201111432 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種紫外線硬化型樹脂組成物、該組成 物用於^層光碟的用途（尤其是用於中間樹脂廣的用途）、 具有該樹脂組成物的硬化層之光碟，尤其關於一種用以有 &率地生產出次世代高密度多層光碟之樹脂組成物，該多 、、系從聚石及酸酯製壓模（stamper)(光碟用的模具）之 性”’且於硬化時的翹曲、高溫多濕下的翹曲變化小。 【先前技術】 旦f年來，光碟的大容量化進展顯著，為了增加記憶容 ~夕9里光碟乃急速地普及◊提高光碟的記錄容量之技 術’可列舉出記錄/再生光束的短波長化、記錄/再生光束 =射光學系之物鏡的高(開口數）化、記錄層的多層化 此等當中，藉由記錄層的多層化所達成之大容量化， 與短波長化及高NA化相比，能約以低成本來達成大容量 化0 例如，具有2層記錄層之DVD碟片中，係採用2層記 錄層隔著透明樹脂中間層(以下亦稱為透明中間樹脂層曰)積 層而成之構造。倾而言，為料的第ι透明 樹脂基板、第1記錄層、第i半透明反射膜層、接著層、 透明樹脂中間層、第2記錄層、第2反射膜層、接著^、 〇. 6mm的第2透明樹脂基板而成之構造。此時之透明^脂 中間層的形成方法，例如將用以形成透明樹脂中間層之紫 外線硬化型樹脂組成物，置於第1半透明反射膜層I所形 322209 4 201111432 ‘ 成之接著層上’將具有記錄/再生光束的導引用導引溝槽等 •凹凸圖案之透明樹脂壓模載置於其上方’進行旋轉塗佈， 使所形成之紫外線硬化型樹脂組成物層硬化後，將壓模剝 ‘離，以將凹凸轉印至紫外線硬化型樹脂組成物的表面，而 " 形成透明樹脂中間層之方法；或者是，將前述樹脂組成物 的硬化物層形成於壓模上後’將附有該硬化物層之壓模載 置於第1半透較㈣層上所放置之接著層形成樹脂上， 藉由旋轉塗佈形成接著層後，使該接著層硬化，然後將該 壓模從前述樹脂细成物的硬化物層剝離，而形成透明樹脂 中間層之方法（轉印法）。 _藍光光碟中，讀取專用的碟片係在作為基板之例如直 徑120mm、厚度的聚碳酸酯基板的單面上轉印凹坑 (pit)狀的„己錄圖案，而於此基板的表面成膜成為第1記錄 層之第1反射膜層，例如銀合金反射膜層。此外，於第^ 反射膜層上，隔著接著層形成經轉印凹坑狀的記錄圖案之 透明樹脂中間層，而於此透明樹脂中間層（中間膜）上成膜 成為第2記錄層之第2反射膜層，例如銀合金反射模層。、 然後於該反射膜層上形成積層透明樹脂層之構成。銀^ 反射膜層係提案出一種例如藉由賤鑛法在真空中成膜丰 法。 、于 層、第1記錄層、第2電介質層’然後在第2電介質: 記錄型碟片係例如形成下列構造，亦即在經 12〇咖、厚度l.lmm的聚碳酸g旨基板的單面上轉印凹坑: 記錄圖案之基板的表面上積層第！反射膜層、帛 餅 爲、楚1亡7々立丨貝 上 % 322209 201111432 隔著接著層依序積層透明樹脂中間層、第2反射膜層、第 3電介質層、第2記錄層、第4電介質層、及透明樹脂層 而成之構造。 此時，係隔著接著層將用以形成透明樹脂中間層之紫 外線硬化型樹脂組成物塗佈於反射膜層或電介質層上，並 按壓於具有記錄/再生光束的導引用導引溝槽等凹凸圖案 之透明樹脂壓模，使紫外線硬化型樹脂組成物硬化後，將 壓模剝離，以將凹凸轉印至紫外線硬化型樹脂組成物的表 面而形成（轉印法）。 在此，在讀取專用的碟片中，透明樹脂中間層通常在 該凹凸面上形成第2反射膜層，相反面則透過接著層而接 著於第1反射膜層。此外’在記錄型碟片中，該透明樹脂 中間層係在該凹凸面上形成第2反射膜層，相反面則透過 接著層而接著於第2電介質層。 一般而言’該轉印法稱為2P(Photo Polymerization ; 光聚合）法，所使用之紫外線硬化型樹脂組成物稱為2p劑。 透明樹脂壓模用的透明樹脂，可列舉出丙烯酸系樹 脂 '甲基丙烯醆系樹脂、聚碳酸酯樹脂、聚烯烴系樹脂（尤 為非晶質聚烯烴）、聚酯系樹脂、聚笨乙烯樹脂、環氧樹脂 等。此等當中，就使2P劑硬化後之剝離性、低吸濕性、形 狀安定性等觀點來看，較佳為非晶f聚烯煙，就材料成本 之觀點來;f幸交佳為聚破酸酉旨樹脂。因此，以降低成本者 為目的而=出—種光記錄媒體（多層光記錄媒體）的製造 方法’該a方法係即使使用便宜的聚碳賴製壓模其剝 322209 6 201111432 離i·生亦佳，而可提升良率，並且具有複數層記錄層， ’開發出適合該製造方法之樹脂（專利文獻1)。 、Z別，成為使用2P法時之紫外線硬化型樹脂組成物 ^的主^者，例如可列舉出⑷含有可進行光自由基聚合之預 '光聚合起始劑之組成物；⑻含有可進行光陽 = 之預聚物、單體及光聚.合起始劑之組成物；（c) 光自由絲合性及騎子聚合性組成物而成之組成物 等。 备物’可列舉出各種環氧基（甲基）丙烯酸醋（於環 烯=(::(甲基)丙烯醯基而成者)或/及胺醋(甲基)丙 者）如旨（urethane)骨架中加成（曱基）丙烯酿基而 以及對反射膜層或電介質層之==之脱模性的成型性； 光碟，求特性會帶來重大影響。14、㈣性、柔軟性的 單體°»°此休*'有（甲基）@坤酿基作為官能基之 =二卜’亦可使用具有乙稀基者。一般而言，預聚物 在單想中難以使用作為2P劑，所以係將單體 稀釋劑。例如，籍由使用3官能以上的單體， =使硬化物的交聯密度増加，提升Μ、楊氏模數、耐濕 熱性。 多層光碟時’當從透明樹腊壓模之剝離性差時， 會產生透明樹脂中間層的一部分與透明樹脂塵模一同剝離 轉:性差時，記錄/再生時會產生錯誤。當進行紫 外線硬化後起曲較大時，無法將記錄層或反射膜層均一地 a 322209 201111432 形成於所形成之凹凸圖案，或是為DVD時，無法貼合第2 基板，或是為藍光光碟時，無法均一地形成〇· lmm的光穿 透層。此外’在尚溫多濕下凹凸圖案產生變形時，第1、2 記錄層的記錄特性（例如訊號抖動特性）無法成為同等程 度。 專利文獻2至5所記載之2P劑中，係使用金屬製的 壓模將凹凸圖案形成於玻璃基板上所形成之層。此外，專 利文獻6至10中亦記載有各種2P劑。 [先前技術文獻] [專利文獻] [專利文獻1]日本特開2007-224057號公報 [專利文獻2]日本特開平5_59139號公報 [專利文獻3]日本特開平5_132534號公報 [專利文獻4]曰本特開平5_14〇254號公報 [專利文獻5]曰本特開平5_1325〇6號公報 [專利文獻6]日本特開2003-331463號公報 [專利文獻7]曰本特開2004-288242號公報 [專利文獻8]日本特開2〇〇4_288264號公報 [專利文獻9]日本特開2005-332564號公報 [專利文獻10]日本特許第4193916號 【發明内容】 (發明欲解決之課題） ^通常，用作為2P劑之紫外線硬化型樹脂，藉由壓模 形成凹凸圖案後，必須在保持該圖案之狀態下容易從壓模 8 322209 201111432 剝=(攸壓j莫之剝離性高)。此時，當不易從壓模剝離時， ?月“附著於壓拉’產生樹脂層的缺陷或凹凸圖案的缺陷 等使反射膜或電介質層的形成產生問題，而導致生產效 率的降低。此外’即使是從壓模之剝離性高的樹脂，於紫 外線，化日τ或是將多層碟片放置在高溫多濕下時，若輕曲 變化里大，則會造成讀取錯誤等問題。 匕因此’本發明之目的係㈣於上述情形，藉由使用具 有月曰肪鏈之（甲基）丙埽酸醋，尤其是具有特定脂肪鏈之（甲 土 ^晞曰來提供一種樹脂組成物，該樹脂組成物係從 壓模之剝離性’尤其是從聚石炭酸®旨製壓模之剝離性佳，且 於所形成之樹脂層的硬化時、以及將具有該硬化物層之多 層光碟放置在高溫多識下後，翹曲變化量亦小。 ^ x 料脂組成物，由於是藉由硬化而直接 接著於反射膜或電介質層的任—層上，所以在從壓模制 時’不/需先設置接著層來將硬化樹脂層接著於反射膜 介質層後再從壓模剝離。亦即，直接將樹脂層形成 膜或電介質層的任1上，並進行以壓模所進行之凹凸^ 形成及/或硬化，藉此可容㈣直接將壓模娜。因此，可 省略用以將用料2P劑之紫外線硬化型樹脂組成物 化物接著於反射膜或電介㈣的表面之接著層。 (解決課題之手段） 本發明者們係發現—賴肖旨纟讀，雜脂减儀籍由 使用具有脂肪鏈之（甲基）丙稀酸醋，尤其是具有特定月^妨 鏈之（曱基）丙mm，而可提高從壓M，尤其是從聚雙駿 322209 9 201111432 醋製壓模之剝離性’且於硬化時以及將多層碟片放置在高 溫多濕下後翹曲變化量亦小。藉此開發出一種紫外線硬化 型樹脂組成物’該樹脂組成物係從聚碳酸酯製壓模之剝離 性佳，且於硬化時以及將多層碟片放置在高溫多濕下後， 翹曲變化量亦小。 本發明係關於下列（1)至（12)。 (1) 一種多層光碟用紫外線硬化型樹脂組成物，其特 徵為含有.（A)具有脂肪鏈之（甲基）丙烯酸酯、（β)(甲基） 丙烯酸酯單體及/或（C)胺酯（甲基）丙烯酸酯、以及（D)光聚 合起始劑。 (2) 如（1)所述之多層光碟用紫外線硬化型樹脂組成 物，其中，（A)具有脂肪鏈之（曱基）丙烯酸酯係選自由（甲 基）丙烯酸十二烷酯、（甲基）丙烯酸十八烷酯、（曱基）丙烯 酸十六烷酯、（甲基）丙烯酸二十二烷酯、（甲基）丙烯酸異 十二烷酯、（甲基）丙烯酸異十八烷酯、（甲基）丙烯酸異^ 六烷酯、以及（曱基）丙烯酸異二十二烷酯所組成之群組的 1種或2種以上。 (3)如（1)或（2)所述之多層光碟用紫外線硬化型樹脂 組成物，其中，（Β)(甲基）丙烯酸酯單體係選自由（甲基） 丙烯酸異莰酯、經環氧丙烷改質之新戊二醇二（甲基）丙烯 酸酯、二（甲基）丙烯酸三環癸烷二羥甲酯、以及經声美三 甲基乙酿改質之三經甲基丙烧二（甲基）丙婦酸酉旨戶 群組的1種或2種以上。 ⑷如⑴至⑶中任-項所述之多層光碟用紫外線硬 322209 10 201111432 化型樹脂組成物，其中，相對於樹脂組成物全體而言，（A) 成分為5至90重量％，（B)成分及/或（C)成分為5至90重 量％，（D)成分為1至15重量％。 (5) —種光碟，其係具有對前述（1)至（4)中任一項所 述之樹脂組成物照射紫外線所得之硬化物。 (6) —種紫外線硬化型樹脂組成物，其係含有：（A)由 下列式（1)所表示之具有脂肪鏈之（甲基）丙烯酸酯， R 〇 _1 I (1) H2C-C-C-0 CnH2n+i 式中，R表示Η或CH3, η表示10至25的整數；以及 (Β)選自由（曱基）丙烯酸異莰酯、經環氧丙烷改質之 新戊二醇二（甲基）丙烯酸酯、二（曱基）丙烯酸三環癸烷二 羥甲酯、以及經羥基三甲基乙醛改質之三羥曱基丙烷二（曱 基）丙烯酸酯所組成之群組的至少一種（甲基）丙烯酸酯單 體，或是（C)藉由有機多異氰酸酯與羥基（甲基）丙烯酸酯化 合物之反應所得之胺酯（甲基）丙烯酸酯；以及 (D )光聚合起始劑，並且， 相對於樹脂組成物的總量而言， (i) (A)成分為5至90重量％， (ii) (B)成分或（C)成分或是（B)及（C)兩者為5至90 重量％，（A)至（C)成分的總量為85至99重量％， (iii) (D)成分為1至15重量％。 (7) 如（6)所述之紫外線硬化型樹脂組成物，其中，具 11 322209 201111432 有脂肪鏈之（T基）丙烯酸酯的脂肪鏈為具有分枝鏈之脂肪 鏈。 (8) 如（7)所述之紫外線硬化型樹脂組成物，其中，具 有脂肪鏈之（甲基）丙烯酸酯係選自由丙烯酸異癸酯、（曱基） 丙稀酉文異十一燒酉旨、（曱基）丙稀酸異十八烧酉旨、（曱基）丙 烯酸異十六烷酯 '以及（甲基）丙烯酸異二十二烷酯所組成 之群組的至少'~種。 (9) 如上述（6)至（8)中任一項所述之紫外線硬化型樹 脂組成物，其中，有機多異氰酸酯為選自由異佛爾酮二異 氰酸醋、六亞甲基二異氰酸酯、甲苯二異氰醆醋、二甲苯 二異氰酸酯、以及二笨基甲烷_4, 4, _二異氰酸酯所組成之 群組的至少一種二異氰酸酯，或是二環戊基異氰酸酯。 (10) 如上述（6)至（9)中任一項所述之紫外線硬化型 樹脂組成物，其中，羥基（甲基）丙烯酸酯化合物為經羥基 取代之C2至C10脂肪族（曱基）丙烯酸酯。 (11) 一種上述（6)至（10)中任一項所述之紫外線硬化 型樹脂組成物之用途，其係用於多層碟片的中間樹脂層。 (12) —種多層碟片，其係具有上述（6)至（1〇)中任一 項所述之紫外線硬化型樹脂組成物的硬化物層。 (發明之效果） 本發明之紫外線硬化型樹脂組成物及其硬化物，係有 用於作為2P劑，該2P.劑係從壓模之剝離性，尤其是從聚 碳酸酯製壓模之剝離性佳（從壓模之剝離強度低/，'且於硬 化時之硬化前後的翹曲變化量以及將具有該硬化物層之多 322209 12 201111432 層碟片放置在高溫多濕下時之放置前後的趣曲變化量均 ，小。此外，本發明之紫外線硬化型樹脂組成物中，可省略 接著層而以單液來形成中間樹脂層。再者，可 .與⑻成分或/及⑹成分之組合來適當地調整黏度，而能夠 - 有效率地形成多層碟片的中間樹脂層。 【實施方式】 本發明係關於-種多層光碟用紫外線硬化型樹脂組 成物，其特徵為含有：⑴⑴具有脂肪鏈之（甲基）丙稀酸 酯、（ii)(B)(甲基）丙烯酸酯單體及/或（(：）胺酯（甲基）丙烯 酸酯、以及（iii)(D)光聚合起始劑。 本發明中，「（甲基）丙烯酸酯」的用語，與一般所用 者相同，以丙烯酸酯及甲基丙烯酸酯中的任一者或兩者的 意義來使用。 此外，本發明中，％或份等，只要無特別註明時，即 意指重量％或重量份。此外，本發明之紫外線硬化型樹脂組 成物，亦簡略地記載為「本發明之樹脂組成物」。 本發明之樹脂組成物中，係使用（A)具有脂肪鏈之（甲 基）丙烯酸酯作為必要成分。具有脂肪鏈之（甲基）丙烯酸酯 的脂肪鏈，較佳為C10至C25的脂肪鏈，尤佳為以下列式 (1)所記載之-CnKn為10至25的整數）所表示之C10至 C25的烷基。因此，具有脂肪鏈之（甲基）丙烯酸酯，較佳 為由下列式（1)所表示之（甲基）丙烯酸酯。 322209 13 0)201111432 R H2C=c 〇BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ultraviolet curable resin composition, the use of the composition for a laminated optical disc (especially for the use of an intermediate resin), and the use of the resin A disc of a hardened layer of a composition, in particular, a resin composition for producing a next-generation high-density multilayer optical disc having a <RTIgt;rate" from a polystone and an acid ester stamper (disc) The mold used has the property "" and the warpage at the time of hardening and the warpage change under high temperature and high humidity are small. [Prior Art] In the past fifteen years, the large-capacity of the optical disc has progressed remarkably, in order to increase the memory capacity. The technique of rapidly increasing the recording capacity of the optical disk, the short-wavelength of the recording/reproducing beam, the recording/reproducing beam, the height of the objective lens of the optical system (the number of openings), and the multilayering of the recording layer. In the case of the increase in the capacity of the recording layer, it is possible to achieve a large capacity at a low cost compared with the short wavelength and high NA. For example, a DVD disc having two recording layers. In the sheet, a two-layer recording layer is formed by laminating a transparent resin intermediate layer (hereinafter also referred to as a transparent intermediate resin layer 。), and the first transparent resin substrate and the first recording layer are formed. a structure in which the i-th semi-transparent reflective film layer, the adhesive layer, the transparent resin intermediate layer, the second recording layer, the second reflective film layer, and the second transparent resin substrate of 6 mm are formed. In the method of forming the intermediate layer, for example, the ultraviolet curable resin composition for forming the intermediate layer of the transparent resin is placed on the first semi-transparent reflective film layer I. The shape of the first semi-transparent reflective film layer 322209 4 201111432 'on the layer of the layer will be recorded/regenerated. The guide groove for guiding the light beam, etc., the transparent resin stamper of the concave-convex pattern is placed on the upper side, and the spin coating is performed to harden the formed ultraviolet curable resin composition layer, and then the stamper is peeled off to Transferring the unevenness to the surface of the ultraviolet curable resin composition, and " a method of forming a transparent resin intermediate layer; or, after forming the cured layer of the foregoing resin composition on the stamper, the cured product is attached Floor The stamper is placed on the adhesive layer forming resin placed on the first semi-transparent (four) layer, and