TW201022304A - Curable resin composition for optical disk, and optical disk - Google Patents

Abstract

Disclosed is a curable resin composition for an optical disk, which is highly transparent, can achieve recording/reproduction with high reliability, and has excellent long-term storage stability (which has excellent low-warpage properties in a storage test under a high-temperature environment or a low-temperature environment, has low film-remaining properties under a high-temperature environment, and rarely causes permanent deformation such as dents). Also disclosed is an optical disk in which the curable resin composition is used as a protective layer. The curable resin composition is intended to be used in an optical disk comprising a base material, a reflective film that is arranged on the base material and can reflect a laser beam for information reading, and a protective layer that is arranged on the reflective film and has a thicknes s of 20 to 150 μm inclusive. The curable resin composition comprises an oligomer and/or a polymer each having a radical-polymerizable group, an adduct-containing polyfunctional (meth)acrylic acid ester, and a photopolymerization initiator. The curable resin composition meets a requirement represented by the formula 6.6 ≤A÷B≤35 [Wherein A represents the equivalent amount (g/eq) of a radical-polymerizable unsaturated group in the curable resin composition and B represents the content (mass%) of the adduct-containing polyfunctional (meth)acrylic acid ester in the curable resin composition].

Description

201022304 四、 指定代表圖： (一） 本案指定代表圖為：第（1)圖》 (二） 本代表圖之元件符號簡單說明：無。 五、 本案若有化學式時，請揭示最能顯示發明特徵的化學 無。 工. 六'發明說明： 【發明所屬之技術領域】 本發明係關於光碟用硬化性樹脂組成物及光碟。 【先前技術】 近年來，開始高畫質的數位高畫質（digital hi — vision)廣播，使得對應於全高畫質之高晝質 乃Α八置囱之液 晶或電漿電視開始普及起來。但以往的光記錄媒體 DVD(digital versatile disc)的記錄容量小，因此無法長 時間將高品質之動態影像錄像。為對應於此，以具有dvd 5 倍以上之記錄容量的新穎光記錄媒體之規格而言，以藍色 雷射光將資訊記錄、再生之藍光碟片（Blue〜rayDisc)(註 冊商標）已開發並開始販賣。 此新規格中，為了光記錄媒體大容量化，採用波長 405nm之藍色雷射光。而且，將記錄、再生光學系統的物 鏡之開口數（NA)增大到0.85,記錄、再生時之雷射光束點 徑縮小至約DVD之約〇. 44倍，及使記錄訊號之軌道間距（間 201022304 隔）窄至約〇· 43倍，以達成5倍以上的大記錄容量化。 ❹ 再說明一個為大容量化而採用的技術。光記錄媒體 中，從雷射入射側觀察到的碟片表面上具有保護層以保護 反射膜或記錄層。該保護層之厚度（碟片表面與訊號之記錄 面2的距離），於DVD約6〇〇#m，但藍光碟片為約1〇〇#瓜， 相田地薄如此，藍光碟片藉由使保護層之厚度變薄，可 抑制由於碟片龜曲等造成碟片表面傾斜而產生之雷射光束 點的失焦’能達成高可靠性的記錄、再生。 曰本特開2006 — 351 1 02號公報中，記載保護層（光穿 透膜)之厚度不均，由於對於資訊記錄、再生造成大問題， 因此保護層之厚度要求高均勻性。日本特開2007 - 1 15356 號公報中，記載保護層（透明覆蓋層）之厚度需控制 l〇〇#m±2㈣。日本特開2_— 126518號公報，因為光呓 錄媒體之凹陷等損害（永久性變形）的原因可能使雷射點位 :變動j在資訊之記錄、再生造成問題。從長期穩定進行 貝訊之》己錄 '再生之觀點’希望於光記錄媒體保存時，保 護層厚度的變化小。曰本特開2000- 322768號公報中，記 載防止保護層（光穿透層）產生損害或變形，使記錄再生不 產生妨礙之技術。測定變形量之方法，採用一面推入微小 的鑽石壓件，一面測定變形中之負荷及變位之方法。 132州^特開謂2 — 157782號公報或日本特開2003 — 132596號公報中，記載於 # 向濕環境下或低溫環境下 置發生妨2 §己錄媒體發生翹曲，則會對於裝填到驅動裝 置發生妨害，或者料隨扭轉（twis〇產生_，會發生讀 3 201022304 取錯誤，因此，對於於各種環境下發生翹曲少的光記錄媒 體有需求。 保護層之形成方法，主要可列舉2種方法。有將聚碳 酸酯製之片材以紫外線硬化型之接著劑貼合之片材接著 法，及將紫外線硬化型樹脂以旋塗法塗布，並照射紫外線 使樹脂硬化之旋塗法。現在從成本面之觀點，以旋塗法為 主流。但是，若使用紫外線硬化型樹脂形成保護層，則除 了要求上述膜厚均勻性，尚會發生主要因為紫外線硬化型 樹脂之硬化收縮而於光記錄媒體發生翹曲之問題。因此， 有時會在與紫外線硬化型樹脂之硬化收縮產生翹曲之相反 方向，預先使記錄媒體基板翹曲而進行紫外線硬化型樹脂 塗布、硬化之方法之情形，或於再生記錄裝置進行修正等 情形。但是，若翹曲超過容許範圍（可修正範圍），會有無 法對光記錄媒體正確記錄或再生資料之情形，或無法進出 再生記錄裝置之情形。又，該翹曲不僅要求起始之翹曲小， 於確認長期安定性之試驗時（於高溫環境下或低溫環境下 之保存試驗），亦要求翹曲不增加（翹曲變化量小）。 又，日本特開2003- 263780號公報中，記載為了成為 具有透明性、耐磨性、機械特性優異之保護層（光穿透層） 之光碟’ |望保護層之拉伸彈性率在特定範圍。日本特開 2007- 213744號公報中，記載經過紫外線照射得 塗膜對於環境變化之尺寸安定性優異的光記錄媒體。然 而於反射膜上具有保護層（光穿透層）之光碟（例如，以藍 光雷射進行資訊讀取之藍光碟片），》了長期保存安定性 201022304 -(於高溫環境下或低溫環境下之保存㈣中之低赵曲性、高 概環境下之殘膜性）’或推入保護層後之凹陷造成永久變形 量減小’需要進一步改良之探討。 另一方面，關於保護層亦有人進行各種探討。例如於 日本特開2006 — 4458號公報及日本特開2〇〇3_ 26378〇號 公報中，關於光碟保護層，記載為了成為具有透明性、機 械特性優異之保護層（光穿透層）之光碟，希望保護層之拉 〇伸彈性率為特定範圍。日本特開2007— 1 02980號公報中， 為了抑制光碟發生翹曲（以紫外線硬化形成保護層時及光 碟之尚溫高濕試驗時），使保護層之膜厚與保護層於3〇艺 之彈性率之積為特定值以了。但是，&amp;彈性率低之保護層 上形成硬質之硬塗層時，由於使用條件，有時硬塗層會產 生裂痕（crack)，造成問題。 如此，在反射膜上具有保護層（光穿透過層）之光碟（例 如，利用藍光雷射讀取資訊之藍光碟片）中，當保護層由實 鲁質不含有機溶劑之低黏度樹脂組成物所形成，彈性率低 時，為了防止光碟變形或從硬塗層上推入後之凹陷或裂 痕’必需探討硬塗材之進一步改良。 【發明内容】 於上述狀況下’本發明待解決之問題，係提供一種光 碟用硬化性樹脂組成物，及以該硬化性樹脂組成物之硬化 物作為保護層使用之光碟，該光碟（例如，於波長4〇〇#m 附近之藍色光進行資訊讀取之藍光碟片）具有：反射膜，使 5 201022304 資訊讀取用之雷射光於基板上反射；及前述反射膜上厚度 2M 的保護層（透明覆蓋層），透明性高且能達成 可靠性高之記錄、再生’長期保存安定性(於高溫環境下或 低溫環境下之保存試驗中之低翹曲性、高溫環境下之殘膜 性）優異’凹陷等永久變形量小。 本案發明人等經過努力探討之結果，發現於光碟用硬 :性樹脂性組成物’藉由將使用之自由基聚合性不飽和基 當量與特定之（甲基）丙烯酸酯類之含量設定在特定範圍， 可得到透明性兩、長期保存安定性（於高溫環境下或低溫環 境下之保存試驗中的低翹曲性、高溫環境下之殘膜性）優 異，將保護層推入後之凹陷等永久變形量小的光碟，乃完 成本發明。又，若調整組成物使得硬化性樹脂組成物中之 自由基聚合性不飽和當量與特定之（甲基）丙烯酸酯類之關 係在某個範圍，則即使將硬化性樹脂組成物硬化得到之硬 化物之彈性率高或低之情形，均為推入保護膜後之產生之 凹陷所造成永久變形量極小，適用在光碟。 即’本發明之光碟硬化性樹脂性組成物，為了解決上 述課題’為包含：反射膜’存在於基體上，且使資訊讀取 用之雷射光反射；及保護層，存在於前述反射膜上且厚度 為20#m以上i50//m以下之光碟中所使用之硬化性樹脂性 組成物’含有：選自於具有氨酯（甲基）丙烯酸酯、環氧（甲 基）丙烯酸酯及聚酯（曱基）丙烯酸酯所構成族群中至少1 種自由基聚合性基之寡聚物及/或聚合物；及含有環氧烧煙 (alkylene 〇又丨(16)加成物之多官能（甲基）丙烯酸酯類或含 201022304 _ 有己内酯加成物之多官能（甲基）丙烯酸酯類，及光聚合開 始劑，該硬化性樹脂組成物中之自由基聚合性不飽和基當 量（g/eq)為A，前述硬化性樹脂組成物中之含環氧烷煙加 成物之多官能（甲基）丙烯酸酸酯類含有己内酯加成物之多 官能（甲基）丙烯酸酯類之含量（質量％)為B時，滿足 6. 6SA+BS 35。 即，因應導入軟質成分得到的含加成物之（甲基）丙歸 酸酸酯類之含量（B)’調整能形成交聯構造之自由基聚合性 ❿ 不飽和基當量（A)’且使A+B於上述範圍内，藉此硬化物具 所望硬度，且抑制永久變形量、翹曲，且能使長期保存安 定性提高。 前述含有環氧烷烴加成物之多官能（甲基）丙烯酸酸酿 類，以雙酚A之環氧烷烴加成物之二丙烯酸酯較佳。 本發明之硬化性樹脂組成物，於25 °C之黏度為 800mPa · s以上3500mPa · s以下為佳。 ❹ 前述硬化性樹脂組成物硬化得到之硬化物，於25¾之 貯藏彈性率E’宜為lOMPa以上150MPa以下。又，將硬化 性樹脂組成物硬化得到之硬化物於25°C之貯藏彈性率e， 以1200MPa以上2100MPa以下亦為較佳態樣。又，將前述 硬化性樹脂組成物硬化得到之硬化物之厚度100# m時，各 波長之光線穿過率，於（X)4〇〇nm為85.0%以上，（γ)38〇ηιη 為35. 0%以上85. 0%以下，且於（Z)於360nm，為〇. 1%以上 50%以下為宜。又，前述硬化性樹脂組成物，宜含有多官能 (甲基）丙烯酸醋及/或多分支型反應性化合物。 7 201022304 本發明之光碟，特徵在於具有使 之上述光碟用硬化性樹 脂性組成物硬化而成之保護層。前述光碟宜具有之硬塗 層，係將含有直接形成於前述保護層上之多分支型反應性 化合物及/或侧鏈具反應性基之聚合物及聚合起始劑之硬 塗用樹脂組成物予以硬化得到。前述多分支型反應性化合 物宜為末端具2個以上反應性基之樹枝狀聚合物 (dendrimer)及/或高度分支聚合物。又，前述光碟較佳具 有硬塗層，該硬塗層係得自硬化硬塗用樹脂組成物，該硬 塗用樹脂組成物直接形成於前述保護層上，包含從4元以 上多元醇的每1元的加成重複單位為n=1或2之環氧烷烴 加成物所得的含環氧烷烴加成物之多官能（甲基）丙烯酸酯 類及/或從4元以上之多元醇之每丨元的加成重複單位為 n=l或2之己内酯加成物所得的含己内酯加成物之多官能 (甲基）丙烯酸酯類及光聚合起始劑。 【實施方式】 &lt;&lt;光碟用硬化性樹脂組成物&gt;&gt; 本發明之光碟用硬化性樹脂組成物，係包含存在於基 體上且使資訊讀取用之雷射光反射的反射膜，及存在於前 述反射膜上且厚度20/ζιη以上150#m以下之保護層之光碟 所使用之硬化性樹脂組成物，包含：具有選自於胺酯（甲基） 丙稀酸酯、環氧（甲基）丙烯酸酯及聚酯（甲基）丙烯酸酯所 構成族群中至少1種自由基聚合性基之寡聚物及/或聚合 物；含有環氧烷烴加成物之多官能（甲基）丙烯酸酯類或含 201022304 • 有己内酯加成物之多官能（甲基）丙烯酸酯類；及光聚合起 始劑，當則述硬化性樹脂組成物中之自由基聚合性不飽和 基當量（g/eq)為A ’前篇硬化性樹脂組成物中之含有環氧 烧烴加成物之多官能（甲基）丙烯酸酸酯類及含有己内酯加 成物之多官能（甲基）丙烯酸酯類之含量（質量％)為B時，滿 足 6. 6S A+B客 35。 以下說明構成本發明之光碟用硬化性柑脂組成物（以 ❸ 下有時單純稱為「硬化性樹脂組成物」）之各成份。 〈含有環氧烷烴加成物之多官能（甲基）丙烯酸酯類及/或含 有己内酯加成物之多官能（曱基）丙烯酸酯類〉 本發明之硬化性樹脂組成物，包含：含有環氧烷烴加 成物之多官能（甲基）丙稀酸酯類及/或含有己内酯加成物 之多官能（甲基）丙烯酸酯類（以下，有時單純稱為「含有加 成物之（甲基）丙烯酸酯類」）。該含有加成物之（甲基）丙烯 酸酯類’係分子中含有環氧烷烴骨架或己内酯之開環物， φ 且藉由與（甲基）丙烯酸酯之酯化得到之（甲基）丙烯酸酯 類。藉由含有該等含有加成物之（甲基）丙烯酸酯類，能調 整液體黏度或硬化物之物性。 含有環氧烷烴加成物之多官能（甲基）丙烯酸酯類，例 如：雙酚A之環氧乙烷加成物之二（甲基）丙烯酸酯、雙酚 A之環氧丙烷加成物之二（甲基）丙烯酸酯、環己二甲醇之 環氧乙烷加成物之二（甲基）丙烯酸酯、環己二甲醇之環氧 丙烷加成物之二（甲基）丙烯酸酯、新戊二醇之環氧乙烷加 成物之二（甲基）丙烯酸酯、新戊二醇之環氧丙烷加成物之 9 201022304 二（曱基）丙烯酸酯、己二醇之環氧乙烷加成物之二（甲基） 丙烯酸酯、己二醇之環氧丙烷加成物之二（甲基）丙烯酸 si、三羥甲基丙烷之環氧乙烷加成物之三（曱基）丙烯酸 醋、三羥甲基丙烷之環氧丙烷加成物之三（甲基）丙烯酸 醋、甘油之環氧乙烷加成物之三（甲基）丙烯酸酯、甘油之 環氧丙烷加成物之三（甲基）丙烯酸酯、環氧烷烴變性羥基 三甲基乙酸新戊二醇酯二（曱基）丙烯酸酯、二乙二醇二（甲 基）丙烯酸酯等前述多元醇之環氧烷烴加成物之多官能（甲 基）丙烯酸酯類；丙烯酸2—(2 —乙烯氧基乙氧基）乙酯、（丙 稀酸2 — (2 —乙烯氧基乙氧基）乙酯之陽離子聚合物等。 該等含有環氧烷烴加成物之多官能（甲基）丙烯酸酯類 中之環氧烷烴骨架之重複數，以4以上16以下為佳，6以 上14以下更佳。 含有己内酯加成物之多官能（甲基）丙烯酸酯類，例如 經基三甲基乙酸新戊二醇等ε —己内酯加成物之二丙烯酸 ^、己内酯變性六（甲基）丙稀酸二季戊四酯等。 又’本發明中，含有加成物之多官能（甲基）丙烯酸酯 類’可具有含有加成了環氧烷烴及己内酯兩者之加成物的 多官能（甲基）丙烯酸酯。 該等之中’含有加成物之多官能（甲基）丙烯酸酯類， 宜為雙酚Α之環氧乙烷加成物之二（甲基）丙烯酸酯、三羥 甲基丙院之環氧乙烷加成物之三（甲基）丙烯酸酯、羥基三 甲基乙酸新戊二醇之ε —己内酯加成物之二丙稀酸酯。該 等之中’尤其宜為雙酚Α之環氧乙烷10莫耳加成物之二（甲 10 201022304 _ 基）丙烯酸酯。 前述含有加成物之多官能（甲基）丙烯酸酯類之調配 量，宜為硬化性樹脂組成物中8質量％以上，更佳為2〇質 量％以上，又更佳為30質量％，70質量％以下，再更佳為65 質量％以下，又再更佳為60質量％以下。前述調配量若不滿 8質量％，推入保護層有時會有凹陷，若超過7〇質量％，有 時硬化收縮率或内部應變增大，有時例如光碟翘曲會增大 • 或者保護層會產生裂隙或破裂。 〈具有自由基聚合性不飽和基之化合物〉 本發明之硬化性樹脂組成物，除了前述含有環氧燒煙 加成物之夕gfb (甲基）丙稀酸醋及/或含有己内醋加成物 之多官能（甲基）丙烯酸酯類以外，可含有具自由基聚合性 不飽和基之材料。 前述具自由基聚合性不飽和基之材料，例如： 丨、 丹有至 &gt; 1個以上自由基聚合性基之寡聚物及/或聚合物；多分支 ♦型反應性化合物；聚合性單體。具有自由基聚合性不飽和 2之化合物’能由於熱、紫外線、電子束、伽瑪線等活性 能量射線而硬化。 前述具自由基聚合性不飽和基之寡聚物及/或聚人 物，例如：飽和或不飽和之多元酸或其酸酐（例如：馬來酸、 琥拍酸、己一酸、鄰苯二曱睃、間苯二甲酸、對笨二甲暖 四氫鄰苯二甲酸等），及飽和或不飽和之多元醇(例如.乙 t醇、丙二醇、新戊二醇、U—丁二醇、h 6—已二醇、乙3 甲基―1，5 —戊二醇、聚乙二醇、聚丙二醇' 1，4— _ 11 201022304 甲基苯、三經甲基丙烧、季戊四醇等），及與（甲基）丙稀酸 反應得到之聚醋（甲基）丙烯酸醋；飽和或不飽和之多元醇 (例如：乙二醇、新戊二醇、聚四甲二醇、聚醋多元醇、聚 己内酯多元醇等），及有機聚異氰酸酯（例如：甲苯撐二異 氰酸酯、異佛爾酮二異氰酸酯、二甲苯撐二異氰酸酯等）， 及與含有羥基之（甲基）丙烯酸酯（例如：2一羥基（甲基）丙 烯酸乙酯、2 —羥基（甲基）丙烯酸丙酯、14—丁二醇單（甲 基）丙烯酸酯等）之反應得到之胺酯（甲基）丙烯酸酯；聚矽 氧烷與（甲基）丙烯酸反應得到之聚矽氧烷聚（甲基）丙烯酸 〇 酯；樹枝狀聚合物、高度分支聚合物等多分支型反應性（甲 基）丙烯酸酯化合物等。 同時具有自由基聚合性基及離子聚合性基之募聚物及 /或聚合物’例如：環氧樹脂（例如：苯酚酚醛環氧樹脂、 甲苯盼紛路環氧樹脂、雙酚A型環氧樹脂、雙酚F型環氧 樹脂、三酚甲烷型環氧樹脂、聚丁二烯變性環氧樹脂、脂 環式環氧樹脂、溴化苯酚酚醛環氧樹脂、溴化雙酚A型環 _ 氧樹脂、含胺基之環氧樹脂等）與（曱基）丙烯酸反應得到之 環氧（曱基）丙烯酸酯；上述環氧（甲基）丙烯酸酯與多元酸 酐（例如馬來酸酐、號珀酸酐、鄰苯二甲酸酐、四氫鄰苯二 甲酸酐、六氫鄰苯二甲酸酐等）反應得到之羧酸變性環氧 (甲基）丙烯酸酯。 其中’本發明之硬化性樹脂組成物，就具有至少1個 以上自由基聚合性基之募聚物及/或聚合物而言’必需含有 選自於胺酯（甲基）丙烯酸酯、環氧（曱基）丙烯酸酯及聚酯 12 201022304 - (甲基）丙烯酸酯所構成族群中至少1種。 尤其，使用胺酯（甲基）丙烯酸酯時，構成該胺酯（甲基） 丙烯酸酯之異氰酸酯成分，宜為具有脂環骨架或芳香環骨 架之多價異氰酸酯’尤佳為具有脂環骨架之2價異氰酸 酯。具有脂環骨架之2價異氰酸酯，例如：異佛爾酮二異 氰酸醋。構成前述胺酯（甲基）丙烯酸酯之多元醇成分，宜 為具有環氧院煙骨架之多元醇，更佳為2元醇。具有環氧 φ 烷烴骨架之2元醇，例如：寡乙二醇、募丙二醇、募丁二 醇、募（乙烯一丙烯）二醇。寡乙二醇、募（乙烯—丙烯）二 醇尤佳。環氧烷烴骨架之重複數宜為4以上12以下，更佳 為6以上10以下。構成前述胺酯（甲基）丙烯酸酯之含經基 之（甲基）丙烯酸酯成分，宜為含羥基之丙烯酸酯，例如2 —羥基丙烯酸乙酯、2 —羥基丙烯酸丙酯、ι，4一丁二醇單 丙烯酸醋，其中’尤佳為2 —羥基丙烯酸乙酯。 又’胺醋（甲基）丙烯酸酯，可包含於組成中異氰酸醋 參成分與含經基之（甲基）丙稀酸酯成分直接以胺酯鍵結之胺 酯（甲基）丙烯酸酯。含有異氰酸酯成分與含羥基之（曱基） 丙烯酸醋成分直接以胺酯鍵結之胺酯（甲基）丙烯酸酯時， 較佳之異氛酸酯成分與含羥基之（曱基）丙烯酸酯成分與上 述同。 胺醋（甲基）丙烯酸酯，原料組成1 〇〇質量％中，原料異 氱酸酯成分為15質量!ιό以上30質量％以下、原料多元醇成 分為45質量％以上65質量％以下、原料含羥基之（甲基）丙 烯酸醋成分為5質量％以上40質量％以下為宜，更佳為原料 13 201022304 異氰酸醋成分為18質量％以上25質量％以下、原料多元醇 成分為50質量％以上60質量％以下、原料含羥基之（甲基） 丙稀酸酯成分為15質量!*0以上32質量％以下。 又，含有異氰酸酯成分與含羥基之（甲基）丙烯酸酯成 分直接以胺酯鍵結之胺酯（甲基）丙烯酸酯時，其含量當與 具有多元醇成为之胺S曰（甲基）丙稀酸醋之合計定為1〇〇質 量％時’宜為1質量％以上20質量％以下，尤佳為5質量；κ0 以上15質量％以下。 可作為具有自由基聚合性不飽和基之材料使用之胺醋 ® (甲基）丙烯酸酯之合成方法不特別限制，例如：依序使原 料異氱酸酯成分及原料含羥基之（甲基）丙烯酸酯反應，接 著再與多元醇成分反應之方法；將原料異氰酸醋成分、原 料含羥基之（甲基）丙烯酸酯’及多元醇成分一次加入並反 應之方法，使原料異氣酸醋成分及多元醇成分反應，接著 使含經基之（甲基）丙烯酸酯反應之方法。該等之中，藉由 使用依序使原料異氰酸酯成分及原料含有羥基之（甲基）丙 粵 稀酸醋反應，接著使多元醇成分反應之方法，也能同時合 成將上述異氰酸酯成分與含羥基之（甲基）丙烯酸酯成分直 接胺醋化之胺醋（甲基）丙浠酸醋，能提升生產性，故尤佳。 又’採用依序使原料異氰酸酯成分及原料含經基之（甲基） 丙稀酸酯反應，接著，使多元醇成分反應之方法時，亦宜 將原料含羥基之（甲基）丙烯酸酯分割為起始添加及後段添 加’於多元醇成分添加後，將一部分原料含羥基之（甲基） 丙烯酸酯分割添加。 14 201022304 -硬化性樹脂組成物中含有具自由基聚合性基之募聚物 /聚合物時，其含量宜為硬化性樹脂組成物中2〇質量％以 上，更佳為30質量％以上、80質量％以下，又更佳為質 量％以下。該等成分，可各含有1種或2種以上。合計含量 若不滿20質量％，則光碟之長期保存安定性有時會劣化， 右多於80質量％ ’則黏度提高’有時作業性降低。 光碟用硬化性樹脂組成物令含有之具自由基聚合性基 #之寡聚物/聚合物可任意選擇。使本發明之光碟用硬化性樹 脂組成物硬化得到之硬化物其彈性率欲設計為低時具有 自由基聚合性基之寡聚物/聚合物單獨之硬化物（以下有時 稱為「單獨硬化物」）之玻璃轉移溫度，宜為—1(rc以上， 更佳為一5。(：以上，宜為45。(：以下，更佳為4〇t以下。又， 單獨硬化物於25t之彈性率宜為5〇MPa以上，更佳為 以上，宜為900MPa以下，更佳為85〇MPa以下又更佳為 800MPa 以下。 又，前述單獨硬化物，以使光碟用硬化性樹脂組成物 硬化之條件為同樣條件製作。亦即，將光❹硬化性樹脂 組成物使用之光聚合開始劑，添加、混合於寡聚物/聚合物 使成為同樣添加率後，與製作保護層時之硬化條件(光照射 時間、照射高度、昭斯县 ® ric、止 …射量硬化物厚度）為相同使硬化。玻 璃點移轉溫度，係由動態黏彈性測定得到之值 值之溫^ ° ^，測定條件採用拉伸模式、頻率1Hz、 夾頭距離25mm、振幅Ql%、升溫速度代/分。前述單獨 硬化物之玻璃點移轉溫度若超過狀，則有時光碟之翹曲 15 201022304 會增大。若前述單獨硬化物之玻璃點移轉溫度不滿— 10°C，有時光碟會有凹陷或長期保存安定性變差之情形。 又，前述單獨硬化物之彈性率，係同樣使用得到之單獨硬 化物由動態黏彈性測定得到之值，為25t之貯藏彈性率 E之值。前述單獨硬化物之彈性率若不滿5〇Mpa，有時光 碟之長期保存安定性變差。尤其，若將保護層推入，有時 會凹Pa又，若前述單獨硬化物之彈性率超過90 OMPa，則 有時得到之光碟之翹曲會增大，或長期保存安定性變差。 另一方面，使本發明之光碟用硬化性樹脂組成物硬化β 得到之硬化物之彈性率設計為高時，前述單獨硬化物之玻 璃轉移溫度宜n 6(rc以下，更佳為肌 以下’又更佳| 5『c以下。又，前述單獨硬化物於饥之 彈性率宜為l〇〇MPa以上2000MPa以下，更佳為i5〇〇MPa以 下’又更佳為l〇〇〇MPa以下。 前述單獨硬化物之玻璃點移轉溫度超過6〇它時或彈性 率超過2_MPa時，有時光碟之鍾曲會增大。又，若前述@ 單獨硬化物之玻璃轉移溫度不滿3(rc，光碟有時會有凹 ^彈性率若不滿100MPa，有時光碟之長期保存安定性變 差。尤其，若推入保護層，有時會有凹陷。玻璃轉移溫度 及彈性率採用前述測定方法。 又，單獨硬化物之彈性率不特別限制，前述低彈性率、 南彈性率以外亦可採用’但，前述低彈性率為尤佳之實施 形態。 〈乙烯基系聚合體〉 16 201022304 關於將本發明之硬化性樹脂組成物硬化得到之硬化 物，於物性上需要高硬度時，宜使用具有以下述式（1)表示 之重複單位的乙烯基系聚合體。又，具有下述式（丨）表示之 重複單位之乙烯基聚合體，於式中m2 2時，為含有加成物 之多官能（甲基）丙烯酸酯類，於式中JJ^O或1時，為具自 由基聚合性基之寡聚物/聚合物。 [化1]201022304 IV. Designated representative map: (1) The representative representative of the case is: (1) Figure (2) The symbol of the symbol of the representative figure is simple: None. 5. If there is a chemical formula in this case, please disclose the chemical that best shows the characteristics of the invention. [Technical Field of the Invention] The present invention relates to a curable resin composition for an optical disk and an optical disk. [Prior Art] In recent years, high-quality digital hi-vision broadcasting has begun, and the high-quality enamel corresponding to the full-height image quality has begun to spread in the liquid crystal or plasma TV. However, the conventional optical recording medium DVD (digital versatile disc) has a small recording capacity, so that it is impossible to record high-quality motion pictures for a long time. In response to this, in the specification of a novel optical recording medium having a recording capacity of 5 times or more of dvd, a Blu-ray Disc (registered trademark) in which information is recorded and reproduced by blue laser light has been developed and registered. Start selling. In this new specification, in order to increase the capacity of the optical recording medium, blue laser light having a wavelength of 405 nm is used. Further, the number of apertures (NA) of the objective lens of the recording and reproducing optical system is increased to 0.85, and the spot diameter of the laser beam during recording and reproduction is reduced to about 44 times of the DVD, and the track pitch of the recording signal is made ( The interval between 201022304 is as narrow as about 43 times, to achieve a large recording capacity of 5 times or more. ❹ Describe a technique used for capacity expansion. In the optical recording medium, a protective layer is provided on the surface of the disc viewed from the incident side of the laser to protect the reflective film or the recording layer. The thickness of the protective layer (the distance between the surface of the disc and the recording surface 2 of the signal) is about 6 〇〇 #m on the DVD, but the Blu-ray disc is about 1 〇〇 #瓜, which is so thin as the field, the Blu-ray disc is used by By making the thickness of the protective layer thin, it is possible to suppress the defocusing of the laser beam spot caused by the inclination of the disk surface due to the tortuosity of the disk, and to achieve high reliability recording and reproduction. In JP-A-2006-351-01, the thickness of the protective layer (light-transmissive film) is uneven, and since the information recording and reproduction cause a large problem, the thickness of the protective layer is required to have high uniformity. Japanese Laid-Open Patent Publication No. 2007-1515356 discloses that the thickness of the protective layer (transparent cover layer) needs to be controlled by l〇〇#m±2 (four). Japanese Patent Laid-Open No. 2_-126518, because of the damage (permanent deformation) of the sag of the optical recording media, may cause the laser spot: the change j causes problems in the recording and reproduction of information. From the long-term stability of Beixun's "Review of Regeneration", it is hoped that the change in the thickness of the protective layer will be small when the optical recording medium is stored. In Japanese Laid-Open Patent Publication No. 2000-322768, there is a technique for preventing damage or deformation of the protective layer (light-transmitting layer) and preventing recording and reproduction from occurring. The method of measuring the amount of deformation is a method of measuring the load and displacement during deformation by pushing a small diamond compact on one side. In the case of a wet environment or a low temperature environment, the occurrence of warpage may occur in the case of the wet state or the low temperature environment. The drive device is hindered, or it is expected to be reversed (twis〇 produces _, and reading 3 201022304 takes an error. Therefore, there is a need for an optical recording medium with less warpage in various environments. The formation method of the protective layer is mainly listed Two methods include a sheet bonding method in which a polycarbonate sheet is bonded with an ultraviolet curing type adhesive, a spin coating method in which an ultraviolet curable resin is applied by a spin coating method, and ultraviolet rays are applied to harden the resin. From the viewpoint of cost, the spin coating method is the mainstream. However, if a protective layer is formed using an ultraviolet curable resin, in addition to the uniformity of the above film thickness, the curing of the ultraviolet curable resin mainly occurs. The optical recording medium has a problem of warpage. Therefore, the recording medium may be previously made in the opposite direction to the warpage of the curing shrinkage of the ultraviolet curable resin. The case where the substrate is warped and the method of applying and curing the ultraviolet curable resin is performed, or the correction is performed on the reproducing recording device. However, if the warpage exceeds the allowable range (correctable range), the optical recording medium cannot be correctly recorded. In the case of regenerative data, or in the case where it is impossible to enter or exit the regenerative recording device. Moreover, the warpage requires not only the initial warpage is small, but also the test for confirming the long-term stability (preservation test under high temperature or low temperature environment) In addition, it is also required to have a protective layer (light-transmitting layer) which is excellent in transparency, abrasion resistance, and mechanical properties, as disclosed in Japanese Laid-Open Patent Publication No. 2003-263780. The optical disk of the optical disk is excellent in the dimensional stability of the coating film which is excellent in dimensional change with respect to the environmental change by the irradiation of the ultraviolet ray. a disc with a protective layer (light transmissive layer) (for example, a Blu-ray disc that reads information with a blue laser), Stability 201022304 - (low preservation in high temperature environment or low temperature environment (4), low residual curvature in the high environment) or depression caused by pushing into the protective layer to reduce the amount of permanent deformation On the other hand, the protective layer is also discussed in various ways. For example, in the Japanese Patent Publication No. 2006-4458 and Japanese Patent Application Laid-Open No. Hei. In the optical disk of the protective layer (light-transmitting layer) having excellent transparency and mechanical properties, it is desirable that the elastic modulus of the protective layer is in a specific range. In Japanese Laid-Open Patent Publication No. 2007-01082, the warpage of the optical disk is suppressed. When the ultraviolet ray hardening forms the protective layer and when the optical disk is subjected to the temperature and high humidity test, the product of the thickness of the protective layer and the elastic modulus of the protective layer at a specific value is a specific value. However, when a hard hard coat layer is formed on the protective layer having a low modulus of elasticity, the hard coat layer may crack due to the use conditions, causing a problem. Thus, in a disc having a protective layer (light penetrating through the layer) on the reflective film (for example, a Blu-ray disc that reads information using a blue laser), when the protective layer is composed of a low-viscosity resin containing no organic solvent. When the material is formed and the modulus of elasticity is low, further improvement of the hard coating material must be investigated in order to prevent deformation or cracking of the optical disk after being deformed or pushed from the hard coating layer. [Problems to be Solved by the Invention] The above-mentioned problem to be solved by the present invention is to provide a discurable resin composition for an optical disc, and a disc using the cured product of the curable resin composition as a protective layer, for example, The Blu-ray disc for reading information of blue light near the wavelength 4〇〇#m has a reflective film for reflecting the laser light for reading 201022304 on the substrate; and a protective layer having a thickness of 2M on the reflective film. (Transparent cover layer), high transparency and high reliability record and reproduction 'long-term storage stability (low warpage in high temperature environment or low temperature environment, residual film property under high temperature environment) ) Excellent 'depression and other permanent deformation. As a result of intensive studies, the inventors of the present invention have found that the hard: resinous composition of the optical disk is set to be specific by the content of the radical polymerizable unsaturated group equivalent and the specific (meth) acrylate used. In the range, it is possible to obtain transparency, long-term storage stability (low warpage in a storage test under a high-temperature environment or a low-temperature environment, and residual film property in a high-temperature environment), and the depression of the protective layer is pushed in, etc. The optical disc having a small amount of permanent deformation is the completion of the present invention. In addition, when the composition is adjusted so that the relationship between the radical polymerizable unsaturated equivalent in the curable resin composition and the specific (meth) acrylate is within a certain range, the hardening resin composition is cured by hardening. In the case where the elastic modulus of the material is high or low, the amount of permanent deformation caused by the depression generated after being pushed into the protective film is extremely small, and is applied to the optical disc. In other words, in order to solve the above problems, the optical disk-curable resin composition of the present invention includes: a reflective film is present on the substrate, and the laser light for reading information is reflected; and a protective layer is present on the reflective film. The curable resin composition used in the optical disk having a thickness of 20 #m or more and i50//m or less contains: selected from the group consisting of urethane (meth) acrylate, epoxy (meth) acrylate, and poly An oligomer and/or a polymer of at least one radical polymerizable group in a group consisting of ester (mercapto) acrylate; and a polyfunctional (including an alkylene oxime (16) adduct) a methyl acrylate or a polyfunctional (meth) acrylate containing a 201022304 _ caprolactone adduct, and a photopolymerization initiator, a radical polymerizable unsaturated group equivalent in the curable resin composition ( g/eq) is A, a polyfunctional (meth) acrylate containing an alkylene oxide adduct in the above curable resin composition, and a polyfunctional (meth) acrylate containing a caprolactone adduct 6S when the content (% by mass) is B. A+BS 35. That is, the content (B) of the (meth)acrylic acid ester-containing adduct obtained by introducing a soft component can be adjusted to form a radically polymerizable ❿ unsaturated group equivalent of a crosslinked structure. (A)' and A+B is in the above range, whereby the cured product has a desired hardness, and the amount of permanent deformation and warpage are suppressed, and the long-term storage stability can be improved. The foregoing contains an alkylene oxide adduct. The functional (meth)acrylic acid brewing is preferably a diacrylate of an alkylene oxide adduct of bisphenol A. The curable resin composition of the present invention has a viscosity at 25 ° C of 800 mPa · s or more and 3500 mPa · Preferably, s. The cured product obtained by curing the curable resin composition has a storage modulus E' of 253⁄4 or more and is preferably 10 MPa or more and 150 MPa or less. Further, the cured product obtained by curing the curable resin composition is cured at 25 ° C. The storage elastic modulus e is preferably 1200 MPa or more and 2100 MPa or less. Further, when the thickness of the cured product obtained by curing the curable resin composition is 100 # m, the light transmittance of each wavelength is (X). ) 4〇〇nm is 85.0% or more, (γ) 38 〇ηιη is 35. 0% or more and 85. 0% or less, and (Z) is at 360 nm, preferably 1% or more and 50% or less. Further, the curable resin composition preferably contains a polyfunctional group (methyl group). Acrylic vinegar and/or multi-branched reactive compound. 7 201022304 The optical disc of the present invention is characterized in that it has a protective layer obtained by curing the curable resin composition for the optical disc, and the optical disc preferably has a hard coat layer. A hard coating resin composition containing a multi-branched reactive compound and/or a side chain reactive group directly formed on the protective layer and a polymerization initiator is obtained by curing. The above-mentioned multi-branched reactive compound is preferably a dendrimer and/or a highly branched polymer having two or more reactive groups at the terminal. Further, the optical disk preferably has a hard coat layer obtained from a resin composition for hardening hard coating, and the resin composition for hard coating is directly formed on the protective layer, and contains each of a polyol of 4 or more yuan. a monofunctional addition repeating unit of an alkylene oxide adduct of n = 1 or 2, and a polyfunctional (meth) acrylate containing an alkylene oxide adduct and/or a polyol having a molecular weight of 4 or more The addition repeat unit per unit is a polyfunctional (meth) acrylate containing a caprolactone adduct obtained from a caprolactone adduct of n = 1 or 2, and a photopolymerization initiator. [Embodiment] &lt;&lt;&gt; The curable resin composition for optical discs&gt; The curable resin composition for optical discs of the present invention includes a reflective film which is present on the substrate and reflects the laser light for information reading. And a curable resin composition used for the optical disk of the protective layer which is present on the reflective film and has a thickness of 20/μm or more and 150#m or less, comprising: having an amine ester (meth) acrylate, epoxy An oligomer and/or a polymer of at least one radical polymerizable group in a group consisting of (meth) acrylate and polyester (meth) acrylate; and a polyfunctional (methyl group) containing an alkylene oxide adduct Acrylates or polyfunctional (meth) acrylates containing 201022304 • caprolactone adducts; and photopolymerization initiators, when the radically polymerizable unsaturated group equivalents in the curable resin composition (g/eq) is a polyfunctional (meth) acrylate containing an alkylene oxide adduct and a polyfunctional (methyl group) containing a caprolactone adduct in the A's first hardenable resin composition. When the content (% by mass) of the acrylate is B Meet 6. 6S A + B off 35. The components constituting the curable citrus composition for optical discs of the present invention (hereinafter sometimes referred to simply as "curable resin composition" under the sputum) will be described. <Polyfunctional (meth) acrylate containing an alkylene oxide adduct and/or a polyfunctional (fluorenyl) acrylate containing a caprolactone adduct> The curable resin composition of the present invention comprises: A polyfunctional (meth) acrylate containing an alkylene oxide adduct and/or a polyfunctional (meth) acrylate containing a caprolactone adduct (hereinafter, simply referred to as "additional addition" The (meth) acrylates of the products"). The (meth)acrylate-based molecule containing an adduct contains an alkylene oxide skeleton or a caprolactone ring-opening material, φ and is obtained by esterification with a (meth) acrylate (methyl group). ) acrylates. The physical properties of the liquid viscosity or the cured product can be adjusted by containing the (meth) acrylate containing the adduct. A polyfunctional (meth) acrylate containing an alkylene oxide adduct, for example, a bis(meth) acrylate of an ethylene oxide adduct of bisphenol A, or a propylene oxide adduct of bisphenol A a bis(meth) acrylate of an ethylene oxide adduct of bis(meth) acrylate or cyclohexanedimethanol, or a bis(meth) acrylate of a propylene oxide adduct of cyclohexanedimethanol, Ethylene oxide adduct of neopentyl glycol, bis(meth) acrylate, neopentyl glycol propylene oxide adduct 9 201022304 bis(indenyl) acrylate, hexylene glycol epoxy B a dialkyl adduct of a di(meth)acrylate, a propylene oxide adduct of hexanediol, a di(meth)acrylic acid, a trimethylolpropane, an ethylene oxide adduct Acetic acid vinegar, trimethylolpropane propylene oxide adduct of tris(meth)acrylic acid vinegar, glycerol ethylene oxide adduct tris(meth)acrylate, glycerol propylene oxide addition Tris(meth)acrylate, alkylene oxide-modified hydroxytrimethylacetate neopentyl glycol ester bis(indenyl) acrylate a polyfunctional (meth) acrylate of an alkylene oxide adduct of the above polyol such as diethylene glycol di(meth)acrylate; 2-(2-vinyloxyethoxy)ethyl acrylate, (cationic polymer of 2-(2-vinyloxyethoxy)ethyl acrylate), etc. The alkylene oxide skeleton of the polyfunctional (meth) acrylates containing the alkylene oxide adducts The number of repetitions is preferably 4 or more and 16 or less, more preferably 6 or more and 14 or less. Polyfunctional (meth) acrylates containing a caprolactone adduct, such as ε-methyltrimethylacetate neopentyl glycol, etc. The dicaprolactone adduct of diacrylate, caprolactone denatured hexa(methyl) acrylate dipentaerythritol, etc. Further, in the present invention, a polyfunctional (meth) acrylate containing an adduct It may have a polyfunctional (meth) acrylate containing an addition product of both an alkylene oxide and a caprolactone. Among these, a polyfunctional (meth) acrylate containing an adduct is suitable. It is a di(meth) acrylate of ethylene oxide adduct of bisphenol oxime, and an epoxy of trimethylol propyl a tris(meth)acrylate of an ethane adduct, a diacrylate of an ε-caprolactone adduct of hydroxytrimethylacetic acid neopentyl glycol. Among these, 'especially bisphenol quinone The ethylene oxide 10 molar addition product (A 10 201022304 _ group) acrylate. The amount of the above-mentioned polyfunctional (meth) acrylate containing an adduct is preferably a curable resin composition. 8质量% or more, more preferably 2% by mass or more, still more preferably 30% by mass, 70% by mass or less, still more preferably 65% by mass or less, and still more preferably 60% by mass or less. When the amount is less than 8% by mass, the protective layer may be recessed. If it exceeds 7% by mass, the hardening shrinkage or the internal strain may increase. Sometimes, for example, the warpage of the disc may increase. <Compound having a radical polymerizable unsaturated group> The curable resin composition of the present invention contains gfb (meth) acrylate vinegar and/or containing hexahydrate in addition to the above-mentioned epoxy-containing smoky adduct. In addition to polyfunctional (meth) acrylates of vinegar adducts, A material having a radical polymerizable unsaturated group. The above-mentioned material having a radical polymerizable unsaturated group, for example, 丨, 丹有至&gt; one or more radical polymerizable groups of oligomers and/or polymers; multi-branched ♦ type reactive compound; polymerizable single body. The compound having radical polymerizable unsaturated 2 can be hardened by active energy rays such as heat, ultraviolet rays, electron beams, and gamma rays. The above-mentioned oligomer and/or polyradical having a radical polymerizable unsaturated group, for example, a saturated or unsaturated polybasic acid or an anhydride thereof (for example, maleic acid, succinic acid, hexanoic acid, orthophthalic acid)睃, isophthalic acid, styrene, tetrahydrophthalic acid, etc., and saturated or unsaturated polyols (eg, ethyl t, propylene glycol, neopentyl glycol, U-butylene glycol, h 6-hexanediol, ethylene-3-methyl-1,5-pentanediol, polyethylene glycol, polypropylene glycol '1,4— _ 11 201022304 methylbenzene, trimethyl methacrylate, pentaerythritol, etc.), and Poly (meth)acrylic acid vinegar obtained by reaction with (meth)acrylic acid; saturated or unsaturated polyol (for example: ethylene glycol, neopentyl glycol, polytetramethylene glycol, polyglycol polyol, a polycaprolactone polyol or the like), and an organic polyisocyanate (for example, tolylene diisocyanate, isophorone diisocyanate, xylene diisocyanate, etc.), and a hydroxyl group-containing (meth) acrylate (for example: 2-hydroxy(meth)acrylate, 2-hydroxy(meth)acrylate,14-butyl An amine ester (meth) acrylate obtained by reacting an alcohol mono(meth)acrylate or the like; a polyoxyalkylene poly(meth)acrylate obtained by reacting a polyoxyalkylene with (meth)acrylic acid; A multi-branched reactive (meth) acrylate compound such as a polymer or a highly branched polymer. A polymerizable polymer and/or a polymer having a radical polymerizable group and an ionic polymerizable group, for example, an epoxy resin (for example, a phenol novolac epoxy resin, a toluene epoxy resin, a bisphenol A epoxy resin) Resin, bisphenol F type epoxy resin, trisphenol methane type epoxy resin, polybutadiene modified epoxy resin, alicyclic epoxy resin, brominated phenol novolac epoxy resin, brominated bisphenol A type ring _ Epoxy (mercapto) acrylate obtained by reacting an oxo resin, an amine group-containing epoxy resin or the like with (mercapto)acrylic acid; the above epoxy (meth) acrylate and a polybasic acid anhydride (for example, maleic anhydride, horn A carboxylic acid denatured epoxy (meth) acrylate obtained by reacting an acid anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride or the like. The 'curable resin composition of the present invention' must have a selected from the group consisting of amine ester (meth) acrylate and epoxy in the case of a polymer and/or a polymer having at least one radical polymerizable group. (Mercapto) acrylate and polyester 12 201022304 - At least one of the groups formed by (meth) acrylate. In particular, when an amine ester (meth) acrylate is used, the isocyanate component constituting the amine ester (meth) acrylate is preferably a polyvalent isocyanate having an alicyclic skeleton or an aromatic ring skeleton, and particularly preferably has an alicyclic skeleton. Divalent isocyanate. A divalent isocyanate having an alicyclic skeleton, for example, isophorone diisocyanate. The polyol component constituting the aforementioned amine ester (meth) acrylate is preferably a polyol having an epoxy cinnamic skeleton, more preferably a dihydric alcohol. A dihydric alcohol having an epoxy φ alkane skeleton, for example, oligoethylene glycol, propylene glycol, butyl diol, and ethylene (propylene) propylene. Ethylene glycol and ethylene (propylene-propylene) diol are particularly preferred. The number of repetitions of the alkylene oxide skeleton is preferably 4 or more and 12 or less, more preferably 6 or more and 10 or less. The hydroxyl group-containing (meth) acrylate component constituting the amine ester (meth) acrylate is preferably a hydroxyl group-containing acrylate such as 2-hydroxyethyl acrylate, 2-hydroxy propyl acrylate, ι, 4 Butanediol monoacrylic acid vinegar, wherein 'more preferably is 2-hydroxyethyl acrylate. And 'amine vinegar (meth) acrylate, which may be included in the composition of the isocyanate vinegar component and the amino group-containing (meth) acrylate component directly bonded with an amine ester (meth) acrylate ester. When the isocyanate component and the hydroxyl group-containing (mercapto)acrylic acid vinegar component are directly bonded with an amine ester (meth) acrylate, the preferred isocyanate component and the hydroxyl group-containing (mercapto) acrylate component are The same as above. Amine vinegar (meth) acrylate, the raw material composition is 1% by mass, the raw material isononate component is 15 masses; ιό is 30% by mass or less, and the raw material polyol component is 45 mass% or more and 65 mass% or less; The hydroxyl group-containing (meth)acrylic acid vinegar component is preferably 5% by mass or more and 40% by mass or less, more preferably the raw material 13 201022304 isocyanate component is 18% by mass or more and 25% by mass or less, and the raw material polyol component is 50% by mass. The amount of the (meth) acrylate component having a hydroxyl group content of the raw material is 15 mass% or more and 60 mass% or less; *0 or more and 32 mass% or less. Further, when the amino ester (meth) acrylate having an isocyanate component and a hydroxyl group-containing (meth) acrylate component directly bonded with an amine ester is used, the content thereof is the same as the amine S 曰 (methyl) propyl having a polyol. When the total amount of the dilute vinegar is 1% by mass, it is preferably 1% by mass or more and 20% by mass or less, more preferably 5% by mass; and κ0 or more and 15% by mass or less. The synthesis method of the amine vinegar® (meth) acrylate which can be used as the material having a radical polymerizable unsaturated group is not particularly limited, for example, the raw material isononate component and the hydroxyl group-containing (meth) The acrylate reaction, followed by the reaction with the polyol component; the raw material isocyanate component, the raw material hydroxyl group-containing (meth) acrylate' and the polyol component are added and reacted at one time to make the raw material sulphuric acid vinegar The reaction of the component and the polyol component, followed by a method of reacting the group-containing (meth) acrylate. Among these, the isocyanate component and the hydroxyl group can be simultaneously synthesized by reacting the raw material isocyanate component and the raw material containing a hydroxyl group of (meth) propylene sulfate, followed by reacting the polyol component. It is especially preferable that the (meth) acrylate component is directly amine-amined with amine acetonate (methyl) propionate vinegar, which can improve productivity. Further, when the raw material isocyanate component and the raw material containing the trans group (meth) acrylate are sequentially reacted, and then the polyol component is reacted, the raw material hydroxyl group-containing (meth) acrylate is also preferably separated. After the addition of the polyol component is added to the initial addition and the subsequent stage, a part of the raw material hydroxyl group-containing (meth) acrylate is divided and added. When the polymerizable polymer/polymer having a radical polymerizable group is contained in the curable resin composition, the content thereof is preferably 2% by mass or more, more preferably 30% by mass or more, and 80% by weight of the curable resin composition. The mass% or less is more preferably the mass% or less. These components may each contain one type or two or more types. When the total content is less than 20% by mass, the long-term storage stability of the optical disk may be deteriorated, and if the right is more than 80% by mass, the viscosity may be improved. The curable resin composition for an optical disk can be arbitrarily selected from the oligomer/polymer having a radical polymerizable group. The cured product obtained by curing the curable resin composition for a photosensitive optical disk of the present invention has an elastic modulus of an oligomer/polymer alone having a radical polymerizable group (hereinafter sometimes referred to as "single hardening alone". The glass transition temperature of the material ") is preferably -1 (rc or more, more preferably one or five. (: above, preferably 45. (: below, more preferably 4 〇t or less. Also, alone hardened at 25t) The elastic modulus is preferably 5 〇 MPa or more, more preferably the above, preferably 900 MPa or less, more preferably 85 MPa MPa or less and more preferably 800 MPa or less. Further, the above-mentioned single cured product is used to harden the curable resin composition for the optical disk. The conditions are the same conditions, that is, the photopolymerization initiator used for the pupil-curable resin composition is added and mixed in the oligomer/polymer to have the same addition ratio, and the curing conditions when the protective layer is formed. (Light irradiation time, irradiation height, Zhaosi County® ric, stop...radiation hardened material thickness) are the same to harden. The glass point transfer temperature is measured by dynamic viscoelasticity and measured by the temperature ^ ° ^, measured Stretch mode The frequency is 1 Hz, the chuck distance is 25 mm, the amplitude Ql%, and the temperature increase rate is sub-divided. If the glass point transition temperature of the individual cured product exceeds the shape, the warpage of the optical disk 15 201022304 may increase. The temperature of the glass point of the object is not full - 10 ° C, sometimes the disc may have a depression or long-term preservation stability is deteriorated. Moreover, the elastic modulus of the above-mentioned single hardened material is the same as that obtained by the single hardened material by dynamic viscosity The value obtained by the elastic measurement is a value of the storage elastic modulus E of 25 t. If the elastic modulus of the above-mentioned individual cured product is less than 5 〇Mpa, the long-term storage stability of the optical disk may be deteriorated. In particular, if the protective layer is pushed in, there is When the elastic modulus of the individual cured product exceeds 90 OMPa, the warpage of the obtained optical disk may increase or the long-term storage stability may deteriorate. On the other hand, the optical disk of the present invention is hardened. When the modulus of elasticity of the cured product obtained by curing the resin composition is high, the glass transition temperature of the above-mentioned individual cured product is preferably n 6 (rc or less, more preferably below the muscle) and more preferably 5 5 or less. The aforementioned separate The elastic modulus of the compound in hunger should be l〇〇MPa or more and 2000 MPa or less, more preferably less than i5〇〇MPa, and more preferably less than 10 MPa. The glass point shift temperature of the above single hardened material exceeds 6 〇. When the elastic modulus exceeds 2 MPa, the curvature of the disc may increase. If the glass transition temperature of the @ individual cured product is less than 3 (rc, the optical disc sometimes has a concave modulus of elasticity of less than 100 MPa, sometimes The long-term storage stability of the optical disc is deteriorated. In particular, if the protective layer is pushed in, there may be a depression. The glass transition temperature and the elastic modulus are determined by the above-described measurement method. Further, the elastic modulus of the cured product alone is not particularly limited, and the aforementioned low elastic modulus In addition to the south elastic modulus, 'the above-mentioned low elastic modulus is particularly preferable. <Vinyl Polymer> 16 201022304 When a cured product obtained by curing the curable resin composition of the present invention requires high hardness in physical properties, a vinyl group having a repeating unit represented by the following formula (1) is preferably used. Polymer. Further, the vinyl polymer having a repeating unit represented by the following formula (丨) is a polyfunctional (meth) acrylate containing an adduct in the formula m2 2, wherein JJ^O or 1 In the case of an oligomer/polymer having a radical polymerizable group. [Chemical 1]

