TW201137051A - Hydrazide chelate complex compound and optical recording medium using same - Google Patents

Hydrazide chelate complex compound and optical recording medium using same Download PDF

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TW201137051A
TW201137051A TW100105051A TW100105051A TW201137051A TW 201137051 A TW201137051 A TW 201137051A TW 100105051 A TW100105051 A TW 100105051A TW 100105051 A TW100105051 A TW 100105051A TW 201137051 A TW201137051 A TW 201137051A
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Wataru Satou
Rieko Fujita
Takeshi Nakamura
Kenichi Satake
Hisashi Shoda
Naoyuki Uchida
Takashi Miyazawa
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Mitsubishi Kagaku Media Co Ltd
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    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
    • C07D233/61—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms with hydrocarbon radicals, substituted by nitrogen atoms not forming part of a nitro radical, attached to ring nitrogen atoms
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    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/04—Indoles; Hydrogenated indoles
    • C07D209/10—Indoles; Hydrogenated indoles with substituted hydrocarbon radicals attached to carbon atoms of the hetero ring
    • C07D209/14—Radicals substituted by nitrogen atoms, not forming part of a nitro radical
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    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/84—Nitriles
    • C07D213/85—Nitriles in position 3
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    • C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
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    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
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    • C07—ORGANIC CHEMISTRY
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    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/08—Bridged systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D513/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00
    • C07D513/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00 in which the condensed system contains two hetero rings
    • C07D513/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B26/00—Hydrazone dyes; Triazene dyes
    • C09B26/02—Hydrazone dyes
    • C09B26/04—Hydrazone dyes cationic
    • 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
    • G11B7/242—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers
    • G11B7/244—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only
    • G11B7/246—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only containing dyes
    • 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
    • G11B7/242—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers
    • G11B7/244—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only
    • G11B7/249—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only containing organometallic compounds
    • G11B7/2498—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only containing organometallic compounds as cations

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Optical Record Carriers And Manufacture Thereof (AREA)
  • Thermal Transfer Or Thermal Recording In General (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Indole Compounds (AREA)
  • Pyridine Compounds (AREA)
  • Plural Heterocyclic Compounds (AREA)

Abstract

Disclosed is a hydrazide chelate complex compound, which exhibits both excellent solubility in a coating solvent and excellent light resistance when used as a dye for forming a recording layer of an optical recording medium, and which is applicable to high speed recording (especially to BD-R) using blue laser light. Specifically disclosed is a hydrazide chelate complex compound represented by general formula (I).

Description

201137051 六、發明說明： 【發明所屬之技術領域】 本發明係關於當作光學記錄媒體之記錄層形成用色素的 有用醯肼螯合錯合化合物、以及含該化合物的光學記錄媒體 之記錄層形成用色素。特定而言，本發明係關於當作因應藍 色雷射光的光學記錄媒體之記錄層形成用色素的有用新穎 鹽型醯肼螯合錯合化合物、以及含該化合物的光學記錄媒體 之記錄層形成用色素。 本發明尚關於具有使用該色素之記錄層的光學記錄媒 體、以及該光學記錄媒體之記錄方法。 【先前技術】 近年，因為可進行高密度資訊的記錄保存/再生，故而針 對使用雷射光之光學記錄媒體（特別係光碟）的開發係持續 演進。光碟中最近備受矚目者有寫入式光碟(CD-R)。CD-R 通常係具有在具導溝的圓形塑膠基板上，依序積層：以色素 為主成分的記錄層、金屬反射膜及保護膜之構造。對CD-R 的資訊記錄主要係藉由照射雷射光，且該照射能量係在記錄 層被吸收，藉以使雷射光照射部分的記錄層、反射層或基板 發生分解、蒸發、溶解等熱變形的方法（熱模式）而實施。又， 所記錄資訊的再生係藉由讀取因雷射光照射而產生熱變 形、或產生色素構造變化的部分、與未產生的部分對雷射光 的反射率差而實施。所以，光學記錄媒體的記錄層係必須效 100105051 3 201137051 〃子地吸收雷射光能量，且記錄層巾一般係使用雷射 收色素。 r、i用有機色素作為雷射光吸收色素的光學崎媒體，因 ，依照塗佈有機色素溶㈣簡單方法便可形成記錄層，因而 "期待作為廉價的光學記錄媒體，而於今後越益普及。 再者近年為求記錄的高密度化，記錄所使用雷射光的波 長係從習知以半導體雷射發光波長的780細為中心，朝 405nm前後的藍色光區域短波長化。 再者，近年為求記錄媒體的高容量化，而就藉由在記錄媒 體中製作雙層記錄層以達記錄容量雙倍化的雙層記錄媒體 製作、以及記錄高速化進行檢討，因而⑽層用色素化合物 將要求對δ己錄雷射更高一層的高感度化與高耐光性。 再者，當使用色素形成記錄層時’一般而言，使用旋塗法 對基板塗佈的方法，相較於真空蒸鍍法之下，就成本面而士 屬有利，且所使用的光學記錄媒體用色素必須對塗佈溶劑呈 高溶解性。目前一般係使用2,2,3,3、四氟丙醇（TFp)、 2,2,3,3,4,4,5,5_八氟戊醇（0FP)等貌系醇溶劑作為塗佈溶 劑，並塗佈於聚碳酸酯基板，因而作為記錄層形成色素，必 須對該等塗佈溶劑呈高溶解性。 再者’一般而言’資料的記錄及讀出i句係利用雷射光實 施’讀出雷射光係使用強度較弱於記錄雷射光者。所以，若 形成光學記錄媒體之記錄層的色素係該色素的耐光性低至 100105051 4 201137051 會因屬於讀出光的較弱雷射光照射而分解之程度，則當施行 記錄資料讀出時’會成為出現資料錯誤的原因。又，光學記 t i ’因為對記錄面長時間照射太陽^或照明 等機會頗多’因而若色素的耐光性差，光學記錄媒體的記錄 身料便難以長期保存。所以，對記錄層形成用色素亦一併要 求同耐光性。 使用目則所開發藍色半導體雷射的記錄方法，例如在 HD(High Definition ’ 高解析)DVD(Digital 〜咖业 Disc，數 位多功能光碟）-R、或BD(Blue_ray Disc)_R等，係有與習知 通稱CD-R或DVD-R的光學記錄媒體同樣的記錄機制，即 Hlght〇LGW記錄的實用化困難之問題。所謂「Hight〇L〇w 記錄」係指未記錄時的反射率相較於記錄時更高的記錄方 法，未記錄部分的反光多之材料便屬優異記錄材料。 再者’本發明者等思索上述情況，在專利文獻i中得知， 作為對塗佈溶韻轉性及狀性均優異，且耗因應使用 藍色雷射光高速光記錄之光學記錄媒體之記料形成用亞 胺系色素’具特定構造的酿肼螯合錯合化合物係'屬有效。 再者’得知利用不同於習知記錄機制的L〇w如己 進行高密度的料訊記錄/再生。料，所謂 Η灿記錄」，係指記錄時的反射率較高於未記 法，必須降低未記錄時的反射率。 其他，針對醯肼螯合錯合物，在專利 又獻2〜6切各種提 100105051 5 201137051 案。 [先行技術文獻] [專利文獻] 專利文獻1: 專利文獻2 : 專利文獻3 : 專利文獻4 : 專利文獻5 : 專利文獻6 : 【發明内容】 曰本專利特開2008-195915號公報 曰本專利特開昭60-252659號公報 曰本專利特開昭63-202669號公報 國際公開WO1999/011262號公報 國際公開W02009/013163號公報 曰本專利特開2004-106370號公報 (發明所欲解決之問題) 專利文獻1係報告指出將醯肼螯合錯合物使用為 HDDVD-R用色素，此化合物在HD_DVD_R用途中，因對 塗佈溶劑的溶解性高，且屬高感度，因而屬優異的化合物， 但另一方面，在BD_R用途中則記錄感度不足。 專利文獻2係報告指出將醯肼螯合錯合物使用於染色，雖 為忐提升水溶性以作為染料而導入續酸基，但卻與本發明所 必要之對有機溶劑的溶解性提升屬完全相反方向。 專利文獻3係報告指出將醯肼螯合錯合物使用為顏料。顏 料對溶劑類的溶解性極低，難以適用於本發明目的用途。 專利文獻4係報告指出醯肼螯合錯合物的生理活性。 專利文獻5係報告指出將醯肼螯合錯合物使用為漂白劑。 100105051 201137051 上述任-文獻均與本發明目的用途完全無關聯。 專利文獻6雖報告指出將醯肼螯合錯合物使用為 HDDVD_R用色素’但必須是不㈣本發明的特定構造(二 戊鐵）’且記錄評估結果不明。 本發明之目的在於提供：當使用為光學記錄媒體的記錄層 形成用色素時，對塗佈溶劑的溶解性及耐光性均優異，且能 因應使用藍色雷射光的高速光記錄(特別係bd_r)之⑽整 合錯合化合物。 (解決問題之手段） 本發明者等在為解決上述問題而深人鑽研的過程中進行 如下述推論。 P 根據 J. Clayden et al.，Organic Chemistry(2001)，已知 四級錢鹽係m及電子性。本發明者料為鱗藉由在酿耕 配位基導人料吸電子性強的銨鹽，使輯配位基内的電子 呈現局部化之同時，當記錄時的雷射光吸㈣，由於局部化 部位的鐵餘易破壞，而導致記騎性(Ii_的良化及記錄 感度提升。 另方面，根據日本專利特開2005-271587號公報，多數 情況係光學記錄媒體的記錄雜㈣光性呈相反特性，特別 m色雷㈣有機色素大多屬於耐光性差的色素。本發明者 等⑽為或許選擇雜原子為N的各種含氮雜環構造鏘鹽，並 利用可藉由其酸性度的不同而改變吸電子性的強度，俾將該 100105051 7 201137051 等吸電子性不同的各種鏽鹽導人酿肼配位基中，藉此能適度 地控制醯肼配位基_電子局部化程度，而兼顧記錄特性與 而才光性。 本發明者等便以此種推論為基礎，更進一步深入鑽研，結 果發現具有含鏽鹽之醯肼配位基與過渡金屬陽離子的以下 -般式(I)或(II)所示醯肼螯合錯合化合物，對塗佈溶劑的溶 解性及薄膜狀態的耐紐均優異，且將其使用於記錄層的光 學記錄媒體，可依藍色雷射光進行良好的記錄（特別係 BD-R)。 本發明係根據此種發現而達成，主旨如下。 [1]一種醯肼螯合錯合化合物，係由下述一般式⑴所示： [化1] w yJ Mb+ (x-)m Z a (i) [一般式(I)中， 環A係至少具有1個以上N原子的單一五員環或六員環 雜環、或由五員環及/或六員環構成的2或3環式縮合雜環； 環A係可為芳香環、亦可為非芳香環，當芳香環的情況， 環内的1個以上N原子形成四級化的鑌鹽，當非芳香環的 情況，環内的1個以上N原子形成四級化的敍鹽； ί衣A係由作為必要原子的N、以及C、Ν'、Ο及S中之任 100105051 g 201137051 一者以上的原子形成；構成環A的C&N係可為無取代、 亦可具有以下的取代基； C的情況，可具有選自下述基團中之任一者作為取代基： 可經1個以上氟原子取代的直鏈或分支的碳數1至4之燒 基；具有直鏈或分支的碳數丨至4之烷基的烷氧基；無取代、 或具有1或2個直鏈或分支的碳數丨至4之烷基的醯胺基； 具有直鏈或分支的碳數1至4之烧基的燒氧幾基；氰基；苯 基；及苄基； N的情況’可具有直鏈或分支的碳數1至4之燒基作為取 代基； L係表示將環A與C*連結的2價連接基L，或直接鍵結； 該2價連接基L’係可具有直鏈或分支的碳數丨至*之烷基 的亞曱基、伸乙基、伸苯基、伸苯亞甲基、或伸咬喃基 (furanylene group)； R!係表示氫原子、或直鏈或分支的碳數丨至4之烷基； z係表示減或可_化㈣基；從z的經基、z的叛基 經烯醇化而生成_基、—般式_醯肼部位之絲經婦醇 化而生成的羥基、以及醯肼部位的NH基中之任一者以上部 位，脫離活性氫而形成錯合物； 環B係表示由下式(B_a)或(B_b)所示，除z之外尚亦可具 有取代基的五員環或六員環芳香環或雜環； [化2] 100105051 9 201137051 Q3 0 Z (B—a) Z (B-b) (上式中，原子B!係表示C、s、或N ; 當B〗為C的情況’可為無取代、亦可具有選自可經1個 以上氟原子所取代之直鏈或分支的碳數1至4之烧基、及經 基中之任一者作為取代基；亦可構成由C與〇利用雙鍵連 結的叛基， 當K為S的情況，可為無取代、亦可構成由s與〇利用 雙鍵連結的亞柯基、或；ε風基； 當Βι為Ν的情況，可為無取代、亦可具有可經1個以上 氟原子所取代支直鏈或分支的碳數1至4之烷基作為取代 基； 原子B疒队係指分別獨立表示c、N、或〇 ; 當&〜B4為C的情況，可為無取代、亦可具有選自： 可經1個以上氟原子所取代之直鏈或分支的碳數1至4 之烧基；羥基，具有直鍵或分支的碳數1至4之烧基的烧氧 基；具有1或2個直鏈或分支的碳數1至4之燒基的胺基； 可含有1個氧原子之三員環至七員環的脂肪族環狀胺基；無 取代、或具有1或2個直鏈或分支的碳數1至4之烷基的酿 胺基；具有直鏈或分支的碳數1至4之院基的烷氧羰基；具 有直鏈或分支的碳數1至4之烷基的烷羰基；笨基；及氰基 100105051 10 201137051 者作為取代基；亦可構成由C與〇利用雙鍵連結的 、 由c與s利用雙鍵連结的碰代叛基、或者由匚與可 二直鏈或分支的碳數丨至4之烷基所取代的Ν利用雙鍵連 結的㈣基；亦可形成亦可經4鏈或分支的碳數丨至4之烧 代的二員環至七員環的環烧、稻燒(b〇rnane)、或金剛 . 烷的螺環； 田〜^為N的情況，可為無取代、亦可具有直鏈或分 數1至4之烧基、具有直鏈或分支的碳數1至*之烧 基的烧氧基、或苯基作為取代基； 又，Βι〜A中相鄰接的2個原子之取代基亦可相互鍵結， 形，缩合於環B的五員環或六員環；此情況，縮合於環β 的環係由上式(B-a)或(B-b)所示） &係表示配位基數，且為1或2; M係表示Co、Ni、或Fe ; b係表示Μ的價數，且為2或3 ; .X係表不醋酸根離子、氯化物離子、溴化物離子、碘化物 ‘ 離子、過氣酸根離子、四氟硼酸根離子、四笨基硼酸根離子、 六氟碟駿根離子、甲笨確酸根離子、三氟甲績酸根離子、或 雙(二氟曱磺醯基)醯亞胺離子； m係將錯合物的正電射以中和所必要的數目當瓜為2 以上時，m個X-係可為相同、亦可為不同]。 [2]一種醯肼螯合錯合化合物，係由下述-般式(II)所示： 100105051 11 201137051 [化3] 9 μ Ri 9[Technical Field] The present invention relates to a useful chelating chelating compound which is a dye for forming a recording layer of an optical recording medium, and a recording layer formed of an optical recording medium containing the compound. Use pigments. In particular, the present invention relates to a useful novel salt type cerium chelating compound which is a dye for recording layer formation of an optical recording medium which is responsive to blue laser light, and a recording layer formation of an optical recording medium containing the same Use pigments. The present invention relates to an optical recording medium having a recording layer using the pigment, and a recording method of the optical recording medium. [Prior Art] In recent years, since the recording and storage/reproduction of high-density information is possible, the development of an optical recording medium (especially a compact disc) using laser light has continued to evolve. The most recently watched discs on the disc are written discs (CD-R). The CD-R usually has a structure in which a recording layer, a metal reflective film, and a protective film having a pigment as a main component are laminated on a circular plastic substrate having a guide groove. The information recording of the CD-R is mainly by irradiating the laser light, and the irradiation energy is absorbed in the recording layer, so that the recording layer, the reflective layer or the substrate of the portion irradiated with the laser light is thermally deformed, such as decomposition, evaporation, dissolution, and the like. The method (hot mode) is implemented. Further, the reproduction of the recorded information is performed by reading a portion which is thermally deformed by the irradiation of the laser light or which has a change in the texture of the dye, and a difference in the reflectance of the portion which is not generated with respect to the laser light. Therefore, the recording layer of the optical recording medium must absorb the laser light energy in the manner of 100105051 3 201137051, and the recording layer towel generally uses the laser coloring. r, i uses an organic dye as an optical smear medium for laser light absorbing pigments, and a recording layer can be formed by a simple method of applying an organic dye solution. Therefore, it is expected to be an inexpensive optical recording medium, and it will become more popular in the future. . In addition, in recent years, in order to increase the density of recording, the wavelength of the laser light to be used for recording is shorter than the wavelength of 780 of the semiconductor laser light emission wavelength, and the wavelength of the blue light region before and after 405 nm is shortened. In addition, in recent years, in order to increase the capacity of the recording medium, a double-layer recording layer is produced in a recording medium to make a double-layer recording medium that doubles the recording capacity, and the recording speed is reviewed, and thus (10) layer The use of a pigment compound will require a higher sensitivity and high lightfastness to a higher level of δ-recorded laser. Further, when a recording layer is formed using a pigment, 'in general, a method of coating a substrate by a spin coating method is advantageous in terms of a cost surface compared to a vacuum evaporation method, and an optical recording is used. The pigment for the media must have high solubility in the coating solvent. At present, generally used 2,2,3,3, tetrafluoropropanol (TFp), 2,2,3,3,4,4,5,5-octafluoropentanol (0FP) and other alcohols as coating Since the solvent is applied to the polycarbonate substrate and the dye is formed as a recording layer, it is necessary to have high solubility in the coating solvent. Further, 'generally' the recording and reading of the data is performed by laser light. The readout laser light is weaker than the recorded laser light. Therefore, if the coloring matter of the recording layer of the optical recording medium is formed, the light resistance of the dye is as low as 100105051 4 201137051, which is decomposed by the weaker laser light irradiation of the read light, and when the recording data is read, Became the reason for the data error. Further, since the optical recording t i ' has a large chance of irradiating the recording surface with the sun for a long time or illumination, the optical recording medium is difficult to store for a long period of time if the light resistance of the dye is poor. Therefore, the coloring matter for forming a recording layer is also required to have the same light resistance. The recording method of the blue semiconductor laser developed by the program is, for example, HD (High Definition 'High Definition) DVD (Digital to Digital Disc)-R, or BD (Blue_ray Disc)_R. There is a recording mechanism similar to that of the optical recording medium commonly known as CD-R or DVD-R, that is, the practical difficulty of the Hlght〇LGW recording. The "Hight〇L〇w record" refers to a recording method in which the reflectance at the time of unrecording is higher than that at the time of recording, and the material of the unrecorded portion which is more reflective is an excellent recording material. In addition, the inventors of the present invention have considered the above-mentioned situation, and it is known in the patent document i that it is excellent in the application of the optical properties of the optical recording medium, which is excellent in the application of the rhythmic properties and the use of blue laser light. The imide-based dye of the material formation is a genus of a brewing chelating compound compound having a specific structure. Furthermore, it is known that a high-density material recording/reproduction is performed using L〇w which is different from the conventional recording mechanism. The material, the so-called "record", means that the reflectance at the time of recording is higher than that of the unrecorded, and the reflectance at the time of unrecording must be lowered. Others, for the chelating chelate complex, in the patent also offer 2 to 6 cut various mentions 100105051 5 201137051 case. [Prior Art Document] [Patent Document] Patent Document 1: Patent Document 2: Patent Document 3: Patent Document 4: Patent Document 5: Patent Document 6: [Summary of the Invention] Patent Publication No. 2008-195915 Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. 2004-106370. Patent Document 1 reports that the ruthenium chelate complex is used as a dye for HDDVD-R, and this compound is an excellent compound in HD_DVD_R application because it has high solubility in a coating solvent and is highly sensitive. However, on the other hand, in the BD_R use, the sensitivity is insufficient. Patent Document 2 reports that the ruthenium chelate complex is used for dyeing, and although the water solubility is increased to introduce a reductive acid group as a dye, the solubility enhancement to an organic solvent necessary for the present invention is completely improved. opposite direction. Patent Document 3 reports that a ruthenium chelate complex is used as a pigment. The pigment has extremely low solubility in solvents and is difficult to apply to the intended use of the present invention. Patent Document 4 reports that the physiological activity of the ruthenium chelate complex is indicated. Patent Document 5 reports that a chelating complex is used as a bleaching agent. 100105051 201137051 All of the above-mentioned documents are completely unrelated to the intended use of the present invention. Patent Document 6 reports that the ruthenium chelate complex is used as the dye for HDDVD_R', but it must be (4) the specific structure (diferric) of the present invention, and the evaluation result of the recording is unknown. An object of the present invention is to provide a dye for recording layer formation in an optical recording medium, which is excellent in solubility and light resistance to a coating solvent, and can be used for high-speed optical recording using blue laser light (particularly bd_r) (10) Integrating a mismatched compound. (Means for Solving the Problem) The inventors of the present invention conducted inferences in the course of solving the above problems as follows. P According to J. Clayden et al., Organic Chemistry (2001), the quaternary money salt system m and electrons are known. The inventors expect that the scales of the electrons in the complexing sites are localized by the ammonium salt which attracts electrons in the fermenting ligand, and the laser light when recording (four) is due to local The iron content of the chemical part is easily broken, which leads to the riding property (Ii_ is improved and the recording sensitivity is improved. On the other hand, according to Japanese Patent Laid-Open Publication No. 2005-271587, most cases are recording recordings of optical recording media. In particular, m-ray (4) organic pigments are mostly pigments having poor light resistance. The inventors of the present invention (10) may select various nitrogen-containing heterocyclic structural sulfonium salts having a hetero atom of N, and may utilize the difference in acidity thereof. While changing the intensity of the electron-withdrawing property, the various rust salts having different electron-withdrawing properties such as 100105051 7 201137051 are introduced into the ligand, whereby the degree of electron localization of the ruthenium ligand can be appropriately controlled, and The inventors of the present invention have further studied in depth based on such inferences, and found that the following general formula (I) has a ruthenium-containing ruthenium ligand and a transition metal cation. Or (II) The ruthenium chelating compound is excellent in solubility in a coating solvent and in a film state, and is used for an optical recording medium of a recording layer, and can be well recorded by blue laser light (especially BD- R) The present invention has been made in view of such findings, and the gist thereof is as follows. [1] A hydrazone chelate-coordinated compound is represented by the following general formula (1): [Chemical Formula 1] w yJ Mb+ (x-)m Z a (i) [In general formula (I), ring A is a single five-membered or six-membered ring heterocyclic ring having at least one or more N atoms, or a five-membered ring and/or a six-membered ring. Or a 3-ring condensed heterocyclic ring; the ring A system may be an aromatic ring or a non-aromatic ring, and in the case of an aromatic ring, one or more N atoms in the ring form a quaternary phosphonium salt, when a non-aromatic ring In the case, one or more N atoms in the ring form a quaternized salt; ί A is formed from N as a necessary atom, and an atom of 100105051 g 201137051 or more of C, Ν', Ο, and S. The C&N system constituting the ring A may be unsubstituted or may have the following substituents; in the case of C, it may have any one selected from the group consisting of Substituent: a straight or branched carbon number of 1 to 4 which may be substituted by one or more fluorine atoms; an alkoxy group having a linear or branched carbon number of 丨 to 4; unsubstituted, or 1 or 2 linear or branched decylamino groups having a carbon number of 4 to 4; an aerobic group having a linear or branched carbon number of 1 to 4; a cyano group; a phenyl group; a case where N may have a linear or branched carbon number of 1 to 4 as a substituent; L represents a divalent linking group L linking ring A and C*, or a direct bond; The linker L' may have a linear or branched carbon number to the alkyl group of an alkylene group, an extended ethyl group, a phenylene group, a benzylidene group, or a furanylene group; Is a hydrogen atom, or a linear or branched carbon number of 丨 to 4 alkyl; z is a subtractive or a cyclizable (tetra) group; a radical from z, a thiol group of z is enolized to form a _ group, In the general formula, the hydroxyl group formed by the alcoholization of the fluorene moiety and the NH group of the oxime site are separated from the active hydrogen to form a complex; the ring B system is represented by the following formula (B_a) ) or (B_b) A five-membered or six-membered aromatic ring or a heterocyclic ring which may have a substituent other than z; [Chemical 2] 100105051 9 201137051 Q3 0 Z (B-a) Z (Bb) (In the above formula, atom B ! indicates C, s, or N; when B is C, 'may be unsubstituted, or may have a carbon number of 1 to 4 selected from a straight chain or a branch which may be substituted by one or more fluorine atoms. Any one of a base group and a base group may be used as a substituent; and a rebel group in which C and 〇 are linked by a double bond may be formed. When K is S, it may be unsubstituted or may be composed of s and yt. a bond-bonded benzyl group or an ε-wind group; when Β is yttrium, it may be unsubstituted or may have a carbon number of 1 to 4 which may be substituted by one or more fluorine atoms. The base is a substituent; the atomic B 疒 team means independently representing c, N, or 〇; and when &~B4 is C, it may be unsubstituted or may be selected from: one or more fluorine atoms. a substituted linear or branched carbon group having 1 to 4 carbon atoms; a hydroxyl group having a direct bond or a branched alkoxy group having 1 to 4 carbon atoms; having 1 or 2 linear or branched carbon numbers To 4 base Amine group; an aliphatic cyclic amine group which may contain a three-membered ring to a seven-membered ring of one oxygen atom; an unsubstituted or one or two linear or branched alkyl group having 1 to 4 carbon atoms; An alkoxycarbonyl group having a straight or branched carbon number of 1 to 4; an alkylcarbonyl group having a linear or branched C 1 to 4 alkyl group; a stupid group; and a cyano group 100105051 10 201137051 As a substituent; it may also constitute a ring-bonded group which is linked by a double bond between C and oxime by a double bond, or a carbon number of 4 to 4 by a ruthenium or a bilinear or branched chain. a group substituted with a (4) group bonded by a double bond; or a ring-ring or rice-fired (b〇rnane) of a two-membered ring to a seven-membered ring which can also be fired by a 4-chain or branched carbon number of 丨4 ), or a diamond ring of an alkane; a case where the field ~^ is N, which may be unsubstituted, or may have a linear or fractional group of 1 to 4, a straight or branched carbon number of 1 to * a base of an alkoxy group, or a phenyl group as a substituent; further, the substituents of two adjacent atoms in the Βι~A may be bonded to each other, and are condensed to the five-membered or six-membered ring of the ring B; This situation The ring system condensed to the ring β is represented by the above formula (Ba) or (Bb)) & represents the number of coordination groups and is 1 or 2; the M system represents Co, Ni, or Fe; The number of valences is 2 or 3; .X is not acetate, chloride, bromide, iodide's, peroxyacid, tetrafluoroborate, tetraphenylborate, six Fluorine ion, ion, ion, trifluoromethane ion, or bis(difluorosulfonyl) ruthenium ion; m system is necessary for positive ionization of the complex When the number is 2 or more, m X-systems may be the same or different. [2] A hydrazine chelate compound which is represented by the following general formula (II): 100105051 11 201137051 [Chemical 3] 9 μ Ri 9

