TW200306555A - Optically information-recording medium - Google Patents

Optically information-recording medium Download PDF

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Publication number
TW200306555A
TW200306555A TW092104687A TW92104687A TW200306555A TW 200306555 A TW200306555 A TW 200306555A TW 092104687 A TW092104687 A TW 092104687A TW 92104687 A TW92104687 A TW 92104687A TW 200306555 A TW200306555 A TW 200306555A
Authority
TW
Taiwan
Prior art keywords
layer
recording medium
recording
substrate
optical information
Prior art date
Application number
TW092104687A
Other languages
English (en)
Other versions
TWI308749B (en
Inventor
Yoshihisa Usami
Original Assignee
Fuji Photo Film Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2002062173A external-priority patent/JP2003263785A/ja
Priority claimed from JP2002062175A external-priority patent/JP2003263782A/ja
Priority claimed from JP2002062174A external-priority patent/JP3742021B2/ja
Application filed by Fuji Photo Film Co Ltd filed Critical Fuji Photo Film Co Ltd
Publication of TW200306555A publication Critical patent/TW200306555A/zh
Application granted granted Critical
Publication of TWI308749B publication Critical patent/TWI308749B/zh

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    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
    • G11B7/252—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers
    • G11B7/254—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of protective topcoat layers
    • G11B7/2542—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of protective topcoat layers consisting essentially of organic resins
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
    • G11B7/252—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers
    • G11B7/257—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of layers having properties involved in recording or reproduction, e.g. optical interference layers or sensitising layers or dielectric layers, which are protecting the recording layers
    • G11B7/2578—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of layers having properties involved in recording or reproduction, e.g. optical interference layers or sensitising layers or dielectric layers, which are protecting the recording layers consisting essentially of inorganic materials
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