如-严+ ⑴ 0十1〇七|一〒=如2 OR2 [式中’ R1為碳數2〜8之伸烷基，R2為氫原子或甲基，m為 正整數。]Such as - 严 + (1) 0 1:1 | | 〒 = = 2 OR2 [wherein R1 is a C 2 to 8 alkylene group, R 2 is a hydrogen atom or a methyl group, and m is a positive integer. ]

上述式（1)中，以表示之碳數2〜8之伸烷基，例如： 伸乙基、二亞甲基、伸丙基、四亞甲基、五亞曱基、六亞 甲基、七亞曱基、八亞甲基、環伸己基、1,4—二甲基環己 燒一〇:，〇：’—二基、ι，3_二甲基環己烷 7 基、1，2—二甲基環己烷—α α，—二基、14—二甲基苯 基—α，α，〜二基、1，3—二甲基苯基_二基、 1,2 一甲基笨基—二基等。以R]表示之取代 基，在上式（1)存在有m個，可為相同也可為相異。 上述式（1)中，m為正整數，宜為1以上2〇以下之整 數更佳為1以上10以下之整數，又更佳為1以上5以下 之整數。 乂上述式（1)表示之乙烯基系聚合物，可為具有來自於 17 201022304 °早體之構造單位的共聚物，較佳之共聚物 …方法可採用與前述同樣之實施形態。 〈多分支型反應性化合物〉 刚述多分支型反應化合物，係從一分子中具有1個反 應性基Χ以及具有可與該反應性基X反獻2個以上反應 性基Υ《化合物製造之具有I維分支之重複構造(以下有 時稱為「分支重複單位」）之化合物。In the above formula (1), an alkylene group having a carbon number of 2 to 8 is represented, for example, an ethyl group, a dimethylene group, a propyl group, a tetramethylene group, a penta, a hexamethylene group, or a hexamethylene group. Hexamethyl, octamethyl, cyclohexyl, 1,4-dimethylcyclohexanone: 〇: '-diyl, ι, 3 dimethylcyclohexane 7-base, 1, 2-dimethylcyclohexane-α α,—diyl, 14-dimethylphenyl-α,α,~diyl, 1,3-dimethylphenyl-diyl, 1,2-A Base stupid - two bases and so on. The substituent represented by R] has m in the above formula (1), and may be the same or different. In the above formula (1), m is a positive integer, and preferably an integer of 1 or more and 2 Å or less is more preferably an integer of 1 or more and 10 or less, and more preferably an integer of 1 or more and 5 or less. The vinyl polymer represented by the above formula (1) may be a copolymer having a structural unit derived from 17 201022304 °, and the preferred copolymer method may be the same as the above. <Multi-branched reactive compound> The multi-branched reactive compound has one reactive group in one molecule and two or more reactive groups in the reactive group X. A compound having a repeating structure of an I-dimensional branch (hereinafter sometimes referred to as a "branched repeating unit").

該種多为支型反應性化合物，與習知之直鏈高分子大 不相同之點，例如（丨）可溶於有機溶劑且黏度低；（〖丨）為非 晶性材料，（I π )分子内部為稀疏，但愈往外側愈為緊密， 因此不因環境而改變形狀，保持球狀；（IV)密度低；（ν) 存在多數末端基等。因此’多分支型反應性化合物，具有 例如（I)硬化速度迅速；（II)硬化後之塗膜不易受傷；（111) 收縮率小，因此塗佈於基材後之翹曲小；（XV )韌性優異， 塗膜不易發生裂痕破裂及剝離等特徵。This type is mostly a branched reactive compound, which is quite different from the conventional linear polymer, for example, (丨) is soluble in an organic solvent and has low viscosity; (丨) is an amorphous material, (I π ) The inside of the molecule is sparse, but the closer it is to the outside, the more it does not change its shape due to the environment, and it remains spherical; (IV) the density is low; (v) there are many terminal groups. Therefore, the 'multi-branched reactive compound has, for example, (I) rapid curing rate; (II) the coating film after hardening is not easily injured; (111) the shrinkage rate is small, so the warpage after application to the substrate is small; (XV) ) Excellent toughness, and the coating film is not susceptible to crack cracking and peeling.

多分支型反應性化合物，係由下述式（2)表示之樹枝狀 化合物及/或下述式（3)表示之高度分支聚合物所構成之分 子骨架高度分支之化合物，宜為規則性高之樹枝狀聚合物 與規則性低之高度分支聚合物。尤其，樹枝狀化合物相較 於一般使用之直線狀高分子，能將反應性官能基以高密度 且集中配置於其最外面。又，高度分支聚合物雖不如樹枝 狀聚合物，但能於最外面導入多數反應性官能基，硬化性 優異。 [化2] 18 201022304The multi-branched reactive compound is a compound having a highly branched molecular skeleton composed of a dendrimer represented by the following formula (2) and/or a highly branched polymer represented by the following formula (3), and is preferably highly regular. Dendrimers and highly branched highly branched polymers. In particular, the dendrimer can be disposed at a high density and concentrated on the outermost surface of the linear polymer in comparison with a generally used linear polymer. Further, although the highly branched polymer is not as good as the dendritic polymer, most of the reactive functional groups can be introduced on the outermost surface, and the curability is excellent. [Chemical 2] 18 201022304

將具有核部且具有從核部以放射狀規則的分支重複單 位且分支重複單位有2個以上之化合物，稱為樹枝狀化合 物。可作為多分支型反應性化合物使用之樹枝狀化合物， • 可將多個末端基中（通常為反應性基Y)的一部分或全部取 代為其他反應性基。可使用為分支型反應性化合物之樹枝 狀聚合物，必需至少2個以上末端基具反應性。末端基， 較佳為自由基聚合性之雙鍵基，更佳為（曱基）丙烯酿基。 又，末端基之一部分可取代為非反應性之取代基。 前述可作為多分支型反應性化合物使用之高度分支聚 合物，與上述樹枝狀化合物同樣具有分支重複單位之構 成，但核部非必要。又，可作為多分支型反應性化合物使 用之高度分支聚合物’分支重複單位可有一部分欠缺或不 19 201022304 規則或不連續處。可作為多分支型反應性化合物使用之高 度分支聚合物，多數末端基中（通常為反應性基Y)的一部 分或全部可取代為其他反應性基。可作為多分支型反應性 化合物使用之高度分支聚合物，必需至少2個以上末端基 具反應性。末端基較佳為自由基聚合性之雙鍵基，更佳為 (甲基）丙烯醯基。又，末端基之一部分可取代為非反應性 之取代基。 本發明中，使用多分支型反應性化合物時，其調配量 在硬化性樹脂組成物中，宜為1 〇質量％以上不滿9 〇質量％， 更佳為30質量％以上70質量％以下。多分支型反應性化合 物之調配量若不滿10質量％，則由於交聯密度低，有時硬 化速度降低或硬化物之塗膜強度不足。又，若分支型反應 性化合物之調配量為90質量％以上，有時塗佈於基體並使 硬化得到之層積體之翹曲會增大或硬化物會產生破裂。 〈單官能及/或多官能之聚合性單體〉 本發明之硬化性樹脂組成物，於上述具自由基聚合性 基之寡聚物/聚合物以外，在不使保護層之物性下降之範 圍’可使用單官能及/或多官能之聚合性單體。 月1J述单官能及/或多官能之聚合性卓體，例如：苯乙 烯、乙烯基甲苯、4_第三丁基苯乙烯、α —甲基苯乙稀、 4一氣苯乙烯、4一甲基苯乙稀、4 —氣甲基苯乙烯、二乙稀 基苯等苯乙烯系單體；鄰苯二甲酸二烯丙酯、間笨二曱酸 二稀丙酯、三聚氰酸三稀丙酯、三聚異氰酸三烯丙酯等稀 丙酯系單體；（甲基）丙烯酸甲酯、（甲基）丙烯酸乙醋、（甲 201022304 基）丙稀酸丙酯、（甲基）丙烯酸丁酯、2 —乙基（甲基）丙烯 己酯、（曱基）丙烯酸環己酯、（曱基）丙烯酸異萡酯、（甲基） 丙烯酸1 一金剛酯、四氫呋喃（曱基）丙烯酸酯、2_羥基（甲 基）丙烯酸乙酯、2—羥基（甲基）丙烯酸丙酯、（甲基）丙烯 酸縮水甘油酯、聚乙二醇單（曱基）丙烯酸酯、聚丙二醇單 (甲基）丙烯酸酯、甲氧基二乙二醇（甲基）丙烯酸酯、丁氧 基二乙二醇（甲基）丙烯酸酯、苯氧基（曱基）丙烯酸乙酯、 ©(甲基）丙烯酸三氟乙酯、全氟辛基（甲基）丙烯酸乙酯、（甲 基）丙烯酸二環戊烯酯、（甲基）丙烯酸二環戊氧乙酯、（甲 基）丙歸酸二環戊醋等1官能（甲基）丙稀酸醋化合物；乙二 醇二（甲基）丙烯酸酯、1，6—己二醇二（甲基）丙烯酸酯、1，9 —壬二醇二（甲基）丙烯酸酯、新二醇二（甲基）丙烯酸酯、3 —甲基一1，5 —戊二醇二（甲基）丙烯酸酯、2 — 丁基一 2—乙 基~1，3 —丙二醇二（甲基）丙烯酸酯、二羥曱基三環癸烷二 (甲基）丙烯酸酯、五環十五烷二甲醇二（甲基）丙烯酸酯、 • 雙紛A縮水甘油醚之二（甲基）丙烯酸加成物、環己烷二甲 醇二（甲基）丙烯酸酯、降萡烷二甲醇二（甲基）丙烯酸酯、 對蓋院一1，8 —二醇二（甲基）丙烯酸酯、對蓋烧—2, 8 —二 醇二（甲基）丙烯酸酯、對蓋烷—3, 8一二醇二（甲基）丙烯酸 酯、雙環[2.2.2.]—辛一1—甲基_4_異丙基_56_二羥 甲基二（甲基）丙烯酸酯、羥基三甲基乙酸新戊二醇酯（甲基） 丙烯酸酯、雙（（甲基）丙烯醯氧新戊二醇）己二酯等2官能 (甲基）丙烯酸酯化合物；三羥甲基丙烷三（甲基）丙烯酸 知、二羥甲基乙烷三（曱基）丙烯酸酯、甘油三（甲基）丙烯 21 201022304A compound having a core portion and having a branching repeating unit which is radially regular from the core portion and having two or more branch repeating units is referred to as a dendritic compound. A dendrimer which can be used as a multi-branched reactive compound, • A part or all of a plurality of terminal groups (usually a reactive group Y) can be substituted with other reactive groups. A dendrimer which is a branched reactive compound may be used, and at least two or more terminal groups are required to be reactive. The terminal group is preferably a radically polymerizable double bond group, more preferably a (fluorenyl) propylene group. Further, a part of the terminal group may be substituted with a non-reactive substituent. The highly branched polymer which can be used as the multi-branched reactive compound has a branch repeating unit similarly to the dendrimer described above, but the core portion is not essential. Further, the highly branched polymer 'branched repeating unit which can be used as a multi-branched reactive compound may be partially deficient or not 19 201022304 regular or discontinuous. A highly branched polymer which can be used as a multi-branched reactive compound, and a part or all of a plurality of terminal groups (usually a reactive group Y) may be substituted with other reactive groups. A highly branched polymer which can be used as a multi-branched reactive compound requires at least two or more terminal groups to be reactive. The terminal group is preferably a radically polymerizable double bond group, more preferably a (meth) acrylonitrile group. Further, a part of the terminal group may be substituted with a non-reactive substituent. In the present invention, when the multi-branched reactive compound is used, the amount of the curable resin composition is preferably 1% by mass or more and less than 9% by mass, more preferably 30% by mass or more and 70% by mass or less. When the amount of the multi-branched reactive compound is less than 10% by mass, the crosslinking density may be lowered, and the hardening rate may be lowered or the coating strength of the cured product may be insufficient. In addition, when the blending amount of the branched reactive compound is 90% by mass or more, the warpage of the laminate which is applied to the substrate and hardened may increase or the cured product may be cracked. <Monofunctional and/or polyfunctional polymerizable monomer> The curable resin composition of the present invention has a range in which the physical properties of the protective layer are not lowered in addition to the oligomer/polymer having a radical polymerizable group 'A monofunctional and/or polyfunctional polymerizable monomer can be used. 1 1 describes monofunctional and/or polyfunctional polymerizable compounds, such as: styrene, vinyl toluene, 4_t-butyl styrene, α-methyl styrene, 4 gas styrene, 4 A Styrene monomer such as styrene, 4-methylmethyl styrene, and diphenyl benzene; diallyl phthalate, diisopropyl propyl phthalate, trisuccinate a propyl ester monomer such as propyl ester or triallyl isocyanate; methyl (meth)acrylate, ethyl (meth)acrylate, propyl acrylate (201022304), (methyl) ) butyl acrylate, 2-ethyl (meth) hexyl acrylate, cyclohexyl (decyl) acrylate, isodecyl (meth) acrylate, 1-adamantyl (meth) acrylate, tetrahydrofuran (fluorenyl) Acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxy(meth)acrylate, glycidyl (meth)acrylate, polyethylene glycol mono(decyl)acrylate, polypropylene glycol single ( Methyl) acrylate, methoxy diethylene glycol (meth) acrylate, butoxy diethylene glycol (meth) acrylate , phenoxy (meth) acrylate, ethyl (tri) ethyl (meth) acrylate, ethyl perfluorooctyl (meth) acrylate, dicyclopentenyl (meth) acrylate, (methyl) a monofunctional (meth)acrylic acid vinegar compound such as dicyclopentyloxyethyl acrylate or (meth)propionic acid dicyclopentanacetic acid; ethylene glycol di(meth)acrylate, 1,6-hexanediol Di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, neodiol di(meth)acrylate, 3-methyl-1,5-pentanediol di(methyl) Acrylate, 2-butyl-2-ethyl-1,3-1,3-propanediol di(meth)acrylate, dihydroxydecyltricyclodecane di(meth)acrylate, pentacyclopentadecane dimethanol Di(meth)acrylate, • Di(meth)acrylic acid adduct of di-glycidyl ether, cyclohexanedimethanol di(meth)acrylate, norbornane dimethanol di(meth)acrylic acid Ester, glutamic acid-1,8-diol di(meth) acrylate, cap calcined-2,8-diol di(meth) acrylate, p-alkane-3, 8 Diol di(meth)acrylate, bicyclo[2.2.2.]-octyl-1-methyl-4-isopropanyl-5-dihydroxymethyldi(meth)acrylate, hydroxytrimethylacetic acid a bifunctional (meth) acrylate compound such as neopentyl glycol ester (meth) acrylate or bis((meth) propylene oxime neopentyl glycol hexane dicarboxylate; trimethylolpropane tri(methyl) Acrylic acid, dimethylolethane tris(mercapto) acrylate, glycerol tris(meth) propylene 21 201022304

