TWI357599B - Limited play data storage media and method for lim - Google Patents

Limited play data storage media and method for lim Download PDF

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Publication number
TWI357599B
TWI357599B TW093126287A TW93126287A TWI357599B TW I357599 B TWI357599 B TW I357599B TW 093126287 A TW093126287 A TW 093126287A TW 93126287 A TW93126287 A TW 93126287A TW I357599 B TWI357599 B TW I357599B
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Taiwan
Prior art keywords
substrate
layer
storage medium
group
limited
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TW093126287A
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English (en)
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TW200522049A (en
Inventor
Marc Brian Wisnudel
Kathryn Lynn Longley
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Gen Electric
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Publication of TW200522049A publication Critical patent/TW200522049A/zh
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    • 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
    • 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
    • G11B7/2595—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 gold
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/146—Laser beam

Landscapes

  • Laminated Bodies (AREA)
  • Optical Record Carriers And Manufacture Thereof (AREA)

Description

1357599 九、發明說明： 本發明與同在中請中美國專利中請案第腿57,63 1號（摘 要第124366號）相關，其係Μ用之方式併人本文中。 【發明所屬之技術領域】 本發明係關於光學資料儲存媒介。本發明更特別關於有 限運轉光學資料儲存媒介。 【先前技術】 光子磁性及磁-光媒介為高效能儲存技術的原始來 源，這使高健存容量能夠與所儲存的每百萬位元組資料之 合理代價相配。使用光學媒介在音頻、視頻和電腦資料儲 存應用中已很普遍，如在I缩光碟_、數位通用光碟 (DVD ’包括多層結構（如DVD_5，dvd 9)和多側格式如， 卿-10和DVD_18)、磁光光碟（m〇)以及其他一次寫入和 可再寫格式（如，CD_R、CD_RW、dvd r、dvd rw、 DVD+RW、DVD_RAM及類似者），以後統稱為"資料 媒介"。在此等格式中，資料在基材上被編碼成數位資料 系列°在預記錄的光學媒介中，如⑶，資料-般為用— 種方法（如，注模、衝塵或類似方法）凹凸於塑膠基 上的坑和槽。
在可記錄媒介中，資料由雷射編碼，雷射照明活 層，該層經歷相變化，因此產生組成資料流的 J 射或非反射區域。在此料式中，雷射束在達則料: 剛首先通過塑膠基材。在諸層，雷射束根據所編 料反射或非反射。雷射錢後向回通過鄉並進人' 心予檢 95607.doc 15系統’ f料在檢測系統得到解釋。 在—些應用中’理想限制光 起廣泛興趣者A斟立舭 建轉可"卩。例如，引 時存取 曰樂、電影和其他數位娛樂形式提供臨 了存取，而不需要購買者 捉供匕 商。罝髁Λ 貝科储存裝置返回到其供應 許有= 買有限運轉DVD上電影的顧客將僅被允 有π運:取電影’因為按照設計’在其最初使用後，存取 一:例rvD内包含的資料將經相對較短時間被禁止。另 購買軟俨，σσ電細耘式，以誘使它們 它庫期使用有限時間。在此等應用及其， 匕應用中，在彼時間到期 限使用方索^ U〗必須返回該光碟。由此等有 方案㈣的再循環關係將由有限運轉_ 循％性及清除達到dvd 町丹 汽車中）二者平衡。購貝琢所的至少-個行程（-般在 :此’需要提供有限存取音樂、電影及其它數位娱樂形 限存取適用的任何其他資料之機器可讀光碟，其中 1碟不需要在有限存取時間結束返回到供應者。有限運 轉的光碟提供此問題之解決方法。 、有限運轉光碟（如’ DVD’S)已由多種方法產生一種方 法包括形成包含反射層之光碟，反射層由多孔性屏障層保 d ’以使反射層經預定時間氧化。一旦反射層達到一定氧 t水平，光碟不再能夠可讀。因此，氧通過基材層耗費的 b間對有限運轉光碟的運轉時間至關重要。另外，在有限 子取了間單獨依據DVD的氧敏感性時必須採取多個步 、使基材具有所需的氧渗透率水平，以在預定時間前 95607.doc 使氧不達到反應層 全可運轉。 如此D V D能夠在有限存取期間保持完 鑒於前述’需要保護有限運轉資料存儲媒介 短資料儲存媒介的使用期限。 “百 本發明提供此等及相關問題的新穎解決方法，如以 明、實例及請求項顯示。 5 【發明内容】 本發明提供-㈣於資料之有限運轉光學料 包括： ' 〃 第一基材； 反射層； 设於該基材和該反射層間之資料層； 包括至少一種載體和至少一種反應物質之反應層；及 在25 °C具有於約〇·1拜爾和約1.35拜爾間範圍之氧滲透率 之光學透明性第二基材’其中該第二基材係設於反應層和 雷射入射表面之間，其中該第二基材包括聚甲基丙烯酸酯 共聚物或含聚甲基丙烯酸酯同聚物或共聚物之摻合物。 【實施方式】 在以下說明及請求項中，提及具有以下意義的數個詞 語。 早數形式一"（a)、" — "（an)和”该”（the)包括複數個對 象，除非本文另外清楚指明。 ”視需要"或”視需要地”指隨後所述事件或情況可能或可 月b不發生’且描述包括該事件或情況發生之例及不發生之 95607.doc 例0 ”運轉時間”係界定為有限 轉貝枓儲存媒介在重運轉裝 置中無錯误一般運轉的總時間。 在本文中，"DMBPC”係界定Λ 基）環己^ 01，1·雙（⑼基·3·甲基笨 在本文中’ "DMBPA”係界定為 經基-3-曱基笨基）丙烷。