after forming the adhesive layer by spin coating, the adhesive layer is hardened, and then the stamper is formed from the resin fine structure. A method in which a cured resin layer is peeled off to form a transparent resin intermediate layer (transfer method). In a Blu-ray disc, a read-only disc is rotated on a single surface of a polycarbonate substrate having a diameter of, for example, 120 mm as a substrate. A pit-shaped pattern is printed, and the surface of the substrate is formed into a first reflective film layer of the first recording layer, for example, a silver alloy reflective film layer. Further, on the second reflective layer, a transparent resin intermediate layer of a transfer pattern having a transfer pit shape is formed via an adhesive layer, and a film is formed on the transparent resin intermediate layer (intermediate film) to form a second recording layer. The second reflective film layer is, for example, a silver alloy reflective mold layer. Then, a laminated transparent resin layer is formed on the reflective film layer. The silver ^ reflective film layer proposes a film forming method in a vacuum, for example, by a bismuth ore method. In the layer, the first recording layer, the second dielectric layer 'and then in the second dielectric: the recording type disc is formed, for example, in the following structure, that is, a single substrate of a polycarbonate substrate having a thickness of 1.2 mm and a thickness of 1.1 mm Surface transfer pit: The layer on the surface of the substrate on which the pattern is recorded! The reflective film layer, the enamel cake, and the Chu 1 々 7 々 丨 322209 201111432 The transparent resin intermediate layer, the second reflective film layer, the third dielectric layer, the second recording layer, and the fourth layer are sequentially laminated via the subsequent layer. A structure in which a dielectric layer and a transparent resin layer are formed. In this case, the ultraviolet curable resin composition for forming the transparent resin intermediate layer is applied onto the reflective film layer or the dielectric layer via the adhesive layer, and is pressed against a guiding groove having a recording/reproducing light beam. In the transparent resin stamper of the uneven pattern, after the ultraviolet curable resin composition is cured, the stamper is peeled off, and the unevenness is transferred to the surface of the ultraviolet curable resin composition to form (transfer method). Here, in the disc for reading, the transparent resin intermediate layer usually forms the second reflective film layer on the uneven surface, and the opposite surface passes through the adhesive layer and is attached to the first reflective film layer. Further, in the recording type disc, the transparent resin intermediate layer forms a second reflection film layer on the uneven surface, and the opposite surface passes through the subsequent layer and follows the second dielectric layer. In general, the transfer method is called 2P (Photo Polymerization), and the ultraviolet curable resin composition used is called 2p. Examples of the transparent resin for the transparent resin stamper include an acrylic resin, a methacrylic oxime resin, a polycarbonate resin, a polyolefin resin (especially an amorphous polyolefin), a polyester resin, and a polystyrene resin. , epoxy resin, etc. Among these, from the viewpoints of releasability, low hygroscopicity, and shape stability after curing of the 2P agent, it is preferred that the amorphous f-olefinized smog is in terms of material cost; Broken acid resin. Therefore, the method for manufacturing an optical recording medium (multilayer optical recording medium) for the purpose of reducing the cost is a method of using a cheap polycarbon-based stamper to peel off 322209 6 201111432 from i. In addition, it is possible to improve the yield and have a plurality of layers of recording layers, and a resin suitable for the production method has been developed (Patent Document 1). And Z, the main component of the ultraviolet curable resin composition when the 2P method is used, for example, (4) a composition containing a pre-photopolymerization initiator capable of photoradical polymerization; (8) Gwangyang = a prepolymer, a monomer, and a composition of a photopolymerization initiator; (c) a composition obtained by optically free-knitability and a rider polymerizable composition. The preparations may be exemplified by various epoxy (meth)acrylic acid vinegars (in the case of cycloolefin = (:: (meth) acrylonitrile group) or / and amine vinegar (methyl) propyl). Urethane) The addition of a mercapto (acrylic) propylene base and the moldability of the release film of the reflective film layer or the dielectric layer; the optical disk has a significant influence on the properties. 14. (4) Sexual and flexible monomer °»°This Hugh*' has (methyl)@坤酿基 as a functional group =二卜' can also be used with a vinyl base. In general, the prepolymer is difficult to use as a 2P agent in a single idea, so a monomer diluent is used. For example, by using a trifunctional or higher monomer, = the crosslinking density of the cured product is increased, and the enthalpy, Young's modulus, and moist heat resistance are improved. In the case of a multilayer optical disc, when the peeling property from the transparent wax mold is poor, a part of the transparent resin intermediate layer is peeled off together with the transparent resin dust mold. When the properties are poor, an error occurs during recording/reproduction. When the sharpening is performed after the ultraviolet curing, the recording layer or the reflective film layer cannot be uniformly formed in the formed concave-convex pattern, or when the DVD is used, the second substrate cannot be bonded, or the Blu-ray disc is not provided. When it is impossible to form a light transmissive layer of 〇·lmm uniformly. Further, when the concave-convex pattern is deformed under the temperature and humidity, the recording characteristics (e.g., signal jitter characteristics) of the first and second recording layers cannot be equal. In the 2P agent described in Patent Documents 2 to 5, a concave-convex pattern is formed on a layer formed on a glass substrate by using a metal stamper. Further, various 2P agents are also described in Patent Documents 6 to 10. [PATENT DOCUMENT] [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. [Patent Document 5] JP-A-2003-331463 [Patent Document 7] JP-A-2004-288242 [Patent Document 7] JP-A-2004-288242 [ [Patent Document 10] Japanese Laid-Open Patent Publication No. 2005-332564 [Patent Document 10] Japanese Patent No. 4,193,916 [Summary of the Invention] (Problems to be Solved by the Invention) ^ Normally, When the concave-convex pattern is formed by a stamper by using an ultraviolet curable resin as a 2P agent, it is necessary to peel it from the stamper 8 322209 201111432 while maintaining the pattern (the peeling property is high). At this time, when it is difficult to peel off from the stamper, the defect of the resin layer or the defect of the uneven pattern caused by "attachment to the press-pull" causes a problem in the formation of the reflective film or the dielectric layer, resulting in a decrease in production efficiency. Even in the case of a resin having high peeling property from a stamper, when the ultraviolet ray is turned on, or when the multilayer disc is placed under high temperature and high humidity, if the change in the light curve is large, a problem such as a reading error may occur. 