TW200814051A - Optical information recording media and manufacturing method thereof - Google Patents
Optical information recording media and manufacturing method thereof Download PDFInfo
- Publication number
- TW200814051A TW200814051A TW096114642A TW96114642A TW200814051A TW 200814051 A TW200814051 A TW 200814051A TW 096114642 A TW096114642 A TW 096114642A TW 96114642 A TW96114642 A TW 96114642A TW 200814051 A TW200814051 A TW 200814051A
- Authority
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- Taiwan
- Prior art keywords
- layer
- light absorbing
- bca
- absorbing layer
- light
- Prior art date
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Landscapes
- Optical Record Carriers And Manufacture Thereof (AREA)
- Optical Recording Or Reproduction (AREA)
- Manufacturing Optical Record Carriers (AREA)
Abstract
Description
200814051 (1) 九、發明說明 【發明所屬之技術領域】 本發明係關於光資訊記錄媒體等，進而詳言之，特別 是關於除使用者資訊以外以條碼記錄管理資訊的光資訊記 錄媒體等。 【先前技術】 從前，於DVD-ROM等光資訊記錄媒體的最內圈，設 有紀錄條碼資訊的字符組切割區（B u r s t C u 11 i n g A r e a :以下 簡稱「BCA」）。被紀錄於BCA的資訊，不需要進行循跡 伺服控制就可以讀取。此外，於BCA，序號等管理資訊 ，作爲各個光資訊記錄媒體的識別資訊而被紀錄，這些被 利用於著作權保護等（參照專利文獻1〜3 )。 此外，管理記錄於使用者資訊區域的使用者資訊’或 者保護該著作權的方式已有文獻報告。作爲使用者資訊’ 例如可舉出程式、資料、應用程式資訊等。根據該方式， 管理資訊，在光資訊記錄媒體之使用者資訊區域外之系統 讀入（system read-in)以與使用者資訊區域相同的調變方式 被紀錄，另一方面，於BCA，管理資訊以與使用者資訊 區域不同的調變方式被記錄（參照專利文獻4)。 這樣的BCA在光資訊記錄媒體的製造階段被形成。 具體而言，DVD-ROM的場合’例如以YAG雷射除去反射 膜而形成之（參照專利文獻5)。另一方面’在追記型光資 訊記錄媒體之DVD-R的場合，如果如DVD-ROM那樣以 200814051 (2) YAG雷射除去反射膜的話，紀錄層與反射膜會有剝離之 虞。因此，藉由使用專用的BCA寫入器，在控制區域內 的溝部分記錄條碼而形成BCA。 [專利文獻1]日本專利特開2000 — 149423號公報 [專利文獻2]曰本專利特開2000 — 222783號公報 [專利文獻3]日本專利特開200 1 — 043 5 3 3號公報 [專利文獻4]日本專利特開平1 0 — 1 8 83 6 1號公報 [專利文獻5]日本專利特開平06 — 203 4 1 2號公報 【發明內容】 [發明所欲解決之課題] 然而近年來，因應於資訊量的大容量化，開發出具有 2個之光吸收層（記錄層）之2層型光資訊記錄媒體。其中， 使用吸收雷射光的色素材料之追記型光資訊記錄媒體’因 爲不能改寫而被利用於許多用途。於這些2層型的光資訊 記錄媒體，於一方之層被形成 BCA。例如，在2層型 DVD-R由光入射之側來看，在前側的第1層之光吸收層被 形成BCA。 將這樣的2層型光資訊記錄媒體安裝於記錄再生裝置 ，讀入被記錄於BCA的管理資訊的場合，記錄再生裝置 對焦於一方之層之後使光學頭移動至被形成BCA的半徑 位置，讀入B C A管理資訊。 但是，在最初對焦之層不存在BCA的場合’要對焦 另一方之層而尋找BCA。這樣的場合’會有S3錄再生裝 200814051 (3) 置之存取很花時間的問題。 本發明係爲了解決前述之類的問題而發明者。 亦即，本發明之目的，在於提供於具有包含可記錄再 生的光吸收材料的2個光吸收層之光資訊記錄媒體，具有 可以縮短記錄再生裝置的存取時間之BCA的光資訊記錄 媒體。 此外，本發明之其他目的，在於提供於具有包含光吸 收材料的2個光吸收層之光資訊記錄媒體，於兩方之層設 有可得優異的訊號品質之BCA的光資訊記錄媒體之製造 方法。 [供解決課題之手段] 在此經本案發明人等銳意檢討的結果，於具有2個光 吸收層的光資訊記錄媒體，藉由在兩方之光吸收層設置記 錄管理資訊的BCA，可以解決前述課題。此處，使用者 資訊，係於光資訊記錄媒體之包含光吸收材料的2個光吸 收層，藉由從單側照射的藍光雷射，沿著同心圓形狀或者 螺旋狀的軌道被記錄，或者被再生。 亦即，首先，適用於本發明之光資訊記錄媒體，具有 2個光吸收層，由光入射側來看前側之第1層包含BCA， 在與第1層之BCA相同半徑的位置，被形成記錄著與第1 層之BCA相同的管理資訊的第2層之BCA。 第二，於適用本發明的光資訊記錄媒體，設於第2號 之光吸收層的BCA之記錄開始位置（BCA2S)，與設於第1 200814051 气 (4) 號之光吸收層的 BCA之記錄開始位置（BCA1S)，滿足 AS = BCA2S-BCAlS$15pm 之關係。 第三，於適用本發明的光資訊媒體，由設於第1號之 光吸收層的BCA所得的訊號振幅，比由設於第2號之光吸 收層的BCA所得的訊號振幅還要小。 第四，於適用本發明的光資訊記錄媒體，由光入射側 來看前側之第1號之光吸收層所記錄的標記的反射率，變 得比記錄前的反射率還要高（低至高Lowto High記錄）。 第五，於適用本發明的光資訊記錄媒體，BCA由記 錄使用者資訊的方向照射雷射光，對第1號之光吸收層與 第2號之光吸收層，同時記錄條碼資訊而形成。 如此，根據本發明，提供以下（1 )〜（1 3 )。 (1) 一種光資訊記錄媒體，其特徵爲：具備具有可藉 由從單側照射的光，而沿著同心圓或者螺旋狀的軌道記錄 或者再生使用者資訊的資訊區域之2層光吸收層，由前述 光之入射側來看前側之第1號之光吸收層，於前述資訊區 域的內側，具有將特定的管理資訊以條碼資訊記錄之第1 層之字符組切割區（BCA)，由前述光之入射側來看裡側之 第2號之光吸收層，於與前述第1層之字符組切割區（BCA) 相同半徑的位置，具有記錄著與被記錄於該第1層之字符 組切割區（BCA)的前述管理資訊相同的管理資訊之第2層 之字符組切割區（BCA)。 (2) 如前述（1)之光資訊記錄媒體，其中前述第2層之字 符組切割區（BCA)的半徑方向之寬幅的中央之記錄開始位 200814051 (5) 置（BCA2S)，與前述第1層之字符組切割區（BCA)的半徑方 向之寬幅的中央之記錄開始位置（BCA1S)，滿足下述式（1) 之關係。 AS = (BCA2S)-(BCAlS)S15em 式（1)(其中、於式（1)，as 係 (BCA2S)與（BCA1S)之差（單位爲 μιη))。 (3) 如前述（1)之光資訊記錄媒體，其中由前述第1層之 字符組切割區（BCA)所得到的訊號振幅，比由前述第2層 之字符組切割區（BCA)所得到的訊號振幅還要小。 (4) 如前述（1)之光資訊記錄媒體，其中前述第1號之光 吸收層與前述第2號之光吸收層包含有機色素，且前述第2 號之光吸收層之膜厚，比前述第1號之光吸收層的膜厚還 要厚。 (5) 如前述（1)之光資訊記錄媒體，其中前述管理資訊 被記錄的前述第1層之字符組切割區（BCA)的反射率，係 比前述管理資訊被記錄以前的該第1層之字符組切割區 (BCA)被形成的區域的反射率還要高的低至高（Low to High)記錄，而且前述管理資訊被記錄的前述第2層之字符 組切割區（BCA)的反射率，係比前述管理資訊被記錄以前 的該第2層之字符組切割區（BCA)被形成的區域的反射率 還要高的低至高（Low to High)記錄。 (6) 如前述（1)之光資訊記錄媒體，其中前述第1號之光 吸收層與前述第2號之光吸收層之間，具有膜厚40 μηι以下 的透明中間層。 (7) 如前述（1)之光資訊記錄媒體，其中前述光係藍光 (6) (6)200814051 雷射。 (8) —種光資訊記錄媒體’係具有包含有機色素的2層 光吸收層的光資訊記錄媒體，其特徵爲具備：從單側照射 的光的入射側來看設於前側的第1號之光吸收層’與從前 述光的入射側來看設於裡側而具有比前述第1號之光吸收 層的膜厚（D1)更厚的膜厚（D2)之第2號之光吸收層，與設 於前述第1號之光吸收層與前述第2號之光吸收層之間的膜 厚40μιη以下之透明中間層；至少於前述第2號之光吸收層 ，具有記錄著特定的管理資訊之字符組切割區（BCA)。 (9) 如前述（8)之光資訊記錄媒體，其中前述第2號之光 吸收層的膜厚（D2)比前述第1號之光吸收層的膜厚（D1)厚 上1 〇 %以上。 (10) 如前述（8)之光資訊記錄媒體，其中前述字符組切 割區（BCA)之反射率，係比前述特定的管理資訊被記錄之 前的該字符組切割區（BCA)被形成的區域的反射率變得更 高的低至高（Low to High)記錄。 (1 1)如前述（8)之光資訊記錄媒體，其中進而在前述第 1號之光吸收層之，與被形成於前述第2號之光吸收層的前 述字符組切割區（BCA)相同的半徑位置，具有記錄與被記 錄於該字符組切割區（BCA)的前述管理資訊相同的管理資 訊之其他字符組切割區（BCA)。 (12)—種光資訊記錄媒體之製造方法，係具有包含可 藉由光而記錄再生的有機色素的2層光吸收層的光資訊記 錄媒體之製造方法，其特徵爲：於透明基板上，依序形成 -10- 200814051 (7) :由前述光之入射側來看前側之第1號之光吸收層，及膜 厚40 μιη以下之透明中間層，及由該光的入射側來看裡側 之第2號之光吸收層由前述光之入射側透過前述透明基 板照射藍光雷射，在前述第1號之光吸收層與前述第2號之 光吸收層，同時形成將特定的管理資訊作爲條碼資訊記錄 之字符組切割區（BCA)。 (13)如前述（12)之光資訊記錄媒體之製造方法，其中 前述第2號之光吸收層的膜厚（D2)對前述第1號之光吸收層 的膜厚（D1)之比（D2/D1)在 1.1以上（D2/D1 2 1.1)。 [發明之效果] 根據本發明，可以在短時間認識記錄於具有2個光吸 收層之光資訊記錄媒體所記錄之條碼資訊，進而，可重現 高訊號品質的條碼資訊。 【實施方式】 [供實施發明之最佳型態] 以下，詳細說明供實施本發明之最佳型態（以下簡稱 爲發明之實施型態）。又，本發明並不以下列實施型態爲 限定內容，在不逸脫其要旨的範圍內可以進行種種變形而 實施。此外’使用的圖面係供說明本實施型態之用者，並 不代表實際的大小。 本實施型態適用的光資訊記錄媒體，由從單側照射的 光之入射側來看，係由設於前面的第1層、及設於後側的 -11 - 200814051 (8) 第2層所構成。 圖1係供說明本實施型態適用的光資訊記錄媒體之圖 。圖1(a)係說明光資訊記錄媒體之第丨層之各區域之圖， 圖1(b)係說明光資訊記錄媒體之第2層之各區域之圖。 如圖1(a)所示，光資訊記錄媒體丨之第丨層，於圓盤狀 之中央部設有中心孔C。於中心孔C的周圍，被形成不具 有溝或坑之平坦的第1層之反射鏡區域2。於第1層之反射 鏡區域2的外周側，設有以條碼記錄管理資訊的第1層之 BCA3 ’與沿著同心圓或者螺旋狀的軌道記錄特定的使用 者資訊的第1層之資訊區域5。 此外，應需要，在第1層之BCA3與第1層之資訊區域 5之間，以及第1層之資訊區域5的外側，分別設置第1層之 反射鏡區域4、第1層之反射鏡區域6。 又，於第1層之資訊區域5的內側，亦可形成顯示管理 資訊等之坑（pit)。此外，以條碼記錄管理資訊的第1層之 BC A3的形狀亦可爲反射鏡，亦可形成溝或者坑。 其次，如圖1(b)所示，光資訊記錄媒體1的第2層，與 第1層同樣，於中心孔C的周圍，具有未被形成溝或者坑 的平坦的第2層之反射鏡區域7。於第2層之反射鏡區域7的 外周側，設有以條碼記錄管理資訊的第2層之BCA8，與 沿著同心圓或者螺旋狀的軌道記錄特定的使用者資訊的第 2層之資别區域1〇。 此外，應需要，在第2層之BCA8與第2層之資訊區域 10之間，以及第2層之資訊區域10的外側，分別設置第2層 12- 200814051 η (9) 之反射鏡區域9、第2層之反射鏡區域1 1。 又，於第2層之資訊區域1 0的內側，亦可形成顯示管 理資訊等之坑（pit)。此外，以條碼記錄管理資訊的第2層 之BCA8的形狀亦可爲反射鏡，亦可形成溝或者坑。 其次，圖2係供說明本實施型態適用的光資訊記錄媒 體之剖面構成圖。如圖2所示，光資訊記錄媒體1 2，由光 (L)入射之側所見的前方側之第1層（L0)，係由透光性的第 1透明基板1 3，與被形成於第1透明基板1 3上的第1號之光 吸收層（I)所構成。 第1號之光吸收層（I)，具有：記錄特定的使用者資訊 的第1層之資訊區域17(使用者資訊區域）、設於比第1層之 資訊區域1 7更靠內周側，而以條碼記錄著管理資訊等的第 1層之BCA15，及比第1層之BCA15更靠近內周側之第1層 之反射鏡區域1 4。 此外，應需要，而具有在第1層之BCA 15與第1層之 資訊區域17之間，以及第1層之資訊區域17的外周側，分 別設置的第1層之反射鏡區域1 6、第1層之反射鏡區域1 8。 其次，由光入射側來看後側之第2層（L 1 )，與第1層 (L0)同樣，由第2透明基板25，及被形成於第2透明基板25 上而比前述之第1層（L0)之第1號之光吸收層（I)膜厚更厚的 第2號之光吸收層（II)所構成。 第2號之光吸收層（II)，具有：記錄特定的使用者資訊 的第2層之資訊區域23 (使用者資訊區域）、設於比第2層之 資訊區域23更靠內周側而半徑位置與第1層之BCA 15幾乎 -13- 200814051 (10) 相同的位置，而以條碼記錄著管理資訊等的第2層之 BCA21，及比第2層之BCA21更靠近內周側之第2層之反射 鏡區域2 0。 此外，應需要，而具有在第2層之BCA21與第2層之 資訊區域23之間，以及第2層之資訊區域23的外周側，分 別設置的第2層之反射鏡區域22、第2層之反射鏡區域24。 接著，第1層（L0)與第2層（L1)，係藉由透明黏接劑等 中介著膜厚40μιη以下的透明中間層19而被貼合、一體化 〇 於適用本實施型態的光資訊記錄媒體1 2，第2層之 BCA21最好被形成於與第1號之光吸收層（I)之第1層之 BC A 15幾乎相同半徑的位置。 此處，所謂「第2層之BCA21以及第1層之BCA15被 形成於幾乎相同的半徑位置」，係指第2層之BCA21的記 錄開始位置（BCA2S)，與第1層之BCA1 5的記錄開始位置 (BCA1S)滿足下列式（1)之關係。 AS = (BCA2S)-(BCAlS)S15pm 式⑴ 又，於式（1)，△ S係在第2號之光吸收層（II)設爲同 心圓狀的第2號之BCA21的半徑方向之寬幅的中央之記錄 開始位置（BCA2S)，與在第1層之光吸收層（I)設爲同心圓 狀的第1層之B C A 1 5的半徑方向之寬幅的中央之記錄開始 位置（BCA1S)之差（單位爲μηι)。 -14- (11) 200814051 進而，於適用本實施型態的光資訊記錄媒體1 2，在設 於第2號之光吸收層（II)的第2層之字符組切割區（BCA)， 被記錄著與被記錄於第1層之字符組切割區（BCA)的管理 資訊相同的管理資訊。 藉由第1層之字符組切割區（BCA)與第2層之字符組切 割區（BCA)被記錄著相同的管理資訊，可以在短時間認識 記錄於光資訊記錄媒體12的條碼資訊，進而可以再現高訊 號品質的條碼資訊。 其次，說明設於本實施型態適用的光資訊記錄媒體之 BCA的剖面構成。 首先，作爲具有2層光吸收層之光資訊記錄媒體之調 製方法已有種種被提出。例如，可以舉出將第1號之光吸 收層（I)與第2號之光吸收層（II)形成於分別的透明基板上 ，接著，以透明黏接劑貼合這些透明基板，亦即所謂的逆 層積法。 此外，還可以舉出在透明基板上製作第1號之光吸收 層（I)，於其上塗布透明樹脂，在抵壓於模具後使透明樹 脂硬化而製作第2層之透明基板，進而於其上堆積第2號之 光吸收層（II)之2P法。 圖3係供說明本實施型態適用的光資訊記錄媒體之 BCA被形成的區域（BCA區域）的剖面構造之圖。此處，舉 藉由逆層積法調製之光資訊記錄媒體26爲例。 如圖3所示，光資訊記錄媒體26的BCA區域，由光入 射側所見的前方側之第1層（L0)，具有：由透光性材料所 15- 200814051 (12) 構成的第1透明基板27，與包含形成於第1透明基板27上的 光吸收材料之第1號之光吸收層28，以及形成於第1號之光 吸收層28上之半透明反射層29。 此外，由光入射側來看裡側之第2層（L1)具有第2透明 基板34，依序設於第2透明基板34上的光入射側之反射層 33、包含光吸收材料的第2號之光吸收層32、界面層31。 接著，以使第1層之半透明反射層29與第2層之界面層 31對向的方式，使第1層（L0)與第2層（L1)藉由透明中間層 3 0而被黏接、一體化。此處，第1層之BCA被形成於第1 號之光吸收層28，而第2層之BCA被形成於第2號之光吸 收層3 2。 又，在此例，把形成被記錄條碼資訊的B C A的部分 之透明基板做成反射鏡形狀，但並不以反射鏡形狀爲限， 例如也可以做成包含溝或者坑的形狀。 其次，說明構成光資訊記錄媒體26的各層。 (第1透明基板、第2透明基板） 第1透明基板27及第2透明基板34的材料，最好爲例如 對雷射光的折射率爲1.4〜1.7的範圍之透明度很高的材料 ，而且耐衝擊性優異的樹脂。具體而言，可以舉出聚碳酸 酯、非結晶聚烯烴、丙烯酸樹脂等，但不以此爲限。 又，在第1透明基板27與第1號之光吸收層28之間，亦 可因應需要而設置Si02、ZnS-Si02等增強層或耐溶劑層。 弟1透明基板27以及第2透明基板34，最好製作原盤以 -16- 200814051 (13) 及壓模（stamper)，藉由射出成型進行調製。此處，原盤例 如藉由以下方式製作。亦即，準備直徑200mm厚度6mm 的玻璃原盤，於玻璃原盤一方的表面上藉由旋轉塗布法均 勻塗布光阻劑。光阻劑的厚度因應於坑或溝槽的深度而調 整。其次，將塗布光阻劑的玻璃原盤安裝於切割裝置。 又，供製作原盤之切割裝置的記錄光學頭，係藉由與 原盤相對在直徑方向上移動的伺服系來驅動。記錄半徑位 置以線性刻度監視，以閉伺服迴圏進行控制。格式化器 (formatter)產生資訊資料、管理資訊、溝訊號等而驅動光 學頭。系統全體以控制器管理，也進行軌道間距（track pitch)的伺服控制。在此伺服控制之中控制軌道間距。原 盤係以主軸馬達旋轉驅動，形成獨自的伺服迴圈。主軸馬 達以主軸馬達驅動器來驅動。 藉由切割裝置，因應於由格式化器所送來的資訊，由 光學頭對光阻劑照射雷射光而曝光，形成同心圓或者螺旋 狀的坑或者溝。調節雷射光量，控制坑的大小、溝幅。結 束切割的玻璃原盤，於圖案形成面施以作爲電鍍前處理之 無電解電鍍。進而，將此電鍍層作爲導電膜藉由電鑄法形 成鎳層。接著，硏磨形成於玻璃原盤上的鎳層的表面，進 而，藉由從玻璃原盤剝離前述鎳層而得壓模（stamper)。又 ，亦可使用濺鍍法或蒸鍍法來進行前述電鍍之前處理之導 電膜形成。 (第1號之光吸收層、第2號之光吸收層） -17- 200814051 (14) 作爲第1號之光吸收層28、第2號之光吸收層32的材料 ，最好爲吸光性的有機色素。具體而言，例如可以舉出氰 藍色素、聚甲炔色素、三芳基甲烷色素、吡喃鑰色素、菲 色素、偶氮色素、四脫氫膽鹼色素、三芳基胺色素、方酸 菁色素、克酮次甲基（croconic methine)色素等，但不以此 爲限。 這些有機色素可以單獨使用種類或者混合2種以上的 有機色素使用。此外，亦可包含驟冷劑（q u e n c h e r)或其他 色素、添加劑、高分子（例如硝化纖維等熱塑性樹脂、熱 塑性彈性體）、金屬微粒子等。 於本實施型態是用的光資訊記錄媒體26，第1層（L0) 之第1號之光吸收層28以及第2層（L2)之第2號之光吸收層 3 2 ’最好是，最好是在記錄資訊後的反射率比記錄資訊之 前的反射率還要高之低至高（Low to High)記錄。在此場合 ，前述有機色素，最好是記錄再生光的波長之吸收相當大 的有機色素，亦即光學常數的衰減係數k很大的有機色素 〇 第1號之光吸收層28與第2號之光吸收層32係藉由以下 方法形成的。亦即，首先，使用習知的有機溶媒溶解前述 有機色素及任意之添加劑調製溶媒媒合之溶液。其次，第 1號之光吸收層28的場合，直接將此溶液塗布於第1透明基 板27上。此外，第2號之光吸收層32的場合，塗布於形成 在第2透明基板3 4上的反射層3 3上。作爲有機溶媒，例如 可舉出四氟丙醇、酮醇 '乙醯丙酮、甲基溶纖劑（methyl -18- (15) (15)200814051 cellosolve)、甲苯等。 塗布方法通常採用旋轉塗布法。旋轉塗布的條件，係 由內周往外周，以旋轉數3 00rmP〜5000rPm之間組合數條 件而進行即可。藉由調整這些旋轉塗布的條件、有機色素 溶液的濃度、黏度、溶劑的乾燥速度’可以控制第1號之 光吸收層28與第2號之光吸收層32的膜厚。 於適用本實施型態的光資訊記錄媒體26 ’第1號之光 吸收層28與第2號之光吸收層32的膜厚’通常分別爲20nm 〜100nm，較佳者爲在30nm〜60nm的範圍來調製。 進而，於適用本實施型態的光資訊記錄媒體2 6，如前 所述，第2號之光吸收層32的膜厚（D2)比第1號之光吸收層 28的膜厚（D1)更厚（D2>D1)。具體而言，以第2號之光吸收 層32的膜厚（D2)比第1號之光吸收層28的膜厚（D1)厚上10 %以上的方式調製。 亦即，第2號之光吸收層32的膜厚（D2)對第1號之光吸 收層28的膜厚（D1)之比（D2/D1)在1.1以上（D2/D1 - 1.1)。 其中，（D2/D1)通常爲2.0以下。 (半透明反射層） 半透明反射層2 9，最好光的吸收很小，光的透過率在 30%以上，且具有適度之光反射率。例如，藉由減薄反射 率高的金屬膜，可以使透過率與反射率之平衡維持於適當 的範圍。此外，因爲半透明反射層2 9很薄，所以最好是具 有耐蝕性的材料。進而，爲了防止對透明中間層3 0之有機 -19- 200814051 (16) 色素的滲出最好具有遮蔽性。 作爲供形成半透明反射層29的金屬，例如可以舉出金 、銀、鋁或含有這些的合金。半透明反射層29可以藉由使 用這些金屬的濺鍍法等手段來形成。以銀爲主成分者，成 本低廉、反射率很高所以最佳。 半透明反射層2 9因爲金屬膜的結晶粒太大的話會成爲 再生雜訊的原因，所以最好使用結晶粒小的材料。銀的場 合，因爲純銀有結晶粒變大的傾向，所以最好使用銀合金 〇 作爲銀合金，最好以銀爲主成分’而含有由Ga、Bi 、Ti、Zn、Cu、Pd、Au、Ca、In及稀土族金屬所形成的 群所選出之至少1種元素含有原子百分比〜5原子百分 比。 