一曱基雙齡A 2,2-雙（4- 在本文中，"DDDA，，係界定為十二烷雙酸。 根據本發明之資料儲存媒介包括，第—基材；反射層； 責料層；反應Ή第二基材。資料儲存媒介可進一步包 *光吸收層及黏著劑層。在一具體實施例中，資料層設於 第—基材和反射層之間1於第—基材和第二基材的塑膠 理想具有足夠熱和機械較性，以防止在不同層沈積步驟 / 1及由用戶儲存期間變形。即，塑膠應能夠經受隨後處 ，數例如，在把加隨後層時，如，約室溫（約25。〇 )至 同、力150 c之濺鍍溫度，並能夠經受隨後儲存條件，例 士在具有約70°c溫度的熱箱中。在本發明一具體實施例 中第一基材和第二基材可包括具有約i〇〇°c或更高玻璃 轉移溫度之熱塑膠。 L用於第一基材和第二基材的材料之實例包括（但不限 於）無疋形、結晶及半結晶熱塑膠，如聚氯乙烯、聚烯烴 (包括（但不限於）線性及環性聚烯烴，且包括聚乙烯、氯化 的+乙埽、聚丙烯及類似者）、聚酯（包括（但不限於）聚對 酞駄乙二醇酯、聚對酞酸丁二醇酯、聚對酞酸環己曱二醇 95607.doc 1357599 醋（polycyclohexylmethylene terephthalate)及類似者）、聚 醯胺、聚砜（包括（但不限於）經氫化的聚颯及類似者）、聚 醯亞胺、聚醚醯亞胺、聚醚砜、聚苯硫、聚醚酮、聚醚醚 酮、ABS樹脂、聚苯乙烯（包括（但不限於）經氫化的聚苯乙 烯、間同立構及無規立構聚苯乙烯、聚環己基乙烯、苯乙 烯-共-丙婦腈、苯乙烯-共·馬來酸酐及類似者）、聚丁二 烯、聚丙烯酸酯（包括（但不限於）聚曱基丙烯酸甲酯 (PMMA)、甲基丙烯酸曱酯-聚醯亞胺共聚物及類似者）、 聚丙細腈、聚縮酸、聚碳酸醋、聚伸苯喊（包括（但不限於） 自2，6-二甲基苯紛衍生者及與2,3,6-三曱基苯紛之共聚物及 類似者）、乙烯-乙酸乙烯酯共聚物、聚乙酸乙烯酯、液晶 聚合物、乙烯-四氟乙烯共聚物、芳族聚酯 '聚氟乙烯、 聚一氧亞乙烯、聚二氯亞乙烯及四氟乙烯（例如， Teflon)。 在本發明一具體實施例中，第二基材包括至少一種熱塑 膠，且其中該第二基材在25〇C具有於約0.1拜爾和約丨.35拜 爾間範圍之氧滲透率，更佳在25°C具有於約〇·2和約1 2拜 爾間之氧滲透率。雙酚A聚碳酸酯之滲透率為丨·39拜爾。 由於其相對較高氧滲透率，雙酚Α聚碳酸酯不能極佳適合 作為第一基材，因為其不適用於延長本發明有限運轉 DVDs的運轉時間。在本發明一具體實施例中，第二基材 為聚甲基丙烯酸酯共聚物或含聚曱基丙烯酸酯同聚物或共 聚物之摻合物。聚（曱基丙烯酸曱酯）同聚物自身在Ml具 有〇·116χ1〇13釐来釐米/(釐米2.秒·帕）之滲透率，此滲透 95607.doc -9- 1357599 率相當於Ο.154拜爾（聚合物學百科全書（Encyclopedia of
Polymer Science)，第VI卷，第549頁）。由於低氧滲透率， 聚甲基丙烯酸曱酯同聚物自身不能極佳適用於有限運轉的 DVDs。但’在本發明一具體實施例中，可使甲基丙烯酸 酯與其他單體共聚，以產生具有在所需範圍内的氧滲透率 之聚甲基丙烯酸酯共聚物組合物。在另一具體實施例中， 可使聚（甲基丙烯酸曱酯）同聚物與其他聚合物摻合，以產 生具有在所需範圍内的氧滲透率之摻合物組合物。在另一 具體實施例中，可使聚曱基丙烯酸酯共聚物與另一種熱塑 膠摻合，以產生具有在所需範圍内的氧滲透率之摻合物組 在25°C具有於約0.1拜爾和約丨.35拜爾間範圍之氧滲透率 之典型聚丙烯酸酯包括含對應結構⑴之結構單位之聚丙烯
其中y為氫、cvc12烷基、c4-c10芳基，ri為Ci_Ci2烷氧 基，η為1至10000之整數。 在另一具體實施例中，第二基材包括至少—種含對應結 構（Π)之結構單位之聚合物： 95607.doc -10· 1357599 c=o X\R2 / L !] 2> Π 其中Y為氫、Cl-C,2燒基、C4.Cl。芳基；Rl係如結構！中所 界定者；R2為C4-C10芳基、Cl_Cl2烷氧基、氰基、硝基或 函素；乂和2獨立為1至1〇〇〇〇之整數，且11為1至1〇〇〇〇之整 數。如在本發明之不同具體實施例中使用，"烷基”指線性 烷基和分支烷基、芳烷基、環烷基、雙環烷基、三環烷基 及多環烷基，該烷基包含碳和氫原子，且除碳和氫外，亦 視需要包含選自週期表第15、16和17族之實例原子。，，烷 基亦涵蓋烷氧基之烷基部分。在不同具體實施例中，直 及分支烷基為含1至約32個碳原子者，且包括視需要用一 或多個選自C,-C32烷基、eve”環烷基或芳基之基團取代 之c】-C32烷基以及視需要用一或多個選自烷基之基 團取代之C3-Cls環烷基作為說明性非限制實例。一些特定 •兒月丨生貫例包括甲基、乙基、正丙基異丙基、正丁基、 第一丁基、第三丁基、戊基、新戊基、己基、庚基、辛 基壬基、癸基、十一烷基及十二烷基。環烷基和雙環烷 基的一些說明性非限制實例包括環丁基、環戊基、環己 基甲基環己基、環庚基、雙環庚基及金剛烧基。在不同 具體貫施例中，芳烷基為含7至約14個碳原子者；此等包 括（但不限於）苄基、苯基丁基、苯基丙基及苯基乙基。在 95607.doc 1357599 不同具體實施例中，在本發明不同具體實施例中所用的芳 基為含6至約1 8個環碳原子的經取代或未經取代芳基。此 等芳基的一些說明性非限制實例包括視需要用一或多個選 自Ci-Cu烷基、Cs-Cu環烷基或芳基之基團取代之C6_Ci5烷 基。芳基的一些特定說明性實例包括經取代或未經取代的 苯基、聯笨基、曱苯基及萘基。 用於第一基材的聚甲基丙稀酸酯共聚物可為無規、交替 或嵌段共聚物。在本發明一具體實施例中，聚甲基丙烯酸 酯共聚物為無規共聚物。在一具體實施例中，第二基材為 甲基丙烯酸曱酯和苯乙烯之共聚物。在本發明一交替具體 貫施例中，第二基材包括聚甲基丙烯酸酯共聚物，其中約 10至約90莫耳％之結構單位係衍生自甲基丙烯酸甲酯。可 使聚甲基丙烯酸酯與相溶混的其他聚合物摻合，以獲得具 有適應滿足特殊有限運轉光學資料儲存媒介（例如，有限 運轉的DVD)需要之氧渗透率之組合物。 在本發明—具體實施例中，第二基材之氧滲透率亦可由 叫、加摻入含聚曱基丙烯酸酯之組合物之小分子添加劑改 變。小分子添加劑之實例包括反增塑劑、顏料、脫模劑、 熱穩定劑、紫外吸收劑及其混合物。 