200927849 九、發明說明 【發明所屬之技術領域】 本發明有關於硬塗佈層用硬化性組成物以及使 而成之硬化膜。更詳言之，係有關一種儘管無溶劑 優異塗佈性且可於各種基材之表面上形成高硬度且 性以及與基材之密著性優異之塗膜（被膜）之硬塗 硬化性組成物，以及有關一種捲曲性小且耐藥品性 0 硬塗佈層用之硬化膜。 【先前技術】 近幾年來，要求有：用以防止各種基材表面損 傷）或防止污染之保護塗佈材；各種基材之接著劑 材；作爲印刷油墨之黏合材而具有優異塗佈性且可 基材表面上形成硬度、彎折性、耐擦傷性、耐磨耗 捲曲性（意指硬化膜之翹曲小）、密著性、透明性 φ 品性以及塗膜面之外觀均優異之硬化膜之硬化性組 爲滿足該等要求，雖提出有各種組成物，但目 況爲尙無法獲得具有作爲硬化性組成物之優異塗佈 爲硬化膜時所需具備之高硬度同時捲曲性小之特性 例如，爲提高塗佈性，提出有使用有機溶劑使 低之方法（專利文獻1 )。 專利文獻2則揭示爲了維持硬度而含有具有異 酯環構造之化合物之組成物的硬化物，但此發明利 膜厚而展現高硬度。 其硬化 仍具有 耐擦傷 佈層用 優異之 傷（擦 、密封 於各種 性、低 、耐藥 成物。 前之現 性或作 〇 黏度降 氰脲酸 用大的 -4- 200927849 [專利文獻1]特開2003-313329號公報 [專利文獻2]特開2004-141732號公報 【發明內容】 [發明欲解決之課題] 作爲硬塗佈層用組成物，雖有種種提案提出具有良好 塗佈性之含溶劑之組成物，但於形成硬塗層時，有必要使 Q 用使其溶劑揮發之裝置以及需要加溫靜置之製程。若能省 略該等裝置及製程則有利於產業上成本，爲達此目的，而 希望有無溶劑之硬塗佈層用組成物。 然而，以往的組成物，自以無溶劑而可顯示良好塗佈 性且硬化膜爲良好耐磨傷性、高硬度、低捲曲性並存之觀 點觀之，尙無可滿足上述者。 本發明係鑑於上述問題而成者，其目的在於提供一種 於無溶劑仍具有優異塗佈性且可於各種基材表面上形成具 〇 備高硬度及低捲曲性之塗膜之硬化性組成物耐藥品性優異 之硬塗佈層用之硬化膜。 [用以解決發明之方法] 依據本發明，可提供下述之硬化性組成物以及其硬化 物。 [發明效果] 依據本發明，可提供一種儘管無溶劑仍具有優異塗佈 -5- 200927849 性且可於各種基材[例如塑料（聚碳酸酯、聚甲基丙烯酸 甲酯、聚苯乙烯、聚酯'聚烯烴、環氧樹脂、三聚氰胺樹 脂、三乙醯基纖維素樹脂、ABS樹脂、AS樹脂、降冰片 院系樹脂寺）、金屬、木材、紙、玻璃 '石板等]之表面 上形成高硬度且耐擦傷性以及與基材之密著性優異之塗膜 (被膜）之硬塗佈層用硬化性組成物，以及有關一種捲曲 性小且耐藥品性優異之硬塗佈層用之硬化膜。 【實施方式】 以下’對本發明之硬化性組成物、其硬化物以及層合 體之實施形態加以具體說明。 I.硬化性組成物 本發明之無溶劑型之硬塗佈層用硬化性組成物（以下 稱爲「本發明之組成物」）係含有下述成分（A)〜（F) Q 。該等成分中，（a)~(e)成分爲必要成分，係以特定 調配量調配。（F)成爲爲視需要而添加之任意添加成分 。所謂「無溶劑」是指不含有因添加溶劑而展現影響之程 度之溶劑量，因所調配之原料中所含之雜質等，而使組成 物中含有1重量％左右之溶劑也無妨。 (A) 於分子中具有環構造且具有3個以上（甲基） 丙烯醯基之胺基甲酸酯（甲基）丙烯酸酯； (B) 1分子中具有2個以上（甲基）丙烯醯基之（A )成分以外之聚合性多官能化合物； -6- 200927849 (C )聚合性單官能化合物； (D) 聚矽氧化合物 (E) 自由基聚合起始劑； (F )其他添加劑。 以下就本發明之硬化性組成物之 說明。 0 (A)於分子中具有環構造且具； 丙烯醯基之胺基甲酸酯（甲基）丙烯 (A)成分係於分子中具有環構 甲基）丙烯醯基之胺基甲酸酯（甲基 )丙烯醯基之數較好爲6個以上，更 )成分具有維持使本發明之硬化性組 物的硬度且減低捲曲之功能。 認爲藉由含有（A)成分，使交 〇 而可減低捲曲，又認爲由於具有特定 (甲基）丙烯酸酯具有結晶性，故可 且即使交聯點間之距離增大亦可維持 作爲（A)成分之化合物中之環 但較好爲脂肪族環、苯環、萘環、恵 環等之縮合苯環、噻吩環、耻略環、 雜環芳香環等。 (A)成分較好爲（A)成分所; )丙烯酿基之分子量爲400以下。更^ 各構成成分具體加以 每3個以上（甲基） 酸酯 豈且具有3個以上（ )丙燔酸醋，（甲基 :好爲8個以上。（A 成物硬化所成之硬化 聯點間之距離增大， 芳香環之胺基甲酸酯 提高機械強度、韌性 與硬度間之平衡。 構造並無特別限制， 環、菲環、茚環、芘 呋喃環、吡啶環等之 具有之每一個（甲基 好爲300以下。藉由 200927849 在400以下可提高耐擦傷性。 (A)成分之胺基甲酸酯（甲基）丙烯酸酯可使具有 環之二異氰酸酯與具有羥基之（甲基）丙烯酸酯化合物在 適當胺基甲酸酯化觸媒存在下，在6〇t、6小時之條件下 攪拌而得。 此處’作爲具有環之二異氰酸酯之具體例，2,4-伸甲 苯基二異氰酸酯、2，6 -伸甲苯基二異氰酸酯、ι，3 -伸二甲 0 苯基二異氰酸酯、1,4 -伸二甲苯基二異氰酸酯、1,5 -萘二 異氰酸酯、間-伸苯基二異氰酸酯、對-伸苯基二異氰酸酯 、3,3’-二甲基-4,4’-二苯基甲烷二異氰酸酯、4,4’-二苯基 甲烷二異氰酸酯、3，3’-二甲基伸苯基二異氰酸酯、4,4’-伸聯苯基二異氰酸酯、6 -異丙基-1，3 -苯基二異氰酸酯、4-二苯基丙烷二異氰酸酯、四甲基伸甲苯基二異氰酸酯、異 佛爾酮二丙烯酸酯等。該等中，尤其較好爲2,4-伸甲苯基 二異氰酸酯、異佛爾酮二丙烯酸酯等。 〇 作爲具有羥基之（甲基）丙烯酸化合物之具體例，可 舉例爲（甲基）丙烯酸2-羥基乙酯、（甲基）丙烯酸2-羥基丙酯、（甲基）丙烯酸2-羥基丁酯、（甲基）丙烯 酸2-羥基-3-苯基氧基丙酯、（甲基）丙烯酸1，4-丁二醇 酯、2-羥基烷基（甲基）丙烯醯基膦酸酯、（甲基）丙烯 酸4-羥基環己酯、（甲基）丙烯酸丨，6_環己二醇酯、單（ 甲基）丙烯酸新戊二醇酯、二（甲基）丙烯酸三羥甲基丙 酯、二（甲基）丙烯酸三羥甲基乙酯、三（甲基）丙烯酸 季戊四醇酯、五（甲基）丙烯酸二季戊四醇酯、下述式（ ~ 8 - 200927849 5)或（6)所示之（甲基）丙烯酸： 【化2】 CH2=CR1-COOCH2CH2_(-〇C〇CH2CH2CH2CH2CH2-^-〇H (5) CH2=CR1-COOCH2CH(OH)CH2-〇 (式中，R1表示氫原子或甲基，η爲1~15之數）。 以及烷基縮水甘油醚、烯丙基縮水甘油醚、如（甲基 )丙烯酸縮水甘油酯等之含有縮水甘油基之化合物與（甲 〇 基）丙烯酸藉加成反應獲得之化合物等。該等含有羥基之 (甲基）丙烯酸酯中，較好爲三（甲基）丙烯酸季戊四醇 酯等。 作爲胺基甲酸酯化觸媒之具體例，可舉例爲通常之環 烷酸銅、環烷酸鈷、環烷酸鋅、二丁基錫二月桂酸鹽、三 乙胺、1,4-二氮雜雙環[2.2.2]辛烷、2,6,7-三甲基-1，4-二 氮雜雙環[2 ·2_2]辛烷等。該等中，較好爲二丁基錫二月桂 酸鹽等。 ¥ 作爲（Α)成分之較佳化合物，舉例有下述式（1) 或（2)所示之化合物： -9- 200927849[Technical Field] The present invention relates to a curable composition for a hard coat layer and a cured film obtained by the present invention. More specifically, it relates to a hard coat hardening composition of a coating film (film) which is excellent in coating properties without a solvent and which can form a high hardness on the surface of various substrates and which is excellent in adhesion to a substrate. And a cured film for a hard coating layer having a small curling property and a chemical resistance. [Prior Art] In recent years, protective coating materials for preventing damage to various substrate surfaces or preventing contamination; adhesive materials for various substrates; excellent coating properties as adhesive materials for printing inks have been required. It can form hardness, bendability, scratch resistance, abrasion resistance curl (meaning warpage of the cured film), adhesion, transparency φ, and appearance of the coated surface. In order to satisfy the above requirements, the curable group of the cured film has various compositions. However, it is difficult to obtain a high hardness and a small curling property which are required to have an excellent coating as a curable composition. For example, in order to improve the coating property, a method of using an organic solvent is proposed (Patent Document 1). Patent Document 2 discloses a cured product containing a composition of a compound having an isoester ring structure in order to maintain hardness, but the invention has a thick film and exhibits high hardness. The hardening still has an excellent wound with a scratch-resistant cloth layer (wipe, seal, and various, low-resistance, drug-resistant products. The former or the viscosity is reduced by cyanuric acid. -4-200927849 [Patent Document 1 [Problem to be Solved by the Invention] As a composition for a hard coating layer, various proposals have been proposed to have good coating properties. a solvent-containing composition, but in the formation of a hard coat layer, it is necessary to use a device for volatilizing a solvent and a process for warming and resting. If the device and the process can be omitted, the industrial cost is favorable. In order to achieve this, it is desirable to have a composition for a hard coating layer without a solvent. However, the conventional composition can exhibit good coating properties without solvent and the cured film is excellent in abrasion resistance, high hardness, and low. In view of the above problems, the present invention has been made in view of the above problems, and an object thereof is to provide an excellent coating property without a solvent and to form a flaw on various substrate surfaces. High A cured film for a hard coat layer having excellent chemical resistance of a curable composition of a film having a low curling property. [Method for Solving the Invention] According to the present invention, the following curable composition and the like can be provided. [Effect of the Invention] According to the present invention, it is possible to provide an excellent coating of -5 - 200927849 in spite of no solvent and can be used in various substrates [for example, plastic (polycarbonate, polymethyl methacrylate, polyphenylene) Surface of ethylene, polyester 'polyolefin, epoxy resin, melamine resin, triethyl fluorene cellulose resin, ABS resin, AS resin, Reed Film Institute resin, metal, wood, paper, glass 'slate, etc.' A hardenable layer for a hard coat layer of a coating film (film) having high hardness and scratch resistance and excellent adhesion to a substrate, and a hard coat layer having a small curling property and excellent