酸醋、四（曱基）丙烯酸季戊四酯、六（甲基）丙烯酸酯二季 戊四自曰等3官能以上之（曱基）丙稀酸醋化合物等（甲基）丙 烯酸系衍生物；甲氧基（甲基）丙烯酸乙酯、2_ρ氧基—2 一甲基（甲基）丙烯酸乙酯、2 —甲氧基一 1—甲基（曱基）丙 浠酸乙S旨、乙氧基（曱基）丙浠酸乙醋、2一乙氧基一 2_甲 基（甲基）丙烯酸乙酯、2 —乙氧基一 1 一甲基（甲基）丙烯酸 乙酯、丙氧基（曱基）丙烯酸乙酯、丙氧基（甲基）丙烯酸丙 酯、異丙氧基（甲基）丙烯酸乙酯、丁氧基（甲基）丙烯酸乙 酯，二乙二醇二乙烯醚、環己烧二甲醇二乙烯醚、羥基丁 基乙烯醚、十二烷基乙烯醚等乙烯醚系單體；三羥甲基丙 院二烯丙醚、季戊四醇烯丙醚、烯丙基縮水甘油醚、三羥 甲基二t氰胺之稀丙_、甘油二烤丙醚之己二酸酯、稀丙 基縮醛、三羥甲基己二醛之烷基脲之烯丙醚等烯丙醚系單 體；馬來酸二乙酯、馬來酸二丁酯等馬來酸酯單體；富馬 酸二丁酯、富馬酸二辛酯等富馬酸酯系單體；4—(曱基） 丙烯醯氧基甲基一 2 —甲基一 2—乙基_1，3 —二氧雜環戊 烷、4一（甲基）丙烯醯氧基甲基一2 一甲基一 2 —異丁基一 1，3—二氧雜環戊烷、4~(甲基）丙烯醯氧基曱基—2—環己 基一 13 —二氧雜環戊烷、4一（甲基）丙烯醯氧基曱基—2,2 一二甲基一 1，3—二氧雜環戊烷等1&gt;3一二氧雜環戊烷系單 體；（曱基）丙烯醯胺、N—乙烯基甲醯胺、n，N —二甲基（甲 基）丙烯醯胺、N—（曱基）丙烯醯胺、N 一羥曱基（甲基）丙烯 醯胺、N—曱氧基曱基（甲基）丙烯醯胺、N 一乙氧基甲基（甲 基）丙烯醯胺、N—丙氧基甲基（甲基）丙烯醯胺、N —第三丁 22 201022304 - 基（曱基）丙烯醯胺、N — 丁氧基甲基（甲基）丙烯醯胺、亞甲 基雙（甲基）丙烯醯胺、羥乙基（甲基）丙烯醯胺、N—乙烯基 他洛咬_、N—乙烯基己内醯胺、n—乙烯基甲醯胺、（曱基） 丙烯醯基嗎啉等酿胺化合物等。該等聚合物單體可單獨使 用’亦可併用2種以上。 又’從與通常使用之聚碳酸酯基板之密合性為良好之 觀點，宜使用異種聚合性單體，其中，宜使用（甲基）丙烯 ❹ 酸2 —乙烯氧乙酯、（甲基）丙烯酸3 —乙烯氧乙酯、（曱基） 丙稀酸2—乙烯氧丙酯、（甲基）丙烯酸1—甲基一2 —乙稀 氧乙醋、（甲基）丙烯酸4 —乙烯氧丁酯、（曱基）丙烯酸6 一乙稀氧己酯、（甲基）丙烯酸4 —乙稀氧環己酯、（曱基） 丙烯酸4一乙烯氧甲基環己基曱酯。 該等聚合性單體之中，2官能以上之（曱基）丙烯酸系 醋化合物、具脂環構造取代基之（甲基）丙烯酸系酯化合 物、具喊構造之（甲基）丙烯酸系衍生物硬化性良好，藉由 • 使用該等，例如保護層之透明性或硬度高，且光碟之長期 保存安定性（加熱促進試驗時之翹曲變化、殘膜性）優異， 故為理想的。 使用聚合性單體時，其調配量在硬化性樹脂組成物 中，宜為0質量％以上，更佳為1〇質量％以上，又更佳為 20質量％以上’較佳為70%質量以下，更佳為6〇質量％以下， 又更佳為50質量％以下。聚合性單體之調配量若超過7〇質 量％，則硬化收縮率或内部應變增大，例如有時光碟之翹曲 增大，保護層有時發生裂隙或破裂。 23 201022304 〈光聚合起始劑&gt; 本發明之硬化性樹脂組成物，含有光聚合起始劑為必 要成分。藉由含有光聚合起始劑’能發揮由於光照射而迅 速硬化之效果。 光自由基聚合起始劑’例如：二乙氧基苯乙酮、2—經 基一2—甲基一1—苯基丙一1—酮、苄基二甲基縮醛、4_ (2—經基乙氧基）苯基一（2 —經基一 2 —丙基）嗣、1—經基 環己基苯酮、2 —甲基一1_[4一（甲硫基）苯基]一 2 —嗎啉 丙一1-酮、2 -苄基一2 -二曱胺基一1_(4_嗎啉苯基）參 丁酮、寡{2—羥基一2—甲基一 1~[4— (1 一甲基乙烯基） 苯基]丙酮}、2—羥基一1— {4— [4 — (2—羥基一2 —曱基丙 醯基）苄基]苯基}—2 —甲基丙一1 一酮等苯乙酮類；苯偶 因、苯偶因甲醚、苯偶因***、苯偶因異丙醚、苯偶因異 丁醚等苯偶因類；二苯基酮、鄰苯甲醯基苯甲酸甲酯、4 —苯基二苯基酮、4 一苯曱醯基—4， 一甲基一二苯硫、 3,3’ ，4,4’ 一四（第三丁基過氧化羰基）二苯基酮、2,4 6 _ 一二甲基二苯基酮、4_苯甲醯基一n，N -二甲基一N— [2 —(1 一側氧基—2 —丙醯氧基）乙基]苄基三曱基溴化銨 (benzene met hanaminium bromide)、（4 —苯甲醢基节基） 三甲基氣化銨等二苯基酮類；2—異丙基硫化氧二苯甲酮、 4 —異丙基硫化氧二苯甲酮、2,4_二乙基硫化氧二笨甲 酮、2, 4 —二氣硫化氧二苯甲酮、1—氣_4 —丙氧基硫化氧 二苯甲酮、2—(3 —二甲胺基一 2_羥基）_ 3, 4_二甲基〜 9H硫化氧二苯甲酮一9 —酮四紫質（mesocr〇i He)等硫化 24 201022304 氧一苯甲嗣類；等。該等光自由基聚合起始劑’可單獨使 用也可併用2種以上。該等光自由基聚合起始劑之中，以 苯乙酿1類為宜，具體而言，宜為1—羥基環己基二苯基酮、 募丨2—羥基―2—甲基一1— [4—(1—甲基乙烯基）苯基]丙 酮}、2—羥基—2~甲基一1 一苯基丙一1—酮、2 —羥基一1 —{4 — [4~(2 一經基—2 —曱基丙醯基）苄基]苯基}—2_ 甲基丙一1網。其中，從使將光碟用硬化性樹脂組成物作 • 為保護層使用之光碟之耐久性提升，抑制耐熱試驗時之翹 曲増加之理由，尤佳為募{2 —羥基一 2 —曱基一 1_[4—(1 —甲基乙烯基）苯基]丙酮}。 光聚合起始劑之調配量，於硬化性樹脂組成物中宜為 〇. 1質量％以上1〇質量％以下，更佳為i質量％以上8質量％ 以下，又更佳為1質量％以上5質量％以下。光聚合起始劑 之調配量若不滿〇. 1質量％，則組成物有時不會充分硬化。 反之，若光聚合起始劑之調配量超過質量％，則有時臭 鲁味之發生或硬化物之著色增大，或組成物之回收性降低、 光碟之長期保存安定性惡化。 本發明之硬化性樹脂組成物，可含有熱聚合起始劑作 為聚合起始劑。 熱聚合起始劑，宜為因加熱而產生開始聚合自由基之 熱自由基聚合起始劑。含熱聚合起始劑時，可利用將組成 物以紫外線使硬化時產生之熱’具有能進一步硬化之效果。 熱自由基聚合起始劑’例如：甲乙酮過氧化物、環己 嗣過氧化物、1，1 一雙（第三己基過氧化）—環己烷、枯烯過 25 201022304 ^雙（4第二丁基環己基）過氧化二碳酸酯、枯稀過 氧化新癸酸酯、丨，1，3, 3 —四甲基丁基過氧化新癸酸酯、25 一甲基〜2’5 —雙（2 —乙基己醯基過氧化）己酸酯、第三 丁基過氧化—2_乙基己酸醋、第三丁基過氧化苯甲酸醋等 有機過氧化物系起始劑；2, 2’ -偶氮二異丁腈、2, 2，一 偶氮雙(2, 4—一甲基戊腈）、2,2’ —偶氮雙(2,4—二甲基 -4-曱氧基戊腈）、2,2’ —偶氮雙(2—甲基丙脒)二鹽酸 鹽、，2,2’ ~偶氮雙（2—甲基一N—苯基丙脒）二鹽酸鹽、 2’2’ -，偶氮雙[N— (4—氣苯基)_2—甲基丙脒”二鹽酸⑩ 鹽2,2 ~偶氮雙[N—(4—氫苯基）~ 2—甲基丙脒]]二鹽 酸鹽、4,4’ 一偶氮雙（4_氰基戊酸）等偶氮起始劑；等。 該等熱自由基起始劑，可單獨使用也可併用2種以上。該 等熱自由基起始劑當中，宜為甲乙酮過氧化物、環己酮過 氧化物、栝烯過氧化氫、第三丁基過氧化苯甲酸酯、苯甲 醯基過氧化物等金屬肥息及/或胺化合物等以觸媒作用能 有效產生自由基之化合物’或2,2，_偶氮雙異丁腈、22， —偶氮雙（2,4—二甲基戊腈）。 聚合起始劑之調配量，於硬化性樹脂組成物中宜為 〇.〇5質量％以上20質量％以下，更佳為〇1質量％以上15 質量％以下，又更佳為0.2質量％以上1〇質量％以下。聚合 起始劑之調配量若不滿〇·05質量％，則有時硬化性樹脂組 成物不會充为硬化。反之，若聚合起始劑之調配量超過 質量％，則有時臭味之發生或硬化物之著色增大，或例如塗 佈於塑膠基材並使硬化得到之層積體之長期保存安定性 26 201022304 •(加熱促進試驗時之翹曲變化、殘膜性）惡化。 〈其他成分〉 本發明之硬化性樹脂組成物，其他可含紫外線吸收 劑、熱聚合促進劑、光增感劑、光聚合促進劑。 含有紫外線吸收劑時，可發揮提高組成物之回收性、 調整硬化速度並減小光碟之翹曲等的效果。紫外線吸收 劑，例如：苯并***系紫外線吸收劑、羥基苯基三畊系紫 ❿外線吸收劑、二苯基酮系紫外線吸收劑、水揚酸系紫外線 吸收劑、無機氧化物系紫外線吸收劑等。 具體而言，例如水揚酸苯酯、（2, 2，—羥基_ 5 —甲基 苯基）苯并***、2—羥基二苯基酮、水楊酸二醇酯、第三 丁基甲氧基二苯曱醯基甲烷、曱氧基桂皮酸乙基己酯、二a (meth)acrylic derivative such as a citric acid, a pentaerythritol tetrakis(meth)acrylate, a hexa(meth)acrylate dipentaerythritol or the like; a (meth)acrylic acid derivative such as a trifunctional or higher (mercapto) acrylic acid vinegar compound; Ethyl methoxy (meth) acrylate, ethyl 2-phenoxy-2-methyl (meth) acrylate, 2-methoxy-1-methyl (decyl) propionate B, ethoxy Ethyl (mercapto) ethyl acetoacetate, ethyl 2-ethoxy- 2-methyl (meth) acrylate, ethyl 2-ethoxy-l-methyl (meth) acrylate, propoxy (fluorenyl) ethyl acrylate, propoxy propyl (meth) acrylate, isopropoxy ethyl (meth) acrylate, butoxy (ethyl) acrylate, diethylene glycol divinyl ether, a vinyl ether monomer such as dimethicone divinyl ether, hydroxybutyl vinyl ether or lauryl vinyl ether; trimethylol propyl diallylate, pentaerythritol allyl ether, allyl glycidyl ether , trimethylol di-t-cyanamide dilute propyl, glycerol di-bromo ether adipate, dipropyl acetal, trimethylol adipaldehyde alkyl urea olefin An allyl ether monomer such as propyl ether; a maleate monomer such as diethyl maleate or dibutyl maleate; a fumarate such as dibutyl fumarate or dioctyl fumarate; Monomer; 4-(fluorenyl) propylene methoxymethyl 2- 2-methyl-2-ethyl-1,3-dioxolane, 4-(methyl)propenyloxymethyl- 2 monomethyl-2-isobutyl-1,3-dioxolane, 4~(methyl)propenyloxyfluorenyl-2-cyclohexyl-13-dioxolane, 4 1 (meth) propylene fluorenyl fluorenyl-2,2-dimethyl 1,3-1,3-dioxolane, etc. 1 &gt; 3 dioxolane monomer; (fluorenyl) propylene Indoleamine, N-vinylformamide, n,N-dimethyl(meth)acrylamide, N-(mercapto)propenamide, N-hydroxydecyl (meth)acrylamide, N —曱-methoxy-mercapto (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, N-propoxymethyl (meth) acrylamide, N — third butyl 22 201022304 - Alkyl (decyl) acrylamide, N-butoxymethyl (meth) acrylamide, methylene (Meth) acrylamide, hydroxyethyl (meth) acrylamide, N-vinyl talion _, N-vinyl caprolactam, n-vinyl formamide, (mercapto) propylene Alkaloid compounds such as mercaptomorpholine. These polymer monomers may be used singly or in combination of two or more kinds. Further, from the viewpoint of good adhesion to a commonly used polycarbonate substrate, it is preferred to use a heterogeneous polymerizable monomer, wherein (meth)acrylic acid 2-vinyloxyethyl ester or (methyl) is preferably used. Acrylic acid 3-vinyl oxyethyl ester, (mercapto) acrylic acid 2-vinyl oxypropyl acrylate, (methyl) acrylate 1-methyl -2- ethoxy ethoxy ketone, (meth) acrylate 4 - ethylene oxybutyl Ester, (meth)acrylic acid 6-ethylene oxide hexyl ester, (meth)acrylic acid 4-ethyleneoxycyclohexyl ester, (fluorenyl) 4-vinyloxymethylcyclohexyl decyl acrylate. Among these polymerizable monomers, a bifunctional or higher (fluorenyl) acrylic vinegar compound, a (meth)acrylic ester compound having an alicyclic structure substituent, and a (meth)acrylic derivative having a structure The curability is good, and it is preferable that the protective layer has high transparency and hardness, and the long-term storage stability of the optical disk (warpage change and residual film property in the heating promotion test) is excellent. When a polymerizable monomer is used, the amount thereof is preferably 0% by mass or more, more preferably 1% by mass or more, even more preferably 20% by mass or more, preferably 70% by mass or less, in the curable resin composition. More preferably, it is 6 〇 mass% or less, and more preferably 50 mass% or less. When the amount of the polymerizable monomer exceeds 7 〇% by mass, the curing shrinkage ratio or the internal strain increases. For example, the warpage of the optical disk may increase, and the protective layer may be cracked or broken. 23 201022304 <Photopolymerization initiator> The curable resin composition of the present invention contains a photopolymerization initiator as an essential component. The effect of rapidly curing due to light irradiation can be exhibited by containing a photopolymerization initiator. Photoradical polymerization initiators such as: diethoxyacetophenone, 2-carbyl-2-methyl-1-phenylpropan-1-one, benzyldimethylacetal, 4_(2- (Ethyl ethoxy)phenyl-(2-di-yl-2-propyl) fluorene, 1-cyclohexyl benzophenone, 2-methyl-1,4-[4-(methylthio)phenyl]- 2 - morpholine propan-1-ketone, 2-benzyl-2-oxanylamino-1-(4-morpholinylphenyl) butanone, oligo{2-hydroxy-2-methyl- 1~[4- (1 -Methylvinyl)phenyl]acetone}, 2-hydroxyl-1—{4—[4 —(2-hydroxy-2-indolylpropyl)benzyl]phenyl}-2-yl Acetophenones such as acetophenone; benzoin, benzoin methyl ether, benzoin ether, benzoin isopropyl ether, benzoin isobutyl ether and other benzoin; diphenyl ketone, Methyl benzhydrylbenzoate, 4-phenyldiphenyl ketone, 4 phenyl fluorenyl-4, monomethyl diphenyl sulphide, 3,3', 4,4' 1-4 (third Butyl peroxycarbonyl)diphenyl ketone, 2,4 6 dimethyl dimethyl ketone, 4 benzylidene fluorenyl-n,N-dimethyl-N-[2—(1 side oxygen Base-2 to C Ethyl]ethyl]benzyltriammonium bromide, (4-benzylhydrazino) diphenyl ketones such as trimethylammonium hydride; 2-isopropyl sulphide Oxybenzophenone, 4-isopropylsulfoxybenzophenone, 2,4-diethylsulfide dibenzophenone, 2,4-dioxysulfide benzophenone, 1-gas_4 —propoxy oxysulfide benzophenone, 2-(3-dimethylamino 2-hydroxy)_ 3, 4 dimethyl to 9H oxy benzophenone-9 ketone tetrapurin (mesocr 〇i He) and other vulcanization 24 201022304 Oxygen-benzoic guanidine; These photoradical polymerization initiators may be used singly or in combination of two or more. Among the photo-radical polymerization initiators, it is preferred to use phenylethylidene 1 , specifically, 1-hydroxycyclohexyldiphenyl ketone, 2-hydroxy-2-methyl- 1 - [4-(1-methylvinyl)phenyl]acetone}, 2-hydroxy-2~methyl-1-1-phenylpropan-1-one, 2-hydroxyl-1 —{4 — [4~(2 A benzyl-2-ylmercapto)benzyl]phenyl}-2-methylpropan-1-one network. Among them, it is preferable to increase the durability of the optical disk using the curable resin composition for the optical disk as the protective layer, and to suppress the warpage during the heat resistance test, and it is preferable to raise the {2-hydroxy-2 fluorenyl group. 1_[4-(1-methylvinyl)phenyl]acetone}. The amount of the photopolymerization initiator to be used in the curable resin composition is preferably 1% by mass or more and 1% by mass or less, more preferably 1% by mass or more and 8% by mass or less, and still more preferably 1% by mass or more. 5 mass% or less. If the amount of the photopolymerization initiator is less than 0.1% by mass, the composition may not be sufficiently cured. On the other hand, when the amount of the photopolymerization initiator is more than the mass%, the occurrence of the odor or the color of the cured product may increase, or the recovery property of the composition may be lowered, and the long-term storage stability of the optical disk may be deteriorated. The curable resin composition of the present invention may contain a thermal polymerization initiator as a polymerization initiator. The thermal polymerization initiator is preferably a thermal radical polymerization initiator which starts to polymerize a radical by heating. When the thermal polymerization initiator is contained, the heat generated when the composition is cured by ultraviolet rays can be further cured. Thermal radical polymerization initiator 'for example: methyl ethyl ketone peroxide, cyclohexyl peroxide peroxide, 1, 1 double (third hexyl peroxide) - cyclohexane, cumene over 25 201022304 ^ double (4 second Butylcyclohexyl)peroxydicarbonate, diluted peroxy neodecanoate, hydrazine, 1,3,3-tetramethylbutyl peroxy neodecanoate, 25-methyl~2'5-double Organic peroxide-based initiators such as (2-ethylhexyl ruthenium peroxy) hexanoate, t-butyl peroxy-2-ethylhexanoic acid vinegar, and tert-butyl peroxybenzoic acid vinegar; , 2'-azobisisobutyronitrile, 2, 2, azobis(2,4-methylpentanenitrile), 2,2'-azobis(2,4-dimethyl-4-曱oxyvaleronitrile), 2,2'-azobis(2-methylpropionamidine) dihydrochloride, 2,2'-azobis(2-methyl-N-phenylpropanthene) Dihydrochloride, 2'2'-, azobis[N-(4-phenylene)_2-methylpropionamidine dihydrochloride 10 salt 2,2 ~ azobis[N-(4-hydrobenzene) Azo initiators such as 2)methylpropanol]]dihydrochloride, 4,4'-azobis(4-cyanovaleric acid), etc. The initiator may be used singly or in combination of two or more. Among the thermal radical initiators, it is preferably methyl ethyl ketone peroxide, cyclohexanone peroxide, decene hydrogen peroxide, and tert-butyl hydroperoxide. a metal compound such as a formate or benzammonium peroxide, and/or an amine compound, which is a compound capable of generating a radical by a catalyst, or 2,2,_azobisisobutyronitrile, 22, Nitrogen bis(2,4-dimethylvaleronitrile). The amount of the polymerization initiator to be added is preferably 5% by mass or more and 20% by mass or less, more preferably 〇1% by mass in the curable resin composition. The amount of the above-mentioned 15% by mass or less is more preferably 0.2% by mass or more and 1% by mass or less. If the amount of the polymerization initiator is less than 5% by mass, the curable resin composition may not be cured. When the compounding amount of the polymerization initiator exceeds the mass%, the occurrence of odor or the coloration of the cured product may be increased, or the long-term storage stability of the laminate obtained by, for example, coating on a plastic substrate may be obtained. 201022304 • (warpage change and residual film property during heating promotion test) deteriorated. Component: The curable resin composition of the present invention may contain an ultraviolet absorber, a thermal polymerization accelerator, a photosensitizer, or a photopolymerization accelerator. When the ultraviolet absorber is contained, the composition can be improved in recyclability and hardening. Speed and reduce the effect of warpage of the disc, etc. UV absorbers, for example, benzotriazole-based UV absorbers, hydroxyphenyl tri-till, purpura external absorbent, diphenylketone-based UV absorber, Shuiyang An acid-based ultraviolet absorber, an inorganic oxide-based ultraviolet absorber, etc. Specifically, for example, phenyl salicylate, (2, 2,-hydroxy-5-methylphenyl)benzotriazole, 2-hydroxydiyl Phenyl ketone, salicylic acid glycol ester, tert-butyl methoxy diphenyl decyl methane, decyl cinnamic acid ethyl hexyl ester, two

甲基 PABA(para— amino benzoic acid)辛醋、二甲基 PABA 乙基己酯等以往公知之紫外線吸收劑。又，紫外線吸收劑 如後述實施例，宜為2— (2 —羥基一5 —第三丁基苯基）一 ❿ 2Η—苯并***（商品名「TINUVIN(註冊商標）ps」、ChibaA conventionally known ultraviolet absorber such as methyl PABA (para-amino benzoic acid) or dimethyl PABA ethylhexyl ester. Further, the ultraviolet absorber is preferably 2-(2-hydroxy-5-t-butylphenyl)- ❿ 2Η-benzotriazole (trade name "TINUVIN (registered trademark) ps", Chiba, as in the examples described below.

Specialty Chemical s(股）公司製）、2 — {2 -經基一4-(1 一辛氧基幾基乙氧基）苯基} — 4, 6 —雙（4 —苯基苯基）一 1，3，5 —二 D井（商品名「TINUVIN 479」、Chiba Specialty (：1^111卜813(股）公司製）、2—{2-羥基一5—(2_甲基丙烯 醯氧基乙基）苯基}苯并三峻（商品名「RUVA 93」、大塚化 學（股）公司製）、辛基一3 — {3 —第三丁基一 4_羥基—5 — (5 —氣一2H —苯并三&quot;坐一2 —基）苯基}丙酸· 2—乙基己基 —3 — {3 —第三丁基一 4 -羥基一5—(5 —氣一2Η —苯并三 27 201022304 峻一 2—基）苯基}丙酸（商品名「TINUVIN」109」、Chiba Specialty Chemicals(股）公司製）。 紫外線吸收劑之添加量，於硬化性樹脂組成物中，較 佳為0.03質量%以上0.4質量%以下，較佳為〇 〇3質量％ 以上0. 3質量/◦以下’更佳為〇. 〇5質量％以上〇· 2質量％以 下，最佳為0. 05質量％以上0,丨質量％以下。 使用熱自由基聚合起始劑時，為了降低熱自由基聚合 起始劑之分解溫度’可使用能促進熱聚合起始劑之分解而 有放產生自由基之熱聚合促逯劑。熱聚合促進劑例如始、❹ 銅、錫、辞、錳、鐵、鍅、鉻、釩、鈣、鉀等金屬肥皂、i 級、2級、3級胺化合物、4級銨鹽、硫脲化合物銅化合 物等。該等熱聚合促進劑’可單獨使用也可併用2種以上。 該等熱聚合促進劑之中，較佳為：辛酸鈷環烷酸鈷、辛 酸銅、環晚酸銅、辛酸猛、環燒酸猛、三甲基苯胺、三乙 醇胺、二乙基节基氯化録、二（2一經乙基）對甲苯胺、伸乙 基硫脲、乙醯基丙酮、乙酿基乙酸。 春 熱聚合促進劑之調配量，於硬化性樹脂組成物中，較 佳為0.001質量％以上20質量％以下，較佳為〇〇〇1質量％ 以上10質量％以下’更佳為〇. 〇1質量％以上5質量％以下， 最佳為0. 05質量％以上3質量％以下之範圍内。熱聚合促進 劑之調配量若為該範圍内，則從組成物之硬化性、硬化物 之物性、經濟性之觀點較佳。 本發月之硬化性樹脂組成物，可使用由於光激發產生 之激發狀態將激發能量轉移到光聚合起始劑，並促進光聚 28 201022304 合起始劑之分解而有效產生自由基之光增感劍。 光增感劑例如：2—氯硫化氧二苯p酮、2, 4一二乙基 硫化氧二苯f酮、2, 4一二異丙基硫化氧二苯甲酮等。該 等光增感劑可單獨使用也可併用2種以上。 光增感劑之調配量，於硬化性樹脂組成物中，較佳為 0.05質量份以上20質量%以下，較佳為〇」質量份以上15 質量％以下’更佳A 0. 2質量份以上1〇質量％以下之範圍 内。光增感劑之調配量若為該範圍内，則組成物之硬化性、 硬化物之物性、經濟性之觀點為較佳。 、本發明之組成物中，可使用能促進光聚合起始劑之分 解並有效使自由基產生之光聚合促進劑。光聚合促進劑， J如一乙醇胺、甲基二乙醇胺、三異丙醇胺、4 一二甲基 胺基苯甲酸甲醋、4-二甲基胺基苯甲酸乙醋、4-二甲基 胺基苯J酸異戊_、4—二甲基胺基苯甲酸-2-正丁氧基 ，甲酸2 —甲基胺基乙酯、N，N—二曱基對甲苯胺、 4’4 —二甲基胺基二苯基酮、44，—二乙基胺基二苯基 嗣等:該等光聚合促進劑，可單獨使用也可併用2種以上。 :等光聚。促進劑之中，較佳為三乙醇胺、甲基二乙醇胺、 二異丙醇胺。 兔Λ聚•合促進劑之調配量，於硬化性樹脂組成物中，宜 量。/ 4 %20質量％以下’較佳為0.1質量％以上15質 重Am下，更#炎Λ # ^ , .質量％以上10質量％以下之範圍内。 性料=劑之調配量若為如該範圍内’從組成物之硬化 、硬化物之物性、經濟性之觀點為較佳。 29 201022304 組合熱聚合起始劑、光聚合起始劑、熱聚合促進劑、 光增感劑、光聚合促進劑等調配時，其調配量之合計量， 相對於硬化性樹脂組成物中之合計量，較佳為0.05質量％ 以上20質量％以下，較佳為〇· 1質量％以上15質量％以下， 更佳為0.2質量％以上1〇質量；以下之範圍内。聚合起始劑 等之組合調配量之合計量若為如該範圍内’則硬化性樹脂 組成物之硬化性、使硬化性樹脂組成物硬化得到之硬化物 之物性、經濟性之觀點為較佳。 本發明之硬化性樹脂組成物，視需要’可含有表面機 能調整劑。藉由添加表面調整劑，财指紋除去性會變良好。 表面機能調整劑一般使用氟系化合物或矽酮系化合物。本 發明中’視用途可使用聚醚變性氟系化合物、具反應性基 (例如（曱基）丙烯酸酯）之聚醚變性氟系化合物、非反應性 矽酮、反應性（例如（曱基）丙烯酸酯）矽酮、高分子矽酮、 巨單體系矽酮中任一者。 本發明之硬化性樹脂組成物，可含有由金屬氧化物構 成之微粒。含有由金屬氧化物構成之微粒時，可發揮硬化 後塗膜之硬度提升’更不易受傷、可得低反射性包覆之效 果。 構成微粒之金屬氧化物較佳為包含選自於由Si、Ti、 Zr、Zn、Sn、In、La及Y所構成族群中至少1種金屬元素。 構成微粒之金屬氧化物，可為含該等元素之單獨之氧化 物，也可為含該等元素之複合氧化物。構成微粒之金屬氧 化物之具體例例如：SiO、Si〇2、Ti〇2、Zr〇2、ZnO、Sn〇2、 201022304Specialty Chemicals Co., Ltd.), 2 — {2-transyl- 4-(1-octyloxymethyloxy)phenyl}-4,6-bis(4-phenylphenyl)- 1,3,5 - two D well (trade name "TINUVIN 479", Chiba Specialty (:1^111 813 (share) company), 2-{2-hydroxy-5-(2_methacrylofluorene) Ethyl ethyl) phenyl} benzotris (trade name "RUVA 93", manufactured by Otsuka Chemical Co., Ltd.), octyl-1 - {3 - tert-butyl 4-hydroxy- 5 - (5 - Gas - 2H - benzotriene &quot; sit a 2-yl) phenyl} propionic acid · 2-ethylhexyl - 3 - {3 - tert-butyl 4-hydroxy- 5 - (5 - gas - 2 - Benzene III 27 201022304 Jun 2 -yl)phenyl}propionic acid (trade name "TINUVIN" 109", manufactured by Chiba Specialty Chemicals Co., Ltd.). The amount of the ultraviolet absorber added to the curable resin composition. It is preferably 0.03 mass% or more and 0.4 mass% or less, preferably 〇〇3 mass% or more, and 0.3 mass% or less is more preferably 〇. 5 mass% or more 〇 2 mass% or less, and most preferably 0. . 05 mass% or more 0, 丨 mass% When a thermal radical polymerization initiator is used, in order to lower the decomposition temperature of the thermal radical polymerization initiator, a thermal polymerization promoter capable of promoting the decomposition of the thermal polymerization initiator and generating a radical may be used. Polymerization accelerators such as metal soaps such as bismuth, bismuth copper, tin, rhodium, manganese, iron, bismuth, chromium, vanadium, calcium, potassium, etc., i-grade, grade 2, grade 3 amine compounds, grade 4 ammonium salts, thiourea copper compounds The above-mentioned thermal polymerization accelerators may be used singly or in combination of two or more. Among the thermal polymerization accelerators, cobalt octoate cobalt naphthenate, copper octoate, copper late copper, and octanoic acid are preferred. , ring-burning acid, trimethylaniline, triethanolamine, diethyl benzyl chloride, bis (2-ethyl) p-toluidine, ethyl thiourea, acetonitrile, ethyl acetate. The amount of the thermal polymerization accelerator is preferably 0.001% by mass or more and 20% by mass or less, more preferably 〇〇〇1% by mass or more and 10% by mass or less based on the curable resin composition. More preferably 〇. 〇. 1% by mass or more and 5% by mass or less, preferably 0. 05% by mass or more and 3 masses When the amount of the thermal polymerization accelerator is within this range, it is preferably from the viewpoints of the curability of the composition, the physical properties of the cured product, and the economy. The curable resin composition of the present month can be used. The excitation state generated by photoexcitation transfers the excitation energy to the photopolymerization initiator, and promotes the photo-sensitization of the photopolymerization 28 201022304 and the initiator to effectively generate free radicals. Photosensitizer such as: 2-chloro Sulfated oxydiphenyl ketone, 2, 4-diethyl sulfoxy oxybenzene ketone, 2, 4 isopropyl sulfoxy benzophenone, and the like. These photosensitizers may be used alone or in combination of two or more. The amount of the photosensitive sensitizer is preferably 0.05 parts by mass or more and 20% by mass or less, more preferably 5% by mass or more and 15% by mass or less, more preferably 2 parts by mass or more. 1〇% by mass or less. When the amount of the photosensitizer is within this range, the viewpoint of the hardenability of the composition, the physical properties of the cured product, and the economy is preferable. Further, in the composition of the present invention, a photopolymerization accelerator which promotes the decomposition of the photopolymerization initiator and effectively generates a radical can be used. Photopolymerization accelerator, J such as monoethanolamine, methyldiethanolamine, triisopropanolamine, 4-dimethylaminobenzoic acid methyl ketone, 4-dimethylaminobenzoic acid ethyl acetonate, 4-dimethylamine Benzyl J acid isoamyl, 4-dimethylaminobenzoic acid-2-n-butoxy, 2-methylaminoethyl formate, N,N-di-p-toluidine, 4'4 — Dimethylaminodiphenyl ketone, 44, diethylaminodiphenyl hydrazine, etc.: These photopolymerization accelerators may be used alone or in combination of two or more. : Wait for the light to gather. Among the accelerators, preferred are triethanolamine, methyldiethanolamine, and diisopropanolamine. The blending amount of the rabbit sputum polymerization accelerator is preferably in the curable resin composition. / 4 % 20% by mass or less 'preferably 0.1% by mass or more and 15 masses Am, more #炎Λ # ^ , .% by mass or more and 10% by mass or less. The amount of the agent = the amount of the agent is preferably within the range of 'from the viewpoint of hardening of the composition, physical properties of the cured product, and economy. 29 201022304 When a thermal polymerization initiator, a photopolymerization initiator, a thermal polymerization accelerator, a photosensitizer, a photopolymerization accelerator, etc. are blended, the total amount of the blending amount is compared with the total amount of the curable resin composition. The amount is preferably 0.05% by mass or more and 20% by mass or less, preferably 〇·1% by mass or more and 15% by mass or less, more preferably 0.2% by mass or more and 1% by mass or less; or less. The total amount of the combination of the polymerization initiators and the like is preferably such that the curability of the curable resin composition is within the range, and the physical properties and economy of the cured product obtained by curing the curable resin composition are preferable. . The curable resin composition of the present invention may contain a surface function adjusting agent as needed. By adding a surface conditioner, the fingerprint removal property becomes good. As the surface function modifier, a fluorine-based compound or an anthrone-based compound is generally used. In the present invention, a polyether-modified fluorine-based compound, a polyether-modified fluorine-based compound having a reactive group (for example, (mercapto) acrylate), a non-reactive fluorenone, and a reactivity (for example, (fluorenyl) can be used. Acrylate) Any of anthrone, macromolecular ketone, and macrosystem fluorenone. The curable resin composition of the present invention may contain fine particles composed of a metal oxide. When the fine particles composed of the metal oxide are contained, the hardness of the coating film after curing can be improved, and the effect of the low-reflective coating can be obtained. The metal oxide constituting the fine particles preferably contains at least one metal element selected from the group consisting of Si, Ti, Zr, Zn, Sn, In, La, and Y. The metal oxide constituting the fine particles may be a single oxide containing the elements, or may be a composite oxide containing the elements. Specific examples of the metal oxide constituting the fine particles are, for example, SiO, Si〇2, Ti〇2, Zr〇2, ZnO, Sn〇2, 201022304