'The object of the present invention is (4) in the above case, by using a (meth) propionate vinegar having a lunar fat chain, especially a specific fat chain (a soil) to provide a resin composition, The resin composition is excellent in peelability from a stamper, particularly from a polycarbamic acid-based stamper, and at the time of hardening of the formed resin layer, and placing the multilayer disc having the cured layer at a high temperature. After much knowledge, the amount of warpage change is also small. ^ x The fat composition is directly adhered to any layer of the reflective film or the dielectric layer by hardening, so it is not required during the molding process. First set the next layer to The hardened resin layer is then peeled off from the stamper after the reflective film dielectric layer, that is, the resin layer is directly formed on either of the film or the dielectric layer, and the unevenness and/or hardening by the stamper is performed. This allows for the direct application of the UV-curable resin composition of the material 2P to the surface of the reflective film or the dielectric (4). The inventors found that Lai Xiaoyi was reading, and that the fat-reducing instrument was made by using (meth)acrylic acid vinegar with a fatty chain, especially with a specific month. Improve the peeling property of the pressure M from the pressure M, especially from the shuangjun 322209 9 201111432 vinegar, and the amount of warpage change is small when hardening and placing the multilayer disc under high temperature and humidity. The ultraviolet curable resin composition 'the resin composition is excellent in peelability from a polycarbonate stamper, and the amount of warpage change is small after hardening and placing the multilayer disc under high temperature and high humidity. Relating to the following (1) to (12). (1) An ultraviolet curable resin composition for a multilayer optical disc, characterized by containing (A) a (meth) acrylate having a fatty chain, a (β) (meth) acrylate monomer, and/or a (C) urethane ( (A) A UV-curable resin composition for a multilayer optical disc according to (1), wherein (A) has a fatty chain (mercapto) acrylic acid. The ester is selected from the group consisting of dodecyl (meth)acrylate, octadecyl (meth)acrylate, cetyl (meth)acrylate, behenyl (meth)acrylate, (meth)acrylic acid. 1 or 2 of a group consisting of isododecyl ester, isostearyl (meth)acrylate, isohexadecyl (meth)acrylate, and isodecyl (meth)acrylate (3) The ultraviolet curable resin composition for a multilayer optical disc according to (1) or (2), wherein the (meth)acrylate single system is selected from (meth)acrylic acid isophthalide. Ester, neopentyl glycol di(meth)acrylate modified by propylene oxide, di(meth)acrylic acid Decane-glyoxylic ester, and modified by the sound of the United States of pivaloyl stuffed triple-methylpropan-burning of two or more (meth) one kind or two or propionic acid women unitary purpose household group. (4) The ultraviolet-ray hard 322209 10 201111432-type resin composition for a multilayer optical disk according to any one of (1) to (3), wherein (A) is 5 to 90% by weight based on the entire resin composition, (B) The component and/or the component (C) is 5 to 90% by weight, and the component (D) is 1 to 15% by weight. (5) A cured film obtained by irradiating ultraviolet rays to the resin composition according to any one of (1) to (4) above. (6) An ultraviolet curable resin composition comprising: (A) a (meth) acrylate having a fatty chain represented by the following formula (1), R 〇_1 I (1) H2C-CC -0 CnH2n+i wherein R represents deuterium or CH3, η represents an integer from 10 to 25; and (Β) is selected from neopentyl glycol acrylate modified by isopropionyl (decyl) acrylate. a group consisting of methyl acrylate, tricyclodecane dimethyl dimethyl (meth) acrylate, and trihydroxy decyl propane bis(indenyl) acrylate modified with hydroxytrimethyl acetaldehyde At least one (meth) acrylate monomer or (C) an amine ester (meth) acrylate obtained by reacting an organic polyisocyanate with a hydroxy (meth) acrylate compound; and (D) photopolymerization The starting agent, and (i) the component (A) is 5 to 90% by weight, (ii) the component (B) or the component (C) or (B) and (C) with respect to the total amount of the resin composition. Both are from 5 to 90% by weight, the total amount of the components (A) to (C) is from 85 to 99% by weight, and (iii) the component (D) is from 1 to 15% by weight. (7) The ultraviolet curable resin composition according to (6), wherein the aliphatic chain having a fatty chain (T-based) acrylate is a fatty chain having a branched chain. (8) The ultraviolet curable resin composition according to (7), wherein the (meth) acrylate having an aliphatic chain is selected from the group consisting of isodecyl acrylate and (indenyl) acesulfame. At least one of the group consisting of (indenyl) acrylic acid isodecyl sulphate, (fluorenyl) isohexadecyl acrylate, and isobutylene (meth) acrylate. (9) The ultraviolet curable resin composition according to any one of the above (6), wherein the organic polyisocyanate is selected from the group consisting of isophorone diisocyanate and hexamethylene diisocyanate. At least one diisocyanate of the group consisting of toluene diisocyanine vinegar, xylene diisocyanate, and dimethane methane 4,4,diisocyanate, or dicyclopentyl isocyanate. (10) The ultraviolet curable resin composition according to any one of the above (6), wherein the hydroxy (meth) acrylate compound is a C2 to C10 aliphatic (fluorenyl) group substituted with a hydroxy group. Acrylate. (11) Use of the ultraviolet curable resin composition according to any one of the above (6) to (10), which is used for an intermediate resin layer of a multilayer disc. (12) A multi-layered disc having a cured layer of the ultraviolet curable resin composition according to any one of the above (6) to (1). (Effect of the Invention) The ultraviolet curable resin composition of the present invention and a cured product thereof are used as a 2P agent, which is exfoliable from a stamper, particularly a peeling property from a polycarbonate stamper. Good (the peel strength from the stamper is low, 'and the amount of warpage change before and after hardening at the time of hardening and before and after placing the 322209 12 201111432 layer disc with the hardened layer under high temperature and humidity Further, in the ultraviolet curable resin composition of the present invention, the intermediate layer may be formed as a single liquid by omitting the subsequent layer. Further, it may be combined with the component (8) or/(6). The intermediate resin layer of the multilayer disc can be efficiently formed by appropriately adjusting the viscosity. [Embodiment] The present invention relates to an ultraviolet curable resin composition for a multilayer optical disc, which comprises: (1) (1) having a fatty chain (meth) acrylate, (ii) (B) (meth) acrylate monomer and / or ((:) amine ester (meth) acrylate, and (iii) (D) photopolymerization Starting agent. In the present invention, "(methyl) The term "acrylic ester" is used in the sense of either or both of acrylate and methacrylate, as in the case of the general use. In addition, in the present invention, % or parts, etc., unless otherwise specified, In other words, the ultraviolet curable resin composition of the present invention is also simply referred to as "the resin composition of the present invention". In the resin composition of the present invention, (A) has a fat. The chain (meth) acrylate is an essential component. The aliphatic chain having a fatty chain (meth) acrylate, preferably a C10 to C25 aliphatic chain, is preferably a CnKn as described in the following formula (1). The alkyl group of C10 to C25 represented by the integer of 10 to 25. Therefore, the (meth) acrylate having a fatty chain is preferably a (meth) acrylate represented by the following formula (1). 13 0)201111432 R H2C=c 〇
II C—0—CnH2n+1 (式中，R表示H或CH3，n表示10至25的整數）。 具體例’例如可列舉出（曱基）丙烯酸十二烷醋、（甲 丙婦酸十八燒酯、（曱基）丙稀酸十六烧酯、（甲基）丙稀 馱一十一烷酯、（曱基）丙烯酸異十二烷酯、（曱基）丙烯酸 異十八烷酯 '(甲基）丙烯酸異十六烷酯、以及（甲基）丙烯 酸異二十二烷酯等。 具有脂肪鏈之（f基）丙烯酸酯的脂肪鏈係，就從壓模 之剝離容易性等觀點來看，分枝鍵較直鏈更佳，較佳為具 有分枝脂肪鏈之（甲基）丙烯酸酯。尤佳為具有cl〇至 的分枝鏈之（曱基）丙烯酸酯。因此，上述具體例中，尤佳 為（甲基）丙烯酸異十二烷酯、（甲基）丙烯酸異十八烷酯、 (甲基）丙烯酸異十六烷酯或（甲基）丙烯酸異二十二烷酯。 級成物中之（A)具有脂肪鏈之（甲基）丙烯酸酯的含 篁，相對於樹脂組成物的總量（全體）而言為5至9〇重量％ 左右’較佳為10至80重量％左右。此含量雖亦因所併用之 (B)或（C)成分而有不同’故無法一概而論，但依情況之不 同’較佳為5至50重量％左右，尤佳為5至40重量％左右， 更佳為10至4〇重量％左右，最佳為10至30重量％左右。 U)具有脂肪鏈之（甲基）丙烯酸酯，市售品例如有日 油化學公司製的 Blemmer SA、Blemmer CA、Blemmer VA ; 新中村化學工業公司製的Isostearyl Acrylate;共榮社 14 322209 201111432 化學公司製的 Light-Acrylate IS-A、Light-Acrylate • IM-A 等。 本發明之樹脂組成物中，係使用（3)(甲基）丙烯酸酯 * 單體。所用之（甲基）丙烯酸酯單體，只要是（A)成分及（c) - 成分以外之一般所知的（甲基）丙烯酸酯單體即可，可無特 別限制地使用。例子可舉出三環癸烷（甲基）丙烯酸酯、（甲 基）丙烯酸苯甲酯、（甲基）丙烯酸二環戊酯、（甲基）丙烯酸 異莰酯、（甲基）丙烯酸金剛烷酯、（甲基）丙烯酸四氫糠酯、 嗎啉（甲基）丙烯酸酯、經環氧丙烷改質之新戊二醇二（甲基） 丙烯酸酯、二（甲基）丙烯酸三環癸烷二羥甲酯、經羥基三 曱基乙醛改質之三羥甲基丙烷二（甲基）丙烯酸酯、羥基三 甲基乙酸新戊二醇二（甲基）丙烯酸酯等。 為了與如述（A )成分的併用並提升剝離性等，（甲基） 丙烯酸酯單體較佳係使用選自由（甲基）丙烯酸異莰酯、經 環氧丙烷改質之新戊二醇二（甲基）丙烯酸酯、二（曱基） 丙烯酸三環癸烷二羥甲醋、以及經羥基三甲基乙醛改質"之 一羥甲基丙烷二（曱基）丙烯酸酯所組成之群組的至少一 種。 此等單體係藉由與作為前述（A)成分之具有分枝脂肪 鏈f(曱基）丙婦酸醋併用，而可製成剝離強度低且龜曲變 化里亦少之本發明之樹脂組成物。此等當中，尤佳為（甲基） 丙烯酸異莰酯或/及經羥基三甲基乙醛改質之三羥甲基丙 烷二（甲基）丙烯酸酯，更佳為兩者之併用。 本發明之樹脂組成物中所使用之（c)胺酯（甲基）丙烯 322209 15 201111432 酸醋，係用以取代前述（B)成分所用，亦可製成含有（a)成 分及（C )成分而不含（B )成分作為樹脂成分之樹脂組成物， 但通常該（C)成分係與（B)成分併用。 (C)成分之胺醋（曱基）丙烯酸酯，較佳為藉由使有機 多異氰酸酯與經基（甲基）丙烯酸酯化合物進行反應所得之 化合物。 有機多異氰酸酯，例如可列舉出異佛爾酮二異氰酸 西曰、六亞甲基二異氰酸酯、曱苯二異氰酸酯、二甲苯二異 氰酸酯、以及二苯基甲烷_4,4，-二異氰酸酯等二異氰酸酯 類，或疋二環戊基異氰酸酯等異氰酸酯類。 此等虽中，尤佳為異佛爾酮二異氰酸酯或甲苯二異氰 酸酉旨。 '毯基（甲基）丙烯酸酯化合物，例如可列舉出經經基取 代之C2至C10脂肪族（甲基）丙婦酸醋或經基己内醋（甲基） 丙烯酸酉旨等。經經基取代之C2至cl〇脂肪族（甲基）丙稀酸 酯，較佳者具體可列舉出（曱基）丙烯酸經乙醋、（甲基）丙 烯酸經丙醋、（甲基）丙婦酸經丁醋、單（甲基）丙婦酸二經 甲基環己酷、季戊四醇三（甲基）丙烯酸醋、二季戊四醇五 (甲基）丙稀酸酯等。 