chemical resistance [Embodiment] Hereinafter, embodiments of the curable composition, the cured product, and the laminate of the present invention will be specifically described. I. Curable Composition The solvent-free hard coat layer of the present invention The curable composition (hereinafter referred to as "the composition of the present invention") contains the following components (A) to (F) Q. Among these components, the components (a) to (e) are essential components and are specified. (F) is an optional component added as needed. The term "solvent-free" means the amount of solvent that does not contain the influence of the addition of a solvent, and impurities contained in the raw materials to be blended. Further, it is also possible to contain a solvent of about 1% by weight in the composition. (A) A urethane (meth) acrylate having a ring structure in the molecule and having three or more (meth) acrylonitrile groups; (B) a polymerizable polyfunctional compound other than the component (A) having two or more (meth) acrylonitrile groups in one molecule; -6- 200927849 (C) a polymerizable monofunctional compound; (D) a polyoxyxene compound (E) a free radical polymerization initiator; (F) other additives. The following is a description of the curable composition of the present invention. 0 (A) has a ring structure in the molecule and has a methacrylic methacrylate (meth) propylene (A) component which is a urethane group having a cyclic methyl group in the molecule The number of (meth)acrylonyl groups is preferably 6 or more, and the component has a function of maintaining the hardness of the curable composition of the present invention and reducing the curl. It is considered that by containing the component (A), the curl can be reduced, and it is considered that since the specific (meth) acrylate has crystallinity, it can be maintained even if the distance between the crosslinking points is increased. The ring in the compound of the component (A) is preferably a condensed benzene ring such as an aliphatic ring, a benzene ring, a naphthalene ring or an anthracene ring, a thiophene ring, a succinct ring, a heterocyclic aromatic ring or the like. The component (A) is preferably a component (A); and the molecular weight of the acryl-based base is 400 or less. Further, each of the constituent components is specifically added to each of three or more (meth) acid esters and has three or more () propionate vinegars. (Methyl: preferably eight or more. (A hardening by solidification) The distance between the points increases, and the urethane of the aromatic ring improves the balance between mechanical strength, toughness and hardness. The structure is not particularly limited, and the ring, phenanthrene ring, anthracene ring, furfuran ring, pyridine ring, etc. Each of the methyl groups is preferably 300 or less. The scratch resistance can be improved by the use of 200927849 below 400. The urethane (meth) acrylate of the component (A) can have a diisocyanate having a ring and a hydroxyl group ( The methyl acrylate compound is obtained by stirring in the presence of an appropriate urethane catalyst at 6 Torr for 6 hours. Here, 'as a specific example of a diisocyanate having a ring, 2,4- Streptyl diisocyanate, 2,6-tolyl diisocyanate, iota, 3-dimethyl phenyl diisocyanate, 1,4 -exityl diisocyanate, 1,5-naphthalene diisocyanate, meta-extended benzene Diisocyanate, p-phenylene diisocyanate, 3,3' -Dimethyl-4,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3'-dimethylphenylene diisocyanate, 4,4'-extension Phenyl diisocyanate, 6-isopropyl-1,3-phenyl diisocyanate, 4-diphenylpropane diisocyanate, tetramethyl-tolyl diisocyanate, isophorone diacrylate, etc. In particular, 2,4-tolyldiisocyanate, isophorone diacrylate, etc. are preferable. As a specific example of the (meth)acrylic compound having a hydroxyl group, 2-hydroxy(meth)acrylate can be exemplified. Ethyl ester, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenyloxypropyl (meth)acrylate, (meth)acrylic acid 1, 4-butylene glycol ester, 2-hydroxyalkyl (meth) propylene decyl phosphonate, 4-hydroxycyclohexyl (meth) acrylate, hydrazine (meth) acrylate, 6-cyclohexanediol, Neopentyl glycol (meth)acrylate, trimethylolpropyl di(meth)acrylate, trimethylolethyl di(meth)acrylate, tris(A) Pentaerythritol acrylate, dipentaerythritol penta(meth)acrylate, (meth)acrylic acid represented by the following formula (~ 8 - 200927849 5) or (6): [Chemical 2] CH2=CR1-COOCH2CH2_(-〇 C〇CH2CH2CH2CH2CH2-^-〇H (5) CH2=CR1-COOCH2CH(OH)CH2-〇 (wherein R1 represents a hydrogen atom or a methyl group, and η is a number from 1 to 15), and an alkyl glycidyl ether, Allyl glycidyl ether, a compound obtained by reacting a glycidyl group-containing compound such as glycidyl (meth)acrylate with (meth)acrylic acid by addition reaction. Among these hydroxyl group-containing (meth) acrylates, pentaerythritol tris(meth)acrylate or the like is preferred. Specific examples of the urethane catalyst are exemplified by usual copper naphthenate, cobalt naphthenate, zinc naphthenate, dibutyltin dilaurate, triethylamine, 1,4-diazo Heterobicyclo[2.2.2]octane, 2,6,7-trimethyl-1,4-diazabicyclo[2 ·2_2]octane, and the like. Among these, dibutyltin dilaurate or the like is preferred. ¥ As a preferred compound of the (Α) component, a compound represented by the following formula (1) or (2) is exemplified: -9- 200927849
上述式（1)及（2)中，Z分別獨立表示丙烯醯基或 甲基丙嫌醯基，較好各Z均爲丙燦醯基之化合物。式（1 )中，Z爲丙烯醯基之化合物稱爲「PTP」，式（2)中， Z爲丙烯醯基之化合物稱爲「PIP」。 (A)成分之每一個（甲基）丙烯醯基之分子量較好 爲400以下，更好爲3 00以下。若每一個（甲基）丙烯醯 基之分子量超過400,則有無法獲得充分的膜強度之情況 ❹ 上述PTP及PIP之每一個丙烯醯基之分子量分別爲 124.5 及 134.5。 本發明組成物中（A )成分之含量，以組成物全量作 ' 爲100重量％時，有必要在30〜50重量％之範圍內，較好 在33~48重量％之範圍內，更好在35〜45重量％之範圍內 。（A)成分之含量若未達30重量％ ’則有無法獲得添加 效果之情況，若超過50重量％則有樹脂液黏度上升使塗 佈性變差的情況。 -10- 200927849 (B) 1分子中具有2個以上（甲基）丙烯醯基之（a )成分以外之聚合性多官能化合物 本發明組成物中之（B)成分，爲分子內具有2個以 上（甲基）丙烯醯基之（A)成分以外之聚合性多官能化 合物。由於爲「（A)成分以外」，故（B)成分包含「 分子中具有環構造、具有2個（甲基）丙烯醯基之胺基甲 0 酸酯（甲基）丙烯酸酯」、「分子中具有環構造、具有2 個以上（甲基）丙烯醯基、不具有胺基甲酸酯鍵之（甲基 )丙烯酸酯」、「不具有環構造、具有2個以上（甲基） 丙烯醯基之胺基甲酸酯（甲基）丙烯酸酯」、「不具有環 構造、具有2個以上（甲基）丙烯醯基、不具有胺基甲酸 酯鍵之（甲基）丙烯酸酯」等。（B)成分尤其較好使用 於提高硬化膜之彎折性。 (B)成分所具有之聚合性基’可僅爲（甲基）丙烯 φ 醯基，亦可進而具有（甲基）丙烯醯基以外之聚合性基。 作爲（B)成分，較好爲多官能（甲基）丙烯酸酯。多官 能（甲基）丙烯酸酯化合物較好使用以提高硬化膜之硬化 性、硬度。此處所謂多官能，意指1分子中具有2個以上 (甲基）丙烯醯基者，由製膜性、硬度之觀點觀之，較好 爲3官能以上之（甲基）丙烯酸酯化合物，更好爲5官能 以上之（甲基）丙烯酸酯化合物。 較佳之多官能（甲基）丙烯酸酯化合物之具體例’作 爲（甲基）丙烯酸酯類，可舉例有三（甲基）丙烯酸三羥 -11 - 200927849 甲基丙酯、四（甲基）丙烯酸二（三羥甲基丙基）酯、三 (甲基）丙烯酸季戊四醇酯、四（甲基）丙烯酸季戊四醇 酯、五（甲基）丙烯酸二季戊四醇酯 '六（甲基）丙烯酸 二季戊四醇酯、三（甲基）丙烯酸甘油酯、叁（2-羥基乙 基）異氰尿酸酯三（甲基）丙烯酸酯、二（甲基）丙烯酸 乙二醇酯、二（甲基）丙烯酸1,3 -丁二醇酯、二（甲基） 丙烯酸1，4· 丁二醇酯、二（甲基）丙烯酸1，6-己二醇酯、 Q 二（甲基）丙烯酸新戊二醇酯、二（甲基）丙烯酸二乙二 醇酯、二（甲基）丙烯酸三乙二醇酯、二（甲基）丙烯酸 二丙二醇酯、雙（2-羥基乙基）異氰尿酸酯二（甲基）丙 烯酸酯、以及對該等之起始醇類加成環氧乙烷或環氧丙烷 之加成物之聚（甲基）丙烯酸酯類、分子內具有2個以上 (甲基）丙烯醯基之寡聚酯（甲基）丙烯酸酯類、寡聚醚 (甲基）丙烯酸酯類、及寡聚環氧基（甲基）丙烯酸酯類 等。