在一些光學媒介格式中，第二基材之厚度可不同於對 所規疋的厚度。例如，在所提出的藍色光線視頻光碟 中，貝料層由100微米薄膜與空氣分離。在此例中，所需 勺薄膜^透率需要降低，以提供適當擴散延遲時間。例 士 對於具有1.39拜爾滲透率之1〇〇微米厚聚甲基丙烯酸 95607.doc 1357599 ^膜：預測延遲時間為13分鐘。對於具有_… 透率之溥臈·’預測延遲時間為” 中，第二基材具有在約05毫〜：在一具體貫施例 许^故 和約〇·7毫米間範圍之厚 度。在本發明另一具體實施例中， 毫米（mm)和約〇.3毫米間範圍之厚度。& 〃 約〇·〇5 ^本發明—具體實施例中，資㈣存媒介包 波長（即，在光學媒介裝置中可 μ茧射 率之第—其# s ^ 广、有低又折射和高透光 : 基材。通讀雷射波長在約390奈米和約43〇太 =耗圍内(藍和藍-紫雷射)。或者，讀雷射波長在約630 奈米和約650奈米之範圍内（紅色雷射）。第二基材包括 足夠光學透明度之媒介，例如’約侧奈米或更小之雙折 射，以使資料儲存材料在媒介裝置中可讀。 已發現’通過使用在饥具有於約〇1拜爾和約a拜爾 間辄圍之氧滲透率之光學透明基材’有限運轉資料存儲媒 3介所用之運轉時間得到有效延長，在此，i拜爾=ι〇•，米 3(STP) j米/楚米2·秒·楚米Hg。光學透明基材係位於反應 層=雷射人射表面之間，且被稱V，第二基材'在暴露於 氧時，基本無色的反應物質（例如，無色亞曱藍）氧化生成 不透明或半不透明層（例如，深藍色染料亞曱藍）。具有不 透明/半不透明層的貢料儲存媒介不再能夠於媒介播放器 中運轉。藉由調節變得不透明的時間，可用染料層對特定 應用提供具有所需壽命之有限運轉資料儲存媒介。在其中 染料層初始由具有〇·5和〇·7毫米間厚度之第二基材與空氣 y刀離之例中，與其中使用具有大於約1.35拜爾之氧滲透率 95607.doc -13- 1357599 1拜爾和約1 _35拜 得不透明的時間 爾 之第二基材比較，使用在25°C具有約〇 間範圍之氧滲透率之基材使其中染料變 質上延長。 在延長其中染料層變成不透明的時間方面，第二 聚甲基丙稀酸醋組成)之效力部分依賴氧能夠：過 第一材擴散進入反應染料層所處之速率。在延遲時間 後’氧開始漏過第二基材，延遲時間由 L2/(6D)(公式 1) 估計[克朗克（Crank)，擴散數學（The d
Won) ’第2版，牛津大學出版（〇xf〇rd υηιν6Γ^ ，聰]，其中L為第二基材之厚纟，D為第二基材令 氧之擴散係數。擴散係數D可自滲透率p及溶解度“ ㈣/S獲得，其中D的單位為餐米2/秒，在聚甲基丙稀酸醋 中的氧溶解度一般為約6 69 χ丨〇_3[立方釐米][立方釐 米][釐米Hg])(聚合物學百科全書，第VI卷第頁卜在 其中第二基材#度為0.6毫米且第二基材為具有139拜爾之 氧滲透率及2.1 X 1 〇 -8釐米2 /秒之擴散係數之聚碳酸酯之例 中，延遲時間為約8小時。但，如果擴散係數減到〇.7χ1〇-8 釐米2/秒，假定溶解度不變，滲透率為約〇47拜爾，則延 遲時間變為約24小時。 在一具體實施例中，第一基材為聚碳酸酯。在本文中， ”聚碳酸酯"指結合衍生自一或多種二羥基芳族化合物之結 構單位之聚碳酸酯’包括具有式（ΠΙ)結構單位之共聚碳酸 酯及聚酯碳酸酯： 95607.doc 14 1357599 ο "°— (III) -R3~〇- ”中占總數至少約6G%之R3基®為芳族有機基團，其餘為脂 族或脂環族基® β較佳為㈣有機基團，更佳為式— 之基團： -Υ1—Α2- 其中各為單環二價芳基，γ1為具有q、_個使ν 與Α2分離之原子之橋接基團。在一典型具體實施例中，一 個原子使Αι與A!分離。此類型基團的說明性、非限制實例 為 Hn-sdnwf 甲基、雙環亞庚基、亞？其 ，Η哀ώ録亞乙基、亞異丙基、亞新戊 =、亞環己基、亞環十五烧基、亞環十二燒基、亞金剛烧 :及類似者。在另一具體實施例中，有。個原子使〜 說明性實例為雙絲。橋接基團為煙基或飽和 ^ f基S &己基或亞異丙基或雜原子 (如，-〇-或-S-)。 聚碳酸酯可由其中僅一個原 合物反應產生。在本文中，”丄與刀離的二經基化 有以下通加……基化合物，，包括(例如)具
0H (V) 其申R4和R5在各情況下獨立為 π -. yV p,j ίΚ ^ ^ Λ 、_ >、，、子或單價烴基丨Ρ和 刀別獨立為〇至4之整數；且 代表一個式（VI)之基團： 95607.doc (VI)1357599 R6 R8 •C· C一 其中R6和R7分別獨立代表氫原 且Rh-僧風原子或早價線性或環系烴基， 且R為二價烴基。 適合二經基化合物的—些說明性、非限制實例包括二經 ^及經二經基取代的芳族烴，如美國專利第a?，·號 中的名稱或式（-般或具體）所揭示者。可由式（v)代表的此 類型雙紛化合物具體實例之非唯—性列舉包括下列者. 】山雙屮經基苯基）甲烧；U_雙（4·經基苯基）乙烧；U雙 (4_叙基苯基）丙烷（以後稱為”雙酚A”或”BPA") ; 22雙（4 經基苯基)丁院’· 2,2_雙(4_經基苯基)辛炫；!山雙:4經基 苯基）丙烷；-雙（4_經基苯基）丁烷；雙（心羥基苯基）苯基 "甲烷；2,2-雙(4_羥基I甲基苯基）丙烷（以後稱為 "DMBPA") ; 1，1-雙（4_羥基·第三·丁基苯基）丙烷；雙（羥基 芳基）烷，如2,2-雙（4_羥基_3·溪苯基）丙烷；丨山雙⑷羥二 苯基）¾戊烷；4,4’·雙苯酚；雙（羥基芳基）環烷，如〗，卜雙 (4-經基苯基）環己烷和^卜雙^—羥基·3_甲基苯基）環己烷 (以後稱為"DMBPC"或"BCC")及類似者。適用的雙酚之額 外實例包括芴酮衍生的雙酚，如9,9，_雙（4_羥基笨基）芴及 9,9'·雙（4-羥基曱基苯基）芴。 亦可利甩自二或多種不同二羥基酚聚合產生的聚碳醆 醋’或者’如果需要使用聚碳酸酯共聚物而不是同聚物， 則使用二羥基酚與二醇或羥基-或酸-為終端的聚酯或與二 凡酸或與羥基酸或與脂族二酸之共聚物。通常，有用的脂 95607.doc •16· 1357599 才矢一酸具有約2和約4〇問夕石由75 7 ]之灰原子。較佳脂族二酸為十 烷雙酸（DDDA)。 亦可利用聚丙婦酸酷、耳又通匕山a ^ t知妷酸酯樹脂及含聚丙烯酸酯 或聚醋碳酸酉旨之摻合妨j。八± & β 物 刀支的聚碳酸酯以及線性聚碳酸 S曰及分支聚碳酸g旨之換合物亦可田 0物亦了用。分支的聚碳酸酯可由 在聚合期間加入分支劑溆借，i^ 2 w e u 刀又川展備，如叁（4-羥基苯基）乙烷。 較佳聚碳m雙盼Α為基礎’ 為對-伸苯 基’且υ1為亞異丙基。聚碳酸醋之重量平均分子量較佳在 约5,0_子質量單位和約刚，咖原子質量單位間之範圍 内，更佳在約1〇,〇〇〇原子質量單位和約65,〇〇〇原子質量單 4之Ιϋ圍内’最佳在約15,000原子質量單位和約35,綱原 子質量單位之範圍内。 聚碳酸酯組合物亦可包括各種普通混入此類型樹脂組合 物的添加劑。