去性 (次） 指紋拭去 耐久性 耐麥克筆油 墨附著性 耐麥克筆油 墨栻去性 實施例1 102 56 L4 2 〇 〇 〇 實施例2 101 55 L4 2 〇 〇 〇 實施例3 101 58 L4 2 〇 〇 〇 實施例4 100 55 L4 2 〇 〇 〇 實施例5 100 54 L4 2 〇 〇 〇 實施例6 95 52 L4 2 〇 〇 〇 實施例7 102 56 L4 2 〇 〇 〇 實施例8 96 38 L4 2 〇 〇 〇 實施例9 96 35 L4 2 〇 〇 〇 實施例10 94 35 L4 2 〇 〇 〇 實施例11 94 36 L4 2 〇 〇 〇 實施例12 98 37 L4 2 〇 〇 〇 實施例13 99 35 L4 2 〇 〇 〇 實施例14 99 36 L4 2 〇 〇 〇 實施例15 94 34 L3 2.5 〇 〇 〇 實施例16 91 31 L3 3 〇 〇 〇 實施例17 106 59 L4 2.5 〇 〇 〇 〈比較例1〜5〉 以表4所示之組成，以與實施例1〜17同樣之方式調配成 分（A)、（B)、（C)、（D-1)，而獲得作為透明液體之活性能量 線硬化性樹脂組成物。該組成物之物性如表4所示，硬化性 之評價結果如表5所示。比較例1〜5中，成分(A)、（B)、 (C)、（D-1)以及其組成比係在本申請案發明之範圍内，於25 °C下之黏度皆超過500 mPa · s，因此塗佈性差，難以進行 無塗佈缺陷之塗佈或獲得均勻膜厚之塗佈。 &lt;比車交例6〜10&gt; 以表4所示之組成，以與實施例1〜17同樣之方式調配各 098113982 79 201000547 成分作為成分(A)、（B)、（C)、（D-l)，而獲得作為透明液體 之活性能量線硬化性樹脂組成物。該組成物之物性如表4 所示’硬化性之評價結果如表5所示。再者，比較例1 〇中， 作為成分(B) ’係使用9重量份之KAYARAD DPHA、及18 重量份之季戊四醇三丙烯酸酯與季戊四醇四丙烯酸酯之混 合物。上述比較例中，於25°C下之黏度皆係在較佳範圍内， 塗佈性優異。 接著，使用表4所示之組成之活性能量線硬化性樹脂組成 物，以與實施例1〜17同樣之方式獲得硬化膜，將該硬化膜 之物性示於表5。上述比較例中，（A)成分之比例皆較多， 因此鉛筆硬度為2B以下、或者於溫和的活性能量線之照射 條件下殘留有黏性等’硬化性不足。又，耐劃傷性等物性亦 差，因而欠佳。 &lt;比較例11、12&gt; 以表4所示之組成，以與實施例丨〜17同樣之方式調配各 成分作為成分(A)、（B)、（C)、（D—i)，而獲得作為透明液體 之活性能量線硬化性樹脂組成物。該組成物之物性如表4 所示，硬化性之評價結果如表5所示。上述比較例中，於 25〇C下之黏度&quot;錢佳範_，㈣性優異。 接著’使用表4所示之έ ^ t _ 、、，成之活性能量線硬化性樹脂組成 物，以與貫施例1〜17间# 中’（C)成分之量皆較少 因 僳之方式獲得硬化臈，將該硬化膜 之物性不於表5。上逑比較例 098113982 80 201000547 此鉛筆硬度為2B以下、或者於、、Θ^ΑΑ、 飞考於，里和的活性能量線之照射條 件下殘留有黏性等，硬化性不足。7 』 f不足又，耐劃傷性等物性亦較 差，因而欠佳。 &lt;比較例13&gt; 以表4所示之組成，以與實施例Μ?同樣之方式調配各 成分作為成分⑷、⑼、（c)、（D_i)i獲得作為透明液體 之活性能讀硬化性樹脂組成物。該組成物之物性如表4 所示’硬化性之㈣結果如表5_。作為成分⑷，係使 用32重量份之三經甲基丙烧三丙烯酸略及30重量份之新戊 二醉一丙烯酸醋。於坑下之黏度係在較佳範圍内，塗佈 性優異。 接著，使用表4所示之組成之活抖θ 性此罝線硬化性樹脂組成 物，以與實施例1〜17同樣之方式緙彡日成， 一 式獲侍硬化膜，將該硬化膜 之物性示於表5。錯筆硬度為3Β，於溫和的活性能量線之 照射條件下殘留有黏性，硬化性不^。又，射彳傷性等之物 性亦較差，因而欠佳。 &lt;比較例14&gt; 以表4所示之組成，以與實施例卜17同樣之方式調配成 刀（A)、（Β)、（C)、（D-1) ’而獲得活性能量線硬化性樹脂組 成物。再者，對於㈣，於調配後，—面吹人氧氣—面將殘 留溶劑減壓除去直至未滿組成物中之5重量％。該組成物之 物性如表4所示’硬化性之評價結果如表5所示。於坑 098113982 81 201000547 下之黏度係錢域圍内，塗佈性優異。 然後’使用表4所示之組成之活性能量線硬化性樹脂組成 物’與貝化例1〜17同樣地獲得硬化膜，將該硬化膜之物性 不於表5。錯筆硬度為3B ’於溫和之活性能量線之照射條 件下殘留黏性，從而硬化性不足。又，耐劃傷性等物性亦差 而欠佳。 &lt;比車交例15〜17&gt; 以表4所不之組成，以與實施例1〜17同樣之方式調配成 刀（A) (B)、”而獲得作為透明液體之活性能量 線硬化性姆脂組成物。該組成物之物性如表4所示，硬化性 之《平U如表5所示。又’比較例15中，作為成分⑷， 係使用16.7重量份之丙烯酸環己@旨及8 3重量份之三經甲基 丙烧丙稀酉欠酉曰，作為成分（Q，係使用8.3重量份之 IRGACURE 184 及 8.3 重量份之 DAROCUR 1173。比較例 Μ中作為成分⑷’係使用32重量份之二丙二醇二丙稀 酸酉旨及49重量份夕&amp; &gt; 里伤之内三醉之3莫耳環氧乙烷加成物之二丙 烯酸酯。於25°C下夕# &amp; α + 站度係在較佳範圍内，塗佈性優異。 接著，使用表4戶斤；a , J_、、 ，、 /、之、、且成之活性能量線硬化性樹脂組成 物’以與實施例1〜17 /同樣之方式獲得硬化膜，將該硬化膜 之物性示於表5。 、 比較例15中 h①-1)之比例較多，鉛筆硬度為3B 而Ά f生等物性亦較差，接觸角較低，耐污染性亦差，因 而 098113982 82 201000547 欠佳。 比較例16〜17中，成分(A)之比例較多，錯筆硬度為3B 或者硬化性不足，因而欠佳。PC. Polycarbonate film (lup Sheet made by Mitsubishi Engineering Plastics Co., Ltd. (thickness: 1 mm, haze value: 〇1〇/〇)) im 098113982 78 201000547 [Table 3] Contact angle of water (degrees) Hexadecane Contact angle (degrees) Fingerprint adhesion fingerprint wiping (times) Fingerprint wiping durability Durable Mike pen ink adhesion Resistance Mac pen ink ink removal Example 1 102 56 L4 2 〇〇〇 Example 2 101 55 L4 2 〇〇〇 Example 3 101 58 L4 2 〇〇〇 Example 4 100 55 L4 2 〇〇〇 Example 5 100 54 L4 2 〇〇〇 Example 6 95 52 L4 2 〇〇〇 Example 7 102 56 L4 2 〇〇〇 Example 8 96 38 L4 2 〇〇〇 Example 9 96 35 L4 2 〇〇〇 Example 10 94 35 L4 2 〇〇〇 Example 11 94 36 L4 2 〇〇〇 Example 12 98 37 L4 2 〇〇〇Example 13 99 35 L4 2 〇〇〇 Example 14 99 36 L4 2 〇〇〇 Example 15 94 34 L3 2.5 〇〇〇 Example 16 91 31 L3 3 〇〇〇 Example 17 106 59 L4 2.5 〇〇〇 <Comparative Examples 1 to 5> The compositions shown in Table 4 were compared with Examples 1 to 1 In the same manner, the components (A), (B), (C), and (D-1) were blended to obtain an active energy ray-curable resin composition as a transparent liquid. The physical properties of the composition are shown in Table 4, and the evaluation results of the hardenability are shown in Table 5. In Comparative Examples 1 to 5, the components (A), (B), (C), (D-1) and the composition ratio thereof were within the scope of the invention of the present application, and the viscosity at 25 ° C exceeded 500 mPa. · s, so the coatability is poor, and it is difficult to apply without coating defects or to obtain a uniform film thickness. &lt;Comparative Example 6 to 10&gt; With the composition shown in Table 4, each of 098113982 79 201000547 was blended as a component (A), (B), (C), (Dl) in the same manner as in Examples 1 to 17. ), an active energy ray-curable resin composition as a transparent liquid is obtained. The physical properties of the composition are shown in Table 4. The evaluation results of the hardening property are shown in Table 5. Further, in Comparative Example 1, as the component (B)', 9 parts by weight of KAYARAD DPHA and 18 parts by weight of a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate were used. In the above comparative examples, the viscosity at 25 ° C was within a preferred range, and the coating property was excellent. Next, using the active energy ray-curable resin composition of the composition shown in Table 4, a cured film was obtained in the same manner as in Examples 1 to 17, and the physical properties of the cured film are shown in Table 5. In the above comparative examples, since the ratio of the component (A) is large, the pencil hardness is 2 B or