該等中，較好爲六（甲基）丙烯酸二季戊四醇酯、五 〇 (甲基）丙烯酸二季戊四醇酯、四（甲基）丙烯酸季戊四 醇酯 '四（甲基）丙烯酸二（三羥甲基丙基）酯。 至於多官能（甲基）丙烯酸酯化合物之市售品，可舉 例有三和化學（股）製之商品名：NICARACK MX-3 02 ; 東亞合成（股）製之商品名：ARONIX M-400、M-402、 M-403、M-404、M-4 08、M-45 0、M-3 05、M-3 09、M-310 、M-313、M-315、M-320、M-325、M-3 26、M-3 27、M-3 5 0、M-3 60、M-20 8、M-210、M-215、M-220 ' M-225、 Μ - 2 3 3 、Μ - 2 4 0、Μ - 2 4 5、 Μ - 2 6 0、Μ - 2 7 0、Μ -1 1 0 0、Μ- -12- 200927849In the above formulae (1) and (2), Z each independently represents an acryloyl group or a methyl propyl group, and it is preferred that each Z is a compound of a propylene group. In the formula (1), a compound in which Z is an acrylonitrile group is referred to as "PTP", and in the formula (2), a compound in which Z is an acrylonitrile group is referred to as "PIP". The molecular weight of each (meth)acryl fluorenyl group of the component (A) is preferably 400 or less, more preferably 300 or less. If the molecular weight of each (meth)acryl fluorenyl group exceeds 400, sufficient film strength cannot be obtained. 分子量 The molecular weight of each of the above PTP and PIP propylene groups is 124.5 and 134.5, respectively. The content of the component (A) in the composition of the present invention is preferably in the range of 30 to 50% by weight, preferably 33 to 48% by weight, based on the total amount of the composition of '100% by weight, more preferably It is in the range of 35 to 45 wt%. If the content of the component (A) is less than 30% by weight, the effect of addition may not be obtained. When the content is more than 50% by weight, the viscosity of the resin liquid may increase to deteriorate the coating property. -10-200927849 (B) A polymerizable polyfunctional compound other than the component (a) having two or more (meth) acrylonitrile groups in one molecule, the component (B) in the composition of the present invention has two molecules in the molecule. A polymerizable polyfunctional compound other than the component (A) of the above (meth) acrylonitrile group. (B) contains "amino acid (meth) acrylate having a ring structure in the molecule and having two (meth) acryl fluorenyl groups", and "molecular" a (meth) acrylate having a ring structure, having two or more (meth) acryl fluorenyl groups, having no urethane bond, and having no ring structure and having two or more (meth) acrylonitrile groups Amino amide (meth) acrylate, "(meth) acrylate having no ring structure, having two or more (meth) acryl fluorenyl groups, and having no urethane bond" . The component (B) is particularly preferably used for improving the bending property of the cured film. The polymerizable group which the component (B) has may be a (meth)acryl φ fluorenyl group, and may further have a polymerizable group other than the (meth) acryl fluorenyl group. The (B) component is preferably a polyfunctional (meth) acrylate. A polyfunctional (meth) acrylate compound is preferably used to improve the hardenability and hardness of the cured film. The term "polyfunctional" as used herein means a compound having two or more (meth) acrylonitrile groups in one molecule, and is preferably a trifunctional or higher (meth) acrylate compound from the viewpoint of film formability and hardness. More preferably, it is a 5-functional or higher (meth) acrylate compound. Specific examples of the preferred polyfunctional (meth) acrylate compound 'As (meth) acrylates, tris(hydroxy) acrylate trihydroxy-11 - 200927849 methyl propyl ester, tetra (meth) acrylate (trishydroxymethylpropyl) ester, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, three ( Methyl) glyceryl acrylate, bis(2-hydroxyethyl)isocyanurate tri(meth) acrylate, ethylene glycol di(meth)acrylate, 1,3-(di)(meth)acrylate Glycol ester, 1,4·butylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, di(a) Diethylene glycol acrylate, triethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, bis(2-hydroxyethyl)isocyanurate di(meth)acrylic acid Ester, and the addition of the starting alcohols to ethylene oxide or propylene oxide a poly(meth)acrylate of a product, an oligoester (meth)acrylate having two or more (meth)acryloyl groups in the molecule, an oligoether (meth)acrylate, and an oligo Polyepoxy (meth) acrylates and the like. Among these, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, pentaerythritol tetrakis(meth)acrylate, bis(trishydroxymethylpropyl)tetrakis(meth)acrylate are preferred. Base) ester. As a commercial product of a polyfunctional (meth) acrylate compound, a trade name of MICARACK MX-3 02, manufactured by Sanwa Chemical Co., Ltd.; and ARONIX M-400, M, manufactured by East Asia Synthetic Co., Ltd. can be exemplified. -402, M-403, M-404, M-4 08, M-45 0, M-3 05, M-3 09, M-310, M-313, M-315, M-320, M-325 , M-3 26, M-3 27, M-3 5 0, M-3 60, M-20 8, M-210, M-215, M-220 'M-225, Μ - 2 3 3 , Μ - 2 4 0, Μ - 2 4 5, Μ - 2 6 0, Μ - 2 7 0, Μ -1 1 0 0, Μ- -12- 200927849
❹ 1 200、Μ-1210、Μ-1310、Μ- 1 600、Μ-221、Μ-203、ΤΟ-924、ΤΟ-1 270、ΤΟ-1231、ΤΟ-595、ΤΟ-756、ΤΟ-1 343、 ΤΟ- 1 3 82、ΤΟ-902、ΤΟ-904、ΤΟ-905、ΤΟ- 1 3 3 0 ;日本化 藥（股）製之商品名：KAYARAD D-310、D-330、DPHA 、DPCA-20、DPCA-30、DPCA-60、DPCA-120、DPHA、 DN-0075、DN-2475、SR-295、SR-3 55、SR-399E、SR-494 、SR-9041、SR-3 68、SR-415、SR-444 > SR-454、SR-492 、SR-499、SR-502、SR-9020、SR-9035、SR-111、SR-212、SR-213、SR-230、SR-259、SR-268、SR-272、SR-344 、 SR-349 、 SR-368 、 SR-601 、 SR-602 、 SR-610 、 SR-9003 ' PET-30、T- 1 420、GPO-303、TC-120S、HDDA、 NPGDA、TPGDA、PEG400DA、MANDA、HX-220、HX-620、R-551、R-712、R-167、R-526、R-551、R-712、R-604、R-684、TMPTA、THE-3 3 0、TPA-320、TPA-3 3 0、 KS-HDDA、KS-TPGDA > KS-TMPTA ；共榮化學公司（股 )製之商品名：LITEACRYLATE PE-4A、DPE-6A、 DTMP-4A等。上述化合物可單獨使用一種或組合2種以 上使用。 作爲（B)成分，於上述多官能（甲基）丙烯酸酯以 外，亦可使用（A)成分以外之具有2個以上（甲基）丙 烯醯基之胺基甲酸酯（甲基）丙烯酸酯，亦即具有環構造 之胺基甲酸酯多官能（甲基）丙烯酸酯。 該等胺基甲酸酯多官能（甲基）丙烯酸酯並無特別限 制，但基本上是由（a)聚異氰酸酯化合物與（b)具有羥 -13- 200927849 基之（甲基）丙烯酸酯單體反應而得。胺基甲酸酯（甲基 )丙烯酸酯亦可爲以其他寡聚物作爲主鏈，於其上鍵結胺 基甲酸酯者。 胺基甲酸酯多官能（甲基）丙烯酸酯必須具有2個以 上（甲基）丙烯醯基’較好具有4個以上’進而更好爲具 有6個以上。該等胺基甲酸酯（甲基）丙烯酸酯，通常爲 於各具有2~6個異氰酸酯基之（a)聚異氰酸酯化合物之 各異氰酸酯基上鍵結有（b)含有羥基之（甲基）丙烯酸 酯單體之構造。 本發明所用之胺基甲酸酯（甲基）丙烯酸酯之市售品 ，可舉例爲例如荒川化學工業（股）製之商品名： BEAMSET 102、502H、5 05A-6、510、550B、551B、575 、57 5CB、EM-90、EM92 ; SANNOPCO (股）製之商品名 :PHOTOMER 6008、621 0 ;新中村化學工業（股）製之 商品名：NK OLIGO U-2PPA、U-4HA、U-6HA、H-15HA 、UA-32PA、U-324A、U-4H、U-6H;東亞合成（股）製 之商品名：ARONIX M-1100、M-1 200、M-1210、M-1310 、M-160 0、M-1 960 ;共榮化學公司（股）製之商品名： AH-600、AT606、UA-306H ;日本化藥（股）製之商品名 ：KAYARAD UX-220 1、UX-230 1、U X 3 2 0 4、UX - 3 3 0 1、 UX-4101、UX-6101、UX-7101;日本合成化學工業（股） 製之商品名：紫光 UV-1 700B、UV-3000B、UV-6100B、 UV-6300B、UV-7000、UV-2010B ;根上工業（股）製之 商品名·· ALTRESIN UN- 1 25 5、UN-5200、HDP-4T、HMP- -14- 200927849 2、UN-901T、UN-3320HA、UN-3320HB、UN-3320HC、 UN-3 3 20HS、H-61、HDP-M20 ； SAICEL UCB (股）製之 商品名：Ebecryl 6700 、 204 、 205 、 220 、 254 、 1259 、 1290K 、 1748 、 2002 、 2220 、 4833 、 4842 、 4866 、 5129 、 6602、8301等。