Mb+ (X-)m [一般式(II)中，Mb+ (X-)m [in general formula (II),

Ru〜Rn係分別獨立表示可經1個以上氟原子所取代之直 鏈或分支的碳數1至4之烷基、或可經直鏈或分支的碳數1 至4之烷基(其係可經1個以上氟原子取代)所取代的苯基； L係表示將與C*連結的2價連接基L'或直接 鍵結；該2價連接基L'係可具有直鏈或分支的碳數1至4 之烷基的亞甲基、伸乙基、伸苯基、伸苯亞曱基、或伸咬味 基；Ru~Rn each independently represents a linear or branched alkyl group having 1 to 4 carbon atoms which may be substituted by one or more fluorine atoms, or a linear or branched alkyl group having 1 to 4 carbon atoms (these are a phenyl group which may be substituted by one or more fluorine atoms; L system represents a divalent linking group L' or a direct bond to C*; the divalent linking group L' may have a straight chain or a branched a methylene group having an alkyl group having 1 to 4 carbon atoms, an ethyl group extending, a phenylene group, a benzoquinone group, or a stretching base;

Ri係表示氫原子、或直鏈或分支的碳數1至4之烧基； Z係表示羥基或可烯醇化的羰基；從Z的羥基、z的幾基 經烯醇化而生成的羥基、一般式(I)的醯肼部位之羰基經烯醇 化而生成的羥基、以及醢肼部位的NH基中之任一者以上部 位，脫離活性氫而形成錯合物； 環B係表示由下式(B-a)或(Β-b)所示，除z之外尚亦可具 有取代基的五員環或六員環芳香環或雜環； [化4] 100105051 12 201137051 泛0 Ζ (Β—a) Ζ (Β—b) (上式中，原子Β!係表示C、S、或Ν ; 當Bi為C的情況’可為無取代、亦可具有選自可經1個 以上氟原子所取代之直鏈或分支的碳數1至4之烧基、及羥 基中之任一者作為取代基；亦可構成由C與〇利用雙鍵連 結的羰基； 當I為S的情況，可為無取代、亦可構成由S與Ο利用 雙鍵連結的亞礙基、或颯基； Βι為N的情況，可為無取代、亦可具有可經1個以上氟 原子所取代之直鏈或分支的碳數i至4之烷基作為取代基； 原子I〜Β#係分別獨立表示c、N、或〇 ; 當B2〜Β#為C的情況，可為無取代、亦可具有選自： 可經1個以上I原子所取代之直鏈或分支的碳數1至4 之烷基；羥基；具有直鏈或分支的碳數丨至4之烷基的烷氧 基；具有1或2個直鏈或分支的碳數1至4之烷基的胺基； 可含有1個氧原子之三員環至七員玉裒的脂肪族環狀胺基；無 取代、或具有1或2個直鏈或分支的碳數丨至4之烷基的醯 胺基；具有直鏈或分支的碳數1至4之烷基的烷氡羰基；具 有直鍵或分支的碳數1至4之减的絲基；苯基；及氰基 之任一者作為取代基；亦可構成由C與Ο利用雙鍵連結的 100105051 13 201137051 羰基、由C與S利用雙鍵連結的硫代羰基、或者由C與可 經直鏈或分支的碳數1至4之烷基所取代的N利用雙鍵連 結的亞胺基；亦可形成可經直鏈或分支的碳數1至4之烷基 所取代的三員環至七員環的環烷、稻烷、或金剛烷的螺 環； 當B2〜B4為N的情況，可為無取代、亦可具有直鏈或分 支的碳數1至4之烷基、具有直鏈或分支的碳數1至4之烷 基的烷氧基、或苯基作為取代基； 又，Bi-h中相鄰接的2個原子之取代基亦可相互鍵結， 形成縮合於環B的五員環或六員環；此情況，縮合於環B 的環係由上式(B-a)或(B-b)所示） a係表示配位基數，且為1或2 ; Μ係表示Co、Ni、或Fe ; b係表示Μ的價數，且為2或3; Χ3系表示醋酸根離子、氯化物離子、溴化物離子、碘化物 離子、過氯酸根離子、四氟硼酸根離子、四苯基硼酸根離子、 六氟磷酸根離子、曱苯磺酸根離子、三氟曱磺酸根離子、或 雙（三氟曱磺醯基）醯亞胺離子； m係將錯合物的正電荷予以中和所必要的數目，當m為2 以上時，m個X-係可為相同、亦可為不同]。 [3]如上述[1]或[2]所記載的醯肼螯合錯合化合物，其中， 環Β係具有選自可具有取代基之°比σ定酮衍生物、0密咬衍生 100105051 14 201137051 物、吡唑啶衍生物、苯并噻畊衍生物、及丙二酸環亞異丙畴 (Meldrum’s acid)衍生物之環構造。 [4] 如上述[1]所記載的醯肼螯合錯合化合物，其中，環a 係具有選自可具有取代基之吼啶環、咪唑環、苯并咪唾環、 喹啉環、異喹啉環、吼咯烷環、哌啶環、哌畊環、味啉環、 1，2,3,4-四氫喹啉環、i，2,3,4-四氫異喹啉環、吲哚啉環、及 吡唑環之環構造；環B係具有選自可具有取代基之吡啶酮 衍生物、嘧啶衍生物、吡唑啶衍生物、笨并噻畊衍生物、及 丙二酸環亞異丙酯衍生物中之任一者之環構造。 [5] -種光學記錄媒體之記錄層形成用色素，係含有上述⑴ 至[4]中任一項所記載的醯肼螯合錯合化合物。 [6卜種光學記錄雜，魏少具有基板、與在該基板上 形成的記錄層；該記㈣錢用±述_記制絲記錄 媒體之記錄層形成用色素形成。 m-種光學記錄親之記錄方法，係對上述剛記載的 光學記錄媒體，使用波長35G〜53Gnm m如上述[7]所記_絲記錄媒體之記錄方法，立中， 在猜記制雷射光之波長中，記錄部岐料錄高於記 錄則及未記錄部的反射率。 (發明效果） 本發明的紐螯合錯合化合物係⑴對_的溶解性、⑺ 对光性、以及⑶藍色雷射記錄雜均料。所以，藉由將 100105051 15 201137051 含有該醯肼螯合錯合化合物的色素使用於光學記錄媒體的 記錄層，便可在良好膜性基礎下，廉價提供利用藍色雷射光 執行的記錄(特別係BD-R)特性優異、且耐光性亦良好的高 密度光學記錄媒體。 【實施方式】 以下，針對本發明實施形態進行具體說明，惟本發明並不 僅侷限於以下實施形態，在其主旨範圍内均可進行各種變更 實施。 [1.醯肼螯合錯合化合物] 本發明的醯肼螯合錯合化合物係由下述一般式（I)或下述 一般式(II)所示： [化5]Ri is a hydrogen atom, or a linear or branched carbon group having 1 to 4 carbon atoms; Z is a hydroxyl group or an enolizable carbonyl group; a hydroxyl group formed by enolification of a hydroxyl group of Z and a group of z, generally Any one or more of the hydroxyl group formed by the enolization of the carbonyl group of the formula (I) and the NH group of the oxime moiety are decomposed from the active hydrogen to form a complex; the ring B system is represented by the following formula ( a five-membered or six-membered aromatic ring or a heterocyclic ring which may have a substituent other than z, as shown by Ba) or (Β-b); [Chemical 4] 100105051 12 201137051 Pan 0 Ζ (Β—a) Ζ (Β—b) (In the above formula, the atom Β! means C, S, or Ν; when Bi is C, 'may be unsubstituted, or may be selected from one or more fluorine atoms. a straight or branched carbon group having 1 to 4 carbon atoms and a hydroxyl group as a substituent; or a carbonyl group in which C and oxime are bonded by a double bond; and when I is S, it may be unsubstituted Further, an sulfhydryl group or a fluorenyl group which is bonded by S and hydrazine by a double bond may be formed; and when Βι is N, it may be unsubstituted or may have a linear chain which may be substituted by one or more fluorine atoms. Or an alkyl group having a carbon number of i to 4 as a substituent; the atoms I to Β# are independently represented by c, N, or 〇; and when B2 Β# is C, it may be unsubstituted or may be selected. From: a linear or branched alkyl group having 1 to 4 carbon atoms which may be substituted by one or more I atoms; a hydroxyl group; an alkoxy group having a linear or branched carbon number of 丨 to 4; 2 linear or branched amine groups having 1 to 4 carbon atoms; an aliphatic cyclic amine group which may contain one oxygen ring of one to three members; unsubstituted or have 1 or 2 a linear or branched guanamine group having a carbon number of 4 to 4; an alkyl carbonyl group having a linear or branched alkyl group having 1 to 4 carbon atoms; a carbon number of 1 to 4 having a straight bond or a branch Any one of a reduced silk group; a phenyl group; and a cyano group as a substituent; or a carbonyl group in which C and Ο are bonded by a double bond, a carbonyl group, a thiocarbonyl group in which C and S are bonded by a double bond, or An imine group in which N is substituted with a linear or branched alkyl group having 1 to 4 carbon atoms by a double bond; or a linear or branched alkyl group having 1 to 4 carbon atoms may be formed. Replace a three-membered to seven-membered ring of a cycloalkane, a rice alkane, or an adamantane; if B2 to B4 are N, it may be unsubstituted or may have a linear or branched carbon number of 1 to 4 a group having a linear or branched alkoxy group having 1 to 4 carbon atoms or a phenyl group as a substituent; and, in addition, substituents of two adjacent atoms in Bi-h may be bonded to each other. Forming a five-membered or six-membered ring condensed to ring B; in this case, the ring system condensed to ring B is represented by the above formula (Ba) or (Bb)) a is the number of coordination groups, and is 1 or 2; Μ indicates Co, Ni, or Fe; b indicates valence of ruthenium and is 2 or 3; Χ 3 indicates acetate ion, chloride ion, bromide ion, iodide ion, perchlorate ion, tetrafluoro Borate ion, tetraphenylborate ion, hexafluorophosphate ion, sulfonate ion, trifluorosulfonate ion, or bis(trifluorosulfonyl) ruthenium ion; m system will be mismatched The positive charge of the substance is necessary for neutralization. When m is 2 or more, m X-systems may be the same or different. [3] The oxime chelating compound according to the above [1] or [2], wherein the guanidine series has a ratio of sigma ketone derivative selected from the group which may have a substituent, and a stagnation derivative of 100105051 14 201137051 Ring structure of a substance, a pyrazole pyridine derivative, a benzothianium derivative, and a Meldrum's acid derivative. [4] The oxime chelating compound according to the above [1], wherein the ring a has an acridine ring, an imidazole ring, a benzimidyl ring, a quinoline ring, and a different one selected from the group which may have a substituent. Quinoline ring, pyrrolidine ring, piperidine ring, piperazine ring, porphyrin ring, 1,2,3,4-tetrahydroquinoline ring, i,2,3,4-tetrahydroisoquinoline ring, a ring structure of a porphyrin ring and a pyrazole ring; the ring B system has a pyridone derivative, a pyrimidine derivative, a pyrazolidine derivative, a stupid thiophene derivative, and malonic acid selected from the group consisting of a substituent. Ring structure of any of the cycloisopropylidene derivatives. [5] The dye for forming a recording layer of the optical recording medium, which comprises the oxime chelating compound according to any one of the above (1) to [4]. [6] Optical recording, Wei Shao has a substrate, and a recording layer formed on the substrate; and this (4) money is formed by using a recording layer forming dye for recording a recording medium. The m-type optical recording recording method is a recording method using a wavelength of 35 G to 53 Gnm m as described in the above [7], and the laser recording medium is used for the recording of the laser light. Among the wavelengths, the recording unit records higher than the reflectance of the recorded and unrecorded portions. (Effect of the Invention) The chelating complex compound of the present invention is (1) soluble in _, (7) optical, and (3) blue laser-recorded. Therefore, by using 100105051 15 201137051 a pigment containing the ruthenium chelate compound for use in a recording layer of an optical recording medium, it is possible to inexpensively provide recording using blue laser light under a good film property (especially BD-R) A high-density optical recording medium excellent in characteristics and excellent in light resistance. [Embodiment] The embodiments of the present invention are specifically described below, but 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. [1. Anthraquinone chelate compound] The indole chelate compound of the present invention is represented by the following general formula (I) or the following general formula (II):

Mb+ (X')m (i) [一般式(I)中， 環A至少具有1個以上N原子的單一五員環或六員環雜 環、或由五員環及/或六員環構成的2或3環式縮合雜環； 環A係可為芳香環、亦可為非芳香環，當芳香環的情況， 環内的1個以上N原子形成四級化的鏽鹽，當非芳香環的 情況，環内的1個以上N原子形成四級化的敍鹽。 環A係由作為必要原子的N、以及C、N、Ο及S中之任 100105051 16 201137051 一者以上的原子形成；構成環A的C及N係可為無取代、 亦可具有以下的取代基。 C的情況，可具有選自下述基團中之任一者作為取代基： 可經1個以上氟原子取代的直鏈或分支的碳數1至4之烷 基，具有直鏈或分支的碳數丨至4之烷基的烷氧基；無取代、 或具有1或2個直鏈或分支的碳數丨至4之烷基的醯胺基； 具有直鏈或分支的碳數1至4之烷基的烷氧羰基；氰基；苯 基；及节基。 N的情況’可具有直鏈或分支的碳數1至4之燒基作為取 代基。 … L係表示將環A與C*連結的2價連接基L，或直接鍵結； 該2價連接基L’係可具有直鏈或分支的碳數丨至4之烷基 的亞甲基、伸乙基、伸苯基、伸苯亞甲基、或伸呋喃基。Mb+ (X') m (i) [In general formula (I), ring A has a single five-membered ring or a six-membered ring heterocyclic ring having at least one N atom, or a five-membered ring and/or a six-membered ring. a 2 or 3 ring condensed heterocyclic ring; the ring A system may be an aromatic ring or a non-aromatic ring. In the case of an aromatic ring, one or more N atoms in the ring form a quaternary rust salt. In the case of an aromatic ring, one or more N atoms in the ring form a quaternary salt. Ring A is formed by N as an essential atom, and any one of 100,105,051, 16, 2011,370,51, C, N, Ο, and S; the C and N lines constituting the ring A may be unsubstituted or may have the following substitutions. base. In the case of C, it may have any one selected from the group consisting of a straight chain or a branched alkyl group having 1 to 4 carbon atoms which may be substituted with one or more fluorine atoms, and has a straight chain or a branched chain. An alkoxy group having a carbon number of 4 to an alkyl group; an amidino group having no substitution or having 1 or 2 linear or branched carbon groups of 丨 to 4; having a linear or branched carbon number of 1 to Alkoxycarbonyl group of 4 alkyl; cyano; phenyl; and a benzyl group. The case of N may have a linear or branched carbon group of 1 to 4 as a substituent. L system represents a divalent linking group L linking ring A and C*, or directly bonded; the divalent linking group L' is a methylene group which may have a linear or branched carbon number of 丨 to 4 alkyl groups. , ethyl, phenyl, benzylidene, or furan.

Rl係表示氫原子、或直鏈或分支的碳數1至4之烷基。 z係表示羥基或可烯醇化的羰基；從Z的羥基、z的羰基 經烯醇化而生成的經基、一般式(1)的醯肼部位之幾基經稀醇 化而生成的羥基、以及醯肼部位的NH基中之任一者以上部 位，脫離活性氫而形成錯合物。 ° %Β係表不由下式(B-a)或(B-b)所示，除Ζ之外尚可具有 取代基的五員環或六員環芳香環或雜環。 [化6] 100105051 17 201137051R1 represents a hydrogen atom, or a linear or branched alkyl group having 1 to 4 carbon atoms. z is a hydroxy group or an enolizable carbonyl group; a hydroxyl group formed by enolization of a hydroxyl group of Z, a carbonyl group of z, a hydroxyl group formed by dilute alcoholization of a group of a general formula (1), and an anthracene Any one or more of the NH groups in the oxime site is desorbed from the active hydrogen to form a complex. The % oxime is not a five-membered or six-membered aromatic ring or a heterocyclic ring which may have a substituent other than hydrazine, as shown by the following formula (B-a) or (B-b). [Chemical 6] 100105051 17 201137051

