TWI307713B - Compositions, systems, and methods for imaging - Google Patents
Compositions, systems, and methods for imaging Download PDFInfo
- Publication number
- TWI307713B TWI307713B TW092122241A TW92122241A TWI307713B TW I307713 B TWI307713 B TW I307713B TW 092122241 A TW092122241 A TW 092122241A TW 92122241 A TW92122241 A TW 92122241A TW I307713 B TWI307713 B TW I307713B
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- activator
- dye
- imaging
- receiver
- composite material
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- 238000003384 imaging method Methods 0.000 title claims description 31
- 238000000034 method Methods 0.000 title claims description 18
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- QKJAZPHKNWSXDF-UHFFFAOYSA-N 2-bromoquinoline Chemical compound C1=CC=CC2=NC(Br)=CC=C21 QKJAZPHKNWSXDF-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B23/00—Record carriers not specific to the method of recording or reproducing; Accessories, e.g. containers, specially adapted for co-operation with the recording or reproducing apparatus ; Intermediate mediums; Apparatus or processes specially adapted for their manufacture
- G11B23/38—Visual features other than those contained in record tracks or represented by sprocket holes the visual signals being auxiliary signals
- G11B23/40—Identifying or analogous means applied to or incorporated in the record carrier and not intended for visual display simultaneously with the playing-back of the record carrier, e.g. label, leader, photograph
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
- B41M5/323—Organic colour formers, e.g. leuco dyes
- B41M5/327—Organic colour formers, e.g. leuco dyes with a lactone or lactam ring
- B41M5/3275—Fluoran compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
- B41M5/333—Colour developing components therefor, e.g. acidic compounds
- B41M5/3333—Non-macromolecular compounds
- B41M5/3335—Compounds containing phenolic or carboxylic acid groups or metal salts thereof
- B41M5/3336—Sulfur compounds, e.g. sulfones, sulfides, sulfonamides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
- B41M5/46—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography characterised by the light-to-heat converting means; characterised by the heat or radiation filtering or absorbing means or layers