    • G11B7/252—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers
    • G11B7/258—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of reflective layers
    • G11B7/259—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of reflective layers based on silver

Landscapes

  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Optical Record Carriers And Manufacture Thereof (AREA)

Description

4 4 200306555 玖、發明說明 (發明說明應敘明：發明所屬之技術領域、先前技術、內容、實施方式及圖式簡單說明） [發明所屬之技術領域] 本發明係關於光資訊記錄媒體，尤其是和熱模式之一次 寫入型光資訊記錄媒體相關。 [先前技術] 以往’大家都知道有利用雷射光之只可執行一次資訊記 錄的光資訊記錄媒體（光碟）。此光碟又被稱爲一次寫入型 CD(所謂CD-R)，其代表構造爲，在透明之圓盤狀基板上依 · 序疊層由有機染料所構成之記錄層、由金等金屬所構成之 反射層、以及樹脂製之保護層（覆蓋層）。而對此CD-R之資 訊記錄，係以近紅外線之雷射光（通常爲7 80nm附近之波長 的雷射光）照射CD-R，記錄層之照射部份會吸收該光而出 現局部溫度上昇，利用物理或化學變化（例如，小洞之形成） 使該部份產生光學之特性變化來實施資訊之記錄。另一方 面，資訊之讀取（再生）上，亦以對CD-R照射和記錄用雷射 光相同波長之雷射光，檢測出記錄層之光學特性變化部位 · (記錄部份）及未變化部位（未記錄部份）之反射率的差異，用 以執行讀取。 近年來，要求具有高記錄密度之光資訊記錄媒體。針對 此要求，有人提出被稱爲一次寫入型數位多媒體光碟（所謂 DVD-R)之光碟（例如，「日經NEW MEDIA」附刊「DVD」、 1995年發行）。此DVD-R之構造上，一般而言，係在形成 寬度只有C D - R之一半以下（0 · 7 4〜0 · 8 // m)、以照射雷射光 之追蹤爲目的的溝槽（預溝槽）之透明圓盤狀基板上，依序 200306555 疊層著含有有機染料之記錄層、反射層、及保護層，將具 有前述構成之2光碟以記錄層朝內側之方式互相貼合的構 造，或者，將此光碟、及相同形狀之圓盤狀保護基板以記 錄層朝內側之方式互相貼合的構造。其次，此D V D - R之資 訊的記錄及再生上’係利用可見雷射光（通常爲63 0nm〜 6 8 Onm之波長範圍的雷射光）之照射，可實施高於CD-R密 度的記錄。 最近，網際網路等網路、及高視覺TV急速普及。又， HDTV (High Definition Television :高畫質電視）亦將在不久 的將來開始放映。在此狀況下，需要可以更便宜之成本及 以更簡單之方式記錄圖像資訊的大容量光資訊記錄媒體。 以現狀而言’ DVD-R充分發揮其大容量記錄媒體之機能， 然而，對大容量化、高密度化之要求卻仍然持續昇高，故 必須開發能滿足這些要求之光資訊記錄媒體。因此，積極 開發可以比D V D - R更短之波長的光來實施高密度記錄且具 有大容量之光資訊記錄媒體。 例如，以適合高密度記錄之通過高NA透鏡的光來實施 記錄爲前提，並依序在基板上設置金屬反射層、記錄層、 以及比基板更薄之覆蓋層的光資訊記錄媒體，又如，利用 從記錄層側朝光反射層側照射波長5 5 0 n m以下之短波長側 雷射光，實施資訊之記錄再生的記錄再生方法。其次，利 用此種短波雷射光之光資訊記錄媒體的記錄層形成染料如 卟啉化合物、偶氮染料、金屬偶氮系染料、喹酞酮系染料、 三甲基酞菁染料、雙氰基乙烯基苯酚架構染料、以及香豆 素化合物等（例如，日本特開平4-74690號公報、日本特開 4 4200306555 平7 -3 0425 6號公報、日本特開平7-3 0425 7號公報、日本特 開平1 1 - 5 3 7 5 8號公報、日本特開平丨號公報、日 本特開平1 1 - 3 34205號公報、日本特開平π_3 342〇6號公 報、日本特開平11—334207號公報、日本特開2000-43423 號公報、日本特開2000-108513號公報、日本特開2000-1 49 3 20號公報、日本特開2000- 1 5 88 1 8號公報、日本特開 2000-228028號公報、及日本特開2001-146074號公報）。然 而’其他化合物方面，只要爲可吸收記錄用雷射光之化合 物，則原理上可當做記錄層用染料來使用，相關業者應該 很容易可以了解此點。其次，記錄再生用雷射光如藍紫色 (波長405nm或410nm)、藍色（波長430nm或488nm)、或藍 綠色（波長5 1 5 n m)。 可利用以上之短波雷射光實施資訊之記錄再生的光資 訊記錄媒體，一般係在基板上依序具有如反射層、記錄層、 隔離層、黏結劑層或黏著劑層、以覆蓋膜，其構成上和CD-R 及DVD-R不相同。因此，雷射光之照射方向正好和CD-R 及DVD-R相反，有時會發生CD-R及DVD-R上不會出現之 層剝離問題，故對各層間要求具有高粘著性。然而，有機 物（記錄層等）及無機物（反射層、隔離層等）相鄰接之層構成 上，因存在容易剝離之界面而無法得到充分之貼合強度， 故尙有改善之空間。 