此等添加劑為’例如，填料或增強劑；熱: 定劑；抗氧化劑；光穩定劑；增塑劑；抗靜電劑；脫模 背J，額外的樹脂；發泡劑；及類似者以及包含至少一種前 述添加劑之組合。 反射層應具有足夠厚度，以反射足夠量能量，如光，以 便能夠檢索資料。通常，反射層具有至高約700人之厚度， 厚度一般較佳在約300Α和約600人間之範圍内。適合2射 層包括任何能夠反射用於讀出光學資料儲存媒介内所包含 資料之特定光線波長之材料。反射金屬特別適合用作反射 層。金屬（如鋁、銀、金、矽、鈦和包含至少一二 夕 樘則述金 屬之合金及混合物）一般極適合用作反射性金屬層。在本 95607.doc 1357599 發明一具體實施例中’反射層基本由鋁組成。在本發明另 一具體實施例中’反射層基本由銀組成。在本發明另一具 體實施例中，反射層基本由金組成。 在可記錄媒介中’資料由雷射編碼，雷射照明活性資料 層，該層經歷相變化，因此產生組成資料流的一系列高反 射或非反射區域。在此等格式中，雷射束在達到資料層之 前首先通過基材。在資料層，雷射束根據所編碼的資料反 射或非反射。雷射光然後向回通過基材並達到光學檢測系 統’資料在檢測系統得到解釋。因此，在一具體實施例 中，資料層設於基材和反射層之間。用於光學應用的資料 層一般包括在基材層上的坑、陸面、槽及其組合。資料層 較佳嵌入基材表面。一般注模壓縮技術產生該基材’在 此，模用本文中界定的熔融聚合物填充。在本發明一具體 實施例中，資料層凹凸於第一基材之表面上。該模可包含 預型件、插件等。聚合物經冷卻，且在至少部分熔融態時 緊壓，以使所需表面特徵（例如，以螺旋同心或其他定向 設的坑和陸面）壓印在基材的所需部分上，例如，所需區 域中的一側或雙側。 ^於磁性或磁·光應用的可能資料層可包括任何能夠儲 存可檢索資料之材料’實例包括（但不限於）氧化物（如，氧 ::矽醐）、稀土元素-過渡金屬合金、鎳、鈷、鉻、鈕、 鉑、軾、釓、鐵、硼 '其他及包含至少一種前述之合金 矣且人 女 入 :° '有機染料（例如’菁或醜菁型染料）和無機相變化合 物（例如，TeSeSll τ Α lebebn、InAgSb及類似者）。 95607.doc 1357599 反射層-般包括载體和反應物質二者。反應物質可作為 塗料調配物包含於儲存媒介中’或可包含於黏著劑調配物 中。在-具體實施例中，反應物質為氧敏感性染料。在本 發明另-具體實施例中，可能的反應物質包括氧敏感性亞 甲藍的無色或還原形式、亮甲酚藍、鹼性藍3和甲笨胺〇以 及含至少一種前述物質的反應產物及組合。在本發明一較 佳具體實施例中，氧敏感性染料為無色亞甲藍。亞甲藍染 料VII和相關染料νιπ-χ之結構如下所示： 俨C f H CHj
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IX 驗性藍3 95607.doc 19 1357599
X 3 Η Η3 \c c—< 、 CIC / \\ HIC, C—H W / CIC 甲苯胺ο 可使第二基材適應包含染料，以過濾達到反應層的光。 可限制能夠通過第二基材進入反應層的光之波長，以改良 光致褪色阻力。適合濾光可由光吸收化合物混入第二基材 完成。可用於此目的的光吸收化合物包括蒽醌、茈、哌瑞 酮（perinone)、陰丹酮（indanthrone)、嗤 °丫 °定 S同（quinacridone)、 口占0镇（xanthene)、°惡嗓、〇惡 σ坐淋、喧 B頓（thi〇xanthene)、韵 藍類、硫散藍、萘二曱醯亞胺（naphthalimide)、菁、咕 噸、次甲基染料、内酯、香豆素、雙-苯並噁唑基噻吩 (bis-benzoxaxolyithiopheneKBBQT)、萘四羧酸衍生物' 單 偶氮及雙偶氮染料、三芳基甲烷、胺基酮、雙（苯乙烯基 聯笨衍生物和類似者及其組合。可使光吸收化合物與清氧 添加劑組合。清氧添加财效降低第：基材的氧渗透率。 反應層中的反應物質之量可依資料儲存媒介的所需可用 壽命調節。在一些具體實施例中，以反應層之總重量吁， 反應層中的反應物質之量小約〇1重量％，較佳約
%，反應物質的上限量A约〗Λ舌θ I 里為、力10重置％，較佳約7 6重量％更佳，更佳約5重量％。 ^ 除前述氧敏感性無色染料外， J σ成大；^其他华粗R Ν 阻材料’並使其併人反應層，以限制資料储存媒;的= 95607.doc 1357599 期限。例如，其他適合材料揭示於美國專利第4,4〇4,257號 及美國專利第5,8 1 5,484號。在本發明的一些具體實施例 中，反應層中存在的反應物質進一步包括二或多種反應物 質之混合物，如本文所示者。 在本發明一具體實施例中，反應層基本由反應物質組 成，反應物質較佳與載體混合並且沈積於或浸入至少部分 反射層表面或沈積與浸入組合，以形成反應層。依賴調配 物之類型，以調配物之總重量計，載體_般以約65%和約 99.9%間範圍之量存在，更一般以約7〇%和約娜間範圍之 量存在。在反應物質包含於黏著劑調配物時，以黏著劑調 配物之總重量計，載體一般以約9〇至99.9%間範圍之量存 在’更一般以約95。/〇和約99.5%間範圍之量存在。在一具 體實施例中，載體係選自由熱塑性丙烯酸系聚合物 '聚酯 樹月曰、環氧樹脂、聚琉醇（P〇lythi〇lene)、UV可固化有機 樹脂、聚胺基曱酸酯、可熱固丙烯酸系聚合物、醇酸樹脂 (alkyds)、乙烯基樹脂及類似者以及包含至少一種前述載 體之反應產物及組合所組成之群組。例如，聚醋包括脂族 二羧酸（例如，富馬酸或馬來酸）與二醇（如，乙二醇、丙_ 醇、新戊二醇及類似者）之反應產物以及包含至少一種前 述之反應產物及混合物。在一具體實施例中，反應層之載 體基本由UV可固化有機樹脂組成。能夠用於提供載體的 適合氧化合物包括含一或複數個環氧官能基的單體性、 二聚、养聚或聚合性環氧材料。載體可包括環氧化合物之 反應產物，如雙酚A二縮水甘油醚。亦包括環氧衍生物與 95607.doc 21 1357599 酚醛樹脂及類似者的反應產物作為適合载體組分。適合用 作載體的其他有機材料包括聚烯烴及聚硫醇之混合物，如 凱爾（Kehr)等人的美國專利第3,697,395號及第3,697,402號 所示。在一具體實施例中，載體包括在照射時提供交聯丙 烯酸系樹脂的UV可固化有機樹脂。在本發明另一具體實 加例中’載體為熱丙稀酸系聚合物。在本發明另一具體實 施例中，載體包括聚（甲基丙烯酸曱酯）。在另一具體實施 例中’反應層包括含聚（甲基丙稀酸甲酯）之載體及無色亞 甲藍作為氧敏感性反應物質。含熱塑性丙烯酸系聚合物之 載體一般具有0.300立方釐米/克（cni3g·1)之特性黏度，更一 般小於約0.250立方釐米/克，最一般小於約〇2〇〇立方釐米/ 克。 為增強反應層對第二基材之黏著力，可在反應層和第二 基材之間利用底漆。