less, or the viscosity or the like is insufficient under the irradiation conditions of the mild active energy ray. Moreover, physical properties such as scratch resistance are also poor, which is not preferable. &lt;Comparative Examples 11 and 12&gt; In the same manner as in Examples 丨 to 17, the components shown in Table 4 were blended as components (A), (B), (C), and (D-i). An active energy ray-curable resin composition as a transparent liquid was obtained. The physical properties of the composition are shown in Table 4, and the evaluation results of the hardenability are shown in Table 5. In the above comparative example, the viscosity at 25 ° C &quot; Qian Jiafan _, (four) is excellent. Then, using έ ^ t _ , , shown in Table 4, the composition of the active energy ray-curable resin, and the amount of the component (C) in Example 1 to 17 are less. The hardened crucible was obtained in a manner that the physical properties of the cured film were not in Table 5. Comparative example of the upper jaw 098113982 80 201000547 This pencil has a hardness of 2B or less, or has a viscosity or the like under the irradiation conditions of the active energy ray of the y, Θ^ΑΑ, and the test, and the curability is insufficient. 7 』 f is insufficient, and the physical properties such as scratch resistance are also poor, so it is not good. &lt;Comparative Example 13&gt; With the composition shown in Table 4, each component was blended as the components (4), (9), (c), and (D_i)i in the same manner as in Example 获得 to obtain the active energy hardenability as a transparent liquid. Resin composition. The physical properties of the composition are shown in Table 4. The results of the hardening (IV) are shown in Table 5_. As the component (4), 32 parts by weight of trimethoprimic triacrylic acid and 30 parts by weight of fresh pentahydrate-acrylic vinegar were used. The viscosity under the pit is in a preferred range, and the coating property is excellent. Then, using the composition of the composition shown in Table 4, the composition of the crepe-curable resin was used in the same manner as in Examples 1 to 17, and the cured film was obtained in one form, and the physical properties of the cured film were obtained. Shown in Table 5. The erroneous pen hardness is 3 Β, and the viscous property remains under the irradiation conditions of the mild active energy ray, and the hardenability is not. Moreover, the physical properties such as shooting damage are also poor, which is not good. &lt;Comparative Example 14&gt; The active energy ray hardening was obtained by blending the knives (A), (Β), (C), (D-1) ' in the same manner as in Example 17 in the composition shown in Table 4 Resin composition. Further, with respect to (4), after the blending, the surface was blown with oxygen to remove the residual solvent under reduced pressure until it was less than 5% by weight of the composition. The physical properties of the composition are shown in Table 4. The evaluation results of the hardenability are shown in Table 5. The viscosity under the pit of 098113982 81 201000547 is excellent in coating properties in the money area. Then, using the active energy ray-curable resin composition of the composition shown in Table 4, a cured film was obtained in the same manner as in Bayesan Examples 1 to 17, and the physical properties of the cured film were not in Table 5. The erroneous pen hardness of 3B' remains viscous under the irradiation conditions of the mild active energy ray, and thus the hardenability is insufficient. Moreover, physical properties such as scratch resistance are also poor and poor. &lt;Comparative Example 15 to 17&gt; With the composition of Table 4, the knives (A) (B) and "B" were prepared in the same manner as in Examples 1 to 17, and the active energy ray hardening property as a transparent liquid was obtained. The composition of the composition is as shown in Table 4, and the sclerosing property is as shown in Table 5. In Comparative Example 15, as the component (4), 16.7 parts by weight of acryl ring was used. And 83 parts by weight of methicone was used as a component (Q, 8.3 parts by weight of IRGACURE 184 and 8.3 parts by weight of DAROCUR 1173 were used. In the comparative example, the component (4) was used. 32 parts by weight of dipropylene glycol dipropionate and 49 parts by weight of bis &amp;&gt; 3 intoxication of 3 moles of ethylene oxide adduct diacrylate. At 25 ° C under the eve # &amp The α + station is in a preferred range and is excellent in coatability. Next, using Table 4, a, J_, , , , /, and the active energy ray-curable resin composition A cured film was obtained in the same manner as in Examples 1 to 17 and the physical properties of the cured film are shown in Table 5. In Comparative Example 15, h1-1) There are many cases, the pencil hardness is 3B, and the physical properties such as Άf are also poor, the contact angle is low, and the stain resistance is also poor, so 098113982 82 201000547 is not good. In Comparative Examples 16 to 17, the ratio of the component (A) is large. The wrong pen hardness is 3B or the hardenability is insufficient, so it is not good.