In2〇3、La2〇3、Y2〇3、Si〇2 — AI2O3、Si〇2 — ΖΓ2Ο3、Si〇2 — Ti2〇3、 A12〇3 — Zr〇2、Ti 〇2 — Zr〇2等。由該等金屬氧化物構成之微 粒，可單獨使用也可併用2種以上。該等金屬氧化物所構 成之微粒中，宜為Si〇2、Ti〇2、Zr〇2、Zn〇2。 由金屬氧化物構成之微粒之平均粒徑，較佳為lnm# 上300nm以下，較佳為lnm以上50nm以下。微粒之平均粒 徑若超過30Onm，則硬化物之透明性有時會受損。又，微 • 粒之平均粒徑意指：使用動態光散射式粒徑分布測定裝置 測定求得之體積平均粒徑。 由金屬氧化物構成之微粒之調配量，於硬化性樹脂組 成物中，較佳為0質量％以上80質量!以下、較佳為〇質量 %以上50質量％以下。微粒之調配量若超過質量％，硬化 物有時會變脆。 本發明之硬化性樹脂組成物，又視需要，就添加物而 言，可添加低收縮化劑（反應性募聚物或聚合物、非反應性 ❹ 寡聚物或聚合物）、著色顏料、可塑劑、鏈移轉劑、聚合禁 止劑、近紅外線吸收劑、光安定劑、抗氧化劑、難燃化劑、 消光劑、染料、消泡劑、塗平劑、抗靜電劑、分散劑、滑 動劑、表面改質劑、搖變化劑、搖變助劑等。該等添加物 之存在，並不特別影響本發明之效果。該等添加物，可單 獨使用也可併用2種以上。 添加物之調配量，可視添加物之種類或使用目的、硬 化性樹脂組成物之使用方法等適當設定，不特別限定。例 如，低收縮化劑、著色顏料、可塑劑或援變化劑之調配量， 31 201022304 於硬化性樹脂組成物中，較佳為i質量％以上4〇質量％以 下，較佳為5質量％以上30質量％以下，更佳為10質量％ 以上2 5質量％以下之範圍内。聚合禁止劑、抗氧化劑、消 光劑、染料、消泡劑、塗平劑、抗靜電劑、分散劑、滑動 劑、表面改質劑或援變助劑之調配量’於硬化性樹脂組成 物中’較佳為〇. 0001質量％以上10質量％以下，較佳為0. 〇〇1 質量％以上5質量％以下，更佳為〇.〇1質量％以上3質量％ 以下之範圍内。 本發明之光碟用硬化性樹脂組成物，當前述硬化性樹 ® 脂組成物中之自由基聚合性不飽和基當量（g/eq)為A，前 述硬化性樹脂組成物中之含環氧烷烴加成物之多官能（甲 基）丙烯酸酯類及含己内酯加成物之多官能（甲基）丙烯酸 酯類之含量（質量％)為B時，需滿足6.6SA+BS35。 本發明之硬化性樹脂組成物，藉由自由基聚合性不飽 和基形成交聯構造，又，藉由含加成物之（甲基）丙烯酸酯 類具有之環氧烷烴骨架及/或己内酯成分，導入軟質成分，_ 亦即’本發明，藉由調配含加成物之（甲基）丙烯酸酯類， 並調整設定A及B之比（A+B)為既定範圍内，能減低本發明 之硬化性樹脂組成物之硬化收縮，又，能使本發明之硬化 性樹脂組成物硬化得到之硬化物於變形時之復原性提升， 可調整彈性率、損失正切及玻璃轉移溫度。 又’本發明中，對於A及B未規定個別的適當範圍而 規定A+B之理由，在於本發明之硬化性樹脂組成物中，因 應於能導入軟質成分之含加成物之（甲基）丙烯酸酯類之含 32 201022304 量（B)，能形成交聯構造之自由基聚合性不飽和基當量（A) 之適當範圍也會變動。 例如，當B為約60質量％，A為約500g/eq則得到硬 化物會變得過於柔軟，永久變形量變得極小。但是，於B 為約10質量％時，A即使為約5〇〇g/eq，得到之硬化物也會 變得過硬，永久變形量顯著增大。另一方面，當B為約2〇 質量％時，A為約31〇g/eq，則得到之硬化物變得過硬，永 ❿久變形量變得極小。但是，當B為約50質量％時，即使a 為約320g/eq，得到的硬化物仍會過於柔軟，永久變形量 顯著增大。 如此’ A之適當範圍會因應於b之值變動，因此，為 了適當規定本發明之較佳實施態樣，規定A+b之範圍。本 發明中’藉由將前述A+B定為6.6〜35之範圍，可具有彈 性率 '損失正切及玻璃轉移溫度為可實用之物性，且復原 性或層積體之翹曲極小，於作為光碟之保護層時具優異效 鲁果。當前述A+B不滿6. 6時，交聯構造變少，因此，彈性 率與知失正切之平衡變差’永久變形量增大，亦即推入保 護層時容易凹陷。另一方面，當前述A+B超過35時，交聯 構造多、由於硬化收縮造成層積體之翹曲變大，又，變形 時之復原性變差，容易凹陷。 &lt;自由基聚合性不飽和基當量&gt; 說明自由基聚合性不飽和基當量（g/eq)。自由基聚合 性不飽和基當量，係自由基聚合性不飽和基每1莫耳之硬 化性樹脂組成物質量。在此，計算自由基聚合性不飽和基 33 201022304 當量時’係不考慮光聚合起始劑之質量。又，前述自由基 聚合性不飽和基，係具自由基聚合性之乙烯性不飽和基。 本發明中，硬化性樹脂組成物中之自由基聚合性不飽 和基當量係使用光DSC(photo DSC)裝置從反應發熱量計 算。光DSC裝置係於DSC裝置具備UV照射部之構造的熱分 析裝置’藉由將uv硬化性樹脂樣本配置於光DSC裝置，並 以裝置内之UV燈照射UV，能觀測DSC曲線係伴隨硬化反 應之硬化發熱。硬化發熱量之測定方法，宜為以下所示方 法。 ❸ 〈光DSC測定方法〉 精秤約5mg硬化性樹脂組成物至直徑約5随之銘皿。 於30°C、氮氣氛圍下使用紫外線照射裝置（精工電子工業 公司製、UV— 1(光源：200W水銀一氣燈、濾片：365ηιη干 涉濾片及20%ND濾片）），一面照射照射強度5mJ/cm2 .秒之 紫外線5分鐘，一面以差示掃描熱量計（DSC)(精工電子工 業公司製、DSC6200)測定單位硬化性樹脂組成物之發熱量 ❺ (mJ/mg:樹脂組成物lmg(不含光聚合起始劑）之硬化發熱 量）。測定2—乙基丙烯酸己酯（分子量184)之硬化發熱 量’為420mJ/mg ’故以此為基準計算自由基聚合性不飽和 基之量。例如，測定某硬化性樹脂組成物之硬化發熱量， 為250m J/mg。該硬化性樹脂組成物之自由基聚合性不飽和 基量，成為（184x420+250)= 309。 本發明之硬化性樹脂組成物中，自由基聚合性不飽和 基當量宜為250g/eq以上’較佳為300g/eq以上，更佳為 34 201022304 350g/eq以上，宜為600g/eq以下，較佳為550g/eq以下， 更佳為500g/eq以下。前述自由基聚合性不飽和基當量若 為上述範圍内’則可將得到之硬化物之硬度調整在更適當 的範圍，能形成永久變形量更小的保護層。 本發明之硬化性樹脂組成物，於該組成物之厚度 時，各波長之光線穿透率，於（^4〇〇11111為85〇%以In2〇3, La2〇3, Y2〇3, Si〇2 — AI2O3, Si〇2 — ΖΓ2Ο3, Si〇2 — Ti2〇3, A12〇3 — Zr〇2, Ti 〇2 — Zr〇2, and the like. The fine particles composed of the metal oxides may be used singly or in combination of two or more. Among the fine particles composed of the metal oxides, Si 2 , Ti 2 , Zr 2 , and Zn 2 are preferable. The average particle diameter of the fine particles composed of the metal oxide is preferably 300 nm or less on 1 nm #, preferably 1 nm or more and 50 nm or less. When the average particle diameter of the fine particles exceeds 30 nm, the transparency of the cured product may be impaired. Further, the average particle diameter of the microparticles means that the volume average particle diameter obtained is measured by a dynamic light scattering type particle size distribution measuring apparatus. The amount of the fine particles in the curable resin composition is preferably 0% by mass or more and 80% by mass or less, preferably 〇% by mass or more and 50% by mass or less. If the amount of fine particles exceeds % by mass, the hardened material sometimes becomes brittle. In the curable resin composition of the present invention, if necessary, a low shrinkage agent (reactive polymer or polymer, non-reactive fluorene oligomer or polymer), a coloring pigment, or the like may be added as an additive. Plasticizer, chain transfer agent, polymerization inhibitor, near infrared ray absorbing agent, light stabilizer, antioxidant, flame retardant, matting agent, dye, antifoaming agent, coating agent, antistatic agent, dispersant, sliding Agent, surface modifier, shake modifier, shake aid, etc. The presence of such additives does not particularly affect the effects of the present invention. These additives may be used singly or in combination of two or more. The amount of the additive to be added is appropriately determined depending on the type of the additive, the purpose of use, the method of using the hard resin composition, and the like, and is not particularly limited. For example, the amount of the low shrinkage agent, the coloring pigment, the plasticizer, or the modifier is 31, 2010,304, preferably, in the curable resin composition, i% by mass or more and 4% by mass or less, preferably 5% by mass or more. 30% by mass or less, more preferably 10% by mass or more and 25% by mass or less. Polymerization inhibitor, antioxidant, matting agent, dye, antifoaming agent, coating agent, antistatic agent, dispersant, slip agent, surface modifier or modifier additive in the curable resin composition It is preferably 0.001% by mass or more and 10% by mass or less, preferably 0. 〇〇1% by mass or more and 5% by mass or less, more preferably 〇1% by mass or more and 3% by mass or less. In the curable resin composition for an optical disk of the present invention, the radical polymerizable unsaturated group equivalent (g/eq) in the curable resin composition is A, and the alkylene oxide-containing compound in the curable resin composition When the content (% by mass) of the polyfunctional (meth) acrylate of the adduct and the polyfunctional (meth) acrylate containing the caprolactone adduct is B, it is necessary to satisfy 6.6 SA + BS35. The curable resin composition of the present invention forms a crosslinked structure by a radical polymerizable unsaturated group, and further comprises an alkylene oxide skeleton having an adduct (meth) acrylate and/or The ester component is introduced into a soft component, that is, in the present invention, by adjusting the (meth)acrylate containing the adduct and adjusting the ratio of the combination of A and B (A+B) to a predetermined range, the composition can be reduced. In the hardening shrinkage of the curable resin composition of the present invention, the cured product obtained by curing the curable resin composition of the present invention can be improved in restorability upon deformation, and the elastic modulus, loss tangent, and glass transition temperature can be adjusted. In the present invention, the reason why A+B is defined in the case where A and B are not individually defined is that the curable resin composition of the present invention is based on the addition-containing product capable of introducing a soft component (methyl group). The acrylate group contains 32 201022304 (B), and the appropriate range of the radical polymerizable unsaturated group equivalent (A) capable of forming a crosslinked structure also fluctuates. For example, when B is about 60% by mass and A is about 500 g/eq, the resulting hardened article becomes too soft and the amount of permanent deformation becomes extremely small. However, when B is about 10% by mass, even if A is about 5 〇〇g/eq, the obtained cured product becomes too hard and the amount of permanent deformation remarkably increases. On the other hand, when B is about 2 〇 mass%, and A is about 31 〇g/eq, the obtained cured product becomes too hard, and the amount of permanent deformation is extremely small. However, when B is about 50% by mass, even if a is about 320 g/eq, the obtained cured product is too soft and the amount of permanent deformation is remarkably increased. Thus, the proper range of 'A' will vary depending on the value of b. Therefore, in order to appropriately define the preferred embodiment of the present invention, the range of A+b is specified. In the present invention, by setting the above A+B to a range of 6.6 to 35, the elastic modulus 'loss tangent and the glass transition temperature can be practical, and the recovery or the warp of the laminate is extremely small. The protective layer of the disc has excellent effect. When the A+B is less than 6.6, the cross-linking structure is reduced, so that the balance between the elastic modulus and the loss tangent is deteriorated. The amount of permanent deformation is increased, that is, it is likely to be dented when pushed into the protective layer. On the other hand, when the above A+B exceeds 35, the crosslinked structure is large, the warpage of the laminate is increased due to the hardening shrinkage, and the restorability at the time of deformation is deteriorated, and the depression is liable to occur. &lt;Radical Polymerizable Unsaturated Group Equivalent&gt; The radical polymerizable unsaturated group equivalent (g/eq) will be described. The radical polymerizable unsaturated group equivalent is a mass of a hard resin composition per 1 mole of the radical polymerizable unsaturated group. Here, when the radical polymerizable unsaturated group 33 201022304 equivalent is calculated, the quality of the photopolymerization initiator is not considered. Further, the radically polymerizable unsaturated group is a radically polymerizable ethylenically unsaturated group. In the present invention, the radical polymerizable unsaturated base equivalent in the curable resin composition is calculated from the reaction calorific value using a light DSC (photo DSC) apparatus. The optical DSC device is a thermal analysis device having a structure in which a UV irradiation unit is provided in a DSC device. By arranging a uv curable resin sample in an optical DSC device and irradiating UV with a UV lamp in the device, the DSC curve can be observed to be accompanied by a hardening reaction. Hardening and heating. The method for measuring the calorific calorific value is preferably the method shown below. 〈 <Light DSC measurement method> The scale is about 5 mg of the curable resin composition to a diameter of about 5 with the name of the dish. Ultraviolet irradiation apparatus (UV-1 (light source: 200W mercury-gas lamp, filter: 365ηιη interference filter and 20% ND filter)) was used at 30 ° C under a nitrogen atmosphere, and the irradiation intensity was irradiated on one side. The calorific value of the unit curable resin composition was measured by a differential scanning calorimeter (DSC) (manufactured by Seiko Instruments Inc., DSC6200) at a frequency of 5 mJ/cm2. Does not contain the photopolymerization initiator) hardening calorific value). The amount of hardening heat generation of 2-ethyl hexyl acrylate (molecular weight 184) was measured to be 420 mJ/mg. Therefore, the amount of the radical polymerizable unsaturated group was calculated based on this. For example, the hardening calorific value of a certain curable resin composition is measured and found to be 250 m J/mg. The amount of the radical polymerizable unsaturated group of the curable resin composition was (184 x 420 + 250) = 309. In the curable resin composition of the present invention, the radical polymerizable unsaturated group equivalent is preferably 250 g/eq or more, preferably 300 g/eq or more, more preferably 34 201022304 350 g/eq or more, and preferably 600 g/eq or less. It is preferably 550 g/eq or less, more preferably 500 g/eq or less. When the radical polymerizable unsaturated group equivalent is within the above range, the hardness of the obtained cured product can be adjusted to a more appropriate range, and a protective layer having a smaller amount of permanent deformation can be formed. In the curable resin composition of the present invention, at the thickness of the composition, the light transmittance at each wavelength is (85% by mass in (^4〇〇11111).

上、（Y)380nm為35.0%以上85.0%以下之範圍内，且於 (Z)360nm為0· 1%以上50.0%以下之範圍内較佳。各波長之 光線穿透率藉由設定於上述範圍，組成物之回收性優異， 且使該組成物硬化而成之具保護層之光碟透明性優異、可 得反射膜之腐蝕性小、表面之潤滑性及長期保存安定性（加 熱促進試驗時之低翹曲性或殘膜性）優異之光碟。 波長40〇nm之光線穿透率，較佳為85 〇%以上更佳 為88%以上，最佳為90%以上。浊4 “η ,, 及長400ηιη之光線穿透率不 滿85.0%時，透明性差，有時|法料 π «τ热忐對先碟進行正確資料記 錄或無法再生。 ' 波長380ηπι之光線穿透率，較佳 蚁佳為35. 0%以上85. 0% 以下，更佳為45.0%以上85. 0%以 r 最佳為45. 0%以上 75. 0%以下。於波長38 Onm之光線穿读慶从 茅透率右落於上述範圍外 時’有時組成物之回收性差、夯雄 尤碟之長期保存安定性（加熱 促進試驗時之翹曲變化、殘膜性）變 反射膜之腐钱性降 低、或表面潤滑性降低。 下 波長360nm之光線穿透率， 更佳為0. 5 %以上5 0. 〇 %以下 較佳為0 · 1 %以上 ’最佳為5%以上 50. 0%以 30.0%以 35 201022304 下。波長360nm之光線穿透率落於上述範圍外時，有時組 成物之回收性差、光碟之長期保存安定性（加熱促進試驗時 之翹曲變化、殘膜性）變差、反射膜之腐蝕性降低、或表面 之潤滑性降低。 又，光線穿透率，係於隔著l〇〇&quot;m之間隔件之石英玻 璃比色管中，注入硬化性樹脂組成物，使用分光光度計測 定於各波長之光線穿透率之值。此時，採用空氣作為空白 值。 本發明之硬化性樹脂組成物之黏度，於25 〇c宜為 〇 800mPa · s 以上’較佳為 1 〇〇〇mpa · s 以上、3500mPa · s 以 下，宜為2500mPa · s以下。在此，黏度係於溫度25°c之 條件下，使用β型黏度計（型式「rB80L」：東機產業（股） 公司製）計算之值。黏度若為8〇〇mPa· s〜3500mPa. s之範 圍外，有時保護層之厚度無法控制在1 00 # m±2 // in，詳言 之’有時中心部之保護層厚度會較薄或端部之保護層厚度 變厚。 ❺ &lt;組成物之製造方法、及其硬化方法&gt; 本犛明之硬化性樹脂組成物’可藉由將前述含環氧烷 垣加成物之多官能（曱基）丙烯酸酯類及/或含己内酯加成 物之多官能（甲基）丙稀酸酯類、光聚合起始劑等，以公知 方法混合、攪拌而得。 本發明之硬化性樹脂組成物’可藉由照射紫外線使硬 化。此處’硬化係指無流動性之狀態。使用之紫外線之波 長’為150nm以上450nm以下之範圍内即可。發出如此波 36 201022304 • 長之光源，例如：太陽光線、低壓水銀燈、高壓水銀燈、 超高壓水銀燈、金屬齒化物燈、鎵燈、氙燈、閃型氙燈、 碳弧燈等。照射累積光量，宜為〇 1 J/Cm2以上3 j/cm2以下， 較佳為〇.2J/cm2以上2.0J/Cm2以下，更佳為〇 3J/cm2以上 1. 〇J/cm2以下之範圍内。 可與該等光源同時併用紅外線、遠紅外線、熱風、高 頻加熱等之熱。加熱溫度，可視基材種類等適當調節，不 ❿特別限定，較佳為80。(：以上200t以下，較佳為9(rc以上 180°C以下，更佳為100。〇以上17(rc以下之範圍内。加熱 時間視塗佈面積等適當調節即可，不特別限定，但較佳為 1分鐘以上24小時以下、較佳為1〇分鐘以上12小時以下， 更佳為30分鐘以上6小時以下之範圍内。 同時進行以光照射硬化及電子束照射硬化時，加速電 壓且為10kV以上500kV以下，較佳為20kV以上300kV以 下，更佳為30kV以上200kV以下之範圍内使用電子束。又， ❿ 電子束之照射量’較佳為2kGy以上500kGy以下，較佳為 3kGy以上300kGy以下，更佳為4kGy以上200kGy以下之 範圍内。 將本發明之硬化性樹脂組成物塗佈於基體使硬化得到 光碟時，塗佈方法從凹版印刷等各種印刷法、桿塗法、旋 塗法等習知公知方法依使用目的選擇即可。 &lt;硬化物&gt; 使本發明之硬化性樹脂組成物硬化得到之硬化物，於 l〇〇em之厚度’於405nm之光線穿透率宜為85%以上，較 37 201022304 佳為88%以上，更佳為89%以上。光線穿透率係使用得到之 硬化物以分光光度計測定之值。使本發明之硬化性樹脂組 成物硬化得到之硬化物，適當含有（甲基）丙烯酸酯類、光 聚合起始劑、具至少1種以上自由基聚合性基及/或離子聚 合性基之寡聚物及/或聚合物、聚合性單體，且依既定硬化 條件或方法充分進行硬化，可達成上述光線穿透率。4〇5ηω 之光線穿透率不滿85%時，由於透明性差，使用為光碟之 保護層時，有時讀取記錄資訊時，增加會錯誤。 使本發明之硬化性樹脂組成物硬化得到之硬化物，於 _ 70°C之烘箱中保持1〇〇小時時，質量減量（以下有時單稱為 「質量減少」）以〇」質量％以上為佳，較佳為〇·2質量％ 以上、2.0質量％以下，更佳為15質量％以下，最佳為工〇 質量％以下。測定之硬化物之厚度採用100/z±2/zme 、質量減少之原因，可認為係未反應之（甲基）丙烯酸酯 類成分或起始劑之殘渣及其分解產物、或低分子量之添加 劑所致。質量減少’可藉由含有具自由基聚合性基之寡聚 物及或聚合物、（甲基）丙烯酸醋類、光聚合起始劑，並藉 由既定之硬化條件或方法充分進行硬化，而落於上述範圍 内。 ,右質量減少不滿0. 1質量％，硬化物需要乾燥（減壓） 步驟等，成本升高，另一方面，若質量減少超過2.0質量％， 則有時揮發成分會漏滲到硬化物表面或由於保護層之厚 度變化造成記錄之資訊讀取時錯誤增加，或光碟之長期保 存安定性變差。亦即，藉由使質量減量為0. 1質量％以上 38 201022304 .2.0質量％以下，能使例如光碟中經時之表面精度降低少， 保存安定性提升，且可於汽車内等使用或保存。 使本發明之硬化性樹脂紅成物硬化得到之硬化物，於 硬化物之彈性率較低時，於25t之貯藏彈性率e，* 1〇胸 以上、較佳為2GMPa以上、！贈a以下，更佳為歷pa 以下，又更佳為100MPa以下。貯藏彈性率E，係使用得到 之硬化物測定動態黏彈性得到之值。測定條件於後述。藉 φ㈣前述硬純樹脂組成物以既定硬化條件或硬化方法充 分硬化，能得到貯藏彈性率E，1〇MPa以上i5〇Mpa以下之 硬化物。貯藏彈性率E，不滿1〇MPa時，有時光碟之長期 保存女疋性變差。尤其，光碟有時會凹陷。又，貯藏彈性 率大於15_a時，有時得到之光碟之翹曲增大，或長期保 存安定性變差》 使本發明之硬化性樹脂組成物硬化得到之硬化物，於 硬化物之彈性率較低為佳時，25t之損失正切士抓占以The upper (Y) 380 nm is in the range of 35.0% or more and 85.0% or less, and is preferably in the range of (Z) 360 nm of from 0.1% to 50.0%. The light transmittance at each wavelength is set to be in the above range, and the composition is excellent in recyclability, and the protective layer is cured by the composition, and the transparency of the optical disk is excellent, and the surface of the reflective film is less corrosive. A disc that is excellent in lubricity and long-term storage stability (low warpage or residual film property in the heating promotion test). The light transmittance at a wavelength of 40 〇 nm is preferably 85 〇% or more, more preferably 88% or more, and most preferably 90% or more. When the light transmittance of turbidity 4 “η , , and length 400ηιη is less than 85.0%, the transparency is poor. Sometimes, the π «τ 忐 忐 忐 忐 进行 进行 进行 进行 进行 进行 先 先 先 先 380 380 380 380 380 380 380 380 The rate is preferably 35. 0% or less, 85. 0% or less, more preferably 45.0% or more, 85. 0% by r, preferably 45. 0% or more, 75. 0% or less, at a wavelength of 38 Onm. When reading from the Mao ping rate right outside the above range, 'sometimes the composition is poorly recycled, the long-term preservation stability of the 夯雄尤碟 (the warpage change during the heating promotion test, the residual film property) Decreased rot, or reduced surface lubricity. The light transmittance of the lower wavelength of 360 nm is more preferably 0.5% or more and 5 0. 〇% or less is preferably 0 · 1 % or more 'best 5% or more 50 0% is 30.0% at 35 201022304. When the light transmittance at a wavelength of 360 nm falls outside the above range, the recovery of the composition is poor, and the long-term storage stability of the optical disk (warpage change during heating promotion test, residual) The film properties are deteriorated, the corrosion of the reflective film is lowered, or the lubricity of the surface is lowered. In a quartz glass colorimetric tube with a spacer of l〇〇&quot;m, a composition of a hardening resin is injected, and a value of light transmittance at each wavelength is measured using a spectrophotometer. At this time, air is used. The viscosity of the curable resin composition of the present invention is preferably 〇800 mPa·s or more at 25 〇c, preferably 1 〇〇〇mpa·s or more and 3500 mPa·s or less, preferably 2500 mPa·s or less. Here, the viscosity is calculated at a temperature of 25 ° C using a β-type viscometer (type "rB80L": manufactured by Toki Sangyo Co., Ltd.). If the viscosity is outside the range of 8〇〇mPa·s~3500mPa.s, sometimes the thickness of the protective layer cannot be controlled at 100# m±2 // in, in detail, the thickness of the protective layer at the center may be more The thickness of the thin or end protective layer becomes thicker. ❺ &lt;Production method of composition and hardening method thereof&gt; The curable resin composition of the present invention can be obtained by using the above-mentioned polyfunctional (fluorenyl) acrylate containing an alkylene oxide adduct and/or A polyfunctional (meth) acrylate such as a caprolactone adduct, a photopolymerization initiator, and the like are obtained by mixing and stirring by a known method. The curable resin composition ' of the present invention' can be hardened by irradiation with ultraviolet rays. Here, "hardening" refers to a state of no fluidity. The wavelength "the wavelength of the ultraviolet ray used" may be in the range of 150 nm or more and 450 nm or less. Such a wave 36 201022304 • Long light source, such as: sun light, low pressure mercury lamp, high pressure mercury lamp, ultra high pressure mercury lamp, metal toothed lamp, gallium lamp, xenon lamp, flashing xenon lamp, carbon arc lamp, etc. The amount of accumulated light is preferably 〇1 J/cm 2 or more and 3 j/cm 2 or less, preferably 〇2 J/cm 2 or more and 2.0 J/cm 2 or less, more preferably 〇3 J/cm 2 or more and 1. 〇J/cm 2 or less. Inside. The heat sources such as infrared rays, far infrared rays, hot air, and high frequency heating can be used in combination with the light sources. The heating temperature is appropriately adjusted depending on the type of the substrate, and the like, and is not particularly limited, and is preferably 80. (: 200 t or less, preferably 9 (rc or more, 180 ° C or less, more preferably 100. 〇 or more 17 (in the range of rc or less. The heating time may be appropriately adjusted depending on the coating area, etc., and is not particularly limited, but It is preferably 1 minute or longer and 24 hours or shorter, preferably 1 minute or longer and 12 hours or shorter, more preferably 30 minutes or longer and 6 hours or shorter. When the light is irradiated and cured by electron beam irradiation, the voltage is accelerated. The electron beam is used in a range of 10 kV or more and 500 kV or less, preferably 20 kV or more and 300 kV or less, more preferably 30 kV or more and 200 kV or less. Further, the irradiation amount of the ❿ electron beam is preferably 2 kGy or more and 500 kGy or less, preferably 3 kGy or more. 300kGy or less, more preferably 4kGy or more and 200kGy or less. When the curable resin composition of the present invention is applied to a substrate to cure the optical disk, the coating method is various printing methods such as gravure printing, bar coating, and spin coating. A conventionally known method such as a method may be selected depending on the purpose of use. &lt;Cured product&gt; A cured product obtained by hardening the curable resin composition of the present invention, is immersed in a light of 405 nm at a thickness of 10 μm The rate is preferably 85% or more, preferably 88% or more, more preferably 89% or more, compared with 37 201022304. The light transmittance is a value measured by a spectrophotometer using the obtained cured product, and the hardenable resin composition of the present invention is hardened. The cured product obtained contains a (meth) acrylate, a photopolymerization initiator, an oligomer and/or a polymer having at least one type of radical polymerizable group and/or an ionic polymerizable group, and polymerizability. The light transmittance can be achieved by the monomer alone and sufficiently hardened according to the predetermined curing conditions or methods. When the light transmittance of 4〇5ηω is less than 85%, the transparency is poor, and when used as a protective layer of a disc, sometimes read When the recording information is taken, the increase is erroneous. When the cured product obtained by curing the curable resin composition of the present invention is kept in an oven at _70 ° C for 1 hour, the mass loss (hereinafter sometimes referred to as "quality" The reduction is preferably 质量% by mass or more, more preferably 〇·2% by mass or more, 2.0% by mass or less, more preferably 15% by mass or less, and most preferably 5% by mass or less. Adopt 100/z±2/ Zme, the reason for the decrease in mass, can be considered as the unreacted (meth) acrylate component or the residue of the initiator and its decomposition products, or the low molecular weight additive. The mass reduction can be achieved by containing free radicals. The polymerizable group oligomer and the polymer, the (meth)acrylic acid vinegar, and the photopolymerization initiator are sufficiently hardened by a predetermined curing condition or method to fall within the above range. Less than 0.1% by mass, the hardened material needs to be dried (reduced pressure), etc., and the cost is increased. On the other hand, if the mass is reduced by more than 2.0% by mass, the volatile component sometimes leaks to the surface of the cured product or due to the protective layer. The thickness variation causes an error in the reading of the recorded information, or the long-term preservation stability of the optical disc deteriorates. In other words, by reducing the mass by 0.1% by mass or more and 38 201022304 .2.0% by mass or less, for example, the surface accuracy of the optical disk can be reduced less, the storage stability can be improved, and it can be used or stored in a car or the like. . The cured product obtained by curing the curable resin red product of the present invention has a storage modulus of e, i 1 〇 chest or more, preferably 2 GMPa or more at 25 t when the modulus of elasticity of the cured product is low. The gift is a below, preferably for the following pa, and more preferably 100 MPa or less. The storage modulus E is a value obtained by measuring the dynamic viscoelasticity of the obtained cured product. The measurement conditions will be described later. By the above-mentioned hard pure resin composition of φ(4), it is sufficiently hardened by a predetermined hardening condition or a hardening method, and a cured product having a storage modulus of E, 1 〇 MPa or more and i5 〇 Mpa or less can be obtained. When the storage modulus E is less than 1 MPa, the long-term preservation of the female disc is worse. In particular, the disc sometimes dents. Further, when the storage modulus is more than 15 mm, the warpage of the obtained optical disk may increase, or the long-term storage stability may deteriorate. The cured product obtained by curing the curable resin composition of the present invention has a higher elastic modulus than that of the cured product. When the low is good, the loss of 25t is the slasher