Z (B—a) 2 (B—b) (上式中，原子B!係表示c、s、或N。 當A為C的情況，可為無取代、亦可具有選自可經i個 以上氟原子所取代之直鏈或分支的碳數i至4之烷基、及羥 基中之任一者作為取代基；亦可構成由C與〇利用雙鍵連 結的羰基。 當^為S的情況，可為無取代、亦可構成由s與〇利用 雙鍵連結的亞砜基、或砜基。 當艮為N的情況，可為無取代、亦可具有可經丨個以上 氟原子所取代之直鏈或分支的碳數1至4之烷基作為取代 基。 原子B2〜B4係分別獨立表示c、N、或Ο。 當B2〜B4為C的情況，可為無取代、亦可具有選自： 可經1個以上氟原子所取代之直鏈或分支的碳數1至4 之烷基；羥基；具有直鏈或分支的碳數1至4之烷基的烷氧 基；具有1或2個直鏈或分支的碳數1至4之烷基的胺基； 可含有1個氧原子之三員環至七員環的脂肪族環狀胺基；無 取代、或具有1或2個直鏈或分支的碳數1至4之烷基的醯 胺基；具有直鏈或分支的碳數1至4之烷基的烷氧羰基；具 1⑻105051 18 201137051 有直鏈或分支的碳數1至4之烷基的烷羰基；苯基；及氰美 之任一者作為取代基；亦可構成由c與〇利用雙鍵連纟士的 羰基、由c與s利用雙鍵連結的硫代羰基、或者由c與可 經直鏈或分支的碳數1至4之烷基所取代的N利用雙鍵連 . 結的亞胺基；亦可形成可經直鏈或分支的碳數1至4之烷義 • 所取代的三員環至七員環的環烷、稻烷、或金剛烷的螺 環。 ’、 當 亦可具有直鏈或分 B2〜B4為N的情況，可為無取代、 支的碳數1至4之烧基、具有直鏈或分支的碳數丨至4 基的烷氧基、或苯基作為取代基。 又’ ΒρΒ4中相鄰接的2個原子之取代基亦可相互鍵、名士 形成縮合於環Β的五員環或六員環；此情況，縮合於變^ 的環係由上式(B-a)或(B-b)所示） a係表示配位基數，且為1或2。 Μ係表示Co、Ni、或Fe。 b係表示Μ的價數，且為2或3。 ΧΜ系表示醋酸根離子、氣化物離子、溴化物離子、峨化物 離子、過氣酸根離子、四氟硼酸根離子、四苯基爛酸根離子 六氟構酸根離子、曱苯續酸根離子、三I曱石黃酸根離子戈 雙(三氟甲磺醯基）醯亞胺離子。 m係將錯合物的正電荷予以中和所必要的數目，♦ 田m為2 以上時，m個X-係可為相同、亦可為不同]。 100105051 19 201137051 [化7] R” + R 13Z (B—a) 2 (B—b) (In the above formula, the atom B! represents c, s, or N. When A is C, it may be unsubstituted or may be selected from i. Any one of a straight chain or a branched alkyl group having 1 to 4 carbon atoms and a hydroxyl group substituted by the above fluorine atom may be used as a substituent; and a carbonyl group in which C is bonded to a hydrazine by a double bond may be used. In the case, it may be unsubstituted or may constitute a sulfoxide group or a sulfone group which is bonded by a double bond between s and oxime. When 艮 is N, it may be unsubstituted or may have more than one fluorine atom. a substituted straight or branched alkyl group having 1 to 4 carbon atoms as a substituent. The atoms B2 to B4 each independently represent c, N, or Ο. When B2 to B4 are C, they may be unsubstituted or And having an alkyl group having 1 to 4 carbon atoms which may be substituted by one or more fluorine atoms; or a hydroxyl group; an alkoxy group having a linear or branched alkyl group having 1 to 4 carbon atoms; 1 or 2 linear or branched amine groups having 1 to 4 carbon atoms; an aliphatic cyclic amine group which may contain a three-membered ring to a seven-membered ring of one oxygen atom; no substitution, or 1 or 2 straight chains or points a mercapto group having a C 1 to 4 alkyl group; an alkoxycarbonyl group having a linear or branched C 1 to 4 alkyl group; having 1 (8) 105051 18 201137051 having a linear or branched carbon number of 1 to 4 Any one of an alkylcarbonyl group; a phenyl group; and a cyano group as a substituent; or a carbonyl group in which c is bonded to a hydrazine by a double bond, a thiocarbonyl group in which a double bond is bonded by c and s, or N substituted with c and a linear or branched alkyl group having 1 to 4 carbon atoms may be bonded by a double bond; an alkyl group having a carbon number of 1 to 4 which may be linear or branched may be formed. The three-membered ring to the seven-membered ring of cycloalkane, rice, or adamantane. ', when there is a straight chain or B2~B4 is N, it can be unsubstituted, a carbon group having 1 to 4 carbon atoms, a linear or branched carbon number 丨 to 4 group alkoxy group, or a phenyl group as a substituent. Further, a substituent of two adjacent atoms in 'ΒρΒ4 may also be used. The mutual bond and the celebrity form a five-membered ring or a six-membered ring condensed to the ring ;; in this case, the ring system condensed to change is represented by the above formula (Ba) or (Bb)) a system represents the number of coordination groups, and 1 2. The lanthanide represents Co, Ni, or Fe. b is the valence of Μ and is 2 or 3. Lanthanide is an acetate ion, a vapor ion, a bromide ion, a telluride ion, a peroxyacid ion, a tetrafluoroborate ion, a tetraphenyl sulphate ion hexafluoroate ion, a quinone benzoate ion, a triple I The strontium sulphate ion is bis (trifluoromethanesulfonyl) quinone imine ion. The m system is necessary for neutralizing the positive charge of the complex compound. ♦ When the field m is 2 or more, the m X-systems may be the same or different. 100105051 19 201137051 [Chemical 7] R" + R 13

Mb+ (X')m a (H) [般式(II)中，L(將RuRuR⑽與連結的2價連接基L’ 或直接鍵結）、Rl、環B、Z、Μ、χ、a、b、及m，分別同 一般式(I)中的定義。Mb+ (X')ma (H) [In the general formula (II), L (RuRuR(10) and the linked divalent linking group L' or direct bonding), R1, ring B, Z, Μ, χ, a, b And m are respectively the same as defined in the general formula (I).

Ru〜R13係分別獨立表示可經i個以上氟原子所取代之直 鏈或分支的碳數1至4之、卜# 几基’或者可經下述烷基所取代的 苯基，該烧基係可經1個以卜> 碳數之綠。]_子所取代之錢或分支的 另外’本發明中，所謂「 姐^ 即具(4r+2)Tr電子料係、自然2私具芳香族性的環’ 或六員環之由單環或2或3個\^骨架構造通常係五 香環係涵蓋芳香族烴環、芳香族雜成的芳香環；該芳 個氫 等「· · · ·環基」，係指從此種=等香環基」 原子的1價取代基、或去掉2個氫原子的2去掉1 可具有1 再者，本發明中，所謂「可具有取代旯/接基 個以上取代基。 」係寺 [1-1·醯肼配位基] [1-1-1.醯肼配位基（1Α)] 錯合化合 首先，針對構成一般式（I)所示本發明醯肼螯人 100105051 20 201137051 物，具有N-陽離子骨架（環狀鑌鹽）的醯肼配位基，即下述一 般式（IA)所示醯肼配位基（以下亦稱「醯肼配位基（1A)」）進 行說明。 [化8]Ru to R13 each independently represent a straight or branched carbon number of 1 to 4, which may be substituted by i or more fluorine atoms, or a phenyl group which may be substituted with an alkyl group which is substituted by the following alkyl group. It can pass through 1 green with a carbon number. In addition, in the present invention, the so-called "sister ^ (4r + 2) Tr electronic system, natural 2 private aromatic ring' or six-membered ring by a single ring Or 2 or 3 skeleton structures are generally a five-fragrance ring system containing an aromatic hydrocarbon ring or an aromatic heterocyclic ring; the aromatic hydrogen such as "· · · · a ring group" means an aromatic ring from such = The "monovalent substituent" of the atom or the removal of 2 of the two hydrogen atoms may have one. In the present invention, "the substituent may have a substituent or a substituent." · 醯肼-ligand] [1-1-1. 醯肼-ligand (1Α)] Alignment and combination First, for the composition of the present invention (I) shown in the general formula (I) 100105051 20 201137051, with N The oxime ligand of the cation skeleton (cyclic sulfonium salt), that is, the oxime ligand represented by the following general formula (IA) (hereinafter also referred to as "anthracene ligand (1A)") will be described. [化8]

{環A} 環A係至少具有1個以上N原子的單一五員環或六員環 雜環、或由五員環及/或六員環構成的2或3環式縮合雜環； 環A係可為芳香環、亦可為非芳香環，當芳香環的情況， 環内的1個以上N原子形成四級化的鑌鹽，當非芳香環的 情況，環内的1個以上N原子形成四級化的銨鹽。 環A係由作為必要原子的N、以及C、N、Ο及S中之任 一者以上的原子形成；構成環A的C及N係可為無取代、 亦可具有以下的取代基。 C的情況，可具有選自下述基團中之任一者作為取代基： 可經1個以上氟原子取代的直鏈或分支的碳數1至4之烷 基；具有直鏈或分支的碳數1至4之烷基的烷氧基；無取代、 或具有1或2個直鏈或分支的碳數1至4之烷基的醯胺基； 具有直鏈或分支的碳數1至4之烷基的烷氧羰基；氰基之苯 基；及苄基。 100105051 21 201137051 至4之燒基作為取 N的情況’可具有直鏈或分支的碳數 代基。 田¥ A㈣香環時之例u卿分 咪唾環、㈣環、異•環、異啊環吻絲^之 環、苯并料環、笨并㈣環、三唾環、=本并· ㈣環、苯并異侧、物、w、物1二并 料環、異料環、如琳環、嗤㈣環、啊環展、 ㈣。比麵、蝴咪娜、啡㈣、笨并 %、啡啉環、啡畊環、咔唑環等。 班芳=環A的較佳例較佳為可具有取代基之㈣環味。坐 環、苯并心環、π㈣環、料環、㈣琳環、十坐環等， 其中’更佳係可具有取代基之，環、咪销H米嗤環、 匕坐衣啥琳J衣、異啥琳環，特別係從感度、記錄特性的觀 點，較佳係可具有取代基之Μ環、料環、異料環，而 從記錄雜與耐光㈣均峨點，較㈣可具有取代基的笨 并咪唑環。 當環Α係料香環時之例，係可舉例如分別可具有取代 基之吡咯烷環、吡咯啉環、咪唑啶環、咪唑啉環、吡唑啉環、 吡唑啶％、1，2,3,4-四氫喹啉環、四氫異喹啉環、吲 "朵啭環、異。引㈣環、.定環、μ環、味琳環、π昆咬環 (quinuclidinering)、二氮雜雙環辛烷環、十氫喹啉環、十氫 異喹啉環等。 100105051 22 201137051 非方香％ A的較佳例較佳為可ι .、有取代基之哌啶環、吡 各烷ί衷、咮啉環、二氮雜雙環辛燒 .0 . ^ w 衣12,3,4-四氫喹啉環、 ,，3,4-四氫異喹啉環、吲哚啉環 I.J. ΛΑ -a + 特別係從感度、記錄 特性的親點，較佳係可1有取代美 /、有取代基之哌啶吡咯烷環、二 氮雜雙環辛財、丨，2，认四氫異啥琳環。 環A形成鑌鹽的方法 杳係可考慮.對環A所含的N原子導 入取代基的情況 '以及T政道λ 9± 夂L係導入2價連接基的情況。 壞Α係°比0定的情況，係如下式(IA-a)與(IA-b)所示。以下， 2價連減，R絲示取代基。 [化9]{Ring A} Ring A is a single five-membered or six-membered ring heterocyclic ring having at least one N atom, or a two- or three-membered fused heterocyclic ring composed of a five-membered ring and/or a six-membered ring; The A system may be an aromatic ring or a non-aromatic ring. In the case of an aromatic ring, one or more N atoms in the ring form a quaternary phosphonium salt, and in the case of a non-aromatic ring, one or more N in the ring. The atom forms a quaternized ammonium salt. The ring A is formed of N as an essential atom and an atom of any one of C, N, oxime and S; and the C and N groups constituting the ring A may be unsubstituted or may have the following substituents. In the case of C, it may have any one selected from the group consisting of a straight chain or a branched alkyl group having 1 to 4 carbon atoms which may be substituted by one or more fluorine atoms; and has a straight chain or a branched chain. An alkoxy group having an alkyl group having 1 to 4 carbon atoms; an unsubstituted or decylamino group having 1 or 2 linear or branched alkyl groups having 1 to 4 carbon atoms; having a linear or branched carbon number of 1 to Alkoxycarbonyl group of 4 alkyl; phenyl group of cyano; and benzyl group. 100105051 21 201137051 The alkyl group of 4 to 4 may have a linear or branched carbon number base as the case of taking N. Tian ¥ A (four) fragrant ring example u 分 咪 唾 唾 唾 、 、 、 、 、 、 唾 唾 唾 唾 唾 唾 唾 唾 唾 唾 唾 唾 唾 唾 唾 唾 唾 唾 唾 唾 唾 唾 唾 唾 唾 唾 唾 唾 唾 唾 唾 唾 唾 唾 唾 唾 唾 唾 唾 唾 唾 唾Ring, benzoside, material, w, material 1 two-material ring, heterogeneous ring, such as Lin ring, 嗤 (four) ring, ah ring exhibition, (four). Specific surface, butterfly Mina, brown (four), stupid and %, phenanthroline ring, cultivating ring, indazole ring and so on. A preferred example of Banfang = Ring A is preferably a (iv) cyclic taste which may have a substituent. Ring, benzocentric ring, π (four) ring, ring, (four) ring, ten ring, etc., where 'better can have a substituent, ring, rice pin H m ring, 匕 啥 啥 J J J From the viewpoint of sensitivity and recording characteristics, it is preferred to have a ring, a ring, and a heterogeneous ring which may have a substituent, and from a recording impurity to a light-tolerant (four), it may have a substitution. The stupid and imidazole ring of the base. Examples of the ring-shaped oxime ring are, for example, a pyrrolidine ring, a pyrroline ring, an imidazolidinium ring, an imidazoline ring, a pyrazoline ring, a pyrazinidine %, and 1, 2 each having a substituent. , 3,4-tetrahydroquinoline ring, tetrahydroisoquinoline ring, 吲" (4) ring, ring, μ ring, taste ring, quinuclidine ring, diazabicyclooctane ring, decahydroquinoline ring, decahydroisoquinoline ring and the like. 100105051 22 201137051 A preferred example of non-fragrance % A is preferably ι, a substituted piperidine ring, a pyridinium, a porphyrin ring, a diazabicyclooctane. 0 . ^ w , 3,4-tetrahydroquinoline ring, , 3,4-tetrahydroisoquinoline ring, porphyrin ring IJ ΛΑ -a + especially from the sensitivity, recording characteristics of the parent point, preferably 1 Substituting the US/, a substituted piperidinylpyrrolidine ring, a diazabicyclooctane, an anthracene, 2, a tetrahydroisoindole ring. The method of forming a sulfonium salt by the ring A is considered to be the case where a substituent is introduced to the N atom contained in the ring A, and the case where the T-thrace λ 9± 夂L is introduced into a divalent linking group. The case where the gangrene ratio is 0 is as shown in the following formulas (IA-a) and (IA-b). Hereinafter, the divalent linkage is reduced, and the R filament shows a substituent. [Chemistry 9]

當％ A中導入取代基而形成陽離子的情況，對N的取代 基R係可列舉直鏈或分支的碳數1 JL 4之烧基。 燒基之例係可列舉：曱基、乙基、正丙基、異丙基、正丁 基、異丁基、1_甲基丙基。 較佳係甲基、乙基、正丙基、正丁基、異丁基，更佳係曱 基、乙基。 未參與陽離子形成的N之情況，係可列舉無取代(具氫原 子）、或者具有直鏈或分支的碳數1至4之烷基作為取代基 的情況。 100105051 23 201137051 烧基之例係可列舉：曱基、 基、異丁基、1-甲基丙基。 乙基、正丙基、異丙基、正丁 較佳者為無取代或具有甲基、乙基、正丙基m 丁基作為取代基者，更佳者為無取代或具有甲基、乙基作 取代基者。 ” 如前述’形成環A的C原子，係可為無取代、亦可具有 選自下述基團中往-者作為取代基：可經ι個以上氟原子 取代的直鏈或分支的碳數！至4之絲；具有直鏈或分支的 碳數1至4之烧基的絲基；無取代、或具有1或2個直鏈 或分支的碳數丨至4之絲的醯胺基；具有直鏈或分支的碳 數1至4之貌基的烧氧幾基；氰基；苯基；及节基。 C原子的取代基中，烧基之例係可列舉：曱基、乙基、正 丙基、異丙基、正丁基、異丁基、卜曱基丙基、三氟甲基、 2,2,2-三氟乙基、五氟乙基、六氟異丙基等。 烧氧基之例係可列舉：曱氧基、乙氧基、正丙氧基、異丙 氧基、正T氣基、異τ氧基、丨甲基丙氧基等。 酿胺基之例係可列舉：職基、研二曱胺基絲、N，N_ 二乙胺基羰基、N，N_二正丙基胺基羰基、n，n•正二丁基胺基 罗炭基、N-甲基I苯胺基羰基、N-乙基-N-笨胺基羰基等。 烷氧羰基之例係可列舉：曱氧羰基、乙氧羰基、正丙氧羰 基、異丁氧羰基、正丁氧羰基等。 形成裒A的c原子較佳係無取代、或可列舉下述基團作 100105051 24 201137051 為取代基：甲基、乙基、異丙基等直鏈或分支的破數1〜4 之烷基；三氟甲基等經氟原子取代的碳數1〜4之氟烷基；甲 氧基、乙氧基、異丙氧基等碳數1〜4的烷氧基；無取代或具 有碳數1至4之烷基的醯胺基；果有碳數丨至4之烷基的烷 氧裁基；氰基’更佳係無取代，或者從不會降低莫耳吸光係 數的觀點，較佳為具有下述基團作為取代基者：甲基、乙基、 異丙基等直鏈或分支的碳數1至4之烷基；甲氧基、乙氧基、 異丙氧基等直鏈或分支的碳數丨炱4的烷氧基等。 裱A的較佳構造具體例係如下所圖示，惟並不僅侷限於 下述者。 [化 10] (1)環A為吼啶的情況 (M)具連接基When a substituent is introduced into % A to form a cation, the substituent R for N may be a linear or branched carbon group having 1 JL 4 . Examples of the alkyl group include a mercapto group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, and a 1-methylpropyl group. Preferred are methyl, ethyl, n-propyl, n-butyl and isobutyl groups, more preferably an alkyl group or an ethyl group. In the case of N which does not participate in the formation of a cation, a case where there is no substitution (having a hydrogen atom) or an alkyl group having a linear or branched carbon number of 1 to 4 as a substituent may be mentioned. 100105051 23 201137051 Examples of the base are fluorenyl, benzyl, isobutyl and 1-methylpropyl. Ethyl, n-propyl, isopropyl, n-butyl is preferably unsubstituted or has a methyl, ethyl, n-propyl m butyl group as a substituent, more preferably unsubstituted or has a methyl group, a Base as a substitute. As described above, the C atom forming the ring A may be unsubstituted or may have a substituent selected from the group consisting of a straight chain or a branched carbon group which may be substituted with 1 or more fluorine atoms. a filament of 4 to 4; a filament group having a linear or branched carbon number of 1 to 4; an amine group having no substitution or having 1 or 2 linear or branched carbon numbers 丨 to 4; An aerobic acid group having a linear or branched carbon number of 1 to 4; a cyano group; a phenyl group; and a benzyl group. Among the substituents of the C atom, examples of the alkyl group include a mercapto group and an ethyl group. , n-propyl, isopropyl, n-butyl, isobutyl, bromopropyl, trifluoromethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, hexafluoroisopropyl, etc. Examples of the oxy group include a decyloxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a normal T gas group, an isoτoxy group, a fluorenylmethylpropoxy group, and the like. For example, it can be exemplified by: N, N-diethylaminocarbonyl, N,N-di-n-propylaminocarbonyl, n, n-n-dibutylaminocarbocarbyl, N-methyl Ianilinecarbonyl, N-ethyl-N-phenylaminocarbonyl, etc. Examples of the carbonyl group include an anthraceneoxycarbonyl group, an ethoxycarbonyl group, a n-propoxycarbonyl group, an isobutoxycarbonyl group, a n-butoxycarbonyl group, etc. The c atom forming the fluorene A is preferably unsubstituted or may be exemplified by the following groups. 100105051 24 201137051 is a substituent: a linear or branched alkyl group having a number of 1 to 4 such as a methyl group, an ethyl group or an isopropyl group; a fluoroalkane having a carbon number of 1 to 4 substituted with a fluorine atom such as a trifluoromethyl group; Alkoxy group having a carbon number of 1 to 4 such as a methoxy group, an ethoxy group or an isopropoxy group; an amidino group having no alkyl group having 1 to 4 carbon atoms; and having a carbon number of 4 to 4 The alkyl alkoxy group; the cyano group is more preferably unsubstituted, or from the viewpoint of not lowering the molar absorption coefficient, preferably having the following groups as a substituent: methyl, ethyl, isopropyl a linear or branched alkyl group having 1 to 4 carbon atoms; a linear or branched alkoxy group having a carbon number of 4 such as a methoxy group, an ethoxy group or an isopropoxy group; Specific examples of the structure are as follows, but are not limited to the following: (1) The case where the ring A is acridine (M) has a linking group

〇 • I .C* (1-2)無連接基〇 • I .C* (1-2) no connection base

(2)環A為笨并咪唑的情 (2-1)具連接基 100105051 25 201137051(2) Ring A is stupid and imidazole (2-1) with a connecting base 100105051 25 201137051

(3)環A為咪唑的情況 (3-1)具連接基(3) When ring A is imidazole (3-1) with a linker

(3-2)無連接基(3-2) No connection base

(4)環A為吡唑的情況 (4-1)具連接基(4) When ring A is pyrazole (4-1) has a linking group

(4-2)無連接基 100105051 26 201137051(4-2) No connection base 100105051 26 201137051

[化 11] (5)環A為旅°定的情況 (5-1)具連接基 (5-2)無連接基[5] (5) Ring A is determined by the trip (5-1) with a linker (5-2) without a linker

(6)環A為π比嘻烧的情況 (6-1)具連接基(6) Ring A is π than smoldering (6-1) with a linker

(6-2)無連接基(6-2) No connection base

(7)環Α為1，2,3,4-四氫異喹啉的情況 (7-1)具連接基 100105051 27 201137051(7) The case where the ring oxime is 1,2,3,4-tetrahydroisoquinoline (7-1) has a linking group 100105051 27 201137051

(7-2)無連接基(7-2) No connection base

[化 12] (8)環A為1，2,3,4-四氫喹啉的情況 (8-1)具連接基(8) Case where ring A is 1,2,3,4-tetrahydroquinoline (8-1) has a linking group