098113982 83 201000547 【寸尨 外觀 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 X 〇 〇 〇 黏度(mPa · s) 700 1220 1450 780 990 00 (N § \〇 in CO 175 105 350 110 120 組成比(A/B/C/D-1)(重量份） 30/70/4/3 33/67/4/3 33/67/4/3 33/67/4/3 33/67/4/3 75/25/4/3 80/20/4/3 75/25/4/3 75/25/4/3 73/(9 + 18)/4/4 40/60/1/3 33/67/1/3 (32 + 30)/38/4/0.5 40/60/4/3 (16.7 + 8.3)/75/(8.3 + 8.3)/50 (32 + 49)/19/5.4/2.7 95/5/5/2.5 成分(D-1) (d-2) (d-2) (d-2) (d-2) (d-2) (d-2) (d-2) (d-2) (d-1) (d-1) (d-2) (d-2) 2200N (d-3) BISCOAT 8F 2200N 2200N 成分(C) 1907 1907 1907 1907 1907 1907 1907 1907 1907 1907 1184 1907 1184 D1173 1184 1184 成分(B) DPHA DPHA DPHA DPHA PETA DPHA PETA AD-TMP PETA DPHA PETA DPHA DPHA PETA DPHA U6HA BPADGE-EA BPADGE-EA 成分(A) A400 702A A-DCP TMPTA3EO A-BPE-4 THFA ACMO A200 A-DCP NPGDA THFA CHA TMPTA NPGDA THFA CHA TMPTA DPGDA A-GLY-3E TMPTA3EO 比較例1 比較例2 比較例3 比較例4 比較例5 比較例6 比較例7 比較例8 比較例9 比較例10 比較例11 比較例12 比較例13 比較例14 比較例15 比較例16 比較例17 寸0°s6aIS60 201000547 A400 :聚乙二醇#400之二丙烯酸酯（黏度：60 mPa · s) TMPTA3EO:三羥甲基丙烷之3莫耳環氧乙烷加成物之三 丙烯酸S旨(黏度：60〜90mPa · s) A-BPE-4:雙酚A之4莫耳環氧乙烷加成物之二丙烯酸酯 (黏度：500 mPa · s) TMPTA:三羥甲基丙烷三丙烯酸酯(黏度：60〜lOOmPa · s) f DPGDA :二丙二醇二丙烯酸酯（黏度：12 mPa · s) A-GLY-3E :丙三醇之3莫耳環氧乙烷加成物之二丙烯酸 酯（黏度：20 mPa . s) U6HA :具有6個丙烯基之多官能胺基曱酸乙酯丙烯酸酯 (新中村化學）(黏度：未滿10000 mPa · s) BPADGE-EA:雙酚A之二環氧丙基醚之丙烯酸加成物(黏 度：85000 mPa · s) (j Dll 73 : DAROCUR 1173(Ciba Specialty Chemicals 公司製 造） 2200N :側鏈上具有丙烯基之聚二甲基矽氧烷衍生物 (EVONIK公司（原；Degussa公司）製造） BISCOAT8F:含有8個氟原子之丙烯酸酯單體（大阪有機 化學工業公司製造） 098113982 85 201000547 [表5] 基材 硬化膜厚度 (# m) 硬化性 透明性 (霧值(％)) 鉛筆 硬度 比較例6 PC 3 X 一 一 比較例7 PC 3 X 一 一 比較例8 PC 3 Δ 0.1 2Β 比較例9 PC 3 Δ 0.1 2Β 比較例10 PC 3 X 比較例11 PC 3 Δ 0.1 4Β 比較例12 PC 3 X 比較例13 PC 3 Δ 0.1 3Β 比較例14 PC 3 Δ 0.1 3Β 比較例15 PC 3 〇 0.2 3Β 比較例16 PC 3 X 比較例17 PC 3 ~~δ 「0.2 3Β098113982 83 201000547 [Inch 〇〇〇〇〇〇〇〇〇〇〇〇〇 appearance 〇〇〇 X 〇〇〇 viscosity (mPa · s) 700 1220 1450 780 990 00 (N § \〇in CO 175 105 350 110 120 composition ratio (A/B/C/D-1) (parts by weight) 30/70/4/3 33/67/4/3 33/67/4/3 33/67/4/3 33/67/4/3 75/25/4/3 80/20/4/3 75/25/4/3 75/25/4/3 73/(9 + 18)/4/4 40/60/1/3 33/67/ 1/3 (32 + 30)/38/4/0.5 40/60/4/3 (16.7 + 8.3)/75/(8.3 + 8.3)/50 (32 + 49)/19/5.4/2.7 95/5 /5/2.5 Composition (D-1) (d-2) (d-2) (d-2) (d-2) (d-2) (d-2) (d-2) (d-2) (d-1) (d-1) (d-2) (d-2) 2200N (d-3) BISCOAT 8F 2200N 2200N Composition (C) 1907 1907 1907 1907 1907 1907 1907 1907 1907 1907 1184 1907 1184 D1173 1184 1184 Ingredients (B) DPHA DPHA DPHA DPHA PETA DPHA PETA AD-TMP PETA DPHA PETA DPHA DPHA PETA DPHA U6HA BPADGE-EA BPADGE-EA Ingredient (A) A400 702A A-DCP TMPTA3EO A-BPE-4 THFA ACMO A200 A-DCP NPGDA THFA CHA TMPTA NPGDA THFA CHA TMPTA DPGDA A-GLY-3E TMPTA3EO Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 Comparative Example 9 Comparative Example 10 Comparative Example 11 Comparative Example 12 Comparative Example 13 Comparative Example 14 Comparative Example 15 Comparative Example 16 Comparative Example 17 Inch 0°s6aIS60 201000547 A400: Polyethylene glycol #400 diacrylate (viscosity: 60 mPa · s) TMPTA3EO : Tris-ethylene oxide adduct of trimethylolpropane to trisacrylic acid S (viscosity: 60 to 90 mPa · s) A-BPE-4: 4 molar ethylene oxide adduct of bisphenol A Diacrylate (viscosity: 500 mPa · s) TMPTA: trimethylolpropane triacrylate (viscosity: 60 to 100 mPa · s) f DPGDA: dipropylene glycol diacrylate (viscosity: 12 mPa · s) A-GLY- 3E: Diacrylate of 3 molar ethylene oxide adduct of glycerol (viscosity: 20 mPa. s) U6HA: polyfunctional amine phthalate acrylate having 6 propylene groups (Xin Nakamura Chemical) (Viscosity: less than 10000 mPa · s) BPADGE-EA: Acrylic acid adduct of bisphenol A diglycidyl ether (viscosity: 85000 mPa · s) (j Dll 73 : DAROCUR 1173 (manufactured by Ciba Specialty Chemicals) 2200N: Polydimethyloxane derivative having an acryl group in a side chain (Manufactured by EVONIK Co., Ltd. (formerly; Degussa)) BISCOAT8F: containing Eight fluorinated acrylate monomers (manufactured by Osaka Organic Chemical Industry Co., Ltd.) 098113982 85 201000547 [Table 5] Substrate cured film thickness (# m) Curable transparency (fog value (%)) Pencil hardness Comparative Example 6 PC 3 X -1 Comparative Example 7 PC 3 X - Comparative Example 8 PC 3 Δ 0.1 2 Β Comparative Example 9 PC 3 Δ 0.1 2 Β Comparative Example 10 PC 3 X Comparative Example 11 PC 3 Δ 0.1 4 Β Comparative Example 12 PC 3 X Comparative Example 13 PC 3 Δ 0.1 3 Β Comparative Example 14 PC 3 Δ 0.1 3 Β Comparative Example 15 PC 3 〇 0.2 3 Β Comparative Example 16 PC 3 X Comparative Example 17 PC 3 ~~δ "0.2 3 Β

* ^ v —次：丄往塑月* ^ v — times: 丄 to plastic moon