- B41M5/465—Infrared radiation-absorbing materials, e.g. dyes, metals, silicates, C black
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
- B41M5/42—Intermediate, backcoat, or covering layers
Landscapes
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Heat Sensitive Colour Forming Recording (AREA)
- Optical Record Carriers And Manufacture Thereof (AREA)
- Paints Or Removers (AREA)
- Ink Jet Recording Methods And Recording Media Thereof (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
- Adhesives Or Adhesive Processes (AREA)
Description
1307713 玖、發明說明： 【發明戶斤屬之技術領域】 發明領域 本發明係有關用於成像之組合物、系統及方法。 5 【先前技術】 發明背景 在諸如光或熱的能量刺激之際產生顏色變化的材料， 可能具有成像用途。例如，可在熱印紙與立即成像薄膜中 發現該等材料。一般而言，目前已知的材料與組合物可能 10 需要多層膜結構，及需要進一步的處理以產生影像(如立即 成像薄膜諸如拍立得(Polaroid))。在傳真與感熱頭媒體之情 況下，需要大於1焦耳/平方公分之能量輸入以產生良好的 影像。多層膜媒體中的組合物可能需要控制成色化學物質 的擴散作用及需要進一步的處理，及係位於分開的相與層 15 中。大部分的感熱與傳真紙塗層包含藉由製造二種以上組 份的細微分散而製備之塗層。在施用能量之際，該等組份 混合與反應，而產生一有色物質。為達成所需的混合作用， 三或更多相或層的顆粒必需接觸及合為一個新層。因為該 等多重相與層，故需要高能量以進行該製程。例如，可能 20 需要能量密度為3焦耳/平方公分之相當強力的二氧化碳雷 射遠大於100微秒的時間，以產生一標記。在一些情況下， 高能量之使用可能導致成像基材的損傷。在許多情況下， 較有效率地使用強度較低、功率較小及/或較短時間的能量 使用以產生一可見標記，可能為有利的。因此，需要快速 1307713 標記塗層，其可能由少於三相所組成及處於單一層中。可 藉由輻射作用，特別是在少於100微秒的時間輸送能量密度 低於1焦耳/平方公分者，所引發與選址之單一層成色物 質，迄今尚屬未知。 5 【發明内容】 發明概要
在此揭露成像材料及用於製造成像材料的方法。在此 所揭露的材料可包括同時分散於一基質中之一接收體、一 成色劑及一活化劑。成色劑與活化劑係以二個分開的相存 10 在於成像材料中。接收體即可吸收依成影像方式施用於成 像材料之能量。所吸收的能量加熱該混合物，造成該成色 劑與活化劑混合與反應，而導致成色劑的顏色改變及產生 一標記。 圖式簡單說明 15 就本發明實施例的詳細說明而言，現在將參照所附圖
式，其中： 第1圖顯示用於製備如本發明實施例的一成像材料之 一種方法。 第2圖顯示如本發明的一實施例之一成像媒體。 20 符號與命名原則 在下列說明部份與申請專利範圍中所用的一些辭彙， 係指特定的系統組份。嫻熟技藝者將瞭解該等組份在不同 公司的名稱可能不同。本文件無意區分該等名稱不同但功 能相同的組份。在下列論述部份與申請專利範圍中，“包括” 6 1307713 與“包含”等詞係以開放方式使用，及因此應解釋為“包括但 不限於.…”。“無色染料”一詞係指一種成色物質，其在非活 化狀態為無色或單色，而在活化狀態產生或改變顏色。如 用於此，“活化劑”一詞係指一物質，其與無色染料反應而 5 使得該無色染料改變其化學結構及改變或產生顏色。舉例 而言，活化劑可為可達成該項變化之酚類或其他質子供給 性物種。“接收體”一詞係指任一種輻射吸收物料，該接收 體即可吸收標記輻射之所欲的特定波長。 I：實施方式3 10 較佳實施例之詳細說明 下列論述係有關本發明的不同實施例。所揭露的實施 例不應視作或以其他方式用作限制包括申請專利範圍的揭 露内容之範疇，除非另外說明之。此外，嫻熟技藝者將瞭 解下列說明部份具有廣泛的適用性，及任一實施例的論述 15 僅意欲作為該實施例的例示部份，而非意欲表示包括申請 專利範圍的揭露内容之範疇係受限於該實施例。 本發明的實施例包括塗層，當以在45 mw運作的780奈 米雷射進行標記時，該塗層產生透明標記及極佳的影像品 質。用以在能量刺激時產生顏色變化之材料，可包括一成 20 色劑諸如螢烧無色染料(fluoran leuco dye)與一活化劑諸如 磺醯苯酚，其等係分散在施用於一基材上的一基質諸如輻 射固化型丙烯酸酯寡聚物與單體中。在特定的實施例中， 無色染料或活化劑在環境條件下可能實質不溶於該基質。 在塗層中亦存在一種有效率的輻射能吸收劑，其作用係吸 1307713 收能量及將其傳送至反應物。能量則可藉由例如雷射或紅 外線的方式施用。在施用能量之際’活化劑或成色劑或二 者受熱及混合，使得成色劑活化及產生一標記。 