於銀合金中，含有 Ga、Bi、Ti、Zn、Cu、Pd、Au、[Technical Field] The present invention relates to an optical information recording medium and the like, and more particularly to an optical information recording medium in which management information is recorded in a bar code in addition to user information. [Prior Art] In the past, on the innermost circumference of an optical information recording medium such as a DVD-ROM, a character group cutting area (B u r s t C u 11 i n g A r e a : hereinafter referred to as "BCA") for recording bar code information is provided. The information recorded in the BCA can be read without tracking servo control. In addition, the management information such as the BCA and the serial number is recorded as the identification information of each optical information recording medium, and these are used for copyright protection and the like (see Patent Documents 1 to 3). In addition, the manner in which user information recorded in the user information area is managed or the copyright is protected has been reported in the literature. As user information, for example, programs, materials, application information, and the like can be cited. According to this method, the management information is recorded in the system read-in outside the user information area of the optical information recording medium in the same manner as the user information area, and on the other hand, in the BCA, management The information is recorded in a modulation manner different from the user information area (see Patent Document 4). Such BCA is formed at the manufacturing stage of the optical information recording medium. Specifically, in the case of a DVD-ROM, for example, a YAG laser is used to remove the reflective film (see Patent Document 5). On the other hand, in the case of the DVD-R of the write-on optical recording medium, if the reflective film is removed by the 200814051 (2) YAG laser as in the case of the DVD-ROM, the recording layer and the reflective film may be peeled off. Therefore, the BCA is formed by recording a bar code in the groove portion in the control area by using a dedicated BCA writer. [Patent Document 1] Japanese Patent Laid-Open Publication No. 2000-149423 [Patent Document 2] Japanese Patent Laid-Open Publication No. 2000-222783 (Patent Document 3) Japanese Patent Laid-Open Publication No. 2001- 043 [Patent Document 5] Japanese Patent Laid-Open No. Hei 06-203 4 1 2 [Invention] [Problems to be Solved by the Invention] However, in recent years, in response to the problem In order to increase the capacity of information, a two-layer type optical information recording medium having two light absorbing layers (recording layers) has been developed. Among them, a write-once optical information recording medium using a pigment material that absorbs laser light is used for many purposes because it cannot be rewritten. In these two-layer type optical information recording media, BCA is formed on one layer. For example, in the case where the two-layer type DVD-R is incident on the side from which light is incident, the light absorbing layer of the first layer on the front side is formed into BCA. When such a two-layer type optical information recording medium is mounted on a recording/reproducing device and the management information recorded on the BCA is read, the recording/reproducing device focuses on one layer, and then moves the optical head to a radial position where the BCA is formed, and reads Enter BCA management information. However, in the case where there is no BCA in the layer where the focus is initially focused, it is necessary to focus on the other layer to find the BCA. In such a case, there will be a problem that access to the S3 recording reproduced device 200814051 (3) is very time-consuming. The present invention has been made in order to solve the above problems. That is, an object of the present invention is to provide an optical information recording medium having two light absorbing layers including a recordable reproduction light absorbing material, and an optical information recording medium having a BCA capable of shortening the access time of the recording and reproducing apparatus. Further, another object of the present invention is to provide an optical information recording medium having two light absorbing layers including a light absorbing material, and to provide a BCA optical information recording medium having excellent signal quality in both layers. method. [Means for Solving the Problem] As a result of the intensive review by the inventors of the present invention, the optical information recording medium having two light absorbing layers can solve the above problem by providing BCA for recording management information in the light absorbing layers of both sides. . Here, the user information is the two light absorbing layers of the optical information recording medium including the light absorbing material, and is recorded along a concentric circle shape or a spiral track by a blue laser light irradiated from one side, or It is regenerated. In other words, the optical information recording medium to which the present invention is applied has two light absorbing layers, and the first layer on the front side including the BCA is formed by the light incident side, and is formed at the same radius as the BCA of the first layer. The BCA of the second layer that records the same management information as the BCA of the first layer. Secondly, in the optical information recording medium to which the present invention is applied, the recording start position (BCA2S) of the BCA of the light absorbing layer No. 2 and the BCA of the light absorbing layer of the first (2008) No. Record the start position (BCA1S) and satisfy the relationship of AS = BCA2S-BCAlS$15pm. Third, in the optical information medium to which the present invention is applied, the amplitude of the signal obtained by the BCA of the light absorbing layer No. 1 is smaller than the amplitude of the signal obtained by the BCA of the light absorbing layer of the second. Fourth, in the optical information recording medium to which the present invention is applied, the reflectance of the mark recorded by the light absorbing layer No. 1 on the front side as viewed from the light incident side becomes higher than the reflectance before recording (low to high) Lowto High record). Fifth, in the optical information recording medium to which the present invention is applied, the BCA is formed by irradiating the laser light in the direction in which the user information is recorded, and recording the bar code information on the light absorbing layer No. 1 and the light absorbing layer No. 2 at the same time. Thus, according to the present invention, the following (1) to (1 3) are provided. (1) An optical information recording medium characterized by comprising: a two-layer light absorbing layer having an information area capable of recording or reproducing user information along a concentric circle or a spiral track by light irradiated from one side The light absorbing layer of the first side of the front side is viewed from the incident side of the light, and has a character group cutting area (BCA) of the first layer for recording specific management information by bar code information on the inner side of the information area. The light absorbing layer of the second side on the back side of the light incident side has a character recorded and recorded on the first layer at a position having the same radius as the character group cutting area (BCA) of the first layer. The second layer of the character group cutting area (BCA) of the management information of the group cutting area (BCA) is the same as the management information. (2) The optical information recording medium according to (1) above, wherein the recording start position of the center of the width direction of the character group cutting area (BCA) of the second layer is 200814051 (5) (BCA2S), and the foregoing The recording start position (BCA1S) at the center of the width in the radial direction of the character group cutting area (BCA) of the first layer satisfies the relationship of the following formula (1). AS = (BCA2S)-(BCAlS)S15em Formula (1) (wherein, the difference between formula (1), as system (BCA2S) and (BCA1S) (unit: μιη)). (3) The optical information recording medium according to (1) above, wherein the signal amplitude obtained by the character group cutting area (BCA) of the first layer is obtained by the character group cutting area (BCA) of the second layer The signal amplitude is even smaller. (4) The optical information recording medium according to (1), wherein the light absorbing layer of the first No. 1 and the light absorbing layer of the second No. 2 comprise an organic dye, and the film thickness of the second light absorbing layer is smaller than The film thickness of the light absorbing layer of the above No. 1 is also thick. (5) The optical information recording medium according to (1) above, wherein the reflectance of the character group cutting area (BCA) of the first layer in which the management information is recorded is the first layer before the management information is recorded. The reflectance of the area where the character group cutting area (BCA) is formed is still high to Low to High, and the aforementioned management information is recorded by the reflectance of the second layer of the character group cutting area (BCA) The recording is higher than the low to high (Low to High) of the reflectance of the region in which the second layer of the character group cutting area (BCA) is formed before the management information is recorded. (6) The optical information recording medium according to (1) above, wherein the light absorbing layer of the first No. 1 and the light absorbing layer of the second No. 2 have a transparent intermediate layer having a film thickness of 40 μm or less. (7) The optical information recording medium according to (1) above, wherein said light-based blue light (6) (6) 200814051 is laser. (8) A light information recording medium is an optical information recording medium having a two-layer light absorbing layer containing an organic dye, and is characterized in that it includes a first number provided on the front side as viewed from the incident side of the light irradiated on one side. The light absorbing layer 'and the second light absorption (D2) having a thickness (D2) thicker than the film thickness (D1) of the first light absorbing layer as viewed from the incident side of the light a layer and a transparent intermediate layer having a thickness of 40 μm or less between the light absorbing layer of the first No. 1 and the light absorbing layer of the No. 2; at least the light absorbing layer of the No. 2 has a specific recording Management Information Character Group Cutting Area (BCA). (9) The optical information recording medium according to the above (8), wherein the film thickness (D2) of the second light absorbing layer is more than 1% by weight larger than the film thickness (D1) of the first light absorbing layer . (10) The optical information recording medium according to (8) above, wherein the reflectance of the aforementioned character group cutting area (BCA) is an area formed by the character group cutting area (BCA) before the specific management information is recorded. The reflectivity becomes higher and the Low to High record. (1) The optical information recording medium according to (8) above, wherein the light absorbing layer of the first No. 1 is the same as the character group dicing area (BCA) formed in the light absorbing layer of the second No. The radial position has another character group cutting area (BCA) that records the same management information as the aforementioned management information recorded in the character group cutting area (BCA). (12) A method of producing a light information recording medium, comprising: a light information recording medium comprising a two-layer light absorbing layer containing an organic dye that can be recorded and reproduced by light, characterized in that: on a transparent substrate, Formed sequentially - -10-200814051 (7): The first light absorbing layer on the front side and the transparent intermediate layer having a film thickness of 40 μm or less, as viewed from the incident side of the light, and the incident side of the light The light absorbing layer of the second side is irradiated with a blue laser light through the transparent substrate from the incident side of the light, and the light absorbing layer of the first No. 1 and the light absorbing layer of the second No. 2 are simultaneously formed with specific management information. A character group cutting area (BCA) that is used as a bar code information record. (13) The method for producing an optical information recording medium according to the above (12), wherein a ratio of a film thickness (D2) of the second light absorbing layer to a film thickness (D1) of the first light absorbing layer ( D2/D1) is above 1.1 (D2/D1 2 1.1). [Effect of the Invention] According to the present invention, bar code information recorded on an optical information recording medium having two light absorbing layers can be recognized in a short time, and further, bar code information of high signal quality can be reproduced. [Embodiment] [Best Mode for Carrying Out the Invention] Hereinafter, the best mode for carrying out the invention (hereinafter simply referred to as an embodiment of the invention) will be described in detail. Further, the present invention is not limited to the following embodiments, and various modifications can be made without departing from the spirit and scope of the invention. Further, the drawings used are for the purpose of illustrating the embodiments and do not represent actual size. The optical information recording medium to which the present embodiment is applied is viewed from the incident side of the light irradiated from one side by the first layer provided on the front side and the -11 - 200814051 (8) second layer provided on the rear side. Composition. Fig. 1 is a view for explaining an optical information recording medium to which the present embodiment is applied. Fig. 1(a) is a view showing each region of the second layer of the optical information recording medium, and Fig. 1(b) is a view showing each region of the second layer of the optical information recording medium. As shown in Fig. 1(a), the second layer of the optical information recording medium has a center hole C at the center of the disk. Around the center hole C, a mirror region 2 of a first layer which is flat without grooves or pits is formed. On the outer peripheral side of the mirror area 2 of the first layer, a BCA3' of the first layer in which the management information is recorded by the bar code and an information area of the first layer which records the specific user information along the concentric circle or the spiral track are provided. 5. In addition, a mirror layer 4 of the first layer and a mirror of the first layer are respectively disposed between the BCA 3 of the first layer and the information area 5 of the first layer and the outside of the information area 5 of the first layer. Area 6. Further, pits for displaying management information or the like may be formed inside the information area 5 of the first floor. Further, the shape of the BC A3 of the first layer in which the management information is recorded by the bar code may be a mirror or a groove or a pit. Next, as shown in FIG. 1(b), the second layer of the optical information recording medium 1 has a flat second layer mirror which is not formed with a groove or a pit around the center hole C, similarly to the first layer. Area 7. On the outer peripheral side of the mirror area 7 of the second layer, a BCA 8 of a second layer in which management information is recorded in a bar code, and a second layer in which specific user information is recorded along a concentric circle or a spiral track are provided. Area 1〇. In addition, it is necessary to provide a mirror region 9 of the second layer 12-200814051 η (9) between the BCA 8 of the second layer and the information area 10 of the second layer, and the outside of the information area 10 of the second layer. The mirror area 1 of the second layer. Further, pits for displaying management information or the like may be formed inside the information area 10 of the second layer. Further, the shape of the BCA 8 of the second layer in which the management information is recorded by the bar code may be a mirror or a groove or a pit. Next, Fig. 2 is a cross-sectional structural view for explaining an optical information recording medium to which the present embodiment is applied. As shown in FIG. 2, the first layer (L0) on the front side seen from the side on which the light (L) is incident is the light-transmissive recording medium 12, and is formed of a translucent first transparent substrate 13 and formed thereon. The first light-transmitting layer (I) of the first transparent substrate 13 is formed. The light absorbing layer (I) of No. 1 has an information area 17 (user information area) of the first layer for recording specific user information, and is disposed on the inner circumference side of the information area 177 of the first layer. The BCA 15 of the first layer in which the management information and the like are recorded in a bar code, and the mirror region 14 of the first layer on the inner peripheral side of the BCA 15 of the first layer are displayed. Further, if necessary, there is a mirror region 16 of the first layer provided between the BCA 15 of the first layer and the information area 17 of the first layer, and the outer peripheral side of the information area 17 of the first layer. The mirror area of the first layer is 18. Next, the second layer (L 1 ) on the rear side viewed from the light incident side is formed on the second transparent substrate 25 and on the second transparent substrate 25 in the same manner as the first layer (L0). The light absorbing layer (I) of the first layer (L0) of the first layer (L0) is composed of the second light absorbing layer (II) having a thicker thickness. The second light absorbing layer (II) has a second layer information area 23 (user information area) for recording specific user information, and is disposed on the inner circumference side of the information layer 23 of the second layer. The radius position is the same as the BCA 15 of the first layer, which is almost the same as the position of the 13th, and the BCA21 of the second layer, which is the management information, and the BCA21, which is closer to the inner circumference side than the BCA 21 of the second layer. 2 layer mirror area 20. Further, if necessary, the second layer mirror region 22 and the second layer are provided between the BCA 21 of the second layer and the information area 23 of the second layer, and the outer peripheral side of the information area 23 of the second layer. The mirror area 24 of the layer. Then, the first layer (L0) and the second layer (L1) are bonded and integrated by a transparent intermediate layer 19 having a film thickness of 40 μm or less by a transparent adhesive or the like, and are integrated and applied to the present embodiment. The optical information recording medium 1 2, the BCA 21 of the second layer is preferably formed at a position almost the same as the BC A 15 of the first layer of the first light absorbing layer (I). Here, "the BCA 21 of the second layer and the BCA 15 of the first layer are formed at almost the same radial position" mean the recording start position (BCA2S) of the BCA 21 of the second layer, and the record of the BCA 15 of the first layer. The start position (BCA1S) satisfies the relationship of the following formula (1). AS = (BCA2S)-(BCAlS)S15pm Formula (1) Further, in the formula (1), the ΔS is in the radial direction of the No. 2 light absorbing layer (II) which is concentrically shaped as the second BCA21. The recording start position (BCA2S) at the center of the web, and the recording start position (BCA1S) at the center of the width of the BCA 15 in the first layer of the first layer, which is concentrically arranged in the first layer (BCA2S) The difference (in μηι). Further, in the optical information recording medium 1 2 to which the present embodiment is applied, in the character group cutting area (BCA) of the second layer of the second light absorbing layer (II), Management information identical to the management information recorded in the character group cutting area (BCA) of the first layer