該等中，作爲具有3個以上（甲基）丙 烯醯基者，較好爲U-6HA等。 本發明組成物中（B )成分之含量，以組成物全量作 爲1 00重量％時，有必要在1 0〜5 0重量％之範圍內，較好 在15~45重量％之範圍內，更好在15〜40重量％之範圍內 。（B)成分之含量若未達10重量％，則有無法獲得充分 耐擦傷性之情況，若超過5 0重量％則有硬化物翹曲變大 的情況。 (C)聚合性單官能化合物 本發明組成物中之（C)成分爲聚合性單官能化合物 φ ，亦即具有1個聚合性基之單體。作爲聚合性基，並無特 別限制，但較好爲例如乙烯基、（甲基）丙烯醯基等。聚 合性單官能化合物係爲調整樹脂液的黏度以及降低黏度之 硬化物之翹曲而添加者。 作爲（C )成分之聚合性單官能化合物之例’可舉例 爲例如如N-乙烯基吡咯啶酮、N-乙烯基己內醯胺等之含 有乙烯基之內醯胺、如（甲基）丙烯酸異冰片酯、（甲基 )丙烯酸冰片酯、（甲基）丙烯酸三環癸酯、（甲基）丙 烯酸二環戊烯酯之含有脂環式構造之（甲基）丙烯酸酯、 -15- 200927849 如（甲基）丙烯酸苄酯、（甲基）丙烯酸4-丁基環己酯 、丙烯醯基嗎啉、乙烯基咪唑、乙烯基吡啶、（甲基）丙 烯酸2-羥基乙酯、（甲基）丙烯酸2-羥基丙酯、（甲基 )丙烯酸2-羥基丁酯、（甲基）丙烯酸甲酯、（甲基） 丙烯酸乙酯、（甲基）丙烯酸丙酯、（甲基）丙烯酸異丙 酯、（甲基）丙烯酸丁酯、（甲基）丙烯酸戊酯、（甲基 )丙烯酸異丁酯、（甲基）丙烯酸第三丁酯、（甲基）丙 U 嫌酸戊酯、（甲基）丙烯酸異戊酯、（甲基）丙烯酸己酯 、（甲基）丙烯酸庚酯、（甲基）丙烯酸辛酯、（甲基） 丙烯酸異辛酯、（甲基）丙烯酸2-乙基己酯、（甲基） 丙烯酸壬酯、（甲基）丙烯酸癸酯、（甲基）丙烯酸異癸 醋、（甲基）丙烯酸十一烷酯、（甲基）丙烯酸十二烷酯 、（甲基）丙烯酸月桂基酯、（甲基）丙烯酸硬脂基酯、 (甲基）丙烯酸異硬脂基酯、（甲基）丙烯酸四氫糠酯、 (甲基）丙烯酸丁氧基乙酯、（甲基）丙烯酸乙氧基二乙 φ 一醇醋、壬基酚環氧乙烷改性之（甲基）丙烯酸酯、（甲 基）丙嫌酸苄酯、（甲基）丙烯酸苯氧基乙酯、單（甲基 )丙烯酸聚乙二醇酯、單（甲基）丙烯酸聚丙二醇酯、（ 甲基）丙烯酸甲氧基乙二醇酯、（甲基）丙烯酸乙氧基乙 醋、（甲基）丙烯酸甲氧基聚乙二醇酯、（甲基）丙烯酸 甲氧基聚丙二醇酯、二丙酮（甲基）丙烯醯胺、異丁氧基 甲基（甲基）丙烯醯胺、N，N_二甲基（甲基）丙烯醯胺、 第二辛基（甲基）丙烯醯胺、（甲基）丙烯酸二甲胺基乙 醋、（甲基）丙烯酸二乙胺基乙酯、（甲基）丙烯酸7- -16- 200927849 胺基-3,7-二甲基辛酯、N，N-二乙基（甲基）丙烯醯胺、 N，N-二甲基胺基丙基（甲基）丙烯醯胺、羥基丁基乙烯基 醚、月桂基乙烯基醚、鯨蠟基乙烯基醚、2 -乙基己基乙烯 基醚以及以下式（3) ~(6)表示之化合物。 【化4】 CH2=CR2-CO—(R30)m-R4 (3) Ο❹ 1 200, Μ-1210, Μ-1310, Μ-1 600, Μ-221, Μ-203, ΤΟ-924, ΤΟ-1 270, ΤΟ-1231, ΤΟ-595, ΤΟ-756, ΤΟ-1 343 , ΤΟ- 1 3 82, ΤΟ-902, ΤΟ-904, ΤΟ-905, ΤΟ-1 3 3 0; Nippon Chemical Co., Ltd. trade name: KAYARAD D-310, D-330, DPHA, DPCA- 20. DPCA-30, DPCA-60, DPCA-120, DPHA, DN-0075, DN-2475, SR-295, SR-3 55, SR-399E, SR-494, SR-9041, SR-3 68, SR-415, SR-444 > SR-454, SR-492, SR-499, SR-502, SR-9020, SR-9035, SR-111, SR-212, SR-213, SR-230, SR -259, SR-268, SR-272, SR-344, SR-349, SR-368, SR-601, SR-602, SR-610, SR-9003 'PET-30, T-1 420, GPO- 303, TC-120S, HDDA, NPGDA, TPGDA, PEG400DA, MANDA, HX-220, HX-620, R-551, R-712, R-167, R-526, R-551, R-712, R- 604, R-684, TMPTA, THE-3 3 0, TPA-320, TPA-3 3 0, KS-HDDA, KS-TPGDA >KS-TMPTA; Co., Ltd. under the trade name: LITEACRYLATE PE-4A, DPE-6A, DTMP-4A, etc. The above compounds may be used alone or in combination of two or more. As the component (B), in addition to the above polyfunctional (meth) acrylate, a urethane (meth) acrylate having two or more (meth) acrylonitrile groups other than the component (A) may be used. That is, a urethane polyfunctional (meth) acrylate having a ring structure. The urethane polyfunctional (meth) acrylate is not particularly limited, but is basically composed of (a) a polyisocyanate compound and (b) a (meth) acrylate having a hydroxy-13-200927849 group. The body reaction comes. The urethane (meth) acrylate may also be one in which other oligomers are used as a main chain to which a urethane is bonded. The urethane polyfunctional (meth) acrylate must have two or more (meth) acrylonitrile groups, preferably four or more', and more preferably six or more. The urethane (meth) acrylate is usually bonded to each isocyanate group of the (a) polyisocyanate compound having 2 to 6 isocyanate groups, and (b) a hydroxyl group-containing (meth) group. The construction of an acrylate monomer. The commercial product of the urethane (meth) acrylate used in the present invention may, for example, be a trade name of Arakawa Chemical Industry Co., Ltd.: BEAMSET 102, 502H, 5 05A-6, 510, 550B, 551B. , 575, 57 5CB, EM-90, EM92; SANNOPCO (share) product name: PHOTOMER 6008, 621 0; New Nakamura Chemical Industry Co., Ltd. trade name: NK OLIGO U-2PPA, U-4HA, U -6HA, H-15HA, UA-32PA, U-324A, U-4H, U-6H; East Asia Synthetic Co., Ltd. trade names: ARONIX M-1100, M-1 200, M-1210, M-1310 , M-160 0, M-1 960; Co., Ltd. under the trade name: AH-600, AT606, UA-306H; Nippon Chemical Co., Ltd. trade name: KAYARAD UX-220 1. UX-230 1, UX 3 2 0 4, UX - 3 3 0 1, UX-4101, UX-6101, UX-7101; Japan Synthetic Chemical Industry Co., Ltd. Product Name: Violet UV-1 700B, UV- 3000B, UV-6100B, UV-6300B, UV-7000, UV-2010B; the name of the industrial (stock) system of the roots · ALTRESIN UN- 1 25 5, UN-5200, HDP-4T, HMP- -14- 200927849 2. UN-901T, UN-3320HA, UN-3320HB, UN-3320HC, UN-3 3 20HS, H-6 1. HDP-M20; SAICEL UCB (share) system name: Ebecryl 6700, 204, 205, 220, 254, 1259, 1290K, 1748, 2002, 2220, 4833, 4842, 4866, 5129, 6602, 8301, etc. Among these, as the one having three or more (meth) acrylonitrile groups, U-6HA or the like is preferable. When the content of the component (B) in the composition of the present invention is 100% by weight based on the total amount of the composition, it is necessary to be in the range of 10 to 50% by weight, preferably 15 to 45% by weight, more preferably It is preferably in the range of 15 to 40% by weight. If the content of the component (B) is less than 10% by weight, sufficient scratch resistance may not be obtained, and if it exceeds 50% by weight, the cured product may become warped. (C) Polymerizable monofunctional compound The component (C) in the composition of the present invention is a polymerizable monofunctional compound φ, that is, a monomer having one polymerizable group. The polymerizable group is not particularly limited, and is preferably, for example, a vinyl group or a (meth)acryl fluorenyl group. The polymerizable monofunctional compound is added to adjust the viscosity of the resin liquid and to warp the cured product which lowers the viscosity. The example of the polymerizable monofunctional compound as the component (C) can be exemplified by a vinyl group-containing decylamine such as N-vinylpyrrolidone or N-vinyl caprolactam, such as (methyl). Isobornyl acrylate, borneol (meth) acrylate, tricyclodecyl (meth) acrylate, dicyclopentenyl (meth) acrylate (meth) acrylate containing alicyclic structure, -15- 200927849 Such as benzyl (meth) acrylate, 4-butylcyclohexyl (meth) acrylate, acryl morpholine, vinyl imidazole, vinyl pyridine, 2-hydroxyethyl (meth) acrylate, (a 2-hydroxypropyl acrylate, 2-hydroxybutyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, (meth) acrylate Propyl ester, butyl (meth) acrylate, amyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, (methyl) propyl uric acid, ( Isoamyl methacrylate, hexyl (meth) acrylate, glycol (meth) acrylate , octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, decyl (meth) acrylate, (methyl) Isophthalic acid acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, (meth)acrylic acid Stearyl ester, tetrahydrofurfuryl (meth) acrylate, butoxyethyl (meth) acrylate, ethoxydiethyl phthalate (meth) acrylate, nonyl phenol oxirane modified (meth) acrylate, (meth) propyl benzyl acrylate, phenoxy ethyl (meth) acrylate, polyethylene glycol mono(meth) acrylate, polypropylene mono(meth) acrylate , (meth)acrylic acid methoxyethylene glycol, (meth)acrylic acid ethoxyacetate, (meth)acrylic methoxypolyethylene glycol ester, (meth)acrylic acid methoxypolypropylene glycol ester , diacetone (meth) acrylamide, isobutoxymethyl (meth) acrylamide, N, N dimethyl (Meth) acrylamide, second octyl (meth) acrylamide, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, (meth) acrylate 7 - -16- 200927849 Amino-3,7-dimethyloctyl ester, N,N-diethyl(meth)acrylamide, N,N-dimethylaminopropyl (meth) propylene oxime An amine, hydroxybutyl vinyl ether, lauryl vinyl ether, cetyl vinyl ether, 2-ethylhexyl vinyl ether, and a compound represented by the following formulas (3) to (6). [Chemical 4] CH2=CR2-CO—(R30)m-R4 (3) Ο