(9)環A為吲哚啉的情況 (9-1)具連接基(9) When ring A is a porphyrin (9-1) has a linking group

(9-2)無連接基 100105051 28 201137051(9-2) No connection base 100105051 28 201137051

{直接鍵結或連接基L} L係表示將環A與C*予以連結的2價連接基l，或直接鍵 結’該2價連接基I；係可具有直鏈或分支的碳數1至4之 烷基作為取代基之亞甲基、伸乙基、伸苯基、伸苯亞曱基、 或伸呋喃基。 如前述，針對醯肼配位基的電子局部化控制，利用含氮鏽 鹽的構造選擇便有可達成的可能性’另一方面，從醢肼螯合 錯合化合物的觀點，可考慮下述者。 已知與過渡金屬的錯合物一般係會提升耐光性，本發明醯 肼配位基與過渡金屬的錯合物之配位形態，可考慮下述三種 形態： (1) 使具醯肼配位基的取代基Z脫離活性氫，而與過渡金屬 形成配位鍵的形態； (2) Z為叛基的情況’由醯拼的幾基進行稀醇化而使活性氫脫 離，形成配位鍵的形態； (3) 從取代基Z及醯肼部位的NH使氫原子脫離而形成配位 鍵的形態。 本發明者等認為利用改變屬於該等錯合物形成部位的醯 肼骨架、與含氮鑌間之鍵結距離、及/或L的骨架，便可對 錯合物的安定化造成影響。預估該錯合物的安定程度會對記 100105051 29 201137051 錄特性、耐光性造成影響。 以下’針對可改變醯肼骨架與含氮鑌鹽間之鍵結距離、及 骨架的L(直接鍵結或連接基)進行敘述。 本發明的鏽鹽係經由L而鍵結於形成醯肼骨架的碳原子 C*上。 該L係可列舉直接鍵結、或以下的2價連接基L，： 可具有直鏈或分支的碳數1〜4之烷基的亞曱基、 可具有直鏈或分支的碳數1〜4之烷基的伸乙基、 可具有直鏈或分支的碳數1〜4之烷基的伸苯基、 可具有直鏈或分支的碳數1〜4之烷基的伸苯亞曱基、 可具有直鏈或分支的碳數1〜4之烷基的伸呋喃基。 從感度的觀點，連接基L'較佳係未具取代基的亞曱基。 理由係由具吸電子性的鏽鹽與醯肼的羰基所包夾的亞曱基 會成為活性亞甲基’喊高亞甲基的酸性度，#此便提高酿 耕配位基分子㈣電子局部化，更可期待提升記錄時的雷射 感度。 另-方面，從耐光性提升的均衡觀點，較佳係可具有取代 基的亞曱基、可具有取代基的伸乙基、可具有取代基的伸苯 基、可具有取絲的伸吱絲’純係未錄代基的伸苯基。 連接基L，具取代基的情況，可列舉直鍵或分支的碳數卜4 的烷基作為取代基。 該烷基係可列舉： 曱基、乙基、正丙基、異丙基、正丁基、 100105051 30 201137051 異丁基、1-曱基丙基，較佳係甲基、乙基。 環A係芳香族雜環的情況、以及非芳香族雜環A上的碳 原子與醯肼骨架的碳原子C*相連結的情況，L係可為直接 鍵結，環A與碳原子C*可直接键結。 另一方面，非芳香族雜環A上的氮原子、與醯胼·骨架的 碳原子C*相連結之情況、以及為確保後述一般式(II)所示醯 肼螯合錯合化合物的化合物安定性，相較於醯肼骨架的碳原 子C*係直接鍵結，較佳係經由適當的連接基L’。 屬於鏽鹽的環A與碳原子C*亦可為未經由連接基L’而直 接鍵結的構造。 此情況，形成鏽鹽的含氮雜環A之骨架構造，係與具連 接基L'的醯肼螯合錯合物為同樣的，在屬於由五員環或六 員環構成之具單環或縮合環構造的前提下，並無特別的限 制，因為鑌鹽的吸電子性會直接對醯肼螯合骨架造成影響， 因而相較於具取代基L’的情況下，較佳的環狀鏽鹽會有若 干差異。 L為直接鍵結時的環A之較佳例，具體而言，環A為芳 香環時之例，可列舉： °比σ坐環、味σ坐環、苯并σ米β坐環、異崎σ坐環、°塞σ坐環、苯并 售17坐環、吼11 定環、啥琳環、異喧琳環、喧°号淋環、喧峻琳環、 σ辛琳環、吹β井環等； 環Α為非芳香環時之例，係可列舉： 100105051 31 201137051 鱗烧環、轉琳環、㈣魏、_㈣環、_ 口比錢環、12,3,4-四氫啥琳環、1>2，认四氣異喧琳環"引 哚琳環、異十朵啦環、派咬環、旅讲環、味嘴環"昆咬产等 L為直接鍵結的情況、以2價連接基叫情況，= 類係 A致同樣，但L為直接鍵結的情況，藉由選擇形成醯肼基 的C*與該等環A的鍵結位置，便可調整化合物的特性。 例如㈣肺的情況，當形祕肼骨架的碳原子c*鍵社 於。比謂鹽的4位時，因為受強吸電子性的影響導致吸收: 長呈長波長化，因而可確保記錄再生時的充分反射率，另一 方面卻會有記錄感度降低的可能性。為能利用i種色素便獲 得充分的記錄感度與反射率，形成醢肼骨架的碳原子c*較 佳係鍵結於㈣鏽鹽的2位或3位，當併用2種以上色素的 情況，藉由將使長波長化的細肼色素添加於反射率較低的 其他色素中’便可調整反射率。 環A係2環式縮合環，且未形成鏘鹽之一側的環與形成 醯肼基的C*相鍵結之情況，具體而言，σ引嗤環、笨并B米唾 環、苯并十坐環、苯并㈣環、苯并三^坐環“㈣琳環、異 吲哚啉環、喹啉環、異喹啉環、喹嘮啉環、喹唑啉環、咔咻 環、吹啡環、1，2,3,4-四氫喧琳環、^4-四氣異嗤琳環等 的苯環側之碳原子與形成醯肼骨架的碳原子c*相鍵結^情 況’因為可視同在雜環陽離子構造、與形成醯肼骨架的碳^ 子C*之間’介存著縮合環的笨環，因而[為直接鍵結的情 100105051 32 201137051 況亦與經由連接基L，的情況係同樣地可調整記錄特性 光性的均衡。 τ 再者’ ％ Α為非芳香環的情;兄，因為環a上的碳原子、 與醯肼的&料〇間之直接鍵結可確保安料，故而較佳。 {配位性取代基Z} 配位!生取代基z係含有氧原子，具體而言，係經基 烯醇化的羰基。 Z中所含的鍵結•配位性原子，係具有與中心金屬相鍵結、 或作為配純原子的機能，對本發魏肼螯合錯合化合物的 8面體構造安疋化具貢獻，被認為對耐久性提升具有作用、。 為幾基的If况，雖有揭示利用後述環B的構造而改變歸 醇化輕易度的可能性，但此情況，醯肼構造的縣進行稀醇 化所生成的Μ基’亦可與過渡金屬陽離子進行配位而成 面體構造。 {環Β} 環Β係可具有配錄取代基ζ的環狀基從抑制所形 錯合物的變形、以及記錄特性的觀點，係設為五員環或六。 環的環狀構造。若相當於環Β的部分為鏈狀構造時，因= 吸收形狀會呈展寬化、吸㈣度讀低、且安紐與記 性會降低等，非屬較佳ϋ β必須為環狀基。 本發明中，環Β係表示由下式(B_a)或(B_b)所示除Ζ 外尚亦可射取代基的五員環或以料錢或雜環于'。即之 100105051 33 201137051 環B係可具Z的五員環或六員環之單環或2環式縮合環構 造，而五員環、六員環係可為芳香環、亦可為非芳香環。 [化 13]{Direct bond or linker L} L represents a divalent linker l linking ring A and C*, or a direct bond 'the divalent linker I; a carbon number which may have a straight chain or a branch 1 The alkyl group to 4 is a methylene group of a substituent, an ethyl group, a phenyl group, a benzoquinone group, or a furyl group. As described above, for the electronic localization control of the ruthenium ligand, there is a possibility that the structure selection using the nitrogen-containing rust salt is possible. On the other hand, from the viewpoint of chelating the chelating compound, the following can be considered. By. It is known that a complex with a transition metal generally enhances light resistance. The coordination form of the complex of the ruthenium ligand and the transition metal of the present invention can be considered in the following three forms: (1) The substituent Z of the group is deactivated from the active hydrogen and forms a coordinate bond with the transition metal; (2) The case where Z is a tickyl group's dilute alcoholization by a few groups of the hydrazine to deactivate the active hydrogen to form a coordinate bond (3) A form in which a hydrogen bond is removed from the substituent Z and the NH in the oxime to form a coordinate bond. The inventors of the present invention thought that it is possible to influence the stability of the complex by changing the skeleton of the ruthenium skeleton belonging to the site of formation of the complexes, the bonding distance with the nitrogen-containing ruthenium, and/or the skeleton of L. It is estimated that the stability of the complex will affect the recording characteristics and light resistance of 100105051 29 201137051. Hereinafter, the bonding distance between the anthracene skeleton and the nitrogen-containing phosphonium salt and the L (direct bonding or linking group) of the skeleton will be described. The rust salt of the present invention is bonded to the carbon atom C* forming the anthracene skeleton via L. The L system may be a direct bond or a divalent linking group L: a fluorenylene group having a linear or branched alkyl group having 1 to 4 carbon atoms, and a carbon number which may have a straight chain or a branch 1~ An alkyl group having 4 alkyl groups, a phenyl group which may have a linear or branched alkyl group having 1 to 4 carbon atoms, and a phenylene group having a linear or branched alkyl group having 1 to 4 carbon atoms. A furfuryl group which may have a linear or branched alkyl group having 1 to 4 carbon atoms. From the viewpoint of sensitivity, the linking group L' is preferably an unindenylene group. The reason is that the sulfhydryl group with the electron-withdrawing rust salt and the ruthenium carbonyl group will become the acidity of the active methylene group, and the acidity of the active methylene group will increase the electron localization of the cultivating ligand molecule. It is also expected to improve the laser sensitivity when recording. On the other hand, from the viewpoint of the balance of improvement in light resistance, a fluorenylene group which may have a substituent, an ethyl group which may have a substituent, a phenyl group which may have a substituent, and a silk which may have a wire are preferably used. 'Pure phenyl is not recorded on the base. In the case where the linking group L has a substituent, a linear or branched alkyl group having 4 carbon atoms may be mentioned as a substituent. The alkyl group may, for example, be an alkyl group, an ethyl group, a n-propyl group, an isopropyl group or an n-butyl group, and 100105051 30 201137051 isobutyl group or 1-mercaptopropyl group, preferably a methyl group or an ethyl group. In the case of the ring A-based aromatic heterocyclic ring and the case where the carbon atom on the non-aromatic heterocyclic ring A is bonded to the carbon atom C* of the anthracene skeleton, the L system may be a direct bond, and the ring A and the carbon atom C* Can be directly bonded. On the other hand, the nitrogen atom on the non-aromatic heterocyclic ring A is bonded to the carbon atom C* of the fluorene skeleton, and the compound which ensures the chelating compound of the oxime compound shown in the general formula (II) to be described later. The stability is preferably directly bonded to the carbon atom C* of the anthracene skeleton via a suitable linking group L'. The ring A and the carbon atom C* which are rust salts may also be a structure which is not directly bonded via the linking group L'. In this case, the skeleton structure of the nitrogen-containing heterocyclic ring A forming the rust salt is the same as the ruthenium chelate complex having the linker L', and is a single ring composed of a five-membered ring or a six-membered ring. Or the condensed ring structure is not particularly limited, since the electron withdrawing property of the cerium salt directly affects the cerium chelating skeleton, and thus the ring is preferred as compared with the substituent L'. There are several differences in rust salts. L is a preferred example of the ring A in the case of direct bonding, and specifically, an example in which the ring A is an aromatic ring, and examples thereof include: a ratio σ ring, a taste σ ring, a benzo σ meter β ring, and a different Saki σ seat ring, ° plug σ seat ring, benzene and sell 17 seat ring, 吼11 ring, 啥琳环, 喧喧琳环, 喧°号 淋环, 喧君琳环, σ辛琳环, 吹β井环Etc.; when the ring is a non-aromatic ring, it can be cited as: 100105051 31 201137051 scaly ring, turn ring, (four) Wei, _ (four) ring, _ mouth than money ring, 12,3,4-tetrahydro 啥 ring , 1 > 2, recognize the four-way heterogeneous ring ring " lead 哚 环 ring, different ten ring ring, send bite ring, travel ring, taste mouth ring " Kun bite production and other L is a direct bond, In the case of a 2-valent linkage, the same is true for the class A, but L is a direct bond. By selecting the bonding position of the C* forming the thiol group and the ring A, the properties of the compound can be adjusted. . For example, (iv) the condition of the lungs, when the carbon atom of the skeleton skeleton is c* bond. When the ratio is 4, the absorption is caused by the strong electron absorption: the long wavelength is long, so that sufficient reflectance during recording and reproduction can be ensured, and on the other hand, there is a possibility that the recording sensitivity is lowered. In order to obtain sufficient recording sensitivity and reflectance by using the i-type pigment, the carbon atom c* which forms the anthracene skeleton is preferably bonded to the 2 or 3 position of the (4) rust salt, and when two or more kinds of pigments are used in combination, The reflectance can be adjusted by adding a long-wavelength fine ruthenium pigment to other pigments having a low reflectance. Ring A is a 2-ring condensed ring, and the ring on one side of the sulfonium salt is not bonded to the C* phase forming the sulfhydryl group, specifically, the σ 嗤 ring, the stupid B B ring, and the benzene. And ten-ring, benzo (tetra) ring, benzotriazine ring "(four) ring, isoporphyrin ring, quinoline ring, isoquinoline ring, quinoxaline ring, quinazoline ring, anthracene ring, The carbon atom on the benzene ring side of the blowing ring, the 1,2,3,4-tetrahydroindenyl ring, the ^4-tetraisoxanthene ring, and the carbon atom c* which forms the anthracene skeleton are bonded to each other. 'Because it can be seen that the heterocyclic cation structure and the carbon group C* forming the anthracene skeleton 'have a stupid ring of a condensed ring, so [for direct bonding, 100105051 32 201137051 also via a linker. In the case of L, the balance of the recording characteristic light can be adjusted in the same way. τ In addition, '% Α is a non-aromatic ring; brother, because the carbon atom on the ring a, and the 醯肼 & The bond is preferred to ensure the charge, so it is preferred. {Coordination substituent Z} Coordination! The substituent z contains an oxygen atom, specifically a carbonyl group-based carbonyl group. • Coordination The sub-system has a function of bonding with a central metal or as a pure atom, and contributes to the octahedral structure of the fluorene-chelating compound of the present invention, and is considered to have an effect on durability improvement. In the case of the case, it is revealed that the structure of the ring B described later is used to change the ease of alcoholization. However, in this case, the sulfhydryl group formed by the leaning of the 醯肼 structure can also be coordinated with the transition metal cation. Concave structure. {Circle Β} The cyclic ruthenium may have a cyclic group in which a substituent oxime is attached, and is a five-membered ring or a hexacyclic ring from the viewpoint of suppressing deformation of the shaped complex and recording characteristics. If the part corresponding to the ring is a chain structure, the shape of the absorption will be broadened, the reading of the suction (four) degree will be low, and the value of the Anu and the memory will be reduced. In the present invention, the cyclic oxime system means a five-membered ring which may be substituted by a substituent represented by the following formula (B_a) or (B_b) or may be a distillate or a heterocyclic ring. 100105051 33 201137051 Ring B series single or two ring condensed rings with a five-membered or six-membered ring of Z Made, the five-membered ring, six-membered rings may be aromatic ring system, may also be a non-aromatic ring. [Formula 13]

Z (B - a) Z (B—b) (上式中，原子B〗係表示C、S、或N。Z (B - a) Z (B-b) (In the above formula, the atom B is C, S, or N.

Bi為C的情況，可為無取代、亦可具有選自可經1個以 上氟原子所取代之直鏈或分支的碳數1至4之烷基、及羥基 中之任一者作為取代基；亦可構成由C與0利用雙鍵連結 的羰基。 當I為S的情況，可為無取代、亦可構成由S與0利用 雙鍵連結的亞砜基、或砜基。In the case where Bi is C, it may be unsubstituted or may have a substituent selected from a straight chain or a branched alkyl group having 1 to 4 carbon atoms which may be substituted by one or more fluorine atoms, and a hydroxyl group. Or a carbonyl group in which C and 0 are linked by a double bond. When I is S, it may be unsubstituted or may constitute a sulfoxide group or a sulfone group which is bonded by S and 0 by a double bond.

Bi為N的情況，可為無取代、亦可具有可經1個以上氟 原子所取代之直鏈或分支的碳數1至4之烷基作為取代基。 原子B2〜B4係分別獨立表示C、N、或Ο。 B2〜B4為C的情況，可為無取代、亦可具有選自： 可經1個以上氟原子所取代之直鏈或分支的碳數1至4 之烷基；羥基；具有直鏈或分支的碳數1至4之烷基的烷氧 基；具有1或2個直鏈或分支的碳數1至4之烷基的胺基； 亦可含有1個氧原子之三員環至七員環的脂肪族環狀胺 基；無取代、或具有1或2個直鏈或分支的碳數1至4之烷 100105051 34 201137051 基的醯胺基；具有直鏈或分支的碳數1至4之烷基的烷氧羰 基；具有直鏈或分支的碳數1至4之烷基的烷羰基；苯基； 及氰基之任一者作為取代基；亦可構成由C與〇利用雙鍵 連結的羰基、由C與S利用雙鍵連結的硫代羰基、或者由c 與可經直鏈或分支的碳數1至4之烷基所取代的N利用雙 鍵連結的亞胺基；亦可形成可經直鏈或分支的碳數丨至4 之烷基所取代的三員環至七員環的環烷、稻烷、或金剛烷的 螺環； B2〜B4為N的情況，可為無取代、亦可具有直鏈或分支的 碳數1至4之烷基、具有直鏈或分支的碳數丨至4之烷基的 烷氧基、或苯基作為取代基。 又’ 中相鄰接的2個原子之取代基亦可相互鍵結， 形成縮合於環B的五員環或六員環。此情況，縮合於環b 的環係由上式(B-a)或(B-b)所示。） 上述J衣構造之例係有如Aldrich Chemistry 2009-2010, ρ·ρ.2935-2938所舉例者等，具體而言，可列舉：水楊酿衍 生物、吼啶酮衍生物、嘧啶衍生物、吡啶酮衍生物、巴比妥 酸衍生物、吡唑啶衍生物、丙二酸環亞異丙酯衍生物、硫巴 比妥酸衍生物、乙内醯脲衍生物' 硫代乙内醯脲 (thiohydantoin)衍生物、噚唑酮衍生物、環己酮衍生物、環 己二烯酮衍生物、茚酮衍生物、《比喃酮衍生物、香豆素衍生 物、吡唑啶衍生物、萘酮衍生物、喹啉二_衍生物 100105051 35 201137051 (quinolinedione derivative)、並 人_ 明讨生物、啥嚇酮衍生物、 異喹啉酮衍生物、吼唑啉g同衍峰4 物、異α号唑啉酮衍生物、哌 咬酮衍生物、η比唑咬酮衍生物、 四氫噻唑酮衍生物、苯醌衍 生物、萘酿衍生物、嗟讲衍生物 4畊衍生物、2-羥喹啉衍 生物、噻唑啶酮衍生物等。 從記錄特性的觀點，環Β的軔 季交佳月架構造為環Β内具醯 胺鍵結的吼咬酮衍生物、0密咬料斗 王物、吡唑啶衍生物、苯并 噻讲衍生物，會呈現較佳結果。 ^ ^ 难具有醯胺鍵結到底為何會 牽連於特性提升的詳細情形雖尚 禾月朗’但從相較於諸如水 揚醛之類環内電子豐富的構造之 / 卜’環内缺乏電子的吡啶酮 衍生物與嘧啶衍生物之記錄特 ^ L ^ 較良好，以下所詳細說明的 取代基效果觀之例如從的情m絲㈣ 酮與具絲絲㈣铜大Μ於雜良好的錯合物等情 況觀之，可認為環Β亦是較伟发4由 心平乂佳為適度的吸電子性，且較佳 係可對醯肼配位基的電子局部化具貢獻之環Β。 其他較佳的環Β之骨架構造係可列舉丙1酸環亞異丙醋 衍生物。理由可認為丙二酸環亞異丙賴本身為容易因熱而分 解的構造或許是理由之—。即，可認為彻雷射光吸收而激 發醯肼錯合物，再利用此時所味士、拍 所生成的熱使丙二酸環亞異丙酯 骨架分解，便形成記錄標記。 針對較佳的環Β與取代基之組合，係如下示。 環Β為吡啶酮衍生物的6_羥基 丞2比啶酮裱之情況，取代 100105051 36 201137051 或燒氧，又，顺生物的 二St代基係具有二㈣，基，再者二 成_ = ^ 基#苯并嗟啡環之情況，將s形 成風構k而成為吸電子 均屬較佳。 K合成上、以及記錄特性上而言 再者’為確保具有該等環δ的醯肼錯合物之溶劑溶解性 =取代基必須具有絲㈣況，而崎況絲從記錄特 而吕、，較佳為碳數1〜4的烧基，特佳為甲基、乙基。 j Β為丙—⑽亞異丙g旨衍生物的情況為求錯合物的 女疋化’藉由將丙二酸環亞異㈣構造的2位取代基形成破 數3 7的螺減構造，諸如金職基之類的交 等，便可魏靖躲財料的均衡。 含有作為配位性取代其7 另外 的鍵結位置 如下示，惟並不抑一下^^基絲基的環^具體例 ’以下標註「來 一 J的部位係酼肼配位基對 [化 14] < 0比唆酮衍生物之例 100105051 37 201137051When Bi is N, it may be unsubstituted or may have a linear or branched alkyl group having 1 to 4 carbon atoms which may be substituted by one or more fluorine atoms as a substituent. The atoms B2 to B4 each independently represent C, N, or Ο. When B2 to B4 are C, it may be unsubstituted or may have a linear or branched alkyl group having 1 to 4 carbon atoms which may be substituted by one or more fluorine atoms; a hydroxyl group; having a straight chain or a branch An alkoxy group having 1 to 4 carbon atoms; an amine group having 1 or 2 linear or branched alkyl groups having 1 to 4 carbon atoms; or a three-membered ring containing one oxygen atom to seven members Acyclic aliphatic amine group; unsubstituted, or having 1 or 2 linear or branched carbon number 1 to 4 alkyl 100105051 34 201137051 base amide group; having a linear or branched carbon number 1 to 4 An alkoxycarbonyl group of an alkyl group; an alkylcarbonyl group having a linear or branched alkyl group having 1 to 4 carbon atoms; a phenyl group; and a cyano group as a substituent; or a double bond derived from C and hydrazine a linked carbonyl group, a thiocarbonyl group in which C and S are bonded by a double bond, or an imine group in which N is substituted with a linear or branched alkyl group having 1 to 4 carbon atoms by a double bond; a ring of a three-membered to seven-membered ring of a cyclohexane, a rice alkane or an adamantane which may be substituted by a linear or branched alkyl group having a carbon number of 4 to 4; wherein B2 to B4 are N, for It is unsubstituted, and may have a linear or branched alkyl group having 1 to 4 carbon atoms, an alkoxy group having a linear or branched carbon number of 丨 to 4, or a phenyl group as a substituent. Further, the substituents of two adjacent atoms may be bonded to each other to form a five-membered ring or a six-membered ring condensed to the ring B. In this case, the ring system condensed to the ring b is represented by the above formula (B-a) or (B-b). Examples of the J-cloth structure described above are exemplified by Aldrich Chemistry 2009-2010, ρ·ρ. 2935-2938, and specific examples thereof include a watery-fermented derivative, an acridone derivative, a pyrimidine derivative, and the like. Pyridone derivatives, barbituric acid derivatives, pyrazolidine derivatives, isopropylidene malonate derivatives, thiobarbituric acid derivatives, beta-urea urea derivatives 'thiobenzamide (thiohydantoin) derivative, oxazolone derivative, cyclohexanone derivative, cyclohexadienone derivative, anthrone derivative, "pyrone derivative, coumarin derivative, pyrazolidine derivative, Naphthalenone derivatives, quinoline di-derivatives 100105051 35 201137051 (quinolinedione derivative), _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Α-oxazolinone derivative, piperidone derivative, η-Bizozolone derivative, tetrahydrothiazolone derivative, benzoquinone derivative, naphthalene derivative, 嗟 衍生物 derivative 4 cultivating derivative, 2- A quinolinol derivative, a thiazolidinone derivative or the like. From the viewpoint of recording characteristics, the structure of the Β 交 交 交 交 架 构造 构造 构造 构造 构造 构造 构造 构造 构造 构造 构造 构造 构造 构造 构造 构造 构造 构造 构造 构造 构造 构造 构造 构造 构造 构造 构造 构造 构造 构造 构造 构造 构造 构造 构造 构造 构造Things will show better results. ^ ^ It is difficult to have a detailed description of why the indole bond is implicated in the characteristic improvement, although it is still sturdy, but it lacks electrons from the structure of the electrons rich in the ring such as salicylaldehyde. The recording of the pyridone derivative and the pyrimidine derivative is particularly good, and the effect of the substituents described in detail below is, for example, from the case of the ketone (tetra) ketone and the silk (tetra) copper. In view of the situation, it can be considered that the ring is also moderately electron-absorbable by Weixin 4, and is preferably a ring that contributes to the electronic localization of the ruthenium ligand. Other preferred skeleton structures of the cyclic oxime include a propionic acid isopropylidene vinegar derivative. The reason may be that the malonate cycloisopropylidene itself is a reason for the structure that is easily decomposed by heat. In other words, it is considered that the laser light is absorbed to excite the complex compound, and the heat generated by the taste and the film is used to decompose the isopropylidene malonate skeleton to form a recording mark. For the preferred combination of ring and substituent, the following is shown. In the case where the cyclic oxime is a pyridone derivative of 6-hydroxyindole 2 in the case of a ketoxime, it is substituted for 100105051 36 201137051 or oxygenated, and the second st-based system of the cis-gene has two (four), base, and then 20% _ = ^ In the case of the base benzoxanthene ring, it is preferred to form s wind structure k and absorb electrons. In terms of K synthesis and recording characteristics, in order to ensure the solvent solubility of the ruthenium complex having such a ring δ = the substituent must have a silk (four) condition, and the condition of the silk is from the record, The alkyl group having a carbon number of 1 to 4 is preferably a methyl group or an ethyl group. j Β is a C-(10) isopropylidene derivative in the case of a virginization of a complex compound, which is formed by a snail reduction structure in which a 2-position substituent of a malonate ring heterotetra(4) structure is broken. For example, such as the gold base, the balance of Wei Jing can hide. In addition, as a ligating substitution, the other bonding position is as follows, but the ring of the base group is not inhibited. The specific example of the following is the following: ] < 0 example of ketone derivative 100105051 37 201137051