is recorded. The same management information is recorded by the character group cutting area (BCA) of the first layer and the character group cutting area (BCA) of the second layer, and the bar code information recorded on the optical information recording medium 12 can be recognized in a short time, and further Bar code information with high signal quality can be reproduced. Next, the cross-sectional configuration of the BCA of the optical information recording medium to which the present embodiment is applied will be described. First, various methods of modulation as an optical information recording medium having two layers of light absorbing layers have been proposed. For example, the light absorbing layer (I) of No. 1 and the light absorbing layer (II) of No. 2 are formed on the respective transparent substrates, and then the transparent substrates are bonded together by a transparent adhesive, that is, The so-called inverse stacking method. Further, a light absorbing layer (I) of No. 1 is formed on a transparent substrate, a transparent resin is applied thereon, and the transparent resin is cured after being pressed against the mold to form a transparent substrate of the second layer, and further The 2P method of depositing the light absorbing layer (II) of No. 2 thereon. Fig. 3 is a view showing a cross-sectional structure of a region (BCA region) in which a BCA of the optical information recording medium to which the present embodiment is applied is described. Here, the optical information recording medium 26 modulated by the inverse layering method is taken as an example. As shown in FIG. 3, the BCA region of the optical information recording medium 26 has a first layer (L0) on the front side seen from the light incident side, and has a first transparent layer composed of a light-transmitting material 15-200814051 (12). The substrate 27 and the first light absorbing layer 28 including the light absorbing material formed on the first transparent substrate 27, and the semi-transparent reflective layer 29 formed on the first light absorbing layer 28. Further, the second layer (L1) on the back side of the light incident side has the second transparent substrate 34, and the reflective layer 33 on the light incident side of the second transparent substrate 34 is sequentially provided, and the second layer including the light absorbing material is provided. The light absorbing layer 32 and the interface layer 31. Next, the first layer (L0) and the second layer (L1) are adhered by the transparent intermediate layer 30 so that the semi-transparent reflective layer 29 of the first layer faces the interface layer 31 of the second layer. Connected and integrated. Here, the BCA of the first layer is formed on the light absorbing layer 28 of the first layer, and the BCA of the second layer is formed by the light absorbing layer 32 of the second layer. Further, in this example, the transparent substrate forming the portion of the B C A in which the bar code information is recorded is formed into a mirror shape. However, the shape of the transparent substrate is not limited to the shape of the mirror, and may be, for example, a shape including grooves or pits. Next, each layer constituting the optical information recording medium 26 will be described. (First transparent substrate, second transparent substrate) The material of the first transparent substrate 27 and the second transparent substrate 34 is preferably a material having a high transparency in a range of a refractive index of 1.4 to 1.7 for laser light, and is resistant to light. A resin excellent in impact. Specific examples thereof include polycarbonate, amorphous polyolefin, and acrylic resin, but are not limited thereto. Further, a reinforcing layer such as SiO 2 or ZnS-SiO 2 or a solvent resistant layer may be provided between the first transparent substrate 27 and the first light absorbing layer 28 as needed. On the other hand, the transparent substrate 27 and the second transparent substrate 34 are preferably prepared by injection molding using -16-200814051 (13) and a stamper. Here, the original disc is produced, for example, by the following method. Namely, a glass master having a diameter of 200 mm and a thickness of 6 mm was prepared, and the photoresist was uniformly coated on the surface of one of the glass masters by spin coating. The thickness of the photoresist is adjusted depending on the depth of the pit or trench. Next, the glass master coated with the photoresist is mounted on the cutting device. Further, the recording optical head for producing the original cutting device is driven by a servo system that moves in the radial direction with respect to the original disk. The recording radius position is monitored on a linear scale and controlled by a closed servo return. The formatter generates information, management information, channel signals, etc. to drive the optical head. The entire system is managed by a controller, and servo control of track pitch is also performed. The track pitch is controlled in this servo control. The original disc is driven by a spindle motor to form a separate servo loop. The spindle motor is driven by a spindle motor drive. By means of the cutting device, the photoresist is irradiated with the laser light by the optical head in response to the information sent from the formatter to form a concentric or spiral pit or groove. Adjust the amount of laser light, control the size of the pit, and the groove width. The cut glass master is finished, and electroless plating is applied as a pre-plating treatment on the pattern forming surface. Further, this plating layer was used as a conductive film to form a nickel layer by electroforming. Next, the surface of the nickel layer formed on the glass master was honed, and a stamper was obtained by peeling the nickel layer from the glass master. Further, the formation of the conductive film before the plating may be performed by a sputtering method or a vapor deposition method. (Light absorbing layer No. 1 and light absorbing layer No. 2) -17- 200814051 (14) The material of the light absorbing layer 28 of No. 1 and the light absorbing layer 32 of No. 2 is preferably light absorbing. Organic pigments. Specific examples thereof include cyanine blue, polymethine dye, triarylmethane dye, pyranyl dye, phenanthrene dye, azo dye, tetrahydrohydrocholine dye, triarylamine dye, and squarylium pigment. , Croconic methine pigment, etc., but not limited to this. These organic dyes can be used singly or in combination of two or more organic pigments. Further, it may contain a quenching agent (q u e n c h e r) or other dyes, additives, polymers (for example, thermoplastic resins such as nitrocellulose, thermoplastic elastomers), metal fine particles, and the like. In the optical information recording medium 26 used in the present embodiment, the light absorbing layer 28 of the first layer (L0) and the second light absorbing layer 3 2 of the second layer (L2) are preferably Preferably, the reflectance after recording the information is higher than the reflectance before the information is recorded. In this case, the organic dye is preferably an organic dye having a relatively large absorption wavelength of the recording and reproducing light, that is, an organic dye 很大 No. 1 light absorbing layer 28 having a large optical constant attenuation coefficient k and No. 2 The light absorbing layer 32 is formed by the following method. That is, first, a solution of the solvent-mediated solution is prepared by dissolving the organic dye and any additives using a conventional organic solvent. Next, in the case of the light absorbing layer 28 of No. 1, the solution is directly applied onto the first transparent substrate 27. Further, in the case of the second light absorbing layer 32, it is applied onto the reflective layer 3 3 formed on the second transparent substrate 34. Examples of the organic solvent include tetrafluoropropanol, ketol 'acetamidine acetone, methyl cellosolve (methyl -18-(15) (15) 200814051 cellosolve), toluene, and the like. The coating method is usually a spin coating method. The conditions of the spin coating may be carried out by combining several conditions from the inner circumference to the outer circumference by a number of rotations of 300 rpm to 5000 rpm. The film thickness of the first light absorbing layer 28 and the second light absorbing layer 32 can be controlled by adjusting the conditions of the spin coating, the concentration of the organic dye solution, the viscosity, and the drying speed of the solvent. In the optical information recording medium 26' to which the present embodiment is applied, the film thicknesses of the first light absorbing layer 28 and the second light absorbing layer 32 are generally 20 nm to 100 nm, preferably 30 nm to 60 nm. Range to modulate. Further, in the optical information recording medium 2 to which the present embodiment is applied, as described above, the film thickness (D2) of the second light absorbing layer 32 is larger than the film thickness (D1) of the first light absorbing layer 28. Thicker (D2>D1). Specifically, the film thickness (D2) of the second light absorbing layer 32 is made thicker than the film thickness (D1) of the first light absorbing layer 28 by 10% or more. That is, the ratio (D2/D1) of the film thickness (D2) of the light absorbing layer 32 of No. 2 to the film thickness (D1) of the light absorbing layer 28 of No. 1 is 1.1 or more (D2/D1 - 1.1). Among them, (D2/D1) is usually 2.0 or less. (Semi-transparent reflective layer) The semi-transparent reflective layer 2 9 preferably has a small absorption of light, a transmittance of light of 30% or more, and a moderate light reflectance. For example, by thinning the metal film having a high reflectance, the balance between the transmittance and the reflectance can be maintained in an appropriate range. Further, since the semitransparent reflective layer 29 is very thin, it is preferably a material having corrosion resistance. Further, in order to prevent the bleeding of the organic -19-200814051 (16) pigment of the transparent intermediate layer 30, it is preferable to have a shielding property. As the metal for forming the semi-transparent reflective layer 29, for example, gold, silver, aluminum or an alloy containing these may be mentioned. The semi-transparent reflective layer 29 can be formed by a sputtering method using these metals or the like. Silver-based components are the best at low cost and high reflectivity. Since the semi-transparent reflective layer 2 9 is a cause of regenerative noise because the crystal grains of the metal film are too large, it is preferable to use a material having a small crystal grain. In the case of silver, since pure silver tends to have large crystal grains, it is preferable to use silver alloy iridium as a silver alloy, and it is preferable to contain Ga, Bi, Ti, Zn, Cu, Pd, Au, and silver as a main component. At least one element selected from the group consisting of Ca, In, and rare earth metals contains atomic percentages to 5 atomic percent. In silver alloy, it contains Ga, Bi, Ti, Zn, Cu, Pd, Au,