現在參照第2圖所說明之實施例，其顯示成像媒體 5 100、能量110、基材12〇、成像組合物130及懸浮顆粒140。 成像媒體100可包含一基材120。基材120可為在其上欲製造 一標記之任一基材，舉例而言諸如紙張(如標籤、票券、收 據或文具）、投影片或—媒體諸如CD-R/ROM或 DVD-R/RW/ROM的力口標記表面。 10 成像組合物130可包含一基質、一活化劑、一輻射吸收 物料諸如-染料以及一成色染料。當活化劑與成色染料混 合％，可改變顏色。活化劑或成色染料可溶於基質中。其 他組份（活化劑或成色染料）可實質上不溶於基質，及可以均 一分布的顆粒M0之形式懸浮於基質中。成像組合物13〇可 15經由任-可接受的方法施用至基材，例如諸如親式、喷霧 式或網目印刷。 能量110可以成影像方式導向成像媒體1〇〇。能量的形 式可依可取得的設備、環境條件及所欲的結果而異。適用 的能量實例包括紅外線輻射、紫外線幸畐射、X射線或可見 20光。接收體可吸收該能量，及加熱成像組合物130。該敎使 得懸浮顆粒14〇達到足以造成最初存在於顆粒中的成色物 種相互擴散之一溫度（如顆粒14〇與基質的玻璃態化溫度 (Tg)或炫點(Tm))。活化劑與染料，然後可反應而形成顏色。 第1與2例說明本發明的例示性實施例。可進行位於本 8 1307713 發明範疇内之數項修飾。例如，接收體60可為任一材料， 其可有效吸收施用於成像媒體以製造一標記之能量類型。 舉例而言，下列物料可為適用的接收體：IR780(Aldrich 42,531-1)(1) ' IR783(Aldrich 54,328-2)(2) ' Syntec 9/1(3) > 5 Syntec 9/3(4)或金屬錯合物（諸如二嘍茂烧金屬錯合物（5)及 碘代苯胺金屬錯合物（6))。
9 1307713
Ri
其中^^為一過渡金屬，心、R2、尺3與尺4為具有或不具 有鹵代基取代基之烷基或芳基，及Al、A2、A3與A4可為硫、 SH或硒；
其中M2為鎳或銅，R5#R6為具有或不具有鹵代基取代 基之芳基或烷基。 接收體的其他實例可見於Matsuoka, Masaru編輯及 Plenum Press公司於1990年出版之“紅外線吸收性染料，，乙 10 書（ISBN 0-306-43478-4)及Daehne，S.、Resch-Genger, U.、 Wolfbeis，Ο.編輯及Kluwer Academic Publishers公司出版之 “用於高科技用途之近紅外線染料，，乙書（ISBN 0-306-43478-4) ’ 一者在此併入本案以為參考資料。 活化费K如雙酌"-A)與成色染料9〇(如bK_4〇〇)可以串聯 15方式作用以產生一標記。活化劑與染料可為當一起反應時 產生顏色變化之任一種物質。當反應時，活化劑可起始染 10 1307713 料中的顏色變化或使染料顯色。活化劑與染料中 環境條件下可溶於基質(如快乾漆聊另—^一者在 可實質上不溶於快乾漆。“實質上不溶，，係指另 條件下在快乾料㈣解度料低，藉此料料·^ 妙如 仏微的顏色變化。雖 Μ在上述的實施例中，在環境條件 而染料仍以mu形式懸浮於基.化j可溶於快乾漆 可溶於基質巾m胸以_ 而在％境條件下染料 ,. 圯式懸浮之情況，亦為可 接叉的。在不限於此之情況下，活 10 15
化劑可包括質子供給體 及酉分類化合物諸如雙齡-A盘雙齡Q 、 6。在不限於此之情況 下’成色劑可包括無色染料諸如替 資埃·無色染料及苯酞成色 劑，如述於麻yala，Ramiah編輯及ρι瞻⑺p麗公司於 年出版之“無色染料化學及應用”乙書（細 議携9·9)，其在此併人本“為參考資料。可接受的 螢烧無色染料包括化學式(7)所示之社構·
R ⑺ 其中Α與R為芳基或烧基。 快乾漆30可為用於溶解及/或分散活化劑、接收體及成 色劑之任-適宜基質。舉例而言，可接受的快乾漆可包括 2〇具有一個光包裝之紫外線固化型基質諸如丙稀酸酷衍生 11 1307713 物寡聚物及單體。光包裝可包括一種吸光物種，其引發 ! 夬乾漆例如諸如二笨甲酮衍生物的固化作用之反應。用於 自由基聚合早體與預聚合物之光引發劑的其他實例，包括 不限方、·彳'了生物、蒽騎生物、乙醯苯及二苯乙醇酮喊 ;頁^擇藉由造成顏色變化的輕射類形以外之輕射形式加 以固化之一某暂 土貝’可能為有利的。以陽離子聚合樹脂為主 的基質可月匕而要以芳香族重氮鹽類、芳香族歯鐵鹽類、芳 香知硫1羽鹽鎖及金屬茂化合物為主的光引發劑。可接受的 W乾漆或基質之—實例可包括Nor-Cote CDGGGG(紫外線固 W化型丙烯_單體及寡聚物之一混合物），其含有1引發 劑(經基酮)及有機溶劑丙稀_(如曱基丙稀酸甲⑽、; 基丙稀酉文己基酷、苯氧基乙基丙烯酸酷及六亞甲基丙稀 西义®曰）。其他可接受的快乾漆或基質可包括丙烯酸 聚物，諸如可自薩托默（Sartomer)公司取得之CN2931 !5 CN294。 /、 實例 第1例 參照第1圖之音s ±1 、、_<貫施例，顯示用於製備如本發明實施例的 20 i液之#方法；該方法可包括-活化劑溶化物 純劑/接收體溶卿、—紫外_化型快乾漆溶液 、一快乾漆/接收體/活化劑溶液40及一種兩相紫外線固化 i糊50在弟i圖所示的實施例中，將2克草酸二节酷加熱 ^化（、’恤C )。將2{)克活化劑雙IA與】克接收體I讀 岭方'这化的傾H中。將活化劑/接收體溶液2〇冷卻， 12 1307713 及研磨成細微粉末70。 將5克經研磨的活化劑/接收體粉末7〇溶於153克 N〇r-Cote CDG_紫外線型快乾漆3〇(紫外線固化型丙稀酸 醋單體及寡聚物之-混合物）中，以形成快乾漆/接收體/活 化劑溶液40，及在其中添加14.5克BK-400無色染料9〇(可自 Nagase公司取得之2，_苯胺_3，_曱基_6，·（二丁基胺基）螢 烷’其結構係如下列化學式8所示）： r>-Bu