<嘧啶衍生物之例><Example of pyrimidine derivative>

<苯并噻畊衍生物之例><Example of benzothipine derivatives>

<丙二酸環亞異丙酯衍生物之例><Example of isopropylidene malonate derivative>

{Ri} 100105051 38 201137051{Ri} 100105051 38 201137051

Rl係表示氫原子、或直鏈或分支的碳數1至4之烧基。 Ri的烧基之例係可列舉：曱基、乙基、正丙基、異丙基、 正丁基、異丁基、甲基丙基等，較佳係氫原子或曱基，更 佳係氫原子。 醢肼配位基(ΠΑ)] 其次，針對構成一般式(Π)所示本發明醯肼螯合錯合化合 物、具有Ν陽離子骨架的醯肼配位基，即下述一般式(ha) 所示醯肼釔位基（以下亦稱「醯肼配位基(ΙΙΑ)」）進行說明。 [化 15]R1 represents a hydrogen atom, or a linear or branched carbon group having 1 to 4 carbon atoms. Examples of the alkyl group of Ri include a mercapto group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a methylpropyl group and the like, and preferably a hydrogen atom or a mercapto group, and more preferably a hydrogen atom or a mercapto group. A hydrogen atom.醢肼ligand (ΠΑ)] Next, the oxime ligand having the ruthenium cation skeleton of the present invention represented by the general formula (Π), that is, the following general formula (ha) The indication base (hereinafter also referred to as "醯肼-based base (ΙΙΑ)") will be described. [化15]

Rn Ri2~N-L + ^13 ΟRn Ri2~N-L + ^13 Ο

Ri (ΠΑ) 該醯肼配位基(ΠΑ)中，L(將RUR12R13N與C*予以連結的 2價連接基或直接鍵結）、環b、配位性取代基z、過渡金屬 Μ及其價數b、相對離子χ-及其數目m、以及醯肼配位基數 a，分別與表示醯肼配位基(IA)的一般式(IA)同義，關於其具 體例及較佳例亦相同。Ri (ΠΑ) In the oxime ligand (ΠΑ), L (a divalent linking group or a direct bond linking RUR12R13N to C*), a ring b, a coordinating substituent z, a transition metal ruthenium and The valence number b, the relative ion enthalpy-and its number m, and the enthalpy coordination group a are synonymous with the general formula (IA) representing the fluorene ligand (IA), respectively, and the specific examples and preferred examples thereof are also the same. .

Ru〜R13係將N成為銨陽離子的取代基，取代基 係分別獨立地可列舉可經丨個以上氟原子取代的直鏈或分 支烷基、或可具有可經〗個以上氟原子取代之直鏈或分支烷 基的苯基。 烧基之例係可列舉：曱基、乙基、正丙基、異丙基、正丁 100105051 39 201137051 基、異丁基、1-曱基丙基、三氟甲基、2,2,2-三氟乙基、五 氟乙基、六氟異丙基等。 苯基之例係可列舉：苯基、對甲基苯基、鄰曱基苯基、間 甲基苯基、對乙基苯基、鄰乙基苯基、間乙基苯基 '對(正 丙基)苯基、鄰(正丙基)苯基、間（正丙基)苯基、對異丙基笨 基、鄰異丙基苯基、間異丙基苯基、對(正丁基)笨基、鄰(正 丁基）苯基、間（正丁基）苯基、對異丁基苯基、鄰異丁基苯基、 間異丁基苯基、對三I曱基苯基、鄰三I曱基笨芙、門=氣 曱基苯基、對-2,2,2-三氟乙基苯基、鄰-2,2,2-三氣乙基苯A、 間-2,2,2-二氟乙基苯基、對五氣乙基笨基、間六氟異丙基笨 基等。 取代基Rll〜Rl3的較佳例分別獨立地係可列舉曱基、乙 基、正丙基、異丙基、正丁基、異丁基、三氣曱基、222 三氟乙基、五氟乙基、苯基。 取代基Ru〜Rn的較佳組合’即基的較佳例較 佳為三烧基胺、二苯胺、本基炫•基胺專’其中較佳係呈有碳 數1至4之烷基的三烷基胺、可具有碳數1至4之取代基的 單苯二烷基胺’特佳係三曱胺、三乙胺、二曱基笨胺、二乙 基苯胺。 [1-2.相對陰離子X] 相對陰離子X'係醋酸根離子、氣化物離子、漠、化物離子、 峨化物離子、過氣酸根離子、四n鄉酸根離子、四笨基侧酸 100105051 40 201137051 根離子根離子1笨魏根離子、三Μ續酸根 離子、或雙（三氣甲績酿基）鲰亞胺離子。 藉由該等陰離子的選擇’便可調整對塗佈溶劑的溶解性， 或改變陰離子與_子的^作用強度，俾提升錯合物的耐 久性。 該等之中，從财光性的觀點，X-較佳係六氣璘酸根離子、 三氟曱雜根離子、雙(三h顧基)輕胺離子。 [1-3.中心金屬Μ及價數b] M係表示選自Ni、C〇、及仏中的過渡金屬。 從錯合物的耐光性觀點，Μ較佳係c〇。 b係表示上述過渡金屬陽離子的價數。b係2或3。 [1-4.醯肼配位基數a及相對陰離子數 a係表示醯肼配位基的數目，且為1戍2 m係表示相賴離子Χ·的數目，且為將含有配位基與金 屬的錯合物整體之正電荷予以中和所需要的數量。 通常，m係0〜2，當m=2的情況，2個χ-係可為相同〈亦 可為不同。 [Ι_5.錯合物構造] 本發明酿耕螯合錯合化合物係從環Β上的配位性取代基 Ζ之教基、或ζ的幾基進行稀醇化而生成的羥基中脫離氫原 子’再與過渡金屬Μ形成錯合物。或者’亦有從醯拼部位 的叛基進行婦醇化而生成的經基、或從醯肼部位的Νη脫離 41 100105051 201137051 氫原子，再與過渡金屬M形成錯合物的情況。 以下，針對該錯合物形成的形態進行說明。 況] 此情況， 基數a為2 I：1 5 h僅從配位性取代基z脫離氫原子而形成錯合物的情 例如若過渡金屬Μ為c〇2+、電荷b為2、配位 土 ’’、、，便如下式（Ia)所示，為將整體予以中和所必要 的相對陰離子χ-數m係2個。 [化 16]Ru to R13 are a substituent in which N is an ammonium cation, and each of the substituents may independently be a linear or branched alkyl group which may be substituted with one or more fluorine atoms, or may have a straight one or more substituted with one or more fluorine atoms. A phenyl group of a chain or branched alkyl group. Examples of the base are: mercapto, ethyl, n-propyl, isopropyl, n-butyl 100105051 39 201137051 base, isobutyl, 1-mercaptopropyl, trifluoromethyl, 2, 2, 2 -Trifluoroethyl, pentafluoroethyl, hexafluoroisopropyl, and the like. Examples of the phenyl group include a phenyl group, a p-methylphenyl group, an o-nonylphenyl group, a m-methylphenyl group, a p-ethylphenyl group, an o-ethylphenyl group, and a m-ethylphenyl group. Propyl)phenyl, o-(n-propyl)phenyl, m-(n-propyl)phenyl, p-isopropylphenyl, o-isopropylphenyl, m-isopropylphenyl, p-(n-butyl Stupid, o-(n-butyl)phenyl, m-(n-butyl)phenyl, p-isobutylphenyl, o-isobutylphenyl, iso-isobutylphenyl, p-trimethoxyphenyl , o-three I 曱 笨 芙, door = gas phenyl, p--2,2,2-trifluoroethyl phenyl, o--2,2,2-tris-ethyl benzene A, m-2 2,2-difluoroethylphenyl, p-pentaethylethyl stupyl, m-hexafluoroisopropyl stylyl and the like. Preferred examples of the substituents R11 to Rl3 are each independently fluorenyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tris-decyl, 222 trifluoroethyl, pentafluoro. Ethyl, phenyl. A preferred example of the preferred combination of the substituents Ru to Rn is preferably a trialkylamine, a diphenylamine or a fluorenylamine which preferably has an alkyl group having 1 to 4 carbon atoms. A trialkylamine, a monophenyldialkylamine which may have a substituent of 1 to 4 carbon atoms, is preferably a tridecylamine, a triethylamine, a dimercaptoamine, or a diethylaniline. [1-2. Relative anion X] Relative anion X' is an acetate ion, a vaporized ion, a desert ion, a telluride ion, a peroxyacid ion, a tetra n-acid ion, a tetrabasic acid 100105051 40 201137051 Root ion ion 1 stupid Weigen ion, trisodium citrate ion, or bis (three gas) yttrium ion. By the choice of these anions, the solubility in the coating solvent can be adjusted, or the strength of the anion and the cation can be changed, and the durability of the complex can be improved. Among these, X- is preferably a hexafluoroantimonate ion, a trifluoromethane ion, or a bis(tri-h-carbyl) light amine ion from the viewpoint of luminosity. [1-3. Center metal ruthenium and valence b] M represents a transition metal selected from the group consisting of Ni, C 〇, and 仏. From the viewpoint of the light resistance of the complex, Μ is preferably c〇. b represents the valence of the above transition metal cation. b is 2 or 3. [1-4. 醯肼 Coordination base a and relative anion number a represents the number of 醯肼 ligands, and 1 戍 2 m represents the number of Χ Χ ions, and will contain a ligand The positive charge of the metal complex as a whole is neutralized by the amount required. Usually, m is 0 to 2, and when m = 2, two χ-systems may be the same <may be different. [Ι_5. Complex structure] The fermented chelate compound of the present invention is derived from the teaching group of the coordinating substituent oxime on the ring oxime, or the hydroxy group formed by the dilute alcoholization of the sulfonium group. Further, a complex is formed with the transition metal ruthenium. Alternatively, there may be a case where a radical formed by the alcoholization of the rebel base of the splicing site or a Mn of 41 100105051 201137051 is removed from the 醯肼 of the 醯肼 site, and a complex compound is formed with the transition metal M. Hereinafter, the form in which the complex is formed will be described. In this case, the base a is 2 I: 15 h, and only the hydrogen substituent is removed from the coordinating substituent z to form a complex. For example, if the transition metal ruthenium is c 〇 2+ and the charge b is 2, coordination The soil '', and, as shown in the following formula (Ia), is a relative anion χ-number m system necessary for neutralizing the whole. [Chemistry 16]

[1-5-2.從配位性取代基z⑽耕部位的数基進行稀醇化 所生成的羥基，脫離氫原子之情況] 此情況，若過渡金屬Μ為Ni2+、電荷b為2、配位基數a 為2，便如下式(ib)所示，為將整體予以中和的相對陰離子 X—數m係〇個。 [化Π][1-5-2. Hydroxy group formed by dilute alcoholization from the number base of the ligand substituent z(10), and the case where the hydrogen atom is removed] In this case, if the transition metal ruthenium is Ni2+ and the charge b is 2, coordination The base a is 2, and is represented by the following formula (ib), which is a relative anion X-number m which neutralizes the whole. [Π化]

[1-5-3.從配位性取代基Z及醯肼部位的NH，脫離氫原子之 情況] 此情況，若過渡金屬Μ為Co3+、電荷b為3、配位基數a 100105051 42 201137051 中和所必要的相對 為2 ’便如下式(ic)所示，為將整體予以 陰離子X·數m係1個。 [化 18][1-5-3. From the coordination substituent Z and the NH in the oxime moiety, the hydrogen atom is removed] In this case, if the transition metal ruthenium is Co3+, the charge b is 3, and the number of ligands is a 100105051 42 201137051 The relative is 2', and as shown in the following formula (ic), the whole is an anion X·number m. [Chem. 18]

C〇3+ (Χ)ι (Ic) 再者’環A的陽離子部位與相對陰離 麻 个Χ形成鹽的情況’ 不官過渡金屬Μ的電荷b、與有無進料&amp; ..丁烯醇化，可認為亦 有相對陰離子X·數m係與配位基數a相a 伸同的情況。 本發明的醯肼螯合錯合化合物亦可兔 , 馬务聚物構造或團簇 構造，從耐久性的觀點，更佳為8面體構造 [1-6.分子量] 本發明醯肼螯合錯合化合物的分子量斜 7對配位基[即，醯 肼配位基(ΙΑ)或(ΙΙΑ)]，通常在1500以 卜、更佳係1000以 下、特佳係750以下。 再者，具有該醯肼配位基與過渡金屬陽離子的本發明醯肼 螯合錯合化合物之分子量（但，未含相對陰離子χ-的分子 量）’通常係3,000以下，其中較佳係以下。 [Ι·7.水溶性] 本發明的醯肼螯合錯合化合物從提升記錄媒體之保存安 定性的理由，通常較佳係水不溶性。 處所s胃「水不溶性」’係指饥、i氣㈣條件下，對 100105051 43 201137051 水的溶解度通常在0.1重量％以下、較佳在0.01重量％以下。 [1-8.具體例] 構成上述一般式⑴或(II)所示本發明醯肼螯合錯合化合物 的醯肼配位基(IA)或（IIA)、與相對陰離子又_的組合具體例， 係如下所例示，惟本發明在不逾越主旨的前提下，並不僅侷 限於該等。另外，以下中，Tf係表示三氟甲磺醯基，Me係 表示曱基，Et係表示乙基，TS係表示甲苯磺醯基，NTf2 係表示雙（三氟曱磺醯基）醯亞胺。 [化 19] 100105051 44 201137051C〇3+ (Χ)ι (Ic) Further, the case where the cation portion of the ring A forms a salt with the opposite anion and the sputum is not the charge b of the transition metal ruthenium, and the presence or absence of the feed &amp; The alcoholization is considered to be the case where the relative anion X·number m system is the same as the coordination group a phase a. The hydrazine chelate compound of the present invention may also be a rabbit, a racemic polymer structure or a cluster structure, and more preferably an octahedral structure from the viewpoint of durability [1-6. Molecular weight] The molecular weight of the compound is 7 to the ligand [ie, an anthracene ligand (ΙΑ) or (ΙΙΑ)], and is usually 1,500 or less, more preferably 1,000 or less, and particularly preferably 750 or less. Further, the molecular weight of the oxime-chelating complex compound of the present invention having the ruthenium ligand and the transition metal cation (however, the molecular weight of the cation-free complex) is usually 3,000 or less, and preferably hereinafter or less. [Ι7. Water-Solubility] The ruthenium-chelating complex compound of the present invention is generally preferably water-insoluble for the reason of improving the storage stability of the recording medium. In the case of "soil-insoluble" in the stomach, the solubility in water of 100105051 43 201137051 is usually 0.1% by weight or less, preferably 0.01% by weight or less. [1-8. Specific Example] The combination of the oxime ligand (IA) or (IIA) constituting the oxime chelating compound of the present invention represented by the above general formula (1) or (II), and the relative anion _ For example, the present invention is exemplified as follows, but the present invention is not limited to the above, without exceeding the subject matter. Further, in the following, Tf represents a trifluoromethanesulfonyl group, Me represents an indenyl group, Et represents an ethyl group, TS represents a toluenesulfonyl group, and NTf2 represents a bis(trifluorosulfonylsulfonyl) imine. . [化 19] 100105051 44 201137051

100105051 45 201137051 [化20100105051 45 201137051 [Chemical 20

100105051 46 201137051 [化 21]100105051 46 201137051 [Chem. 21]

100105051 47 201137051 [化 22]100105051 47 201137051 [Chem. 22]

100105051 48 201137051 [化 23]100105051 48 201137051 [Chem. 23]

100105051 49 201137051 [化 24]100105051 49 201137051 [Chem. 24]

100105051 50 201137051 5 2 化100105051 50 201137051 5 2

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100105051 51 201137051 [化 26]100105051 51 201137051 [Chem. 26]

100105051 52 201137051 [化 27]100105051 52 201137051 [Chem. 27]