〇.1〇以上為佳、0.70以下較佳’更佳為〇 6〇以下，又更 佳為0. 50以下，最佳為〇 4〇以下。損失正切士抓5係與 貯藏彈性率E同樣由動態黏彈性測定得到之值。又，測 疋條件也採用同樣條件。損失正切t如占超過〇· 7〇時有 時光碟之長期保存安定性變差。尤其’或許光碟有凹陷。 又，損失正切*滿〇1〇時，有時得到光碟之龜曲增 大’或長期保存安定性變差。 使本發明之硬化性樹脂組成物硬化得到之硬化物，於 硬化物之彈性率較低為佳時’玻璃點移轉溫度以〇。匚以上 39 201022304 為佳’較佳為5°C以上，更佳為l〇°C以上、3(TC以下。玻 璃點移轉溫度，係與貯藏彈性率E，同樣由動態黏彈性測 定得到之值’採用最大tan 5值之溫度。又，測定條件， 採用與貯藏彈性率E’同樣的條件。若破璃點移轉溫度超 過30°C ’有時光碟之翹曲會增大。又，若玻璃點移轉溫度 不滿0C，有時光碟會有凹陷，有時長期保存安定性變差。 使本發明之硬化性樹脂組成物硬化得到之硬化物，於 硬化物之彈性率較高為佳時，於25〇c之貯藏彈性率E，以 1200MPa以上為佳，較佳為nooMPa以上，更佳為16〇〇Mpa 〇 以上，最佳為1800MPa以上、2100MPa以下。貯藏彈性率 E ，係與前述同樣使用得到之硬化物測定動態黏彈性得到 之值。藉由將前述硬化性樹脂組成物以既定硬化條件或硬 化方法充分硬化，可得貯藏彈性率E，12〇〇MPa以上 2100MPa以下之硬化物。貯藏彈性率e’小於12〇〇Mpa時， 有時光碟之長期保存安定性變差◦尤其，會有凹陷。 使本發明之硬化性樹脂組成物硬化得到之硬化物，於 硬化物之彈性率較高為佳時，於25£&gt;c之損失正切七抓占以 _ 0.03以上較佳，0.12以下較佳，較佳為〇 1〇以下，更佳 為0.07以下損失正切tan 5，係與貯藏彈性率e，同樣 由動態黏彈性測定得到之值。又，測定條件也採用同樣條 件。損失正切tan5若超過〇.12,有時光碟之長期保存安 定性變差。尤其，光碟有凹陷。 使本發明之硬化性樹脂組成物硬化得到之硬化物，於 硬化物之彈性率較高為佳時，玻璃點移轉溫度以以上 40 201022304 為佳，較佳為7(Tc以上，更佳為75°C以上，最佳為8(TC 以上、90 C以下較佳，較佳為85°C以下。玻璃點移轉溫度 係與貯藏彈性率E，同樣由動態黏彈性測定得到之值，採 用最大tan (5值之溫度。又’測定條件採用與貯藏彈性率 E同樣之條件。玻璃點移轉溫度不滿6(TC時，有時光碟 會有凹陷或長期保存安定性變差。 本發明之硬化性樹脂組成物適於使用在光碟。使本發 明之硬化性樹脂組成物硬化得到之硬化物，耐擦傷性、硬 度特別優異，且長期間經過，基材之翹曲仍小，因此，適 用於光碟尤其資訊讀寫用雷射光使用藍紫色雷射光之光碟 (藍光碟片（註冊商標））。 &lt;&lt;光碟〉〉 本發明之光碟，特徵在於具有使上述本發明之光碟用 硬化性樹脂組成物硬化成之保護層。 本發明之光碟，係藉由於基體上形成之反射膜上，使 • 本發明之光碟用硬化性樹脂組成物硬化形成保護層而得。 本發明之光碟製造方法中，除保護層之製造方法以外使用 以往公知之光碟之製造方法。 使本發明之硬化性樹脂組成物硬化得到之保護層，厚 度以2〇em以上較佳，較佳為3〇&quot;以上，更佳為5〇&quot;m 以上，尤佳為70&quot;以上，最佳為8(^m以上。又，前述 保護層厚度以15〇em以下較佳，較佳為12〇“以下，更 佳為l〇5//m以下。使用於光碟時’保護層厚度不滿20/zm 時，有時保護層β之記錄層等機能層歧射層之保護不充 41 201022304 分，若超過150#m’有時膜厚等的控制變難。 光碟使用之基體例如：聚甲基丙烯酸甲醋（PMma)、聚 苯乙烯（PS)、聚對苯二甲酸乙二酯（PET)、丙烯腈_ 丁二烯 —苯乙烯共聚物（ABS)、聚碳酸酯（PC)等樹脂成形物及薄 膜；玻璃等。其中，以聚碳酸酯（pC)較佳。 又，本發明中，反射膜上，不僅意指是在反射膜直接 昼層保護層之形癌’尚指在反射膜上疊層記錄層或介電體 層等機能層，並於該機能層上疊層保護層之形態。又，為 了提高光碟之記錄容量，製作資訊記錄層為2層以上之具參 多層構造之光碟。該等資訊記錄層之間，形成將透明的紫 外線硬化型樹脂以紫外線使硬化成之中間層。本發明之組 成物，適於形纟光碟之保護層，也可作為該中間層用之紫 外線硬化型樹脂。 本發明之光碟’例如：藍光碟片（註冊商標)等。本發 明之光碟由於透明性優異’適用於使用例如380nm〜 430nm 之振盈子進行記錄.再生之光碟。藍光碟片（註冊商標）用 之保護層，要I低翹曲性(低收縮性)、透明性(光穿透性）、 與聚碳酸醋基板之密合性、低腐純、回收性、速硬化性（生 產性）、尺寸安定性（促進試料之W變化、殘膜性、凹 陷等永久變形量小)等特性’但是使本發明之光碟用硬化性 樹脂組成物硬化成之保護層’滿足上述全部特性。又，本 發明不限於上述實施形態，可在申請專利範圍所示範圍進 行各種改變。 本發明之光碟 具有直接形成在前述保護層上之硬塗 42 201022304 -層亦為較佳態樣。形成前述硬塗層之硬塗用樹脂組成物， 宜為例如：（〇硬塗用樹脂組成物（以下有時稱為第1硬塗 用樹脂組成物），含有多分支型反應性化合物及/或側鏈具 反應性基之聚合物與聚合起始劑；（2)硬塗用樹脂組成物 (乂下有時稱為第2硬塗用樹脂組成物），包含：從對於4 兀以上之多元醇的每1元之加成重複單位為n=l，2之環 氧烧烴加成物得到之含環氧烷烴加成物之多官能（甲基）丙 ❹烯酸酯類及/或從對於4元以上之多元醇的每i元的加成重 複單位為n=1，2之己内酯加成物得到之含己内酯加成物 之多官能（甲基）丙烯酸酯類，及光聚合起始劑。 說明前述第1硬塗用樹脂組成物。 前述多分支型反應性化合物，例如能使用可構成本發 明之硬化性樹脂組成物之具有自由基聚合性不飽和基之化 合物中例示者。 刖述多分支型反應性化合物，宜為以上述式（3)表示樹 •枝狀化合物及/或以上述式（4)表示之高度分支聚合物。 前述側鏈具反應性基之聚合物，例如可使用：可構成 本發明之硬化性樹脂組成物之具自由基聚合性基之寡聚物 /聚口物所例不，具有上述式（1)表示之重複單位之乙烯基 系聚合體。 上述式（1)所示之乙烯基系聚合體以外之側鏈具反應 性基之聚合物，例如日本特開平u_ 263893號公報記載之 甲基丙烯酸甲輯與甲基丙烯酸之共聚物於分子内具有多數 將不飽和環氧化合物縮水甘油基甲基丙稀酸醋化而成之聚 43 201022304 合性雙鍵之（甲基）丙烯酸系聚合物。 前述多分支型反應性化合物及/或侧鏈具反應性基之 聚合物之調配量’在第1硬塗用樹脂組成物中，較佳為1〇 質量％以上不滿90質量％，較佳為30質量％以上70質量％ 以下。多分支型反應性化合物及/或側鏈具反應性基之聚合 物之調配量若不滿10質量％，由於交聯密度下降，因此有 時硬化速度下降或硬化物之塗膜強度變得不夠。又，前述 調配量若為90質量％以上，則有時塗佈於基體使硬化得到 之層積體之翹曲會增大。 前述第1硬塗用樹脂組成物’以聚合起始劑為必要成 分，例如.藉由加熱產生聚合起始自由基之熱聚合起始劑； 藉由紫外線照射產生聚合起始自由基之光聚合起始劑，又 藉由紫外線照射產生聚合起始陽離子之光陽離子聚合起始 劑；等。該等聚合起始劑可單獨使用也可併用2種以上。 又，進一步添加熱聚合促進劑、光增感劑' 光聚合促進劑 等亦佳。該等聚合起始劑、熱聚合促進劑、光增感劑、光 聚合促進劑等，可使用能構成本發明之硬化性樹脂組成物 者所例示者。又，該等之調配量之較適範圍與本發明之硬 化性樹脂組成物同。 刚述第1硬塗用樹脂組成物’除了多分支型反應性化 合物、側鏈具反應性基之聚合物、聚合起始劑以外，可含 有具反應性基之寡聚物及/或聚合物。位於募聚物及或聚合 物之反應性基，以（甲基）丙烯醯基較佳。具（甲基）丙烯醯 基之募聚物或聚合物，以胺酯（曱基）丙烯酸酯、（曱基）丙 201022304 -稀醯基懸垂（pendant)聚合物、環氧樹脂、乙烯鰱基懸垂聚 合物、環氧（甲基）丙烯酸酯、聚酯（甲基）丙烯酸酯較佳。 前述第1硬塗用樹脂組成物十，前述具（甲基）丙稀醯 基之寡聚物及或聚合物之調配量，於硬塗用樹脂組成物 中’宜為20質量！ίό以上80質量％以下，較佳為30質量％以 上質量％以下。前述具（甲基）丙烯醯基之寡聚物及或聚 合物之調配量若超過80質量％，由於多分支型反應性化合 φ 物之含量減少，因此’有時塗佈於基材後之翹曲增大，或 動性降低’塗膜產生裂隙破裂及剝離等，或長期保存安定 性變差》 又，第1硬塗用樹脂組成物，可含有（曱基）丙烯酸基 單官能單體、（甲基）丙烯酸基多官能單體等聚合性單體。 聚合性單體只要是能與多分支型反應性化合物共硬化者， 即不特別限定，具體而言，例如可使用能構成本發明之硬 化性樹脂組成物之單官能及/或多官能聚合性單體所例示 ❿ 者。 第1硬塗用樹脂組成物中，前述聚合性單體之調配 量’在硬塗用樹脂組成物中，宜為〇質量％以上質量％ 以下’較佳為10質量％以上6〇質量％以下。前述聚合性單 體之調配量若超過8〇質量％，則硬化收縮率或内部應變增 大’例如塗佈於塑膠基材並使硬化得到之層積體之翹曲有 時會增大。 其次’說明前述第2硬塗用樹脂組成物。 前述從對於4元以上之多元醇的每丨元之加成重複單 45 201022304 4為η 1或2之環氧烷烴加成物得到之含有環氧烷烴加成 多g能（甲基）丙烯酸酯類及/或從對於4元以上之多 元醇之每1元之加成重複單位為n=l或2之己内酯加成物 得到之含有己内醋加成物之多官能（甲基）㈣酸酿類，例 如使用♦季戊四醇、二季戊四醇、二—三經甲基丙烧、山 梨醇、甘露醇等4元以上之多元醇對於每丨元羥基以加成 重複早位n=1或2加成環氧烷烴及/或己内酯而成之多元 醇加成物得到之多官能（甲基）丙烯酸酯類。 前述從對於4元以上之多元醇的每工元的加成重複單參 位為n=l或2之環氧烷烴加成物得到之含有環氧烷烴加成 物之多g能（甲基）丙稀酸酯類，例如：季戊四醇之環氧乙 烷4莫耳加成物之四（甲基）丙烯酸酯、季戊四醇之環氧乙 院8莫耳加成物之四（曱基）丙烯酸酯、季戊四醇之環氧丙 院4莫耳加成物之四（甲基）丙烯酸酯、季戊四醇之環氧丙 院8莫耳加成物之四（曱基）丙烯酸酯、二季戊四醇之環氧 乙院6莫耳加成物之六（甲基）丙烯酸酯、二季戊四醇之環 參 氧乙烷12莫耳加成物之六（甲基）丙烯酸酯、二季戊四醇之 環氧丙娱：6莫耳加成物之六（甲基）丙稀酸酯、二季戊四醇 之環氧丙烷12莫耳加成物之六（甲基）丙烯酸酯、二季戊四 醇之環氧乙烷5莫耳加成物之五（甲基）丙烯酸酯、二季戊 四醇之環氧乙烷10莫耳加成物之五（甲基）丙烯酸酯、二一 三羥甲基丙烷之環氧乙烷6莫耳加成物之六（甲基）丙烯酸 酯、二一三羥甲基丙烷之環氧乙烷丨2莫耳加成物之六（甲 基）丙烯酸酯、二一三羥甲基丙烷之環氧丙烷6莫耳加成物 46 201022304 - 之六（甲基）丙烯酸酯、二一三羥甲基丙烷之環氧丙烷12莫 耳加成物之六（甲基）丙烯酸酯、山梨醇之環氧乙烷6莫耳 加成物之六（甲基）丙烯酸酯、甘露醇之環氧乙烷6莫耳加 成物之六（甲基）丙烯酸酯等。 前述從對於4元以上之多元醇的每1元的加成重複單 位為η—1或2之己内酯加成物得到之含有己内酯加成物之 多g能（甲基）丙稀酸酯類，例如：季戊四醇之ε _己内酯 ❿ 4莫耳加成物之四（甲基）丙烯酸酯、季戊四醇之ε 一己内 醋8莫耳加成物之四（甲基）丙烯酸酯、二季戊四醇之ε 一 己内酯6莫耳加成物之六（曱基）丙烯酸酯、二季戊四醇之 ε —己内酯12莫耳加成物之六（甲基）丙烯酸酯、二季戊四 醇之ε —己内酯5莫耳加成物之五（甲基）丙烯酸酯、二季 戊四醇之ε —己内酯10莫耳加成物之五（甲基）丙烯酸 酯、二—三羥曱基丙烷之ε —己内酯6莫耳加成物之六（甲 基）丙稀酸醋、二一三經曱基丙燒之ε —己内醋12莫耳加 ❶ 成物之六（甲基）丙稀酸醋、山梨醇之ε ~己内醋6莫耳加 成物之六（甲基）丙稀·酸醋、甘露醇之e —己内醋6莫耳加 成物之六（甲基）丙烯酸酯等。 第2硬塗用樹脂組成物中之前述從對於4元以上之多 元醇的每1元之加成重複單位為n=l或2之環氧烧烴加成 物得到之含有環氧烷烴加成物之多官能（曱基）丙烯酸酯類 及/或從對於4元以上之多元醇的每1元的加成重複單位為 n=l或2之己内酯加成物得到之含有己内酯加成物之多官 能（甲基）丙烯酸酯類之合計量，以30質量％以上為佳，較 47 201022304 佳為40質量％以上、80質量％以下，更佳為7〇質量％以下。 前述合計量若超過80質量％，塗佈於基板/保護層之層積體 後之翹曲有時增大，另一方面，若不滿3〇質量％，則耐擦 傷性或硬度降低’有時無法展現硬塗性能。 前述第2硬塗用樹脂組成物，以光聚合起始劑為必要 成分。光聚合起始劑例如：藉由紫外線照射而產生聚合起 始自由基之光聚合起始劑，又，藉由紫外線照射而產生聚 合起始陽離子之光陽離子聚合起始劑；等。該等聚合起始 劑可單獨使用，也可併用2種以上。又，進一步添加熱聚 Θ β促進劑、光增感劑、光聚合促進劑等亦佳。該等聚合起 始劑、熱聚合促進劑、光增感劑、光聚合促進劑等，可使 用能構成本發明之硬化性樹脂組成物所例示者。光聚合起 始劑之調配量，相對於第2硬塗用樹脂組成物之合計量， 宜佳為0.5質量％〜20質量％，較佳為1質量％〜15質量％， 更佳為2質量％〜10質量％。光聚合起始劑之調配量若不滿 0·5質量％，有時組成物不會充分硬化。反之，光聚合起始 ❹ 劑之調配量若超過2 0質量％ ’有時硬化物之物性不會進一 步提升，反而產生不利影響，損及經濟性。 刚述第2硬塗用樹脂組成物，宜包含含有乙稀越基之 (甲基）丙烯酸酯類。含有乙烯醚基之（甲基）丙烯酸酯類， 具有使與通常使用為基板之聚碳酸酯間的密合性，及稀釋 效果而、降低硬塗材黏度之效果。含有乙稀趟基之（甲基） 丙烯酸酯類，例如：（甲基）丙烯酸2 —乙烯氧基乙酯、（曱 基）丙烯酸3 —乙烯氧基乙酯、（甲基）丙烯酸2—乙烯氧基 48 201022304 .丙酯、（甲基）丙烯酸1 一甲基一2 —乙烯氧基乙酯、（甲基） 丙烯酸4 一乙烯氧基丁酯、（甲基）丙烯酸6—乙烯氧基己 酯、（甲基）丙烯酸4_乙烯氧基環己酯、（曱基）丙烯酸4 一乙烯氧基曱基環己基甲酯、（甲基）丙烯酸2-(2—乙烯 氧基乙氧基）乙酯、（甲基）丙烯酸2 —（2 —乙烯氧基異丙氧 基）丙酯、（甲基）丙烯酸2— {2—(2 —乙烯氧基乙氧基）乙 氧基}乙酯。其中，（甲基）丙烯酸2-(2 —乙烯氧基乙氧 ©基）乙酯較佳。第2硬塗用樹脂組成物中之含有乙烯醚基之 (甲基）丙烯酸酯類之調配量，較佳為5質量％〜35質量％， 更佳為10質量％〜30質量％。 前述第2硬塗用樹脂組成物，於25°C，以20mPa. s 以上lOOmPa . s以下較佳。較佳為30mPa · s以上80mPa · s、更佳為40mPa · s以上70mPa，s。硬塗用樹脂組成物之 黏度若為上述範圍内，則硬塗層能以均勻厚度形成。但是， 硬塗用樹脂組成物之黏度若為上述範圍外，則有時硬塗層 φ 之中心部厚度減薄，或端部厚度變厚。在此，黏度，係於 溫度25°C之條件下使用B型黏度計（型式「RB80L」：東機 產業（股）製）計算之值。 前述第2硬塗用樹脂組成物’可含有具反應性基之募 聚物及或聚合物。位於該寡聚物及或聚合物之反應性基， 以（甲基）丙烯醯基較佳。具（曱基）丙烯醯基之寡聚物或聚 合物’以胺酯（甲基）丙烯酸酯、（曱基）丙烯醯基懸垂聚合 物、環氧樹脂、乙稀轉基懸垂聚合物、環氧（甲基）丙稀酸 S旨、聚醋（甲基）丙烯酸酯較佳。第2硬塗用樹脂組成物中， 49 201022304 具（曱基）丙稀醢基之募聚物及或聚合物之調配量，宜為3 質量！％以上20質量％以下，較佳為5質量％以上15質量％以 下。寡聚物及或聚合物之調配量若超過2〇質量％，則黏度 上升’有時無法形成適當的硬塗層厚度。又，若不滿3質 量％’有時塗佈於基板後之翹曲增大，或韌性降低，塗膜產 生裂隙破裂及剝離等，長期保存安定性變差。Preferably, it is preferably 1 〇 or more, preferably 0.70 or less, more preferably 〇 6 〇 or less, and even more preferably 0.50 or less, and most preferably 〇 4 〇 or less. The loss of the tangent grasped 5 series and the storage modulus E were also determined by dynamic viscoelasticity. Also, the same conditions are used for the measurement conditions. If the loss tangent t exceeds 〇·7〇, the long-term preservation stability of the optical disc may deteriorate. Especially, perhaps the disc has a depression. In addition, when the loss is tangential*, when the 〇 〇 〇 , , , , , , , , 。 。 。 。 。 。 。 。 。 。 。 。 。 The cured product obtained by curing the curable resin composition of the present invention has a glass transition temperature of 玻璃 when the elastic modulus of the cured product is low.匚 above 39 201022304 is better 'better than 5 ° C, more preferably l 〇 ° C above, 3 (TC below. Glass point transfer temperature, system and storage elastic modulus E, also obtained by dynamic viscoelasticity measurement The value 'uses the maximum tan 5 value. Further, the measurement conditions are the same as those of the storage elastic modulus E'. If the glass transition temperature exceeds 30 ° C, the warpage of the optical disc may increase. If the glass point shift temperature is less than 0C, the disc may be recessed, and the long-term storage stability may be deteriorated. The cured product obtained by hardening the curable resin composition of the present invention has a higher modulus of elasticity in the cured product. The storage modulus E at 25 〇c is preferably 1200 MPa or more, preferably nooMPa or more, more preferably 16 〇〇Mpa 〇 or more, and most preferably 1800 MPa or more and 2100 MPa or less. Storage modulus E, The value obtained by measuring the dynamic viscoelasticity of the obtained cured product is also obtained. The hardening resin composition is sufficiently cured by a predetermined curing condition or a curing method to obtain a storage elastic modulus E, a hardness of 12 MPa or more and 2100 MPa or less. Storage When the elastic modulus e' is less than 12 〇〇Mpa, the long-term storage stability of the optical disk may be deteriorated, in particular, there may be dents. The cured product obtained by curing the curable resin composition of the present invention has a higher elastic modulus than that of the cured product. When Gao is good, the loss of tangential cut at 25£&gt;c is preferably _ 0.03 or more, preferably 0.12 or less, preferably 〇1〇 or less, more preferably 0.07 or less, tangent tan 5, and storage. The modulus of elasticity e is also determined by the dynamic viscoelasticity measurement. The same conditions are used for the measurement conditions. If the loss tangent tan5 exceeds 〇.12, the long-term storage stability of the optical disc may deteriorate. In particular, the disc has a depression. The cured product obtained by curing the curable resin composition of the present invention has a glass transition temperature of preferably 40 201022304, preferably 7 (Tc or more, more preferably 75) when the elastic modulus of the cured product is high. Above °C, the optimum is 8 (TC or more, preferably 90 C or less, preferably 85 ° C or less. The glass point shift temperature is the storage elastic modulus E, and the value obtained by dynamic viscoelasticity measurement is the largest. Tan (5-value temperature. Also 'measurement conditions The same conditions as the storage modulus E are used. When the glass point shift temperature is less than 6 (TC, the disc may be dented or the long-term storage stability may be deteriorated. The curable resin composition of the present invention is suitable for use on a disc. The cured product obtained by curing the curable resin composition of the present invention is particularly excellent in scratch resistance and hardness, and the warpage of the substrate is still small over a long period of time. Therefore, it is suitable for use in optical discs, especially for reading and writing laser light. The optical disk of the laser light (Blu-ray Disc (registered trademark)). &lt;&lt;&lt;&gt;&gt; The optical disk of the present invention is characterized by having a protective layer for curing the curable resin composition for optical disks of the present invention. The optical disk of the present invention is obtained by curing the curable resin composition for a photosensitive optical disk of the present invention by a reflective film formed on a substrate to form a protective layer. In the optical disc manufacturing method of the present invention, a conventionally known method of manufacturing an optical disc is used in addition to the method of manufacturing the protective layer. The protective layer obtained by curing the curable resin composition of the present invention has a thickness of 2 〇 or more, preferably 3 Å or more, more preferably 5 〇 &quot; m or more, and particularly preferably 70 Å or more. Preferably, the thickness of the protective layer is 15 〇 or less, preferably 12 〇 or less, more preferably l 〇 5 / / m or less. When used on a disc, the thickness of the protective layer When the thickness is less than 20/zm, the protection layer of the functional layer such as the recording layer of the protective layer β may not be charged as 41 201022304. If it exceeds 150 #m', the control of the film thickness may become difficult. Polymethylmethacrylate (PMma), polystyrene (PS), polyethylene terephthalate (PET), acrylonitrile-butadiene-styrene copolymer (ABS), polycarbonate (PC) Such as a resin molded article and a film; glass, etc. Among them, polycarbonate (pC) is preferred. Further, in the present invention, the reflective film means not only the shape of the protective layer directly on the reflective film. A functional layer such as a recording layer or a dielectric layer is laminated on the reflective film, and a protective layer is laminated on the functional layer. The recording capacity of the optical disc is increased, and a disc having a multi-layer structure in which the information recording layer is two or more layers is formed, and an intermediate layer in which a transparent ultraviolet curable resin is hardened by ultraviolet rays is formed between the information recording layers. The composition is suitable for forming a protective layer of a disc, and can also be used as an ultraviolet curable resin for the intermediate layer. The optical disc of the present invention is, for example, a Blu-ray disc (registered trademark), etc. The optical disc of the present invention is excellent in transparency. It is suitable for recording and reproducing optical discs using, for example, 380 nm to 430 nm. The protective layer for Blu-ray discs (registered trademark) requires low warpage (low shrinkage) and transparency (light penetration). Characteristics such as adhesion to polycarbonate substrate, low rot, purity, rapid hardenability (productivity), dimensional stability (promoting W change of sample, small residual film, and permanent deformation such as dent) However, the protective layer which cures the curable resin composition for optical disks of the present invention 'satisfies all of the above characteristics. Further, the present invention is not limited to the above embodiment, and can be expressed in the scope of the patent application. Various changes are made. The optical disk of the present invention has a hard coat 42 formed directly on the protective layer. 201022304 - a layer is also preferred. The hard coating resin composition for forming the hard coat layer is preferably, for example, a resin composition for coating (hereinafter sometimes referred to as a first resin composition for hard coating), a polymer having a multi-branched reactive compound and/or a side chain reactive group, and a polymerization initiator; (2) hard The resin composition for coating (sometimes referred to as a second resin composition for hard coating) includes an epoxy having a repeating unit of n=l, 2 from 1 to 1 for a polyol of 4 Å or more. The polyfunctional (meth) acrylate of the alkylene oxide-containing adduct obtained by burning the hydrocarbon adduct and/or the addition repeat unit per element of the polyol of 4 or more is n= A polyfunctional (meth) acrylate containing a caprolactone adduct obtained from a 1,2 caprolactone adduct, and a photopolymerization initiator. The resin composition for the first hard coating described above will be described. The above-mentioned multi-branched reactive compound can be exemplified, for example, by using a compound having a radical polymerizable unsaturated group which can constitute the curable resin composition of the present invention. The multi-branched reactive compound is preferably a tree-like compound represented by the above formula (3) and/or a highly branched polymer represented by the above formula (4). The polymer having a reactive group in the side chain can be, for example, an oligomer/agglomerate having a radical polymerizable group which can constitute the curable resin composition of the present invention, and has the above formula (1). A vinyl-based polymer representing a repeating unit. A polymer having a side chain reactive group other than the vinyl polymer represented by the above formula (1), for example, a copolymer of methacrylic acid and methacrylic acid described in JP-A-263893 A (meth)acrylic polymer having a polycondensation of a polycondensation epoxy compound glycidylmethacrylic acid, which is formed by agglomeration of a polycondensation epoxy compound, 201043304. In the first hard-coating resin composition, the amount of the multi-branched reactive compound and/or the side-chain-reactive polymer is preferably from 1% by mass to less than 90% by mass, preferably from 1% by mass to less than 90% by mass. 30% by mass or more and 70% by mass or less. When the amount of the polymer having a multi-branched reactive compound and/or a side chain having a reactive group is less than 10% by mass, the crosslinking density is lowered, so that the curing rate is sometimes lowered or the coating strength of the cured product is insufficient. In addition, when the amount is 90% by mass or more, the warpage of the laminate obtained by applying to the substrate may be increased. The first hard coating resin composition 'is a polymerization initiator as an essential component, for example, a thermal polymerization initiator which generates a polymerization initiation radical by heating; and photopolymerization which generates a polymerization initiation radical by ultraviolet irradiation. An initiator, a photocationic polymerization initiator which generates a polymerization starting cation by ultraviolet irradiation; and the like. These polymerization initiators may be used singly or in combination of two or more. Further, a thermal polymerization accelerator, a photosensitizer, a photopolymerization accelerator, and the like are further preferably added. As the polymerization initiator, the thermal polymerization accelerator, the photosensitizer, the photopolymerization accelerator, and the like, those constituting the curable resin composition of the present invention can be used. Further, the suitable range of the blending amounts is the same as that of the hardenable resin composition of the present invention. The resin composition for the first hard coating layer described above may contain a reactive group-containing oligomer and/or polymer in addition to the multi-branched reactive compound, the polymer having a side chain reactive group, and a polymerization initiator. . The reactive group located in the polymer and/or the polymer is preferably a (meth) acrylonitrile group. A (meth) acrylonitrile-based polymer or polymer, with an amine ester (mercapto) acrylate, (mercapto) C 201022304 - a dilute based pendant polymer, an epoxy resin, a vinyl fluorenyl group The pendant polymer, epoxy (meth) acrylate, and polyester (meth) acrylate are preferred. In the first hard coating resin composition, the amount of the oligomer (meth) propylene group-based oligomer and the polymer is preferably 20% in the resin composition for hard coating! The amount is preferably 80% by mass or less, more preferably 30% by mass or more. When the amount of the oligomer and the polymer having a (meth)acrylonitrile group is more than 80% by mass, the content of the multi-branched reactive compound φ is reduced, so that it may be applied to the substrate. The warpage is increased, or the kinetic property is lowered, and the film is cracked and peeled off, or the long-term storage stability is deteriorated. Further, the first hard coating resin composition may contain a (fluorenyl)acrylic monofunctional monomer. A polymerizable monomer such as a (meth)acrylic polyfunctional monomer. The polymerizable monomer is not particularly limited as long as it can be co-cured with the multi-branched reactive compound. Specifically, for example, monofunctional and/or polyfunctional polymerizable groups constituting the curable resin composition of the present invention can be used. The monomer is exemplified. In the resin composition for the first hard coating, the amount of the polymerizable monomer is preferably from 〇% by mass to 5% by mass in the resin composition for hard coating, preferably from 10% by mass to 65% by mass. . When the amount of the polymerizable monomer is more than 8% by mass, the curing shrinkage ratio or the internal strain is increased. For example, the warpage applied to the plastic substrate and the hardened laminate may increase. Next, the resin composition for the second hard coat will be described. The above-mentioned addition of a per-molecular weight of a tetrahydric or higher polyhydric alcohol repeating single 45 201022304 4 is an alkylene oxide adduct of η 1 or 2 and containing an alkylene oxide addition polyg energy (meth) acrylate a polyfunctional (meth) group containing an hexane vinegar adduct obtained from a caprolactone adduct having a repeating unit of n=l or 2 for a unit of 4 or more polyols (4) Acidic brewing, for example, using ♦ pentaerythritol, dipentaerythritol, bis-trimethyl methacrylate, sorbitol, mannitol, etc., for more than 4 yuan of polyol, for each hydroxy group, repeating the early position n=1 or 2 A polyfunctional (meth) acrylate obtained by adding a polyhydric alcohol adduct of an alkylene oxide and/or caprolactone. The above-mentioned addition of an alkylene oxide adduct containing n-l or 2 to an alkylene oxide adduct having a single-parameter of n=l or 2 for the addition of a unit of 4 or more polyols (meth) Acrylates, for example, tetrakis (meth) acrylate of ethylene oxide 4 molar addition of pentaerythritol, tetrakis (meth) acrylate of pentaerythritol 8 molar addition of pentaerythritol, Four (meth) acrylates of pentaerythritol, 4 moles of ethylene oxide, 4 (meth) acrylates of pentaerythritol, 8 moles of ethylene, and epoxy pentene of dipentaerythritol Hexameric hexa(meth) acrylate, dipentaerythritol, cyclohexyloxyethylene 12 molar addition of hexa(meth) acrylate, dipentaerythritol, hexamethene acrylate: 6 molar addition Hexa(methyl) acrylate, dipentaerythritol, propylene oxide 12 molar addition of hexa(meth) acrylate, dipentaerythritol, ethylene oxide 5 molar addition of five (A) Acetate, dipentaerythritol, ethylene oxide 10 molar addition of penta (meth) acrylate, two Hexa(meth)acrylate of ethylene oxide 6 molar addition of hydroxymethylpropane, hexa(meth)acrylic acid of ethylene oxide oxime 2 molar addition of ditrimethylolpropane Ester, ditrimethylolpropane propylene oxide 6 molar addition compound 46 201022304 - hexa(meth) acrylate, ditrimethylolpropane propylene oxide 12 molar addition of six (meth) acrylate, hexa(meth) acrylate of ethylene oxide 6 molar addition of sorbitol, hexa(meth) acrylate of ethylene oxide 6 molar addition of mannitol Wait. The above-mentioned multi-g energy (meth) propylene containing a caprolactone adduct obtained from a caprolactone adduct having a repeating unit of η-1 or 2 for a monovalent or higher polyhydric alcohol. Acid esters, for example: ε-caprolactone of pentaerythritol ❿ 4 (meth) acrylate of 4 molar addition, ε of pentaerythritol, 4 (meth) acrylate of 8 molar addition of vinegar, Ethyl pentaerythritol ε-caprolactone 6-mol addition of hexa(indenyl) acrylate, dipentaerythritol ε-caprolactone 12 molar addition of hexa(meth) acrylate, dipentaerythritol ε — Five (meth) acrylate of caprolactone 5 molar addition product, ε-caprolactone of dipentaerythritol, pentadyl lactone, 10 molar addition of penta (meth) acrylate, di-trihydroxyhydrinyl propane ε - Caprolactone 6 molar addition of hexa(methyl) acrylate vinegar, 213 thiol propyl ε - caprolactone 12 moles ❶ hexa(methyl) propylene Sour vinegar, sorbitol ε ~ hexamethylene vinegar 6 molar addition of hexa(methyl) propylene vinegar, mannitol e - caprolactone 6 molar addition of six Meth) acrylate. In the resin composition for the second hard coat, the above-mentioned alkylene oxide-containing addition product obtained by adding an alkylene oxide adduct of n = 1 or 2 to each of the above-mentioned polyols having a repeating unit of 4 or more is obtained. a polyfunctional (fluorenyl) acrylate and/or a caprolactone derived from a caprolactone adduct having a repeating unit of n=l or 2 for a unit of 4 or more polyols The total amount of the polyfunctional (meth) acrylates of the adduct is preferably 30% by mass or more, more preferably 40% by mass or more and 80% by mass or less, and still more preferably 7% by mass or less, compared with 47 201022304. When the total amount is more than 80% by mass, the warpage after application to the laminate of the substrate and the protective layer may increase. On the other hand, if the amount is less than 3% by mass, the scratch resistance or the hardness may be lowered. Can not show hard coating performance. The resin composition for the second hard coat layer contains a photopolymerization initiator as an essential component. The photopolymerization initiator is, for example, a photopolymerization initiator which generates a polymerization starting radical by ultraviolet irradiation, and a photocationic polymerization initiator which generates a polymerization starting cation by ultraviolet irradiation; These polymerization initiators may be used singly or in combination of two or more. Further, it is also preferable to further add a thermal poly(β) accelerator, a photosensitizer, a photopolymerization accelerator, and the like. These polymerization initiators, thermal polymerization accelerators, photosensitizers, photopolymerization accelerators, and the like can be exemplified as the curable resin composition of the present invention. The blending amount of the photopolymerization initiator is preferably 0.5% by mass to 20% by mass, preferably 1% by mass to 15% by mass, more preferably 2% by mass based on the total amount of the second hard coating resin composition. %~10% by mass. If the amount of the photopolymerization initiator is less than 0.5% by mass, the composition may not be sufficiently cured. On the other hand, if the amount of the photopolymerization initiator is more than 20% by mass, the physical properties of the cured product may not be further increased, which may adversely affect the economy. The resin composition for the second hard coat is preferably a (meth) acrylate containing an ethylene group. The (meth) acrylate containing a vinyl ether group has an effect of improving the adhesion between the polycarbonate which is usually used as a substrate and the effect of diluting, and lowering the viscosity of the hard coating material. (meth) acrylates containing ethylene sulfhydryl groups, for example: 2-vinyloxyethyl (meth)acrylate, 3-vinyloxyethyl (meth)acrylate, 2-vinyl (meth)acrylate Oxygen 48 201022304. Propyl ester, (meth)acrylic acid 1-methyl-2-vinyloxyethyl ester, (meth)acrylic acid 4-vinyloxybutyl ester, (meth)acrylic acid 6-vinyloxy Ester, 4_vinyloxycyclohexyl (meth)acrylate, 4-vinyloxydecylcyclohexylmethyl (meth)acrylate, 2-(2-vinyloxyethoxy)(meth)acrylate Ethyl ester, 2-(2-vinyloxyisopropoxy)propyl (meth)acrylate, 2-{2-(2-vinyloxyethoxy)ethoxy}ethyl (meth)acrylate . Among them, 2-(2-vinyloxyethoxy-methoxy)ethyl (meth)acrylate is preferred. The blending amount of the vinyl ether group-containing (meth) acrylate in the resin composition for the second hard coat is preferably 5% by mass to 35% by mass, more preferably 10% by mass to 30% by mass. The resin composition for the second hard coat is preferably 20 mPa·s or more and 100 mPa·s or less at 25 ° C. It is preferably 30 mPa · s or more and 80 mPa · s, more preferably 40 mPa · s or more and 70 mPa, s. When the viscosity of the resin composition for hard coating is within the above range, the hard coat layer can be formed with a uniform thickness. However, if the viscosity of the resin composition for hard coating is in the above range, the thickness of the central portion of the hard coat layer φ may be reduced or the thickness of the end portion may be increased. Here, the viscosity is calculated using a B-type viscometer (type "RB80L": manufactured by Toki Sangyo Co., Ltd.) at a temperature of 25 °C. The second hard coating resin composition ' may contain a polymer having a reactive group and a polymer. The reactive group located in the oligomer and the polymer is preferably a (meth) acrylonitrile group. An oligomer or polymer having a (fluorenyl) acrylonitrile group, an amine ester (meth) acrylate, a (fluorenyl) propylene fluorene-based pendant polymer, an epoxy resin, an ethylene-based pendant polymer, and a ring Oxy (meth)acrylic acid S is preferred as the polyester (meth) acrylate. In the resin composition for the second hard coating, 49 201022304 The amount of the polymer and the polymer of the (fluorenyl) acrylonitrile group is preferably 3 masses! % or more is 20% by mass or less, preferably 5% by mass or more and 15% by mass or less. When the amount of the oligomer and the polymer is more than 2% by mass, the viscosity is increased. In some cases, an appropriate hard coat thickness may not be formed. In addition, when the amount is less than 3% by mass, the warpage after application to the substrate is increased, or the toughness is lowered, and the coating film is cracked and peeled off, and the long-term storage stability is deteriorated.

又，前述第2硬塗用樹脂組成物，可含有（甲基）丙烯 酸系單官能單體、（甲基）丙烯酸系多官能單體等聚合性單 體。該等聚合性單體，例如：可使用能構成本發明之硬化 性樹脂組成物之單官能及/或多官能之聚合性單體所例示 者。第2硬塗用樹脂組成物中，聚合性單體之調配量，相 對於組成物之合計量’宜超過〇質量％不滿6〇質量％，較佳 為10質量％以上50質量％以下。聚合性單體之調配量若超 過60質量％，則硬化收縮率或内部應變增大，例如塗佈於 基板/保護層之層積體並使硬化後之翹曲有時增大。Further, the second hard coating resin composition may contain a polymerizable monomer such as a (meth)acrylic monofunctional monomer or a (meth)acrylic polyfunctional monomer. As the polymerizable monomer, for example, a monofunctional and/or polyfunctional polymerizable monomer which can constitute the curable resin composition of the present invention can be used. In the resin composition for the second hard coating, the amount of the polymerizable monomer is preferably more than 〇% by mass to less than 6% by mass, more preferably from 10% by mass to 50% by mass based on the total amount of the composition. When the amount of the polymerizable monomer is more than 60% by mass, the curing shrinkage ratio or the internal strain increases, for example, it is applied to the laminate of the substrate/protective layer and the warpage after curing may increase.