熱塑性丙稀酸系聚合物可作為有用的 底漆’包括：自單種丙烯酸酯單體衍生的丙烯酸系同聚 物，自單種曱基丙稀酸酿單體衍生的甲基丙烤酸系同聚 物；自二或多種不同丙烯酸酯單體、二或多種不同甲基丙 稀酸酷單體或一種丙烯酸酿單體和一種曱基丙烯酸酯衍生 的共聚物及類似者，以及包含至少一種前述底漆之組合。 亦可使用二或多種前述熱塑性丙稀酸系聚合物、二或多種 不同丙烯酸系同聚物、二或多種不同丙烯酸系共聚物、二 或多種不同曱基丙烯酸系同聚物、二或多種不同曱基丙烯 酸系共聚物、丙烯酸系同聚物及曱基丙烯酸系同聚物、丙 烯酸系共聚物及曱基丙烯酸共聚物、丙烯酸系同聚物及甲 95607.doc -22· α/599 基丙稀酸系共聚物以及丙烯酸系共聚物和甲基丙烯酸同聚 物及其反應產物之混合物。 可視需要用各種塗覆技術將反應層施加到基材，如塗 漆、浸潰、噴塗、旋塗、絲網印刷、噴墨印刷及類似方 法。在一具體實施例中，可使反應層相對揮發性溶劑混 合，較佳為有機溶劑，該溶劑對聚碳酸酯實質為惰性，且 不應侵蝕及不利影響聚碳酸酯，但應能夠使載體溶解❶溶 劑中載體的濃度一般為約5重量％或更大，較佳約1〇重量％ 或更大而聚合物之上限為約25重量％，較佳約2〇重量0/〇 或更小。一些適合有機溶劑包括乙二醇二乙酸酯'丁氧基 乙醇、甲氧基丙醇、較低碳烷醇及類似者。塗料溶液中溶 劑的濃^ —般為約70重量％或更大，較佳約75重量％或更 而聚σ物之上限為約90重量°/。，較佳約85重量y❶或更 應層亦可視需要包含各種添加劑，如平光劑、界,
劑觸I劑和類似者及至少—種前述添加劑之反應, 及組合。 哄W Γ儲存媒介的所需壽命依賴反應物質氧化成雷射-光- 木料所在的速率。氧化速率又依賴反應層巾反應物質 後1， ’、、、色木料）和氧之濃度。資料儲存媒介暴露於空氣 之、堯泰’Ό的氧之濃度作為時間之函數依賴氧通過基材 渗透率及氧清_的存在與否。 =如，對於無色亞甲藍（lmb)氧化成亞 迷率可由以下速率公式描述： 95607.doc 1357599 d[MB]/dt = keff[02] [LMB](公式 2 )
其中，keff為有效速率係數，該係數依賴數個環境及化學 因素，包括（但不限於）溫度、壓力、酸性及反應染料層中 反應劑之流動性。氧擴散通過基材所需的時間可由公式i 估计因此，擴散係數和滲透率越低，擴散延遲時間越 長，無色染料開始氧化前的延遲越大。在媒介中各層的適 合邊界條件下，藉由解菲克擴散第二定律(咖— Law of DlffUS10n)，反應層中氧之濃度[〇2]與氧擴散係數 可呈反向關係[克朗克，擴散數學，第2版，+津大學出 版’ 1975]。對於其中反應染料處於黏著劑之例，在透明 基材和反應層間界面的氧濃度[〇2]之結果為下列者： [〇2] = [02；Uerfc{L/(4m)A.5}(公式 3) 其中，erfc為補餘誤差函數，L為基材之厚度（單位，爱 米）’t為時間（單位，秒假定氧之擴散係數（單位，楚米^秒） 恒定。基材中氧在平衡之濃度陶0〇可認作為氧的溶解度 (單位，莫耳/升）。 反應屢之厚度依賴所用的特定反應物質、其在反應層 之濃度以及初始及所需時間後所需的層之吸收特性二 料調配物中施加反應物質時， 亏反應層可具有低約1微米（ 之厚度，較佳約2微米，更任4 文佳約3微未。在上端，厚度 兩約15微米或更大，較伟51 Λ 較佳至向約10微米，更佳至高約6 米。在黏著劑中應用反廊物 應物為日守，反應層可在30和80微 之間，更佳在40和60微米之間。 一旦超過有限運轉光學蚀六说人 予儲存媒介的所需使用期限，反 95607.doc •24- 1357599 層應在所給裝置中於雷射之波長吸收足夠量入射光、反射 光或其組合，以防止有限運轉光學儲存媒介被讀出。在本 發明一具體實施例中’可利用允許自反射層约50%或更大 之初始百分反射率之層，較佳約65或更大，更佳約75。/。 或更大。一旦媒介已暴露於氧 '空氣歷經所需時間（為所 而可允°午的媒介運轉時間）’該層較佳包括約45%或更小之 百刀反射率，較佳約30°/〇或更小，更佳約20。/❶或更小，小 於約10%尤佳。反應物質可作為塗料調配物包含於儲存媒 "中，或可包含於黏著劑調配物中。反應層之實例可包 _ 括，在與反射層相鄰的PMMA塗層+包括氧敏感性染料， 或在第二基材和反射層間的黏著劑層中包括反應染料。 對於未經塗覆光碟或其中反應層仍處於初始、非光吸收 心之有限運轉光碟，在光頭檢測器檢測的自金屬化反射層 反射之光量可由以下公式與入射到光碟的雷射光之強 又〇關耳外.I初始/I〇 = r初始。在時間t = 〇，由於在任何層中 的吸收及散射’對反射率因數R初始應考慮反射層的内在反 射率以及光強度之衰減。在以後時間，反應層暴露於氧 _ 後木料吸收光，這減少向回反射進入光頭檢測器的光之 強度。反應層中的光吸收度Α可用朗伯-比爾 Lambert)定律計算 A = -loga/l。）=ecl (公式 4) /、中I,為入射到反應層的光，ε為染料的莫耳吸光係數（在 不米對亞甲藍為約54000升/莫耳釐米」），1為反應層 之厚度，且c為隨時間而變化的染料之濃度。因此，對於 95607.doc •25· 1357599 利用光吸收反應層之有限運轉光碟，其中光在 吸收層中吸收，反射率尺可由以下關係估計： R = I/I〇 = RMlO(_2ecl)(公式 5) 利用公式5,可計算取得特定反”所需的 :反，層厚度。例如，在其中反應層厚度為3微米之： ““ 〇.027莫耳/升之濃度存在於反應 曰中’先碟之反射率在無光吸收染料下為7〇%，則利用光 吸收染料的光碟之預測反射率為丨〇%。 可首先用能夠充分混合各種前驅體之習知反應器形成基 材’如單或雙螺桿擠壓機、捏和機、捧合機或類似者，由 此產生資料儲存媒介。擠壓機應保持在足夠高溫度，以使 基材前驅㈣融’而不使其分解。在擠壓機中的返留時間 應類似控制到使分解最低化。可利用至高約2分鐘（分）或更 長之逗留時間，較佳至高約i 5分鐘，至高⑴分鐘尤佳。 在擠壓成所需形狀前(一般為丸粒、片、網或類似者），可 視需要過濾混合物，如熔融過濾、使用網包或其組合或類 似者，以除去不合乎需要的污染物或分解產物。一旦產生 塑膠組合物，可用各種模製技術、加工技術或其組合使其 形成基材。可能的技術包括注模、薄膜澆鑄、擠壓、壓 模、吹模、衝壓及類似者。一旦基材產生，可利用額外處 理在基材上設所需層，如電鍍、塗覆技術（如，旋塗，喷 塗、蒸氣沈積、絲網印刷、塗漆、浸潰及類似者）、層 合、濺鍍和類似者以及至少一種前述處理技術之組合。基 材一般具有至高約6〇〇微米之厚度。 95607.doc •26· 1357599 在一具體實施例中，有限運轉光學資料儲存媒介包括注 模的聚歹基丙稀酸醋第一基材。可在第一基材上設的各種 其他層包括-或多個資料層、彳電層、反應層、點著劑 層、反射層、保護層、第二基材層、光吸收層。 在施加反應層之前，_般使欲在其上設反應層的多層之 組合件脫氣。