(式中，R2表示氫原子或甲基；R3表示碳數2〜6， 較好2〜4之伸烷基；R4表示氫原子或碳數 1〜12，較好 1〜9之烷基；m表示0〜12，較好爲1〜8之數）。 【化5 (4) CH2^-C^〇-R6-C^p〇-CH2—C3 R5 Ο Ο ° ch2 =?~行寸〇-妒1 十p〇-CH2-C(CH3)2 R5 0 Ο(wherein R2 represents a hydrogen atom or a methyl group; R3 represents a C 2~6, preferably 2 to 4 alkylene group; and R4 represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, preferably 1 to 9 carbon atoms; m represents 0 to 12, preferably 1 to 8). [5 (4) CH2^-C^〇-R6-C^p〇-CH2—C3 R5 Ο Ο ° ch2 =?~行寸〇-妒1 十p〇-CH2-C(CH3)2 R5 0 Ο
(5)(5)
(式中，R5表示氫原子或甲基；R6表示碳數2〜8, 較好2〜5之伸烷基；R7各獨立表示氫原子或甲基；p表示 較好爲1~4之數）。 【化6】(wherein R5 represents a hydrogen atom or a methyl group; R6 represents a C 2~8, preferably 2 to 5 alkylene group; R7 each independently represents a hydrogen atom or a methyl group; and p represents preferably a number of 1 to 4; ). 【化6】
(6) (式中，R8、R9、R10 及 甲基，q表示1~5之整數）。 該等聚合性單官能單體中 R11相互獨立表示氫原子或 ，較好爲如N-乙烯基吡咯 -17- 200927849 啶酮、N-乙烯基己內醯胺之含有乙烯基之內醯胺、（甲基 )丙烯酸異冰片酯。 該等聚合性單官能單體可以市售品IBXA (大阪有機 化學工業（股）公司製造）、ARONIX M-1 1 1、M-1 13、 M114、M-117、TO-1210C以上爲東亞合成（股）公司製 )等獲得。 本發明組成物中（C)成分之含量，以組成物全量作 0 爲 1〇〇重量％時，在 1 5〜40重量％之範圍內，較好在 15〜3 5重量％之範圍內。（C)成分之含量若未達15重量 %，則有樹脂液之黏度變高塗佈性惡化之情況，若超過40 重量％，則有硬化物之耐摩擦傷性變差的情況。 (D)聚矽氧化合物 本發明組成物中之（D)成分爲聚矽氧化合物。矽氧 化合物係較好地使用於改善硬化物之耐擦傷性。 φ 本發明所用之（D )聚矽氧化合物爲例如聚醚改性之 聚矽氧、烷基改性之聚矽氧、胺基甲酸酯丙烯酸酯改性之 聚矽氧、胺基甲酸酯改性之聚矽氧、甲基苯乙烯基改性之 聚矽氧、環氧聚醚改性之聚矽氧、烷基芳烷基醚改性之聚 矽氧等’該等中最好爲聚醚改性聚矽氧。至於聚醚改性聚 矽氧較好爲於至少一個矽原子上鍵結有R22- ( R23〇 ) v_ R24-基（其中，R22表示羥基或碳數1〜10之烷氧基，R23 表示碳數2〜4之伸烷基（其中R22亦可以2種以上之伸烷 基混合存在），R24表示碳數2〜12之伸烷基，v表示 -18- 200927849 1〜2 0之數）之聚二甲基矽氧烷化合物。該等中R24較好爲 伸乙基、伸丙基，最好爲伸乙基。至於該聚矽氧化合物之 市售品，舉例有例如SH28P A ;二甲基聚矽氧烷聚環氧烷 共聚物，東麗道康寧公司，FM0411 ; SAIRAPOLANE，東 曹（股），SF8428;二甲基聚矽氧烷聚環氧烷共聚物（含 有側鏈 OH)，東麗道康寧公司，BYK UV3510C曰本 BYK-Chemie股份有限公司製，二甲基聚矽氧烷-聚環氧烷 ❹ 共聚物）、DC57 (東麗道康寧矽氧股份有限公司，二甲 基聚矽氧烷·聚環氧烷共聚物）等，該等中，較好爲DC57 等。聚矽氧化合物亦可以市售品獲得，例如 SH8400、 DC5 7 (東麗道康寧聚矽氧股份有限公司製）等。聚矽氧 化合物可單獨使用一種或組合複數種使用。 本發明組成物中成分（D)之含量，以組成物全量作 爲 100重量％時，在 0.05〜5重量％之範圍內，較好在 0.1〜4重量％之範圍內。（D)成分之含量若未達0.05重 〇 量％，則有耐擦傷性變差之可能性，若超過5重量％，則 有隨時間經過於塗膜表面析出而成爲表面粗糙原因之情況 (E )自由基聚合起始劑 本發明組成物中（E )成分爲自由基聚合起始劑。該 等中作爲自由基聚合起始劑（E)，可舉例有於熱時發生 活性自由基之化合物（熱聚合起始劑）以及藉由照射輻射 線（光）而發生活性自由基之化合物等（輻射線（光）聚 -19- 200927849 合起始劑），較好使用輻射線（光）自由基聚合起始劑。 作爲輻射線（光）聚合起始劑，只要是可藉由光照射 而分解產生自由基並開始聚合者則無特別限制，可舉例爲 例如苯乙酮、苯乙酮苄基縮酮、1-羥基環己基苯基酮、 2,2 -二甲氧基-1，2 -二苯基乙-1-酮、咕噸酮、芴酮、苯甲醛 、芴、蒽醌、三苯胺、咔唑、3 -甲基苯乙酮、4 -氯二苯甲 酮、4,4’-二甲氧基二苯甲酮、4，4，-二胺基二苯甲酮、苯 φ 偶因丙醚、苯偶因乙醚、苄基二甲基縮酮、1-(4 -異丙基 苯基）-2-羥基-2-甲基丙-1-酮、2-羥基-2-甲基-1-苯基丙- 1- 酮、唾噸酮、二乙基噻噸酮、2 -異丙基噻噸酮、2-氣噻 噸酮、2-甲基- l-[4-(甲硫基）苯基]-2-嗎啉基-丙-1-酮、 2- 苄基-2-二甲胺基-1-(4-嗎咐基苯基）-丁酮-1,4-(2-羥 基乙氧基）苯基-(2-經基-2-丙基）嗣、2,4,6-三甲基苯甲 醯基二苯基氧化氧化膦、雙（2,6-二甲氧基苯甲醯基）-2，4,4-三甲基戊基氧化膦、寡聚（2-羥基-2-甲基-1-(4-( Φ 1-甲基乙烯基）苯基）丙酮）等。 至於輻射線（光）聚合起始劑之市售品可舉例爲汽巴 嘉基特用化學品（股）製之商品名：IRUGACURE 184、 369、65 1、500、819、907、784、2959、CGI 1 700、 CGI 1 750、CGI 1 850、CG24-61、DAROCURE 1116、1173 ;BASF 公司製商品名：LUCILIN TPO、TPO-X ; UCB 公 司製之商品名：UBCRIL P36; LAMBERTI公司製之商品 名：EZACURE KIP1 50、KIP65LT、KIP100F、KT37、 KT55、KTO 46、KIP75/B 等。 -20- 200927849 本發明組成物中之（E )成分之含量，以組成物全量 作爲100重量％時，在0.1~10重量％之範圍內，較好在 〇.5〜5重量％之範圍內。（E)成分之含量若未達0.1重量 %，則有作爲硬化物時硬度不充分之情形，若超過1 〇重 量％，則有作爲硬化物時內部（下層）未硬化之情況。 '使本發明組成物硬化時，依據需要除了光自由基聚合 起始劑以外可倂用熱自由基聚合起始劑。 φ 作爲較隹之熱自由基聚合起始劑，可舉例如過氧化物 、偶氮化合物，作爲具體例，可舉例有苯甲醯過氧化物、 第三丁基過氧苯甲酸酯、偶氮雙異丁腈等。 (F )其他添加劑 本發明組成物，在不損及本發明效果之範圍內，可依 據需要，適當添加光增感劑、聚合抑制劑、聚合起始助劑 、勻化劑、濕潤改良劑、界面活性劑、可塑劑、紫外線吸 〇 收劑、抗氧化劑、抗靜電劑、無機塡充劑、防污劑、顏料 、染料等。 接著對本發明組成物之製造方法加以說明。 具有環構造之胺基甲酸酯（甲基）丙烯酸酯（（A) 成分）、聚合性多官能化合物（（B)成分）、聚合性單 官能化合物（（C)成分）、聚矽氧化合物（（D)成分 )、光自由基聚合起始劑（（E)成分），以個別之調配 量，以及視需要之其他添加劑（（F )成分）加入附有攪 拌機之反應容器內，通常在5 0~60°C攪拌2~4小時，成爲 -21 - 200927849 本發明組成物。 如此所得之本發明組成物之黏度，於25 °C下，爲 400〜1200 mPa· s’較好爲500〜1000 mPa· s。黏度若在 該等範圍以外，以旋轉塗佈等製作薄膜之際，有難以控制 膜厚之情況，又若黏度未達400 mPa · s，則有薄膜變得 太薄而耐擦傷性變差之情況，若超過1 2 0 0 mP a · s，則有 膜厚變厚塗膜之捲曲性惡化之情況。 0 接著，對本發明組合物之硬化方法加以說明。 本發明之組成物，可僅由輻射線（光）硬化，或可由 輻射線（光）及熱而硬化。由熱硬化時，作爲其熱源，可 使用例如電氣加熱器、紅外線燈、熱風等。於輻射線（光 )硬化時，作爲其輻射線源，若爲可使組成物於塗佈後短 時間硬化者則無特別限制，例如作爲紅外線之輻射線源， 舉例有燈、電阻加熱板、雷射等，或作爲可見光之輻射線 源，可舉例有日光、燈、螢光燈 '雷射等，或作爲紫外線 0 之輻射線源，可舉例有水銀燈、鹵素燈、雷射等，或作爲 電子線之輻射線源可舉例有由市售之鎢絲燈發生之熱電子 之方式、對金屬通入高壓電脈衝而發生之冷陰極方式以及 利用藉由離子化之氣體狀分子與金屬電極衝擊所發生之2 次電子之2次電子方式。又，作爲α線、yS線及7*線之輻 射線源，可舉例爲例如6()C()等之核分裂物質，於7線係 利用加速電子朝陽極衝撞之真空管等。該等輻射線可單獨 使用一種或2種以上同時或於一定時間內照射。 本發明組成物之硬化反應，可於空氣氛圍中、亦可於 -22- 200927849 氮氣等之厭氧條件下進行，於厭氧條件下硬化時，其硬化 物亦具有優異之耐擦傷性。 II.硬化膜 本發明之硬化膜可藉由於種種基材例如塑膠基材上塗 佈上述本發明之組成物並硬化而得。具體而言，塗佈組成 物’藉由以輻射線或熱及輻射線進行硬化處理，可獲得被 φ 覆成形體。於熱硬化時之較佳硬化條件爲20〜150°c，在 1 0秒〜24小時之範圍內進行。於輻射線硬化時，較好使用 紫外線或電子線。此等情況下，較好之紫外線照射光量爲 0_01〜10 J/cm2’更好爲〇.1〜2 J/cm2。又，較好之電子線 照射條件爲，加壓電壓爲10〜300KV、電子密度0.02〜0.30 mA/cm2、電子線照射量爲1〜i〇Mrad。 本發明之硬化膜具有高硬度且捲曲性小、耐擦傷性優 異且與基材或低折射率層等之鄰接層之密著性優異之塗膜 〇 (被膜）等特徵’因此特別適用於觸控式面板、塑膠光學 零件等之保護膜等。 於基材上塗佈上述本發明之組成物、經uv硬化所得 之本發明之硬化膜爲捲曲性得以減低、彎曲性、霧濁性優 異、高硬度。 本發明之硬化膜捲曲性小的理由認爲係由於含有（A )分子中具有環構造之多官能胺基甲酸酯（甲基）丙烯酸 酯，故交聯點間距離變大，捲曲性得以減低者，又，認爲 由於具有芳香環之多官能胺基甲酸酯（甲基）丙烯酸酯具 -23- 200927849 有結晶性，故機械強度、韌性得以提高，交聯點間距離得 以變大且亦可維持硬度平衡。 以下，就本發明之實施例詳細說明，但本發明範圍不 限定於實施例所記載者。且實施例中，各成分之調配量若 無特別說明，則「份」意指重量份，「％」意指重量％。 製造例1:胺基甲酸酯（甲基）丙烯酸酯（（A)成 D 分）（ptp )之製造 對於在附有攪拌機之容器內之由2,4 -甲苯二異氰酸醋 14.7份及二丁基錫二月桂酸鹽0.2份所構成之溶液，於 10 °C、1小時之條件滴加93份的新中村化學製之NK ESTER A-TMM-3LM-N (參與反應者僅爲具有羥基之三丙 烯酸季戊四醇酯）後，在6 0 °C、6小時的條件下攪拌，作 成反應液。 此生成物中殘存之異氰酸酯量以FT-IR測定，爲0.1 〇 重量％以下，確認反應大致以定量進行。又，生成物之紅 外線吸收光譜爲原料中之锍基特徵的2550cm·1的吸收峰 及原料異氰酸酯化合物之特徵的2260(:1^1的吸收峰消失 ，觀察到新的胺基甲酸酯鍵及 S(C = 0)NH-基特徵的 1 660CHT1的峰以及丙烯醯基之特徵1 720cm·1的峰，顯示 生成具有作爲聚合性不飽和基之丙烯醯基與-S(C = 0)NH-共同之胺基甲酸酯鍵之丙烯醯氧基修飾之烷氧基矽烷。 由以上，除獲得7 1份以上述式（1 )表示之化合物以 外，混合存在有37份未參與反應之四丙烯酸季戊四醇酯 -24- 200927849 製造例2:胺基甲酸酯（甲基）丙烯酸酯（（a)成 分）（PIP)之製造 對於在附有攪拌機之容器內之由異佛爾酮二異氰酸酯 18.8份及二丁基錫二月桂酸鹽0.2份所構成之溶液，於 10 °C、1小時之條件滴加9 3份的新中村化學製之N K φ ESTER A-TMM-3LM-N (參與反應者僅爲具有羥基之三丙 烯酸季戊四醇酯）後，在6 (TC、6小時的條件下攪拌，作 成反應液。 與製造例1同樣，生成物中殘存之異氰酸酯量以FT-IR測定’爲0.1重量％以下，確認反應大致以定量進行。 又’確認分子內含有胺基甲酸酯鍵以及丙烯醯基（聚合性 不飽和基）。 由以上，除獲得75份以上述式（2 )表示之化合物以 φ 外，混合存在有37份未參與反應之四丙烯酸季戊四醇酯 實施例1 使上述製造例1合成之（A)成分PTP 34.3份、（B )成分TMPTA (大阪有機工業股份有限公司製）14.7份 、同樣爲（B )成分之VR-77 (昭和高分子股份有限公司 製）24.5份，（C)成分N-乙烯基吡咯啶酮（日本IPS公 司製）24.5份、（D)成分DC57(東麗道康寧矽氧股份 -25- 200927849 有限公司製）1份、（E)成分TPO-X(BASF公司製）i 份加入附有攪拌機之燒瓶中，保持在55 °C攪拌3小時， 獲得透明液體。 實施例2〜4及比較例1〜4 除以表1所示組成以外，藉由與實施例1同樣方法， 獲得實施例2〜4及比較例1 ~4之各組成物。 φ 〈液體特性> 對上述實施例及比較例所得之各組成物，使用B型黏 度計，測定在25°C之黏度（mPa · s )，結果示於表1。 <硬化膜特性> 上述實施例及比較例所得之各組成物，旋轉塗佈於 PET上使成l〇ym厚度，使用金屬鹵素燈，在大氣中， 乙1 .〇J/cm2的光照射條件獲得硬化膜。