使前述第2硬塗用樹脂組成物硬化成之硬化物於25t 之貯藏彈性率E，以600MPa以上2000MPa以下為佳，較佳 為700MPa以上1800MPa以下，最佳為7〇〇Mpa以上ΐ6〇〇Μρ&amp; 以下。貯藏彈性率E’若超過2000MPa，有時韌性降低，硬 塗層變形時會發生裂痕。又，貯藏彈性率E，若不滿 600MPa，有時得不到目的之硬度。貯藏彈性率『係使用 得到之硬化物利用動態黏彈性測定得到之值。又第2硬 塗用樹脂組成物之硬化物之玻璃轉移溫度雖不特別限定， 但是’玻璃點移轉溫度以4(rc以上1 〇(rc以下較佳較佳 50 201022304 為45 C以上90°C以下，最佳為50°C以上80°C以下。玻璃 點移轉溫度係與貯藏彈性率E’同樣利用動態黏彈性測定 得到之值，採用最大tan 5值之溫度。又，動態黏彈性測 疋之測定條件’採用樣本尺寸寬長度5〇mmx厚度 100 、拉伸模式、頻率1 Hz、夾頭距離25mm、振幅0.1%、 升溫速度5 °C /分較佳。 别述第1及第2硬塗用樹脂組成物，更可視需要，就The storage elastic modulus E of the cured product obtained by curing the second hard coating resin composition is preferably 600 MPa or more and 2000 MPa or less, more preferably 700 MPa or more and 1800 MPa or less, and most preferably 7 〇〇Mpa or more ΐ6〇〇. Μρ&amp; Below. When the storage modulus E' exceeds 2,000 MPa, the toughness may be lowered, and cracks may occur when the hard coat layer is deformed. Further, when the storage modulus E is less than 600 MPa, the intended hardness may not be obtained. The storage modulus is the value obtained by measuring the dynamic viscoelasticity of the obtained cured product. Further, although the glass transition temperature of the cured product of the resin composition for the second hard coat is not particularly limited, the glass transition temperature is 4 (rc or more and 1 〇 (r is preferably 5% or less, preferably 50, 50, 22,304, 45 C or 90°). Below C, the optimum is 50 ° C or more and 80 ° C or less. The glass point shifting temperature is the same as the storage elastic modulus E', and the value obtained by dynamic viscoelasticity measurement is used, and the temperature of the maximum tan 5 value is used. The measurement conditions of the measurement are as follows: sample size width 5 〇 mm x thickness 100, tensile mode, frequency 1 Hz, chuck distance 25 mm, amplitude 0.1%, and temperature increase rate 5 ° C / min. 2 resin composition for hard coating, more as needed,

添加物而Q，添加非反應性樹脂（例如丙烯酸系樹脂、胺酯 丙烯酸酯樹脂、聚酯樹脂、聚胺酯樹脂、聚苯乙烯樹脂、 聚氣乙烯樹脂等）、著色顏料、可塑劑、鏈移轉劑、聚合禁 止劑、紫外線吸收劑、近紅外線吸收劑、光安定劑、抗氧 化劑、難燃化劑、消,光劑、染料、消泡劑、塗平齊j、抗靜 電劑、分散劑、滑動劑、表面改質劑、搖變化劑、搖變助 劑、金屬氧化物構成之微粒等。該等添加物之存在，不特 別影響本發明之效果。該等添加物，可單獨使用也可併用 2種以上。又’該等添加物之調配量之適當範圍與本發明 之硬化性樹脂組成物同。 别述第1及第2硬塗用樹脂組成物，可藉由將前述多 分支型反應性化合物、侧鏈具反應性基之聚合物、聚合起 始劑等以公知方法混合•授拌得到。χ，使用前述硬塗用 樹脂組成物形成硬塗料，塗佈方法或硬化方法可採用於 本發明之硬化性樹脂組成物之塗佈方法或硬化方法為同樣 方法。 本發明之光碟中 視目的可將抗靜電層、黏接著劑層、 51 201022304 接著層、易接著層、應變緩和層、防眩（nonglare)層、光 觸媒層等防污層、抗反射層、紫外線遮蔽層、熱線遮蔽層、 電磁波遮蔽層、氣體阻障層、反射層、記錄層、介電體層 等各種機能性層分別疊層塗佈。又，使本發明之硬化性樹 脂組成物硬化得到之保護層與各機能性層之疊層順序不特 別限定，疊層方法亦不特別限定。 【實施例】 以下舉實施例及比較例更具體說明本發明，但本發明 不限於下述實施例及比較例，在能適合前•後述趣旨之範 圍可適當加以變更並實施，該等均包含在本發明之技術範 圍。 &lt;&lt;評價方法〉〉 &lt;黏度〉 採用將得到之硬化性樹脂組成物於溫度2 5 °C之條件 下’使用B型黏度計（型式「RB80L」：東機產業（股）製） 測定之值。 &lt;硬化層之透明性&gt; 從得到之基板/硬化層之層積體僅將硬化層（組成物之 硬化膜）剝取既定尺寸，使用分光光度計（型式UV— 3100、 島孝製作所（股）公司製）測定於405nm之光線穿透率。採用 空氣為空白。其次，對於計算之光線穿透率之值，以下列 基準評價。 ◎:穿透率為89%以上 〇：穿透率為85%以上 201022304 0 _ X :穿透率不滿85%。 &lt;質量減量&gt; 從得到之基體/保護層之層積體僅將保護層（組成物之 硬化膜）剝取既定尺寸，以（試驗前之質量—試驗後之質 量）/試驗前之質量xlOO計算加熱促進試驗（於7〇»c之烘箱 中保持100小時）前後之質量減量（％)。其次，對於計算之 光線穿透率之值，依照下列基準評價。 ◎:質量減量為1.0質量％以下 Φ 〇.質量減量為2·0質量％以下 X :質量減量超過2. 0質量％。 &lt;殘膜性&gt; 加熱促進試驗前後之硬化層（形成有硬塗層時，為保護 層與硬塗層之合計）之厚度，使用雷射焦點變位計測定，以 下列通式計算殘膜率（％)，並以下列基準評價殘膜性。Addition and Q, adding non-reactive resin (such as acrylic resin, amine ester acrylate resin, polyester resin, polyurethane resin, polystyrene resin, polyethylene resin, etc.), coloring pigment, plasticizer, chain transfer Agent, polymerization inhibitor, ultraviolet absorber, near-infrared absorber, light stabilizer, antioxidant, flame retardant, light, light, dye, defoamer, coating, antistatic agent, dispersant, A slip agent, a surface modifier, a shake modifier, a rocking aid, a fine particle composed of a metal oxide, or the like. The presence of such additives does not particularly affect the effects of the present invention. These additives may be used singly or in combination of two or more. Further, the appropriate range of the amount of the additives is the same as that of the curable resin composition of the present invention. The resin composition for the first and second hard coats may be obtained by mixing and mixing the above-mentioned multi-branched reactive compound, a polymer having a side chain reactive group, a polymerization initiator, and the like by a known method. χ, a hard coating material is formed by using the above-mentioned resin composition for hard coating, and a coating method or a curing method can be employed in the same method as the coating method or the curing method of the curable resin composition of the present invention. In the optical disc of the present invention, the antistatic layer, the adhesive layer, the 51 201022304 subsequent layer, the easy adhesion layer, the strain relief layer, the antiglare layer, the photocatalyst layer and the like, the antifouling layer, the antireflection layer, and the ultraviolet shielding may be used. Various functional layers such as a layer, a heat ray shielding layer, an electromagnetic wave shielding layer, a gas barrier layer, a reflective layer, a recording layer, and a dielectric layer are laminated and coated, respectively. Further, the order of laminating the protective layer and the functional layers obtained by curing the curable resin composition of the present invention is not particularly limited, and the lamination method is not particularly limited. EXAMPLES Hereinafter, the present invention will be specifically described by way of Examples and Comparative Examples, but the present invention is not limited to the following Examples and Comparative Examples, and can be appropriately modified and implemented in the scope of the present invention. It is within the technical scope of the present invention. &lt;&lt;Evaluation method&gt;&lt;Viscosity> The B-type viscometer (type "RB80L": manufactured by Toki Sangyo Co., Ltd.) was used under the condition of a temperature of 2 5 °C. The value of the measurement. &lt;Transparency of the hardened layer&gt; From the obtained laminate of the substrate/hardened layer, only the hardened layer (hardened film of the composition) was peeled off to a predetermined size, and a spectrophotometer (type UV-3100, Shimao Manufacturing Co., Ltd.) was used. The company's system) measures the light transmittance at 405 nm. Use air as a blank. Next, the value of the calculated light transmittance is evaluated on the following basis. ◎: The penetration rate is 89% or more 〇: The penetration rate is 85% or more 201022304 0 _ X : The penetration rate is less than 85%. &lt;mass depletion&gt; From the obtained laminate of the substrate/protective layer, only the protective layer (hardened film of the composition) is stripped to a predetermined size (quality before the test - mass after the test) / mass before the test XlOO calculates the mass loss (%) before and after the heat promotion test (100 hours in an oven of 7〇»c). Next, for the calculated value of the light transmittance, the following criteria were evaluated. ◎: The mass loss is 1.0% by mass or less Φ 〇. The mass loss is 2.0% by mass or less X: The mass loss is more than 2.0% by mass. &lt;Residual film property&gt; The thickness of the hardened layer (the total of the protective layer and the hard coat layer when the hard coat layer is formed) before and after the heating promotion test is measured by a laser focus variator, and the residue is calculated by the following formula The film ratio (%) was evaluated, and the residual film properties were evaluated on the following basis.

殘膜率（％)=加熱促進試驗後之硬化層之厚度/加熱促 φ 進試驗前之硬化層厚度xlOO 〇：殘膜率為97.0%以上〜不滿103% X :殘膜率不滿97. 0%或為103%以上。 &lt;起始之翹曲增加量&gt; 將得到之基體/硬化層之層積體，放置於水平玻璃板上 使硬化層（組成物之硬化膜）位在上面侧後，使用日本觸媒 (股）公司製之雷射變位讀取方式之翹曲角測定裝置， 度25°C、相對濕度50%環境下，測定於半徑58mm位置之輕 射狀傾斜（radial tilt)值。起始之翹曲增加量，採用塗佈 53 201022304 前後之翹曲變化量。 &lt;加熱促進試驗後之翹曲增加量&gt; 將得到之基體/硬化層之層積體，於70°C烘箱中保持 100小時，又，於溫度25〇c、相對濕度5〇%環境下放置Μ 小時時之翹曲值，與起始翹曲增加量以同樣方式進行，剛 定輻射狀傾斜值。藉此求出加熱促進試驗前後之翹曲增加 量。 &lt; 25°C之貯藏彈性率E，&gt; 從得到之基體/硬化層之層積體將硬化層（硬化物之硬 · 化膜）剝離，使用TA儀器製動態黏彈性測定裝置RSAI11， 以下列測定條件進行測定。 (1) 樣本尺寸：寬8mm、長度5〇随 (2) 夾頭距離25mm (3) 測定模式：拉伸 U)頻率：1Hz ⑸寬：〇. 1% (6)升溫速度：5°c/分 ® 進行動態黏彈性測定， 率E’之值。 採用得到之於25。(：之貯藏彈性 〈25C之損失正切tan占〉 採用與25。(：之貯藏彈性率 得到之值。 〈玻璃點移轉溫度Tg&gt; 以同樣測定方法及條件 與25°C之貯藏彈性率 E’以 同樣測定方法及條件得到 54 201022304 -之值’採用最大tan 5值之溫度。 〈永久變形量&gt; 使用得到之基體/硬化層之層積體，以微小壓縮試驗機 (島津製作所製、型式，—蘭），採用試驗條件使用平 面壓子50^^徑、負載速度2〇mN/秒、最大荷重3〇〇mN、最 大荷重之保持時間9〇秒、釋載速度2〇mN/秒完全释載後 之保持時間90秒時，殘留於基體/保護層之層積體之變形 ❹量測定值。又，該試驗若永久變形量超過1/z瞒，有時由 於凹陷等會使雷射光容易產生讀取錯誤或長期保存安定性 劣化。 &lt;組成物之光線穿透率&gt; 使用分光光度計（型式UV—3100、島津製作所（股）公 司製）測定得到組成物於4〇〇nm、380nm、360nm之光線穿透 率。光線穿透率，係將組成物注入隔著1〇〇众m之間隔件之 石英玻璃比色管中，並使用分光光度計測定於各波長之穿 ❹透率。又，採用空氣為空白。 &lt;組成物之回收性&gt; 以上述方法測定得到之組成物之起始黏度後，回收未 用於光碟之保護層（組成物之硬化膜）之組成物（旋塗時從 基板突出之組成物），並測定黏度。使用得到之起始黏度及 回收後之黏度，從下列通式計算黏度上升率。其次，關於 計算之黏度上升率之值，依照下述基準評價。Residual film rate (%) = thickness of hardened layer after heating promotion test / heating promoted φ thickness of hardened layer before test x100 〇: residual film rate of 97.0% or more ~ less than 103% X: residual film rate less than 97. 0 % or more than 103%. &lt;Initial warpage increase amount&gt; After the obtained laminate of the base/hardened layer was placed on a horizontal glass plate so that the hardened layer (hardened film of the composition) was positioned on the upper side, the Japanese catalyst was used ( The warp angle measuring device of the laser displacement reading method manufactured by the company measures the light tilt value at a position of 58 mm in a radius of 25 ° C and a relative humidity of 50%. The initial increase in warpage was measured by the amount of warpage before and after coating 53 201022304. &lt;Augmentation amount of warpage after heating promotion test&gt; The obtained laminate of the matrix/hardened layer was kept in an oven at 70 ° C for 100 hours, and further, at a temperature of 25 ° C and a relative humidity of 5 % The warp value at the time of placing Μ is performed in the same manner as the initial warpage increase, and the radial tilt value is set. Thereby, the amount of warpage increase before and after the heating promotion test was obtained. &lt;Storage Elasticity E at 25° C.&gt; The hardened layer (hardened film of the cured product) was peeled off from the obtained laminate of the substrate/hardened layer, and a dynamic viscoelasticity measuring device RSAI11 manufactured by TA Instruments was used. The column measurement conditions were measured. (1) Sample size: width 8mm, length 5〇 with (2) Chuck distance 25mm (3) Measurement mode: Stretching U) Frequency: 1Hz (5) Width: 〇. 1% (6) Heating rate: 5°c/ Sub-® for dynamic viscoelasticity determination, rate E'. The use is obtained at 25. (: Storage elasticity <25C loss tangent tan accounted for) The value obtained by using 25: (: storage elastic modulus. < Glass point transfer temperature Tg> The same measurement method and conditions and 25 ° C storage elastic modulus E 'The value of 54 201022304 - the value of the same measurement method and condition is the temperature of the maximum tan 5 value. <The amount of permanent deformation> Using the obtained laminate of the matrix/hardened layer, a micro compression tester (manufactured by Shimadzu Corporation) Type, -Lan), using the test conditions for the plane pressure 50^^ diameter, the load speed 2〇mN/sec, the maximum load 3〇〇mN, the maximum load holding time 9〇 seconds, the release speed 2〇mN/sec The measured value of the deformation amount of the laminate remaining in the substrate/protective layer at the time of the retention time of 90 seconds after the complete release. Further, if the amount of permanent deformation exceeds 1/z 瞒 in the test, it may sometimes be due to depression or the like. The laser light is likely to cause a reading error or long-term storage stability deterioration. <Light transmittance of the composition> The composition is measured by a spectrophotometer (type UV-3100, manufactured by Shimadzu Corporation). 〇nm, 380nm, 360nm Light transmittance: The light transmittance is obtained by injecting a composition into a quartz glass cuvette through a spacer of 1 mm, and measuring the transmittance at each wavelength using a spectrophotometer. Air is used as a blank. &lt;Recyclability of the composition&gt; After the initial viscosity of the composition obtained by the above method, the composition of the protective layer (the cured film of the composition) not used for the optical disk is recovered (during spin coating) The viscosity of the composition protruding from the substrate was measured, and the viscosity increase rate was calculated from the following formula using the obtained initial viscosity and the viscosity after recovery. Next, the value of the calculated viscosity increase rate was evaluated according to the following criteria.