Sheet(厚度為！ mm ,霧值為 0.1%)) 製造例5&gt; ••因硬化性不良故無法進行測定 酸酯製 上 層 準備在製成有用於資訊記錄的溝之光碟狀支 醋製，厚度為umm，直徑為12。麵)之^聚雙 ::成有反射層、第2介電體層、記錄層、=槽的 之^光碟用光記_體（㈣^ 有自由層表:亡’藉由旋塗法塗佈下述纽成之具 為60 W/cm2 f性能讀硬化性材料後’利用輸出密度 之方式照射紫外U銀燈以累计光置達到1000 mJ/cm2 保護層。、線進行硬化後，形成厚度為97 ρ之透光 ，、衣面之鉛筆硬度為4B。 098113982 86 201000547 ((透光保護層用—n &gt; 性材料的組成)） 絲合性之活性能量線硬化 胺基甲酸乙㈣歸酸醋低聚物 60重量份 (使丙烯酸备基4旨與在平均分子量為_之聚丁二醇上 *加成有異佛爾_二異氰酸醋之異氰酸酿末端低聚物進行反 應，而生叙胺基甲酸乙酯丙烯酸醋） 20重量份 20重量份 3重量份 異三聚氰酸環氣己烧改質三丙烯酸醋 &quot;(東亞合成公司製造，ARONIX M313) 丙烯酸四氫糠崎 IRGACURE 184 &lt;實施例18〜2〇:&gt; 、表斤示之級成，以與實施例1〜17同樣之方式獲得活 月匕I、’泉硬化I1 生；^月旨組成物。再者’實施例2〇 *，作為成 刀⑻，係使用20重量份之KAYARAD DPHA、及50重量 〇知之季戊四醇二内烯酸酯與季戊四醇四丙烯酸酯之混合物。 藉由旋塗法，將該組成物塗佈於製造例5中所形成之透明 性保護層上’而成為塗膜。於氧濃度為20%之條件下，使用 於波長254 nm下的放射照度為400 mW/cm2之高壓水銀 &amp; ’以累計光量達到1〇〇〇mj/cm2之方式向該塗膜照射紫外 線進行硬化’製成厚度為3 之硬塗層。再者，此時之 放射照度，係依據JIS(JIS-C 1609-1 2006)，使用具有波長 254 nm用感測器之照度計EYE UV TESTER UV-PFA1受 098113982 87 201000547 光部PD-254(岩崎電氣公司製造）進彳亍測疋。 關於該硬塗層之表面物性，對透明性（以目測進行評價）、 鉛筆硬度、接觸角（水、十六烷）、紂/亏染性（人工指紋液附著 性、人工指紋液拭去性、人工指紋液拭去耐久性）進行評價。 將耐污染性、光滑性之結果示於表8 ’將其他物性之結果示 於表7。 由本發明活性能量線硬化性樹脂組成物（貫施例18〜20) 所製成之硬塗層，係接觸角較高，耐污染性中之附著性尤其 優異，結果拭去性及拭去耐久性亦優異’可獲得作為Blu-ray Disk為較佳者。 再者’在PC基材上以透光保護層為介隔形成有膜厚為3 # m之硬化膜之實施例18〜20,係應對Blu-ray Disk用途者。 [表6] 成分(A) 成分（B) 成分(C) 成分(D-1) 組成比（A/B/C/D-l) (重量份） 實施例18 ,— — THFA DPHA 1907 (d-1) 40/60/4/3 — 實施例19 -— —. CHA DPHA 1907 (d-2) 33/67/4/3 — 實施例20 ---—- HPGDA DPHA PETA 1907 (d-2) 30/(20+ 50)/4/4 [表7] ~ ——r —— _.—- _ 透明性（目測） 鉛筆硬度 水之接觸角(度） 十六烷之接觸角(度） 實施例18 〇 B 102 57 實施例19 〇 HB 101 56 實施例20 〇 B 96 36 098113982 88 201000547 [表8] 指紋附著性 實施例18 L4 實施例19 L4 實▲例20 L4 去性（次） 為 指紋拭去耐久性 〇 〇 了進行參I肖表面上具有將市售的耐污染性硬塗劑進 打塗佈/硬化之硬塗膜之光記錄媒體（次世代型光碟卿谓 Disk))的接觸角、耐污染性進行評價。 將其結果示於表9。 市售口σ A、B、C中’雖然、人卫指紋液之附著性優異，但 拔除性超過3餘返’並且拭切久性亦較低，與將本發明 [表9] 活性能量線硬化性樹脂組成物進行塗佈/硬化之硬化膜相比 明顯地差。 水之接 觸角（度） 十六烷之 接觸角（Jf ) 指紋附 著性 指紋栻去 性（次） 指紋拭去 耐久性 A : Sony 之 BD-RE 96 51 L4 3 1 --—« X B : TDK 之 BD-R 100 ——一--- 36 L3 ——---- X X C :松下電器之BD-R 78 27 L3 3.5 &lt;實施例21、22&gt; 以表10所示之組成，以與實施例丨〜17同樣之方式獲得 活性能量線硬化性樹脂組成物。該組成物之物性如表1〇所 示。再者，實加例21及22中，作為成分(B)，係使用2〇重 量份之KAYARAD DPHA、及50重量份之季戊四醇三丙烯 酸酯與季戊四醇四丙烯酸酯之混合物。 藉由旋塗法將該組成物塗佈於厚度為〗mm之聚碳酸酯薄 098113982 89 201000547 膜上’而形成塗膜。利用電子束照射裝置（岩崎電氣公司製 造）’向該塗膜照射加速電壓為175kV、輻射劑量為5〇kGy(;5 Mrad)之電子束，而製成硬化後的厚度為3 ^ m之硬化膜。 關於所得硬化膜之表面物性，對透明性、鉛筆硬度、耐割 傷性、接觸角（水、十六烷）、耐污染性(指紋附著性、指紋拭 去性、指紋拭去耐久性、耐麥克筆油墨附著性、耐麥克筆油 墨拭去性）進行評價。將接觸角、耐污染性之結果示於表12， 將其他物性之結果示於表11。 [表 10] 成分 (A) 成分 (B) 成分 (D-1) 組成比 (A/B/C/D-l)(重量份） 黏度 (mPa · s) ------..1 外觀 實施例21 NPGDA DPHA PETA (d-2) 30/(20+50)/0/4 125 ---- 〇 實施例22 NPGDA DPHA PETA (d-4) 30/(20 + 50)/0/4 135 -------- 〇 [表 11] 基材 硬化膜厚度 m) 透明性 (霧值(％)) 鉛筆硬度 耐劃傷 實施例21 PC 3 0.1 HB ◎ 實施例22 PC 3 0.1 HB ◎ PC .聚碳酸醋薄膜（二菱工程塑膠公司製造之iUpii〇n Sheet(厚度為1 mm，霧值為0.1%)) [表 12] 水之接 觸角 (度） 十六烷之 接觸角 (度） 指紋附 著性 指紋拭 去性(次） 指紋拭 去耐久 性 耐麥克 筆油墨 附著性 耐麥克 筆油墨 拭去性 實施例21 92 31 L4 2 〇 〇 〇 實施例22 96 47 L4 2 〇 〇 098113982 90 201000547 &lt;實施例23〜26&gt; 藉由使用有塗佈棒之塗佈法，將與實施例1〇、17中所製 成之組成物具有相同組成之活性能量線硬化性樹脂組成物 塗佈於厚度為0.1 mm之聚對苯二曱酸乙二醇酯（pET)薄膜 .上(二曼樹脂公司製造’ Diafoil T600E)、或者厚度為〇.1 mm 之一乙酿纖維素(TAC)薄膜（富士軟片公司製造，fujitaC) 上而形成塗膜。於氧》農度為20%之條件下，使用於波長 ,254nm下的放射照度為4〇〇mW/cm2之高壓水銀燈，以累計 光量達到1000 mJ/cm2之方式向該塗膜照射紫外線，而製成 硬化後的厚度為5，之硬化膜。再者，此時之放射照度， 係依據卿IS_C祕1 2_)，使用具有波長254 nm用感 測益之照度計EYE uv TESTER uv视】受光部 PD-254(岩崎電氣公司製造)進行測定。 關於所得硬化膜之表面物性’對透明性、錯筆硬度、耐劃 I 傷性、接觸角水、十六烷）、耐 去性、浐纹抖土 + ,木f生⑷紋附著性、指紋拭 1 性、克筆油_著L克筆油 評價。將㈣角、耐污染性之結果示於表 將其他物性之結果示於表13。 上述實施例中，鉛筆硬度皆為 割傷性算in 勹H以上，亚且透明性、耐 一其他物性亦優異。因此可 線硬化性;“本兔明之活性能量 尺欠化『生樹月曰組成物，於主要 基材之心〜 PET相或TAC薄膜作為 材之,.，、員不崙（尤其是觸控面 Μ寻用途中，亦可適用於指紋 098113982 91 201000547 污潰等各種污潰成為問題之情況。 [表 13] 光記錄媒體硬塗 用樹脂組成物 基材 硬化膜厚 度（&quot;m) 透明性 (霧值(％)) 鉛筆 硬度 耐劃 傷性 實施例23 與實施例10具有相同組成 PET 5 1.1 2H ◎ 實施例24 與實施例10具有相同組成 TAC 5 0.4 2H ◎ 實施例25 與實施例17具有相同組成 PET 5 1.1 2H ◎ 實施例26 與實施例17具有相同組成 TAC 5 ^ 0.4 2H ◎ PET :聚對苯二甲酸乙二醇酯薄膜（三菱樹脂公司製造， DiafoilT600E(厚度為 0.1 mm，霧值為 1.1〇/0) TAC:三乙醯纖維素薄膜（富士軟片公司製造，fuJITAC(厚 度為0.1 mm，霧值為0.4%)) [表 14] 水之接 觸角 (度） 十六烧之 接觸角 (度） 指紋 附著 性 指紋 拭去 性（次） 指紋拭 去而才久 性 耐麥克 筆油墨 附著性 蛤麥克 筆油墨 拭去性 ¥施例23 97 34 L4 2 〇 〇 〇 實施例24 96 35 L4 2 〇 〇 〇 實施例2 5 實施例2 6 103 55 L4 2 〇 〇 〇 ~ 105 ~ 57 L4 2 〇 〇 又，參照特定實施態樣詳細說明了本發明，但可在不脫離 本發明之精神與範圍的情況下進行各種變更及修正，對於業 者係顯而易見的。 本申請案係基於2008年4月28曰申請之日本專利申請案 (日本專利特願2008-117413)、以及2008年7月4曰申請之 曰本專利申請案（日本專利特願2〇〇8_175244)者，其内容以 參照之方式併入本文中。 (產業上之可利用性） 098113982 92 201000547 本發明之活性能量線硬化性樹脂組成物雖然實質上不含 /合劑’但可進行對應於塗佈方法之寬廣範圍的黏度設定，並 14#異’因此光聚合起始劑的量較少，可利用溫和條 牛 F 、、舌 a 匕窃 此1線進行硬化，進而所得硬化膜之硬度及耐劃 =性（耐磨性）良好。其結果，藉由將該活性能量線硬化性樹 月曰組成物塗佈於光記錄媒體用基板表面上並使其硬化，可使 δ亥光兄錄媒體具有優異的硬化性、耐劃傷性、透明性，進而 亦可提同該等性能之耐久性。特別是，本發明之活性能量線 硬化性樹脂組成物之硬化性良好，因此可提供表面硬度較高 之硬塗層。 又因κ貝上不含溶劑，故亦未硬化溶液之再利用亦較為 容易’而且因實質上不含易揮發之有機溶劑，故環境負荷較 ，即使萬一附著 可提高製品性能 又，耐污染性（特別是指紋污潰難以附著 亦容易拭去，其耐久性亦優異）非常優異， 之耐久性。Sheet (thickness: mm, haze value: 0.1%)) Production Example 5&gt; • It is not possible to measure the upper layer of the acid ester due to poor hardenability. It is umm and has a diameter of 12. ^聚双:: into a reflective layer, a second dielectric layer, a recording layer, a = groove of the optical disc _ body ((4) ^ free layer table: death' by spin coating The following Newcomer has a performance of 60 W/cm2 f after reading the hardenable material. 'Using the output density to irradiate the UV U-silver lamp to accumulate the protective layer to 1000 mJ/cm2. After the wire is hardened, the thickness is formed. 97 ρ light transmission, the pencil hardness of the clothing surface is 4B. 098113982 86 201000547 ((transparent protective layer -n &gt; composition of the material)) silky activity of the active energy line hardening urethane (4) acid 60 parts by weight of vinegar oligomer (the acrylic acid base 4 is reacted with an isocyanic acid-terminated oligomer having isophoric-diisocyanate added to the polytetramethylene glycol having an average molecular weight of _ And sulphate ethyl acrylate vinegar) 20 parts by weight of 20 parts by weight of 3 parts by weight of iso-cyanuric acid hexane-modified glycerin vinegar & vinery (manufactured by Toagosei Co., Ltd., ARONIX M313) tetrahydroanthracene acrylate Saki IRGACURE 184 &lt;Examples 18 to 2::&gt;, and the scales were obtained in the same manner as in Examples 1 to 17.