使用其玻璃上之 硬化膜，評價下述特性，結果示於表1。 〇 ( 1)耐擦傷性 使用日本STEEL WIRE股份有限公司製之Bon Star 型號0000，以荷重5 00克反覆10次摩擦以目視判斷有無 擦傷。 (2)捲曲 所得之附有硬化膜之PET薄膜切成8公分見方的大 小，水平放置’以四角落自水平面浮起之平均作爲捲曲値 -26- 200927849 【1® 比較例4 49.5 1 ο 24.7 1 19.8 1 Ο ο 500 有擦傷 〇 比較例3 1 29.5 t t 19.7 49.3 ο ο ο 300 有擦傷 IT) 〇 比較例2 1 1 29.5 I 1 59.1 ON 〇\ in ο ο ο τ-Η 950 無擦傷 〇 rn 比較例1 59.1 1 I 19.7 1 19.7 ο ο ο ί-Η 1300 無擦傷 00 實施例4 1 49.0 I 1 19.6 29.4 ο ^Η ο ο τ—^ 700 無擦傷 CN 實施例3 1 34.3 14.7 24.5 1 24.5 Ο ρ ο 550 無擦傷 卜 Ο 實施例2 49.0 1 I 1 19.6 29.4 ο ι-Η ο ο 800 無擦傷 in 實施例1 34.3 1 14.7 24.5 1 24.5 ρ ρ »—Η 100.0 600 無擦傷 00 ο 成分(重量％) PTP PIP TMPTA VR-77 KAY ARAD DPHA N-乙烯基吡咯啶酮 DC57 LUCILIN ΤΡΟ-Χ 固體成分合計 黏度(mPa - s) 耐摩擦性 捲曲(mm) S /—N u /—Ν 塗佈性 :卜口$长漱黟您-frI嗽 謹Λ3>¥«枨 u«鹽旺浒«E-lllN^IM<<lfesvPQ: X-Odl - <£QQSid 餾趑缑EH·酹忉鉍阳负醛蚺傘燊屮尔榧显留：$-^> 氍&-稍S4a氍褰1EI11-N绷鉍阳<<5醛蚺甶枭獬H擊擗竖¥ : vHdwl f - δ (链<111匡绷鉍迄)—缑E(sfr)餾氍&«斟^长撇(0牯^:&1<1 -27- 200927849 由表1之結果可知，（A)成分含量較多之比較例1 ，黏度高塗佈性劣化。可知（A )成分含量較少、（B ) 成分含量較多之比較例2，捲曲性大。可知（A)成分及 (B)成分同時較少、（C)成分多之比較例3，黏度低塗 佈性劣化，再者耐擦傷性亦劣化。可知不含有（D)成分 之比較例4之耐擦傷性劣化。相反地，可知實施例1〜4之 塗佈性良好、捲曲性小且耐擦傷性亦優異。 ❹ [產業上之利用性] 本發明之硬塗佈層用硬化性組成物，其硬化膜（硬塗 層）可較好使用作爲防止例如塑膠光學零件、觸控面板、 薄膜型液晶元件、塑膠製品或建築內裝材之地板材、壁材 、人工大理石等之傷痕（擦傷）或防止污染之保護塗覆材 :各種基材之接著劑、塡縫材；印刷油墨之黏合材等。 本發明之硬塗佈層用硬化性組成物可使用作爲金屬、 φ 塑膠、木材等之保護膜用硬塗層、光碟用硬塗層形成用材 料。 -28-(6) (wherein R8, R9, R10 and methyl, q represents an integer from 1 to 5). In the above polymerizable monofunctional monomer, R11 independently represents a hydrogen atom or, preferably, a vinyl-containing decylamine such as N-vinylpyrrole-17-200927849 ketone or N-vinylcaprolactam. Isobornyl (meth)acrylate. These polymerizable monofunctional monomers are commercially available as IBXA (manufactured by Osaka Organic Chemical Industry Co., Ltd.), ARONIX M-1 1 1 , M-1 13 , M114, M-117, and TO-1210C. (share) company system) and so on. The content of the component (C) in the composition of the present invention is in the range of 15 to 40% by weight, preferably 15 to 5% by weight, based on the total amount of the composition of 0% by weight. When the content of the component (C) is less than 15% by weight, the viscosity of the resin liquid may be high and the coating property may be deteriorated. When the content is more than 40% by weight, the scratch resistance of the cured product may be deteriorated. (D) Polyxanthene Compound The component (D) in the composition of the present invention is a polysiloxane. Oxime compounds are preferably used to improve the scratch resistance of hardened materials. φ (D) polyfluorene oxide used in the present invention is, for example, polyether-modified polyfluorene oxide, alkyl-modified polyfluorene oxide, urethane acrylate-modified polyfluorene oxide, urethane. Ester-modified polyfluorene oxide, methylstyryl-modified polyfluorene oxide, epoxy polyether modified polyfluorene oxide, alkyl aralkyl ether modified polyfluorene, etc. Polyether modified polyether. The polyether-modified polyfluorene oxide preferably has R22-(R23〇) v_ R24- group bonded to at least one halogen atom (wherein R22 represents a hydroxyl group or an alkoxy group having a carbon number of 1 to 10, and R23 represents a carbon. a 2 to 4 alkylene group (wherein R22 may be a mixture of two or more kinds of alkylene groups), R24 represents an alkylene group having a carbon number of 2 to 12, and v represents a number of -18 to 200927849 1 to 2 0) Polydimethyloxane compound. Preferably, R24 is an ethyl group, a propyl group, and preferably an ethyl group. As the commercial product of the polyoxyxene compound, for example, SH28P A; dimethyl polyoxyalkylene polyalkylene oxide copolymer, Toray Dow Corning, FM0411; SAIRAPOLANE, Tosoh (share), SF8428; Polyoxyalkylene polyalkylene oxide copolymer (containing side chain OH), Toray Dow Corning, BYK UV3510C, BYK-Chemie Co., Ltd., dimethyl polyoxyalkylene-polyalkylene oxide oxime copolymer ), DC57 (Dongli Dao Kangning Co., Ltd., dimethyl polyoxyalkylene/polyalkylene oxide copolymer), etc., among these, DC57 and the like are preferred. Polyoxyxides can also be obtained from commercially available products, such as SH8400, DC5 7 (manufactured by Toray Dow Corning Co., Ltd.). The polyoxygen compounds may be used singly or in combination of plural kinds. The content of the component (D) in the composition of the present invention is in the range of 0.05 to 5% by weight, preferably 0.1 to 4% by weight, based on 100% by weight of the total amount of the composition. When the content of the component (D) is less than 0.05% by weight, the scratch resistance may be deteriorated, and if it exceeds 5% by weight, the surface may be precipitated on the surface of the coating film over time to cause surface roughness ( E) Radical polymerization initiator The component (E) in the composition of the invention is a radical polymerization initiator. In the above-mentioned radical polymerization initiator (E), a compound which generates an active radical upon heating (a thermal polymerization initiator) and a compound which generates an active radical by irradiation with radiation (light), and the like can be exemplified. (radiation (light) poly-19- 200927849 combined with initiator), radiation (light) radical polymerization initiator is preferably used. The radiation (light) polymerization initiator is not particularly limited as long as it can be decomposed by light irradiation to generate a radical and starts to polymerize, and examples thereof include, for example, acetophenone, acetophenone benzyl ketal, and 1- Hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-1,2-diphenylethan-1-one, xanthone, anthrone, benzaldehyde, hydrazine, hydrazine, triphenylamine, carbazole, 3-methylacetophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,4,-diaminobenzophenone, benzene φ-caine propyl ether, Benzene diethyl ether, benzyl dimethyl ketal, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl-1- Phenylpropan-1-one, sevotonone, diethyl thioxanthone, 2-isopropylthioxanthone, 2-air thioxanthone, 2-methyl-l-[4-(methylthio) Phenyl]-2-morpholinyl-propan-1-one, 2-benzyl-2-dimethylamino-1-(4-ythylphenyl)-butanone-1,4-(2- Hydroxyethoxy)phenyl-(2-carbo-2-propyl)indole, 2,4,6-trimethylbenzimidyldiphenyloxyphosphine oxide, bis(2,6-dimethoxy Benzobenzyl)-2,4,4-trimethylpentylphosphine oxide, oligomeric (2-hydroxyl -2-methyl-1-(4-(Φ 1-methylvinyl)phenyl)acetone). As a commercial product of a radiation (light) polymerization initiator, it can be exemplified by a product name of Ciba Kaki Chemicals (IRUGACURE 184, 369, 65 1, 500, 819, 907, 784, 2959). , CGI 1 700, CGI 1 750, CGI 1 850, CG24-61, DAROCURE 1116, 1173; trade name of BASF company: LUCILIN TPO, TPO-X; UCB company name: UBCRIL P36; LAMBERTI company Name: EZACURE KIP1 50, KIP65LT, KIP100F, KT37, KT55, KTO 