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此種本發明的醯肼螯合錯合化合物係例如依照以下[1-9. 合成方法]所記載的方法進行合成。 [I-9.合成方法] 上述一般式(I)所示本發明的醯肼螯合錯合化合物，係依照 以下所示反應等便可容易地合成。 &lt;醯肼配位基之合成&gt; 100105051 63 201137051 [化 38] 0-J.H-nh2 + 〇=^) -- (a^l1K-nJ^ (上述反應式中，A、B、L、Ri、及X-係與一般式⑴中同義。） 進行上述反應時’反應糸係可為溶劑系、亦可為無溶劑系。 使用反應溶劑時，該溶劑係可使用甲醇、乙醇、乙猜、一 哼烷、四氫呋喃、氯仿、二氣乙烷等極性溶劑、或甲笨、二 曱苯等非極性溶劑’且為促進反應，亦可添加鹽酸、醋酸、 硫酸等無機酸、或p-TsOH(對曱苯磺酸）、PPTS(對甲苯續酸 °比啶鹽）等有機酸作為觸媒。 使用觸媒的情況’觸媒的添加量係在能進行反應的前提 下，並無特別的規定，相對於基質較佳係添加1/1〇〇〜1〇莫 耳倍左右，當酸配位於基質的雜原子上時，較佳係再添加該 基質份的莫耳份。 反應較佳係在室溫至溶劑回流溫度左右實施，反應時間係 1分鐘〜48小時左右，一般係以3小時左右〜1〇小時左右結 束反應。反應終點係可利用TLC(薄層色層分析）、HpLC(高 速液相色層分析）等進行確認。 &lt;醯肼螯合錯合化合物之合成&gt; 本發明的醯肼螯合錯合化合物係將依照上述手法所合成 的醯肼配位基利用鹼施行處理後、或在無鹼且過渡金屬鹽與 溶劑存在下或不存在下，依室溫至溶劑回流程度的溫度施行 100105051 64 201137051 加熱反應便可獲得。反應係以i分鐘〜5小時左右、一般係 30分鐘左右〜卜]、時左右結束。使用反應溶劑的情況該溶 劑係可使用：水、曱醇、乙醇、乙腈、四氫呋喃、二呤烷、 一曱氧基乙烧、二氯乙烧、氯仿等極性溶劑、或甲苯、二甲 ‘苯等非極性溶劑。鹼係可使用：氫氧化納、氫氧化卸、碳酸 鉀、碳酸鈉、碳酸鉋、氫化鈉、第三丁氧基鈉、第三丁氧基 鉀等無機鹼、或：三乙胺、哌啶、DBU(二氮雜雙環十一烯）、 DMAP(4-二甲胺基吡啶）等有機鹼。 再者，過渡金屬的鹽係可使用：氣化録(u)、醋酸始(η)、 硫酸鈷(II)、氣化鎳(π)、醋酸鎳(11)、硫酸鎳(11)、硫酸鐵(π)、 硫酸鐵(III)、氣化鐵(π)、氣化鐵(ΙΠ)、醋酸鐵(叫等。 [ΐ-ιο.本發明醯肼螯合錯合化合物之特徵] [1-10-1.耐光性及對塗佈溶劑的溶解性] 本發明醯肼螯合錯合化合物中較佳者係具有耐光性及對 塗佈溶劑的溶解性均優異，且使用於光學記錄媒體的記錄層 形成時之膜性(膜厚均勻性、平滑性等）均優異的特徵。 此情況所謂「耐光性優異」，係指即便對依成為約30〜50nm 膜厚方式形成的醯肼螯合錯合化合物薄膜，依溫度為室溫 〜58°C、濕度為30〜50%RH，施行氙燈（強度550W/m2)照射 條件的耐光性試驗40小時，該薄膜中的醯肼螯合錯合化合 物通常仍會有達70%以上(較佳係8〇%以上、特佳係90%以 上）未劣化而仍殘留的現象。此處劣化程度係利用波長 !〇〇1〇5051 65 201137051 300〜500nm中的吸收極大之吸收減少率進行判定。 該耐光性的試驗具體而言係依如下述實施。 首先’依乾燥後的膜厚成為約30〜5〇nm方式，將含醯耕 螯合錯合化合物的溶液塗佈於基板上之後，經乾燥，便獲得 含醯肼螯合錯合化合物的層。對所獲得含醯肼螯合錯合化合 物的層’在溫度為室溫〜58°C、濕度30〜5〇%RH的條件下， 施行氙燈（強度550W/m2)照射既定時間，比較照射前後在吸 收極大波長中之吸光度，並求取色素殘留率而實施。 再者’所謂「對塗佈溶劑的溶解性優異」，係指2〇〜5〇ΐ、 常壓條件下，在2,2,3,3-四氟丙醇(TFP)中溶解達〇7重量％ 以上、較佳係10重量％以上、更佳係1.5重量％以上。溶 解的判定係當依特定濃度將化合物與TFP進行混合時，依 溶劑中是否有殘留化合物的結晶殘渣而實施。另外，在本發 月的用途中，，谷解度上限並無特別的限制，通常係2〇重量 %以下、較佳係10重量％以下左右。 依此’本發明醯肼螯合錯合化合物的耐光性及對塗佈溶劑 之溶解性優異的理由，可認為因為具有鏽鹽的錯合物分子係 可視為極性分子，因而對同樣具極性的2,2,3,3_四說丙醇 (TFP)之溶解性較高。 [1-10-2.膜性] 本發明的醯肼螯合錯合化合物係膜性優異。即，在利用旋 塗法形成記錄層後，於碟片表面並未發現源自化合物結晶化 100105051 66 201137051 所造成的白化現象，就此點而言亦有利於工業性。 [1-10-3.用途] 本發明醯肼螯合錯合化合物中，較佳者亦適用於多層媒 體。即，當在多層媒體中，對各層執行資訊記綠時，因為在 執行記錄之目的以外的層亦必定會發生光的吸收、穿透現 象，因而在相較於單層媒體之下，需要使用記錄感度更佳的 色素。因為本發明醯肼螯合錯合化合物具有良好的記錄感 度，因而認為亦能充分適用於多層媒體。 [II.光學記錄媒體之記錄層形成用色素] 本發明光學記錄媒體之記錄層形成用色素，係含有如上述 的本發明醢肼螯合錯合化合物。 本發明光學記錄媒體之記錄層形成用色素中，可僅使用1 種本發明的醯肼螯合錯合化合物，亦可依任意組合及比率併 用2種以上的本發明醢肼螯合錯合化合物。又，除1種或2 種以上的本發明醯肼螯合錯合化合物之外，亦可併用1種或 2種以上其他色素。 但，當併用本發明醯肼螯合錯合化合物以外的色素時，從 使本發明醯肼螯合錯合化合物的優異特性能充分發揮之觀 點，相對於總色素合計，本發明醯肼螯合錯合化合物所佔比 率通常係設為10重量％以上、較佳係50重量％以上、特佳 係70重量％以上。 能與本發明醯肼螯合錯合化合物併用的其他系統之色 100105051 67 201137051 素，較佳係在記錄用的雷射光波長域中具有吸收，且吸收所 照射的雷射光能量，而在所照射部分的記錄層、反射層或基 板，形成伴隨分解、蒸發、溶解等熱變形之凹坑。又，併用 適於利用從因應CD-R的77〇〜83〇mn範圍中所選擇波長之 近紅外雷射光、或從因應DVD-R的620〜690nm範圍中所選 擇紅色雷射光進行記錄的色素，亦可形成因應利用複數波長 域的雷射光進行記錄之光學記錄材料。又，從上述CD_R用 或DVD-R用的色素中選擇耐光性良好者，且併用本發明的 醯肼螯合錯合化合物，便可更加提升耐光性。 能併用的其他系統之色素，具體而言，可列舉：含金屬偶 氮系色素、二苯基酮系色素、酞青系色素、萘酞青系色素、 青色素系色素、偶氮系色素、斯夸琳(Squarylium)系色素、 含金屬靛苯胺系色素、三芳香基曱烷系色素、部花青素系色 素、甘菊藍鐳系色素、萘醌系色素、蒽醌系色素、靛酚系色 素、二苯并哌喃系色素、崎畊系色素、吼喃鏽系色素等，該 等係可單獨使用1種、亦可併用2種以上。 [III.光學記錄媒體] [III-1.記錄層] 本發明光學記錄媒體所設有的記錄層，係使用至少含有j 種本發明醯肼螯合錯合化合物的本發明光學記錄媒體之記 錄層形成用色素（亦簡稱「本發明色素」）而形成。 即’本發明光學5己錄媒體的記錄層係含有本發明醯肼螯合 100105051 68 201137051 錯合化合物1種或2種以上。 記錄層中的本發明色素之比例，通常係1〇重量％以上 較佳係50重量％以上、特佳係7〇重量％以上。 若色素比例過少，因為記錄感度會明顯降低，故而不佳 •當本發明色素係併用2_上色素的料，便使其合= 圭足 ' 上述範圍。又，當使用後述黏結劑與各種添加劑的情況，較 佳係依所形成記錄層中的本發明色素所伯比例滿足上述^ 圍内的方式，調整黏結劑與添加劑的使用量。另外，從使= 發明色素的優異特性能充分發揮之觀點，在本發明/記錄層 中特佳係不要使用黏結劑與添加劑。 記錄層係為能提升成膜性亦可含有黏結劑。作為黏結劑， 可單獨使用1種、或混合使用2種以上之聚乙稀醇、聚乙稀 吡唑啶酮、酮系樹脂、硝基纖維素、醋酸纖維素、丙烯酸系 樹脂、聚苯乙烯系樹脂、胺曱酸醋系樹脂、聚乙婦丁醛、聚 碳酸S旨、聚烯烴等已知物。 • #記錄層中的黏結劑所佔比例過高，則記錄感度會明顯降 低，因而當使用黏結劑、甚至後述各種添加劑時，便使用所 • 形成記錄層巾的本發明色素所佔_會成為上述範圍的量。 再者，記錄層係為求安定性與耐光性的提升，亦可含有單 重態氧消光劑(quencher)與記錄感度提升劑等。 單重態氧消光劑係可列舉：乙醯丙酮酸鹽、雙苯基二硫 醇、水揚醛肟、雙二硫二酮等、與過渡金屬的螯合化合 100105051 69 201137051 物等等，該等係可單獨❹1種、亦可個2種以上。 記錄感度提升劑係可列舉：過渡金屬等金屬依原子、離 子、團鎮等形式而含於化合物中的金屬系化合物等等，例 如：乙二胺系錯合物、甲亞胺系錯合物、苯基經胺系錯合物、 啡琳系錯合物、二減錢以料物、謂&quot;合物、亞 硝胺絲系錯合物、㈣三Μ錯合物、乙㈣酮酸鹽系錯 合2、-戊金屬系錯合物之_ —Μ化合物等，該等係 可單獨使用1種、亦可併用2 ^ 種以上。金屬原子的種類並無 特別的限制，較佳為過渡金屬。 需要亦可併用均塗劑、消泡劑等。 =%重態氧消光劑係相對於色素，通常使用5〜3。重 =士記錄感度提升劑係相對於色素，通常使用1〇〜3〇 里重右〇 ^ 種以上單重態氧消光劑的情況、或併用2種以上 ’感又提升劑的情況，係分別使其合計使用量滿足上述範 圍。 成本發明酿肼螯合錯合化合物的本發明色素而形 成先…己錄媒體的記錄層時’可使 刮漿刀法、*工域法、濺鑛法、 成法。 疋塗法、浸潰法等—般所採行的薄膜形 該等之中，從量產性、成本面觀之 能獲得更㈣厚度記騎峨點，難為㈣法，但從 100105051 空蒸鍍法等。 201137051 田利用旋塗法將記錄層予以成膜的情況，旋轉數較佳係 500〜5_卿’織塗後，視需要亦可施行加熱或曝釀於 溶劑蒸氣中等處理。 記錄層的膜厚躲決於記錄方法等，適合賴厚會有不 因而並無特別的限制，通常至少、1 n m以上、較佳係5 n m 乂上更佳係l〇nm以上、通常係5哗以下較佳係2㈣ 以下、更佳係300nm以下、再更佳係2〇〇nm以下、特佳係 100nm以下。若記錄層财大於此下限值時，便可確保記錄 所需要的光吸收量，可輕易地依良好感度執行記錄。又，因 為記錄信號不易發生失真情形，因而可輕易地形成所需大小 的品質良好標記。若記錄層膜厚小於上述上限值時，可輕易 地確保再生所需要的反射光量，結果便可獲得良好的再^言 當記錄層係利用到漿刀法、繞注法、旋塗法、浸潰法等形 成時’首先使本發明色素、黏結劑、單重態氧消光劑、記錄 感度提升劑及其他色素等溶解於溶劑中，而製作塗佈液。 溶劑就工業面而言較佳係使用TFP，在屬於不會侵餘基板 的溶劑之前提下，並不僅侷限於TFp，尚可使用：二丙嗣醇、 3-經基·3-甲基·2· 丁酮等_醇系溶劑；甲基赛崎、乙基賽 游蘇等賽璐蘇系溶劑；正己燒、正辛料鏈狀烴系溶劑二環 己院、曱基環己烧、乙基環W、二曱紐己院、正丁基環 己烧、第三丁基環己烧、環辛燒等脂環式烴系溶劑；二異丙 100105051 71 201137051 醚、二丁醚等醚系溶劑；2,2,3,3,4,4j 5 氟丁醇等氟系烷基醇系溶劑；乳酸曱八氟戊醇(〇FP)、六 日、乳酸乙酯、異丁酸The oxime chelating compound of the present invention is synthesized, for example, according to the method described in the following [1-9. Synthesis method]. [I-9. Synthetic method] The oxime chelating compound of the present invention represented by the above general formula (I) can be easily synthesized by the following reaction or the like. &lt;Synthesis of anthracene ligand&gt; 100105051 63 201137051 [Chem. 38] 0-JH-nh2 + 〇=^) -- (a^l1K-nJ^ (in the above reaction formula, A, B, L, Ri) And the X-system is synonymous with the general formula (1).) When the above reaction is carried out, the reaction oxime may be a solvent system or a solvent-free system. When a reaction solvent is used, the solvent may be methanol, ethanol or B. a polar solvent such as monooxane, tetrahydrofuran, chloroform or dioxane, or a non-polar solvent such as methyl or diphenylbenzene. In order to promote the reaction, a mineral acid such as hydrochloric acid, acetic acid or sulfuric acid or p-TsOH may be added. An organic acid such as p-toluenesulfonic acid) or PPTS (p-toluene acid-to-pyridyl salt) is used as a catalyst. In the case of using a catalyst, the amount of the catalyst added is based on the premise that the reaction can be carried out without special regulations. Preferably, the matrix is added with about 1/1 〇〇~1 〇 molar ratio, and when the acid is disposed on the hetero atom of the matrix, it is preferred to add the molar portion of the matrix portion. The reaction time is from room temperature to the reflux temperature of the solvent, and the reaction time is from 1 minute to 48 hours, generally about 3 hours to 1 minute. The reaction was terminated to the left and right. The end point of the reaction was confirmed by TLC (thin layer chromatography), HpLC (high-speed liquid chromatography), etc. &lt;Synthesis of chelating chelate compound &gt; The compounding compound is subjected to treatment with a base according to the above-mentioned method, or after treatment with an alkali, or in the absence or presence of a base and a transition metal salt and a solvent, at a temperature ranging from room temperature to solvent reflux. 100105051 64 201137051 It can be obtained by heating the reaction. The reaction system is about 1 minute to 5 hours, usually about 30 minutes, and is finished. When the reaction solvent is used, the solvent can be used: water, decyl alcohol, ethanol, A polar solvent such as acetonitrile, tetrahydrofuran, dioxane, monomethoxy bromide, dichloroethane or chloroform, or a non-polar solvent such as toluene or dimethyl 'benzene. The alkali system can be used: sodium hydroxide or hydroxide. An inorganic base such as potassium carbonate, sodium carbonate, carbonic acid planer, sodium hydride, sodium butoxide or potassium t-butoxide, or: triethylamine, piperidine, DBU (diazabicycloundecene), DMAP (4-dimethylaminopyridyl) And other organic bases. Further, the transition metal salt system can be used: gasification record (u), acetic acid start (η), cobalt sulfate (II), vaporized nickel (π), nickel acetate (11), nickel sulfate (11), iron sulfate (π), iron (III) sulfate, iron (π), gasified iron (ΙΠ), iron acetate (called et al. [ΐ-ιο. 醯肼 chelate compound of the invention [Features] [1-10-1. Light resistance and solubility in a coating solvent] The chelating chelating compound of the present invention preferably has excellent light resistance and solubility in a coating solvent, and The film properties (thickness uniformity, smoothness, and the like) at the time of formation of the recording layer used in the optical recording medium are excellent. In this case, "excellent light resistance" means a film of a ruthenium chelate compound which is formed to have a film thickness of about 30 to 50 nm, and has a temperature of from room temperature to 58 ° C and a humidity of 30 to 50% RH. The light resistance test of the xenon lamp (intensity 550 W/m 2 ) irradiation condition was carried out for 40 hours, and the cerium chelating compound compound in the film usually still had 70% or more (more preferably 8 % or more, and particularly excellent 90). % or more) A phenomenon that remains without deterioration. Here, the degree of deterioration is determined by the absorption reduction rate of the absorption maximum in the wavelength 〇〇1〇5051 65 201137051 300 to 500 nm. The test for light resistance is specifically carried out as follows. First, a solution containing a ruthenium chelate compound is applied to a substrate after the film thickness after drying is about 30 to 5 Å, and then dried to obtain a layer containing a ruthenium-chelating compound. . The layer of the obtained cerium-chelating chelating compound was irradiated with a xenon lamp (intensity of 550 W/m 2 ) at a temperature of room temperature to 58 ° C and a humidity of 30 to 5 〇 % RH for a predetermined time before and after the irradiation. It is carried out by absorbing the absorbance at the maximum wavelength and determining the residual ratio of the dye. In addition, 'the so-called "excellent solubility in a coating solvent" means that it is dissolved in 2,2,3,3-tetrafluoropropanol (TFP) at a pressure of 2 Torr to 5 Torr under normal pressure. The weight% or more is preferably 10% by weight or more, more preferably 1.5% by weight or more. The determination of the dissolution is carried out by mixing the compound with TFP at a specific concentration depending on whether or not the crystal residue of the residual compound is present in the solvent. Further, in the application of the present month, the upper limit of the degree of the solution is not particularly limited, and is usually 2% by weight or less, preferably about 10% by weight or less. According to the reason why the light resistance of the chelating chelating compound of the present invention and the solubility in a coating solvent are excellent, it is considered that a complex molecular molecule having a rust salt can be regarded as a polar molecule, and thus is equally polar. 2, 2, 3, 3_ four said that the solubility of propanol (TFP) is higher. [1-10-2. Membrane Property] The oxime chelating compound of the present invention is excellent in film properties. Namely, after the recording layer was formed by the spin coating method, no whitening phenomenon caused by the crystallization of the compound 100105051 66 201137051 was observed on the surface of the disc, and industrial convenience was also obtained in this point. [1-10-3. Use] Among the oxime chelating complex compounds of the present invention, preferred ones are also suitable for use in a multilayered medium. That is, when the information is recorded on each layer in the multi-layer medium, since the light absorption and penetration phenomenon must occur in the layer other than the purpose of performing the recording, it is required to be used under the single layer medium. Record more sensitive pigments. Since the ruthenium chelate compound of the present invention has a good recording sensitivity, it is considered that it can be sufficiently applied to a multilayer medium. [II. Pigment for forming a recording layer of an optical recording medium] The dye for forming a recording layer of the optical recording medium of the present invention contains the above-described oxime chelating complex compound of the present invention. In the dye for recording layer formation of the optical recording medium of the present invention, only one type of ruthenium chelating compound of the present invention may be used, and two or more kinds of ruthenium chelating compounds of the present invention may be used in any combination and ratio. . In addition, one type or two or more types of other dyes may be used in combination, in addition to one or two or more kinds of the oxime chelating compound of the present invention. However, when the dye other than the conjugated compound of the present invention is used in combination, the chelating chelate of the present invention is obtained from the viewpoint of giving full play to the excellent properties of the oxime chelating compound of the present invention. The ratio of the compound to be mixed is usually 10% by weight or more, preferably 50% by weight or more, and particularly preferably 70% by weight or more. The color of the system 100105051 67 201137051, which can be used in combination with the chelating compound of the present invention, preferably has absorption in the wavelength range of the laser light for recording and absorbs the energy of the irradiated laser light while being irradiated Part of the recording layer, the reflective layer or the substrate forms pits which are thermally deformed by decomposition, evaporation, dissolution, and the like. Further, a pigment suitable for recording with near-infrared laser light of a wavelength selected from the range of 77 〇 to 83 〇 mn in response to CD-R or red laser light selected from the range of 620 to 690 nm corresponding to DVD-R is used. An optical recording material that records in accordance with laser light in a plurality of wavelength domains may also be formed. Further, from the above-mentioned dyes for CD_R or DVD-R, those having good light resistance can be selected, and the chelating chelate compound of the present invention can be used in combination to further improve light resistance. Specific examples of the dyes of other systems which can be used together include metal azo dyes, diphenyl ketone dyes, indigo dyes, naphthoquinone pigments, cyan pigments, azo dyes, and Squarylium pigment, metal-containing anthranil-based pigment, tri-aryl decane-based pigment, merocyanine-based pigment, chamomile-blue radium pigment, naphthoquinone-based pigment, anthraquinone-based pigment, indophenol The dye may be used alone or in combination of two or more kinds, and may be used singly or in combination. [III. Optical recording medium] [III-1. Recording layer] The recording layer provided in the optical recording medium of the present invention is a recording using the optical recording medium of the present invention containing at least j kinds of the cerium chelating compound of the present invention. The layer forming pigment (also referred to as "the pigment of the present invention") is formed. Namely, the recording layer of the optical recording medium of the present invention contains one or two or more kinds of the compound of the present invention, which is a chelate compound 100105051 68 201137051. The proportion of the pigment of the present invention in the recording layer is usually 1% by weight or more, preferably 50% by weight or more, and particularly preferably 7% by weight or more. If the ratio of the pigment is too small, the sensitivity of the recording is remarkably lowered, which is not preferable. When the pigment of the present invention is used in combination with the pigment of 2_, it is combined with the above range. Further, in the case where a binder and various additives described later are used, it is preferable to adjust the amount of the binder and the additive to be used in accordance with the manner in which the pigment of the present invention in the recording layer formed satisfies the above-mentioned range. Further, it is particularly preferable to use a binder and an additive in the present invention/recording layer from the viewpoint of giving full play to the excellent properties of the inventive pigment. The recording layer may also have a binder in order to enhance film formability. As the binder, one type or a mixture of two or more kinds of polyethylene glycol, polyvinylpyrrolidone, ketone resin, nitrocellulose, cellulose acetate, acrylic resin, polystyrene may be used alone or in combination. A known product such as a resin, an amine vinegar-based resin, a polybutyry aldehyde, a polycarbonate, or a polyolefin. • If the proportion of the binder in the recording layer is too high, the recording sensitivity will be significantly lowered. Therefore, when a binder or even various additives described later are used, the pigment of the present invention which forms the recording layer towel will become The amount of the above range. Further, the recording layer is intended to improve stability and light resistance, and may also contain a single-state oxygen matting agent (quencher) and a recording sensitivity enhancer. The singlet oxygen matting agent may, for example, be acetoacetate, bisphenyldithiol, salicylaldoxime, bisdithiodione, etc., chelated with a transition metal, 100105051 69 201137051, etc., etc. One type may be used alone or two or more types may be used. Examples of the recording sensitivity enhancer include metal compounds such as transition metals which are contained in the compound in the form of atoms, ions, and groups, and the like, for example, an ethylenediamine-based complex and a azomethine-based complex. , phenyl group, amine-based complex compound, morphine-based complex compound, second-reduced money, material, quotient, nitrosamine complex, (tetra) triterpene complex, ethyl (tetra) keto acid The salt-missing type 2, the pentane metal-based complex compound, and the like may be used singly or in combination of two or more kinds. The kind of the metal atom is not particularly limited, and is preferably a transition metal. A leveling agent, an antifoaming agent, etc. may also be used together. The =% heavy oxygen matting agent is usually used in an amount of 5 to 3 relative to the pigment. The weight-receiving sensitivity enhancer is usually used in the case of a single-state oxygen-matting agent of 1 〇 to 3 〇 〇 〇 种 种 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 The total amount used is in the above range. In the case of the present invention, the dye of the present invention which is entangled with the conjugated compound is formed to form a recording layer of the medium. The squeegee method, the *worker method, the sputtering method, and the method can be used. Among the film shapes such as the smear coating method and the immersion method, it is possible to obtain a more (4) thickness from the mass production and cost. It is difficult to use the (four) method, but from 100105051 air evaporation Law and so on. 201137051 The case where the recording layer is formed into a film by spin coating, the number of rotations is preferably 500~5_qing' after weaving, and if necessary, heating or exposure to solvent vapor may be applied. The film thickness of the recording layer is independent of the recording method, and is not particularly limited, and is usually at least 1 nm or more, preferably 5 nm, preferably more than 10 nm, and usually less than 5 It is preferably 2 (four) or less, more preferably 300 nm or less, still more preferably 2 〇〇 nm or less, and particularly preferably 100 nm or less. If the recording layer is larger than the lower limit value, the amount of light absorption required for recording can be ensured, and recording can be easily performed in accordance with good sensitivity. Further, since the recording signal is less likely to be distorted, it is possible to easily form a good quality mark of a desired size. When the recording layer film thickness is less than the above upper limit value, the amount of reflected light required for regeneration can be easily ensured, and as a result, good re-speech can be obtained. When the recording layer is applied to a pulp knife method, a winding method, a spin coating method, When the impregnation method or the like is formed, the coating liquid is prepared by first dissolving the dye, the binder, the singlet oxygen matting agent, the recording sensitivity enhancer, and other pigments of the present invention in a solvent. The solvent is preferably used in the industrial form using TFP, and is not limited to TFp before being used as a solvent which does not invade the substrate, and can also be used: dipropanol, 3-cyano-3-methyl· 2. Butanone and other alcohol-based solvents; methyl sakisaki, ethyl seiyousu and other cyanobacterial solvents; hexane, nascent chain hydrocarbons, solvent, two-rings, thiol ring, B Ester ring hydrocarbons such as base ring W, dioxin neon, n-butylcyclohexane, tert-butylcyclohexane, and cyclooctane; diisopropyl 100105051 71 201137051 ethers such as ether and dibutyl ether Solvent; 2, 2, 3, 3, 4, 4j 5 Fluorine-based alkyl alcohol solvent such as fluorobutanol; octafluoropentyl lactate (〇FP), six days, ethyl lactate, isobutyric acid