I n*Bu—_ —[yj
(平均顆粒尺寸小於5微米）及1.9克純的雙酚_A(平均顆 1〇粒尺寸小於5微米）。使該混合物成為一細微糊狀物，及以 約7微米之厚度網目印刷至一基材上，以形成一成像媒體 (未顯示）。媒體上的塗層然後藉由水銀燈進行紫外線固化作 用。 在所產生之經塗覆的基材上，以45 mW雷射完成直接 15 標記作用。使用能量約20微秒至100微秒，而產生約20微米 X 45微米之一標記。當在成像媒體上標記所欲的影像時， 發生直接標記作用，而毋需立即使用印刷作用。 第2例 參照第2圖之實施例，將2克草酸二苄酯加熱至熔化（約 13 1307713 85°C)。將20克活化劑TG-SA(苯酚，4,4’-磺醯基雙[2-(2-丙 稀基)-(9Cl)]化學式（9)):
OH 〇
II -s-
II 〇 HO* ⑼ 及1.2克接收體溶於熔化的草酸二节酯中。將活化劑/ 5 接收體溶液20冷卻，及研磨成細微粉末70。 將1.8克經研磨的活化劑/接收體粉末70溶於15.3克 Nor-Cote CDG000紫外線型快乾漆30中，以形成快乾漆/接 收體/活化劑溶液40，及在其中添加15克S-205無色染料 90(可自Nagase公司取得之2-苯胺-3-甲基-6-(N-乙基-N-異 10 戊基胺基）螢烷)(化學式（10)):
(平均顆粒尺寸小於5微米）及2.0克純的雙酚-A(平均顆 粒尺寸小於5微米）。使該混合物成為一細微糊狀物，及以 約7微米之厚度網目印刷至一基材上，以形成一成像媒體
]4 1307713 (未顯示）。媒體上的塗層然後藉由水銀燈進行紫外線固化作 用。使用能量約60微秒至100微秒，而產生約20微米X 45微 米之一標記。 上述論述係意欲說明本發明的原理與不同的實施例。 5 嫻熟技藝者一旦完全瞭解上述揭露内容，則將明白數值方 面的變異與修飾。下列申請專利範圍係意欲涵蓋所有的該 等變異與修飾。 I：圖式簡單說明】 第1圖顯示用於製備如本發明實施例的一成像材料之 1〇 —種方法。 第2圖顯示如本發明的一實施例之一成像媒體。 【圖式之主要元件代表符號表】 10…活化劑熔化物 90…成色染料 20···活化劑/接收體溶液 100···成像媒體 30···紫外線固化型快乾漆溶液 110…能量 40···快乾漆/接收體/活化劑溶 120…基材 液 130···成像組合物 50…兩相紫外線固化型糊 140…懸浮顆粒 60…接收體 70···活化劑/接收體粉末 15
Claims (1)
1307713 第92122241號專利申請案申請專利範圍修正本 95.01.03 拾、申請專利範圍： 1. 一種直接成像複合物料，其包括： 一基質； 一溶於該基質中之接收體； 5 一成色劑；及 一活化劑； 其中該活化劑與該成色劑中之一者在環境條件下 溶於該基質或基質前驅物中； 其中該活化劑與該成色劑中之可溶者係溶解於該 10 基質中； 其中該活化劑與該成色劑中之其它者係實質上均 一地分布於該基質中。 2. 如申請專利範圍第1項之複合物料，其中該成色劑包括 至少一種選自下列所組成之群中的物料：一無色染料與 15 一苯醜染料。 3. 如申請專利範圍第1項之複合物料，其中該活化劑包括 一驗類化合物。 4. 如申請專利範圍第1項之複合物料，其中該接收體包括 至少一種選自下列所組成之群中的物料：苯醌、酞菁、 20 萘献菁、金屬錯合物、偶氮、克羅克尼(croconium)、史 葵林(squarilium)染料、六官能聚酯寡聚物；及由下列化 學式所代表的化合物： 16 1307713
5. 如申請專利範圍第1項之複合物料，其中該接收體經調 整而即可吸收雷射輻射。 6. 如申請專利範圍第1項之複合物料，其中該實質上不溶 5 的組份包括具有一平均直徑不超過約20微米之顆粒。 7. 如申請專利範圍第1項之複合物料，其中該直接成像複 合物料包括3重量％至90重量％的固態顆粒。 8. —種影像記錄媒體，該媒體包括一基材及如申請專利範 17 1307713 圍第1至7項之直接成像複合物料中的任—者，且其中該 成像材料係直接或間接施用於該基材上。 9. -種用於製備—直接成像材料之方法，該方法包括： 提供-黏合m ―顯色劑及—接收體，其 中該染料當無色紅應時改變顏色，其中歸料與顯 色刈中之一者在環境條件溶於該黏合劑中； 將該接收體與可溶於黏合劑之物料溶解於該黏合 劑中； ▲將該染料與顯色劑中之其它者實質均一地分布於 5亥黏合劑中。 10·如申請專利範圍第9項之方法，其中該染料包括一無色 染料。 Π·如申請專利範㈣9項之方法，其中色劑包括-齡 類化合物。 12.如申請專利範圍第9項之方法，其中該接收體包括至少 種選自下列所組成之群中的物料：苯醒、醜菁、茶欧 菁、金屬錯合物、偶氮、克羅克尼㈣c〇mum)、史葵林 (squarilium)木料、六官能聚醋寡聚物；及由下列化學式 所代表的化合物： 1307713