活月匕I, '泉硬化I1生; ^月之组成. Further 'Example 2〇*, as a knife (8), using 20 parts by weight of KAYARAD DPHA, and 50 weights of known pentaerythritol dienoic acid a mixture of an ester and pentaerythritol tetraacrylate. The composition was applied onto the transparent protective layer formed in Production Example 5 by a spin coating method to form a coating film. Under an oxygen concentration of 20%, High-pressure mercury & ampere at a wavelength of 254 nm with a illuminance of 400 mW/cm 2 , which is irradiated with ultraviolet rays in a manner that the cumulative amount of light reaches 1 〇〇〇mj/cm 2 to form a hard coat having a thickness of 3 In addition, the illuminance at this time is based on JIS (JIS-C 1609-1 2006), using an illuminance meter with a wavelength of 254 nm illuminator EYE UV TESTER UV-PFA1 by 098113982 87 201000547 light part PD- 254 (manufactured by Iwasaki Electric Co., Ltd.) About the surface properties of the hard coat layer, transparency (evaluation by visual inspection), pencil hardness, contact angle (water, hexadecane), 纣/loss dyeability (Adhesive fingerprint liquid adhesion, artificial fingerprint liquid wiping, The results of the stain resistance and the smoothness were evaluated in Table 8. The results of other physical properties are shown in Table 7. The active energy ray-curable resin composition of the present invention (Example 18) ~20) The hard coating layer produced has a high contact angle and is particularly excellent in adhesion resistance, and as a result, the wiping property and the wiping durability are excellent. It is preferable to be a Blu-ray Disk. . Further, Examples 18 to 20 in which a cured film having a film thickness of 3 #m was formed on the PC substrate with a light-transmitting protective layer as a barrier to Blu-ray Disk use. [Table 6] Component (A) Component (B) Component (C) Component (D-1) Composition ratio (A/B/C/Dl) (parts by weight) Example 18, — — THFA DPHA 1907 (d-1 40/60/4/3 - Example 19 - -. CHA DPHA 1907 (d-2) 33/67/4/3 - Example 20 ----- HPGDA DPHA PETA 1907 (d-2) 30 /(20+ 50)/4/4 [Table 7] ~ ——r —— _.-- _ Transparency (visual) Pencil hardness Water contact angle (degrees) Contact angle of hexadecane (degrees) Example 18 〇B 102 57 Example 19 〇HB 101 56 Example 20 〇B 96 36 098113982 88 201000547 [Table 8] Fingerprint adhesion Example 18 L4 Example 19 L4 Real ▲ Example 20 L4 De-sex (times) Deterioration of the contact angle of an optical recording medium (sub-generation CD-ROM) having a hard coating film coated with a commercially available stain-resistant hard coating agent on the surface of the surface Evaluation of pollution resistance. The results are shown in Table 9. In the commercially available mouth σ A, B, and C, 'there is excellent adhesion to the fingerprint liquid of the human health, but the plucking property is more than 3 times' and the wiping durability is also low, and the active energy line of the present invention [Table 9] The hardened resin composition is significantly inferior to the cured film coated/hardened. Contact angle of water (degrees) Contact angle of hexadecane (Jf) Fingerprint adhesion fingerprint detachment (times) Fingerprint wipe durability A: Sony BD-RE 96 51 L4 3 1 ---« XB : TDK BD-R 100 - one - 36 L3 ——--- XXC: Panasonic BD-R 78 27 L3 3.5 &lt;Examples 21, 22&gt; The composition shown in Table 10, and implementation In the same manner as in Example 17, the active energy ray-curable resin composition was obtained. The physical properties of the composition are shown in Table 1A. Further, in Examples 21 and 22, as component (B), a mixture of 2 parts by weight of KAYARAD DPHA and 50 parts by weight of pentaerythritol triacrylate and pentaerythritol tetraacrylate was used. The composition was applied by spin coating to a polycarbonate thin 098113982 89 201000547 film having a thickness of 〖mm to form a coating film. An electron beam irradiation device (manufactured by Iwasaki Electric Co., Ltd.) was used to irradiate the coating film with an electron beam having an acceleration voltage of 175 kV and a radiation dose of 5 〇 kGy (5 Mrad) to obtain a hardened thickness of 3 μm after hardening. membrane. Regarding the surface physical properties of the obtained cured film, transparency, pencil hardness, cut resistance, contact angle (water, hexadecane), stain resistance (fingerprint adhesion, fingerprint wiping, fingerprint wiping durability, resistance) The evaluation of the ink adhesion of the microphone pen and the ink wiping resistance of the microphone pen was evaluated. The results of the contact angle and the stain resistance are shown in Table 12, and the results of other physical properties are shown in Table 11. [Table 10] Component (A) Component (B) Component (D-1) Composition ratio (A/B/C/Dl) (parts by weight) Viscosity (mPa · s) ------..1 Appearance implementation Example 21 NPGDA DPHA PETA (d-2) 30/(20+50)/0/4 125 ---- 〇 Example 22 NPGDA DPHA PETA (d-4) 30/(20 + 50)/0/4 135 -------- 〇[Table 11] Thickness of substrate hardened film m) Transparency (haze value (%)) Pencil hardness scratch resistance Example 21 PC 3 0.1 HB ◎ Example 22 PC 3 0.1 HB ◎ PC. Polycarbonate film (iUpii〇n Sheet manufactured by