例如’其上欲設反應層的組合件可由經模製 的第-基材、資料層及反射層組成。去氧化作用—般藉由 在惰性環境對組合件施加反應層取得。此外，用於產生反 應層的反應劑-般在惰性環境中保持。在已產生有限運轉 光學儲存媒介後，應將其保持在惰性環境，直到準備用於 使用。去氧化作用一般用惰性氣體進行，例如氮氣、氣 氣、氦氣或二氧化礙。 用於資料的有限運轉光學儲存媒介可包括一或多個保 層，該層針對塵埃、油及其它污染物提供保護。保護層一 般具有在約ίο埃（A)和約100微米（/〇間範圍之厚度。約 埃或更小之厚度尤佳。保護層之最佳厚度通常至少部分由0 所用讀/寫機制類型決定，例如，磁、光或磁_光。除其他 外’可能的保護層包括抗腐银物質，如金、銀、氮化物 (例如，氮化矽和氮化鋁）、碳化物（例如，碳化矽及其它 者）、氧化物（例如，二氧化矽及其它者）、聚合物質 如，聚丙烯酸酯或聚碳酸酯）、碳薄膜（例如，金剛石、金 剛石樣碳及類似者）及包含至少一種前述物質之組合。、 用於資料的核運轉光學儲存媒介可包括一或多〇個介電 層’該層一般設於資料層的一側或雙側上，且經常用作熱 95607.doc -27· 1357599 控制器。介電層-般具有在約酬埃（A)和約ι测埃間範圍 ，厚度。在某些情況下，具有小於2〇〇埃厚度之介電層可 咸較佳。在環境内相容且較佳不與周圍層反應的其他材料 中’用於介電層的適合物質包括氮化物(例如，氮化矽、 乳化紹及其匕者）、氧化物（例如，氧化紹）、硫化物（例 如’硫化鋅）、碳化物（例如’碳切）及包含至少—種前 物質之組合。 亦可存在能夠黏著任何上述層組合之黏著劑層。黏著劑 層包括任何能夠形成由氧滲透之層且實質不妨礙光自資料 檢索裝置通過媒介並達到資料檢索裝置之物質（例如，在 裝。置所用的光波長實質透明及/或使自媒介的反射率約為 50%或更大，百分反射率較佳為約或更大，更佳約 75/。或更大)。黏著劑層可視需要為反應層，即可包含氧 敏感陡木料。可能的黏著劑物質包括UV物質，如丙烯酸 S曰（例如’經交聯的丙稀酸g|及類似者）、碎硬塗層和類似 :以及包含至少一種前述物質之反應產物及組合。W物 。貝的八他實例描述於美國專利第4,179,548號及第 '州，則 用於製備黏著劑層中所用黏著劑的一些有用單丙烯酸 醋单體包括丙烯酸丁酿 '丙烯酸己酿、丙烯酸十二烷醋及 類4者 些有用的多官能丙烯酸酯單體包括（例如）二丙 烯=、三丙稀酸西旨、四丙稀酸酿及其組合。 *著Μ層可何生自單一多官能丙烯酸酯單體或丙烯酸酯 單體之叱合物。經發現，較佳黏著劑層組合物一般為包含 至少兩種多官能丙烯酸酯單體(較佳二丙烯酸酯及三丙烯 95607.doc 1357599 酸酯）之混合物之uv光誘導的反應產物者。但，單丙烯酸 酯單體在特定例中可能較佳。黏著劑塗層可視需要包括占 未固化黏著劑塗層至高約50重量％之量之非丙烯酸系11乂可 固化脂族不飽和有機單體，包括此類物質，如Ν-乙烯基吡 咯啶酮、苯乙烯和類似者以及包含至少一種前述物質之反 應產物及組合。 當黏著劑層包含丙烯酸酯單體之混合物時，二丙稀酸醋 與二丙烯酸酯之重量比較佳在約1 〇/9〇和約9〇/丨〇間之範圍 内。二丙烯酸酯和三丙烯酸酯之典型混合物包括己二醇二 丙烯酸酯與四級戊四醇三丙烯酸酯、己二醇二丙烯酸酯與 二經甲基丙燒三丙烯酸酯、二乙二醇二丙烯酸酯與四級戍 四醇三丙烯酸酯以及二乙二醇二丙烯酸酯與三羥甲基丙烷 三丙婦酸酯及類似者之混合物。 黏著劑層亦可包括光敏量的光引發劑，即，有效影響黏 著劑塗層光固化之量。以黏著劑塗層之總重量計，此量一 般包括約0.01重量％(較佳約01重量至約1〇重量％(較佳 約5重量％)。可能的光引發劑包括在暴露於UV輻射時形成 適合硬塗層之酮類型及位阻胺類型物質之摻合物。網化合 物與位阻胺化合物之重量比可較佳在約8〇/2〇和約2〇/8〇間 之範圍内。約50/50或約60/40混合物一般令人滿意。 較佳用於非氧化氣氣（如’氮氣）的其他可能鲷類型光引 發劑包括二笨甲酮和其他苯乙酮、二苯基乙二酮、笨甲酿 及鄰氯苯甲醛、咕噸酮、噻噸酮、2_氣噻噸酮、9,丨〇_菲 醌、9,1 〇-蒽醌、甲基二苯甲醇酮醚、乙基二苯甲醇_醚' 95607.doc -29- 1357599 異丙基二苯甲醇酮醚、α，α-二乙氧基苯乙酮、α，α_: 甲氧基苯乙酮、1-笨基_1，2-丙二醇-2-0-苯甲醯肟、α，α 一甲氧基_α -苯基苯乙酮、氧化膦及類似者。進一步包括 包含至少一種前述光引發劑之反應產物及組合。 黏著劑層亦可視需要包括平光劑、界面活性劑、觸變 劑、UV光穩定劑、υν吸收劑及/或穩定劑（如，間苯二酚 單苯甲酸酯、2-曱基間苯二酚二苯甲酸酯）和類似者及包含 至少一種前述添加劑之組合及反應產物。以未固化UV層 之重量計’穩定劑可以約〇. 1重量％(較佳約3重量％)至約j 5 重量％之量存在。 實例 以下實例用如何進行及評估本發明所請求方法之詳細描 述提供此項技藝上的一般技術，不應用於限制本發明者認 作為發明之範圍。 製備利用反應層的有限運轉DVDs之方法 比較實例1 在瓶中將60克自依紐斯丙烯酸材料公司（Ine〇s Acrylics} 的ELVACITE 2010聚（甲基丙稀酸曱酯）力口入3〇〇克1甲氧 基-2-丙醇，並在輥轉機上滾動，以實現溶解，由此製備 PMMA溶於1 ·甲氧基_2_丙醇之溶液。將溶液轉移到燒瓶， 並加熱到約80 C ’同時使緩慢氮氣流在溶液表面上通過。 用氮氣壓將經脫氣的溶液轉移到經脫氣的瓶，瓶用套管以 橡膠隔膜封閉。 在用橡膠隔膜裝配的1〇〇毫升燒瓶中，使12克三水化亞 95607.doc •30· 1357599 曱藍和0·80克樟腦項酸與4〇克丨_甲氧基_2_丙醇混合，由此 製備無色亞甲藍溶液。將經攪拌的混合物在9〇。匸水浴中加 熱，同時用用於氮氣入口和出口的注射器針使氮氣流通入 燒瓶。在熱時，由注射器加入4 2毫升2_乙基己酸錫（π)， 以使亞曱藍還原成暗號#色無色亞甲藍。將自Βγκ化學公 司（BYK Chemie)的〇.6毫升流動添加劑Βγκ·3〇i加入該溶 液。為產生PMMA/無色亞曱藍塗料溶液，將以上無色亞甲 藍溶液引入注射器，然後在已通過 _ 微未注射濾器後注 入PMMA溶液。 比較實例2 此比較實例說明用夾層結構製備先前技藝 比較實例1製備，但使用以下量的原料。 碟 /谷液如 重量(克) 67.1 !5.2 15.2 〇.〇 重量(克) 0.66 0.28 !4.87 2.85 0.15 PMMA溶液 DOWANOL PM[克] 全部 Elvacite[克]
Elvacite 2008 :