此外，尤其是外圍邊緣之記錄層會對外露出’而因環境 溫度、濕度等因素而降低其保存性。 [發明內容] 本發明有鑑於以上之傳統問題，而以達成以下目的爲課 200306555 題。亦即， 本發明之目的，係提供各層間具有高粘著性，且具有高 保存性、安定之記錄再生特性的光資訊記錄媒體。 解決前述課題之手段如下所示。亦即， 在基板上依序具有記錄層、黏結劑層或黏著劑層、以及 覆蓋膜，軌距爲250〜400nm，溝深度爲10〜150nm，照射 5 OOnm以下之波長的雷射光實施資訊之記錄再生，且具中 心孔之碟狀光資訊記錄媒體時，只要將前述基板及前述覆 蓋膜之內圍附近及/或外圍附近的至少一部份區域利用前 | 述黏結劑層或前述黏著劑層粘著在一起，且該粘著區域之 直徑方向長度的最大値爲0.4mm以上即可。 又，在基板上依序具有記錄層、黏結劑層或黏著劑層、 及覆蓋膜，軌距爲250〜400nm，溝深度爲10〜150nm，照 射5 OOnm以下之波長的雷射光實施資訊之記錄再生，且具 有中心孔之碟狀光資訊記錄媒體時，只要使前述隔離層圍 繞於前述記錄層之外圍邊緣及/或內圍邊緣即可。 又，在基板上依序具有記錄層、隔離層、黏結劑層或黏 · 著劑層、及覆蓋膜，軌距爲250〜400nm，溝深度爲10〜 15 0nm，照射500nm以下之波長的雷射光實施資訊之記錄再 生，且具有中心孔之碟狀光資訊記錄媒體時，只要使前述 基板及前述隔離層之內圍附近及/或外圍附近的至少一部 份區域粘著在一起，且該粘著區域之直徑方向長度的最大 値爲0.4mm以上即可。 [實施方式] 以下係針對本發明之光資訊記錄媒體的第1實施形態進 200306555 行說明。本發明第1實施形態之光資訊記錄媒體，係依據 需要而在基板上依序具有反射層、記錄層、以及必要時之 隔離層、黏結劑層或黏著劑層、及覆蓋膜，軌距爲25 0〜 400nm，溝深度爲10〜150nm，可以利用500nm以下之波長 的雷射光照射實施資訊之記錄再生’且具有中心孔之碟狀 光資訊記錄媒體，其特徵爲：前述基板及前述覆蓋膜之內 圍附近及/或外圍附近的至少一部份區域會利用前述黏結 劑層或前述黏著劑層粘著在一起，且該粘著區域之直徑方 向長度的最大値爲0.4mm以上。 _ 第1圖、第2圖係分別爲第1實施形態之光資訊記錄媒 體實例的上視圖、模式剖面圖。光資訊記錄媒體1 0，在基 板1 2上依序具有反射層1 4、記錄層1 6、隔離層1 8、黏結 劑層20、及覆蓋膜22，中央部則具有中心孔24。如第1 圖之虛線所示，光資訊記錄媒體1 0之外圍附近及內圍附近 的4處不同區域（以下，稱爲「粘著區域」。）上，會以黏結 劑層20將基板1 2及覆蓋膜22粘著在一起。這些分別設於 內圍附近及外圍附近之4處粘著區域，其直徑方向長度最 φ 大値爲 0.5 mm。其次，因爲有這些粘著區域之存在，可使 反射層1 4、記錄層1 6、及隔離層1 8強固地粘著於基板1 2 上。因此，可防止光資訊記錄媒體1 0之各層的剝離。又， 第1圖中之粘著區域係分別設於外圍及內圍之4處，然而， 本發明並不限於此。可以設置更多數之粘著區域，亦可將 整個外圍及內圍都設爲粘著區域。 此第1實施形態中，前述粘著區域之直徑方向長度的最 大値爲0.4mm以上，若該最大値小於〇.4mm，則可能因粘 -10- 200306555 著力不足而發生層剝離。更具體而言，該最大値在外圍附 近應爲0.6mm以上，最好爲0.7mm以上。又，外圍附近之 該最大値的上限爲2mm。 又，內圍附近之粘著區域的直徑方向長度之最大値，應 爲2.5mm以上，3mm以上更佳，4mm以上最好。又，內圍 附近之該最大値的上限爲15 m m。 此第1實施形態之光資訊記錄媒體係在內圍及外圍具有 粘著區域之形態，以此形態爲佳，然而，亦可只在內圍及 外圍之其中一方形成粘著區域。 · 其次，針對本發明之光資訊記錄媒體的第2實施形態進 行說明。本發明第2實施形態之光資訊記錄媒體，係依需 要而在基板上依序具有反射層、記錄層、隔離層、黏結劑 層或黏著劑層、及覆蓋膜，軌距爲25 0〜400nm，溝深度爲 10〜150nm，照射5 00nm以下之波長的雷射光實施資訊之記 _ 錄再生，且具有中心孔之碟狀光資訊記錄媒體，其特徵爲： 前述隔離層係圍繞於前述記錄層之外圍邊緣及/或內圍邊 緣。 φ 第3圖、第4圖係分別爲第2實施形態之光資訊記錄媒 體實例的上視圖、模式剖面圖。如第3圖所示，光資訊記 錄媒體30，在基板32上依序具有反射層34、記錄層36、 隔離層38、黏著劑層40、及覆蓋膜42，且中央部具有中心 孔44。第3圖中，外側之虛線係隔離層3 8之外圍，內側之 虛線係記錄層3 6之外圍。亦即，如第4圖所不’隔離層3 8 會形成至記錄層3 6外圍之外側。更具體而言，隔離層3 8 在外圍邊緣係處於環繞記錄層36之狀態，並利用黏著劑層 -11- 200306555 40貼著覆蓋膜42。因此，記錄層36不會向外露出，且受 到隔離層4 8之保護，而具有優良之保存特性。 光資訊記錄媒體30之覆蓋膜42則利用黏著劑層40黏 著於反射層3 4及隔離層3 8，然而，黏著劑層4 0及反射層 34之粘著區域的直徑方向長度最大値應爲0.4mm以上。因 爲該最大値爲0.4mm以上，故可得到充份粘著力而不易發 生層剝離。更具體而言，該最大値在外圍附近應爲0.6mm 以上，最好爲〇.8mm以上。又，內圍附近應爲2.5mm以上， 3mm以上更佳，4mm以上最好。 其次，爲此第2實施形態之光資訊記錄媒體的2個變形 例（第5圖、第6圖）。