此等當中，尤佳者可列舉出（甲基）丙烯酸羥乙酯、（甲 =)丙烯酸㈣g旨、（甲基）丙烯酸經丁醋、季戊四醇三（甲 暴）丙埽酸酯等。 因此，較佳的胺酯(甲基)丙烯酸酯，可列舉出藉由上 機多異氰酸醋與上述經縣取代之^至⑽脂肪族 322209 16 201111432 (甲基）丙烯酸酯或羥基己内酯（甲基）丙烯酸酯之反應所得 之胺酯（曱基）丙烯酸酯。此外，尤佳的胺酯（甲基）丙烯酸 酯，可列舉出藉由列舉為上述較佳的有機多異氰酸酯之異 佛爾酮二異氰酸酯或曱苯二異氰酸酯與例示為上述較佳的 羥基（甲基）丙烯酸酯之化合物之反應所得之胺酯（甲基）丙 烯酸酉旨。 反應係以下列方式進行。亦即，以異氰酸基每1.〇當 量使羥基較佳成為1.0至2. 1當量之方式，將有機多異氰 酸酯與羥基（曱基）丙烯酸酯化合物混合，在70至90°C下 進行反應，而製得目的之胺酯（甲基）丙烯酸酯。 上述胺酯（曱基）丙烯酸酯，可使用1種或以任意比率 混合2種以上來使用。 本發明之樹脂組成物中之（B)(甲基）丙烯酸酯單體或 (C)胺酯（曱基）丙烯酸酯的至少一種之含量，以相對於該樹 脂組成物總量之比率（重量）計為5至90%左右，較佳為10 至80%左右。此外，較佳範圍，依情況的不同可為50至90°/〇, 尤佳為60至85%。 此外，（A)至（C )成分總量相對於本發明之樹脂組成物 總量之含量比率，只要是可達成本發明之效果的範圍者， 則可為任意範圍。通常在考量到樹脂組成物的黏度、硬化 物層從壓模之剝離性及硬化物層的光穿透度、具有該硬化 物層之光碟的勉曲及对久性等，相對於樹脂組成物總量， (A)至（C)成分的總量，較佳係至少含有50%，尤佳至少含 有70%，（A)至（C)成分的總量相對於該樹脂組成物總量， S. 17 322209 201111432 更佳為85至99%，最佳為90至99%。 上述情況時，（A)成分與其他成分（（B)成分及（C)成分） 的比率，相對於（A)成分1份，其他成分（（β)成分或（C)成 分，或是含有（Β)及（C)兩者時為兩者的總量），通常為1 至20份左右，較佳為2至10份左右，更佳為3至7份左 右之比率。 (Β)成分或（C)成分，通常只要在該樹脂組成物中至少 含有任一者，即不會造成問題。因此，相對於兩成分的總 量’（Β)成分較佳為30至1〇〇%，尤佳為5〇至1〇〇%，更佳 為7〇至1〇〇°/。，（c)成分較佳為0至70%，尤佳為〇至5〇%， 更佳為0至30%。 此外’本發日种’可因應必要而適當地含有環氧 基）丙埽酸醋。該環氧基（甲基）丙職醋，較佳者可 ，由於分子+具有2個以上的環氧基之環氧樹脂、盘呈^ ^性不齡基之物鳴物⑽為 烤酸 反應所得之化合物。原料之 土」丙烯馱）之 環氧樹脂、雙酚F型環氧樹镂β列舉出雙酚八型 土衣軋树脂、雙酚ς型淳 雙（4-羥苯基）-1，1，丨3 q ~ 长氣樹脂、2, 2- ，3, 3-六氟丙烷的環f π ^ & :型環氧樹脂、氣化雙紛Α型環氧樹脂、氣::合物等雙 :樹脂、氫化雙酶S型環氧樹脂、氫化】雙紛F型環 4 U，1，3, 3,3'六氟兩燒的環氧化合物等^雙（4-經笨 礼樹脂、溴化雙酚八型 、 4氧化雙酚型環 等鹵化雙酚型環氧樹& θ、/臭化雙酚F型環氧樹浐 知、環己坑二甲醇二缩水甘油喊化合物二:型環氧樹 卞月日％式二縮水甘 322209 18 201111432 油醚化合物、1，6-己二醇二縮水甘油醚、丨，4_丁二醇二縮 水甘油醚、二乙二醇二縮水甘油醚等脂肪族二縮水甘油醚 化合物、多硫化物二縮水甘油醚等多硫化物型二縮水甘油 醚化合物、聯酚型環氧樹脂、聚醚型環氧樹脂等。 此寺氣化合物的市售品，例如可列舉出jERgsg、 jERlOOl、jERl〇〇2、jERl〇03、潭1004(均為 JapanEp〇xyII C—0—CnH2n+1 (wherein R represents H or CH3, and n represents an integer of 10 to 25). Specific examples are exemplified by (decyl)acrylic acid dodecane vinegar, (methyl acetoacetate octadecyl ester, (fluorenyl) hexadecanoate, and (meth) propyl decyl undecane. An ester, an isodecyl (meth) acrylate, an isostearyl (meth) acrylate, an isohexadecyl (meth) acrylate, and an isocosyl (meth) acrylate. The aliphatic chain of the (f-based) acrylate of the aliphatic chain is more preferable from the viewpoint of easiness of peeling from the stamper, etc., and the (meth)acrylic acid having a branched aliphatic chain is preferred. The ester is particularly preferably a (fluorenyl) acrylate having a branched chain of cl〇 to. Therefore, in the above specific examples, it is particularly preferred to be isodecyl (meth)acrylate or isobutyl (meth)acrylate. An alkyl ester, isohexadecyl (meth)acrylate or iso-docosyl (meth)acrylate. (A) a ruthenium containing (meth) acrylate having a fatty chain, relative to The total amount (total) of the resin composition is about 5 to 9 % by weight, preferably about 10 to 80% by weight. Although it is different because of the combination of (B) or (C), it cannot be generalized, but depending on the situation, it is preferably about 5 to 50% by weight, preferably about 5 to 40% by weight, more preferably It is about 10 to 4% by weight, preferably about 10 to 30% by weight. U) (meth) acrylate having a fatty chain, and commercially available products such as Blemmer SA, Blemmer CA, and Blemmer manufactured by Nippon Oil Chemical Co., Ltd. VA; Isostearyl Acrylate, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.; Kyoeisha 14 322209 201111432 Light-Acrylate IS-A, Light-Acrylate, IM-A, etc., manufactured by Chemical Co., Ltd. In the resin composition of the present invention, (3) (meth) acrylate * monomer is used. The (meth) acrylate monomer to be used may be any commonly known (meth) acrylate monomer other than the component (A) and the component (c), and may be used without particular limitation. Examples thereof include tricyclodecane (meth) acrylate, benzyl (meth) acrylate, dicyclopentanyl (meth) acrylate, isodecyl (meth) acrylate, and adamantyl (meth) acrylate. Ester, tetrahydrofurfuryl (meth) acrylate, morpholine (meth) acrylate, neopentyl glycol di(meth) acrylate modified with propylene oxide, tricyclodecane di(meth)acrylate Dimethylol, trimethylolpropane di(meth)acrylate modified with hydroxytrimercaptoacetaldehyde, hydroxytrimethylacetic acid neopentyl glycol di(meth)acrylate, and the like. For use in combination with the component (A) as described above and to improve peelability and the like, the (meth) acrylate monomer is preferably selected from neopentyl glycol modified from isodecyl (meth) acrylate and propylene oxide. Di(meth)acrylate, bis(indenyl)tricyclodecane dimethyl ketone, and hydroxymethyl dimethyl aldehyde modified " hydroxymethylpropane bis(indenyl) acrylate At least one of the groups. These single systems can be used in combination with the branched fatty chain f (mercapto) acetoacetate as the component (A), and can be used as a resin of the present invention having low peel strength and less change in tortuosity. Composition. Among them, trimethylol acrylate (meth) acrylate or / and hydroxy dimethyl acetaldehyde modified by trimethylolpropane di(meth) acrylate are more preferable, and it is more preferable to use them in combination. (c) Amine ester (meth) propylene 322209 15 201111432 vinegar used in the resin composition of the present invention, which is used in place of the above component (B), and may be prepared to contain (a) component and (C) The component does not contain the component (B) as a resin component of the resin component, but usually the component (C) is used in combination with the component (B). The amine acetonate (meth) acrylate of the component (C) is preferably a compound obtained by reacting an organic polyisocyanate with a trans (meth) acrylate compound. Examples of the organic polyisocyanate include isophorone cyanide diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, xylene diisocyanate, and diphenylmethane-4,4,-diisocyanate. Isocyanates such as diisocyanates or quinone dicyclopentyl isocyanate. Among these, it is particularly preferred to use isophorone diisocyanate or toluene diisocyanate. The "rubber-based (meth) acrylate compound may, for example, be a C2 to C10 aliphatic (methyl) acetoacetate or a hexyl vinegar (meth) acrylate or the like. The C2 to cl〇 aliphatic (meth) acrylate, which is substituted by a base, preferably exemplified by (mercapto)acrylic acid, ethyl vinegar, (meth)acrylic acid, propylene vinegar, (meth) propyl The acid is made of butyl vinegar, mono (methyl) propyl benzoic acid, methylcyclohexanol, pentaerythritol tris(meth)acrylic acid vinegar, dipentaerythritol penta (meth) acrylate, and the like. Among them, preferred are hydroxyethyl (meth)acrylate, (meth)acrylic acid (iv) g, (meth)acrylic acid, butyl vinegar, pentaerythritol tris(meth) propyl phthalate, and the like. Therefore, preferred amine ester (meth) acrylates can be exemplified by the above-mentioned polyisocyanate and the above-mentioned substituted by the county to (10) aliphatic 322209 16 201111432 (meth) acrylate or hydroxyhexene An amine ester (mercapto) acrylate obtained by the reaction of an ester (meth) acrylate. Further, a particularly preferred amine ester (meth) acrylate may, for example, be isophorone diisocyanate or toluene diisocyanate exemplified as the above preferred organic polyisocyanate and exemplified as the above preferred hydroxyl group (A) The amine ester (meth) acrylate obtained by the reaction of the acrylate compound. The reaction was carried out in the following manner. That is, the organic polyisocyanate is mixed with the hydroxy(indenyl) acrylate compound in an amount of 1.0 to 2.1 equivalents per isocyanate group, and is carried out at 70 to 90 ° C. The reaction is carried out to obtain the desired amine ester (meth) acrylate. The above-mentioned amine ester (mercapto) acrylate can be used singly or in combination of two or more kinds in any ratio. The content of at least one of (B) (meth) acrylate monomer or (C) urethane (mercapto) acrylate in the resin composition of the present invention in a ratio relative to the total amount of the resin composition (weight It is about 5 to 90%, preferably about 10 to 80%. Further, the preferred range may be 50 to 90 ° / 〇, and particularly preferably 60 to 85%, depending on the case. Further, the content ratio of the total amount of the components (A) to (C) to the total amount of the resin composition of the present invention may be any range as long as it can reach the range of the effect of the invention. Generally, the viscosity of the resin composition, the peeling property of the cured layer from the stamper, and the light transmittance of the cured layer, the distortion and durability of the optical disk having the cured layer, and the like are compared with respect to the resin composition. The total amount of the components (A) to (C) is preferably at least 50%, particularly preferably at least 70%, and the total amount of the components (A) to (C) is relative to the total amount of the resin composition. S. 17 322209 201111432 More preferably 85 to 99%, most preferably 90 to 99%. In the above case, the ratio of the component (A) to the other component (the component (B) and the component (C)) is 1 part with respect to the component (A), and the other component (the (β) component or the (C) component or contains (Β) and (C) are the total amount of the two), usually about 1 to 20 parts, preferably about 2 to 10 parts, more preferably about 3 to 7 parts. The (Β) component or the component (C) usually does not cause any problem as long as it contains at least one of the resin compositions. Therefore, the total amount '(Β) component with respect to the two components is preferably from 30 to 1% by weight, particularly preferably from 5 to 1% by weight, more preferably from 7 to 1%. The component (c) is preferably from 0 to 70%, particularly preferably from 〇 to 5%, more preferably from 0 to 30%. Further, the 'this type of day' may suitably contain an epoxy group acrylic acid vinegar as necessary. The epoxy group (methyl) propyl vinegar is preferably obtained by the reaction of an epoxy resin having two or more epoxy groups, and a substance (10) having a disk of a non-age base. Compound. The epoxy resin of the raw material "acrylonitrile" and the bisphenol F type epoxy resin 镂β exemplify the bisphenol eight type clay coating resin and the bisphenol hydrazine type bis(4-hydroxyphenyl)-1,1.丨3 q ~ long gas resin, 2, 2-, 3, 3-hexafluoropropane ring f π ^ & : type epoxy resin, gasified double bismuth type epoxy resin, gas:: compound, etc. : Resin, Hydrogenated Double Enzyme S-type Epoxy Resin, Hydrogenation] Double F-rings 4 U, 1,3, 3,3' hexafluoro-bi-epoxy compounds, etc. ^Double (4-stupid resin, bromine Halogenated bisphenol type epoxy tree & θ, / stinky bisphenol F type epoxy tree 浐, ring hexamethylene dimethylene diglycidate compound II: type Epoxy tree %月日%式二缩水甘322209 18 201111432 Oil ether compound, 1,6-hexanediol diglycidyl ether, hydrazine, 4_butanediol diglycidyl ether, diethylene glycol diglycidyl ether A polysulfide type diglycidyl ether compound such as an aliphatic diglycidyl ether compound or a polysulfide diglycidyl ether, a biphenol type epoxy resin, a polyether epoxy resin, etc. Commercial products of this temple gas compound ,E.g Include jERgsg, jERlOOl, jERl〇〇2, jERl〇03, Tan 1004 (both JapanEp〇xy
Resins 公司製），EP〇MIKRTMR-140、EPOMIKrtmR-3〇卜 EPOMIKrtmR-304(均為三井化學股份有限公司製），DER—331、 DER-332、DER-324(均為 Dow Chemical 股份有限公司製）， Epiclon 840、Epiclon 850(均為大日本油墨股份有限公司 製）’ UVR-6410(Union Carbide 股份有限公司製），YD-8125 (東都化成股份有限公司製）等雙酚A型環氧樹脂； UVR-6490(Uni〇n Carbide 股份有限公司製），YDF_2〇〇i、 YDF-2004、YDF-8170(均為東都化成股份有限公司製）， Epiclon 830、Epiclon 835(均為大日本油墨股份有限公司 ‘）專雙朌F型環氧樹脂；HBPA-DGE(丸善石油化學股份有 限公司製）’ Rikaresin HBE-100(新日本理化股份有限公司 製）等氫化雙酚A型環氧樹脂；DER-513、DER-514、DER_542 (均為Dow Chemical股份有限公司製）等溴化雙酚A型環氧 树月曰，EPOLIGHT 3002(共榮社化學股份有限公司製）等經 p〇改質之雙酚A型環氧樹脂；cell0Xide 2〇21(Daicel股 份有限公司製）’ Rikaresin DME-100(新日本理化股份有限 △司製），EX-216(Nagase Kasei股份有限公司製）等脂環 式裱氧樹脂；ED-503C旭電化股份有限公司製），Rikaresin S. 322209 19 201111432 w-100(新日本理化股份有限公司製），EX-212、EX-214、 EX-850C均為Nagase Kasei股份有限公司製）等脂肪族二縮 水甘油醚化合物；FLEP-50、FLEP-60(均為 TorayThi〇k〇i 股份有限公司製）等多硫化物型二縮水甘油醚化合物； YX-4000(Japan Epoxy Resins股份有限公司製）等聯盼型 環氧化合物；EPOLIGHTrtm100E、EPOLIGHTrtm200P(均為共榮 社化學股份有限公司製）等聚醚型環氧化合物。 上標RTM係表示註冊商標（以下相同）。 本發明之樹脂組成物中所含有之（D)光聚合起始劑， 可列舉出1-經基環己基苯基酮（IrgacureRTM184 ; Ciba Specialty Chemicals股份有限公司製）、1-[4-（2-經基乙 氧基）笨基]-2-羥基-2-曱基-1-丙烷-1-酮 (IrgacureRTM2959 ; Ciba Specialty Chemicals 股份有限 公司製）、2-羥基-l-{4-[4-(2-羥基-2-甲基-丙醯基）笨曱 基]•苯基}-2-曱基-1-丙烧嗣（IrgacureRTM127 ; Ciba Specialty Chemicals股份-有限公.司製）、2, 2-二甲氧基-2-苯基苯乙酮（IrgacureRTM651 ; Ciba Specialty Chemicals 股份有限公司製）、低聚[2-羥基-2-曱基-l-[4-(卜甲基乙 烯基）笨基]丙_ ](Esacure ONE ; Lamberti股份有限公司 製）、2-羥基-2-曱基-1-苯基-丙烷-1-酮（DarocureRTM1173; Ciba Specialty Chemicals股份有限公司製）、2-甲基 -1-[4-(甲硫基）苯基]-2-(N-嗎啉基）丙烷-1-酮 (IrgacureRTM907 ; Ciba Specialty Chemicals 股份有限公 司製）、2-苯甲基-2-二曱基胺基-1-(4-(Ν-嗎啉基）苯基）- 20 322209 201111432 丁烧-1-酮、2_氣°塞吨酮（2-chlorothioxanthone)、2,4_ . 二甲基嗟吨酮、2, 4-二異丙基嗟吨酮、異丙基嘆吨酮、 2,4,6-三甲基苯曱醯基二苯基膦氧化物〇^以1^111?0; - BASF股份有限公司製）、雙（2, 4, 6-三曱基苯甲醯基）苯基 ^ 膦氧化物（IrgacureRTM819 ; Ciba Specialty Chemicals 股 份有限公司製）、雙（2, 6-二曱氧基苯甲醯基）一2, 4, 4-三曱 基戊基膦氧化物等。 此等光聚合起始劑，可使用1種或以任意比例混合複 數種使用’亦可與胺類等光聚合起始助劑併用。 本發明之樹脂組成物中之（D)光聚合起始劑的含量， 係使用1至15重里％’較佳為3至丨〇重量％左右。 本發明中所能夠使用之胺類等光聚合起始助劑，例如 可列舉出二乙醇胺、苯甲酸2_二甲基胺基乙醋、二甲基胺 基苯乙酮、對二甲基胺基苯甲酸乙i旨、對二曱基胺基笨甲 酸異戊酯。 先^合起㈣本發明之㈣旨組成射的含量為丨 至5%左右，較佳為〇至左右。去 . π η, . , ^ 及右田诉用光聚合起始助劑時 車父佳為0. 05至5重量％，較佳為〇 , 狂符υ· 1至3重量％。通常盔你 用光聚合起始助劑之必要十生。 m 本發明之树脂組成物中，可 « ^ ^^ J固應必要而添加磷酸（曱 基）丙烯魷S曰。磷酸（甲基）丙 ί® A\- AL· 知可提升铭、銀或銀合金 與接者劑硬化物之接著性 ^ 宜用詈右所卩P也丨L 仁有腐蝕金屬膜之疑慮，所以 具用里有所限制。此外， 爯去，夫旅一 亦不會造成問題。 冉者’本發明中，险 '、 义成分外，亦可因應必要而 322209 21 201111432 添加矽烧偶合劑、塗平（leveling)劑、消泡劑、聚合抑制 劑、光安定劑（受阻胺系等）、抗氧化劑、抗靜電劑、表面 潤滑劑、填充劑等添加劑。此般添加劑的例子，可列舉如 下，矽烷偶合劑例如有信越化學（股）公司製的KBM-502、 KBM-503 ' KBM-5103 ' KBM-802 x KBM-803 » Toray Dow Corning(股）公司製的 Z-6062、SH-6062、SH-29PA ;塗平 劑例如有 BYK 公司製的 ΒΥΚ-333、ΒΥΚ-307、ΒΥΚ-3500、 ΒΥΚ-3530、ΒΥΚ-3570，抗氧化劑例如有（股）Adeka公司製 的LA_82等。 此等添加劑，相對於本發明之樹脂組成物的總量而 言，通常可含有0至10%左右，較佳為〇至5%左右。通常 不含有亦不會造成問題。 本發明之樹脂組成物’可在常溫至8(TC下將前述各成 分混合溶解後，因應必要而進行過濾而得。 本發明之樹脂組成物的黏度，以B型黏度計在25°C下 所測定者，為10至800mPa · s，較佳為30至500mPa · s， 尤佳為30至400mPa · s，更佳為50至300mPa . s。 本發明之樹脂組成物的一例，可列舉出相對於樹脂組 成物全體而言，（A)成分為5至90重量％、（B)成分及/或（C) 成分為5至90重量％、（D)成分為1至15重量％並且（A)至 (D)的總量為1〇〇%之紫外線硬化型樹脂組成物。 較佳之本發明之樹脂組成物的組成之較佳的一例，可 列舉出下列樹脂組成物。 22 322209 (I) 201111432 一種樹脂組成物’係相對於樹脂組成物的總量而言， (i)(A)成分為5至90重量％，（ii)(B)成分或（c)成分或是 (B)及（C)兩者為5至90重量％且（4)至（〇成分的總量為85 至99重量％，（iii)(D)成分為1至重量％。 - (II) 尤佳之樹脂組成物的一例為一種樹脂組成物，係（i) (A)成分為1〇至4〇重量％，（ii)(B)成分或（c)成分或是（B) 及（C)兩者為50至90重量％且（八）至（C)成分的總量為90 至99重量％，（iii)(D)成分為1至丨〇重量％。 (III) 如上述（I)或（II)所記载之樹脂組成物，其中，（A)成 分為由下列式（0所表示之具有脂肪鏈之（甲基）丙烯酸酯： R 0 _| | ο) H2c=c-c—〇—cnH2n+1 式中’R表示Η或CH3, η表示10至25的整數。 (IV) 如上述（III)所記載之樹脂組成物，其中，（Α)成分為 具有分枝鏈之（甲基）丙烯酸C10至C25烷基酯。 (V) 如上述（IV)所記載之樹脂組成物，其中，具有分枝鏈 之（曱基）丙烯酸C10至C25烷基酯係選自由丙烯酸異癸 醋、（甲基）丙烯酸異十二烷酯、（甲基）丙稀酸異十八烷酯、 (甲基）丙烯酸異十六烷酯、以及（曱基）丙烯酸異二十二烷 23 322209 201111432 酉9所組成之群組的至少一種。 (VI) 如上述（IV)所記載之樹脂組成物，其中，具有分枝鏈 甲基）丙烯酸C10至C25院基醋係選自由丙稀酸異癸 酯、（甲基）丙婦酸異十八烧醋及（甲基）丙稀酸異十六烧醋 所組成之群組的至少一種。 (VII) 如上述（1\〇所5己載之樹脂組成物，其中，具有分枝鍵 之（甲基）丙_C10至C25燒基醋為（甲基）丙婦酸显十八 烷酯。 、 (VIII) 如上述⑴至（ΠΙ)中任一項所記載之樹脂組成物，盆 .中，⑻成分係選自由（甲基）丙烯酸異获醋、經環氧丙歧 質之新戊二醇二（甲基）丙烯酸醋、二π基）丙婦酸三環癸 烷二經甲酉旨、以及經經基三曱基乙藤改質之三經甲基丙燒 二（甲基）丙烯酸輯組成之群组的至少—種（甲 酯單體。 (IX) 如上述（VIII)所記載之樹脂組成物，其中，⑻成分 為（甲基）丙烯酸異«酉旨或經經基三甲基乙路改質之三經甲 基丙烧一（甲基）丙稀酸醋之任—者。 (X) 如上述⑴至（IX)中任一項所記載之樹月旨組成物，並 中，⑹成分為藉由有機多異氣酸酉旨與經基（〒基）丙婦酸酉旨 322209 24 201111432 化合物之反應所得之胺酯（曱基）丙烯酸酯。 (XI) 如上述（X)所記載之樹脂組成物，其中，羥基（曱基） 丙烤酸酯化合物為經羥基取代之C2至C10脂肪族（〒基） - 丙稀酸酯。 (XII) 如上述（I)至（XI)中任一項所記載之樹脂組成物，其 中’相對於樹脂組成物的總量而言，含有（B)成分50至90%。 (XIII) 如上述（I)至(XII)中任一項所記載之樹脂組成物，其 中’相對於（B)成分及（C)成分的總量而言，含有（C)成分〇 至 50% 〇 本發明之樹脂組成物，係適合用作為多層光碟之透明 中間層用的樹脂組成物。 為DVD時’透明樹脂中間層係以下述方式形成：（！） 藉由旋轉塗佈法、網版印刷法、輥塗佈法等方法，將本發 明之樹脂組成物塗佈於積層有第1透明樹脂基板、第！記 錄層、第1半透明反射膜層之基板與透明樹脂壓模的至少 -者後，進行貼合並從透明樹脂壓模侧照射紫外線 。或者 是以下述Μ形成：⑵#㈣述^將本發日狀樹脂組成 物塗佈於透明樹脂壓模後，進行㈣線硬化，再以任音的 紫外線硬—樹脂與積層有第丨透日物脂基板、第}記錄 層、第！半透明反射膜層之基板貼^⑴的形成方法，就 可省略生虞工序之點來看可望降低生產成本，故較佳。此 S. 322209 25 201111432 外’為藍光光碟時，亦能夠以與DVD相同方法來形成透明 樹脂中間層。一般而言，DVD或HD_DVD般之〇 6mm的第1 透明樹脂基板、藍光光碟之1. 1 _的樹脂基板，係使用聚 碳酸酯樹脂。 透明樹脂壓模，例如可列舉出丙烯酸系樹脂、甲基丙 烯酸系樹脂、聚碳酸酯樹脂、聚烯烴系樹脂（尤為非晶質聚 烯烴）、聚酯系樹脂、聚苯乙烯樹脂、環氧樹脂等。此等當 中，就使2P劑硬化後之剝離性、低吸濕性、形狀安定性等 觀點來看，較佳為非晶質聚烯烴，就材料成本之觀點來看， 較佳為聚碳酸酯樹脂。本發明之沙硬化型樹脂組成物可使 用任一種透明樹脂壓模。 本發明之紫外線硬化型樹脂組成物，係藉由活性能量 線的照射來得到硬化物。該活性能量線，例如可列舉出 1 :至近紫外之光線。該光線的光源，例如可列舉出低壓： 高Μ、超高1水銀燈、金屬鹵化物燈、（脈衝）氤氣燈、I ^極燈、紫外線發光二極體等。前述硬化物亦包含^本發 形成於由前述硬化物所構成之透明樹脂 記錄層’可使用有機色素及相變化材料之任—者。:、 有機色素可列舉出金屬偶氮系、聚m 例如’ 化材料可列舉出於Sb及Te中添加In、Ag、:二,，相變Resins company, EP〇MIKRTMR-140, EPOMIKrtmR-3〇EPOMIKrtmR-304 (all manufactured by Mitsui Chemicals, Inc.), DER-331, DER-332, DER-324 (all manufactured by Dow Chemical Co., Ltd.) ), Epiclon 840, Epiclon 850 (all manufactured by Dainippon Ink Co., Ltd.) 'UVR-6410 (manufactured by Union Carbide Co., Ltd.), YD-8125 (made by Tohto Kasei Co., Ltd.), etc. UVR-6490 (manufactured by Uni〇n Carbide Co., Ltd.), YDF_2〇〇i, YDF-2004, YDF-8170 (both manufactured by Dongdu Chemical Co., Ltd.), Epiclon 830, Epiclon 835 (all are large Japanese ink shares) Co., Ltd.') special double-type F-type epoxy resin; HBPA-DGE (made by Maruzen Petrochemical Co., Ltd.) Rikaresin HBE-100 (manufactured by Nippon Chemical and Chemical Co., Ltd.) and other hydrogenated bisphenol A type epoxy resin; DER -513, DER-514, DER_542 (all manufactured by Dow Chemical Co., Ltd.), etc., such as brominated bisphenol A type epoxy tree, and EPOLIGHT 3002 (manufactured by Kyoeisha Chemical Co., Ltd.) Bisphenol A type epoxy resin; cell0Xide 2 21 (made by Daicel Co., Ltd.) 