Ca、In及稀土族金屬所形成的群所選出之2種以上的場合 ，分別含有0.1原子百分比〜5原子百分比亦可，但最好其 合計爲0.1原子百分比〜5原子百分比。稀土族金屬中，以 銳最佳。 作爲銀合金之具體例，可以舉出AgpdCu、AgCuAu、 AgCuAuNd、AgCuNd、AgCaCu、Agin、AgBi、AgBiNd 等 〇 此外，金的結晶粒雖小，且耐鈾性優異，但是與銀合 金相比稍嫌昂貴。此外，作爲半透明反射層29以3丨02等 金屬以外之材料交互堆疊低折射率薄膜與高折射率薄膜形 -20 - 200814051 (17) 成多層膜，而作爲半透明反射層使用亦可。 作爲形成半透明反射層29的方法，例如可以舉出濺鍍 法、離子佈植法、化學蒸鍍法、真空蒸鍍法等。其中以濺 鍍法在生產性上最佳。 又，在第1號之光吸收層28與半透明反射層29之間，亦 可設置Si02、ZnS-Si02、Al2〇3等增強層或耐氧化層等其他 層。此外，應需要，亦可將保護層形成於半透明反射層29 上。作爲保護層只要可以保護光吸收層、反射層之層即可 ，例如可以藉由紫外線硬化樹脂、矽系樹脂等來形成。 (反射層） 反射層3 3以反射率高、耐鈾性優者爲佳。爲了提高反 射率，反射層33的厚度通常爲50nm以上較佳。更佳者爲 8 〇nm以上。但是爲了提高記錄感度反而以薄至某種程度 較佳，通常以3 0 0nm以下較佳，又以200nm以下尤佳。反 射層33的厚度太大的話，第2透明基板34有翹曲之虞。 作爲反射層3 3的材料，可以舉出在再生光的波長具有 充分高的反射率者。具體而言，例如可以將Au、Al、Ag 、Cu、Ti、Cr、Ni等金屬單獨使用或者以合金的方式使 用。其中以金、鋁、銀或者其合金較佳。作爲形成合金的 成分，例如可以舉出Mg、Se、Hf、V、Nb、Ru、W、Mn 、Re、Fe、Co、Rh、Ir、Cu、Zn、Cd、Ga、In、Si、Ge 、Te、Pb、Po、Sn、Bi以及稀土類金屬等之金屬以及半 金屬。其中以銀合金成本較低、反射率高、耐蝕性優異所 -21 - 200814051 (18) 以較佳。 作爲銀合金，最好以銀爲主成分，而含有由Ga、Bi 、Ti、Zn、Cu、Pd、Au、Ca、In及稀土族金屬所形成的 群所選出之至少1種元素含有〇·1原子百分比〜5原子百分 比。 於銀合金中，含有 Ga、Bi、Ti、Zn、Cu、Pd、Au、When two or more types selected from the group consisting of Ca, In, and a rare earth metal are contained, they may be contained in an amount of 0.1 atom% to 5 atom%, respectively, preferably in a total amount of 0.1 atom% to 5 atom%. Among the rare earth metals, the sharpness is optimal. Specific examples of the silver alloy include AgpdCu, AgCuAu, AgCuAuNd, AgCuNd, AgCaCu, Agin, AgBi, AgBiNd, etc. Further, gold crystal grains are small and excellent in uranium resistance, but slightly more than silver alloy. expensive. Further, as the semi-transparent reflective layer 29, a low-refractive-index film and a high-refractive-index film-shaped -20 - 200814051 (17) are alternately stacked in a material other than a metal such as 3 丨 02 to form a multilayer film, and may be used as a semi-transparent reflective layer. Examples of the method of forming the semi-transparent reflective layer 29 include a sputtering method, an ion implantation method, a chemical vapor deposition method, and a vacuum vapor deposition method. Among them, the sputtering method is the best in productivity. Further, between the light absorbing layer 28 of the first light and the semi-transparent reflective layer 29, other layers such as a reinforcing layer such as SiO 2 , ZnS-SiO 2 , and Al 2 〇 3 or an oxidation resistant layer may be provided. Further, a protective layer may be formed on the semi-transparent reflective layer 29 as needed. The protective layer may be a layer that protects the light absorbing layer or the reflective layer, and may be formed, for example, by an ultraviolet curable resin, a fluorene resin, or the like. (Reflective layer) The reflective layer 33 is preferably one having a high reflectance and excellent uranium resistance. In order to increase the reflectance, the thickness of the reflective layer 33 is usually 50 nm or more. More preferably, it is 8 〇 nm or more. However, in order to improve the recording sensitivity, it is preferably thin to some extent, and is usually preferably 300 nm or less and more preferably 200 nm or less. When the thickness of the reflective layer 33 is too large, the second transparent substrate 34 has warpage. The material of the reflective layer 33 may be a sufficiently high reflectance at the wavelength of the reproducing light. Specifically, for example, a metal such as Au, Al, Ag, Cu, Ti, Cr, or Ni may be used alone or in an alloy. Among them, gold, aluminum, silver or an alloy thereof is preferred. Examples of the alloy forming component include Mg, Se, Hf, V, Nb, Ru, W, Mn, Re, Fe, Co, Rh, Ir, Cu, Zn, Cd, Ga, In, Si, and Ge. Metals such as Te, Pb, Po, Sn, Bi, and rare earth metals, and semimetals. Among them, the silver alloy has a low cost, a high reflectance, and excellent corrosion resistance, preferably -21 - 200814051 (18). As the silver alloy, it is preferable to use silver as a main component, and at least one element selected from the group consisting of Ga, Bi, Ti, Zn, Cu, Pd, Au, Ca, In, and a rare earth metal contains ruthenium. 1 atomic percentage to 5 atomic percent. In silver alloy, it contains Ga, Bi, Ti, Zn, Cu, Pd, Au,
Ca、In及稀土族金屬所形成的群所選出之2種以上的場合 ，分別含有0.1原子百分比〜5原子百分比亦可，但最好其 合計爲0.1原子百分比〜5原子百分比。稀土族金屬中，以 銳最佳。 作爲銀合金之具體例，可以舉出AgPdCu、AgCuAu、 AgCuAuNd、AgCuNd、AgCaCu、Agin、AgBi、AgBiNd 等When two or more types selected from the group consisting of Ca, In, and a rare earth metal are contained, they may be contained in an amount of 0.1 atom% to 5 atom%, respectively, preferably in a total amount of 0.1 atom% to 5 atom%. Among the rare earth metals, the sharpness is optimal. Specific examples of the silver alloy include AgPdCu, AgCuAu, AgCuAuNd, AgCuNd, AgCaCu, Agin, AgBi, AgBiNd, and the like.
O 作爲形成反射層3 3的方法，例如可以舉出濺鍍法、離 子佈植法、化學蒸鍍法、真空蒸鍍法等。其中以濺鍍法在 ， 生產性上最佳。 (界面層） 界面層31被形成於第2層（L1)之第2號之光吸收層32上 。界面層31，遮蔽第2號之光吸收層32與透明中間層3〇， 係爲了防止兩層的混合而設的。透明中間層3 0，最好使用 不會對第2號之光吸收層32造成損傷的材料來形成。使用 液狀紫外線硬化性樹脂形成透明中間層30的場合，紫外，線 硬化性樹脂直接於第2號之光吸收層3 2相接，而爲了防& -22- 200814051 (19) 其相溶最好在透明中間層3〇與第2號之光吸收層32之間設 置界面層31。 界面層3 1的材料，只要不與第2號之光吸收層3 2混合 ’進而不與透明中間層30混合者即可，並未有特別限定。 此外’亦可兼有其他功能，應需要進而挾著其他層亦可。 作爲這樣的材料，最好爲半導體、金屬或半導體的氧化物 、氮化物、硫化物等無機物，進而以介電質等透明的無機 物更佳。具體而言，以氧化矽（特別是二氧化矽）、氧化鋅 、氧化铈、氧化釔等氧化物、硫化鋅、硫化釔等硫化物， 氮化矽等氮化物，碳化矽，氧化物與硫之混合物，以及後 述之合金等較佳。 此外，氧化矽與硫化鋅之（3 0: 70)〜（90: 10)之程度（ 重量比）之混合物亦佳。此外，硫與二氧化釔之混合物與 氧化鋅混合之物（Y2〇2S-ZnO)亦佳。 界面層31的厚度以3nm以上較佳，而以5nm以上尤佳 。界面層31的厚度太薄的話，遮蔽防止變得不夠充分。此 外，以100nm以下較佳，而以50nm以下尤佳。界面層31 太厚的話，有光的透過率降低之虞。此外，藉由無機物形 成界面層3 1的場合，成膜很花時間，有生產性降低、膜應 力增大的傾向。 作爲形成界面層3 1的方法’例如可以舉出灑鍍法、離 子佈植法、化學蒸鍍法、真空蒸鍍法等，但以濺鍍法在生 產性上較佳。 -23- 200814051 (20) (透明中間層） 透明中間層3 0，以在記錄再生光的波長爲透明’且黏 接力高、硬化黏接時之收縮率很小、環境保存安定性很高 的材料較佳。於本實施型態，因爲第2個光吸收層（第1號 之光吸收層28、第2號之光吸收層32)分別加以對焦伺服’ 所以透明中間層3 0的膜厚最好能夠正確地控制。透明中間 層3 0的膜厚，依存於對焦伺服機構，有對物透鏡的開口數 越高則其距離可以越小的傾向。 適用於本實施型態的光資訊記錄媒體2 6，係貼合厚度 0.6mm的2枚基板（第1透明基板27、第2透明基板34)而製 造的，使用藍光雷射（例如波長λ爲405 nm)進行資訊的記 錄或再生。於這樣的光資訊記錄媒體26，透明中間層30的 膜厚，如前所述，以40μιη以下者較佳。其中，透明中間 層3 0的膜厚，通常爲約20μπι以上。 藉由使透明中間層30的膜厚成爲40 μηι以下，通過第1 透明基板27照射藍光雷射時，可以在與第2號之光吸收層 32相比其膜厚較薄地調製之第1號之光吸收層28，與第2號 之光吸收層3 2，同時記錄條碼資訊。 透明中間層3 0，最好使用不會對半透明反射層2 9造成 損傷的材料來形成。此外，於兩層間亦可形成習知之無機 系或有機系之保護層。 作爲透明中間層3〇的材料，例如可以舉出熱塑性樹脂 、熱硬化性樹脂、電子線硬化性樹脂、紫外線硬化性樹脂 (包含延遲硬化型）、感壓式雙面膠帶等。其中，無溶劑型 24- 200814051 (21) 之紫外線硬化性樹脂其環境性與生產性均優異所以較佳。 紫外線硬化性樹脂有各個種類，只要是透明的話均可使用 〇 透明中間層3 0，可以藉由塗布紫外線硬化性樹脂、照 射紫外光而使其硬化的方式形成。作爲塗布方法，與第i 號之光吸收層2 8等的場合相同，可以使用旋轉塗布法、網 版印刷法、澆注法等塗布法，其中以旋轉塗布法較佳。紫 外線硬化性樹脂於1 〇°C〜4〇。(：，若使用黏度20mPa · s〜 100 OmPa· s者，可以不使用溶媒而塗布所以較佳。 紫外線硬化性樹脂可以舉出自由基系紫外線硬化性樹 脂與陽離子系紫外線硬化性樹脂，可以使用任一種。自由 基系紫外線硬化性樹脂，可以使用習知之任一種組成物， 使用包含紫外線硬化性化合物與光聚合開始劑作爲必須成 分的組成物。紫外線硬化性化合物，例如可以分別地單獨 或者並用2種以上之單官能基丙烯酸酯，單官能基異丁烯 酸、多官能基丙烯酸酯、多官能基異丁烯酸作爲聚合性單 體成分。 (其他層） 此外’適用本實施型態的光資訊記錄媒體26，亦可應 需要而在與光入射側相反的第2透明基板34上，設置印刷 層或印刷承受層。 在光資訊記錄媒體26記錄資訊的場合，在設於光資訊 記錄媒體26的第1號之光吸收層28以及第2號之光吸收層32 -25- 200814051 (22) 藉由照射雷射光而進行。在被照射雷射光的部分，吸收雷 射光能量的色素產生分解、發熱、碳化。接著’作爲基板 的熱的變化，引起溶融、變形等。再生被記錄的資訊的場 合，係藉由雷射光來讀取引起熱的變化的部分與未引起熱 的變化的部分之反射率之差而進行的。 於本實施型態，使用於記錄再生的裝置之藍光雷射以 波長爲390nm〜430nm者較佳，而以400nm〜420nm者尤 佳。此外，使用於記錄BCA的寫入器（BCA記錄機）的雷 射的波長，只要是對第1層（L0)之第1號之光吸收層28與第 2層（L1)之第2號之光吸收層32分別顯示吸收的波長即可， 並未有特別限定。這樣的波長，例如可以舉出波長3 90nm 〜43 0nm、620nm 〜720nm、7 8 0 〜8 3 0 nm 〇 其中，BCA 寫 入器（BCA記錄機）的波長並不以此頻帶爲限。 [實施例] 以下根據實施例更具體說明本實施型態。又，本發明 並不以實施例爲限。 (實施例1) 將形成順時針方向的溝的印模A安裝於射出成型機 ’將光資訊記錄媒體等級的聚碳酸酯樹脂射出成型，得到 第1透明基板。第1透明基板係直徑120mm，厚度0.59mm 的聚碳酸酯製基板，在使用者資訊區域形成軌道間距 400nm，半値幅〇.22μηι，深度45nm的被調變的擺動 -26- (23) (23)200814051 (w o b b 1 e )溝。 其次，使用被形成反時針方向的溝的印模B，藉由與 前述同樣的操作得到第2透明基板。第2透明基板係直徑 120mm，厚度〇.59mm的聚碳酸酯製基板，在使用者資訊 區域形成軌道間距4〇nm，半値幅0·22μιη，深度35nm的被 調變的擺動（w 〇 b b 1 e)溝。 接著，調製混合以下列化學式（1)所表示之偶氮系色 素與以化學式（2)表示的添加劑之色素（混合比率75 : 2 5)之 四氟丙醇溶液。此溶液之濃度爲0.7重量百分比（色素溶液 1 )。其次，於第1透明基板之溝形成面上，藉由旋轉塗布 法塗布色素溶液1。第1透明基板之溝部分之色素膜厚爲 3 6nm。又，於塗布前述色素溶液1時，將色素溶液1以過 濾器過濾除去不純物。 接著，將塗布前述色素溶液1的第1透明基板，在9〇 °C 乾燥1小時，進而於室溫冷卻1小時。如此進行’將第1層 之光吸收層形成於第1透明基板上。進而，於第1號之光吸 收層上，藉由濺鍍法形成由AgBi合金所構成的厚度1 lnm 之半透明反射層。 【化1】O As a method of forming the reflective layer 33, for example, a sputtering method, an ion implantation method, a chemical vapor deposition method, a vacuum deposition method, or the like can be given. Among them, the sputtering method is the best in productivity. (Interfacial Layer) The interface layer 31 is formed on the second light absorbing layer 32 of the second layer (L1). The interface layer 31 shields the second light absorbing layer 32 from the transparent intermediate layer 3 to prevent mixing of the two layers. The transparent intermediate layer 30 is preferably formed using a material which does not cause damage to the second light absorbing layer 32. When the transparent intermediate layer 30 is formed using a liquid ultraviolet curable resin, the ultraviolet curable resin is directly in contact with the second light absorbing layer 32, and is compatible with the -22-200814051 (19). It is preferable to provide the interface layer 31 between the transparent intermediate layer 3A and the second light absorbing layer 32. The material of the interface layer 31 is not particularly limited as long as it is not mixed with the second light absorbing layer 32 and is not mixed with the transparent intermediate layer 30. In addition, it can also have other functions, and it is also necessary to carry other layers as needed. As such a material, an inorganic substance such as an oxide, a nitride or a sulfide of a semiconductor, a metal or a semiconductor is preferable, and a transparent inorganic substance such as a dielectric is more preferable. Specifically, an oxide such as cerium