第5圖及第6圖中，和第3圖及第4 圖所示光資訊記錄媒體30爲同一構成要素者賦予同一符 號。第5圖所示之光資訊記錄媒體30a，係隔離層38形成 至基板3 2之外圍邊緣的實例，第6圖所示之光資訊記錄媒 體3 0b，則係隔離層38形成至記錄層36外圍之外側及內圍 之內側的實例。任一實例中，隔離層3 8皆圍繞著記錄層 36，故具有優良保存特性，然而，第6圖所示之實例，係 內圍邊緣及外圍邊緣之記錄層3 6皆爲隔離層3 8所覆蓋， 以此形態最佳。 如上面所述，隔離層及記錄層之外圍直徑及/或內圍直徑 不同，然而，前述隔離層及前述記錄層之外圍直徑差異應 爲0.4〜4mm，最好爲0.8〜2mm。又，前述隔離層及前述記 線層之內圍直徑差異應爲0.4〜15mm，最好爲0.8〜7mm。 又，針對本發明之光資訊記錄媒體的第3實施形態進行 說明。本發明第3實施形態之光資訊記錄媒體，係依需要 -12- 200306555 而在基板上依序具有反射層、記錄層、隔離層、黏結劑層 或黏著劑層、及覆蓋膜，軌距爲250〜400nm，溝深度爲10 〜150nm，照射50〇nm以下之波長的雷射光實施資訊之記錄 再生，且具有中心孔之碟狀光資訊記錄媒體，其特徵爲： 前述基板及前述隔離層之內圍附近及/或外圍附近的至少 一部份區域會粘著在一起，且該粘著區域之直徑方向長度 的最大値爲0.4 m m以上。 第7圖、第8圖係分別爲第3實施形態之光資訊記錄媒 體實例的上視圖、模式剖面圖。光資訊記錄媒體50，在基 · 板52上依序具有反射層54、記錄層56、隔離層58、黏著 劑層60、及覆蓋、膜62，中央部則具有中心孔64。如第7 圖之虛線所示，光資訊記錄媒體50之外圍附近及內圍附近 的4處不同區域（以下，稱爲「粘著區域」。）上，基板52 及隔離層5 8會粘著在一起。這些分別設於內圍附近及外圍 附近之4處粘著區域，其直徑方向長度最大値爲0.5 mm。 其次，因爲有這些粘著區域之存在，可使反射層54及記錄 層5 6強固地粘著於基板5 2上。因此，可防止光資訊記錄 φ 媒體5 0之各層的剝離。又，第7圖中之粘著區域係分別設 於外圍及內圍之4處，然而，本發明並不限於此。可以設 置更多數之粘著區域，亦可將整個外圍及內圍都設爲粘著 區域。 此第3實施形態中，前述粘著區域之直徑方向長度的最 大値爲0.4 m m以上，若該最大値小於〇 . 4 m m，則可能因粘 著力不足而發生層剝離。更具體而言，該最大値在外圍附 近應爲0.6mm以上，最好爲0.7mm以上。又，外圍附近之 -13- 200306555 該最大値的上限爲2mm。 又，內圍附近之粘著區域的直徑方向長度之最大値，應 爲2.5mm以上，3mm以上更佳，4mm以上最好。又，內圍 附近之該最大値的上限爲15mm。 此第3實施形態之光資訊記錄媒體係在內圍及外圍具有 粘著區域之形態，以此形態爲佳，然而，亦可只在內圍及 外圍之其中一方形成粘著區域。 以下，針對本發明之光資訊記錄媒體的基板及各層進行 詳細說明。 <基板〉 基板可以任意選擇傳統上被當做光資訊記錄媒體之基 板材料使用之各種材料。 具體而言，如玻璃；聚碳酸酯、聚甲基丙烯酸酯等之丙 烯酸樹脂；聚氯乙烯、氯乙烯共聚物等之氯乙烯糸樹脂； 環氧樹脂；非晶形聚烯烴；聚酯；以及鋁等之金屬；等， 亦可依需要而倂用。 上述材料中，從耐濕性、尺寸安定性、及價格等方面而 言，以聚碳酸醋、非晶形聚燒烴爲佳，最好爲聚碳酸酯。 又，基板之厚度應爲0.5〜1.4 mm。 基板上，會形成追蹤用之溝槽、或代表位址信號等資訊 之凹凸（預溝槽）。爲了實現更高之記錄密度，必須使用具 有軌距小於CD-R及DVD-R之預溝槽的基板。預溝槽之軌 距應爲25 0〜400nm。又，預溝槽之深度（溝深度）應爲10〜 150nm之範圍，15〜100nm爲佳，20〜80nm更佳，20〜60nm 200306555 又，後述之反射層側的基板表面上，爲了改善平面性及 提高黏著力，最好形成基底層。該基底層之材料如聚甲基 丙烯酸酯、丙烯酸、甲基丙烯酸共聚物、苯乙烯.順丁烯 二酸酐共聚物、聚乙烯醇、N-羥甲基丙烯醯胺、苯乙烯· 甲基苯乙烯共聚物、氯磺醯化聚乙烯、硝基纖維素、聚氯 乙烯、氯化聚烯烴、聚酯、聚醯亞胺、醋酸乙烯·氯乙烯 共聚物、乙烯•醋酸乙烯共聚物、聚乙烯、聚丙烯、聚碳 酸酯等之高分子物質；矽烷偶合劑等表面改質劑。 基底層之形成上，係將上述材料溶解或分散於適當溶劑 內調製成塗敷液後，以旋塗、深塗、或擠壓塗布等塗敷法 將此塗敷液塗敷於基板表面。基底層之層厚方面，一般爲 0.005〜20// m之範圍，最好爲0.01〜10// m之範圍。 <反射層> 反射層採用對雷射光具有高反射率之光反射性物質。該 反射率應爲7 0 %以上。高反射率之光反射性物質如M g、S e、 Y、Ti、Zr、H f 、V、Nb、Ta、Cr、Mo、W、Μη、Re、Fe、 Co、Ni、Ru、Rh、Pd、Ir、Pt、Cu、Ag、Au、Zn、Cd、Al、 Ga、In、Si、Ge、Te、Pb、Po、Sn、Bi 等之金屬及半金屬、 或不銹鋼。可以單獨使用這些光反射性物質，亦可使用二 種以上之組合、或合金。這些物質當中以Cr、Ni、Pt、Cu、 Ag、Au、Al、及不銹鋼爲佳。Au、Ag、Al、或其合金更佳， Au、Ag、或其合金最佳。 反射層之形成，係利用蒸鍍、噴濺、或離子鍍使基板上 形成前述光反射性物質。反射層之層厚方面，一般爲1 0〜 300nm之範圍，最好爲50〜20Onm之範圍。又，爲了確保 200306555 粘著區域，使用遮罩設置不會形成反射層之區域。 以上之反射層，在下述記錄層之反射率夠大時並不一定 需要，此時，記錄層具有反射層之機能。 <記錄層> 記錄層係含有染料化合物之層，染料化合物應爲三唑系 化合物、酞菁化合物、聚菲啉系化合物、胺基丁二烯系化 合物、花青系化合物等之至少其中之一種，酞菁化合物則 應爲烷氧基取代物、磺胺取代物、胺磺醯基取代物、及磺 酸取代物之至少其中一種。 又，亦可倂用日本特開平4-74690號公報、日本特開平 8 · 1 2 7 1 7 4號公報、日本特開平1 1 · 5 3 7 5 8號公報、日本特開 平11-334204號公報、日本特開平11 — 334205號公報、日本 特開平11-334206號公報、日本特開平11 — 334207號公報、 日本特開2000-43423號公報、日本特開2000- 1 085 1 3號公 報、及日本特開2000- 1 5 8 8 1 8號公報所示之染料。 又，並未限定爲上述染料，亦可爲三唑化合物、三畊化 合物、花青化合物、份菁化合物、胺基丁二烯化合物、酞 菁化合物、肉桂酸化合物、氧化還原染料化合物、偶氮化 合物、氧醇苯並噚唑化合物、及苯并三唑衍生物等有機化 合物。其中，又以苯并三唑衍生物、酞菁化合物爲佳。 記錄層之形成上，係將上述染料（有機物等）等之記錄物 質和黏結劑等一起溶解於適當溶劑調製成記錄層塗敷液， 其次，將此記錄層塗敷液塗敷於基板表面上之反射層上（未 設置反射層的基板上），形成塗敷膜後進行乾燥。其次，第 1及第3實施形態中，因設有粘著區域，塗敷後，以溶劑 -16 - 200306555 淸洗該區域，除去塗敷液，又，第2實施形態中，因隔離 層環繞記錄層，在塗敷記錄層塗敷液後，應以溶劑淸洗外 圍部及/或內圍部之區域，除去塗敷液。 記錄層塗敷液之記錄物質的濃度方面，一般爲〇. 〇丨〜1 5 質量百分率之範圍，0.1〜10質量百分率之範圍爲佳，〇.5 〜5質量百分率之範圍更佳，0.5〜3質量百分率之範圍最 佳。 又，記錄物質等之溶解處理方法，可以爲超音波處理、 均質機、加濕等之方法。 · 調製記錄層塗敷液之溶劑如乙酸丁酯、乳酸甲酯、乳酸 乙酯、乙酸溶纖劑等之酯；甲基乙基甲酮、環己酮、甲基 異丁基甲酮等之甲酮；二氯甲烷、1，2-二氯乙烷、三氯甲烷 等之氯化碳氫化合物；二甲基甲醯胺等之胺；甲基環己烷 等之碳氫化合物；四氫呋喃、乙醚、二噚烷等之醚；乙醇、 ' 正丙醇、異丙醇、正丁醇雙丙酮醇等之醇；2,2,3, 3-四氟丙 醇等之氟系溶劑；乙二醇一甲醚、乙二醇一乙醚、丙二醇 一甲醚等之乙二醇醚類。 φ 上述溶劑之使用上，應考慮記錄物質之溶解性而決定單 獨使用或採用二種以上之組合。亦可配合目的，在塗敷液 內添加抗氧化劑、UV吸收劑、塑化劑、及潤滑劑等各種添 加劑。 使用黏結劑時，可使用之黏結劑如明膠、纖維素衍生 物、葡萄糖、松脂、橡膠等天然有機高分子物質；聚乙烯、 聚丙烯、聚苯乙烯、聚異丁烯等碳氫系樹脂；聚氯乙烯、 聚偏二氯乙烯，聚氯乙烯·聚醋酸乙烯共聚物等之乙烯基 -17- 200306555 糸樹脂；聚丙烯酸甲酯、聚甲基丙烯酸甲酯等丙烯酸樹脂； 以及聚乙烯醇、氯化聚乙烯、環氧樹脂、丁縮醛樹脂、橡 膠衍生物、苯酚•甲醛樹脂等熱硬化性樹脂之初期縮聚合 物等合成有機高分子。若倂用黏結劑做爲記錄層之材料 時’相對於一般記錄物質之黏結劑的使用量爲〇. 〇 1倍量〜 50倍量（質量比）之範圍，最好爲0.1〜5倍量（質量比）之範 圍。以此方式調製之塗敷液中的記錄物質濃度，一般爲〇. 〇 i 〜10質量百分率之範圍，最好爲〇·1〜5質量百分率之範 圍。 塗敷方法如噴塗法、旋塗法、深塗法、輥塗法、刮塗法、 刮刀塗布法、及網板印染法等。記錄層可以爲單層，亦可 以多層。又，記錄層之層厚方面，一般爲20〜5 OOnm之範 圍，30〜300nm之範圍更佳，50〜100nm之範圔最佳。 又，塗敷溫度方面，只要介於2 3〜5 0 °C之間即可，2 4 〜40°C更佳，最好爲25〜37°C。 爲了控制黏度，塗敷溫度應爲23〜5 (TC之範圍，24〜40 °C之範圍更佳，25〜37t之範圍最好。 爲了防止光碟反翹，塗敷膜之紫外線照射應採用脈衝型 光照射器（最好爲UV照射器）。脈衝間隔應爲m sec以下， // sec以下更好。1脈衝之照射光量並無限制，但以 3kW/cm2以下爲佳，2kW/cm2以下更好。 又，照射次數並無特別限制，以20次以下爲佳，丨〇次 以下最好。 爲了提局該記錄層之耐光性，記錄層亦可含有各種之抗 退色劑。抗退色劑，一般會使用氧猝滅劑。氧猝滅劑則如 -18- 200306555 已公告之專利說明書等上記載者。 其具體實例如日本特開昭5 8 - 1 7 5 6 9 3號公報、日本特開 昭59-8 1 1 94號公報、日本特開昭60- 1 8 3 87號公報、日本特 開昭60-19586號公報、日本特開昭60-19587號公報、日本 特開昭60-35 054號公報、日本特開昭60-3 6 1 90號公報、日 本特開昭60-36191號公報、日本特開昭60-44554號公報、 曰本特開昭60-445 5 5號公報、日本特開昭60-443 89號公 報、日本特開昭60-44 3 90號公報、日本特開昭60-54892號 公報、日本特開昭60-47069號公報、日本特開昭63-209995 號公報、日本特開平4-25492號公報、日本特公平1 -3 8 6 80 號公報、日本特公平6-26028號公報，德國專利3 503 99號 說明書、以及臼本化學會雜誌1 992年10月號第1 141頁等 記載者。 前述氧猝滅劑等之抗退色劑的使用量，相對於以記錄爲 目的之化合物的量，通常爲〇.