'Rikaresin DME-100 (Nippon Chemical and Chemical Co., Ltd.), EX-216 (Nagase Kasei Co., Ltd.) and other alicyclic epoxy resins; ED-503C Asahi Chemical Co., Ltd. Company system), Rikaresin S. 322209 19 201111432 w-100 (manufactured by Nippon Chemical and Chemical Co., Ltd.), EX-212, EX-214, and EX-850C are all aliphatic diglycidyl ethers manufactured by Nagase Kasei Co., Ltd. Compounds; polysulfide type diglycidyl ether compounds such as FLEP-50 and FLEP-60 (all manufactured by TorayThi〇k〇i Co., Ltd.); Hope-type rings such as YX-4000 (made by Japan Epoxy Resins Co., Ltd.) Oxygen compound; polyether epoxy compound such as EPOLIGHTrtm100E or EPOLIGHTrtm200P (all manufactured by Kyoeisha Chemical Co., Ltd.). The superscript RTM is a registered trademark (the same below). The (D) photopolymerization initiator contained in the resin composition of the present invention may, for example, be 1-cyclohexyl phenyl ketone (Irgacure RTM184; manufactured by Ciba Specialty Chemicals Co., Ltd.), 1-[4-(2) -Phenylethoxy) phenyl]-2-hydroxy-2-mercapto-1-propan-1-one (Irgacure RTM 2959; manufactured by Ciba Specialty Chemicals Co., Ltd.), 2-hydroxy-l-{4-[4 -(2-hydroxy-2-methyl-propenyl) aluminyl]•phenyl}-2-mercapto-1-propanone (Irgacure RTM127; Ciba Specialty Chemicals Co., Ltd.) , 2-dimethoxy-2-phenylacetophenone (Irgacure RTM651; manufactured by Ciba Specialty Chemicals Co., Ltd.), oligomeric [2-hydroxy-2-indolyl-l-[4-(dimethylvinyl) stupid Base] C_] (Esacure ONE; manufactured by Lamberti Co., Ltd.), 2-hydroxy-2-mercapto-1-phenyl-propan-1-one (Darocure RTM1173; manufactured by Ciba Specialty Chemicals Co., Ltd.), 2-A 1-[4-(methylthio)phenyl]-2-(N-morpholinyl)propan-1-one (Irgacure RTM907; manufactured by Ciba Specialty Chemicals Co., Ltd.), 2-benzyl-2- Dimercaptoamino-1-(4-(indole-morpholine) )phenyl)- 20 322209 201111432 butyl ketone-1-yl, 2-chlorothioxanthone, 2,4_. dimethyl xanthone, 2,4-diisopropylxanthone , Isopropyl ketone, 2,4,6-trimethylphenylnonyldiphenylphosphine oxide 〇^ to 1^111?0; - BASF Co., Ltd.), double (2, 4, 6-trimercaptobenzylidene)phenylphosphine oxide (Irgacure RTM819; manufactured by Ciba Specialty Chemicals Co., Ltd.), bis(2,6-dimethoxybenzylphenylidene)-2, 4, 4- Tridecylpentylphosphine oxide and the like. These photopolymerization initiators may be used alone or in combination of a plurality of them in any ratio. Alternatively, they may be used in combination with a photopolymerization starter such as an amine. The content of the (D) photopolymerization initiator in the resin composition of the present invention is from about 1 to 15% by weight, preferably from about 3 to about 3% by weight. Examples of the photopolymerization initiation aid such as an amine which can be used in the present invention include diethanolamine, 2-dimethylaminoethyl benzoate, dimethylaminoacetophenone, and p-dimethylamine. Benzoic acid, p-di-decylamino-p-formic acid isoamyl ester. (4) The content of the composition of (4) of the present invention is from about 5% to about 5%, preferably from about 5% to about. When the π η, . , ^ and the right-hander use the photopolymerization start-up aid, the car is preferably from 0.05 to 5% by weight, preferably 〇, 狂符υ·1 to 3% by weight. Usually you need to use a photopolymerization starter. m In the resin composition of the present invention, phosphoric acid (mercapto) propylene sulfonium S 曰 can be added as necessary. Phosphoric acid (methyl) acryl® A\- AL· knows how to improve the adhesion of Ming, silver or silver alloy to the hardener of the splicer. It is advisable to use 詈 right 卩 P 丨 L 仁 has a corrosive metal film. Therefore, there are restrictions in the use. In addition, if you go, you will not cause problems. In the present invention, in addition to the risk component and the meaning component, 322209 21 201111432 may be added as a simmering coupling agent, a leveling agent, an antifoaming agent, a polymerization inhibitor, a light stabilizer (a hindered amine system). Etc.), antioxidants, antistatic agents, surface lubricants, fillers and other additives. Examples of such additives include the following: decane coupling agents such as KBM-502, KBM-503 'KBM-5103' KBM-802 x KBM-803, manufactured by Shin-Etsu Chemical Co., Ltd. » Toray Dow Corning Co., Ltd. Z-6062, SH-6062, SH-29PA; the leveling agent is, for example, ΒΥΚ-333, ΒΥΚ-307, ΒΥΚ-3500, ΒΥΚ-3530, ΒΥΚ-3570 manufactured by BYK, and antioxidants such as LA_82 manufactured by Adeka Corporation. These additives may usually contain from 0 to 10%, preferably from about 5% to about 5%, based on the total amount of the resin composition of the present invention. Usually does not contain or cause problems. The resin composition of the present invention can be obtained by mixing and dissolving the above components at room temperature to 8 (TC), and then filtering as necessary. The viscosity of the resin composition of the present invention is 25 ° C at a viscosity of B. The measurement is 10 to 800 mPa·s, preferably 30 to 500 mPa·s, more preferably 30 to 400 mPa·s, still more preferably 50 to 300 mPa. s. An example of the resin composition of the present invention is exemplified. The component (A) is 5 to 90% by weight, the component (B) and/or the component (C) is 5 to 90% by weight, and the component (D) is 1 to 15% by weight with respect to the entire resin composition. The ultraviolet curable resin composition having a total amount of A) to (D) of 1% by weight. A preferred example of the composition of the resin composition of the present invention is exemplified by the following resin composition. 22 322209 (I 201111432 A resin composition' is (i) (A) component is 5 to 90% by weight, (ii) (B) component or (c) component or (B) with respect to the total amount of the resin composition. And (C) both are 5 to 90% by weight and (4) to (the total amount of the cerium component is 85 to 99% by weight, and the component (iii) (D) is 1 to 5% by weight. - (II) An example of the resin composition is a resin composition, wherein (i) component (A) is from 1 to 4% by weight, (ii) component (b) or component (c) or (B) and (C) Both are 50 to 90% by weight and the total amount of the components (8) to (C) is 90 to 99% by weight, and (iii) the component (D) is 1 to 丨〇% by weight. (III) As described above (I) Or a resin composition according to (II), wherein the component (A) is a (meth) acrylate having a fatty chain represented by the following formula (0: R 0 _| | ο) H2c=cc - 〇 —cnH2n+1 wherein 'R represents Η or CH3, and η represents an integer of 10 to 25. (IV) The resin composition according to the above (III), wherein the (Α) component has a branched chain (A) (C) The resin composition according to the above (IV), wherein the C10 to C25 alkyl (meth) acrylate having a branched chain is selected from the group consisting of isophthalic acid acrylate , isodecyl (meth) acrylate, isostearyl (meth) acrylate, isohexadecyl (meth) acrylate, and isodecane (meth) acrylate 23 322209 201111432酉9 group (VI) The resin composition according to the above (IV), wherein the branched chain methyl acrylate C10 to C25 basal vinegar is selected from the group consisting of isodecyl acrylate, (A) At least one of the group consisting of acetoin and hexadecyl acetonate (VII) (VII) as described above (1) Among them, the (meth)propane-C10 to C25 alkyl vinegar having a branching bond is (methyl)-propionic acid octadecyl ester. (VIII) The resin composition according to any one of the above (1) to (A), wherein the component (8) is selected from the group consisting of (meth)acrylic acid-derived vinegar, and ethylene-epoxy disproportionate Alcohol di(meth)acrylic acid vinegar, diπ-yl)propanyl tricyclodecane dimethoate, and trimethylmethacrylate di(meth)acrylic acid modified by trimethyl sulfonate At least one type of the group (methyl ester monomer. (IX) The resin composition as described in the above (VIII), wherein the (8) component is (meth)acrylic acid or the transaluminum (3) The composition of the sylvestre of the sulphuric acid of the sulphuric acid In the above, the component (6) is an amine ester (mercapto) acrylate obtained by reacting an organic polyisophthalic acid with a compound of thiophene sulfonate 322209 24 201111432. (XI) as described above (X) The resin composition described, wherein the hydroxy(indenyl)propionate compound is a C2 to C10 aliphatic (fluorenyl)-acrylic acid ester substituted with a hydroxyl group. (XII) The resin composition according to any one of the above (I) to (XI), wherein the component (B) contains 50 to 90% of the total amount of the resin composition. (XIII) The resin composition according to any one of the above (I) to (XII), wherein the component (C) contains ( to 50% of the total