Mitsubishi Engineering Plastics Co., Ltd. (thickness: 1 mm, haze value: 0.1%)) [Table 12] Contact angle of water (degrees) Contact angle of hexadecane (degrees) Fingerprint Adhesive Fingerprint Wipeability (Second) Fingerprint Wipe Durability Resistance Mace Ink Adhesion Resistance Mace Ink Wipe Detachability Example 21 92 31 L4 2 〇〇〇Example 22 96 47 L4 2 〇〇098113982 90 201000547 &lt;Examples 23 to 26&gt; An active energy ray-curable resin composition having the same composition as that of the composition prepared in Examples 1 and 17 was coated by a coating method using a coating bar. Polyethylene terephthalate at a thickness of 0.1 mm An ester (the pET) film (II resin manufactured by Cayman 'Diafoil T600E), or the thickness of one mm 〇.1 brewing acetate cellulose (TAC) film (manufactured by Fujifilm, fujitaC) formed on the coating film. Under the condition that the degree of agronomy is 20%, a high-pressure mercury lamp having a wavelength of 254 nm and having a irradiance of 4 〇〇mW/cm 2 is irradiated to the coating film with a cumulative light amount of 1000 mJ/cm 2 . A cured film having a thickness of 5 after hardening is formed. In addition, the illuminance at this time is measured by the light-receiving unit PD-254 (manufactured by Iwasaki Electric Co., Ltd.) using an illuminance meter EYE uv TESTER uv having a wavelength of 254 nm. About the surface physical properties of the obtained cured film 'transparency, wrong pen hardness, scratch resistance, contact angle water, hexadecane), resistance, striated earth +, wood f (4) grain adhesion, fingerprint Wipe 1 sex, grams of pen oil _ with L grams of pen oil evaluation. The results of the (four) angle and the stain resistance are shown in the table. The results of other physical properties are shown in Table 13. In the above examples, the pencil hardness is calculated to be in the range of 勹H or more, and is excellent in transparency and resistance to other physical properties. Therefore, it can be linearly curable; "The active energy ruler of the rabbit is under-represented by the composition of the raw tree, the heart of the main substrate ~ PET phase or TAC film as a material,.,, and not a member (especially touch For the purpose of searching for the surface, it can also be applied to the fingerprint 098113982 91 201000547. Various kinds of stains such as stains are a problem. [Table 13] Resin film thickness of the resin composition for hard recording of optical recording medium (&quot;m) Transparency (Haze value (%)) Pencil hardness and scratch resistance Example 23 The same composition as Example 10 PET 5 1.1 2H ◎ Example 24 The same composition as Example 10 TAC 5 0.4 2H ◎ Example 25 and Example 17 Having the same composition PET 5 1.1 2H ◎ Example 26 has the same composition as Example 17 TAC 5 ^ 0.4 2H ◎ PET: Polyethylene terephthalate film (manufactured by Mitsubishi Plastics Co., Ltd., Diafoil T600E (thickness 0.1 mm, fog) The value is 1.1〇/0) TAC: Triethylene fluorene cellulose film (manufactured by Fujifilm Co., Ltd., fuJITAC (thickness: 0.1 mm, haze value: 0.4%)) [Table 14] Water contact angle (degrees) Contact angle (degrees) fingerprint adhesion fingerprint wipe De-sex (secondary) fingerprint wiping and long-lasting resistance to Mike pen ink adhesion 蛤 microphone pen ink wiping property Example 23 97 34 L4 2 〇〇〇 Example 24 96 35 L4 2 〇〇〇 Example 2 5 EMBODIMENT 2 6 103 55 L4 2 〇〇〇~ 105 ~ 57 L4 2 〇〇 , 105 105 105 105 105 105 105 105 105 105 105 105 105 105 105 105 105 105 105 105 105 105 105 105 105 105 105 105 105 105 105 105 105 105 105 105 105 105 105 The amendments are obvious to the industry. This application is based on a Japanese patent application filed on April 28, 2008 (Japanese Patent Application No. 2008-117413), and a patent application filed on July 4, 2008 ( Japanese Patent Application No. 2-8175244, the entire contents of which is incorporated herein by reference. Mixture 'but can carry out a wide range of viscosity setting corresponding to the coating method, and 14# different', therefore, the amount of photopolymerization initiator is small, and can be hardened by using a gentle strip of F, and a tongue plagiarizing this 1 line. ,and then The hardness and scratch resistance (abrasion resistance) of the obtained cured film are good. As a result, the active energy ray-curable stannosa composition is applied onto the surface of the substrate for an optical recording medium and cured. The δ haiguang brother recording media has excellent hardenability, scratch resistance, transparency, and can also be used to enhance the durability of these properties. In particular, since the active energy ray-curable resin composition of the present invention has good curability, it can provide a hard coat layer having a high surface hardness. Since κ is free of solvent, it is also easier to reuse the hardened solution. And because it does not contain volatile organic solvents, the environmental load is relatively high. Even if it adheres, it can improve the performance of the product and is resistant to pollution. Sex (especially fingerprint staining is difficult to adhere and easy to wipe off, and its durability is also excellent). It is excellent in durability.