oxide (particularly cerium oxide), zinc oxide, cerium oxide or cerium oxide, a sulfide such as zinc sulfide or strontium sulfide, a nitride such as cerium nitride, cerium carbide, oxide and sulfur The mixture, the alloy described later, and the like are preferred. Further, a mixture of cerium oxide and zinc sulfide in a degree (weight ratio) of (30: 70) to (90: 10) is also preferable. Further, a mixture of sulfur and cerium oxide and a mixture of zinc oxide (Y2〇2S-ZnO) are also preferred. The thickness of the interface layer 31 is preferably 3 nm or more, and more preferably 5 nm or more. When the thickness of the interface layer 31 is too thin, the shielding prevention becomes insufficient. Further, it is preferably 100 nm or less, and more preferably 50 nm or less. If the interface layer 31 is too thick, the transmittance of light is lowered. Further, when the interface layer 31 is formed of an inorganic material, film formation takes a long time, and productivity tends to decrease and film stress tends to increase. The method of forming the interface layer 31 is, for example, a sputter method, an ion implantation method, a chemical vapor deposition method, a vacuum vapor deposition method, or the like, but is preferably produced by sputtering. -23- 200814051 (20) (Transparent intermediate layer) Transparent intermediate layer 30, which is transparent at the wavelength of recording and reproducing light, has high adhesion, small shrinkage when hardened and bonded, and high environmental preservation stability. The material is preferred. In the present embodiment, since the second light absorbing layer (the first light absorbing layer 28 and the second light absorbing layer 32) is focused servo, respectively, the film thickness of the transparent intermediate layer 30 is preferably correct. Ground control. The film thickness of the transparent intermediate layer 30 depends on the focus servo mechanism, and the higher the number of openings of the objective lens, the smaller the distance. The optical information recording medium 2 6 of the present embodiment is manufactured by bonding two substrates (the first transparent substrate 27 and the second transparent substrate 34) having a thickness of 0.6 mm, and uses a blue laser (for example, the wavelength λ is 405 nm) Record or regenerate information. In such an optical information recording medium 26, the film thickness of the transparent intermediate layer 30 is preferably 40 μm or less as described above. The film thickness of the transparent intermediate layer 30 is usually about 20 μm or more. When the thickness of the transparent intermediate layer 30 is 40 μm or less, and the first transparent substrate 27 is irradiated with a blue laser, the first film can be prepared with a thinner film thickness than the second light absorbing layer 32. The light absorbing layer 28 and the light absorbing layer 32 of the second number simultaneously record bar code information. The transparent intermediate layer 30 is preferably formed using a material that does not damage the semi-transparent reflective layer 29. Further, a protective layer of a conventional inorganic or organic system may be formed between the two layers. Examples of the material of the transparent intermediate layer 3 include a thermoplastic resin, a thermosetting resin, an electron beam curable resin, an ultraviolet curable resin (including a retardation curing type), a pressure sensitive double-sided tape, and the like. Among them, the ultraviolet curable resin of the solventless type 24-200814051 (21) is preferable because it is excellent in environmental properties and productivity. The ultraviolet curable resin may be of various types, and may be used as long as it is transparent. The transparent intermediate layer 30 may be formed by applying an ultraviolet curable resin and curing it by irradiating ultraviolet light. As the coating method, as in the case of the light absorbing layer 28 of the i-th, etc., a coating method such as a spin coating method, a screen printing method, or a casting method can be used, and a spin coating method is preferred. The ultraviolet curable resin is at 1 °C ~ 4 〇. (1) It is preferable to use a solvent of 20 mPa·s to 100 MPa to s., and it is preferable to apply it without using a solvent. The ultraviolet curable resin may be a radical ultraviolet curable resin or a cationic ultraviolet curable resin, and may be used. Any of the conventional radical ultraviolet curable resins, any of the conventional compositions may be used, and a composition containing an ultraviolet curable compound and a photopolymerization initiator as essential components may be used. The ultraviolet curable compounds may be used alone or in combination, for example. Two or more kinds of monofunctional acrylates, monofunctional methacrylic acid, polyfunctional acrylate, and polyfunctional methacrylic acid are used as polymerizable monomer components. (Other layers) Further, the optical information recording medium of the present embodiment is applied. 26, a printing layer or a printing receiving layer may be provided on the second transparent substrate 34 opposite to the light incident side as needed. When the information is recorded on the optical information recording medium 26, the optical information recording medium 26 is provided. Light absorbing layer 28 of No. 1 and light absorbing layer No. 2 of the second light 32 - 25 - 200814051 (22) by irradiating laser light In the portion irradiated with the laser light, the pigment that absorbs the laser light energy is decomposed, heated, and carbonized. Then, as the heat of the substrate changes, it causes melting, deformation, etc. When the recorded information is reproduced, it is performed by The laser light is read to read the difference between the reflectance of the portion that causes the change in heat and the portion that does not cause the change in heat. In the present embodiment, the blue laser light used in the recording and reproducing device has a wavelength of 390 nm to 430 nm. Preferably, it is preferably from 400 nm to 420 nm. Further, the wavelength of the laser used for recording the BCA writer (BCA recorder) is as long as the light absorption of the first layer (L0) The layer 28 and the second light absorbing layer 32 of the second layer (L1) are not particularly limited as long as they exhibit absorption wavelengths. Examples of such wavelengths include wavelengths of 3 90 nm to 43 0 nm and 620 nm to 720 nm. 7 8 0 to 8 3 0 nm , wherein the wavelength of the BCA writer (BCA recorder) is not limited to this band. [Embodiment] Hereinafter, the present embodiment will be described in more detail based on embodiments. The invention is not limited to the examples. Example 1) A stamp A in which a groove in a clockwise direction was formed was attached to an injection molding machine to mold a polycarbonate resin of an optical information recording medium grade to obtain a first transparent substrate. The first transparent substrate has a diameter of 120 mm and a thickness of 0.59. The polycarbonate substrate of mm has a modulated pitch of -26-(23) (23)200814051 (wobb 1 e) groove with a track pitch of 400 nm, a half-web width of 2222 μm, and a depth of 45 nm in the user information area. The second transparent substrate was obtained by the same operation as described above using the stamp B in which the groove in the counterclockwise direction was formed. The second transparent substrate is a polycarbonate substrate having a diameter of 120 mm and a thickness of 5959 mm, and has a track pitch of 4 〇 nm, a half-width of 0·22 μm, and a modified oscillation of a depth of 35 nm in the user information area (w 〇bb 1 e) Ditch. Next, a tetrafluoropropanol solution in which the azo-based color represented by the following chemical formula (1) and the additive of the additive represented by the chemical formula (2) (mixing ratio of 75:25) are mixed are prepared. The concentration of this solution was 0.7% by weight (dye solution 1). Next, the dye solution 1 was applied by a spin coating method on the groove forming surface of the first transparent substrate. The pigment film thickness of the groove portion of the first transparent substrate was 36 nm. Further, when the dye solution 1 was applied, the dye solution 1 was filtered through a filter to remove impurities. Next, the first transparent substrate on which the dye solution 1 was applied was dried at 9 ° C for 1 hour and further cooled at room temperature for 1 hour. In this manner, the light absorbing layer of the first layer is formed on the first transparent substrate. Further, on the light absorbing layer No. 1, a semitransparent reflective layer made of an AgBi alloy and having a thickness of 1 lnm was formed by sputtering. 【化1】
-27- (24) 200814051 【化2】-27- (24) 200814051 【化2】
N C4H9 c4h9、 C4H9 NN C4H9 c4h9, C4H9 N