Elvacite 20 10 : 染料溶液 三水化亞曱藍[克] 樟腦磺酸[克] DOWANOL PM[克] (DOWANOL與染料溶液之比為5:1) 氯化亞錫 FLUORAD 5 0% 固體 FC-431 [毫升] 95607.doc 31 . 1357599 利用旋塗器在800轉/分鐘經60秒用溶液將PMMA/無色亞 曱藍底漆塗覆到0.6毫米金屬化的BPA·聚碳酸酯DVD第一 基材。發現平均塗層厚度為約3微米。在氮氣室過夜儲存 一個具有PMMA/無色亞甲藍底漆之光碟後，使UV樹脂 Daicure SD-640在薄環中分配到預先塗覆的金屬化DVD第 一基材之中部。然後，用UV樹脂環將未金屬化的BPA-聚 碳酸酯第二基材置於第一基材光碟頂上。使夹層結構在 1000轉/分鐘旋轉10秒，以均勻分配UV黏著劑。然後使夾 層結構在閃光氙UV燈下通過25秒。在暴露於空氣及反射 率動力學測量之前，使該夾層結構在氮氣室中儲存至少48 小時。 比較實例3 本比較實例說明製備本發明之有限運轉光碟。如實例2 中所述製備有限運轉光碟。但用自BPA/DMBPC/DDDA三 元共聚物（莫耳比49:49:2)模製的未金屬化第二基材代替 BPA-PC基材。金屬化的第一基材亦自BPA/DMBPC/DDDA 三元共聚物模製。合成三元聚碳酸酯描述於美國專利第 6395364號。 比較實例4 如比較實例2中所述製備有限運轉光碟。但用自DMBPC 同聚物模製的未金屬化第二基材代替BPA-PC基材。金屬 化的第一基材自BPA/DMBPC/DDDA三元共聚物模製。 比較實例5 如比較實例2中所述製備有限運轉光碟。但用自DMBPC- 95607.doc -32- 1357599 聚碳酸酯和BPA-聚碳酸酯之摻合物模製的未金屬化第二基 材代替BPA-PC基材。在一種摻合物中，組合物為75重量％ DMBPC-聚碳酸酯和25重量％ΒΡΑ-聚碳酸酯；在另一種摻 合物中，組合物為50重量％DMBPC-聚碳酸酯和50重量％ BPA-聚碳酸酯。金屬化的第一基材自BPA/DMBPC/DDDA 三元共聚物模製。 比較實例6 如比較實例2中所述製備有限運轉光碟。但用自DMBPA-聚碳酸酯和BPA-聚碳酸酯之摻合物模製的未金屬化第二基 材代替BPA-PC基材。在一種摻合物中，組合物為25重量％ DMBPA-聚碳酸酯和75重量％ BPA-聚碳酸酯；在另一種摻 合物中，組合物為50重量％ DMBPA-聚碳酸酯和50重量％ BPA-聚碳酸酯。金屬化的第一基材自BPA/DMBPC/DDDA 三元共聚物模製。 比較實例7 如比較實例2中所述製備有限運轉光碟。但用自PMMA (ACRYLITE DQ501，CYRO工業公司（CYRO Industries))模製 的未金屬化第二基材代替BPA-PC基材。金屬化的第一基 材自BPA/DMBPC/DDDA三元共聚物模製。 使自比較實例2-7的經塗覆光碟在環境條件下保持，在 此期間，用DR. SHENK PROmeteus儀器MT-136E型時時測 量平均反射率％。在反射率％下降時，光碟顏色自基本無 色變藍。用具有不同組合物的未金屬化基材之夾層配置製 備之有限運轉DVDs(比較例2-7)之反射率時間動力學顯示 95607.doc -33- 1357599 於圖1中。圖1中所示的所得此系列之反射率動力學說明， 可用未金屬化基材的不同組合物對有限運轉DVD設計一定 範圍的失效時間。在聚碳酸酯共聚物或摻合物中存在較高 /辰度DMBPC或DMBPA時，失效時間顯示增加。相對於 BPA-聚碳酸醋，這與彼等材料的較低氧滲透率一致。不同 聚碳酸酯和聚甲基丙烯酸酯的氧滲透率列於表丨中。圖i亦 顯示，由PMMA同聚物未金屬化光碟組成的樣品之反射率 動力學比由不同聚碳酸酯組成的樣品緩慢得多。PMMA同 聚物樣品的失效時間長得不可接受，即使在2星期後仍可 運轉。這顯示，相對於PMMA同聚物，仍需要具有增加氧 滲透率的本發明之組合物。 同時解以上公式2-5，以預測反應層中的無色染料氧化 時，有限運轉DVDs的反射率隨之降低的動力學。使用最 佳適合所觀察反射率動力學的參數，如無色染料的初始濃 度及有效速率係數keff。假定初始反射率R()為65%。選擇 邊界條件，以類比其中在未金屬化基材和黏著劑層之間設 無限小薄反應層之條件。在此等情況下，可用公式3預測 氧擴散通過未金屬化基材時反應層中氧之濃度。反射率之 時間-依賴關係在一系列類比中計算，其中基材中的氧擴 散係數自2χ1〇·8釐米秒變到1χ1〇-9釐米~秒。假定恒定氧 料度為6.69Χ1〇-3[立方餐来]/([立方髮米][髮米_，則 分別對應1.35拜爾至〇.〇67拜爾之氧滲透率。所得此系列的 反射率動力學說明’可用具有不同氧渗透率之未金屬化基 材之組合物對有限運轉DVD設計一定範圍的失效時間。土 95607.doc -34- 1357599 實例1-10及比較實例8-9 製備薄膜，以比較具有不同聚碳酸酯的不同聚甲基丙烯 酸酯之氧滲透率。將約2克聚合物溶於30毫升二氣曱烷。 然後使溶液通過0.45微米注射濾器濾入位於玻璃板上的 14.3釐米直徑開口玻璃環。與板接觸的玻璃環之表面為磨 砂玻璃，以防止聚合物溶液滲漏。在聚合物溶液上保持氮 氣氣氛，以防止在乾燥期間，濕氣冷凝在二氯甲烷溶液 中。約4至6小時後，使足夠二氣曱烷蒸發，以除去玻璃環 並使薄膜與玻璃板分離。其餘二氯甲烷由在加熱的真空烘 箱中放置薄膜數小時除去。薄膜厚度為70至100微米，此 厚度可由改變溶液中聚合物之量調節。 將薄膜樣品固定於兩個10釐米Χίο釐米鋁箔罩之間，箔 罩具有圓形5釐米2模切開口，並置於MOCON OX-TRAN 1 000儀器的擴散室。在氧氣氣氛平衡3-4小時後，由試驗 氣體（具有1%氫氣之氮氣）轉到庫侖感測器開始氧傳送速率 之測定。繼續測定，直到達到穩態氧傳送速率，一般12至 24小時0 表1.氧滲透率，在25°C，〇%相對溫度測定 實例 商品名稱 組合物 薄膜 厚度 [毫米] OTR [立方釐米/ 米2.秒] 滲透率 [拜爾] 1 LEXAN BPA-聚碳酸酯 0.055 353 1.36 OQ1030L 2 DMBPC-聚碳酸酯 0.107 15.5 0.13 3 DMBPC-PC/ BPA-PC 75/25 0.114 23.5 0.20 4 DMBPC/BPA/ DDDA 49/49/2 0.094 42.3 0.30 5 DMBPA-PC/ BPA-PC 50/50 0.064 177 0.85 95607.doc •35- 1357599 CE-8 ELVACITE PMMA 0.10 10.3 0.078 2010 CE-9 ACRYLITE PMMA 0.074 12.5 0.070 DQ501 6 CYROLITE MMA/苯乙烯/丙烯腈 0.122 128 1.186 XT8R6 三元共聚物 7 CYROLITE MMA/苯乙烯/丙烯腈 0.071 101 0.546 XTEX375 三元共聚物 8 CYROLITE MMA/苯乙烯/丙烯酸乙酯 0.107 107 0.867 G20-100 三元共聚物 9 CYROLITE MMA/苯乙烯/丙烯酸乙酯 0.061 159 0.737 G20-HF 三元共聚物 10 聚(苯乙烯-共-甲基丙烯酸甲酯） 0.097 274 0.404 表1中的資料說明，PMMA共聚物組合物（實例6-9)尤其 適用於本發明之有限運轉光學儲存媒介。資料進一步說 明，雖然PMMA同聚物不適用於本發明之有限運轉光學儲 存媒介，但可取得具有所需氧滲透率的PMMA同聚物之摻 合物，例如80重量％ MMA/苯乙烯/丙烯腈三元共聚物與20 重量％ PMMA同聚物。 雖然已顯示及描述較佳具體實施例，但可在不脫離本發 明之主旨和範圍下做出各種變更及代替。因此，應懂得， 本發明僅作為說明描述，本文已揭示的此等說明和具體實 施例不應作為限制請求項解釋。 【圖式簡單說明】 圖1描繪一系列有限運轉DVD經時間的反射率變化，各 DVD具有組成DVD第二基材層的不同材料。 -36- 95607. doc