因此，本發明可適祕光學物品（特別是再生專用光碟、 光記錄光碟、磁光記錄光料m媒體、或者如觸控面板 及液晶電視之光學顯示關透明物品）、汽車相關零件(燈相 關、窗相關專之物品（後窗、側窗、天窗 /tL + 囪等））、生活相關物品 (各種電氣設備之殼體、裝飾板、傢且蓉 〇寺）荨廣泛物品之表面 保護，可用作各種物品之硬塗材料。 因此，本發明之工業價值顯著。 098113982 93Therefore, the present invention can be adapted to optical articles (especially for reproducing dedicated optical discs, optical recording optical discs, magneto-optical recording materials, m media, or optical display transparent articles such as touch panels and liquid crystal televisions), and automotive related parts (light related) , window-related items (rear window, side window, skylight/tL + chimney, etc.), life-related items (shells of various electrical equipment, decorative panels, home and Rongji Temple), surface protection of a wide range of items, Used as a hard coating material for various articles. Therefore, the industrial value of the present invention is remarkable. 098113982 93

Claims (1)

201000547 七、申請專利範圍： 1.一種活性能量線硬化性樹脂組成物，係含有下述 ⑻、⑹及㈣，而於饥之黏度為1G〜·㈣· s者； 其特徵在於，在厚度為1mm之聚礙酸醋薄臈上’形成厚 度為3㈣之由該活性能量線硬化性樹脂組成物所構成之 塗胺，於乳濃度為20%之條件下，使用於波長254 _下的 放射照度為400 mWW之高麼水銀燈，以累計光量達到 麵mJW之方式照射紫外線，此時硬化膜表面之錯筆硬 度為8以上’且不含超過該組成物中之5重量％之有機溶劑. (A) l分子内具有卜4個（甲基）两烯酿基，且於坑之黏 度為1〜500 mPa· s之i〜4官能之（甲基）丙稀酸酉旨、（甲旬 丙烯醯胺或者該兩者之混合物：1〇〜7〇重量份. 土 (B) l分子内具有3個以上（甲基）丙_基之由（a)以外之 多官能（曱基)丙烯酸醋以及自其胺基甲酸乙醋改質體、酉匕改 質體及碳酸酉旨改質體中選擇的一種以上所構成之多官^甲 基）丙烯酸醋衍生物：3 0〜90重量份； (c)光聚合起始劑··相對於(A)與(B)之合計量1〇〇重量份 為2〜6.5重量份； (D-1)含有自聚二甲基魏絲、錢院基及全氟伸燒基 中選擇的-種以上基之活性能量線硬化性化合物：相對=) 與(B)之合計量1〇〇重量份為〇丨〜15重量份。 2.如申請專利範圍第1項之活性能量線硬化性樹脂組成 098113982 94 201000547 物’其中’上述活性能量線硬化性化合物(D-1)為下述(d_3): (D-3)具有相當於如下結構的結構之活性能量線硬化性聚 合物’該結構係使1分子内具有1個以上（曱基）丙烯醯基之 羧酸與下述單體混合物的自由基聚合物之環氧基之至少一 ，部分進行反應而形成，該單體混合物係含有具有自聚二曱基 矽氧烷基、全氟烷基及全氟伸烷基中選擇之一種以上基的單 體與具有環氧基之（曱基）丙烯酸酯。 f 3.一種活性能量線硬化性樹脂組成物，係含有下述(A)、（b) 及P-3)者； 其特徵在於，於251之黏度為10〜500 mPa · s，不含超 過該組成物中之5重量％之有機溶劑； (A)於1分子内具有i〜4個（曱基）丙烯醯基，且於乃它下 之黏度為1〜500 mPa · s之i〜4官能之（甲基）丙烯酸酯及/ 或（甲基）丙烯醯胺：10〜70重量份； ( (B)l分子内具有3個以上（甲基）丙烯醯基之由（a)以外的 多官能（甲基）丙烯酸酯以及自其胺基甲酸乙酯改質體、酯改 ，質體及碳_旨改質體中選擇的—㈣上所構成之多官能（曱 ， 基）丙烯酸街生物：30〜90重量份； (D_3)具有相當於如下結構的結構之活性能量線硬化性聚 合物，該結構係使i分子内具有！個以上（甲基）丙稀酿基之 幾酸與下述單體混合物的自由基聚合物之環氧基之至少一 部分進行反應而形成，該單體混合物係含有具有自聚二甲基 098113982 95 201000547 選擇之一種以上基之單 相對於(A)與(B)之合計 石夕氧烧基、全氟炫基及全氟伸烧基中 體與具有％氧基之（曱基）丙稀酸醋： 量100重量份為0.1〜15重量份。 、4.如申請專利範圍第1或3項之活性能量線硬化性樹脂組 成物’其巾，在厚度為lmm之聚碳酸酯薄膜上，形成户产 為3㈣之由上述活性能量線硬化性樹脂組成物所構成= 膜，於氧濃度為20%之條件下，使用於波長Μ* _下的放 射照度為400 mW/cV之高壓水銀燈，以累計光量達到麵 方式照射紫外線，此時硬化膜表面之水的接觸角 為80度以上，十六烷的接觸角為25度以上。 5. 如申請專利範圍第丨或3項之活性能量線硬化性樹脂組 成物，其中，於上述(A)中，（曱基）丙烯酸S旨為丙烯酸酯，（曱 基）丙稀醯胺為内稀醯胺。 6. 如申請專利範圍第1或3項之活性能量線硬化性樹脂組 成物 &gt;、中上述活性能量線硬化性化合物（D-1)或（D-3)含 有（甲基）丙烯醯基，該（甲基）丙烯醯基之含量為6重量％以 7. 如申請專利範圍第1或3項之活性能量線硬化性樹脂組 成物’其中’上逑活性能量線硬化性化合物(D-1)或（D-3)之 數里平均分子量為10000〜100000。 8. 如申請專利範圍第1或3項之活性能量線硬化性樹脂組 成物’其中’上逑活性能量線硬化性化合物（D-1)或(D-3)在 098113982 96 201000547 其單個或兩個之末端上具有（甲基）丙烯醯基。 9. 如申請專利範圍第1或3項之活性能量線硬化性樹脂組 成物，其係光記錄媒體硬塗用。 10. —種硬化膜，其係向申請專利範圍第1或3項之活性 能量線硬化性樹脂組成物照射活性能量線而成。 11. 一種積層體，其係在表面上具有由申請專利範圍第10 項之硬化膜所構成之硬塗層。 12. —種光記錄媒體，係由申請專利範圍第11項之積層體 所構成者，其中，硬塗層存在於光入射側之最表面。 13. 如申請專利範圍第12項之光記錄媒體，其中，在上述 硬塗層與記錄膜面之間係具有至少一層之透光層。 14. 一種硬化膜之製造方法，其係藉由旋塗法而塗佈申請 專利範圍第1或3項之活性能量線硬化性樹脂組成物，形成 塗膜，在不經過使該塗膜乾燥之步驟的情況下，照射活性能 量線而形成硬化膜。 098113982 97 201000547 四、指定代表圖： (一) 本案指定代表圖為：無 (二) 本代表圖之元件符號簡單說明： 無 五、本案若有化學式時，請揭示最能顯示發明特徵的化學式： 無 098113982 3201000547 VII. Patent application scope: 1. An active energy ray-curable resin composition containing the following (8), (6) and (4), and having a viscosity of 1G~·(4)·s in hunger; characterized in that the thickness is An amine coated with a composition of the active energy ray-curable resin having a thickness of 3 (four) on a 1 mm smear of sulphuric acid vinegar, used at a concentration of 20%, and used for radiance at a wavelength of 254 Å For a mercury lamp of 400 mWW, the ultraviolet light is irradiated in such a manner that the cumulative amount of light reaches the surface mJW. At this time, the hardness of the surface of the cured film is 8 or more' and contains no organic solvent exceeding 5% by weight of the composition. l) There are four (meth) olefinic groups in the molecule, and the viscosity of the pit is 1~500 mPa·s i~4 functional (meth) acrylic acid Amine or a mixture of the two: 1 〇 to 7 〇 parts by weight. Soil (B) l having more than three (meth) propyl groups in the molecule, and polyfunctional (fluorenyl) acrylate vinegar other than (a) Selected from its amino urethane modified plastid, plastid modified and carbonated modified body The above-mentioned polyaniline methyl acrylate derivative: 30 to 90 parts by weight; (c) photopolymerization initiator · 1 part by weight relative to the total of (A) and (B) 2 to 6.5 parts by weight; (D-1) Active energy ray-curable compound containing at least one selected from the group consisting of polydimethyl wei wire, Qianyuan base and perfluoroalkylene group: relative =) and ( The total amount of B) is 1 part by weight to 15 15 parts by weight. 