曱酯等經酯系溶劑等等。另外，兮· M 等各劑係可單獨使用1 種、亦可混合使用2種以上，從工紫 们種。 業面而言，較佳係單獨使 塗佈液中的本發明色素濃度係配人 決定，通常係設為G.1重量％以上 ^劑溶解性而適當 1 乂佳係0.2重量％以上， 且通常在10重量％以下、較佳係3 •垔量％以下。若塗佈液 中的色素濃度過低，記錄層的形成料會變差。若塗佈液中 的色素濃度過高，則在成膜步驟中 的可能性會提高。 料色储晶化等問題 當使用真空_法時，例如將本發肼 物、與視需要的其他色素及各種添加劑等記錄螯層成 :=二__中，利用適當真空_真空容器 ^ 曼，加熱坩堝而使記錄層成分蒸 發，並使其蒸鍍於與坩禍呈相 ㈣ 賴向放置的基板上，便形成記 錄層。 [III-2.光學記錄媒體之層構成] 本發明的光學記錄媒體 層形成用色素依如上述所形絲記^設有使用本發明記錄 體：體’列舉實施形態進行* 100105051 過係為說明而舉例者，本發明 72 201137051 並不僅侷限於以下實施形態，在不違反本發明主旨的前提 下’可自由變化實施。 以下’參照圖式，針對本發明光學記錄媒體的實施形態進 行說明。 圖1、圖2係顯示本發明實施形態的光記錄媒體之層構成 一例之示意剖視圖。 [III-2-1.光學記錄媒體之第1實施形態] 首先’針對本發明第1實施形態，參照圖1進行說明。 圖1所示光學記錄媒體20係具有在基板21上，依序積層 著反射層22、記錄層23、阻障層24、及覆蓋層25的構造。 即使反射層22、阻障層24、及覆蓋層25係由複數材料構成 的多層亦毫無問題。該光學記錄媒體20係利用從覆蓋層25 側所照射的雷射光(記錄再生光光束28)，而執行資訊的記錄 /再生。依此相對於習知CD、DVD等的基板入射型媒體， 將從覆蓋層25側照射雷射光的媒體稱「膜面入射型光纪錄 媒體」，並採用為藍光光碟(BD)等的記錄媒體。此處獏面二 射型光學記錄媒體20,將距記錄再生光光束28朝覆蓋層υ 的入射面（記錄再生光光束所入射的面)3〇較遠之導溝部(與 基板21的溝部一致）’稱「覆蓋層乃的溝間部=與 (in-gr〇〇ve) ’將距記錄再生光光束28入射面較 」 部（與基板21的溝間部一致），稱「覆 溝間 )稱覆盍層溝部27 ve) mi由’冓形狀與各層折射率等光學特^ 100105051 73 201137051 進行控制，便可貫現將覆蓋層溝間部(in_gr〇〇ve)26作成s己錄 循軌（以下記「in-groove記錄」）的Lt〇H記錄。 基板21在膜面入射構成方面，不同於習知的基板面入射 構成，因為光並非從基板側入射，因而對透明性與雙折射並 無限制。所以，具有適度加工性與剛性的塑膠、金屬、玻璃 等均可使用。基板係在表面上形成導溝，金屬、玻璃必須在 表面上設置光或熱硬化性的薄樹脂層’並在此形成溝。就此 點而言’在製造上較佳者為，如習知使用塑膠材料，並利用 射出成形’以同時成形加工為基板21所示形狀(特別係圓盤 狀)與表面導溝的手法。 可進行射出成形的塑膠材料係可使用習知CD或DVD所 使用的聚碳酸醋樹脂、聚烯烴樹脂、丙烯酸係樹脂、環氧樹 脂等。 基板尽度較佳係设為〇 5mm〜 12mm左右。基板21的厚 度與覆蓋層25的厚度合計，較佳係設為與習知CD或DVD 同樣的l.2mm。理由係可直接使用習知CD與DVD所使用 的外盒體等。特㈣將基板21的厚度設為l lmm，將覆蓋 層25的厚度没為〇 lmm，此係藍光光碟所規定。 在基板21上形成循轨用導溝。本實施形態中，為能達成 比CD R、DVD-R更高密度化，覆蓋層25的溝間部％成為 記錄溝部的軌距，較佳係設為0.1μιη~0.6/χιη、更佳係設為 Mm 〇.4/mi。溝深度較佳係設在2〇nm〜i⑻nm範圍内。溝 100105051 74 201137051 深度係在上述範圍内’經考慮未記錄狀態的記錄溝部反射 率、记錄號的信號特性、推挽信號特性、記錄層的光學特 性等因素而予以適當最佳化。 本實施形態中’因為利用記錄溝部與記錄溝間部的各反射 光相位差所造成之干涉，因而記錄溝部與記錄溝間部二者均 必須存在於聚焦光光點内。所以，記錄溝寬度（覆蓋層溝間 部26的寬度）較佳係小於記錄再生光光束28之記錄層面的 光點徑（溝橫切方向直徑）。例如記錄再生光波長λ =4〇5ηπι、 ΝΑ(開口數)=0.85的光學系統’將軌距設為〇 32/mi時，較 佳將記錄溝寬度（覆蓋層溝間部26的寬度）設為 Ο.ΐμπι〜範圍。若在料範圍外，溝或溝間部的形成大 多變得困難。 導溝的截面形狀通常係為矩形。特別係利用後述塗佈形成 S己錄層23時’截至含有色素的溶液之溶劑幾乎蒸發為止前 的數十秒鐘内’期望色素選擇轉留於基板21的溝部上。 因而，較佳亦將矩形溝的基板溝間之肩部設成圓形，俾使色 素溶液較容㈣落並滞留於基板溝部中 。具有此種圓肩的溝 形狀’係將歸基板或打印機的表面，在㈣或uv臭氧等 之中韻刻數秒至數分鐘便可獲得。彻電祕行賴刻，因 為-有可選擇性切削如基板溝部之肩（溝間部的邊緣)銳利 部分的性質，因此適於獲得圓形的溝部肩形狀。 導溝通电為了賦予位址與同步信號等附加資訊，而具有溝 100105051 75 201137051 蛇行、溝深度調變等溝形狀調變、記錄溝部或記錄溝間部的 間歇所造成凹凸坑等形成之附加信號(additional signal)。例 如藍光光碟係採取使用MSK(minimum-shift-keying，最小頻 移鍵控）、與STW(saw-t〇〇th-w〇bbles，鋸齒狀擺動）等2種調 變方式的擺動位址方式。 反射層22係形成於基板21上。反射層22的膜厚較佳係 20nm〜300ηπ^反射層22的材料係可使用對再生光的波長具 有充分高反射率的材料，例如單獨使用Au、八卜Ag、Cu、 之中’ Au、A卜及Ag的反射率高，適於當作反射層以的 材料。又’在以料金屬為主成分的前提下，尚可含有其他 材料。此處所謂「主成分」，係指含有率重量％以上者。 主成分以外的其他材料係可列舉：Mg、Se、Hf、V,、An ester solvent such as an oxime ester or the like. In addition, each of the 兮·M and the like may be used singly or in combination of two or more kinds. It is preferable that the pigment concentration of the present invention in the coating liquid is determined by a person to be used alone, and it is usually set to be more than G.1% by weight or more, and more preferably 0.2% by weight or more. It is usually 10% by weight or less, preferably 3% by weight or less. If the concentration of the dye in the coating liquid is too low, the formation of the recording layer may be deteriorated. If the concentration of the dye in the coating liquid is too high, the possibility of forming in the film forming step is increased. Problems such as color storage and crystallization When using the vacuum method, for example, the present hair, the other pigments as needed, and various additives are recorded as a layer: = two __, using a suitable vacuum _ vacuum container ^ Man The recording layer is formed by heating the crucible to evaporate the recording layer component and vapor-depositing it on the substrate placed in the opposite direction. [III-2. Layer Configuration of Optical Recording Medium] The optical recording medium layer forming pigment of the present invention is provided with the above-described type of recording material according to the above-described shape. For example, the present invention 72 201137051 is not limited to the following embodiments, and can be freely implemented without departing from the gist of the present invention. Hereinafter, embodiments of the optical recording medium of the present invention will be described with reference to the drawings. Fig. 1 and Fig. 2 are schematic cross-sectional views showing an example of a layer configuration of an optical recording medium according to an embodiment of the present invention. [III-2-1. First embodiment of optical recording medium] First, the first embodiment of the present invention will be described with reference to Fig. 1 . The optical recording medium 20 shown in Fig. 1 has a structure in which a reflective layer 22, a recording layer 23, a barrier layer 24, and a cover layer 25 are laminated on a substrate 21. Even if the reflective layer 22, the barrier layer 24, and the cover layer 25 are composed of a plurality of layers of a plurality of materials, there is no problem. This optical recording medium 20 performs recording/reproduction of information by using laser light (recording and reproducing light beam 28) irradiated from the side of the cover layer 25. In contrast, a medium that irradiates laser light from the side of the cover layer 25 is referred to as a "film-surface incident type optical recording medium", and a recording medium such as a Blu-ray disc (BD) is used as a medium for a substrate-incident type medium such as a CD or a DVD. . Here, the facet-type two-beam type optical recording medium 20 has a guide groove portion (corresponding to the groove portion of the substrate 21) which is far from the incident surface of the cover layer ( (the surface on which the recording and reproducing light beam is incident) 3 距 from the recording/reproducing light beam 28 "When the "cover layer is the inter-groove portion = and (in-gr〇〇ve) 'will be closer to the incident surface of the recording and reproducing light beam 28" (corresponding to the groove portion of the substrate 21), It is said that the cover layer groove portion 27 ve) mi is controlled by the optical shape of the 冓 shape and the refractive index of each layer, and the inter-groove portion (in_gr〇〇ve) 26 can be continuously recorded. The Lt〇H record of the track (hereinafter "in-groove record"). The substrate 21 is different from the conventional substrate surface incident configuration in that the film surface is incident, and since light is not incident from the substrate side, there is no limitation on transparency and birefringence. Therefore, plastic, metal, glass, etc., which have moderate workability and rigidity, can be used. The substrate is formed with a guide groove on the surface, and the metal or glass must be provided with a light or thermosetting thin resin layer ’ on the surface and a groove is formed therein. In this regard, it is preferable to manufacture a plastic material, and use injection molding to simultaneously form a shape (in particular, a disk shape) and a surface guide groove formed by the substrate 21. As the plastic material which can be injection molded, a polycarbonate resin, a polyolefin resin, an acrylic resin, an epoxy resin or the like which is used in a conventional CD or DVD can be used. The substrate endurance is preferably set to about mm 5 mm to 12 mm. The thickness of the substrate 21 and the thickness of the cover layer 25 are preferably set to be 1.2 mm as in the conventional CD or DVD. The reason is that the outer casing used in the conventional CD and DVD can be directly used. Specifically, the thickness of the substrate 21 is set to l lmm, and the thickness of the cover layer 25 is not 〇 lmm, which is defined by the Blu-ray disc. A tracking groove is formed on the substrate 21. In the present embodiment, in order to achieve higher density than CD R and DVD-R, the inter-groove portion % of the cover layer 25 serves as a track pitch of the recording groove portion, and is preferably 0.1 μm to 0.6/χηη, and more preferably Set to Mm 〇.4/mi. The groove depth is preferably set in the range of 2 〇 nm to i (8) nm. The groove 100105051 74 201137051 has a depth within the above range, and is appropriately optimized in consideration of factors such as the recording groove reflectance in the unrecorded state, the signal characteristic of the recording number, the push-pull signal characteristic, and the optical characteristics of the recording layer. In the present embodiment, the interference between the recording groove portion and the recording groove portion is caused by the phase difference between the recording light portions and the recording groove portion. Therefore, both the recording groove portion and the recording groove portion must exist in the focused light spot. Therefore, the recording groove width (the width of the cover layer groove portion 26) is preferably smaller than the spot diameter (the groove transverse direction diameter) of the recording layer of the recording and reproducing light beam 28. For example, when an optical system that records the wavelength of the reproducing light λ = 4 〇 5 ηπι and ΝΑ (number of openings) = 0.85, when the track pitch is 〇 32 / mi, it is preferable to set the recording groove width (the width of the inter-groove portion 26). For Ο.ΐμπι~ range. If the material is outside the range of the material, it is difficult to form a groove or a groove. The cross-sectional shape of the guide groove is usually rectangular. In particular, when the S recording layer 23 is formed by coating as described later, the desired coloring matter is selected and transferred to the groove portion of the substrate 21 within a few tens of seconds before the solvent of the solution containing the dye is almost evaporated. Therefore, it is preferable to set the shoulder between the substrate grooves of the rectangular groove to be circular, so that the color solution is more likely to fall and stay in the substrate groove. The groove shape having such a round shoulder will be obtained on the surface of the substrate or the printer, and can be obtained in a few seconds to several minutes in (iv) or uv ozone. It is suitable for obtaining a circular groove shoulder shape because it has the property of selectively cutting a sharp portion such as the shoulder of the substrate groove (the edge between the grooves). In order to provide additional information such as address and synchronization signal, the communication communication has an additional signal formed by the groove shape of the groove 100105051 75 201137051, such as meandering and groove depth modulation, and the unevenness caused by the interval between the recording groove portion and the recording groove portion. (additional signal). For example, the Blu-ray Disc adopts two kinds of modulation methods such as MSK (minimum-shift-keying) and STW (saw-t〇〇th-w〇bbles, jagged wobble). . The reflective layer 22 is formed on the substrate 21. The film thickness of the reflective layer 22 is preferably 20 nm to 300 η π ^ The material of the reflective layer 22 can use a material having a sufficiently high reflectance for the wavelength of the regenerated light, for example, Au, Babu Ag, Cu, and ' Au, respectively. A and Ag have high reflectance and are suitable as materials for the reflective layer. In addition, other materials may be included on the premise that the metal is the main component. Here, the "main component" means a content percentage or more. Other materials other than the main component are: Mg, Se, Hf, V,