化學式⑵ PF^ c4h9、 其次，於第2透明基板之溝形成面上，使AgCuNd合 金以成爲厚度120nm的方式使用濺鍍法形成反射層。接著 ，調製混合以化學式（1 )所表示之偶氮系色素與以化學式 (2)表示的添加劑之色素（混合比率75 ·· 2 5)之四氟丙醇溶液 。此溶液之濃度爲1 · 1重量百分比（色素溶液2)。 接著，藉由旋轉塗布法在反射層上塗布色素溶液2。 第2透明基板之溝部分之色素膜厚爲45nm。又，於塗布前 述色素溶液2時，將色素溶液2以過濾器過濾除去不純物。 接著，將塗布前述色素溶液2的第2透明基板，在9 0 °C 乾燥1小時，進而於室溫冷卻1小時。如此進行，在第2透 明基板的反射層上形成第2號之光吸收層。進而，於第2號 之光吸收層上，藉由濺鍍法形成由ZnS-Si02所構成的厚 度1 Onm之界面層。 接著’在第1透明基板的半透明反射層上藉由旋轉塗 布法塗布自由基聚合型UV樹脂，設置於貼合裝置。其次 ’使第1透明基板之塗布了自由基聚合型紫外線硬化性樹 脂之面，與第2透明基板之界面層相對面，設置於貼合裝 置。其次’使裝置內抽真空，以使不在自由基聚合型紫外 -28 - 200814051 (25) 線硬化性樹脂發生氣泡的方式貼合2枚透明基板。 將貼合的2枚透明基板由貼合裝置取出，由第1透明基 板側照射紫外線，使自由基聚合型紫外線硬化性樹脂硬化 ，形成厚度2 5 μιη的半透明中間層，得到光資訊記錄媒體 Α 〇 光資訊記錄媒體A，於第1號之光吸收層與第2號之光 吸收層之資訊區域，以波長405 nm的雷射光記錄資訊的話 ，係記錄的標記的反射率比記錄前的反射率變得更高的低 至高（LowtoHigh)記錄。 對如此得到的光資訊記錄媒體A，在第1號之光吸收 層與第2號之光吸收層同時形成BCA。亦即，於BCA記錄 機’使用波長4 0 7 n m的雷射，對第1號之光吸收層對焦， 由第1號之光吸收層側透過第1透明基板在半徑22.20mm〜 23.20mm之範圍記錄條碼訊號。由BCA所得的訊號的評 估結果顯示於表1。 (實施例2 ) 於實施例1使用的光資訊記錄媒體A，把透明中間層 的膜厚變更爲3 5 μιη，其他藉由與實施例1同樣的操作，得 到光資訊記錄媒體Β。Chemical Formula (2) PF^c4h9 Next, on the groove forming surface of the second transparent substrate, the AgCuNd alloy was formed into a reflective layer by sputtering using a thickness of 120 nm. Next, a tetrafluoropropanol solution of the azo dye represented by the chemical formula (1) and the dye (mixing ratio 75·· 25) of the additive represented by the chemical formula (2) is prepared and mixed. The concentration of this solution was 1:1 by weight (dye solution 2). Next, the dye solution 2 is applied onto the reflective layer by a spin coating method. The pigment film thickness of the groove portion of the second transparent substrate was 45 nm. Further, when the dye solution 2 described above was applied, the dye solution 2 was filtered through a filter to remove impurities. Next, the second transparent substrate on which the dye solution 2 was applied was dried at 90 ° C for 1 hour, and further cooled at room temperature for 1 hour. In this manner, the second light absorbing layer was formed on the reflective layer of the second transparent substrate. Further, on the light absorbing layer No. 2, an interface layer of thickness 1 Onm composed of ZnS-SiO 2 was formed by sputtering. Next, a radical polymerization type UV resin was applied onto the semitransparent reflective layer of the first transparent substrate by a spin coating method, and was placed in a bonding apparatus. Next, the surface of the first transparent substrate to which the radical polymerization type ultraviolet curable resin was applied was placed on the surface opposite to the interface layer of the second transparent substrate. Next, the inside of the apparatus was evacuated so that two transparent substrates were bonded so as not to form bubbles in the radical-polymerized ultraviolet -28 - 200814051 (25) line curable resin. The two transparent substrates to be bonded are taken out by the bonding apparatus, and ultraviolet rays are irradiated from the first transparent substrate side to cure the radical polymerization type ultraviolet curable resin to form a translucent intermediate layer having a thickness of 25 μm to obtain an optical information recording medium. 〇 Shuguang Information Recording Media A, in the information area of the light absorbing layer No. 1 and the light absorbing layer of No. 2, when recording information with laser light of wavelength 405 nm, the reflectance of the recorded mark is higher than that before recording. The reflectance becomes higher and the LowtoHigh record. With respect to the optical information recording medium A thus obtained, BCA is formed simultaneously with the light absorbing layer of No. 1 and the light absorbing layer of No. 2. That is, the BCA recorder uses a laser having a wavelength of 407 nm to focus on the light absorbing layer of No. 1, and the light absorbing layer side of the No. 1 transmits the first transparent substrate at a radius of 22.20 mm to 23.20 mm. The range records the bar code signal. The evaluation results of the signals obtained by BCA are shown in Table 1. (Example 2) In the optical information recording medium A used in the first embodiment, the film thickness of the transparent intermediate layer was changed to 35 μm, and the optical information recording medium was obtained by the same operation as in the first embodiment.
其次，對光資訊記錄媒體Β，藉由與實施例1相同的 操作，對第1號之光吸收層對焦，由第1號之光吸收層側透 過第1透明基板在半徑22.20mm〜23.20mm記錄條碼訊號 ，於第1號之光吸收層與第2號之光吸收層同時形成BCA -29- (26) 200814051 。由BCA所得的訊號的評估結果顯示於表1。 (比較例1) 於在實施例1使用的光資訊記錄媒體A，把形成_ 之光吸收層之用的色素塗布濃度變更爲0.85重量百分 把形成第2號之光吸收層之用的色素塗布濃度變更爲 重量百分比，其他則藉由與實施例1相同的操作而得 資訊記錄媒體C。 其次，對光資訊記錄媒體C，藉由與實施例1相 操作，對第1號之光吸收層對焦，由第1號之光吸收層 過第1透明基板在半徑22.2 0mm〜23.20mm記錄條碼 ，於第1號之光吸收層與第2號之光吸收層同時形成 。由BCA所得的訊號的評估結果顯示於表1。 (比較例2) 於實施例1使用的光資訊記錄媒體A，把透明中 的膜厚變更爲60μπι，其他藉由與實施例1同樣的操作 到光資訊記錄媒體D。 其次，對光資訊記錄媒體D，藉由與實施例1相 操作，對第1號之光吸收層對焦，由第1號之光吸收層 過第1透明基板在半徑22.20mm〜23.20mm記錄條碼 ，於第1號之光吸收層與第2號之光吸收層同時形成 。由BCA所得的訊號的評估結果顯示於表1。Next, in the optical information recording medium, the light absorbing layer of the first light is focused by the same operation as in the first embodiment, and the light absorbing layer side of the first light is transmitted through the first transparent substrate at a radius of 22.20 mm to 23.20 mm. The bar code signal is recorded, and the light absorbing layer of No. 1 and the light absorbing layer of No. 2 form BCA -29-(26) 200814051 at the same time. The evaluation results of the signals obtained by BCA are shown in Table 1. (Comparative Example 1) In the optical information recording medium A used in the first embodiment, the dye coating concentration for forming the light absorbing layer was changed to 0.85 weight percent, and the dye for forming the second light absorbing layer was used. The coating concentration was changed to a weight percentage, and the information recording medium C was obtained by the same operation as in the first embodiment. Next, for the optical information recording medium C, by operating in the first embodiment, the light absorbing layer of the first light is focused, and the light absorbing layer of the first light is passed through the first transparent substrate to record the barcode at a radius of 22.2 0 mm to 23.20 mm. The light absorbing layer of No. 1 is formed simultaneously with the light absorbing layer of No. 2. The evaluation results of the signals obtained by BCA are shown in Table 1. (Comparative Example 2) The optical information recording medium A used in the first embodiment was changed to a film thickness of 60 μm in the transparent state, and the optical information recording medium D was operated in the same manner as in the first embodiment. Next, for the optical information recording medium D, by operating in the first embodiment, the light absorbing layer of the first light is focused, and the light absorbing layer of the first light is passed through the first transparent substrate to record the barcode at a radius of 22.20 mm to 23.20 mm. The light absorbing layer of No. 1 is formed simultaneously with the light absorbing layer of No. 2. The evaluation results of the signals obtained by BCA are shown in Table 1.
I 1號 比， 0.88 到光 同的 側透 訊號 BCAI 1 ratio, 0.88 to the same side, side transmission signal BCA
間層 ，得 同的 側透 訊號 BCA -30- (27) (27)200814051 (比較例3 ) 與在實施例1所使用的光資訊記錄媒體A相同，得到 於第1透明基板的溝形成面上，形成第1號之光吸收層、半 透明反射層之第1透明基板。其後，對如此得到的第1透明 基板，以波長407nm的B C A記錄機，以記錄功率1 9 0 m W ，由第1號之光吸收層側透過第1透明基板在半徑22.20mm 〜23.20mm處，記錄條碼訊號。 其次，與在實施例1所使用的光資訊記錄媒體A相同 ，得到於第2透明基板的溝形成面上，形成反射層、第2號 之光吸收層、界面層之第2透明基板。接著，對如此得到 的第2透明基板，以波長40 7nm的BCA記錄機，以記錄功 率190mW，由界面層側在半徑22.20mm〜23.20mm處，記 錄相同的條碼訊號。 接著，與在實施例1所使用的光資訊記錄媒體A同樣 ，在第1透明基板的半透明反射層上藉由旋轉塗布法塗布 自由基聚合型UV樹脂，設置於貼合裝置。其次，使第i 透明基板之塗布了自由基聚合型紫外線硬化性樹脂之面， 與第2透明基板之界面層以相對面的方式設置於貼合裝置 。使裝置內抽真空，以使不在自由基聚合型紫外線硬化性 樹脂發生氣泡的方式貼合2枚透明基板。將貼合的2枚透明 基板由貼合裝置取出，由第1透明基板側照射紫外線，使 自由基聚合型紫外線硬化性樹脂硬化，形成厚度25 μηι的 半透明中間層，得到光資訊記錄媒體Ε。由BCA所得的 訊號的評估結果顯示於表1。 -31 - (28) (28)200814051 % (BCA訊號評估） 針對以實施例1、實施例2以及比較例1〜比較例3分別 調製之光資訊記錄媒體，以波長405 nm之雷射光以及具有 開口數爲0.65的透鏡之光學拾取頭之測試器，對第1層及 第2層加以對焦而在偏離循跡（tracking)的狀態再生BCA 訊號，測定第1層及第2層之BCA訊號的開始位置與結束 位置、再生訊號的振幅。 BCA訊號的開始位置與結束位置，係以在測試器安 裝測試碟片，對第1層對焦，由基準位置將BCA訊號取入 數位示波器，對基準位置測定第1層之BCA的開始位置。 不從測試器取下碟片，而將對焦切換至第2層，同樣 地由基準位置將BCA訊號取入數位示波器，對基準位置 測定第2層之BCA的開始位置。由分別的開始位置與結束 位置，根據式（1)求出△ S。 BCA訊號的抖動，係將測試器的訊號輸入至時間間 隔分析器（time interval analyzer)，求出對時脈之標準偏 差σ。 圖4係說明BCA訊號之例與BCA開始位置、BCA結 束位置及BCA振幅之圖。如圖4所示，36係BCA開始位 置，3 7係B C Α結束位置，3 8係B C Α振幅，3 9係反射率。 BCA振幅（％)，使用BCA振幅38以及反射率39藉由 下式求出。 BCA振幅（％) = (BCA振幅38/反射率39)χΐ〇〇 -32- (29) 200814051 % 結果顯示於圖1。 [表1] 光資訊 1己錄媒體 BCA 之記錄 方法 透明中 間層之 膜厚 (μιη) 第1號 之光 吸收層 之膜厚 (nm) 第2號 之光吸 收層之 膜厚 (nm) AS (μιη) 第1層之 BCA 振幅 (%) 第2層之 BCA 振幅 (%) 第2層 之 BCA 抖動 (%) 實 施 例 1 A 同時 25 36 45 0 25 36 3.5 2 B 同時 35 36 45 0 24 35 3.3 比 較 例 1 C 同時 25 45 36 0 38 22 4.1 2 D 同時 60 36 45 0 25 3 >10 3 E 分離 25 36 45 315 20 29 4.5 以下說明表1所示之結果。首先，於設置2層包含有機 色素的光吸收層之光資訊記錄媒體，由記錄再生光之入射 側來看前側的第1號之光吸收層的膜厚，與從光的入射側 來看裡側的第2號之光吸收層相比而較薄，藉由使透明中 間層的膜厚爲40μιη以下，可以分別於第1層與第2層，分 別形成將同一管理資訊的條碼資訊記錄於相同半徑位置 (△S = 0)的BCA(實施例1與實施例2)。 其次，由如此形成的BC A所得到的訊號，由第1層之 BCA所得的訊號振幅，比由第2層之BCA所得的訊號振幅 還要小，進而，第2層之BCA的抖動減低，結果，可以由 第2層之BCA再現高訊號品質的條碼資訊。 另一方面，於設置2層包含有機色素的光吸收層之光 資訊記錄媒體，由記錄再生光的入射側來看前方側的第1 -33- (30) 200814051 % 號之光吸收層之膜厚（4 5 Km)與從光的入射側來看裡側的第 2號之光吸收層的膜厚（3 6μιη)相比比較厚（比較例1) ’記錄 於第2光吸收層的BCA形成區域的條碼資訊之BCA振幅 減少，可知抖動（jitter)也成爲不良。 此外，透明中間層的膜厚爲4〇μηι以上（60μηι:比較例 2)的話，由第1號之光吸收層側越過第1透明基板照射藍光 雷射的場合，因爲透明中間層的膜厚太厚，所以要在第1 號之光吸收層與第2號之光吸收層同時記錄條碼資訊是困 難的。結果，於第2號之光吸收層無法充分記錄條碼資訊 ，所以第2層之BCA振幅很小（3% )，抖動成爲10%以上。 進而，分別對第1層之光吸收層與第2層之光吸收層記 錄條碼資訊，而在其後貼合的場合（比較例3)第1號之光吸 收層的條碼資訊與第2號之光吸收層的條碼資訊不一致 (△S = 315pm)。因此，再生各層的條碼資訊的場合，分別 的條碼資訊的訊號相互干涉。結果，可得知BCA振幅減 少，抖動成爲不良（4.5%)。 如以上所詳述的，具有包含藉由從單側照射藍光雷射 而可以記錄再生的光吸收材料之2層光吸收層的光資訊記 錄媒體，由記錄再生光之入射側來看前側的第1號之光吸 收層的膜厚，與從光的入射側來看裡側的第2號之光吸收 層相比而較薄，藉由使透明中間層的膜厚爲40 μιη以下， 可以分別於第1層與第2層，形成將同一管理資訊的條碼資 訊記錄於相同半徑位置的BC Α。 如此，藉由在相同半徑位置形成記錄同一條碼資訊的 -34- (31) 200814051 麵 BCA，而於再生分別的層的條碼資訊的場合，分別的條碼 資訊的訊號成爲增強干涉，BCA振幅增加，抖動也變得 良好，所以可能以高訊號品質再現條碼資訊。 【圖式簡單說明】 圖1係供說明本實施型態適用的光資訊記錄媒體之圖 〇 圖2係供說明本實施型態適用的光資訊記錄媒體之剖 面構成圖。 »1 3係供說明本實施型態適用的光資訊記錄媒體之 BCA被形成的區域的剖面構造之圖。 圖4係說明BCA訊號之例與BCA開始位置及振幅之 圖。 [主要元件符號說明】 1，12,26 :光資訊記錄媒體 2,4,6，14，16，18:第1層之反射鏡區域 7,9，11，20,22,24:第2層之反射鏡區域 ^7 :第1層之資訊區域 1()，23 :第2層之資訊區域In the same layer, the same side-wavelength signal BCA -30-(27) (27) 200814051 (Comparative Example 3) The groove forming surface of the first transparent substrate was obtained in the same manner as the optical information recording medium A used in the first embodiment. The first transparent substrate of the first light absorbing layer and the semi-transparent reflective layer is formed. Thereafter, the first transparent substrate thus obtained was passed through a first transparent substrate at a radius of 22.20 mm to 23.20 mm by a BCA recorder having a wavelength of 407 nm at a recording power of 190 mW and a light absorbing layer side of the first light. At the place, record the bar code signal. Then, similarly to the optical information recording medium A used in the first embodiment, the second transparent substrate in which the reflective layer, the second light absorbing layer, and the interface layer were formed on the groove forming surface of the second transparent substrate was obtained. Next, the same transparent barcode signal was recorded on the second transparent substrate thus obtained by a BCA recorder having a wavelength of 4 7 nm at a recording power of 190 mW and a radius of 22.20 mm to 23.20 mm from the interface layer side. Then, similarly to the optical information recording medium A used in the first embodiment, a radical polymerization type UV resin was applied onto the semitransparent reflective layer of the first transparent substrate by a spin coating method, and was placed in a bonding apparatus. Then, the surface of the i-th