丨〜50質量百分率之範圍， 0.5〜45質量百分率之範圍爲佳，3〜4〇質量百分率之範圍 更佳，5〜25質量百分率之範圍最佳。 <隔離層> 隔離層係在必要時會形成於上述記錄層、以及後述黏結 劑層或黏著劑層之間的層。隔離層之構成材料上，只要雷 射光可透射♦之材料即可，並無特別限制，以介電質爲佳， 具體而言，如 ZnS、Ti〇2、Si02、ZnS — Si〇2、Ge〇2、Si3N4、 Ge3N4、及MgF2等之無機氧化物、氮化物、及硫化物等， 以ZnS — Si02、Si02爲佳。隔離層可以噴濺、離子鍍等方法 形成’其厚度爲1〜l〇〇nm。又’第1及第3實施形態中， 200306555 爲了確保粘著區域，會使用遮罩來設置未形成隔離層之區 域。 本發明之光資訊記錄媒體中，在以上之記錄層或隔離層 上，會利用以下所示之黏結劑層或黏著劑層貼合後述之覆 蓋膜。 <黏結劑層> 黏結劑層係以黏著後述覆蓋膜爲目的而形成之層，可以 使用傳統上已知之物。黏結劑可從丙烯酸系黏結劑、天然 橡膠、苯乙烯-異戊二烯-苯乙烯共聚物（SIS)、苯乙烯·丁二 烯-苯乙烯共聚物（SBS)等之橡膠系黏結劑中適度選取。該 黏結劑應預先塗敷於覆蓋膜之貼合面上。黏結劑層之層厚 應爲1〜最好爲2〜之範圍。 <黏著劑層〉 黏著劑層和黏結劑層相同，係以黏著後述之覆蓋膜爲目 的而形成之層。黏著劑層之構成材料如光硬化性樹脂、2 液硬化型黏著劑等，其中，以光硬化性樹脂爲佳，爲了防 止光碟發生反翘’最好爲硬化收縮率較小者。此光硬化性 樹脂如大日本油墨化學工業（株）製之「SD-640」、「SD-661」、 「SD- 3 47」等之UV硬化性樹脂（uv硬化性黏著劑）。又， 黏著劑層之厚度方面，爲了使其具有彈性，應爲1〜1〇〇〇 之範圍’ 5〜500//m之範圍更佳，1〇〜loovm之範圍 最好。 开夕成黏者劑層之材料的其他實例如下。該材料係可利用 輸射線照射實施硬化之樹脂，係分子中具有2個以上之輻 射線官能性的2重結合之樹脂，如丙烯酸酯類、丙烯醯胺 -20- 200306555 類、甲基丙烯酸酯類、甲基丙烯醯胺類、烯丙基化合物、 乙烯基醚類、乙烯基酯類。 最好爲含2個官能基以上之丙烯酸脂化合物、甲基丙烯 酸酯化合物。 具有2個官能基之具體實例方面，可使用在如乙二醇二 丙烯酸脂、丙二醇二丙烯酸脂、丁二醇二丙烯酸脂、己二 醇二丙烯酸脂、二甘醇二丙烯酸脂、三甘醇二丙烯酸脂、 四甘醇二丙烯酸脂、新戊二醇二丙烯酸脂、三丙二醇二丙 烯酸脂、乙二醇二甲基丙烯酸酯、丙二醇二甲基丙烯酸酯、 丁二醇二甲基丙烯酸酯、己二醇二甲基丙烯酸酯、二甘醇 二甲基丙烯酸酯、三甘醇二甲基丙烯酸酯、四甘醇二甲基 丙烯酸酯、新戊二醇二甲基丙烯酸酯、三丙二醇二甲基丙 烯酸酯等爲代表之脂肪族二元醇添加丙烯酸、甲基丙烯酸 之物。 又，亦可使用在如：聚乙二醇、聚丙二醇、及聚丁二醇 等之聚醚聚醇添加丙烯酸、甲基丙烯酸之聚醚丙烯酸脂； 在從聚醚丙烯酸酯、眾知之二元酸、及乙二醇得到之聚酯 聚醇添加丙烯酸、甲基丙烯酸之聚酯丙烯酸脂；以及聚酯 甲基丙烯酸酯。 又，亦可使用眾知之聚醇、在二元醇及聚異氰酸酯反應 所得之聚胺基甲酸酯添加丙烯酸、甲基丙烯酸之聚胺基甲 酸酯丙烯酸脂；以及聚胺基甲酸酯甲基丙烯酸酯。 又，亦可使用：具有在雙酚A、雙酚F、氫化雙酚A、 氫化雙酚F、及其環氧化物添加物上添加丙烯酸、甲基丙 烯酸者；以及三聚異氰酸環氧化物改質二丙烯酸脂、三聚 -21- 200306555 異氰酸環氧化物改質二間丙烯酸脂、三環癸烷二甲醇二丙 烯酸脂、三環癸烷二甲醇二丙烯酸酯等具有環狀構造者。 前述輻射線可使用電子射線及紫外線。使用紫外線時， 必須在以下之化合物中添加光聚合起始劑。光聚合起始劑 使用芳香族甲酮。芳香族甲酮並無特別限制，紫外線照射 光源若爲一般使用之可產生水銀燈之明線光譜之254、 3 1 3、8 6 5 n m波長時，應以吸光係數較大爲佳。其代表例如 乙醯苯、二苯甲酮、苯偶因乙醚、苄基甲基縮酮、苄基乙 基縮酮、苯偶因異丁基甲酮、羥基二甲苯甲酮、1-羥基環 己基苯基酮、2-2二乙氧基乙醯苯、Michler，s甲酮等，可 使用各種芳香族甲酮。芳香族甲酮之混合比率方面，相對 於化合物（a)100質量份爲0.5〜20質量份，2〜15質量份更 佳，3〜1 0質量份最好。市面上有預先添加光開始劑做爲紫 外線硬化型黏著劑者，亦可使用該品。紫外線光源可使用 水銀燈。水銀燈爲20〜200 W/cm之燈，使用速度應爲〇.3m/ 分〜20m/分。基體及水銀燈之距離，一般應爲1〜30cm。 電子射線加速器可採用掃描方式、雙掃描方式、及簾束 方式，但以較便宜且可得到大輸出之簾束方式爲佳。電子 射線特性方面，加速電壓應爲100〜1 000kV，最好爲150〜 3 00kV，吸收線量應爲〇.5〜20Mrad，最好爲1〜10 Mrad。 加速電壓爲10kV以下時，能量之透射量會不足，超過 1 0 0 0 k V則使用於聚合之能量效率會降低，不符合成本效 益。 <覆蓋膜> 形成覆蓋膜之材質方面，只要爲透明之材質即可，並無 -22- 200306555 特別限制，材質應爲聚碳酸酯、三醋酸纖維素、及丙烯酸 系聚合物。又，2 3 °C、5 0 % R Η之吸濕率應爲5 %以下之材質。 又，覆蓋膜之表面粗細度應爲5nm以下，複折射率應爲l〇nm 以下。又，「透明」係指記錄再生用雷射光可透射（透射 率：80%以上）之意義。 覆蓋膜之厚度應爲0.01〜0.2mm之範圍，0.03〜0.1mm 之範圍爲佳，0.05〜0.095mm之範圍最好。 使用上述黏結劑層將覆蓋膜貼附於記錄層或隔離層上 的方法，例如，將黏結劑塗敷於覆蓋膜上，使溶劑乾燥後， 隔著該黏結劑將覆蓋膜載置於中間層上，以滾輪施加壓力 貼合覆蓋膜的方法。 