46, KIP75/B, etc. -20- 200927849 The content of the component (E) in the composition of the present invention is in the range of 0.1 to 10% by weight, preferably in the range of 5% to 5% by weight, based on 100% by weight of the total amount of the composition. . When the content of the component (E) is less than 0.1% by weight, the hardness may be insufficient as a cured product, and if it exceeds 1% by weight, the inside (lower layer) may not be cured as a cured product. When the composition of the present invention is hardened, a thermal radical polymerization initiator may be used in addition to the photoradical polymerization initiator as needed. φ is a comparatively hot radical polymerization initiator, and examples thereof include a peroxide and an azo compound. Specific examples thereof include benzamidine peroxide, t-butyl peroxybenzoate, and even. Nitrogen diisobutyronitrile and the like. (F) Other Additives The composition of the present invention may be appropriately added with a photosensitizer, a polymerization inhibitor, a polymerization initiator, a homogenizer, a wetting improver, etc., as needed within the range not impairing the effects of the present invention. Surfactants, plasticizers, UV absorbers, antioxidants, antistatic agents, inorganic chelating agents, antifouling agents, pigments, dyes, etc. Next, a method of producing the composition of the present invention will be described. Amino acid ester (meth) acrylate ((A) component) having a ring structure, a polymerizable polyfunctional compound (component (B)), a polymerizable monofunctional compound (component (C)), a polyoxonium compound ((D) component), photoradical polymerization initiator ((E) component), added to the reaction vessel with a blender, in an individual amount, and other additives as needed ((F) component), usually The mixture was stirred at 50 to 60 ° C for 2 to 4 hours to become a composition of the present invention from 21 to 200927849. The viscosity of the composition of the present invention thus obtained is from 400 to 1200 mPa·s' at 25 ° C, preferably from 500 to 1,000 mPa·s. When the viscosity is outside these ranges, it is difficult to control the film thickness when a film is formed by spin coating, and if the viscosity is less than 400 mPa·s, the film becomes too thin and the scratch resistance is deteriorated. In the case where the film thickness exceeds 1 2 0 0 mP a · s, the film thickness becomes thicker and the curling property of the coating film is deteriorated. 0 Next, the hardening method of the composition of the present invention will be described. The composition of the present invention may be hardened only by radiation (light) or may be hardened by radiation (light) and heat. When it is hardened by heat, as the heat source, for example, an electric heater, an infrared lamp, hot air or the like can be used. When the radiation (light) is hardened, as the radiation source, there is no particular limitation if the composition can be hardened for a short time after coating, for example, as a radiation source of infrared rays, for example, a lamp, a resistance heating plate, For lasers, etc., or as a radiation source for visible light, for example, sunlight, a lamp, a fluorescent lamp, a laser, or the like, or a radiation source of ultraviolet light 0, for example, a mercury lamp, a halogen lamp, a laser, etc., or as The radiation source of the electron beam can be exemplified by a method of generating hot electrons from a commercially available tungsten filament lamp, a cold cathode method in which a metal is supplied with a high voltage electric pulse, and a gas-like molecule and a metal electrode by ionization. The 2nd electronic method of the 2nd electrons that occurred during the impact. Further, as the radiation source of the α-line, the yS line, and the 7* line, for example, a nuclear fission material such as 6 () C () or the like, and a vacuum tube in which an accelerated electron collides with the anode is used in the 7-line system. These radiations may be used alone or in combination for a certain period of time or in a certain period of time. The hardening reaction of the composition of the present invention can be carried out under an anaerobic condition in an air atmosphere or under a nitrogen atmosphere of -22-200927849, and the hardened material also has excellent scratch resistance upon hardening under anaerobic conditions. II. Cured film The cured film of the present invention can be obtained by coating the above-described composition of the present invention on various substrates such as a plastic substrate and hardening it. Specifically, the coating composition 'is cured by radiation or heat and radiation to obtain a molded body by φ. The preferable hardening condition at the time of thermosetting is 20 to 150 ° C, and it is carried out in the range of 10 seconds to 24 hours. When the radiation is hardened, it is preferred to use ultraviolet rays or electron wires. In these cases, the amount of ultraviolet light irradiation is preferably 0_01 to 10 J/cm2', more preferably 〇1 to 2 J/cm2. Further, preferred electron beam irradiation conditions are a pressurization voltage of 10 to 300 kV, an electron density of 0.02 to 0.30 mA/cm2, and an electron beam irradiation amount of 1 to i 〇 Mrad. The cured film of the present invention has high hardness, is small in curling property, is excellent in scratch resistance, and is excellent in adhesion to a film adjacent to a substrate or a low refractive index layer (such as a film). Therefore, it is particularly suitable for touch. Protective film for control panels, plastic optical parts, etc. The cured film of the present invention obtained by applying the composition of the present invention to the substrate and cured by uv is reduced in curling property, excellent in flexibility, haze, and high in hardness. The reason why the curable film of the present invention is small in curling property is considered to be because it contains a polyfunctional urethane (meth) acrylate having a ring structure in (A) molecule, so that the distance between crosslinking points becomes large, and curling property is reduced. Further, it is considered that since the polyfunctional urethane (meth) acrylate having an aromatic ring has crystallinity of -23 to 200927849, mechanical strength and toughness are improved, and the distance between crosslinking points is increased. It also maintains a hardness balance. Hereinafter, the embodiments of the present invention will be described in detail, but the scope of the present invention is not limited to those described in the examples. In the examples, the amount of each component means "parts by weight" unless otherwise specified, and "%" means % by weight. Production Example 1: Production of urethane (meth) acrylate ((A) into D) (ptp) For 14.7 parts of 2,4-toluene diisocyanate in a container with a stirrer And a solution of 0.2 parts of dibutyltin dilaurate, and 93 parts of NK ESTER A-TMM-3LM-N from Xinzhongcun Chemical was added dropwise at 10 ° C for 1 hour. After the pentaerythritol acrylate was added, the mixture was stirred at 60 ° C for 6 hours to prepare a reaction liquid. The amount of isocyanate remaining in the product was measured by FT-IR to be 0.1% by weight or less, and it was confirmed that the reaction was carried out substantially quantitatively. Further, the infrared absorption spectrum of the product was an absorption peak of 2550 cm·1 of the thiol characteristic in the raw material and 2260 of the characteristic of the raw material isocyanate compound (the absorption peak of 1^1 disappeared, and a new urethane bond was observed. And the peak of 1 660 CHT1 characterized by S(C = 0)NH- group and the peak of 1 720 cm·1 of propylene fluorenyl group, showing the formation of acryl fluorenyl group as a polymerizable unsaturated group and -S (C = 0) The acryloxy group-modified alkoxy decane of the NH-co-carbamate linkage. From the above, in addition to obtaining 71 parts of the compound represented by the above formula (1), 37 parts are not involved in the reaction. Pentaerythritol tetraacrylate-24-200927849 Production Example 2: Preparation of urethane (meth) acrylate (component (a)) (PIP) For isophorone diisocyanate in a container with a stirrer A solution of 18.8 parts and 0.2 parts of dibutyltin dilaurate, and 9 parts of NK φ ESTER A-TMM-3LM-N from Xinzhongcun Chemical were added dropwise at 10 ° C for 1 hour. Only after the pentaerythritol triacrylate having a hydroxyl group), after 6 (TC, 6 hours) In the same manner as in Production Example 1, the amount of isocyanate remaining in the product was measured by FT-IR to be 0.1% by weight or less, and it was confirmed that the reaction was carried out in a quantitative manner. Further, it was confirmed that the molecule contained a urethane. The bond and the acrylonitrile group (polymerizable unsaturated group). From the above, in addition to 75 parts of the compound represented by the above formula (2), λ is present, and 37 parts of the pentaerythritol tetraacrylate which is not involved in the reaction are mixed and mixed. In the above-mentioned Production Example 1, the component (A) has a PTP of 34.3 parts, (B) a component of TMPTA (manufactured by Osaka Organic Industries Co., Ltd.), 14.7 parts, and the same (B) component, VR-77 (made by Showa Polymer Co., Ltd.). 24.5 parts, (C) component N-vinylpyrrolidone (manufactured by Nippon IPS Co., Ltd.) 24.5 parts, (D) component DC57 (Toray Dow Corning Oxide -25-200927849 Co., Ltd.) 1 part, (E) component IPO was added to a flask equipped with a stirrer and kept at 55 ° C for 3 hours to obtain a transparent liquid. Examples 2 to 4 and Comparative Examples 1 to 4 were divided by the compositions shown in Table 1. By the same method as in the first embodiment, Each of the compositions of Examples 2 to 4 and Comparative Examples 1 to 4 was obtained. φ <Liquid Characteristics> For each of the compositions obtained in the above Examples and Comparative Examples, a viscosity at 25 ° C was measured using a B-type viscometer ( mPa · s ), the results are shown in Table 1. <The cured film characteristics> Each of the compositions obtained in the above examples and comparative examples was spin-coated on PET to have a thickness of 10 μm, and a metal halide lamp was used in the atmosphere. In the light irradiation condition of B1.〇J/cm2, a cured film was obtained. The following properties were evaluated using the cured film on the glass, and the results are shown in Table 1. 〇 (1) Scratch resistance Using a Bon Star model 0000 manufactured by STEEL WIRE Co., Ltd., the load was rubbed for 10 times with a load of 500 g to visually judge the presence or absence of scratches. (2) The PET film with the cured film obtained by crimping is cut into a size of 8 cm square, and placed horizontally as the average of the four corners floating from the horizontal plane as the curl 値-26- 200927849 [1® Comparative Example 4 49.5 1 ο 24.7 1 19.8 1 Ο ο 500 There are abrasions 〇 Comparative Example 3 1 29.5 tt 19.7 49.3 ο ο ο 300 With scratch IT) 〇Comparative example 2 1 1 29.5 I 1 59.1 ON 〇\ in ο ο ο τ-Η 950 No abrasion 〇rn Comparative Example 1 59.1 1 I 19.7 1 19.7 ο ο ο ί-Η 1300 No scratch 00 Example 4 1 49.0 I 1 19.6 29.4 ο ^Η ο ο τ—^ 700 No scratch CN Example 3 1 34.3 14.7 24.5 1 24.5 Ο ρ ο 550 non-abrasive dip Example 2 49.0 1 I 1 19.6 29.4 ο ι-Η ο ο 800 No abrasion in Example 1 34.3 1 14.7 24.5 1 24.5 ρ ρ »—Η 100.0 600 No scratch 00 ο Composition (% by weight PTP PIP TMPTA VR-77 KAY ARAD DPHA N-vinylpyrrolidone DC57 LUCILIN ΤΡΟ-Χ Total solid content viscosity (mPa - s) Friction resistance curl (mm) S /—N u /—Ν Coating properties:卜口$长漱黟你-frI嗽谨Λ3>¥«枨u«盐旺浒«E-lllN^IM<<lfesvPQ: X-Odl - < ;£QQSid Distillation EH·酹忉铋阳负醛蚺蚺燊屮燊屮榧留留:$-^>氍&-Slightly S4a氍褰1EI11-N 铋阳阳<5aldoxime枭獬H 擗 擗 ¥ ¥ : vHdwl f - δ (chain <111匡 铋 铋 缑) - 缑 E (sfr) 氍 氍 & «斟 ^ 长撇 (0牯^:&1<1 -27- From the results of Table 1, it is found that Comparative Example 1 having a large content of the component (A) has high viscosity and poor applicability, and it is known that the content of the component (A) is small and the content of the component (B) is high. In Comparative Example 3, in which the component (A) and the component (B) were both small and the component (C) was small, the viscosity was low, and the coating property was deteriorated, and the scratch resistance was also deteriorated. It is understood that the component (D) is not contained. The scratch resistance of Example 4 was deteriorated. Conversely, it was found that Examples 1 to 4 were excellent in coatability, small in curling property, and excellent in scratch resistance. ❹ [Industrial Applicability] The curable composition for a hard coat layer of the present invention, a cured film (hard coat layer) can be preferably used as a plastic optical component, a touch panel, a film type liquid crystal element, or a plastic. Protective coatings for scratches (scratches) or anti-contamination of floor slabs, wall materials, artificial marbles, etc. of products or building materials: adhesives for various substrates, quilting materials; adhesives for printing inks, etc. The hardenable composition for a hard coat layer of the present invention can be used as a hard coat layer for a protective film such as metal, φ plastic or wood, or a hard coat layer for optical disc. -28-