黏度上升率（％ )==(回收後之黏度—起始黏度）/起始黏 度 xlOO 55 201022304 〇：黏度上升率不滿10% X :黏度上升率為10%以上。 &lt;耐刮性&gt; 對於得到之基體/硬化層之層積體之硬化層（保護層或 硬塗層）表面，使用耐磨損試驗機（型式IMC—154A型、井 元製作所（股）公司製）’於荷重20 0 g/ cm2之條件下，使鋼 棉# 0000號以往返速度3〇mm/秒、往返距離25mm往返10 次後，以目視觀察受傷程度，以下列基準評價。 ◎:無變化（未認為有受傷） 〇：有數條以上極淺的傷痕 X:有無數的深的傷痕。 &lt;硬化層之表面潤滑性&gt; 於得到之基體/硬化層之層積體之硬化層（組成物之硬 化膜）表面，將作為人工指紋液之三油酸甘油醋之液滴 1.5# 1於溫度25。&lt;：、濕度50%之環境下滴加，〇5秒後， 以全自動接觸角計（型式DM500、協和界面科學（股）公司製） 測定接觸角，依下列基準進行評價。料觸角之值愈大， 則即使附著有指紋等時仍能輕易擦取。 ◎:接觸角為55°以上 〇：接觸角為50°以上 X :接觸角不滿50°。 &lt;硬塗層耐刮性&gt; 對於層積體（硬塗層/保護層/基體）之硬塗層表面，使 用耐磨損試驗機（型式IMC—15“型、井元製作所（股）公司 201022304 Λ -製），於既定荷重下，將鋼棉#_〇號以往返速度30mm/ 秒、往返距離25mm往返10次後，以目視觀察受傷程度， 以下列基準評價。 〇：於荷重200g/cm2無變化（未認為有受傷） X :於荷重200g/cm2認為有數條以上之傷痕 &lt;硬塗層耐變形性&gt; 以層積體（硬塗層/保護層/基體（樣本尺寸12cmxl2cm)) 〇之硬塗層為頂面，握著對角線之端部，以目視觀察當f曲 至對角線距離成為1〇cm為止時，層積體上之硬塗層是否發 生裂痕’並以下列基準評價。 〇：未認為有裂痕 △.遇為稱有裂痕 X :認為有大裂痕 &lt;鉛筆硬度&gt; 對於得到之基體/硬化層之層積體之硬化物層表面，使 φ 用船筆刮劃硬度試驗機（安田精機製作所（股）公司製），依 照JIS — K5400進行測定。又，荷重定為i〇〇〇g。 &lt;〈製造例1&gt;&gt; 於安裝有攪拌棒、溫度計、滴加線、氮氣/空氣混合氣 導入管之4 口燒瓶中，加入乙酸乙酯i5〇g，升溫至5〇〇c。 升溫後，將丙烯酸2 — (2-乙烯氧基乙氧基）乙酯（VEEA、 曰本觸媒製（股）公司）2〇〇g、乙酸乙酯25g與磷鎢酸 (phosphotungstic acid)13mg之混合溶解物，各花費3小 時滴加並聚合。聚合結束後，加入三乙胺並結束反應。其 57 201022304 次’以蒸發器濃縮後’得到乙烯基系聚合體p(VEEA)_ 1。 單體之反應率，藉由將反應停止後之混合液以氣相層析（GC) 分析’明瞭為99.6%’並一步得知乙酸乙酯之含量為〇.丨％。 又’得到之乙烯基系聚合體之數平均分子量（Mn)為221〇， 分子量分布（Mw/Mn)為1.60，自由基聚合性不飽和基當量 為 18 6 〇 &lt;&lt;製造例2&gt;&gt; 於安裝有攪拌棒、溫度計' 滴加線、氮氣/空氣混合氣 導入管之4 口燒瓶，加入乙酸乙酯150g，並升溫至5〇。〇。❹ 升溫後’將丙烯酸2—(2 —乙烯氧基乙氧基）乙酯（vj；EA、 曰本觸媒（股）公司製）2〇〇g、甲醇〇.2g、乙酸乙酯25g與 鱗鶴酸13mg之混合溶解物’各花費3小時滴加並聚合。聚 合結束後加入三乙胺並使反應結束。其次，以蒸發器濃縮 後’得到乙烯基系聚合體P(VEEA)—2。單體之反應率，藉 由將反應停止後之混合液以氣相層析（GC)分析，為99. 6%， 又，乙酸乙酯之含量為〇·1%。又，得到之乙烯基系聚合體 ❹ 之數平均分子量（Μη)為970’分子量分布（Mw/Mn)為1. 60。 〈&lt;光碟用硬化性樹脂組成物及硬塗層用硬化性樹脂組成物 之製備〉〉 將各成分以表1〜表4所示比例混合•擾拌，得到光 碟用硬化性樹脂組成物及硬塗層用硬化性樹脂組成物。得 到之組成物以上述評價方法進行評價。評價結果如表1〜 表4所示。又’圖1顯示a+B之值與硬化物之彈性率之關 係0 58 201022304 &lt;〈光碟之製造〉〉 光碟編號1〜44 於厚度1.1職、尺寸120mmxl20mm之聚碳酸醋基板上， 以旋塗機’設定厚度100 塗佈光碟用硬化性樹脂組成 物。將得到之聚碳酸酯基板使用具氙閃式UV燈之UV照射 機（美國Xenon公司製形式RC — 742)，以燈高度2cm照 射15次使硬化。又，於320〜390nm之照射累積光量為約 ❹ 0.6J/cm2。保護層之厚度為100±2em。對於得到之光碟進 行評價之結果，如表1〜4所示。 光碟編號45〜88 使用旋塗機，於尺寸120mmxl2〇mm、厚度lmm之聚碳 酸酯（PC)基板上，以厚度10〇em設定塗佈光碟用硬化性樹 脂組成物。將得到之PC基體，使用具超高壓水銀燈之uv 照射機（Eyegraphics(股）公司製），以照射累積光量 500mJ/cm2使進行紫外線硬化。 ❹ 其次，在疊層有硬化物層之PC基體再以先前已製備之 硬塗層用硬化性樹脂組成物以厚度3口設定進行塗佈。將 同樣得至J之PC基體，使用具超高壓水銀燈之⑽照射機 (EyegraphiCs(股）公司製），以照射累積光量5_^2進 行紫外線硬化。得到之光碟之評價結果如表5所示。 59 201022304 【m 光碟編號 〇 1 1 1 ! g ! 1 ! ! ο ! ί 1 1 I LO ! g ΙΛ 〇 &gt;—n 50.19 | 2,100 | ◎ ◎ 〇 CO CD cc Ο 写 ^4 0.90 05 CM CO σ&gt; s 1 i 1 1 1 1 1 1 ο 1 1 s 1 1 CM OO 05 呀 Ο t 1 49.761 | 2,380 | ◎ ◎ 〇 CO •Ο· 却 ο 1000 寸 C5 c〇 CO Od oi 〇〇 1 宕 1 t 1 Lft CO 1 1 ΙΛ cq 1 1 1 t 1 o LO 1 CO C&lt;1 呀 § Γ 7.03 | | 1,620 | ◎ ◎ 〇 &lt;N1 Ο tM Ο 〇 1»Η 0.98 另 05 ci 卜 1 1 1 写 1 ΙΛ (M 1 o ΙΛ ο 1 1 I 1 1 m ί C&lt;I in 呀 § 7.54 〇 09 ΙΛ ◎ ◎ 〇 Ο CJ ο tn in 〇〇 CO o Oi c— o CO 1 1 I 写 ! LO CNI 1 1 〇&gt; 1 1 ΙΛ (Μ 1 1 ! ΙΛ 1 o g § CO CO 〇6 I 1,430 1 ◎ ◎ 〇 Ό ο CO ΙΛ C5 CO CO o LO 1 1 1 O 〇 o 1 1 ο 1 1 1 1 1 ΙΛ 1 g 兮 | 15.34 | I 2,1001 ◎ ◎ 〇 CM Ο 03 Ο 另 0.60 05 C&lt;I 呀 1 ΙΛ 1 ί s I 1 1 1Λ ! I 1 i 1 Cs3 Lrt ΙΛ LO LO LO 10.09 I 1,760 I ◎ ◎ 〇 »-Η Ο ι^Η CS s 0.25 ! o CO § 1 1 1 1 t 1 ΙΛ 1 ο 1 1 LO ΙΛ [ tn 寸 | 10.47 | [1,550 1 ◎ ◎ 〇 &lt;ΝΙ C5 &lt;Ν3 Ο CM 0¾ 0. 70 CO &lt;NJ o οα 1 1 ! 1 1 1 s Ο 1 1 1 1 1 ID 1 CO 呀 〇 2 CO Ο CO i-Η ◎ ◎ 〇 C5 03 Ο ① CO O ΙΛ 〇 CO (Nl CO &lt;=&gt; Τ—Η 1 1 ί 1 1 I 1 ΙΛ 1 ί 1 1 1 CO σ&gt; § CO 〇〇’ o 寸 ◎ ◎ 〇 Ο Ο o CO 0.44 05 o 1彈性率| i (MPa) I τ—Η ο c— g CN1 g g 1 1 1 1 1 1 1 1 1 1 1 1 (A)自由基聚合性不飽和基當量 (B)含有加成物之（甲基）丙烯酸酯含量 (AMB) 樹脂組成物黏度(mPa · s) 硬化層之透明性 質量減少 殘膜性 起始之翹曲增加量Γ) 加熱促進試驗後之翹曲增加量Γ) 25°C之貯藏彈性率E’（MPa) 玻璃轉移 ,温度(°C) (Nl CNI 1 CO CM 1 1 1 1 1 ! 1 1 1 1 1 1 自由基聚合性 不飽和基當量 寸 〇〇 05 〇 OO oa 00 05 LO 〇〇 00 OO s (Nl CO CM CO ΟΟ ·Τ«Η (NJ S CO OO s s CO in 1 1 UV-6640B CN-981 UV-6100B CN—978 1 CN—991 1 Bis—10EO-A 1 PEGDA-9 TMP-6E0-A 1 TMP-9E0-A VEEA ΗΧ—220 ΗΧ — 620 IB-XA DCP-A HPP-A Irgl84 Esacure One 胺酯丙烯酸酯 含有加成物之（甲基） 丙烯酸酯 聚合性單體 光聚合起始劑 25°C之損失正切tan5 ίΐ'ίΐΐ 轉# 溫度(t') 永久妥形4(&quot;1〇) DID运 K ^ 5 ^ # Si ^ «W ^ ^ S ^ 評價結果 201022304 【i 玻璃轉移彈性率 光碟編號 〇〇 1 1 1 § 1 1 1 〇 1 1 03 — CM CO s cO 1,450 ◎ ◎ 〇 CNI &lt;=&gt; CO G5 m CO 卜 d &lt;NI CNI CO 卜 4 1 1 1 1 1 1 1 o 1 1 CN* CO 1 H o oi 〇 ▼-H ◎ ◎ 〇 C— c&gt; ΙΟ Ο g TO d L〇 〇&gt; o LO c&gt; CO ^4 1 1 S 一.〆 1 1 1 〇 1 s 1 CNI ΙΛ s Q 50.46] TW ◎ ◎ 〇 (N1 〇 CO d m CO S c=? OO to 1 4.48 LO i-M 1 s 1 1 1 1 〇 ^H 1 s CD 49.761 § CO csi ◎ ◎ 〇 CO C5 寸 c&gt; 1,000 寸 〇· CO CO eg 0¾ CnJ g 1 ! 1 1 1 〇 1 1 s S 03 OO CO CO o |33.79 1,750 〇 〇 〇 CM Ο CO c? s cx&gt; ai OO 0.28 CO 1-H CNI 1 m CO 1 1 1 写 ο 1 1 m 1 iNI T-^ L〇 s 9.02 2,040 ◎ ◎ 〇 T-^ d CO o r*H G&gt; § 0.74 〇» L〇 1 1 1 1 1 〇 1 1 03 〇〇 CO CO ◦ t-H 33.79 g 卜 I· ^ 〇 ◎ 〇 C&lt;l ai CO d s s G&gt; Lrt OO 〇 CO o r-H o LO 1 1 1 1 1 ο 1 s 丨 oa L〇 CO CO o ▼&quot;1 33.51 1,680] ◎ ◎ 〇 呀 ci 却 d C&gt; o o (MPa) CD OO o CO g &lt;NI § c— 1 1 1 1 1 1 1 1 κ- 恕 •flU /^N •N 伞 避 爱 ♦1 8 (AMB) • CO i μ 蓉 蓋 硬化層之透明性 丨質量減少 殘膜性 起始之魅曲增加量（°) |Λ〇熱促進試驗後之翹曲增加量Γ ) ω 跻 酰 η v P |25°C之損失正切tan&lt;5 1玻璃轉移溫度(°c) 永久變形量（#m) P s 寸 CO 1 1 1 1 1 1 1 1 鉍砩 δ名 •m OO §S OO s L〇 CO CD OO CO OO OO (NI S τ—1 1 UV-7000B ,UV-6640B UV-6100B CN—2302 1 Bis-4P0-A 1 § 1 CQ VEEA P(VEEA)-1 IB-XA IB-XM DCP-A Esacure One 胺酯丙烯酸酯 聚酯丙烯酸酯 含有加成物之（甲基) 丙烯酸酯 聚合性單體 光聚合起始劑 ins运 BE* /—' 费寒^ ®H 努5W 評價結果 19 201022304 光碟編號 03 CO 1 1 1 CO 1 1 s O 1 1 O oo 1 1 CNI LO CO &lt;〇 I-Η 35.2 〇 2. 09 |1·48| CO 1 1 1 § ! 1 1 o 1 1 o 1 &lt;NI 1 σ» 05 CO ο 05 σί CD X oo c&gt; |-0. 03| 另 1 1 1 § t 1 l o 1 1 o &lt;NI 1 1 Oi CJ3 CO ο 1—I 69. 9 X 0.20 LO 呀 05 〇q [ 1 写 LO oa LO 1 1 t 〇 o 1 1 OJ 1 S S 〇 CD Ο ς〇 oo οα 1 1 1 1 写 1 o 11 1 1 1 1 CO s o CO L〇 &lt;&gt;3 § 00 01 〇 0. 56 LO i ! 1 1 1 o 1 c T~&lt; 1 1 i 1 CO L〇 CSI S 00 01 T**H 〇 § O 0.28 CO (NI 1 1 g 1 1 1 Q 1 o 1 1 Cs3 s O g CO S 呀 LO 1-H 〇 0.56] 0. 65 in CNI 1 1 ο in 1 1 1 o 1 O T—&lt; 1 1 eg 1 TO CO S 寸 LO T&quot;*H 〇 § c&gt; 0. 62 &lt;NI 1 1 s 1 1 1 〇 1 Q t—H 1 &lt;Nl 1 1 § CO 呀 LfS 〇 0. 86 oo co &lt;NI 1 1 s 1 1 1 o t—H f 1 o 1 eg 1 (NI T—H co ο τ—Η CNI 〇 0. 52 完 c&gt; &lt;N1 CN1 1 s 1 t 1 ! o r-H 1 1 C5 1 (NI 1 CO CO CO ο F 1 Ί CO CO CO 〇 | 0.88 I | -0.38 j s 1 1 i 1 c r-H 1 ! 〇 &lt;M 1 1 CO co CO ο CO CO CO 〇 0. 961 CO CD S s i 1 1 ί 1 0 1 · i 1 1 o ί tNI 1 卜 CVJ CO ο | 32.7 1 〇 I 0.68 I |-0.22| 05 T—l g 1 i 1 ί 1 o 1 1 C5 (Nl 1 i 卜 CNJ CO ο y^* 32.7 〇 0.74 1 0. 43 | ti »N φ 4» •ffi萆 •on K- 03 CO g§ 〇〇 oo (N1 oo 05 s CO LT5 CNI oo oo CO CO 00 CO (N1 (N1 1 1 1 (A)自由基聚合性不飽和基當量 (Β)含有加成物之（甲基）丙烯酸酯含量 (AH(B) 耐刮性 起始之翹曲增加量（°) 加熱促進試驗後之翹曲增加量Γ) CN —2300 卜2301 CN—2302 UV-6640B UV-6100B UV-7000B UV-7640B Bis-4E0—A Bis-IOEO-A VEEA 1,6-HX-A Irgl84 Esacure One | TINUVIN479 丨 JtB s m! &lt;rS am 1 胺酯丙烯酸酯 含有加成物之（甲基） 丙烯酸酯 聚合性單體 光聚合起始劑 添加劑 tO /-N κ ^ 5 ^ 評價結果 201022304 光碟編號 g 〇 Η 1 LO 1 0.10 1 LO c=&gt; CO ο LO LO 卜*· 2410 90. 2 71.2 CNI Ο 〇 ◎ 〇 〇 〇 — 0.1 〇 CO 呀 s &lt;〇 1 L〇 s C=5 1 1 LO (=&gt; CO ο LO LO 卜· 2400 90. 5 83.2 49.8 〇 ◎ 〇 〇 οα 〇' 1 &lt;=) 〇 C&lt;1 s C» CO 1 1 ◦ c&gt; 1 LTD ci CO s m 卜· 2100 90.5 LO 05 cd 〇 ◎ 〇 〇 &lt;=) LO &lt;=&gt; 〇 s 〇 LO 1 1 1 ◦ c=&gt; LO C=&gt; CO g LO 卜· 2140 89. 2 71.3 00 01 〇 ◎ 〇 〇 〇 LO C5 1 〇 s 〇 LO 1 1 导· ci 1 LO CD CO g ΙΛ 卜· 2080 9〇·! OJ 耷 卜 &lt;=&gt;· 〇 ◎ 〇 〇 CO ο 〇 〇 CT&gt; CO g 〇 LO 1 1 0. 30 1 LO &lt;=&gt; CO § LO 卜’ 2090 90. 3 cn&gt; od m CH) 〇 ◎ 〇 〇 οα &lt;=&gt; CO &lt;=&gt; 1 〇 oo CO s 〇 LO 1 1 0.10 1 m 〇· CO s LO 2140 90.5 OJ oo CO 〇 ◎ 〇 〇 ο LTD C5 I 〇 g 〇 LO 1 C5 1 1 LO ◦· CO g LO 卜· 1980 88.1 35.1 CO &lt;=&gt; 〇 〇 〇 〇 CO CD ◦ 〇 CO CO g 〇 LO 1 0.30 1 1 LO O’ CO g LO 卜· 1990 88.8 卜 OO CO C5 〇 ◎ 〇 〇 CD CO o’ 1 〇 LO CO g 〇 L〇 1 o CD 1 ! LO d CO s ΙΟ 卜’ 2000 89. 2 66.9 LO od 〇 ◎ 〇 〇 CD LO d 1 〇 CO g 〇 LO 1 S cz&gt; 1 1 LO CD CO o LO LT&gt; 卜· 2090 § CO LO CM 〇 ◎ 〇 〇 τ—Η c=&gt; 1 卜 CD I 〇 CO CO g ◦ LO 1 s d 1 1 LO C3 CO s LTD 卜· I 2120 I 90.3 CD 呀· OO 48. 9 〇 ◎ 〇 〇 οα CD 1 LM 〇 ±1 ®Η -4η &lt;〇Br K- 05 CO LO Csl 05 CD CNI 1 1 1 1 1 1 (A)自由基聚合性不飽和基當量 (B)含有加成物之（曱基）丙烯酸酯含量 (AMB) 組成物於25°C之起始黏度(mPa · s) 組成物之400nm光線穿透率(9〇 組成物之380nm光線穿透率（％) 組成物之360nm光線穿透率(％) 組成物之回收性 硬化層之透明性 对刮性 硬化層之表面潤滑性 起始之魅曲增加量（°) 加熱促進試驗後之翹曲增加量r) 殘棋性 | UV-7000B Bis-4E0-A [9EG-A Irg 184 Escure one TINUBIN PS TINUBIN 479 RUVA 93 BY16-876 胺酯丙烯酸酯 含有加成物之（甲基） 丙烯酸酯 光聚合起始劑 紫外線吸收劑 其他 to iJ® &gt;θ mr # # Ϊ «w ^ ^ S ^ 評價結果 201022304 光碟編號 ς&amp; 1 LO CO 1 1 ΙΛ CNI O 1—M l〇 1—H CO s m CO 03 !&gt;： 1 1 1 L£3 t 1 ΙΛ CNI 1 Lft ◎ ◎ 〇 C&lt;I cJ (NJ Ο &lt;NI C&lt;J 〇 〇 CO CO 1 ΙΛ CO 1 1 id &lt;Ν» O ΙΛ H CO K ΙΛ CD OS 1 1 Ln 1 1 in CNI 1 LO ◎ ◎ 〇 CvJ ο C&lt;I ο 03 CNI 〇 〇 CM CO 1 ΙΛ CO 1 1 ΙΛ Cvl o 1··^ LO H CO ΙΛ ΙΛ CO 〇d Ln 1 1 LO Cv3 1 i Lft ◎ ◎ 〇 &lt;N1 ο 03 Ο Cvl C&lt;I 〇 〇 S 1 ΙΛ CO 1 1 ΙΛ C&lt;1 o ΙΛ - CO ΙΛ ΙΛ CO 0¾ 卜· 1 1 Lrt LO ΙΛ 03 s m ◎ ◎ 〇 CM Ο Osl Ο (Nl &lt;N1 〇 〇 g 1 ΙΛ CO 1 1 Lrt CM o LT5 i H CO s ΙΛ CO 〇d 1 1 Lft Lft 1 i Lft Cvl 1 s ΙΛ ◎ ◎ Ο &lt;N1 C5 C&lt;J c&gt; 03 (Nl 〇 〇 〇d m 1 1Λ 〇〇 i 1 ΙΛ csa o ΙΛ CO s ΙΛ CO ΟΪ 卜· 1 m Ln 1 1 1 1 ΙΛ N 1 1 s ΙΛ ◎ ◎ 〇 Csl o C-3 〇 (Nl C&lt;J 〇 〇 CO in 1 m CO I I ΙΛ 04 o LO 1—M CO s ΙΛ CO 03 卜’ 1 S 1 1 I s g 1 ! 1 ΙΛ ◎ ◎ 〇 Cvl 〇 o* OJ C^3 〇 〇 £ 1 in &lt;n 1 1 ΙΛ C&lt;l o m T&quot;»H CD s IT) CO 03 卜· 1 Lft ΙΛ 1 1 1 in (NJ 1 1 1 ΙΛ ◎ ◎ 〇 CO o Cvl o C&lt;J cq 〇 〇 CD m 1 Lft CO 1 1 m C&lt;1 ID CO ΙΛ LO CO 05 ΙΛ (Ν1 I g 1 I i LO Cvl 1 1 1 ΙΛ ◎ ◎ 〇 CM o (Nl C5 (Nl OJ 〇 〇 in LO 1 ΙΛ CO ! 1 ΙΛ &lt;NI o LO CO s ΙΛ CO 卜· 1 1 1 1 1 1 m &lt;NJ i tn ◎ ◎ 〇 CvJ o OJ o OQ 〇 〇 呀 ΙΛ 1 ΙΛ CO 1 1 in (Si c=&gt; ΙΛ CD T-H ΙΛ 1Λ CD 1 LO 1 1 1 1 ΙΛ CNI 1 LO ◎ ◎ 〇 &lt;N1 o C&lt;1 〇 CO C&lt;l 〇 〇 CO ΙΛ ΙΛ CO 1 1 ID CV3 o LD CO s to CO 05 一 1 I 1 in ΙΛ C&lt;1 1 1 i ΙΛ ◎ ◎ 〇 &lt;N1 cs CNI o C&lt;1 Cvl 〇 〇 &lt;M LTD ΙΛ CO 1 1 LO o in CO s ΙΛ CO ΟΪ 卜· 1 Ln 1 LQ ί 1 1Λ ◎ ◎ 〇 Cvl 〇 &lt;M C5 CNI (Nl 〇 〇 S Ln CO 1 1 ΙΛ &lt;&gt;3 〇 UT3 CO s tn CO 03 卜· 1 Ln 1 1 m CV3 1 t 1 m ◎ ◎ 〇 (Nl 〇 Cvl o CN3 Csl 〇 〇 S ΙΛ CO i 1 ΙΛ CM o in 1-H CO ΙΛ ιλ CD OS 卜· I ΙΛ 1 1 ΙΛ Cv] 1 1 ΙΛ ◎ ◎ 〇 CO o Cvl o C&lt;l CNI 〇 〇 05 呀 1 LO CO 1 1 ΙΛ (NJ o LD CO s m CO 05 … 1 1 1 1 1 Lft &lt;N1 1 1 t in ◎ ◎ 〇 (Nl &lt;=&gt; C&lt;I o (Nl Cs3 〇 〇 oo 1Λ CO 1 宕 1 Lft 03 o ΙΛ C£ s ΙΛ CD σ&gt; 卜· LO 1 I 1 1 1 in OJ I 1 1 LO ◎ ◎ 〇 CM o «Nl ci 03 03 〇 〇 1 1 LD C&lt;3 1 ΙΛ &lt;N1 o LO CO 却 Ln § 〇 05 ΙΛ CvJ 1 s 1 1 1 in (N1 1 1 1 ΙΛ ◎ ◎ 〇 CO c&gt; CO 〇 OO ΙΛ 〇 〇 CO 呀 写 1 LO CN1 1 1 m (SI o in o ΙΛ g ΙΛ 〇〇* tn CO 1 g 1 1 1 Lft &lt;N1 i 1 1 ΙΛ ◎ ◎ 〇 CO G5 CO o 05 CO 〇 〇 ΙΛ 1 Lft Cvl 1 ΙΛ Cvl 1 o in OO g 〇 〇6 ΙΛ Cvl 1 s 1 1 1 ΙΛ &lt;NJ 1 1 1 in ◎ ◎ 〇 CO 〇 eo o OO 另 〇 〇 •φ令9 s銮 •m K- oo 寸 s CO LO C&lt;J S CO ο CN3 却 oo CO CO 00 1 (A)自由基聚合性不飽和基當量 (B)含有加成物之（甲基）丙烯酸酯含量 (ΑΜΒ) CN-2300 [CN—2302 fcN-2304 |viscoat#iooo fviSCOAT#1020 P(VEEA) —2 VEEA [NP-2P0-A TPGDA TMP-3E0-A D1173 硬化層之透明性 硬化層之質量減少 殘膜性 起始之翹曲增加量Γ) 加熱促進試驗後之翹曲增加量Γ) k化物層之貯藏彈性率E(MPa) 对刮性 硬塗層耐變形性 UV-6100B UV-6640B Bis-4E0—A Bis-10EO~A ΗΧ-220 HX—620 VEEA Irgl84 1 胺酯丙烯酸酯 含有加成物之（甲基） 丙烯酸酯 1 光聚合 起始劑 (A)+(B) 多分支型 反應性化合物 側鏈具反應性基之聚合物 I 聚合性 單醴 聚合起始劑 1 調配 (質量份） 1〇 jj〇 ® ππ ffiT ^ ^ J 評價結果 采锥田窜与寒荜嬰鹿噠蓉 201022304 【表6】Viscosity increase rate (%) == (viscosity after recovery - initial viscosity) / initial viscosity xlOO 55 201022304 〇: viscosity increase rate less than 10% X: viscosity increase rate is 10% or more. &lt;Scratch Resistance&gt; For the surface of the hardened layer (protective layer or hard coat layer) of the obtained laminate of the base/hardened layer, an abrasion resistance tester (type IMC-154A, Imoto Manufacturing Co., Ltd.) was used. Under the conditions of a load of 20 0 g/cm2, the steel wool #0000 was reciprocated at a speed of 3 〇mm/sec and a round-trip distance of 25 mm for 10 times, and the degree of injury was visually observed and evaluated on the following basis. ◎: No change (not considered to be injured) 〇: There are several or more extremely shallow scars X: There are countless deep scars. &lt;Surface Lubricity of Hardened Layer&gt; On the surface of the hardened layer (hardened film of the composition) of the obtained laminated body of the base/hardened layer, a droplet of triolein glycerin as an artificial fingerprint liquid 1.5# 1 At a temperature of 25. &lt;:, in an environment of 50% humidity, and after 5 seconds, the contact angle was measured by a fully automatic contact angle meter (type DM500, manufactured by Kyowa Interface Science Co., Ltd.), and evaluated according to the following criteria. The larger the value of the tentacles, the easier the wiping can be even when a fingerprint or the like is attached. ◎: The contact angle is 55° or more 〇: The contact angle is 50° or more X: The contact angle is less than 50°. &lt;Hard coating scratch resistance&gt; For the surface of the hard coat layer of the laminate (hard coat layer/protective layer/base), an abrasion resistance tester (type IMC-15" type, Jingyuan Manufacturing Co., Ltd. was used. 201022304 Λ - system), under the established load, the steel wool #_〇号 was reciprocated at a round-trip speed of 30 mm/sec and a round-trip distance of 25 mm for 10 times, and the degree of injury was visually observed and evaluated on the following basis. 〇: The load was 200 g/ There is no change in cm2 (not considered to be injured) X: There are several or more flaws at a load of 200 g/cm2 &lt;hard coating resistance to deformation&gt; As a laminate (hard coat layer/protective layer/base (sample size 12 cm x 12 cm) The hard coat layer of the crucible is the top surface, and the end portion of the diagonal line is held to visually observe whether the hard coat layer on the laminate body is cracked when the f-curve to the diagonal distance becomes 1 〇 cm. It is evaluated on the following basis: 〇: No crack is considered to be △. It is said to have a crack X: It is considered that there is a large crack &lt; pencil hardness&gt; For the surface of the hardened layer of the obtained matrix/hardened layer, let φ be used Ship pen scratch hardness tester (made by Yasuda Seiki Co., Ltd.) The measurement was carried out in accordance with JIS-K5400. The load was set to i〇〇〇g. <Production Example 1> A 4-necked flask equipped with a stir bar, a thermometer, a dropping line, and a nitrogen/air mixture introduction tube. Ethyl acetate i5 〇g was added, and the temperature was raised to 5 〇〇c. After heating, 2-(2-vinyloxyethoxy)ethyl acrylate (VEEA, 曰本触媒制制股股公司) 2 〇〇g, 25 g of ethyl acetate and 13 mg of phosphotungstic acid were mixed and dissolved, and each was added dropwise for 3 hours and polymerized. After the end of the polymerization, triethylamine was added and the reaction was terminated. 57 201022304 times 'evaporation After the concentration of the device, the vinyl-based polymer p(VEEA)_1 was obtained. The reaction rate of the monomer was analyzed by gas chromatography (GC) by gas chromatography (GC), and it was determined to be 99.6%. The content of ethyl acetate is 〇.丨%. The obtained vinyl-based polymer has a number average molecular weight (Mn) of 221 Å, a molecular weight distribution (Mw/Mn) of 1.60, and a radical polymerizable unsaturated group equivalent. 18 6 〇 &lt;&lt;Production Example 2&gt;&gt; With a stirring rod, a thermometer, a dropping line, and nitrogen A 4-neck flask of gas/air mixture introduction tube, 150 g of ethyl acetate was added, and the temperature was raised to 5 Torr. 〇. 升温 After heating, '2-(2-vinyloxyethoxy)ethyl acrylate (vj; EA)曰 触 触 ( 制 制 、 触 触 触 触 触 触 触 触 触 触 触 触 触 触 触 触 触 触 触 触 触 触 触 触 触 触 触 触 触 触 触 触 触 触 触 触 触 触 触 触 触 触 触 触 触The amine is brought to an end. Next, it was concentrated by an evaporator to obtain a vinyl polymer P (VEEA)-2. The reaction rate of the monomer was analyzed by gas chromatography (GC) with a reaction rate of 99.6%, and the content of ethyl acetate was 〇·1%. Further, the number average molecular weight (?η) of the obtained vinyl polymer ❹ was 970' molecular weight distribution (Mw/Mn) of 1.60. <&lt;Preparation of Curable Resin Composition for Optical Disc and Curable Resin Composition for Hard Coating Layer>> The components are mixed and scrambled in the ratios shown in Tables 1 to 4 to obtain a curable resin composition for an optical disk and A hardenable resin composition for a hard coat layer. The composition obtained was evaluated by the above evaluation method. The evaluation results are shown in Tables 1 to 4. 'Fig. 1 shows the relationship between the value of a+B and the elastic modulus of the cured material. 0 58 201022304 &lt;<Manufacture of optical disc> Optical disc No. 1 to 44 On a polycarbonate substrate having a thickness of 1.1 and a size of 120 mm x 20 mm, The applicator 'set thickness 100 is a curable resin composition for coating a disc. The obtained polycarbonate substrate was cured by using a UV irradiator with a flash-type UV lamp (RC-742, manufactured by Xenon Co., USA) at a lamp height of 2 cm. Further, the cumulative amount of light irradiated at 320 to 390 nm was about J 0.6 J/cm 2 . The thickness of the protective layer is 100 ± 2em. The results of the evaluation of the obtained optical disc are shown in Tables 1 to 4. Disc No. 45 to 88 A curable resin composition for coating a disc was set to a thickness of 10 〇m on a polycarbonate (PC) substrate having a size of 120 mm x 12 mm and a thickness of 1 mm using a spin coater. The obtained PC substrate was subjected to ultraviolet curing by using a uv irradiator (manufactured by Eyegraphics Co., Ltd.) equipped with an ultrahigh pressure mercury lamp to irradiate an accumulated light amount of 500 mJ/cm2. Next, the PC substrate to which the cured layer is laminated is coated with a thickness of three sets using a curable resin composition for a hard coat layer which has been previously prepared. The PC substrate of the same J was used, and the (10) irradiator (manufactured by Eyegraphi Cs Co., Ltd.) equipped with an ultrahigh pressure mercury lamp was used to perform ultraviolet curing by irradiating the cumulative amount of light 5_^2. The evaluation results of the obtained optical disc are shown in Table 5. 59 201022304 [m disc number 〇1 1 1 ! g ! 1 ! ! ο ! ί 1 1 I LO ! g ΙΛ 〇&gt;-n 50.19 | 2,100 | ◎ ◎ 〇CO CD cc Ο Write ^4 0.90 05 CM CO σ&gt ; 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 Lft CO 1 1 ΙΛ cq 1 1 1 t 1 o LO 1 CO C&lt;1 呀§ Γ 7.03 | | 1,620 | ◎ ◎ 〇&lt;N1 Ο tM Ο 〇1»Η 0.98 Another 05 ci Bu 1 1 1 Write 1 ΙΛ (M 1 o ΙΛ ο 1 1 I 1 1 m ί C&lt;I in 呀§ 7.54 〇09 ΙΛ ◎ ◎ 〇Ο CJ ο tn in 〇〇CO o Oi c- o CO 1 1 I Write! LO CNI 1 1 〇&gt; 1 1 ΙΛ (Μ 1 1 ! ΙΛ 1 og § CO CO 〇 6 I 1,430 1 ◎ ◎ 〇Ό ο CO ΙΛ C5 CO CO o LO 1 1 1 O 〇o 1 1 ο 1 1 1 1 1 ΙΛ 1 g 兮| 15.34 | I 2,1001 ◎ ◎ 〇CM Ο 03 Ο Another 0.60 05 C&lt;I 呀1 ΙΛ 1 ί s I 1 1 1Λ ! I 1 i 1 Cs3 Lrt ΙΛ LO LO LO 10.09 I 1,760 I ◎ ◎ 〇 »-Η Ο ι^Η CS s 0.25 ! o CO § 1 1 1 1 t 1 ΙΛ 1 ο 1 1 LO ΙΛ [ tn inch | 10.47 | [1,550 1 ◎ 〇&lt;ΝΙ C5 &lt;Ν3 Ο CM 03⁄4 0. 70 CO &lt;NJ o οα 1 1 ! 1 1 1 s Ο 1 1 1 1 1 ID 1 CO 〇 2 CO Ο CO i-Η ◎ ◎ 〇 C5 03 Ο 1 CO O ΙΛ 〇CO (Nl CO &lt;=&gt; Τ—Η 1 1 ί 1 1 I 1 ΙΛ 1 ί 1 1 1 CO σ&gt; § CO 〇〇' o ◎ ◎ 〇Ο Ο o CO 0.44 05 o 1 elastic modulus | i (MPa) I τ—Η ο c— g CN1 gg 1 1 1 1 1 1 1 1 1 1 1 1 (A) Radical polymerizable unsaturated group equivalent (B) contains adduct (Meth) acrylate content (AMB) Resin composition viscosity (mPa · s) The transparency quality of the hardened layer reduces the amount of warpage increase at the beginning of residual film Γ) The increase in warpage after the heating promotion test Γ) Storage modulus at 25 ° C E' (MPa) Glass transfer, temperature (°C) (Nl CNI 1 CO CM 1 1 1 1 1 ! 1 1 1 1 1 1 Free radical polymerizable unsaturated equivalents 〇〇05 〇OO oa 00 05 LO 〇〇00 OO s (Nl CO CM CO ΟΟ ·Τ«Η (NJ S CO OO ss CO in 1 1 UV-6640B CN-981 UV-6100B CN—978 1 CN—991 1 Bis— 10EO-A 1 PEGDA-9 TMP-6E0-A 1 TMP-9E0-A VEEA ΗΧ—220 ΗΧ — 620 IB-XA DCP- A HPP-A Irgl84 Esacure One Amino ester acrylate containing adduct (meth) acrylate polymerizable monomer photopolymerization initiator 25 ° C loss tangent tan5 ίΐ 'ίΐΐ turn # temperature (t') permanent Shape 4 (&quot;1〇) DID运K ^ 5 ^ # Si ^ «W ^ ^ S ^ Evaluation Results 201022304 [i Glass Transfer Elasticity Disc Number 11 1 1 § 1 1 1 〇1 1 03 — CM CO s cO 1,450 ◎ ◎ 〇CNI &lt;=&gt; CO G5 m CO b d &lt;NI CNI CO Bu 4 1 1 1 1 1 1 1 o 1 1 CN* CO 1 H o oi 〇▼-H ◎ ◎ 〇C — c> ΙΟ Ο g TO d L〇〇&gt; o LO c&gt; CO ^4 1 1 S I.〆1 1 1 〇1 s 1 CNI ΙΛ s Q 50.46] TW ◎ ◎ 〇 (N1 〇CO dm CO S c=? OO to 1 4.48 LO iM 1 s 1 1 1 1 〇^H 1 s CD 49.761 § CO csi ◎ ◎ 〇CO C5 inch c&gt; 1,000 inch 〇· CO CO eg 03⁄4 CnJ g 1 ! 1 1 1 〇1 1 s S 03 OO CO CO o |33.79 1,750 〇〇〇CM Ο CO c? s cx&gt; ai OO 0.28 CO 1-H CNI 1 m CO 1 1 1 Write ο 1 1 m 1 iNI T-^ L〇s 9.02 2,040 ◎ ◎ 〇T-^ d CO or*H G&gt; § 0.74 » L〇1 1 1 1 1 〇1 1 03 〇〇CO CO ◦ tH 33.79 g 卜 I· ^ 〇◎ 〇C&lt;l ai CO dss G&gt; Lrt OO 〇CO o rH o LO 1 1 1 1 1 ο 1 s 丨oa L〇CO CO o ▼&quot;1 33.51 1,680] ◎ ◎ 〇 ci ci but d C&gt; oo (MPa) CD OO o CO g &lt;NI § c-1 1 1 1 1 1 1 1 κ- •flU /^N •N Umbrella Avoidance ♦1 8 (AMB) • CO i μ The transparency of the hardened layer of the slab cover 丨The mass reduces the amount of complication that begins with the residual film (°) | After the heat promotion test Increase in warpage Γ) ω 跻 η η v P | loss of tangent tan 25 ° C tantalum transfer temperature (°c) permanent deformation (#m) P s inch CO 1 1 1 1 1 1 1 1铋砩δ名•m OO §S OO s L〇CO CD OO CO OO OO (NI S τ—1 1 UV-7000B , UV-6640B UV-6100B CN—2302 1 Bis-4P0-A 1 § 1 CQ VEEA P(VEEA)-1 IB-XA IB-XM DCP-A Esacure One Amine Ester Acrylate Polyester Acrylate (Meth) Acrylate Polymerizable Monomer Photopolymerization Initiator insole BE* / —' Fei Han ^ ® H Nu 5W Evaluation Results 19 201022304 Disc Number 03 CO 1 1 1 CO 1 1 s O 1 1 O oo 1 1 CNI LO CO &lt;〇I-Η 35.2 〇2. 09 |1·48| CO 1 1 1 § ! 1 1 o 1 1 o 1 &lt;NI 1 σ» 05 CO ο 05 σί CD X oo c&gt; |-0. 03| Another 1 1 1 § t 1 lo 1 1 o &lt;NI 1 1 Oi CJ3 CO ο 1—I 69. 9 X 0.20 LO 呀05 〇q [ 1 Write LO oa LO 1 1 t 〇o 1 1 OJ 1 SS 〇CD Ο ς〇oo οα 1 1 1 1 Write 1 o 11 1 1 1 1 CO so CO L〇&gt;&gt;3 § 00 01 〇0. 56 LO i ! 1 1 1 o 1 c T~&lt; 1 1 i 1 CO L〇CSI S 00 01 T**H 〇§ O 0.28 CO (NI 1 1 g 1 1 1 Q 1 o 1 1 Cs3 s O g CO S 呀LO 1-H 〇0.56] 0. 65 in CNI 1 1 ο in 1 1 1 o 1 OT—&lt; 1 1 eg 1 TO CO S inch LO T&quot;*H 〇§ c&gt; 0. 62 &lt;NI 1 1 s 1 1 1 〇1 Q t—H 1 &lt;Nl 1 1 § CO 呀 LfS 〇0. 86 oo co &lt;NI 1 1 s 1 1 1 ot-H f 1 o 1 eg 1 (NI T—H co ο τ—Η CNI 〇0. 52 End c&gt;&lt;N1 CN1 1 s 1 t 1 ! o rH 1 1 C5 1 (NI 1 CO CO CO ο F 1 Ί CO CO CO 〇 | 0.88 I | -0.38 js 1 1 i 1 c rH 1 ! 〇&lt;M 1 1 CO co CO ο CO CO CO 〇0. 961 CO CD S si 1 1 ί 1 0 1 · i 1 1 o ί tNI 1 Bu CVJ CO ο | 32.7 1 〇I 0.68 I |-0.22| 05 T—lg 1 i 1 ί 1 o 1 1 C5 (Nl 1 i 卜 CNJ CO ο y^* 32.7 〇0.74 1 0. 43 | ti »N φ 4 » •ffi萆•on K- 03 CO g§ 〇〇oo (N1 oo 05 s CO LT5 CNI oo oo CO CO 00 CO (N1 (N1 1 1 1 (A) Radical Polymerizable Unsaturated Equivalent (Β) Content of (meth) acrylate containing adduct (AH (B) Increase in warpage of scratch resistance (°) Increase of warpage after heating promotion test CN CN — 2300 卜 2301 CN—2302 UV -6640B UV-6100B UV-7000B UV-7640B Bis-4E0—A Bis-IOEO-A VEEA 1,6-HX-A Irgl84 Esacure One | TINUVIN479 丨JtB sm! &lt;rS am 1 Amine Ester Acrylate Contains Addition (meth) acrylate polymerizable monomer photopolymerization initiator additive tO /-N κ ^ 5 ^ Evaluation result 201022304 Disc number g 〇Η 1 LO 1 0.10 1 LO c=&gt; CO ο LO LO 卜* · 2410 90. 2 71.2 CNI Ο 〇 ◎ 〇〇〇 — 0.1 〇CO 呀 s &lt;〇1 L〇s C=5 1 1 LO (=&gt; CO ο LO LO 卜· 2400 90. 5 83.2 49.8 〇◎ 〇〇οα 〇' 1 &lt;=) 〇C&lt;1 s C» CO 1 1 ◦ c&gt 1 LTD ci CO sm 卜· 2100 90.5 LO 05 cd 〇◎ 〇〇&lt;=) LO &lt;=&gt; 〇s 〇LO 1 1 1 ◦ c=&gt; LO C=&gt; CO g LO 卜· 2140 89. 2 71.3 00 01 〇◎ 〇〇〇LO C5 1 〇s 〇LO 1 1 Guide · ci 1 LO CD CO g ΙΛ 卜 · 2080 9〇·! OJ 耷 & = = = 〇〇 CO ο 〇〇CT&gt; CO g 〇LO 1 1 0. 30 1 LO &lt;=&gt; CO § LO 卜 ' 2090 90. 3 cn&gt; od m CH) 〇◎ 〇〇οα &lt;=&gt; CO &lt;= &gt; 1 〇oo CO s 〇LO 1 1 0.10 1 m 〇· CO s LO 2140 90.5 OJ oo CO 〇◎ 〇〇ο LTD C5 I 〇g 〇LO 1 C5 1 1 LO ◦· CO g LO 卜 · 1980 88.1 35.1 CO &lt;=&gt; 〇〇〇〇CO CD ◦ 〇CO CO g 〇LO 1 0.30 1 1 LO O' CO g LO 卜 1990 88.8 OO CO C5 〇◎ 〇〇CD CO o' 1 〇LO CO g 〇L〇1 o CD 1 ! LO d CO s ΙΟ 卜 ' 2000 89. 2 66.9 LO od 〇 ◎ 〇〇CD LO d 1 〇CO g 〇LO 1 S cz&gt; 1 1 LO CD CO o LO LT&gt; · 2090 § CO LO CM 〇 ◎ 〇〇τ—Η c=&gt; 1 卜 CD I 〇CO CO g ◦ LO 1 sd 1 1 LO C3 CO s LTD Bu I 2120 I 90.3 CD 呀· OO 48. 9 〇◎ 〇〇οα CD 1 LM 〇±1 ®Η -4η &lt;〇Br K- 05 CO LO Csl 05 CD CNI 1 1 1 1 1 1 (A) Radical polymerizable unsaturated group equivalent (B) Containing the (mercapto) acrylate content of the adduct (AMB) The initial viscosity at 25 ° C (mPa · s) 400 nm light of the composition Transmittance (380 nm light transmittance (%) of composition 360360 nm light transmittance (%) The transparency of the recovered hardened layer of the composition starts from the surface lubricity of the scratch-hardened layer Increase in enchantment (°) Increase in warpage after heating promotion test r) Residual chess | UV-7000B Bis-4E0-A [9EG-A Irg 184 Escure one TINUBIN PS TINUBIN 479 RUVA 93 BY16-876 Amine ester acrylate (Meth) acrylate photopolymerization initiator UV absorber containing adducts other to iJ® &gt;θ mr # # Ϊ «w ^ ^ S ^ Evaluation Results 201022304 Disc Number ς& 1 LO CO 1 1 ΙΛ CNI O 1—M l〇1—H CO sm CO 03 !&gt;: 1 1 1 L£3 t 1 ΙΛ CNI 1 Lft ◎ ◎ 〇C&lt;I cJ (NJ Ο &lt;NI C&lt;J 〇〇CO C O 1 ΙΛ CO 1 1 id &lt;Ν» O ΙΛ H CO K ΙΛ CD OS 1 1 Ln 1 1 in CNI 1 LO ◎ ◎ 〇CvJ ο C&lt;I ο 03 CNI 〇〇CM CO 1 ΙΛ CO 1 1 ΙΛ Cvl o 1··^ LO H CO ΙΛ ΙΛ CO 〇d Ln 1 1 LO Cv3 1 i Lft ◎ ◎ 〇 &lt;N1 ο 03 Ο Cvl C&lt;I 〇〇S 1 ΙΛ CO 1 1 ΙΛ C&lt;1 o ΙΛ - CO ΙΛ ΙΛ CO 03⁄4 卜 · 1 1 Lrt LO ΙΛ 03 sm ◎ ◎ 〇CM Ο Osl Ο (Nl &lt;N1 〇〇g 1 ΙΛ CO 1 1 Lrt CM o LT5 i H CO s ΙΛ CO 〇d 1 1 Lft Lft 1 i Lft Cvl 1 s ΙΛ ◎ ◎ Ο &lt;N1 C5 C&lt;J c&gt; 03 (Nl 〇〇〇dm 1 1Λ 〇〇i 1 ΙΛ csa o ΙΛ CO s ΙΛ CO ΟΪ 卜 · 1 m Ln 1 1 1 1 ΙΛ N 1 1 s ΙΛ ◎ ◎ 〇Csl o C-3 〇 (Nl C&lt;J 〇〇CO in 1 m CO II ΙΛ 04 o LO 1—M CO s ΙΛ CO 03 卜' 1 S 1 1 I sg 1 ! 1 ◎ ◎ ◎ 〇Cvl 〇o* OJ C^3 〇〇£ 1 in &lt;n 1 1 ΙΛ C&lt;lom T&quot;»H CD s IT) CO 03 Bu· 1 Lft ΙΛ 1 1 1 in (NJ 1 1 1 ◎ ◎ ◎ 〇CO o Cvl o C&lt;J cq 〇〇CD m 1 Lft CO 1 1 m C&lt;1 ID CO ΙΛ LO CO 05 ΙΛ (Ν1 I g 1 I i LO Cvl 1 1 1 ΙΛ ◎ ◎ 〇CM o (Nl C5 (Nl OJ 〇〇in LO 1 ΙΛ CO ! 1 ΙΛ &lt;NI o LO CO s ΙΛ CO 卜 · 1 1 1 1 1 1 m &lt;NJ i tn ◎ ◎ 〇CvJ o OJ o OQ 〇〇 ΙΛ 1 ΙΛ CO 1 1 in (Si c=&gt; ΙΛ CD TH ΙΛ 1Λ CD 1 LO 1 1 1 1 ΙΛ CNI 1 LO ◎ ◎ 〇&lt;N1 o C&lt;1 〇CO C&lt;l 〇〇CO ΙΛ ΙΛ CO 1 1 ID CV3 o LD CO s to CO 05 -1 I 1 in ΙΛ C&lt;1 1 1 i ΙΛ ◎ ◎ 〇&lt;N1 cs CNI o C&lt;1 Cvl 〇〇&lt;M LTD ΙΛCO 1 1 LO o in CO s ΙΛ CO ΟΪ 卜 · 1 Ln 1 LQ ί 1 1Λ ◎ ◎ 〇Cvl 〇&lt;M C5 CNI (Nl 〇〇S Ln CO 1 1 ΙΛ &lt;&gt;3 〇UT3 CO s tn CO 03 Bu·1 Ln 1 1 m CV3 1 t 1 m ◎ ◎ 〇 (Nl 〇Cvl o CN3 Csl 〇〇S ΙΛ CO i 1 ΙΛ CM o in 1- H CO ΙΛ ιλ CD OS 卜· I ΙΛ 1 1 ΙΛ Cv] 1 1 ΙΛ ◎ ◎ 〇CO o Cvl o C&lt;l CNI 〇〇05 呀1 LO CO 1 1 ΙΛ (NJ o LD CO sm CO 05 ... 1 1 1 1 1 Lft &lt; N1 1 1 t in ◎ ◎ 〇 (Nl &lt;=&gt;C&lt;I o (Nl Cs3 〇〇oo 1Λ CO 1 宕1 Lft 03 o ΙΛ C£ s ΙΛ CD σ&gt; Bu· LO 1 I 1 1 1 in OJ I 1 1 LO ◎ ◎ 〇CM o «Nl ci 03 03 〇〇1 1 LD C&lt;3 1 ΙΛ &lt ;N1 o LO CO but Ln § 〇05 ΙΛ CvJ 1 s 1 1 1 in (N1 1 1 1 ΙΛ ◎ ◎ 〇CO c> CO 〇OO ΙΛ 〇〇CO 呀 write 1 LO CN1 1 1 m (SI o in o ΙΛ g ΙΛ 〇〇* tn CO 1 g 1 1 1 Lft &lt; N1 i 1 1 ΙΛ ◎ ◎ 〇CO G5 CO o 05 CO 〇〇ΙΛ 1 Lft Cvl 1 ΙΛ Cvl 1 o in OO g 〇〇6 ΙΛ Cvl 1 s 1 1 1 ΙΛ &lt;NJ 1 1 1 in ◎ ◎ 〇CO 〇eo o OO 〇〇 φ 9 9 s銮•m K- oo 寸 s CO LO C&lt;JS CO ο CN3 oo CO CO 00 1 (A) Radical polymerizable unsaturated group equivalent (B) Content of (meth) acrylate containing an adduct (ΑΜΒ) CN-2300 [CN—2302 fcN-2304 | viscoat#iooo fviSCOAT#1020 P(VEEA) —2 VEEA [NP-2P0-A TPGDA TMP-3E0-A D1173 The quality of the transparent hardened layer of the hardened layer reduces the amount of warpage increase at the beginning of the residual film Γ) The increase in warpage after the heating promotion test Γ) k Storage modulus of the chemical layer E (MPa) Resistance to scratching of the scratched hard coat UV- 6100B UV-6640B Bis-4E0—A Bis-10EO~A ΗΧ-220 HX—620 VEEA Irgl84 1 Amine ester acrylate containing adduct (meth) acrylate 1 photopolymerization initiator (A)+(B Multi-branched reactive compound side chain reactive group polymer I Polymerizable monoterpene polymerization initiator 1 Preparation (parts by mass) 1〇jj〇® ππ ffiT ^ ^ J Evaluation results Harvesting cones and chills Ying Luhan Rong 201022304 [Table 6]

自由基聚合性 不飽和基當量 光碟編號 65 66 67 68 光 碟 用 硬 化 性 樹 脂 組 成 調配 (質量份) 胺酯丙烯酸酯 UV-6100B 828 40 40 40 — UV-6640B 814 — — — 35 含有加成物之（甲基) 丙烯酸酯 Bis—4E0—A 256 25 25 — — Bis—10EO—A 388 — — 25 30 HX—220 270 25 — — — HX-620 384 — 25 25 25 VEEA 186 10 10 10 10 光聚合 起始劑 Irgl84 — 1.5 1.5 1.5 1.5 (AMB) (A)自由基聚合性不飽和基當量 481 510 543 516 (B)含有加成物之（曱基） 丙稀酸醋含量 60 60 60 65 (AMB) 8.0 8.5 9.0 7.9 硬塗層用 硬化性樹脂 組成物之調配 (質量份） 多分支型 反應性化合物 CN-2300 — 25 25 75 CN-2302 — — — — CN-2304 — 50 50 — viscoat*iooo — — — — VISCOAT#1020 — — — — 側鏈具反應性基之 聚合物 P(VEEA)-2 — — — — 聚合性 單體 VEEA 40 40 40 40 NP-2P0-A — — — — TPGDA — — — — ΓΜΡ-3Ε0-Α — — — — DPHA Γ 20 20 20 20 pETA 40 40 40 40 聚合起始劑 Dll 73 5 5 5 5 評價結果 $化層之透明性 ◎ ◎ ◎ ◎ 硬化層之質量減少 ◎ ◎ ◎ ◎ 殘膜性 〇 〇 〇 〇 起始之翹曲增加量（°) 0.3 0.3 0.3 0.2 加熱促進試驗後之翹曲增加量（°) 0.3 0.3 0.3 0.2 硬化物層之貯藏彈性率E(MPa) 308 169 58 22 耐刮性 〇 〇 〇 〇 硬塗層耐變形性 △ Δ X XFree Radical Polymerizable Unsaturated Group Equivalent Disc No. 65 66 67 68 Composition with Curable Resin for Optical Discs (Parts by mass) Amine Ester Acrylate UV-6100B 828 40 40 40 — UV-6640B 814 — — — 35 Containing an adduct (Meth) Acrylate Bis-4E0—A 256 25 25 — — Bis—10EO—A 388 — — 25 30 HX—220 270 25 — — — HX-620 384 — 25 25 25 VEEA 186 10 10 10 10 Photopolymerization Starting agent Irgl84 — 1.5 1.5 1.5 1.5 (AMB) (A) Radical polymerizable unsaturated group equivalent 481 510 543 516 (B) Acetate containing acetal content 60 60 60 65 (AMB) ) 8.0 8.5 9.0 7.9 Preparation of hardenable resin composition for hard coat (parts by mass) Multi-branched reactive compound CN-2300 — 25 25 75 CN-2302 — — — — CN-2304 — 50 50 — viscoat*iooo — — — — VISCOAT#1020 — — — — Side-chain reactive polymer P(VEEA)-2 — — — — Polymerizable monomer VEEA 40 40 40 40 NP-2P0-A — — — — TPGDA — — — — ΓΜΡ-3Ε0-Α — — — — DPHA Γ 20 20 20 20 pETA 40 40 40 40 Polymerization initiator Dll 73 5 5 5 5 Evaluation result The transparency of the layer ◎ ◎ ◎ ◎ The quality of the hardened layer is reduced ◎ ◎ ◎ ◎ The residual warpage of the residual film Increase (°) 0.3 0.3 0.3 0.2 Increase in warpage after heating promotion test (°) 0.3 0.3 0.3 0.2 Storage modulus of hardened layer E (MPa) 308 169 58 22 Scratch resistance 〇〇〇〇 hard coating Resistance to deformation △ Δ XX