黏結劑之塗敷溫度方面，爲了控制黏度，應爲23〜50 °C之範圍，24〜40 °C之範圍爲佳，25〜37 °C之範圍最好。 塗敷後，應實施 5 0〜3 0 0 °C之乾燥，8 0〜2 0 0 °C爲佳，1 〇 0 〜150°C最好。又，貼合覆蓋膜時之溫度應爲0〜100°C之範 圍，1 5〜5 0 °C之範圍更佳。 又，覆蓋膜之貼合方法上，亦可針對使用之黏結劑，在 具有脫模性之脫模薄膜上塗敷黏結劑，等溶劑乾燥後，貼 合覆蓋膜，又在剝離脫模薄膜且在覆蓋膜上舖設黏結劑 後，將覆蓋膜貼合於記錄層或隔離層上。尤其是，若黏結 劑含有之溶劑會溶解覆蓋膜時，應採用此方法。 使用在脫模薄膜上設有黏結劑層之板時，當做基材使用 之膜，若不溶於黏結劑含有之溶劑，則並無特別限制，可 以使用例如：聚對苯二甲酸乙二醇酯、聚丙烯、聚乙烯、 及氯乙烯等之塑膠膜；牛皮紙、道林紙、白土塗布紙、及 -23- 200306555 和紙等之紙；嫘縈及聚酯等之不織布；聚酯、耐綸、及丙 烯酸等之合成纖維所構成之織布；以及鋁、銅、及不銹鋼 等之金屬箔；然而，從在膜上連續塗敷薄而均一之脫模劑 層的觀點而言，以塑膠膜爲佳。 又，使用脫模劑方面，可以從矽系脫模劑、或長鏈烷基 系脫模劑等傳統使用之各種脫模劑中適度選取用。 [實施例] 以下，詳細說明本發明之實施例，然而，本發明並未受 限於此。 (實施例1) 實施例1係對應上述第1實施形態者，在厚度爲 1.1mm、外徑爲120mm、內徑爲i5mm之具有螺旋狀槽（軌 距：3 40nm、溝深度：30nm、全寬：i5nm)之射出成型聚碳酸酯 樹脂基板的具有槽之面上，使用Unaxis公司製Cube，在A r 環境下實施Ag之噴濺，形成120nm之層厚的反射層。噴濺 時，爲了確保粘著區域，利用遮罩，使第1圖虛線部所示 之內圍附近及外圍附近區域不會形成反射層。 其次’將以下述構造式所示之染料A 2 g溶解於2，2，3，3 -四氣丙醇100ml內，調製成染料塗敷液。以旋塗法將此染 料塗敷液均一塗敷於基板上，形成溝內厚度爲1〇〇nm、平 面部厚度爲70nm之記錄層。其後，淸洗不形成前述反射層 之內圍及外圍之部份區域，除去染料塗敷液。其次，使用 乾淨焙箱，實施4(TC、丨小時退火。此時，基板在利用隔 件隔開之狀態下，以垂直之爐柱支撑。 200306555 【化1】
色素A 退火後，在噴濺能量爲4kW、壓力爲2Xl〇_2hPa、10秒 之條件下，實施50nm厚度之ZnS-Si02(8:2)的RF噴濺，形 成隔離層。此時，使用反射層之形成上所使用之遮罩，使 內圍及外圍之部份區域不形成隔離層。 將表面上塗敷著1 5 // m厚度之黏結劑的聚碳酸酯·覆蓋 膜（帝人社製PURE ACE、厚度在使基板及覆蓋膜 之中心爲互相一致之狀態下實施貼合。在外圍及內圍利用 黏結劑層實施基板及覆蓋膜之粘著的粘著區域，其直徑方 向長度之最大値爲0.5 m m。利用以上之步驟，可得到實施 例1之光資訊記錄媒體。 (比較例1) 除了反射層形成至基板之邊緣爲止以外，其餘和實施例 1相同，得到比較例1之光資訊記錄媒體。 (比較例2) -25- 200306555 除了記錄層形成至基板之邊緣爲止以外，其餘和實施例 1相同，得到比較例2之光資訊記錄媒體。 (比較例3) 除了隔離層形成至基板之邊緣爲止以外，其餘和實施例 1相同，得到比較例3之光資訊記錄媒體。 (比較例4)
除了利用黏結劑層粘著基板及覆蓋膜之粘著區域直徑 方向長度爲0.1 mm以外，其餘和實施例1相同，得到比較 例4之光資訊記錄媒體。 [評估] 針對實施例1及比較例1〜4得到之光資訊記錄媒體， 實施以下之（1)剝離試驗、（2)落下試驗、及（3)記錄特性評 估。 (1)剝離試驗
在得到之光資訊記錄媒體的覆蓋膜側之面上貼上膠 帶，實施剝離試驗，並依據以下之評估基準實施評估。結 果如表1所示。 [評估基準] 〇：未發生剝離。 X :發生剝離。 (2)落下試驗 從lm高度使其落至混擬土地板，觀察基板之外側端部 的剝離，依據以下之評估基準實施評估。結果如表1所示。 [評估基準] A :基板外側端部幾乎觀察不到剝離。 >26- 200306555 B :基板外側端部可以觀察到剝離。 (3)記錄特性評估 利用DDU 1 000(PULSETEC(股）製），以線速4.9m/s、凹槽 長度160nm實施記錄，測量上述（！）剝離試驗前後之C/N。 檢測結果如表 1所示。 表1 剝離試驗 落下試驗 C/N(dB)試驗前 C/N(dB)剝離試驗後 實施例1 〇 A 46 46 比較例1 X B 46 42 比較例2 X B 46 41 比較例3 X B 46 42 比較例4 X B 46 42 由表1可知，上述（1)剝離試驗、（2)落下試驗、及（3)記 錄特性評估中，實施例1之光資訊記錄媒體具有高粘著 性、且具有高記錄特性。 (實施例2) 實施例2係對應上述第2實施形態者，在厚度爲1.1 mm、外徑爲120mm、內徑爲15mm之具有螺旋狀槽（軌 距：340nm、溝深度：30nm、全寬：15nm)之射出成型聚碳酸酯 樹脂基板的具有槽之面上，使用Unaxis公司製Cube，在氬 氣環境下實施銀之噴濺，形成120nm之層厚的反射層。 其次，和實施例1相同，形成記錄層及隔離層，然而， 隔離層之形成上，係環繞記錄層之外圍邊緣之方式，隔離 層之外圍會位於前述記錄層之外圍的外側1mm位置。 其次，使大日本油墨化學工業製之ex8204(黏著劑）分配 -27- 200306555 成環狀（固定噴嘴之狀態下使基板實施大約i旋轉），其後， 將聚碳酸酯·覆蓋膜（帝人社製PURE ACE、厚度：85 // m)以 基板及覆蓋膜之中心爲互相一致之狀態下載置於基板上， 以旋轉數5 000rpm實施3秒鐘旋轉，使黏著劑擴散至全面， 且使過多之黏著劑飛散。