Claims (1)

  1. 十、申請專利範圍： 學儲存媒介，其包括 1. 一種用於資料之有限運轉光 a) 第一基材； b) 反射層； 小又於該基材和該反射層間之資料層. 種載體和至少—種反應物質之反應層;及 透率之光：透月於約〇1拜爾和約h35拜爾間範圍之氧滲 迓丰之先學透明性第二基 r, m & ^ 柯其中该第二基材係設於該 反應層和雷射入射表 之間’其中該第二基材包括聚甲 基丙烯酸酯共聚物或会 A 聚甲基丙烯酸酯同聚物或共聚物 之摻合物。 2. 3. 如請求項1之有限運趙伞風 a . 轉先子儲存媒介，其中該第二基材 具有至少約100t之玻璃轉移溫度。 =求項2之有限運轉光學儲存媒介…該第二基材 匕括對應結構（I)之結構單位：
    其中Y為氫、Cl_Ci2烷基、 基，且η為1至1〇〇〇〇之整數 C4_cio芳基；烷軋 4 ‘ :請求項3之有限運轉光學儲存媒介，其中該第二基材 匕括對應結構（Π)之結構單位： 95607.doc 1^57599
    其中Y為氫、CVCu燒基、c4-c10芳基；R1為Ci_Ci2烧氧 基；R2為C4_C10芳基、C】_C】2烷氧基、氰基、硝基或鹵 素；乂和2獨立為1至10000之整數；且11為1至1〇〇〇〇之整 數。 5. 如請求項1之有限運轉光學儲存媒介，其中該第一基材 係選自由聚氣乙烯、聚烯烴、聚醋、聚醯胺、聚颯：聚 醯亞胺、聚醚醯亞胺、聚醚砜、聚苯硫、聚醚酮、聚醚 醚酮、ABS樹脂、聚苯乙烯、聚丁二烯、聚丙烯酸酯、 =甲基丙稀酸@旨、聚丙稀腈、聚、聚碳酸酿、聚伸 苯範乙烯_乙酸乙稀g旨共聚物、聚乙酸乙稀目旨、液晶聚 合物、乙烯四氟乙烯共聚物、芳族聚酷、聚敗乙烯、聚 :氟亞乙烯、聚二氯亞乙烯、四氟乙烯及包含至少—種 前述熱塑膠之混合物、# & u 、 ’、t物、反應產物及複合物所組 成之群組。 6. 如睛求項5之有限谨絲止 運轉先學儲存媒介，其中該熱塑膠句 括聚碳酸酯。 ^匕 第1項之有限運轉光學儲存媒介，其中該反庫 物質為氧敏感性染料。 龜 8. 如請求項第7項之有 有限運轉光學儲存媒介，其中該氧敏 95607.doc 感性染料係選自由無色亞甲藍、亞曱藍的還原形式 '亮 曱酚藍、鹼性藍3和甲苯胺〇所組成之群組。 〜種用於資料之有限運轉光學儲存媒介，其包括： a) 第一基材； b) 反射層； c) 設於該基材和該反射層間之資料層； d) 包括至少一種載體和至少一種反應物質之反應層；及 e) 光學透明性第二基材，其包括選自由甲基丙烯酸甲 s日苯乙烯-丙烯腈三元共聚物及甲基丙烯酸甲酯-苯乙 歸丙稀自文乙g曰二元共聚物所組成之群組之烯烴聚合物， 該烯烴聚合物在25。(：具有於約〇·2拜爾和約12拜爾間範 園之氧滲透率，其中該第二基材係設於該反應層和雷射 入射表面之間。 —種用於資料之有限運轉光學儲存媒介，其包括： a) 基本上由聚碳酸酯組成之第一基材，該聚碳酸酯具 有大於約10CTC之Tg ; b) 基本由鋁組成之反射層； c) 设於該基材和該反射層間之資料層，該資料層包括 凹凸於S亥聚碳酸酿表面上之坑及陸面； d) 包括聚（甲基丙烯酸曱酯）和無色亞甲藍之反應層； e) 光學透明性第二基材，其包括選自由甲基丙稀酸甲 酯-苯乙烯-丙烯腈三元共聚物及甲基丙烯醆甲酯-笨乙 烯-丙烯酸乙酯三元共聚物所組成之群組之烯烴聚合物， 該烯烴聚合物在25。(：具有於約〇.2拜爾和約！ 2拜爾間範 95607.doc 1357599 圍之氧滲透率，其中該第二基材係設於該反應層和雷射 入射表面之間。 95607.doc
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US20030198892A1 (en) * 2002-04-22 2003-10-23 General Electric Company Limited play data storage media and method for limiting access to data thereon
US20030207206A1 (en) * 2002-04-22 2003-11-06 General Electric Company Limited play data storage media and method for limiting access to data thereon
US6866909B2 (en) * 2002-09-04 2005-03-15 General Electric Company Limited play data storage media and method for limiting access to data thereon
US7223520B2 (en) * 2003-02-03 2007-05-29 General Electric Company Limited play optical media device with barrier layers

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EP1671323B1 (en) 2008-08-20
ATE405928T1 (de) 2008-09-15
WO2005027111A1 (en) 2005-03-24
TW200522049A (en) 2005-07-01
US7226720B2 (en) 2007-06-05
DE602004016018D1 (de) 2008-10-02
EP1671323A1 (en) 2006-06-21
US20050053865A1 (en) 2005-03-10
WO2005027111A8 (en) 2006-05-11
JP2007505435A (ja) 2007-03-08
KR20060120010A (ko) 2006-11-24

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