65 201022304 οο CO ΙΛ CO LO OJ 〇 0&lt;Ι CO s s 03 t&gt;-* 1 1 1 1 1 s JS 1 1 Λ r^* o oo ◎ ◎ 〇 CM 〇 03 ο* 1,350 22 X 〇 οο 1 ΙΛ CO 1 1 1 to C&lt;1 1 〇 1 C&lt;l eo LQ s Od 卜‘ m 1 1 1 1 1 〇 1 1 tn 〜 C3 oo ◎ ◎ 〇 CM ο Csl C5 S:&lt;NI s：^ i X 〇 CO 00 1 m CO 1 1 1 LO &lt;M 1 〇 1 c^a CD in s 卜· 1 1 1 运 1 1 1 1 1 s — C3 00 ◎ ◎ 〇 OJ o’ οα ο i：~ X 〇 ΙΑ ΟΟ 1 ΙΛ CO 1 1 1 LO Cvl 1 〇 1 eo o ITS ΙΛ eo Οΐ 1 1 ! 1 另 1 1 t s § T-M c? oo S ◎ ◎ 〇 OJ c&gt; C&lt;I C9 〇 X ΟΟ 1 lA CO 1 1 1 LO CN1 i λ 〇 1 n CO m CD σ» 卜· l 1 1 1 1 1 x&gt; 1 s — o 00 ◎ ◎ 〇 CM o’ c&lt;i sj^ csi丨 〇 X CO 0〇 1 § 1 1 1 1 LO CNI t s 〇 1 CO CO LA s 1 1 1 1 1 1 1 x&gt; 1 s C9 00 ◎ ◎ 〇 CO o CO o S」s CM ' 〇 X CO οο 1 § 1 1 1 1 LO C&lt;I ίο (NJ 1 s ! n 〇 m s LO OO 1 1 1 1 1 i 1 g 1 s o 00 另 ◎ ◎ 〇 CO o c〇 o 1 2,50C &quot;W 〇 X οο 1 § 1 1 i S 1 1Λ CNI 1 ο 1 (M oo 00 § o oo 1 1 1 1 1 i 1 g 1 s o oo ◎ ◎ 〇 CO o CO CD 1 2,50C '&quot;308 ο X S 1 1 Lrt 09 1 1 1 ΙΛ C&lt;J 1 另 ο 1 CO CD in CD 05 卜· i s i 1 1 1 1 1 1 § o’ oo S ◎ ◎ 〇 oa o 03 。· 1，10C 22 〇 〇 Οΐ 1 1 LA CO 1 1 1 ΙΛ CO 1 Ξ 1 CO CO CT&gt; l&gt;： t 1 另 ! 1 1 1 I o oo 茺 ◎ ◎ 〇 CN3 o ΟΌ o i产 ο 〇 00 1 1 ΙΛ CO 1 1 1 m &lt;NI 1 ο 1 OJ CO ID CO &amp;&gt; l 1 g 1 1 1 § i 1 r*H 〇 00 ITD c£&gt; ◎ ◎ 〇 OJ G&gt; (NI d ® !(m 〇 〇 1 ITS CO 1 1 1 LO Cv&gt; 1 ο 1 N c〇 LD s s 1 g 1 I 1 l 1 1 o oo l〇 ◎ ◎ 〇 03 o (NJ 1,00( 22 〇 〇 CO Lrt CO 1 1 1 m CM 1 ο 1 CNi CO s s 0¾ s 1 1 1 1 1 s 1 1 § ψ·^ o oo ◎ ◎ 〇 C&lt;J c&gt; (NI ο l;~ 〇 〇 LO m CO 1 1 1 1Λ csa 1 ο 1 &lt;N1 CO s c-^ s 1 1 1 1 1 S 1 1 s o 00 茭 ◎ ◎ 〇 CM o Csl o )1,28( 22 〇 〇 艺 1 写 ΙΩ (NI 1 ο — 1 C'a CD § LO s σ&gt; S S 1 I 1 1 1 1 I S oo g ◎ ◎ 〇 c&gt; &lt;M o 1,88( Ι'ΊΤ 〇 〇 1 1 1 1 S T—t o 00 g ◎ ◎ 〇 c^a o CJ o Ο 1 〇 〇 CO L〇 CO m (N1 1 另 ο 1 CVJ s 写 m Csl 1 ο ι (N1 CO 寸 in s ψ ^ ai S S o 00 s ◎ ◎ 〇 CO c&gt; CO o i；s 二： rt' ο 〇 m OQ LO Csl ο ι &lt;M o g L〇 OO s s o oo s ◎ ◎ 〇 n o eo o 3]l,88i 1 169 〇 〇 ο 写 LD 03 m Csl 2 C&lt;I 03 00 令 § o oo s § 1—« o oo ο m ◎ ◎ 〇 CO o CO o 〇〇·〇〇 〇 〇 eo s c&gt; oo g ◎ ◎ 〇 呀 o o 1,880 M40 〇 〇 σ&gt; CO g ο Csl 5 CO -ffi «ΓΠ| 不飽和基當jy^ CO 00 ss &lt;&gt;a 〇 oo CQ CO LO C&lt;I §§ C0 00 00 00 § 1 m κ- 趄 /η fr- w 5Ϊ 爻笨 (A)HB) ! -&lt; s PET-8E0-A g 1 PET-12E0-A tiWTA &amp;MP-3E0-A m-m-λ g | i s 1D1173 1 躲 Μ 槳 寒 W k化層之透明性 1«化層之質量減少 k化層之殘旗性 /—N m i? 电 s-/ »w -6 i? w 金 % 4 r-N' £__ 5； ΐΰ；2 # Btrw ag：«- 类:嫌 ^:te e&lt;:维 w 絮 V νβ m « g ο 卜 ϋΥ-6100Β UV-6640B IIV-3000B DCPA-60 HX-220 ,HX-620 IBis-4E0—A |Bis-10EO-A -&lt; &gt;* I ΙΒ-ΧΑ 00 N° ffi mff s-/ 聚合性單體 1 添加劑 |光聚合起始劑 :酯丙烯酸酯 含有加成物 之（甲基） 丙烯酸酯 « 詩 1¾聚合起始劑 1 吖4 _t 5 gsIS 1 1 評價结果 調配 (質量份) 1..— 201022304 又，表1〜表7中之簡稱如下。 光碟用硬化性樹脂組成物材料 • UV — 6640B :胺酯丙烯酸酯（ q不〇成化學工業（ 製）（自由基聚合性不飽和基當量；814) • UV-製）（自 6100B:㈣丙稀酸_(日本合成化學工業（股）公司 由基聚合性不飽和基當量；828) 本合成化學工業（股）公司 ;489)65 201022304 οο CO ΙΛ CO LO OJ 〇0&lt;Ι CO ss 03 t&gt;-* 1 1 1 1 1 s JS 1 1 Λ r^* o oo ◎ ◎ 〇CM 〇03 ο* 1,350 22 X 〇οο 1 ΙΛ CO 1 1 1 to C&lt;1 1 〇1 C&lt;l eo LQ s Od 卜' m 1 1 1 1 1 〇1 1 tn ～ C3 oo ◎ ◎ 〇CM ο Csl C5 S:&lt;NI s:^ i X 〇 CO 00 1 m CO 1 1 1 LO &lt;M 1 〇1 c^a CD in s Bu·1 1 1 Yun 1 1 1 1 1 s — C3 00 ◎ ◎ 〇OJ o' οα ο i:~ X 〇ΙΑ ΟΟ 1 ΙΛ CO 1 1 1 LO Cvl 1 〇1 eo o ITS ΙΛ eo Οΐ 1 1 ! 1 Another 1 1 ts § TM c? oo S ◎ ◎ 〇OJ c&gt;C&lt;I C9 〇X ΟΟ 1 lA CO 1 1 1 LO CN1 i λ 〇1 n CO m CD σ» 卜· l 1 1 1 1 1 x&gt; 1 s — o 00 ◎ ◎ 〇CM o' c&lt;i sj^ csi丨〇X CO 0〇1 § 1 1 1 1 LO CNI ts 〇1 CO CO LA s 1 1 1 1 1 1 1 x&gt; 1 s C9 00 ◎ ◎ 〇CO o CO o S"s CM ' 〇X CO οο 1 § 1 1 1 1 LO C&lt;I Οο (NJ 1 s ! n 〇ms LO OO 1 1 1 1 1 i 1 g 1 so 00 ◎ ◎ 〇CO oc〇o 1 2,50C &quot;W 〇X οο 1 § 1 1 i S 1 1Λ CNI 1 ο 1 (M o o 00 § o oo 1 1 1 1 1 i 1 g 1 so oo ◎ ◎ 〇CO o CO CD 1 2,50C '&quot;308 ο XS 1 1 Lrt 09 1 1 1 ΙΛ C&lt;J 1 another ο 1 CO CD In CD 05 卜·isi 1 1 1 1 1 1 § o' oo S ◎ ◎ 〇oa o 03 . · 1,10C 22 〇〇Οΐ 1 1 LA CO 1 1 1 ΙΛ CO 1 Ξ 1 CO CO CT> l&gt;: t 1 Another! 1 1 1 I o oo 茺 ◎ ◎ 〇CN3 o ΟΌ oi ο 〇 00 1 1 ΙΛ CO 1 1 1 m &lt;NI 1 ο 1 OJ CO ID CO &&gt; l 1 g 1 1 1 § i 1 r*H 〇00 ITD c£&gt; ◎ ◎ 〇OJ G&gt; (NI d ® !(m 〇〇1 ITS CO 1 1 1 LO Cv&gt; 1 ο 1 N c〇LD ss 1 g 1 I 1 l 1 1 o oo l〇◎ ◎ 〇03 o (NJ 1,00 ( 22 〇〇CO Lrt CO 1 1 1 m CM 1 ο 1 CNi CO ss 03⁄4 s 1 1 1 1 1 s 1 1 § ψ·^ o oo ◎ ◎ 〇C&lt;J c&gt; (NI ο l;~ 〇〇LO m CO 1 1 1 1Λ csa 1 ο 1 &lt;N1 CO s c-^ s 1 1 1 1 1 S 1 1 so 00 茭◎ ◎ 〇CM o Csl o )1,28 (22 〇〇艺1 Write ΙΩ (NI 1 ο — 1 C'a CD § LO s σ&gt; SS 1 I 1 1 1 1 IS oo g ◎ ◎ 〇c&gt;&lt;M o 1,88( Ι'ΊΤ 〇〇1 1 1 1 ST-to 00 g ◎ ◎ 〇c ^ao CJ o Ο 1 〇〇CO L〇CO m (N1 1 another ο 1 CVJ s write m Csl 1 ο ι (N1 CO inch in s ψ ^ ai SS o 00 s ◎ ◎ 〇CO c&gt; CO oi;s Two: Rt' ο 〇m OQ LO Csl ο ι &lt;M og L〇OO sso oo s ◎ ◎ 〇no eo o 3]l,88i 1 169 〇〇ο Write LD 03 m Csl 2 C&lt;I 03 00 Order § o Oo s § 1—« o oo ο m ◎ ◎ 〇CO o CO o 〇〇·〇〇〇〇eo s c&gt; oo g ◎ ◎ Oops oo 1,880 M40 〇〇σ&gt; CO g ο Csl 5 CO -ffi « ΓΠ| Unsaturated group when jy^ CO 00 ss &lt;&gt;a 〇oo CQ CO LO C&lt;I §§ C0 00 00 00 § 1 m κ- 趄/η fr- w 5Ϊ 爻 stupid (A)HB)! -&lt; s PET-8E0-A g 1 PET-12E0-A tiWTA &amp;MP-3E0-A mm-λ g | is 1D1173 1 Avoiding the transparency of the paddle cold W k layer 1«The quality of the layer is reduced The residual flag of the k-layer /—N mi? electric s-/ »w -6 i? w gold% 4 rN' £__ 5; ΐΰ;2 # Btrw ag:«- class: suspicion ^:te e&lt;:维克絮 V νβ m « g ο ϋΥ-6100Β UV-6640B IIV-3000B DCPA-60 HX-220 ,HX-620 IBis-4E0—A |Bis-10EO-A -&lt;&gt;* I ΙΒ-ΧΑ 00 N° ffi mff s-/ Polymerizable monomer 1 Additive|Photopolymerization initiator: Ester acrylate containing adduct (methyl) C Ethyl ester « Poetry 13⁄4 polymerization initiator 1 吖4 _t 5 gsIS 1 1 Evaluation results Dispensing (parts by mass) 1..— 201022304 Further, the abbreviations in Tables 1 to 7 are as follows. Curing resin composition material for optical discs • UV — 6640B: Amine ester acrylate (q not chemical industry (manufactured) (radical polymerizable unsaturated equivalent; 814) • UV-based) (from 6100B: (4) C Dilute acid_(Japan Synthetic Chemical Industry Co., Ltd. based on polymerizable unsaturated base equivalent; 828) Synthetic Chemical Industry Co., Ltd.; 489)

❹ * UV—7000B.胺s旨丙稀酸醋（日 製）（自由基聚合性不飽和基當量 • UV— 3000B:胺酯丙烯酸酯（日本合成化學工業（股）公司 製）（自由基聚合性不飽和基當量；3588) .CN—981 .胺酯丙烯酸酯（sartomer (股）公司製）（自由基 聚合性不飽和基當量；709) • CN — 978 :胺酯丙烯酸酯（Sartomer(股）公司製）（自由基 聚合性不飽和基當量；709) • CN — 991 :胺酯丙稀酸酯（Sartomer (股）公司製）（自由基 聚合性不飽和基當量；537) • CN— 2302:高度分支型聚酯丙烯酸酯（SartomerJapan(股） 公司製）（丙烯酸酯官能基數；16、自由基聚合性不飽和基 當量；40) • P(VEEA) — 1 :製造例1之乙烯基系聚合體（自由基聚合性 不飽和基當量；186) • P(VEEA) — 2:製造例2之乙烯基系聚合體（自由基聚合性 不飽和基當量；186) • B i s~ 4E0 — A:雙酚A之環氧乙烧4莫耳加成物之二丙 67 201022304 烯酸醋（商品名「LIGHT-ACRYLATEBP—4EA」、共榮社化學 (股）公司製）（自由基聚合性不飽和基當量；256) • Bi s—lOEO— A:雙酚A之環氧乙烷10莫耳加成物之二 丙稀酸自曰（商品名「SR—602」、Sartomer(股）公司製）（自 由基聚合性不飽和基當量；388) • PEGDA - 9:聚乙二醇二丙烯酸酯以股）公司日本觸媒 製）（自由基聚合性不飽和基當量；186) • TMP — 6EO—A:三羥甲基丙烷之環氧乙烷6莫耳加成物之 三丙稀酸酯（商品名「SR—499」、Sartomer(股）公司製）（自 參 由基聚合性不飽和基當量；187) • TMP—9E0—A:三羥甲基丙烷之環氧乙烷9莫耳加成物之 三丙稀酸酯（商品名「SR—502」、Sartomer(股）公司製）（自 由基聚合性不飽和基當量；231) • VEE A :丙烯酸2—（2 —乙烯氧基乙氧基）乙酯（（股）公司 曰本觸媒製）（乙烯性雙鍵當量；186) •HX—220:經基三甲基乙酸新戊二醇之ε —己内醋2莫 耳加成物之二丙烯酸酯（商品名「KAYARAD(註冊商標）Ηχ — 220」、曰本化藥（股）公司製）（自由基聚合性不餘和基當 量；270) • ΗΧ—620:經基三曱基乙酸新戊二醇之ε —己内醋4莫 耳加成物之二丙烯酸酯（商品名「KAYARAD(註冊商標）Ηχ — 620」、曰本化藥（股）公司製）（自由基聚合性不飽和基當 量；384) • Bi s—4Ρ0—Α:雙紛Α之環氧丙烷加成物之二丙烯酸醋 68 201022304 • (商品名「LIGHT-ACRYLATE BP—4PA」、共榮社化學（股） 公司製）（自由基聚合性不飽和基當量；568) • Bi s~4E0—Μ:雙酚A之環氧乙烷加成物之二甲基丙烯 酸酯（商品名「ΒΡΕ — 200」、新t村化學（股）公司製）（自由 基聚合性不飽和基當量；268) • 9EG-A:聚乙二醇二丙烯酸酯（商品名「light_acrylate 9EG—A」、共榮社化學（股）公司製）（自由基聚合性不飽和 基當量；269) ❿❹ * UV-7000B. Amine s acrylic acid vinegar (made in Japan) (radical polymerizable unsaturated base equivalent • UV-3000B: urethane acrylate (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) (radical polymerization) Unsaturated group equivalent; 3588) .CN—981. Amine ester acrylate (manufactured by Sartomer Co., Ltd.) (radical polymerizable unsaturated equivalent; 709) • CN — 978: Amine ester acrylate (Sartomer) )) (free radically polymerizable unsaturated equivalent; 709) • CN — 991 : Amino ester acrylate (manufactured by Sartomer Co., Ltd.) (radical polymerizable unsaturated equivalent; 537) • CN— 2302: highly branched polyester acrylate (manufactured by Sartomer Japan Co., Ltd.) (number of acrylate functional groups; 16, radically polymerizable unsaturated equivalent; 40) • P(VEEA) - 1 : vinyl of the production example 1 Polymer (radical polymerizable unsaturated equivalent; 186) • P(VEEA) — 2: Vinyl polymer of Production Example 2 (radical polymerizable unsaturated equivalent; 186) • B is~ 4E0 — A: Ethylene bromide of bisphenol A, 4 molar addition of the second propane 67 201022304 Sour vinegar (trade name "LIGHT-ACRYLATEBP-4EA", manufactured by Kyoeisha Chemical Co., Ltd.) (radical polymerizable unsaturated equivalent; 256) • Bi s-lOEO - A: Epoxy B of bisphenol A Alkane 10 molar addition of diacrylic acid (trade name "SR-602", manufactured by Sartomer Co., Ltd.) (radical polymerizable unsaturated equivalent; 388) • PEGDA - 9: polyethylene Alcohol diacrylate (manufactured by Nippon Shokubai Co., Ltd.) (radical polymerizable unsaturated equivalent; 186) • TMP-6EO-A: trimethylolpropane ethylene oxide 6 molar addition Acrylate (trade name "SR-499", manufactured by Sartomer Co., Ltd.) (self-referenced polymerizable unsaturated base equivalent; 187) • TMP-9E0-A: Ethylene B of trimethylolpropane Alkane 9 molar addition triacetate (trade name "SR-502", manufactured by Sartomer Co., Ltd.) (radical polymerizable unsaturated equivalent; 231) • VEE A: acrylic acid 2-(2) —Vinyloxyethoxy)ethyl ester (manufactured by Nippon Chemical Co., Ltd.) (Ethylene double bond equivalent; 186) • HX-220: transmethyltrimethylacetate Alcohol ε - diacrylate of hexane vinegar 2 molar addition (trade name "KAYARAD (registered trademark) Ηχ - 220", manufactured by Sakamoto Chemical Co., Ltd.) (free radical polymerization and base) Equivalent; 270) • ΗΧ-620: diacrylate of ε-caprolactone 4 molar addition product of bis-mercaptoacetic acid neopentyl glycol (trade name "KAYARAD (registered trademark) Ηχ - 620", 曰Manufactured by the Chemical Co., Ltd. (radical polymerizable unsaturated equivalent; 384) • Bi s—4Ρ0—Α: bisacrylic acid acetal acrylate vinegar 68 201022304 • (Product name “ LIGHT-ACRYLATE BP-4PA", manufactured by Kyoeisha Chemical Co., Ltd.) (radical polymerizable unsaturated equivalent; 568) • Bi s~4E0-Μ: ethylene oxide adduct of bisphenol A Dimethacrylate (trade name "ΒΡΕ-200", manufactured by Shintomura Chemical Co., Ltd.) (radical polymerizable unsaturated equivalent; 268) • 9EG-A: polyethylene glycol diacrylate (product) "light_acrylate 9EG-A", manufactured by Kyoeisha Chemical Co., Ltd.) (radical polymerizable unsaturated equivalent; 269) ❿

• IB—XA:異蓓基丙烯酸酯（商品名「LIGHT-ACRYLATE IB —XA」' 共榮社化學（股）公司製）（自由基聚合性不飽和基 當量；208) • DCP — A :三環癸烷二丙烯酸酯（商品名「light_acrylate DCP—A」、共榮社化學（股）公司製）（自由基聚合性不飽和 基當量；152) • 1，6 — Hx— A: 1，6 —己二醇二丙烯酸酯（商品名 φ 「LIGHT-ACRYLATE 1，6Hx - A j 、共榮杜化學（股）公司 製）（自由基聚合性不飽和基當量；226) • HPP—A:羥基三曱基乙酸新戊二醇二丙烯酸酯（商品名 「LIGHT-ACRYLATE HPP — A」、共榮社化學（股）公司製）（自 由基聚合性不飽和基當量；156) • IB- XM :異萡基甲基丙烯酸酯（商品名「UGHT-ESTER IB —X」、共榮社化學（股）公司製）（自由基聚合性不飽和基當 量；222) • DPCA — 60:二季戊四醇之己内酯1莫耳加成物之六丙稀 69 201022304 酸酯（商品名「KAYARAD(註冊商標）DPCA— 60、日本化藥（股） 公司製j • Irgl84: 1 —經基一環己基一苯基一酮（商品名 「 IRGACUR(註冊商標）184 」、Chiba Specialty• IB—XA: isodecyl acrylate (trade name “LIGHT-ACRYLATE IB —XA”' manufactured by Kyoeisha Chemical Co., Ltd.) (radical polymerizable unsaturated equivalent; 208) • DCP — A : three Cyclodecane diacrylate (trade name "light_acrylate DCP-A", manufactured by Kyoeisha Chemical Co., Ltd.) (radical polymerizable unsaturated equivalent; 152) • 1,6 — Hx— A: 1,6 - hexanediol diacrylate (trade name: φ "LIGHT-ACRYLATE 1, 6Hx - A j, manufactured by Kyoei Chemical Co., Ltd.) (radical polymerizable unsaturated equivalent; 226) • HPP-A: hydroxyl group Tridecyl acetic acid neopentyl glycol diacrylate (trade name "LIGHT-ACRYLATE HPP - A", manufactured by Kyoeisha Chemical Co., Ltd.) (radical polymerizable unsaturated equivalent; 156) • IB-XM: Isodecyl methacrylate (trade name "UGHT-ESTER IB-X", manufactured by Kyoeisha Chemical Co., Ltd.) (radical polymerizable unsaturated equivalent; 222) • DPCA - 60: dipentaerythritol Lactone 1 molar addition of hexamethylene 69 201022304 acid ester (trade name "KAYARAD (registered trademark DPCA- 60, Nippon Kayaku (shares) Co., Ltd. j • Irgl84: 1 - through a base-cyclohexyl-phenyl-ketone (trade name "IRGACUR (registered trademark) 184", Chiba Specialty

Chemicals(股）公司製） • Esacure — one :寡{2 —羥基一2 —甲基一1—〔4— (1 —Chemicals Co., Ltd.) • Esacure — one: oligo{2—hydroxyl-2—methyl-1—[4— (1 —

甲基乙烯基）苯基}丙酮）（商品名「Esacure ONE」、LAMBERTI 製）· TINUVIN PS: 2—(2 —羥基一5 —第三丁基苯基）一2H —苯并***（商品名「TINUVIN(註冊商標）PS」、Chiba ® Specialty Chemicals(股）公司製） •TINUVIN 479:2— {2 -羥基一4—(1—辛氧基羰基乙氧 基）苯基}一 4, 6—雙（4一苯基苯基）一 1，3, 5 —三畊（商品名 「TINUVIN(註冊商標）479」、Chiba Specialty Chemicals(股）公司製） • RUVA93 : 2- {2 —羥基一5-(2 -甲基丙烯醯氧乙基）笨 基}苯并***（大塚化學（股）公司製） w • BY16 — 876.環氧變性梦嗣（T〇ray. j)〇wCorning(股）公司 製） 硬塗用硬化性樹脂组成物材料 • PET — 4E0—A:五季戊四醇之環氧乙烷4莫耳加成物之四 丙烯酸酯（商品名「SR494」、Sartomer(股）公司製） • PET — 8E0—A:五季戊四醇之環氧乙烷8莫耳加成物之四 丙稀酸醋 • DPCA- 60Methylvinyl)phenyl}acetone) (trade name "Esacure ONE", manufactured by LAMBERTI) · TINUVIN PS: 2-(2-hydroxy-5-t-butylphenyl)- 2H-benzotriazole (commercial product "TINUVIN (registered trademark) PS", manufactured by Chiba ® Specialty Chemicals Co., Ltd.) • TINUVIN 479: 2 - {2-hydroxy-4-(1-octyloxycarbonylethoxy)phenyl}-4 6-bis(4-phenylphenyl)-1,3,5-three tillage (trade name "TINUVIN (registered trademark) 479", manufactured by Chiba Specialty Chemicals Co., Ltd.) • RUVA93: 2- {2 - hydroxyl 5-(2-Methylacryloxyethyl)p-benzotriazole (manufactured by Otsuka Chemical Co., Ltd.) w • BY16 — 876. Epoxy-denatured nightmare (T〇ray. j)〇wCorning (manufactured by the company) Hardenable resin composition material for hard coating • PET — 4E0—A: Tetraacrylate of ethylene oxide 4 molar addition of pentaerythritol (trade name “SR494”, Sartomer) Made by the company) • PET — 8E0—A: Ethylene oxide 8 molar addition of pentaerythritol, tetraacrylic acid vinegar • DPCA- 60

戊四醇之己内酯 莫耳加成物之六两烯 70 201022304 酸酯（商品名「KAYARAD(註冊商標）DPCA — 60、日本化藥（股） 公司製」 • CN— 2-300 :高度分支型聚酯丙烯酸酯（丙烯酸酯官能基數 8、SartomerJapan(股）公司製） • CN— 2302 :高度分支型聚酯丙烯酸酯（丙烯酸酯官能基數 16、Sartomer Japan(股）公司製） • CN — 2304 :高度分支型聚酯丙烯酸酯（丙烯酸酯官能基數 18、Sartomer Japan(股）公司製） Φ w · VISC0AT# 1000 :樹枝狀化合物型丙烯酸酯（大阪有機化 學工業（股）公司製）· VISC0AT# 1020 :樹枝狀化合物型丙 烯酸酯（大阪有機化學工業（股）公司製）· P — (VEEA) - 2 : 製造例2之乙烯基系聚合體 • VEE A :丙烯酸2 —（2—乙稀氧基乙氧基）乙酯（（股）公司 曰本觸媒製）.NP — 2P0 — A:新戊二醇之環氧丙烷2莫耳加 成物之二丙稀酸醋（商品名「SR — 9003」、Sartomer(股） φ 公司製） • TPGDA :三丙二醇二丙烯酸酯（商品名「SR— 306H」、 Sartomer(股）公司製） • TMP — 3E0 —A:三羥曱基丙烷之環氧乙烷3莫耳加成物之 二丙稀酸醋（商品名「SR—454」'Sartomer(股）公司製） • DPHA :二季戊四醇六丙烯酸酯 (商品名「LIGHT-ACRYLATED PE—6A」、共榮社化學（股） 公司製） • PETA :季戊四醇三丙烯酸酯 71 201022304 (商品名「LIGHT-ACRYLATE PE-3A」、共榮社化學（股）公 司製） • PET—12E0—A:五季戊四醇之環氧乙烷ι2莫耳加成物之 四丙稀酸酉旨 • TMPTA ·•三羥甲基丙烷三丙烯酸酯（曰本觸媒製） • L — 7002 :聚醚變性矽酮（商品名「l — 7002」、Toray ·Hexanediol 70 of the caprolactone molar addition of pentaerythritol 201022304 Acidate (trade name "KAYARAD (registered trademark) DPCA - 60, manufactured by Nippon Kayaku Co., Ltd." • CN-2-300: Height Branched polyester acrylate (acrylate functional group number 8, manufactured by Sartomer Japan Co., Ltd.) • CN-2302: highly branched polyester acrylate (acrylate functional group number 16, manufactured by Sartomer Japan Co., Ltd.) • CN — 2304: Highly branched polyester acrylate (acrylate functional group number 18, manufactured by Sartomer Japan Co., Ltd.) Φ w · VISC0AT# 1000 : Dendrimer type acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.) · VISC0AT # 1020 : Dendritic acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.) · P — (VEEA) - 2 : Vinyl polymer of Production Example 2 • VEE A : Acrylic acid 2 — (2-ethylene Oxyethoxyethyl)ethyl ester (manufactured by Nippon Chemical Co., Ltd.). NP — 2P0 — A: neopentyl glycol propylene oxide 2 molar addition of diacrylic acid vinegar (trade name “ SR — 9003”, Sartomer (share) φ • TPGDA: tripropylene glycol diacrylate (trade name “SR— 306H”, manufactured by Sartomer Co., Ltd.) • TMP — 3E0 — A: trimethylhydrazine propane ethylene oxide 3 molar addition Diacetic acid vinegar (trade name "SR-454", manufactured by Sartomer Co., Ltd.) • DPHA: dipentaerythritol hexaacrylate (trade name "LIGHT-ACRYLATED PE-6A", Kyoeisha Chemical Co., Ltd.) • PETA: Pentaerythritol triacrylate 71 201022304 (trade name “LIGHT-ACRYLATE PE-3A”, manufactured by Kyoeisha Chemical Co., Ltd.) • PET—12E0—A: Ethylene oxide ι2 Moga, pentaerythritol四 丙 • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • •

DowCorning(股）公司製） • D1173: 2 —羥基一2 —甲基一1~苯基—丙—上—酮（商品 名「DAL0CURE 1173」、Chiba Specialty Chemicals(股） 公司製） 【產業利用性】 本發明之光碟用硬化性樹脂組成物，具透明性，同時 能抑制光碟全體之翹曲，又’能利用於於長期保存安定性 (高溫環境下或低溫環境下之保存試驗中之低翹曲性或於 南溫環境下之殘膜性、凹陷等永久變形量小）優異之光碟， 例如藍光碟片（註冊商標）。 【圖式簡單說明】 圖1顯示：本發明之實施例以籲表示，比較例以〇表 示’橫軸代表硬化性樹脂組成物中之自由基聚合性不飽和 基當量（g/eq)A，縱轴表示含有環氧烷烴加成物之多官能 (甲基）丙烯酸酯類及含有己内酯加成物之多官能（甲基）丙 稀酸醋之含量（質量％)B之圖。又，圖上部之線表示（A/6. 6) 201022304 即本申請發 之邊界線，圖下部之線表示（A/35)之邊界線， 明之上下限。 【主要元件符號說明】 無0DowCorning Co., Ltd.) • D1173: 2-hydroxy-2-methyl- 1~phenyl-propyl-e-ketone (trade name “DAL0CURE 1173”, manufactured by Chiba Specialty Chemicals Co., Ltd.) [Industrial use The curable resin composition for optical discs of the present invention has transparency and can suppress warpage of the entire disc, and can be utilized for long-term storage stability (low tilt in a high temperature environment or a low temperature environment) A disc with excellent curvature or small residual deformation such as residual film and depression in a southerly environment, such as a Blu-ray disc (registered trademark). BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 shows an embodiment of the present invention, which is indicated by 吁, and the comparative example is represented by ', where the horizontal axis represents the radical polymerizable unsaturated group equivalent (g/eq) A in the curable resin composition, The vertical axis represents a content (% by mass) B of a polyfunctional (meth) acrylate containing an alkylene oxide adduct and a polyfunctional (meth) acrylate vinegar containing a caprolactone adduct. Further, the upper line of the figure indicates (A/6. 6) 201022304, which is the boundary line of the present application, and the line at the lower part of the figure indicates the boundary line of (A/35), which is the lower limit. [Main component symbol description] No 0

7373

Claims (1)

201022304 七、申請專利範圍·· 1 · 一種光碟用硬化性樹脂組成物’其中，該硬化性樹 脂組成物用於一光碟具有： 反射膜，存在於基體上，且使資訊讀取用之雷射光反 射；及 保護層，存在於該反射膜上，且厚度為20 ym以上 15 0 m 以下； 該光碟用硬化性樹脂組成物包括： 寡聚物及/或聚合物，具有選自於胺酯（曱基）丙烯酸 酯、環氧（甲基）丙烯酸酯及聚酯（曱基）丙烯酸酯所構成族 群中至少1種自由基聚合性基； 含有環氧烷烴加成物之多官能（曱基）丙烯酸酯類或含 有己内酯加成物之多官能（甲基）丙烯酸酯類；及 光聚合起始劑； 當該硬化性樹脂組成物中之自由基聚合性不飽和基當 量（g/eq)為A、該硬化性樹脂組成物中之含有環氧烷烴加 成物之多官能（甲基）丙烯酸酯類及含有己内酯之加成物之 多官能（甲基）丙烯酸酯類之含量（質量％)為B時，滿足6.6 S A+BS 35。 2. 如申請專利範圍第1項所述之光碟用硬化性樹脂組 成物，其中，該含有環氧烷烴加成物之多官能（甲基）丙烯 酸酯類，為雙驗A之環氧燒煙加成物之二丙稀酸醋。 3. 如申清專利範圍第1或2項所述之光碟用硬化性樹 脂組成物，其中，該硬化性樹脂組成物於2 5 °C之黏度為 201022304 • 800mPa · s 以上 3500mPa · s 以下。 4. 如申請專利範圍第ii3項中任一項所述之光碟用 硬化性樹脂組成物，其中，將該硬化性樹脂組成物硬化得 到之硬化物於25°C之貯藏彈性率E，為1〇MPa以上15〇Mpa 以下。 5. 如申請專利範圍第！至3項中任一項所述之光碟用 硬化性樹脂組成物，其中，將該硬化性樹脂組成物硬化得 到之硬化物於25C之貯藏彈性率E，為12〇〇Mpa以上 ® 2100MPa 以下。 6. 如申請專利範圍第1至5項中任一項所述之光碟用 硬化性樹脂組成物，其中，硬化性樹脂組成物含有多官能 (甲基）丙烯酸酯及/或多分支型反應性化合物。 7. 如申請專利範圍第1至6項中任一項所述之光碟用 硬化性樹脂組成物，其中，將該硬化性樹脂組成物硬化得 到之硬化物於厚度l〇〇ym之各波長之光線穿透率為： 粵 （X)於 400nm，85. 0%以上； (Y) 於 380nm ’ 3 5. 0%以上 85· 〇%以下；且 (Z) 於 360nm ’ 0. 1%以上 50. 0%以下。 8. —種光碟’其特徵在於具有使申請專利範圍第1至 7項中任一項所述之光碟用硬化性樹脂組成物硬化形成之 保護層。 9. 如申請專利範圍第8項所述之光碟，更具有硬塗 層’該硬塗層係得自使硬塗用樹脂組成物硬化而得，該硬 塗用樹脂組成物包括直接形成於該保護層上之多分支型反 75 201022304 應性化合物；及/或側鏈具反應性基之聚合物；及聚合起始 劑。 10. 如申請專利範圍第9項所述之光碟，其中，該多分 支型反應性化合物（α)係於末端具2個以上反應性基之樹 枝狀化合物（αΐ)及/或高度分支聚合物（α2)。 11. 如申請專利範圍第8項之所述光碟，更具有硬塗 層，該硬塗層係得自使硬塗用樹脂組成物硬化而得，該硬 塗用樹脂組成物包括直接形成於該保護層上之對4元以上 之多元醇的母1元之加成重複單位為η=1或2之環氧烧烴 加成物所得之含有環氧烷烴加成物之多官能（甲基）丙烯酸 Sa類’及/或對4元以上之多元醇的每1元之加成重複單位 為η—1或2之己内酯加成物所得之含有己内酯加成物之多 s能（甲基）丙烯酸酯類；及光聚合起始劑。201022304 VII. Patent application scope·· 1 · A curable resin composition for optical discs> wherein the curable resin composition is used for a disc having: a reflective film, which is present on the substrate, and allows laser light for reading information a reflective layer and a protective layer present on the reflective film and having a thickness of 20 μm or more and 150 mm or less; the curable resin composition for the optical disc comprising: an oligomer and/or a polymer having a selected from the group consisting of an amine ester ( At least one radical polymerizable group of a group consisting of acrylate, epoxy (meth) acrylate, and polyester (mercapto) acrylate; polyfunctional (fluorenyl) containing an alkylene oxide adduct Acrylate or polyfunctional (meth) acrylate containing caprolactone adduct; and photopolymerization initiator; radical polymerizable unsaturated group equivalent in the curable resin composition (g/eq Is A, a polyfunctional (meth) acrylate containing an alkylene oxide adduct in the curable resin composition, and a polyfunctional (meth) acrylate containing an adduct of caprolactone (quality%) B, the satisfying 6.6 S A + BS 35. 2. The curable resin composition for optical discs according to claim 1, wherein the polyfunctional (meth) acrylate containing an alkylene oxide adduct is a double-test A epoxy smoky The adduct is a diacetic acid vinegar. 3. The sclerosing resin composition for optical discs according to claim 1 or 2, wherein the curable resin composition has a viscosity at 25 ° C of 201022304 • 800 mPa · s or more and 3500 mPa · s or less. 4. The curable resin composition for an optical disk according to any one of the invention, wherein the cured resin composition obtained by curing the curable resin composition has a storage modulus E at 25 ° C of 1 〇 MPa or more and 15 〇 Mpa or less. 5. If you apply for a patent scope! The curable resin composition for a disc according to any one of the above-mentioned items, wherein the curable resin composition obtained by curing the curable resin composition has a storage modulus E of 25 C, which is 12 〇〇Mpa or more and 2100 MPa or less. 6. The curable resin composition for optical discs according to any one of claims 1 to 5, wherein the curable resin composition contains a polyfunctional (meth) acrylate and/or a multi-branched reactivity. Compound. 7. The curable resin composition for an optical disk according to any one of the first to sixth aspect of the invention, wherein the cured product obtained by curing the curable resin composition has a thickness of each wavelength of 10 μm. The light transmittance is: (X) at 400 nm, 85.0% or more; (Y) at 380 nm '3 5. 0% or more 85·〇% or less; and (Z) at 360 nm '0.11% or more 50 . 0% or less. 8. A type of optical disk comprising a protective layer formed by curing a curable resin composition for a compact disk according to any one of claims 1 to 7. 9. The optical disc of claim 8, further comprising a hard coating layer obtained by hardening a resin composition for hard coating, the resin composition for hard coating comprising directly formed thereon a multi-branched reverse 75 201022304 compound on the protective layer; and/or a polymer having a reactive group in a side chain; and a polymerization initiator. 10. The optical disc according to claim 9, wherein the multi-branched reactive compound (α) is a dendrimer (αΐ) and/or a highly branched polymer having two or more reactive groups at the terminal. (α2). 11. The optical disc of claim 8, further comprising a hard coat layer obtained by hardening a resin composition for hard coating, the hard coating resin composition comprising directly formed thereon a multi-functional (methyl) group containing an alkylene oxide adduct obtained by adding an alkylene oxide adduct of η = 1 or 2 to a parent unit of a polyhydric alcohol having a weight of 4 or more on the protective layer. The s-caprolactone containing the caprolactone of the acrylic acid and/or the repeating unit per 10,000 or more of the polyol of 4 or more is the s-caprolactone of the η-1 or 2 Methyl) acrylates; and photopolymerization initiators.