amount of the components (B) and (C). The resin composition is suitable for use as a resin composition for a transparent intermediate layer of a multilayer optical disc. When it is a DVD, the 'transparent resin intermediate layer is formed in the following manner: (!) by spin coating method, screen printing method, In a method such as a roll coating method, the resin composition of the present invention is applied to at least one of a substrate on which a first transparent resin substrate, a recording layer, and a first semi-transparent reflective film layer are laminated, and a transparent resin stamper. The paste is combined and irradiated with ultraviolet rays from the side of the transparent resin stamper, or formed of the following crucibles: (2) #4 (4) The application of the present-day resin composition to a transparent resin stamper, followed by (four) wire hardening, and then Ultraviolet hard-resin and laminated with a diaper-permeable substrate, the first record In the method of forming the substrate paste (1) of the semi-transparent reflective film layer, it is preferable to omit the production process from the viewpoint of omitting the mashing process. This is preferable when S. 322209 25 201111432 is a Blu-ray disc. The transparent resin intermediate layer can also be formed in the same manner as the DVD. In general, a polycarbonate resin is used as the resin substrate of the first transparent resin substrate of 6 mm in the case of DVD or HD_DVD and the optical disk of 1.1 _. Examples of the transparent resin stamper include an acrylic resin, a methacrylic resin, a polycarbonate resin, a polyolefin resin (especially an amorphous polyolefin), a polyester resin, a polystyrene resin, and an epoxy resin. Wait. Among these, from the viewpoints of releasability, low hygroscopicity, and shape stability after curing of the 2P agent, amorphous polyolefin is preferred, and from the viewpoint of material cost, polycarbonate is preferred. Resin. The sand hardening type resin composition of the present invention can be molded by any of transparent resins. The ultraviolet curable resin composition of the present invention is obtained by irradiation with an active energy ray to obtain a cured product. Examples of the active energy ray include light rays of 1: to near ultraviolet rays. Examples of the light source of the light include a low pressure: a high enthalpy, an ultra high mercury lamp, a metal halide lamp, a (pulse) xenon lamp, an I^ pole lamp, and an ultraviolet light emitting diode. The cured product may also include any of an organic dye and a phase change material which are formed on the transparent resin recording layer formed of the cured product. The organic dye may be exemplified by a metal azo type or a poly m. For example, the addition of In, Ag, or two to Sb and Te may be mentioned.
Aimc、v、w、Ta、Zn、Tl、Ce、T:Bl，、 的任一種以上而成者。 n Pb 此外，本發明之樹脂組成物可使用於貼合有聚碳酸酉旨 322209 26 201111432 •製基板而成之構造的光碟及藍光光碟的任一種。 - 塗佈方法，例如可列舉出旋轉塗佈法、2P法、輥塗佈 法、網版印刷法等。 - 此外，次世代的高密度光碟中，讀取及/或寫入係使 - 用400nm前後的藍光雷射，所以在膜厚90至ΙΟΟμιη的硬 化物，較佳為100//m中之405nm的穿透率為80%以上，尤 佳為9 0 %以上。 穿透率，可製作出100//m的膜，並使用分光光度計 (U-3310，Hitachi High Technologies 股份有限公司製）， 測定該膜於405nm的吸光度之值來求得。 (實施例） 以下使用實施例來詳細說明本發明。 表1所記載之黏度值，係以B型黏度計在25°C下所測 定之值。此外，表1所記載之穿透率值，係製作出厚度100 /xm的硬化膜，並使用分光光度計（商品型號：U-3310， Hitachi High Technologies股份有限公司製）所測定之 值。 (實施例及試驗例） 表1係顯示實施例1-6及比較例1-4的樹脂組成物之 構成材料、用量及記載項目的評估結果。記載内容中的「份」 表示重量份。 27 322209 I. 201111432 【表1】 表1.樹脂組成及評估結果Any one of Aimc, v, w, Ta, Zn, Tl, Ce, T: Bl, or the like. n Pb Further, the resin composition of the present invention can be used for any of optical discs and Blu-ray discs having a structure in which a substrate made of polycarbonate 322209 26 201111432 is bonded. - The coating method may, for example, be a spin coating method, a 2P method, a roll coating method, a screen printing method or the like. - In addition, in the next-generation high-density optical discs, reading and/or writing is performed by using a blue laser before and after 400 nm, so that the cured product having a film thickness of 90 to ΙΟΟμηη is preferably 405 nm in 100//m. The penetration rate is 80% or more, and particularly preferably 90% or more. For the transmittance, a film of 100/m was produced, and the value of the absorbance at 405 nm of the film was measured using a spectrophotometer (U-3310, manufactured by Hitachi High Technologies Co., Ltd.). (Examples) Hereinafter, the present invention will be described in detail using examples. The viscosity values shown in Table 1 are values measured at 25 ° C using a B-type viscometer. In addition, the transmittance value described in Table 1 was a cured film having a thickness of 100 / xm, and a value measured by a spectrophotometer (product type: U-3310, manufactured by Hitachi High Technologies Co., Ltd.) was used. (Examples and Test Examples) Table 1 shows the constituent materials, amounts, and evaluation results of the resin compositions of Examples 1-6 and Comparative Examples 1-4. The "parts" in the contents indicate the parts by weight. 27 322209 I. 201111432 [Table 1] Table 1. Resin composition and evaluation results
實施 例1 實施 例2 實施 例3 實施 例4 實施 例5 實施. 例6 tm 例1 tbfe 例2 fcbfe 例3 fcbfe 例4 成分(A)(份） ISA 16 16 ICA 16 IDA 16 SA 16 CA 16 成分(B)(份） IBA 39 R-604 79 63 40 40 40 63 79 79 79 79 R-684 39 NPG-2P 39 FA-512A 16 ΊΉΕ-330 16 RP-1040 16 DPHA 16 成分(0(份） UX-5000 16 Cl 16 成分(D)(份） Irgacure 184D 5 5 5 5 5 5 5 5 5 5 (剝離性) 剝離強度(kgf) 0.9 0.8 0.7 1.3 1.2 0.7 2.0 2.6 2.4 1.3 剝離性判定 〇 〇 〇 〇 〇 〇 X X X 〇 (Μ曲) 硬化時的翹曲變化 量(度） -0.08 -0.09 -0.08 -0.06 -0.06 -0.08 -0.09 -0.15 -0.18 -0. 36 翹曲判定 〇 〇 〇 〇 〇 〇 〇 X X X (耐久性微麵曲） 耐夂性雜後的翹 曲變化量(度） -0.45 -0.49 -0.34 -0.29 -0.27 -0.41 -0.50 -0.66 -0.82 -1.21 翹曲判定 〇 〇 〇 〇 〇 〇 X X X X 表1中的略稱所示之各成分如下所述。 ISA :丙烯酸異十八烷酯，新中村化學工業公司製 ICA :丙烯酸異十六烷酯，共榮社化學股份有限公司 IDA:丙烯酸異癸酯，共榮社化學股份有限公司製 SA:丙烯酸十八烷酯，日油股份有限公司製 28 322209 201111432 CA :丙稀酸十六烧醋，日油股份有限公司製 - IBA :丙烯酸異莰酯，大阪有機化學工業股份有限公 司製 - R-604 :經羥基三曱基乙醛改質之三羥甲基丙烷二丙 - 烯酸酯，日本化藥股份有限公司製 R-684:二丙烯酸三環癸烷二羥甲酯，日本化藥股份 有限公司製 NPG-2P :經環氧丙烷改質之新戊二醇二丙烯酸酯，第 一工業製藥股份有限公司製 FA-512A:丙烯酸二環戊基氧基乙酯，日立化成股份 有限公司製 THE-330 :經羥基三曱基乙醛改質之三羥曱基丙烷丙 烯酸酯，日本化藥股份有限公司製 RP-1040 :經季戊四醇環氧乙烷改質之四丙烯酸酯， 日本化藥股份有限公司製 DPHA :二季戊四醇六丙烯酸酯，日本化藥股份有限公 司製 UX-5000 : 6官能胺酯丙烯酸酯，日本化藥股份有限公 司製Example 1 Example 2 Example 3 Example 4 Example 5 Example. Example 6 tm Example 1 tbfe Example 2 fcbfe Example 3 fcbfe Example 4 Component (A) (part) ISA 16 16 ICA 16 IDA 16 SA 16 CA 16 Composition (B) (Parts) IBA 39 R-604 79 63 40 40 40 63 79 79 79 79 R-684 39 NPG-2P 39 FA-512A 16 ΊΉΕ-330 16 RP-1040 16 DPHA 16 Composition (0 (parts) UX -5000 16 Cl 16 Ingredient (D) (parts) Irgacure 184D 5 5 5 5 5 5 5 5 5 5 (peelability) Peel strength (kgf) 0.9 0.8 0.7 1.3 1.2 0.7 2.0 2.6 2.4 1.3 Peelability determination〇〇〇〇 〇〇XXX 〇(Μ曲) The amount of warpage change during hardening (degrees) -0.08 -0.09 -0.08 -0.06 -0.06 -0.08 -0.09 -0.15 -0.18 -0. 36 Warpage determination〇〇〇〇〇〇〇 XXX (durability micro-curve) The amount of warpage change after the resistance to enthalpy (degrees) -0.45 -0.49 -0.34 -0.29 -0.27 -0.41 -0.50 -0.66 -0.82 -1.21 Warpage 〇〇〇〇〇〇XXXX The components shown in the abbreviated form in Table 1 are as follows. ISA: isooctadecanoacrylate, ICA manufactured by Shin-Nakamura Chemical Co., Ltd.: isohexadecyl acrylate, Kyoeisha Chemical Co., Ltd. IDA: Isodecyl acrylate, manufactured by Kyoeisha Chemical Co., Ltd. SA: Octadecyl acrylate, manufactured by Nippon Oil Co., Ltd. 28 322209 201111432 CA: Acetate 16 vinegar, Nippon Oil Co., Ltd. Company-IBA: Isodecyl acrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd. - R-604: Trimethylolpropane dipropenyl ester modified with hydroxytrimercaptoacetaldehyde, limited by Nippon Chemical Co., Ltd. Company R-684: Tricyclodecane dihydroxymethyl acrylate, NPG-2P manufactured by Nippon Kayaku Co., Ltd.: neopentyl glycol diacrylate modified by propylene oxide, First Industrial Pharmaceutical Co., Ltd. FA-512A: Dicyclopentyloxyethyl acrylate, THE-330, manufactured by Hitachi Chemical Co., Ltd.: Trihydroxydecylpropane acrylate modified by hydroxytrimercaptoacetaldehyde, manufactured by Nippon Kayaku Co., Ltd. RP-1040: pentaerythritol ring Oxygen ethane modified tetraacrylate, manufactured by Nippon Kayaku Co., Ltd. DPHA: dipentaerythritol hexaacrylate, manufactured by Nippon Chemical Co., Ltd. UX-5000: 6-functional amine ester acrylate, manufactured by Nippon Chemical Co., Ltd.