2. Active energy ray-curable resin composition as claimed in claim 1 098113982 94 201000547 The 'active energy ray-curable compound (D-1) is the following (d_3): (D-3) has equivalent An active energy ray-curable polymer having a structure of the following structure: This structure is an epoxy group of a radical polymer having a carboxylic acid having one or more (fluorenyl) acrylonitrile groups in one molecule and a monomer mixture described below. At least one, partially formed by reacting, the monomer mixture containing a monomer having one or more selected from the group consisting of polyfluorenyl sulfoxyalkyl groups, perfluoroalkyl groups, and perfluoroalkyl groups, and having an epoxy group Base (mercapto) acrylate. f 3. An active energy ray-curable resin composition containing the following (A), (b) and P-3); characterized in that the viscosity at 251 is 10 to 500 mPa · s, excluding 5% by weight of the organic solvent in the composition; (A) having i~4 (fluorenyl) acrylonitrile groups in one molecule, and having a viscosity of 1 to 500 mPa·s i~4 Functional (meth) acrylate and/or (meth) acrylamide: 10 to 70 parts by weight; ((B) 1 other than (a) having 3 or more (meth) acryl fluorenyl groups in the molecule Polyfunctional (meth) acrylate and polyfunctional (meth) acrylate street composed of - (iv) selected from its urethane modified body, ester modified, plastid and carbon modified medium Organism: 30 to 90 parts by weight; (D_3) an active energy ray-curable polymer having a structure corresponding to a structure in which one or more (meth) propylene groups in the i molecule have Forming at least a part of an epoxy group of a radical polymer of the following monomer mixture containing a self-polymerization Methyl 098113982 95 201000547 A single or more than one selected from the group consisting of (A) and (B), and a perfluoroalkyl group and a perfluoroalkyl group. An acrylic vinegar: an amount of 100 parts by weight of 0.1 to 15 parts by weight. 4. An active energy ray-curable resin composition of the first or third aspect of the patent application's towel, a polycarbonate having a thickness of 1 mm On the film, a film composed of the active energy ray-curable resin composition of 3 (4) is formed, and the illuminance at a wavelength Μ* _ is 400 mW/cV under the condition of an oxygen concentration of 20%. The high-pressure mercury lamp is irradiated with ultraviolet light in a cumulative manner, and the contact angle of the water on the surface of the cured film is 80 degrees or more, and the contact angle of hexadecane is 25 degrees or more. 5. If the scope of the patent application is 丨 or 3 In the active energy ray-curable resin composition, in the above (A), (mercapto)acrylic acid S is an acrylate, and (mercapto) acrylamide is an internal decylamine. 1 or 3 active energy ray-curable resin compositions&gt;, medium The active energy ray-curable compound (D-1) or (D-3) contains a (meth) acrylonitrile group, and the content of the (meth) acrylonitrile group is 6% by weight to 7. Or the active energy ray-curable resin composition of the three items, wherein the average molecular weight of the upper active energy ray-curable compound (D-1) or (D-3) is 10,000 to 100,000. The active energy ray-curable resin composition of the first or third item, wherein the upper active energy ray-curable compound (D-1) or (D-3) has a single or two ends at 098113982 96 201000547 ( Methyl) acrylonitrile. 9. The active energy ray-curable resin composition according to claim 1 or 3, which is used for hard coating of an optical recording medium. A cured film obtained by irradiating an active energy ray-curable resin composition of claim 1 or 3 with an active energy ray. A laminate comprising a hard coat layer formed of a cured film of claim 10 of the patent application. 12. An optical recording medium comprising the laminated body of claim 11 wherein the hard coat layer is present on the outermost surface of the light incident side. 13. The optical recording medium of claim 12, wherein at least one of the light-transmitting layers is provided between the hard coat layer and the recording film surface. A method for producing a cured film, which comprises applying an active energy ray-curable resin composition of claim 1 or 3 by a spin coating method to form a coating film without drying the coating film. In the case of the step, the active energy ray is irradiated to form a cured film. 098113982 97 201000547 IV. Designation of representative drawings: (1) The representative representative of the case is: None (2) The symbol of the symbol of the representative figure is simple: No. 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: No 098113982 3
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Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4496766B2 (en) 2003-11-25 2010-07-07 Ｔｄｋ株式会社 Method for forming protective layer and method for manufacturing optical information medium
EP1616635B1 (en) * 2004-07-15 2008-09-10 Sidel Participations Method for sorting containers
JP2006079731A (en) * 2004-09-09 2006-03-23 Fuji Photo Film Co Ltd Optical information recording medium
KR101215805B1 (en) * 2004-12-03 2012-12-26 미쓰비시 가가꾸 가부시키가이샤 Composition, cured product and article
WO2006132180A1 (en) * 2005-06-09 2006-12-14 Jsr Corporation Antireflective laminate
US8334039B2 (en) * 2005-07-15 2012-12-18 Dic Corporation Ultraviolet-curable resin composition and optical information recording medium
JP4033224B2 (en) 2005-07-15 2008-01-16 大日本インキ化学工業株式会社 Ultraviolet curable resin composition and optical information recording medium
JP2008044137A (en) * 2006-08-11 2008-02-28 Mitsubishi Plastics Ind Ltd Method for producing active energy ray-cured material laminate, laminate produced by the method, and optical disk using the laminate
JP2009102513A (en) * 2007-10-23 2009-05-14 Mitsubishi Chemicals Corp Polymer, composition, cured material, and optical recording medium

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102207557A (en) * 2010-03-30 2011-10-05 住友化学株式会社 Hard coating film, polarized sheet, and image display device
CN102207557B (en) * 2010-03-30 2015-07-22 住友化学株式会社 Hard coating film, polarized sheet, and image display device
TWI490242B (en) * 2012-03-27 2015-07-01 三菱化學股份有限公司 A resin composition for coating material
TWI623423B (en) * 2013-09-24 2018-05-11 Toray Industries Laminated film

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