transparent substrate coated with the radical polymerization type ultraviolet curable resin is placed on the surface of the interface layer of the second transparent substrate so as to face the bonding apparatus. The inside of the apparatus was evacuated so that two transparent substrates were bonded to each other so that bubbles were not formed in the radical polymerization type ultraviolet curable resin. The two transparent substrates to be bonded are taken out by the bonding apparatus, and ultraviolet rays are irradiated from the first transparent substrate side to cure the radical polymerization type ultraviolet curable resin to form a translucent intermediate layer having a thickness of 25 μm to obtain an optical information recording medium. . The evaluation results of the signals obtained by BCA are shown in Table 1. -31 - (28) (28)200814051% (BCA signal evaluation) The optical information recording mediums respectively modulated in the first embodiment, the second embodiment, and the comparative examples 1 to 3 are laser light having a wavelength of 405 nm and having The optical pickup head of the lens having a number of openings of 0.65 focuses on the first layer and the second layer, and reproduces the BCA signal in a tracked state, and measures the BCA signals of the first layer and the second layer. Start position and end position, amplitude of the reproduced signal. The start position and the end position of the BCA signal are to install the test disc in the tester, focus on the first layer, take the BCA signal into the digital oscilloscope from the reference position, and measure the starting position of the first layer BCA for the reference position. The disc is not removed from the tester, but the focus is switched to the second layer. Similarly, the BCA signal is taken from the reference position into the digital oscilloscope, and the start position of the second layer BCA is determined for the reference position. From each of the start position and the end position, Δ S is obtained from the equation (1). The jitter of the BCA signal is input to the time interval analyzer of the tester to find the standard deviation σ for the clock. Figure 4 is a diagram illustrating an example of a BCA signal and a BCA start position, a BCA end position, and a BCA amplitude. As shown in Fig. 4, the 36 series BCA start position, the 3 7 system B C Α end position, the 3 8 system B C Α amplitude, and the 39 system reflectance. The BCA amplitude (%) was obtained by the following equation using the BCA amplitude 38 and the reflectance 39. BCA amplitude (%) = (BCA amplitude 38 / reflectance 39) χΐ〇〇 -32- (29) 200814051 % The results are shown in Figure 1. [Table 1] Optical information 1 Recording method of recording medium BCA Film thickness of transparent intermediate layer (μιη) Film thickness of light absorption layer No. 1 (nm) Film thickness of light absorption layer No. 2 (nm) AS (μιη) BCA amplitude of layer 1 (%) BCA amplitude of layer 2 (%) BCA jitter of layer 2 (%) Example 1 A simultaneous 25 36 45 0 25 36 3.5 2 B at the same time 35 36 45 0 24 35 3.3 Comparative Example 1 C Simultaneous 25 45 36 0 38 22 4.1 2 D Simultaneous 60 36 45 0 25 3 > 10 3 E Separation 25 36 45 315 20 29 4.5 The results shown in Table 1 are explained below. First, in the optical information recording medium in which two layers of the light-absorbing layer containing the organic dye are provided, the film thickness of the first light absorbing layer on the front side is seen from the incident side of the recording and reproducing light, and the light incident side is viewed from the incident side of the light. The light absorption layer of the second surface is thinner than the light absorption layer of the second layer. By making the thickness of the transparent intermediate layer 40 μm or less, the barcode information of the same management information can be separately recorded on the first layer and the second layer. BCA at the same radial position (ΔS = 0) (Example 1 and Example 2). Secondly, the signal obtained by the BC A thus formed has a signal amplitude obtained by the BCA of the first layer, which is smaller than the amplitude of the signal obtained by the BCA of the second layer, and further, the jitter of the BCA of the second layer is reduced. As a result, bar code information of high signal quality can be reproduced by the BCA of the second layer. On the other hand, in the optical information recording medium in which two layers of the light-absorbing layer containing the organic dye are provided, the film of the light-absorbing layer of the first side - 1 - 33 - (30) 200814051% on the front side is seen from the incident side of the recording and reproducing light. Thickness (45 Km) is thicker than film thickness (3 6 μm) of the second light absorbing layer on the back side from the incident side of light (Comparative Example 1) 'BCA recorded in the second light absorbing layer The BCA amplitude of the bar code information forming the area is reduced, and it is known that the jitter is also bad. In addition, when the film thickness of the transparent intermediate layer is 4 〇μηι or more (60 μηι: Comparative Example 2), when the light absorbing layer side of the first light is irradiated over the first transparent substrate to irradiate a blue laser, the film thickness of the transparent intermediate layer is Too thick, it is difficult to record bar code information at the same time as the light absorbing layer No. 1 and the light absorbing layer No. 2. As a result, the bar code information cannot be sufficiently recorded in the light absorbing layer of No. 2, so the BCA amplitude of the second layer is small (3%), and the jitter becomes 10% or more. Further, the bar code information is recorded on the light absorbing layer of the first layer and the light absorbing layer of the second layer, respectively, and when it is bonded later (Comparative Example 3), the bar code information of the first light absorbing layer and the second number are The bar code information of the light absorbing layer is inconsistent (ΔS = 315 pm). Therefore, when the bar code information of each layer is reproduced, the signals of the respective bar code information interfere with each other. As a result, it was found that the BCA amplitude was reduced and the jitter was poor (4.5%). As described in detail above, the optical information recording medium having the two-layer light absorbing layer including the light absorbing material which can be recorded and reproduced by irradiating the blue laser light from one side, the front side of the recording and reproducing light is seen from the incident side. The film thickness of the light absorbing layer No. 1 is thinner than that of the second light absorbing layer on the back side as viewed from the incident side of light, and the film thickness of the transparent intermediate layer is 40 μm or less, respectively. At the first layer and the second layer, BC Α which records bar code information of the same management information at the same radius position is formed. In this way, by forming the -34-(31) 200814051 face BCA for recording the same bar code information at the same radius position, when the barcode information of the respective layers is reproduced, the signals of the respective bar code information become enhanced interference, and the BCA amplitude increases. The jitter also becomes good, so bar code information may be reproduced with high signal quality. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a view showing a configuration of an optical information recording medium to which the present embodiment is applied. FIG. 2 is a cross-sectional structural view for explaining an optical information recording medium to which the present embodiment is applied. Fig. 3 is a diagram showing the cross-sectional structure of a region in which the BCA of the optical information recording medium to which the present embodiment is applied. Figure 4 is a diagram showing an example of a BCA signal and a BCA start position and amplitude. [Main component symbol description] 1,12,26: Optical information recording medium 2, 4, 6, 14, 16, 18: 1st layer mirror area 7, 9, 11, 20, 22, 24: 2nd floor Mirror area ^7: Information area 1 () of the first layer, 23: Information area of the second layer
3J5 :第1層之BCA3J5: Layer 1 BCA
8,21 :第2層之BCA 13,27 :第1透明基板 19,30 :透明中間層 -35- (32) 200814051 麵 25,34 :第2透明基板 2 8 :第1號之光吸收層 29 :半透明反射層 3 1 :界面層 32:第2號之光吸收層 3 3 :反射層 -36-8,21: BCA 13,27 of the second layer: 1st transparent substrate 19, 30: transparent intermediate layer -35- (32) 200814051 Surface 25, 34: 2nd transparent substrate 2 8 : No. 1 light absorbing layer 29: Translucent reflective layer 3 1 : Interfacial layer 32: No. 2 light absorbing layer 3 3 : Reflective layer - 36-
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| JP2006123107A JP2007294055A (en) | 2006-04-27 | 2006-04-27 | Optical information recording medium and method of manufacturing optical information recording medium |
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| TW200814051A true TW200814051A (en) | 2008-03-16 |
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| TWI457920B (en) * | 2008-07-18 | 2014-10-21 | Nippon Steel & Sumikin Chem Co | A recording / reproducing method for recording the video of the omnipotent pictorial recording medium, and a monolithic recording medium for reading and writing |
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| JP2009181614A (en) * | 2008-01-29 | 2009-08-13 | Sanyo Electric Co Ltd | Optical disk and optical disk device |
| JP2012022734A (en) * | 2010-07-13 | 2012-02-02 | Fujifilm Corp | Optical information recording medium and optical information recording method |
| CN115798524A (en) * | 2022-11-10 | 2023-03-14 | 江苏新广联科技股份有限公司 | Preparation method of ink-free printing-free DVD (digital video disk) |
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| TWI457920B (en) * | 2008-07-18 | 2014-10-21 | Nippon Steel & Sumikin Chem Co | A recording / reproducing method for recording the video of the omnipotent pictorial recording medium, and a monolithic recording medium for reading and writing |
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