IrgacureRTM184 : 1-經基環己基苯基酮，Ciba Specialty Chemicals股份有限公司製 C1 :以莫耳比1 : 2使異佛爾酮二異氰酸酯與丙烯酸 羥乙酯進行反應所得之胺酯丙烯酸酯 (評估用樣本之製作） a 29 322209 201111432 使用所得之紫外線硬化型樹脂組成物，藉由下列1至 3的方法來製作出評估用樣本碟片。 1. 於以不使氣泡進入形成有作為記錄層之偶氮系色 素層、反射膜層、作為電介質層之ZnS· Si〇2層之直徑 120mm/0. 6mm厚的聚碳酸酯製基板（第1基板）内周上之方 式所製作之透明樹脂上載置聚碳酸酯製壓模，在2000rpm 下進行4秒的旋轉塗佈並予以貼合。 2. 從聚碳酸酯製壓模側，以400mJ/cm2照射高壓水銀 燈（80W/cm)，使第2紫外線硬化型樹脂組成物硬化。 3. 使用碟>1剝離裝置（Origin電機股份有限公司製）， 將該聚碳酸酯製壓模（透明樹脂壓模）剝離，製作出評估用 樣本碟片。 (a )剝離性試驗 使用碟片剝離裝置（Origin電機股份有限公司製），並 藉由量測器（FGC-5B，Nidec-Shimpo(股）公司製）測定出上 述評估用樣本碟片（直徑120mm :半徑60mm)製作時之從聚 碳酸酯製壓模的剝離強度來進行。 剝離良好性的判斷係以下列基準進行。 〇· · ·剝離強度1. 5kgf以下 X· · ·剝離強度1.5kgf以上 (b )魅曲試驗 樹脂層的翹曲數值，係藉由旋轉塗佈機，以使膜厚於 硬化後成為l〇±3/zm之方式，將各樹脂組成物塗佈於形成 有作為記錄層之偶氮系色素層、反射膜層、作為電介質層 30 322209 201111432 之ZnS.Si〇2層之直徑12〇，/0.6職厚的聚碳酸醋製基板 •(第1基板）内周上，並使用光碟的機械特性裝置之 (Dr. schenk公司製）來測定。由於趣曲值隨著愈往外周愈 •大，所以似接近最外狀距巾心為56mm - (角度）來進行評估。 初期翹曲係藉由下列（數學式丨）來計算出。 (數學式1)硬化時之翹曲變化量（度^紫外線硬化型 樹脂組成物之塗佈硬化後的碟片翹曲（度）_紫外線硬化型 樹脂組成物之塗佈前的碟片翹曲（度），翹曲單位以度來表 示。 〇..·硬化時之翹曲變化量未達±〇.丨度 X...硬化時之翹曲變化量為±0.丨度以上 (C)耐久性試驗 耐久性試驗，係將翹曲試驗的工序中所製作之樣本碟 片，在80°C、.85%的高溫多濕條件下放置96小時，然後在 室溫下保存24小時後，將所得之翹曲角度與試驗前（放置 於高溫多濕下之前）之翹曲角度比較，計算出該翹曲角度的 變化量。由於翹曲值隨著愈往外周愈大，所以係以接近最 外周之距離碟片中心為56min的翹曲值來進行評估。此外， 測定係使用光碟的機械特性裝置之MT_146(；Dr. schenk公 司製）。 而寸久性試驗後的起曲與初期翹曲之變化量（度），係藉 由下列（數學式2)來計算出。 (數子式2)耐久性式驗後的龜曲變化量=财久性試驗 31 322209 201111432 後的碟片翹曲（度）-試驗前的碟片翹曲（度）。 〇.··耐久性試驗後的輕曲變化量未達±0.5度 X. ··耐久性試驗後的翹曲變化量為±0.5度以上 從表1中可得知’本發明之紫外線硬化型樹脂組成物 及其硬化物之實施例1至6,與未使用具有脂肪鏈之（曱基） 丙烯酸酯之比較例1至4相比，即使放置在高溫多濕下後 (耐久性試驗後），翹曲變化量亦較少。此外，在使用複數 個多官能丙烯酸酯單體之比較例2及比較例3中，剝離強 度較強，所以剝離性惡化，比較例4中’雖然剝離性良好， 但如上述般，耐久性試驗後的翹曲變化量大，並且如下列 所述般，硬化時之翹曲亦大。 亦即，當觀察硬化時之翹曲變化量時，本發明之紫外 線硬化型樹脂組成物中，為0. 08至〇. 09度之極小的值。 比較例1，雖然硬化時之翹曲變化量為同等，但從樹脂壓 模之剝離性差，並且耐久性試驗後的翹曲變化量亦大。比 較例2、比較例3及比較例4中，硬化時之翹曲變化量為 〇· 15至〇· 36度之較大值。 此外，當觀察本發明之紫外線硬化型樹脂組成物的黏 度時，黏度位於30至50〇rapa· s之範圍内，為適合於樹脂 層形成之黏度。再者’硬化物的光穿透率超過9〇%，就光 的穿透度之觀點來看亦較佳。 、從以上内容中可得知，本發明之紫外線硬化型樹脂組 ，物’乃適合於將具有以壓模，尤其是以聚碳酸醋壓模所 衣作之具有凹凸圖案之透明樹脂層（中間樹脂層）直接形成 322209 32 201111432 於碟片基板上的反射層或電介質層上，並且對於將記錄層 或反射膜層均一地形成於該凹凸圖案上者而言是極為有用 之樹脂組成物。 ·(產業上之可利用性） ^ 本發明之紫外線硬化型樹脂組成物及其硬化物，係有 用於作為2P劑，該2P劑係從樹脂壓模之剝離性佳，且於 硬化時以及將多層碟片放置在高溫多濕下後的翹曲變化量 小。此外，可提供一種能夠省略接著層而以單液來形成中 間樹脂層之紫外線硬化型樹脂。 【圖式簡單說明】 無 【主要元件符號說明】 無 33 322209IrgacureRTM184: 1-Phenylcyclohexyl phenyl ketone, C1 manufactured by Ciba Specialty Chemicals Co., Ltd.: Amino ester acrylate obtained by reacting isophorone diisocyanate with hydroxyethyl acrylate at a molar ratio of 1:2 (Evaluation) Manufactured by the sample) a 29 322209 201111432 Using the obtained ultraviolet curable resin composition, the sample disc for evaluation was produced by the following methods 1 to 3. 1. A polycarbonate substrate having a diameter of 120 mm/0. 6 mm thick, which does not allow air bubbles to enter the azo dye layer, the reflective film layer, and the ZnS·Si 2 layer as a dielectric layer. The polycarbonate resin was placed on the transparent resin produced on the inner circumference of the substrate, and was subjected to spin coating at 2000 rpm for 4 seconds and bonded. 2. A high-pressure mercury lamp (80 W/cm) was irradiated from the polycarbonate mold side at 400 mJ/cm2 to cure the second ultraviolet curable resin composition. 3. Using a disc > 1 peeling device (manufactured by Origin Electric Co., Ltd.), the polycarbonate stamper (transparent resin stamper) was peeled off to prepare a sample disc for evaluation. (a) The peeling test was carried out using a disc peeling apparatus (manufactured by Origin Electric Co., Ltd.), and the above-mentioned sample disc for evaluation (diameter) was measured by a measuring instrument (FGC-5B, manufactured by Nidec-Shimpo Co., Ltd.). 120 mm: radius 60 mm) The peel strength of the polycarbonate stamper was produced at the time of production. The judgment of the goodness of peeling was performed on the following basis. 〇 · · · Peeling strength 1. 5kgf or less X· · Peeling strength 1.5kgf or more (b) The warpage value of the distiller's test resin layer is obtained by a spin coater so that the film thickness becomes hard after being hardened. In a manner of ±3/zm, each resin composition is applied to an azo-based dye layer, a reflective film layer as a recording layer, and a ZnS.Si〇2 layer as a dielectric layer 30 322209 201111432, 12 直径, / On the inner circumference of the 0.6-thick polycarbonate substrate (the first substrate), it was measured using a mechanical property device (manufactured by Dr. Schonk). Since the value of the fun is more and more large as it goes to the outer periphery, it is estimated that the outermost distance is 56 mm - (angle). The initial warpage is calculated by the following (mathematical formula). (Formula 1) The amount of warpage change at the time of hardening (degrees of disc warpage after application hardening of the ultraviolet curable resin composition (degree) _ disc warpage before application of the ultraviolet curable resin composition (degrees), the warpage unit is expressed in degrees. 〇..·The amount of warpage change during hardening is less than ±〇.丨X... The amount of warpage change during hardening is ±0. Durability test Durability test is a sample disc prepared in the warping test process, placed at 80 ° C, .85% high temperature and humidity for 96 hours, and then stored at room temperature for 24 hours. The warp angle obtained is compared with the warpage angle before the test (before being placed under high temperature and high humidity), and the amount of change in the warp angle is calculated. Since the warp value increases with the outer circumference, it is The value of the warp value at the center of the disc was 56 min, which was close to the outermost circumference. The measurement was performed using MT_146 (manufactured by Dr. Schenck), which is a mechanical characteristic device of the optical disc. The amount of change in warpage (degrees) is calculated by the following (Formula 2). Formula 2) Tortoise change after durability test = Long-term test 31 322209 Disc warpage (degrees) after 201111432 - Disc warpage (degrees) before test 〇.··After durability test The change amount of the light curve is less than ±0.5 degrees X. The amount of warpage change after the durability test is ±0.5 degrees or more. It can be seen from Table 1 that the ultraviolet curable resin composition of the present invention and the cured product thereof are In Examples 1 to 6, compared with Comparative Examples 1 to 4 in which the aliphatic chain-containing (fluorenyl) acrylate was not used, the amount of warpage change was small even after being placed under high temperature and high humidity (after the durability test). Further, in Comparative Example 2 and Comparative Example 3 in which a plurality of polyfunctional acrylate monomers were used, the peeling strength was strong, and the peeling property was deteriorated. In Comparative Example 4, although the peeling property was good, the durability was as described above. The amount of warpage change after the test is large, and the warpage at the time of hardening is also large as described below. That is, when the amount of warpage change at the time of hardening is observed, the ultraviolet curable resin composition of the present invention is 0. 08 to 〇. The minimum value of 09 degrees. Comparative example 1, although the hardening The amount of change in curvature was the same, but the peeling property from the resin stamper was poor, and the amount of warpage change after the durability test was also large. In Comparative Example 2, Comparative Example 3, and Comparative Example 4, the amount of warpage change at the time of curing was 〇. Further, when the viscosity of the ultraviolet curable resin composition of the present invention is observed, the viscosity is in the range of 30 to 50 〇 rapa·s, which is a viscosity suitable for the formation of the resin layer. Further, the light transmittance of the cured product exceeds 9% by weight, and is also preferable from the viewpoint of light transmittance. From the above, it can be seen that the ultraviolet curable resin group of the present invention, It is suitable for directly forming a transparent resin layer (intermediate resin layer) having a concave-convex pattern by a stamper, especially a polycarbonate stamper, on a reflective layer or a dielectric layer on a disc substrate. And a resin composition which is extremely useful for forming a recording layer or a reflective film layer uniformly on the uneven pattern. (Industrial Applicability) ^ The ultraviolet curable resin composition of the present invention and the cured product thereof are used as a 2P agent, which is excellent in peelability from a resin stamper, and is hardened and The amount of warpage change of the multilayer disc after being placed under high temperature and high humidity is small. Further, it is possible to provide an ultraviolet curable resin which can form an intermediate resin layer in a single liquid by omitting the adhesive layer. [Simple diagram description] None [Main component symbol description] None 33 322209