13. 如申請專利範圍第9項之方法，其中該實質上不溶的組 份包括具有一平均直徑不超過約20微米之顆粒。 14. 如申請專利範圍第9項之方法，其中該直接成像材料包 5 括3重量％至90重量％的固態顆粒。 15. —種成像組合物，其係藉由如申請專利範圍第9至14項 之方法中的任一者所製成。 ]6. —種影像記錄媒體，該媒體包括一基材及一直接成像材 19 1307713 料，其中該直接成像材料係藉由如申請專利範圍第9至 14項之方法中的任一者所製備，且其中該成像材料係直 接或間接施用於該基材上。 20
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| US6613716B2 (en) * | 2001-02-13 | 2003-09-02 | Miami Wabash Paper Llc | Thermal print paper and process |
| AU2002241328B2 (en) | 2001-04-04 | 2005-01-20 | Nippon Soda Co., Ltd. | Recording material and recording sheet |
| JP2002347352A (ja) | 2001-05-25 | 2002-12-04 | Nippon Paper Industries Co Ltd | レーザー記録型感熱記録体 |
| US7172991B2 (en) | 2001-10-11 | 2007-02-06 | Hewlett-Packard Development Company, L.P. | Integrated CD/DVD recording and labeling |
| US6894000B2 (en) * | 2002-04-26 | 2005-05-17 | Kodak Polychrome Graphics Llc | Method for preparing imaged members and imaged members prepared thereby |
| US6974661B2 (en) | 2003-01-24 | 2005-12-13 | Hewlett-Packard Development Company, L.P. | Compositions, systems, and methods for imaging |
| CA2514194A1 (en) | 2003-01-24 | 2004-08-12 | Hewlett-Packard Development Company, L.P. | System for labeling a substrate and method of labeling an optical disk |
-
2003
- 2003-01-24 US US10/351,188 patent/US6974661B2/en not_active Expired - Fee Related
- 2003-02-10 US US10/365,186 patent/US7270865B2/en not_active Expired - Fee Related
- 2003-07-31 TW TW092120972A patent/TWI316076B/zh not_active IP Right Cessation
- 2003-08-04 MY MYPI20032925A patent/MY136847A/en unknown
- 2003-08-13 TW TW092122241A patent/TWI307713B/zh not_active IP Right Cessation
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2004
- 2004-01-23 WO PCT/US2004/001809 patent/WO2004067653A2/en active Application Filing
- 2004-01-23 CN CNB2004800027403A patent/CN100393532C/zh not_active Expired - Fee Related
-
2005
- 2005-07-04 ZA ZA200505404A patent/ZA200505404B/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| CN100393532C (zh) | 2008-06-11 |
| US7270865B2 (en) | 2007-09-18 |
| US20040146812A1 (en) | 2004-07-29 |
| CN1741910A (zh) | 2006-03-01 |
| TW200413512A (en) | 2004-08-01 |
| ZA200505404B (en) | 2006-06-28 |
| MY136847A (en) | 2008-11-28 |
| WO2004067653A2 (en) | 2004-08-12 |
| US6974661B2 (en) | 2005-12-13 |
| TW200413476A (en) | 2004-08-01 |
| TWI316076B (en) | 2009-10-21 |
| US20040147399A1 (en) | 2004-07-29 |
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