其次，照射紫外線使黏著劑硬化。利用以上之方式，可 在無氣泡之情形下形成層厚25 // m之黏著劑層。覆蓋膜及 黏著劑層之厚度合計設爲1 00 // m。利用以上之步驟，可得 到實施例2之光資訊記錄媒體。 (比較例5) 除了記錄層之外圍形成至比隔離層之外圍更爲外側之 位置以外，其餘和實施例2相同，得到比較例5之光資訊 記錄媒體。 [評估]
針對實施例2及比較例5所得到之光資訊記錄媒體，測 量保存前之初期狀態、及80°C、85%RH之環境下放置24 小時後之外圍部的 C/N。又，C/N之測量上，使用 DDU1000(PULSETEC(株）製），以線速 4.9m/s、凹槽長度 160nm 實施記錄。結果如表2所示。 [表2]
C / N (放置前） C/N(放置後） 實施例2 46dB 45dB 比較例5 46dB 40dB (實施例3) 實施例3係對應上述第3實施形態者，使用和實施例1 -28- 200306555 相同之基板，和實施例1相同，實施銀之噴濺’形成反射 層，噴濺時，爲了確保粘著區域，使用遮罩，如第7圖之 虛線部所示之內圍附近及外圍附近之區域不會形成反射 層。 其次，和實施例1相同，形成記錄層及隔離層’此時’ 使用形成反射層時使用之遮罩，使內圍及外圍之部份區域 不會形成隔離層。 其次，使用和實施例2相同之黏著劑及覆蓋膜’以和實 施例2相同之方法，得到實施例3之光資訊記錄媒體。 (比較例6) 除了記錄層形成至全部基板之邊緣以外，其餘和實施例 3相同，得到比較例6之光資訊記錄媒體。 [評估] 針對實施例3及比較例6所得到之光資訊記錄媒體，實 施和實施例1及比較例1〜4相同之（1)剝離試驗、（2)落下 試驗、及（3)記錄特性評估，測量（1)剝離試驗及（2)落下試驗 前後之C/N。結果如表3所示。 表3 剝離試驗 落下試驗 C/N(dB) C/N(dB) C/N(dB) 試驗前 剝離試驗後 落下試驗後 實施例3 〇 A 46 46 46 比較例6 X C 46 43 42 由表3可知’上述（1)剝離試驗、（2)落下試驗、及（3)記 錄特性評估中，實施例3之光資訊記錄媒體具有高粘著 性、且具有高記錄特性。 -29- 200306555 [發明效果] 本發明可提供一種光資訊記錄媒體，可提高各層間之粘 著性、保存性，且可具有安定之高記錄再生特性。 [圖式簡單說明] 第1圖係本發明第1實施形態之光資訊記錄媒體的上視 圖。 第2圖係第1圖之沿II-II線剖面的模式圖。
第3圖係本發明第2實施形態之光資訊記錄媒體的上視 圖。 第4圖係第3圖之沿II-II線剖面的模式圖。 第5圖係本發明第2實施形態之光資訊記錄媒體的變形 例而和第4圖對應之圖。 第6圖係本發明第2實施形態之光資訊記錄媒體的變形 例而和第4圖對應之圖。 第7圖係本發明第3實施形態之光資訊記錄媒體的上視 圖。 第8圖係第7圖之沿II-II線剖面的模式圖。
[元件符號之說明] 10、30、50···光資訊記錄媒體 12 、 32 、 52…基板 1 4、3 4、5 4…反射層 16、36、5 6…記錄層 18、38、5 8···隔離層 20、40、60…黏結劑層 22、42、62···覆蓋膜
2 4、4 4、6 4…中心孑L -30-

Claims (1)

  1. 200306555 拾、申請專利範圍 1. 一種光資訊記錄媒體，其係在基板上依序具有記錄層、 黏結劑層或黏著劑層、以及覆蓋膜，軌距爲250〜400nm， 溝深度爲10〜150nm，照射5 00nm以下之波長的雷射光實 施資訊之記錄再生，且爲具有中心孔之碟狀，其特徵爲： 前述基板及前述覆蓋膜之內圍附近及/或外圍附近的 至少一部份區域係利用前述黏結劑層或前述黏著劑層粘
    著在一起’且該粘著區域之直徑方向長度的最大値爲 0.4mm以上。 2· —種光資訊記錄媒體，其係在基板上依序具有記錄層、 隔離層、黏結劑層或黏著劑層、及覆蓋膜，軌距爲25 〇 〜400nm，溝深度爲10〜150nm，照射500nm以下之波長 的雷射光實施資訊之記錄再生，且爲具有中心孔之碟 狀，其特徵爲： 前述隔離層係圍繞於前述記錄層之外圍邊緣及/或內 圍邊緣。
    3. —種光資訊記錄媒體，其係在基板上依序具有記錄層、 隔離層、黏結劑層或黏著劑層、及覆蓋膜，軌距爲25〇 〜40 0nm，溝深度爲1〇〜15〇nm，照射5 00nm以下之波長 的雷射光實施資訊之記錄再生，且爲具有中心孔之碟 狀，其特徵爲： 前述基板及前述隔離層之內圍附近及/或外圍附近的 至少一部份區域係粘著在一起，且該粘著區域之直徑方 向長度的最大値爲〇.4inm以上。 -31 ·
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US20050102694A1 (en) 2005-05-12
US6961951B2 (en) 2005-11-01
US6959446B2 (en) 2005-10-25
CN100505055C (zh) 2009-06-24
CN1444216A (zh) 2003-09-24
TWI308749B (en) 2009-04-11
US7305690B2 (en) 2007-12-04

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