Ru、 W、Μη、Re、Fe、Co、Ru, W, Μη, Re, Fe, Co,

Rh、ir、Cu、Zn、Cd、Ga、In、 si、Ge、Te、Pb、Po、Sn、Bi、Ta、Tiptpd、Nd 等金 屬及半金屬。其中，從成本廉價、容易形成高反射率、設置 後述P刷接又層時可獲知底色白且美觀等觀點，特佳係將 Ag作為主成分。例如在^中含有〇1原子％〜5原子％左右 之k自Au Pd、pt、Cu、及Nd所構成群組中之i種以上 的合金’係呈高反料、高耐久性、高感度且低成本，屬較 佳。具體而言’為AgPdCu合金、合金、AgCuAuNd σ AgC_合金等。金屬以外的材料亦可使低折射率薄 100105051 76 201137051 並將其使用為 膜與高折射率薄膜呈交錯重疊而形成多層膜， 反射層22。 形成反射層22的方法係丨與 化與;W 係可聽心卿士離子鍵覆法 化干纽去、真空錢法等。糾，_於基板21之上 或反射層22之上或下，為求反射率提升、 =陶等’亦可設置公知無機系或她 著層。 在反射層22上形成記錄層23的方法，係可列舉將已溶角 有機溶劑與本㈣色素的溶液，使錢塗法塗佈成所需， 的方法。所形成記錄層23賴厚，較佳係5nm〜⑽咖、】 佳係l〇nm〜50nm。 在記錄層23上所形成阻障層24的材料，係在能阻礙覆蓋 層25(其係由與有機色素所構成記錄層Μ相同的有機物構 成）的材料發生混合、渗出情況之前提下，並無特別的限制。 可列舉例如：Si〇2、啊、哪、Sn〇2、in2〇3、ZnS等無 機物質、及其混合物等。阻障層24的膜厚較佳係 2nm〜lOOnm、更佳係 3nm〜5〇nm 〇 在阻障層24上所形成的覆蓋層25係選擇對記錄再生光光 束28呈透明且雙折射少的材料，通常係將塑膠板(稱「板片」) 利用接著劑進行貼合’或者在塗佈硬化性樹脂溶液後，利用 光、輻射線、或熱等施行硬化而形成。覆蓋層28係會侵入 光，因而對記錄再生光光束28的波長λ，較佳係穿透率達 100105051 77 201137051 70%以上、更佳係達8〇%以上。 使用為覆蓋層25之皮片的塑膠基材，係例如：聚碳酸酯、 聚烯烴、壓克力、三醋酸纖維素、聚對苯二甲酸乙二酯等。 在接著時’可使用輻射線硬化樹脂、熱硬化樹脂、壓感性接 著劑等。壓感性接著劑係可使用由丙烯酸系、曱基丙烯酸酯 系、橡膠系、石夕系、胺曱酸酯系等各聚合物構成的黏著劑。 例如’將構成接著層的光硬化性樹脂溶解於適當溶劑中而 調製成塗佈液後，將該塗佈液塗佈於阻障層24上而形成塗 佈膜，在塗佈膜上重疊聚碳酸酯板片。然後，視需要在重疊 狀態下，使媒體進行旋轉等而使塗佈液更加延伸展開後，利 用UV燈照射紫外線而使其硬化。或者，將壓感性接著劑預 先塗佈於板片上，再使板片重疊於阻障層24上之後，以適 度壓力按壓而壓接。 上述黏著劑從透明性、耐久性的觀點，較佳為丙烯酸系、 甲基丙烯酸酯系的聚合物黏著劑。更具體而言，可列舉以丙 烯酸2-乙基己g旨、_酸正了 §旨、丙烯酸異辛g旨等為主成 分單體，域料域分單體，㈣騎、？基丙烯酸、丙 稀醯胺衍生物、順丁稀二酸、丙烯酸經乙自旨、叫酸環氧丙 醋等極性單體進行共聚合，而發揮㈣力者。利社成分單 體的分子量織、其賴成分料合、由丙雜所造成的交 聯點密度調整’便可控制朗轉移溫度”、黏著性能（以低 壓力進行接觸時馬上形成的接著力）、剝離強度、剪切保持 100105051 78 201137051 力等物性。丙稀酸系聚合物的溶劑係可使用：醋酸乙醋、醋 酸丁醋、曱笨、甲⑽、環己科。上述黏著劑較佳復含有 聚異氰酸酯系交聯劑。 再者’黏著劑係使用如前述的材料，在覆蓋層25用片材 鄰接錢層㈣表面上均自塗佈既定量，使溶劑乾燥後，使 其貼合於阻障層24的表面上，_鮮施加壓力而使其硬 化將已塗佈該黏著劑的覆蓋層片材黏合於已形成記錄層 及阻IV層24的S己錄媒體表面時，為使不致捲入空氣而形 成氣泡，較佳在真空中進行貼合。 2者’亦可在離型膜上塗佈上述黏著劑，使溶劑乾燥後， 貼口覆蓋層板片’再將離型膜剝離’使覆蓋層板片與黏著劑 層一體化後，再與合記_體貼合。 利用塗佈法形成覆蓋層25時，係使用旋塗法、浸潰法等， 特另J係針對碟片狀媒體大多使用旋塗法。利用塗佈形成覆蓋 θ “時’同樣地，使用胺曱酸醋、環氧化合物、丙稀酸系 樹月曰等’〜仃塗佈後，照射紫外線、電子線、輻射線等，而 促進自由基聚合或陽離子聚合並硬化。 由此塗佈所減的覆蓋層材料，從透明性、敎性的觀 較佳係由丙烯酸系、甲基丙稀酸醋系的寡聚物及/或單 :所構成組成物。更具體而言，較佳係將聚醚(甲基)丙烯酸 曰聚酉曰（曱基）丙烯酸酯、環氧化合物（曱基）丙烯酸酯、胺 甲酉夂酉曰（甲基)丙稀酸醋等（甲基)丙婦酸酷寡聚物 ;丙稀酸正 100105051 79 201137051 丁西曰、丙烯酸2-乙基己酯、丙烯酸異辛酯、（曱基）丙烯酸硬 脂酯、（曱基）丙烯酸異稻酯、（曱基）丙烯酸環己酯、（曱基) 丙烯酸苄酯、（甲基）丙烯酸笨氧乙酯等單官能（曱基）丙烯酸 酉曰單體的1種或2種以上，予以均勻混合而成的組成物。藉 由寡聚物的分子量調整、單體的種類及混合量調整，便可控 制玻璃轉移溫度Tg、黏著性能（以低壓力進行接觸時馬上形 成的接著力）、剝離強度、剪切保持力等物性。 [ΙΙΙ_2-2·光學記錄媒體之第2實施形態] 適用本實施形態的光記錄媒體’若削薄反射層的膜厚，形 成記錄再生光的約5〇%以上能穿透反射層的薄度，便可形成 所谓的多層記錄媒體。即，在基板上設有複數阻障層、記錄 層及反射層（以下併稱「資訊層」）的記錄媒體。 圖2係說明設有雙層資訊層的光記錄媒體之圖。將記錄再 生光光束107入射側的資訊層（112、in、114)稱「L1層」， 將位於深度側的資訊層（1〇2、1〇3、1〇4)稱「L0層」。L1層 較佳係穿透率達50%以上。若u層的半透明反射層112係 例如屬於Ag合金層，較佳係將Ag合金層的膜厚設為 lnm〜50nm、更佳係5nm〜30nm、再更佳係5nm〜20nm。此 種高穿透性的反射層稱「半透明反射層」。在L()層與L1層 之間，為防止各個信號的干擾，便設有透明中間層ηι。又， 圖2中，L0層的反射層1〇2可使用與前述反射層22(圖1) 同樣的材料。 100105051 80 201137051 例如在°己錄再生光光束1〇7(波長人=4〇5nm、ΝΑ(開口 數)=0.85)的光學系統，將中間層lu的厚度設為約2^m、 覆蓋層115的厚度設為約75/xm左右。中間層ln的厚度分 佈較佳係設為±2/im左右以下。 L0層、L1層分別可使用在本實施形態適用之光學記錄媒 體100之層構成範圍内的不同層構成，亦可使用相同的層構 成。各資訊層所使用以色素為主成分的記錄層之組成與材 料，係可不同、亦可為相同。 本實施形態中，特別係主要利用相位變化，因而期待在記 錄前後’穿透L1層的光量幾乎不會有變化。此現象係指不 管L1層係屬於記錄/未記錄，對L0層的穿透光量、來自L〇 層的反射光量幾乎沒有變化，且無關L1層的狀態，均可安 定地執行L0層的記錄再生，因而屬較佳。 其他’在上述所說明各層的形成前或形成後，亦可在記錄 /再生雷射光的入射面與反對側（通常係基板1的下面），設置 能使用喷墨、感熱轉印等各種印表機、或各種筆記用具進行 書寫或印刷的印刷接受層。 [IV.光學記錄媒體之記錄方法] [IV-1.雷射光] 對本發明光學記錄媒體的資訊記錄，通常係藉由對記錄層 照射聚焦於0.4〜0.6/xm左右的雷射光而實施。若記錄層吸收 雷射光的能量，藉由雷射光照射部分發生分解、發熱、熔融 100105051 81 201137051 等熱變形，而使光學的特性產生變化，便可記錄資訊。 另一方面，當執行記錄層中所記錄資訊的再生時，同樣地 對《•己錄層（通常係從與記錄時相同的方向）照射能量較低的 雷射光。在記錄層，利用讀取光學特性有出現變化部分（即 有資訊記錄的部分)的反射率、與沒有出現變化部分的反射 率之差，而執行資訊的再生。 為求尚密度記錄，記錄時所使用雷射光的波長係越短越 佳，特別係本發明的光學記錄媒體，從能充分發揮於該記錄 層中含有上述本發鴨肼g合錯合化合物之優_觀點，較 佳係波長350nm〜530nm的雷射光（以下，將使用此種雷射光 的。己錄方法’適當地稱「本發明光學記錄媒體之記錄方法」、 或簡稱「本發明記錄方法」）。 該雷射光的代表例係可列舉如：中心波長4G5nm、賊 等藍色雷射光、中心波長515nm的藍綠色高輸出半導體雷 射光。該專以外尚可列舉：將(a)基本振盪波長74〇〜 的可連續振料導體雷射光；或(b)可被半導體雷射光激發 且基本振盪波長740〜960nm的可連續振盪之固態雷射光之 任者利用第一諧波產生元件(SHG)進行波長轉換而獲 得的光等。 上述SHG係只要屬於欠缺反射對稱性的壓電元件’即可 為任何物，較佳為：KDP(KH2P〇4)、adp(nh4h2po4)、 BNN(Ba2NaNb5〇15)、KN(KNb03)、LB0(LiB305)、化合物半 100105051 82 201137051 導體等。第二諧波的具體例係可列舉：在基本振盪波長為 860nm的半導體雷射之情況，其倍波的波長43〇nm;又，在 半導體雷射激發的固態雷射之情況，來自經Cr摻雜的Metals and semimetals such as Rh, ir, Cu, Zn, Cd, Ga, In, Si, Ge, Te, Pb, Po, Sn, Bi, Ta, Tiptpd, Nd. Among them, from the viewpoints of low cost, easy formation of high reflectance, and provision of a white color and an aesthetic appearance when a P-brush layer is provided later, it is particularly preferable to use Ag as a main component. For example, in the group containing 〇1 atom% to 5 atom%, k is more than one type of alloy from the group consisting of Au Pd, pt, Cu, and Nd, which is high-reflection, high durability, and high sensitivity. And low cost is preferred. Specifically, 'is an AgPdCu alloy, an alloy, an AgCuAuNd σ AgC_ alloy, or the like. Materials other than metal may also be made of a low refractive index thin 100105051 76 201137051 and used as a multilayer film, reflective layer 22 in a manner that the film and the high refractive index film are alternately overlapped. The method of forming the reflective layer 22 is a combination of enthalpy and enthalpy; the W system is audible to the ionic bond method, the vacuum method, and the like. Correction, _ on the substrate 21 or above or below the reflective layer 22, in order to improve the reflectivity, = Tao, etc., a well-known inorganic or her layer may be provided. The method of forming the recording layer 23 on the reflective layer 22 is a method in which a solution of the organic solvent and the (tetra) dye is applied to a desired coating method. The recording layer 23 is formed to be thick, preferably 5 nm to (10) coffee, and preferably 10 nm to 50 nm. The material of the barrier layer 24 formed on the recording layer 23 is lifted before the material which can hinder the coating layer 25 (which is composed of the same organic substance as the recording layer constituting the organic dye) is mixed and oozing. There are no special restrictions. For example, an inorganic substance such as Si 〇 2, AH, 、, Sn 〇 2, in 2 〇 3, ZnS, or the like, and the like can be cited. The film thickness of the barrier layer 24 is preferably 2 nm to 100 nm, more preferably 3 nm to 5 nm. The cover layer 25 formed on the barrier layer 24 is selected to be transparent to the recording and reproducing light beam 28 and has less birefringence. The material is usually formed by bonding a plastic plate (referred to as "plate") with an adhesive or after applying a curable resin solution, and then curing it by light, radiation, or heat. The cover layer 28 invades light, and thus the wavelength λ of the recording and reproducing light beam 28 is preferably 70105051 77 201137051 70% or more, more preferably 8 % or more. The plastic substrate used as the skin sheet of the cover layer 25 is, for example, polycarbonate, polyolefin, acrylic, cellulose triacetate, polyethylene terephthalate or the like. In the following, a radiation curable resin, a thermosetting resin, a pressure sensitive adhesive or the like can be used. As the pressure-sensitive adhesive, an adhesive composed of a polymer such as an acrylic, a methacrylate, a rubber, a diaphor, or an amine phthalate can be used. For example, after the photocurable resin constituting the adhesive layer is dissolved in a suitable solvent to prepare a coating liquid, the coating liquid is applied onto the barrier layer 24 to form a coating film, and the coating film is superposed on the coating film. Carbonate sheet. Then, if necessary, the medium is rotated or the like in an overlapping state, and the coating liquid is further stretched and expanded, and then irradiated with ultraviolet rays by a UV lamp to be hardened. Alternatively, the pressure-sensitive adhesive is applied to the sheet in advance, and after the sheet is overlaid on the barrier layer 24, it is pressed by a moderate pressure and pressure-bonded. The adhesive is preferably an acrylic or methacrylate polymer adhesive from the viewpoint of transparency and durability. More specifically, it is exemplified by 2-ethylhexyl acrylate, _acid §, isopropyl acrylate, and the like as a main component monomer, and the domain domain is divided into monomers, and (4) riding, ? The acrylic acid, the acrylamide derivative, the cis-succinic acid, and the acrylic acid are copolymerized by a polar monomer such as an acid propylene glycol, and the (four) force is exerted. The molecular weight of the monomer of the company, the composition of the component, the density of the cross-linking point caused by the propylene miscellaneous point 'can control the transfer temperature', and the adhesive property (the adhesive force formed immediately after contact at a low pressure) Peeling strength, shear retention 100105051 78 201137051 Force and other physical properties. Acrylic acid polymer solvent can be used: acetic acid vinegar, acetic acid butyl vinegar, sputum, A (10), cyclohexyl. The above adhesive is better The polyisocyanate-based crosslinking agent is contained. Further, the "adhesive agent" is a material as described above, and the surface of the cover layer 25 adjacent to the surface layer (4) is coated with a predetermined amount, and the solvent is dried and then adhered thereto. On the surface of the barrier layer 24, fresh pressure is applied to harden the cover sheet coated with the adhesive to the surface of the S recording medium on which the recording layer and the resistive layer 24 have been formed, so as not to The air is trapped to form a bubble, and it is preferably laminated in a vacuum. The second adhesive can also be applied to the release film to dry the solvent, and then the adhesive cover sheet is peeled off and the release film is peeled off. 'Making cover sheets and adhesives After the layer is integrated, it is bonded to the joint body. When the cover layer 25 is formed by the coating method, a spin coating method, a dipping method, or the like is used, and in particular, a spin coating method is often used for the disc-shaped medium. When the coating is formed to cover the θ "When the same is applied, it is coated with an amine bismuth vinegar, an epoxy compound, an acrylic acid tree, etc., and then irradiated with ultraviolet rays, electron beams, radiation, etc. to promote radicals. Polymerized or cationically polymerized and hardened. The coating material to be reduced by the coating is preferably composed of an acrylic or methacrylic acid-based oligomer and/or a single composition from the viewpoint of transparency and enthalpy. More specifically, polyether (meth)acrylic acid ruthenium (mercapto) acrylate, epoxy compound (mercapto) acrylate, amine formamidine (meth) acrylate (Methyl)-propyl acetophenone oligo oligo; acrylic acid positive 100105051 79 201137051 Dingxi, 2-ethylhexyl acrylate, isooctyl acrylate, stearyl acrylate, thiol One or two kinds of monofunctional (fluorenyl) fluorene acrylate monomers such as isopropyl acrylate, cyclohexyl acrylate, benzyl (meth) acrylate, and phenoxyethyl (meth) acrylate The composition obtained by uniformly mixing the above. By adjusting the molecular weight of the oligomer, adjusting the type of the monomer, and adjusting the amount of the mixture, it is possible to control the glass transition temperature Tg, the adhesion performance (the adhesion force immediately formed upon contact at a low pressure), the peel strength, the shear retention force, and the like. Physical properties. [ΙΙΙ_2-2·Second Embodiment of Optical Recording Medium] When the optical recording medium of the present embodiment is applied, the film thickness of the reflective layer is reduced, and about 5 % or more of the recording and reproducing light is formed to penetrate the thickness of the reflective layer. Thus, a so-called multi-layer recording medium can be formed. That is, a recording medium having a plurality of barrier layers, a recording layer, and a reflective layer (hereinafter referred to as "information layer") is provided on the substrate. Fig. 2 is a view showing an optical recording medium provided with a two-layer information layer. The information layer (112, in, 114) on the incident side of the reproduced light beam 107 is referred to as "L1 layer", and the information layer (1〇2, 1〇3, 1〇4) located on the depth side is referred to as "L0 layer". The L1 layer preferably has a penetration rate of more than 50%. When the semi-transparent reflective layer 112 of the u layer is, for example, an Ag alloy layer, the film thickness of the Ag alloy layer is preferably from 1 nm to 50 nm, more preferably from 5 nm to 30 nm, still more preferably from 5 nm to 20 nm. This highly penetrating reflective layer is called a "translucent reflective layer." In order to prevent interference of individual signals between the L() layer and the L1 layer, a transparent intermediate layer ηι is provided. Further, in Fig. 2, the same material as the aforementioned reflective layer 22 (Fig. 1) can be used for the reflective layer 1A2 of the L0 layer. 100105051 80 201137051 For example, in an optical system in which a regenerated light beam 1 〇 7 (wavelength person = 4 〇 5 nm, ΝΑ (number of openings) = 0.85) is used, the thickness of the intermediate layer lu is set to about 2 μm, and the cover layer 115 The thickness is set to be about 75/xm. The thickness distribution of the intermediate layer ln is preferably set to about ±2/im or less. Each of the L0 layer and the L1 layer may be formed of a different layer within the layer constitution range of the optical recording medium 100 to which the present embodiment is applied, or may be formed using the same layer. The composition and material of the recording layer using the pigment as the main component in each information layer may be different or the same. In the present embodiment, in particular, since the phase change is mainly used, it is expected that the amount of light penetrating through the L1 layer hardly changes before and after the recording. This phenomenon means that regardless of whether the L1 layer is recorded/unrecorded, the amount of transmitted light to the L0 layer, and the amount of reflected light from the L〇 layer hardly change, and the state of the L1 layer is irrelevant, the recording and reproduction of the L0 layer can be performed stably. Therefore, it is preferred. Others 'Before or after the formation of each layer described above, it is also possible to use various types of printers such as inkjet and thermal transfer printing on the incident surface and the opposite side of the recording/reproducing laser light (usually the lower surface of the substrate 1). A printing receiving layer for writing or printing, or a variety of writing instruments. [IV. Method of Recording Optical Recording Medium] [IV-1. Laser Light] The information recording of the optical recording medium of the present invention is usually carried out by irradiating the recording layer with laser light focused on about 0.4 to 0.6/xm. If the recording layer absorbs the energy of the laser light, the information can be recorded by thermal decomposition such as decomposition, heat generation, and melting of the laser light irradiation portion, thereby changing the optical characteristics. On the other hand, when the reproduction of the information recorded in the recording layer is performed, the "recorded layer (usually in the same direction as the recording) is irradiated with laser light of lower energy. In the recording layer, reproduction of information is performed by using the difference between the reflectance of the reading optical characteristic (i.e., the portion where the information is recorded) and the reflectance of the portion where no change occurs. In order to obtain the density recording, the wavelength of the laser light used for recording is preferably as short as possible, and in particular, the optical recording medium of the present invention can sufficiently exhibit the above-mentioned hairpin g-missing compound in the recording layer. Preferably, the laser light having a wavelength of 350 nm to 530 nm (hereinafter, such a laser light is used. The method of recording is appropriately referred to as "the recording method of the optical recording medium of the present invention", or simply "the recording method of the present invention" "). Representative examples of the laser light include, for example, a central wavelength of 4 G5 nm, blue laser light such as a thief, and blue-green high-output semiconductor laser light having a center wavelength of 515 nm. Other specialties include: (a) a continuous oscillating conductor laser light having a fundamental oscillation wavelength of 74 〇 〜; or (b) a continuously oscillating solid ray excited by semiconductor laser light and having a fundamental oscillation wavelength of 740 to 960 nm. Light or the like obtained by wavelength conversion by the first harmonic generating element (SHG). The SHG system may be any material as long as it belongs to a piezoelectric element lacking reflection symmetry, and is preferably KDP(KH2P〇4), aDP(nh4h2po4), BNN(Ba2NaNb5〇15), KN(KNb03), LB0 ( LiB305), compound half 100105051 82 201137051 conductor, etc. Specific examples of the second harmonic include a case where a semiconductor laser having a fundamental oscillation wavelength of 860 nm has a wavelength of 43 〇 nm; and, in the case of a semiconductor laser excited solid-state laser, from a Cr Doped

LiSrAlF6結晶（基本振盪波長860nm)之倍波的波長43〇nm 等。 該等之中，特佳係使用中心波長405nm的藍色雷射光。 光學s己錄媒體所具有的吸收波長及吸光度中，從膜厚的押： 制及對雷射的高感度化觀點’較佳係本發明醯肼螯合錯合化 合物在乙腈中的吸收光譜最大吸收波長（Xmax)為 380〜500nm，且該；Imax的OD係數通常達3〇以上、較佳 達35以上、特佳達40以上。 [IV-2.本發明所使用的光記錄裝置] 本發明記錄方法所使用記錄裝置的基本構造，係可使用與 習知光記錄裝置同樣者。例如其聚焦伺服方式、循軌饲服方 式’均可適用習知公知的方式。聚焦光束焦點位置的光點， 係只要例如照射於圖1所示覆蓋層溝間部，再利用循軌祠服 追蹤該覆蓋層溝間部便可。通常利用推挽信號。 例如，對圖1所示覆蓋層溝間部執行記錄時，經聚焦的記 錄再生光光束便使記錄層主成分色素開始升溫•發熱，並引 發變質(膨脹、分解、昇華、熔融等）。當執行標記長調變記 錄時，使記錄再生光光束的功率（記錄功率)依照標&amp;長進行 強弱調變。另外，標記長調變方式並無特別的限制，可適用 100105051 83 201137051 通常所使用屬於Run-Length-Limited碼（跳躍長度限制碼， Run-Length-Limited code)的 EFM 調變（CD)、EFM+調變 (DVD)、1-7PP調變(藍光)等。 但，在以HtoL極性信號為前提的記錄再生系統中，於進 行LtoH記錄時，依使標記與間隔的記錄信號極性呈相反方 式，預先使記錄資料信號的極性進行反轉。依此，記錄後的 信號在表觀上，便可與HtoL極性的信號同等。 通常在標記部，將記錄功率設為高位準Pw，在標記間（間 隔）則設為低位準Ps。Ps/Pw通常設為0.5以下。Ps係僅單 次照射並不會使記錄層發生上述變質的功率，為在Pw之前 能預熱記錄層而使用。公知的記錄脈衝策略亦可適當地適用 於本發明記錄方法及記錄裝置。可使用例如對應記錄標記部 的記錄功率Pw照射時間係以更短時間進行間歇式照射，對 複數功率位準進行調變，在Pw照射後，移往ps為止的一 定時間照射比Ps更低的功率位準Pb等記錄策略。 [IV-3.記錄感度] 上述一般式⑴或(II)所示具有醯肼配位基的本發明醢肼螯 合錯合化合物，係記錄雷射感度優異。具體而言，在製作圖 1或圖2所記載的光學記錄媒體後，使用雷射波長405nm、 NA=0.85的測試機(PULSTEC公司製ODU-IOOO)，依線速度 9.834m/s(2X記錄速度。記錄速度IX係4.917m/s)、最短標 記長149nm，且依隨機形態（使用1-7PP調變）進行記錄時， 100105051 84 201137051 滿足灿同測試機進行再生時的餘值為8%以下、較佳 為/〇 乂下且5己錄最佳功率Rw通常在8.0mW以下、較 佳在7.0mW以下。 $發明醯肼螯合錯合化合物如此記錄感度優異的理由，可 推娜係上述-般式(1)所示具有具醯肼配位基的醯肼整合錯 合化合物’藉由具有鹽構造，陽離子便可作為雷射感度部位 而發揮機能。 [IV-4.記錄部之反射率] ， 本發明光學賴的記錄方法之特徵在於：在執行記錄的雷 先波長巾，簡部的反射率健高於記錄前及未記錄部 ^的反射率。為使記錄部的反射率較高於未記錄部的反射率 的^條件’係塗佈色素在記㈣射波長中具有—定量以上 ^者#較佳係具有實施例等另外記載的溝形狀。若為此種 ==用屬於不同於習知的記錄機制的U&gt;Wt0High 。己錄，進仃咼密度的光資訊記錄、再生。 實施例 體說明，惟本發明在 下實施例。 以下列舉實施例針對本發明進行更具 不逾越主旨的前提下’並不僅侷限於以 [溶解性及耐光性評估] {實施例1} 使用表la所示化合物C1 , 施行以下的溶解性試驗。 100105051 85 201137051 &lt;溶解性試驗&gt; 塗佈溶劑係使用2,2,3,3-四氟丙醇，將化合物C1的濃度 設為1.0重量％，於机，依常壓施行3〇分鐘超音波處^ 後，滴至濾紙(東洋濾紙公司製定量濾紙rN〇 5c」）上，於 室溫中進行24小時乾燥，再依目視觀察濾紙上是否有存在 未溶解成分的結晶殘渣。 判斷基準係如下： 〇：未觀察到未溶解殘渣 X:未溶解殘渣頗多 化合物C1並沒有觀察到未溶解殘渣，可知係溶解性優異。 接著，施行膜吸收光譜測定與耐光性試驗。 &lt;耐光性試驗&gt; 使化合物C1依濃度1.0重量％溶解於2,2,3,3-四氟丙醇 中’利用過濾去除細微污物後’再將所獲得溶液滴至直徑 120mm、厚1.2mm的射出成形聚碳酸酯基板上，利用旋塗 法(4900rpm)施行塗佈，依80。(：進行30分鐘乾燥，便製得膜 厚約50nm的塗佈膜。對該塗佈膜，在溫度58°C、濕度50%RH 的條件下，依550W/m2照射強度照射氙燈40小時後，根據 吸收極大波長在照射前後的吸光度，求取色素殘留率。 照射前的吸收極大波長(Xmax)係368nm，耐光性（色素殘 留率）係92%。 此處，上述色素殘留率的計算式係如下： 100105051 86 201137051 色素殘留率（％)=(氙燈照射後的吸收極大波長之吸光 度)/(氙燈照射前的吸收極大波長之吸光度）χ1〇〇 {實施例2〜73} 除將化合物C1變更為表la〜lc所示化合物C2〜C73之 外，其餘均施行與實施例丨同樣的試驗。 評估結果如表1 a〜1 c所示。 {實施例74} &lt;溶解性試驗&gt; 使用表2a所示化合物C74，施行以下的溶解性試驗。 塗佈溶劑係使用2,2,3,3-四氟丙醇，將化合物C74的濃度 設為0.7重量％，於40〜50〇C下，依常壓施行超音波處理後， 於室溫下放置30分鐘後，滴至濾紙(東洋濾紙公司製定量濾 紙「No.5C」）上’於室溫中進行24小時乾燥，再依目視觀 察濾紙上是否有存在未溶解成分的結晶殘渣。 判斷基準係如下： 〇：未觀察到未溶解殘渣 X:未溶解殘渣頗多 化合物C74並沒有觀察到未溶解殘渣，可知係溶解性優 異。 接著，施行膜吸收光譜測定與耐光性試驗。 &lt;耐光性試驗&gt; 使化合物C74依濃度0.7重量％溶解於2,2,3,3_四氣丙醇 100105051 87 201137051 中，利用過濾去除細微污物後，再將所獲得溶液滴至直徑 120mm、厚0.6mm的射出成形聚碳酸酯基板上，利用旋塗 法(4900rpm)施行塗佈，依80°C進行30分鐘乾燥，便製得膜 厚約30nm的塗佈膜。對該塗佈膜，在室温下、濕度 30〜60%RH的條件下，依550W/m2照射強度照射氙燈40小 時後’根據吸收極大波長在照射前後的吸光度，求取色素殘 留率。 照射前的吸收極大波長(Xmax)係415nm，耐光性（色素殘 留率）係90%。 {實施例75〜121} 除將化合物C74變更為表2a及2b所示化合物C75〜C121 之外，其餘均施行與實施例74同樣的試驗。 評估結果如表2a及2b所示。 另外’表la〜lc及表2a及2b所示化合物的配位基：過渡 金屬構成比在過渡金屬為2價陽離子的情況、及3價陽離子 的情況’均為2 : 1 (即一般式⑴中，a=2)。 100105051 88 201137051 [表 la] 實施例 化合物 配位基 過渡金屬 A max 耐光性 溶解性 No. (例示化合物） (nm) (%) 實施例1 Cl L-l Co 368 92 〇 實施例2 C2 L-2 Co 372 85 〇 實施例3 C3 L-3 Co 388 99 〇 實施例4 C4 L-4 Co 370 78 〇 實施例5 C5 L-5 Co 396 100 〇 實施例6 C6 L-6 Co 392 100 〇 實施例7 C7 L-7 Co 377 73 〇 實施例8 C8 L-9 Co 369 92 〇 實施例9 C9 L-10 Co 369 92 〇 實施例10 CIO L-ll Co 371 89 〇 實施例11 Cll L-12 Co 381 91 〇 實施例12 C12 L-13 Co 367 94 〇 實施例13 C13 L-14 Co 368 90 〇 實施例14 C14 L-15 Co 375 86 〇 實施例15 C15 L-16 Co 391 87 〇 實施例16 C16 L-17 Co 368 89 〇 實施例17 C17 L-18 Co 373 95 〇 實施例18 C18 L-19 Co 370 96 〇 實施例19 C19 L-21 Co 370 97 〇 實施例20 C20 L-22 Co 371 96 〇 實施例21 C21 L-23 Co 371 96 〇 實施例22 C22 L-24 Co 367 93 〇 實施例23 C23 L-25 Co 372 92 〇 實施例24 C24 L-26 Co 388 99 〇 實施例25 C25 L-27 Co 389 96 〇 89 100105051 201137051 [表 lb] 實施例 化合物 配位基 過渡金屬 λ max 财光性 溶解性 No. (例示化合物） (nm) (%) 實施例26 C26 L-28 Co 371 95 〇 實施例27 C27 L-29 Co 366 78 〇 實施例28 C28 L-30 Co 384 98 〇 實施例29 C29 L-31 Co 370 91 〇 實施例30 C30 L-32 Co 371 94 〇 實施例31 C31 L-33 Co 373 76 〇 實施例32 C32 L-37 Co 370 95 〇 實施例33 C33 L-43 Co 383 94 〇 實施例34 C34 L-44 Co 383 92 〇 實施例35 C35 L-45 Co 388 92 〇 實施例36 C36 L-46 Co 392 99 〇 實施例37 C37 L-47 Co 387 98 〇 實施例38 C38 L-48 Co 386 100 〇 實施例39 C39 L-49 Co 370 96 〇 實施例40 C40 L-50 Co 370 95 〇 實施例41 C41 L-51 Co 369 96 〇 實施例42 C42 L-52 Co 370 94 〇 實施例43 C43 L-53 Co 399 98 〇 實施例44 C44 L-55 Co 365 99 〇 實施例45 C45 L-56 Co 367 97 〇 實施例46 C46 L-58 Co 368 97 〇 實施例47 C47 L-59 Co 390 100 〇 實施例48 C48 L-60 Co 391 99 〇 實施例49 C49 L-61 Co 391 98 〇 實施例50 C50 L-62 Co 392 97 〇 90 100105051 201137051 [表 lc] 實施例 化合物 配位基 過渡金屬 λ max 耐光性 溶解性 No. (例不化合物） (nm) (%) 實施例51 C51 L-63 Co 394 99 〇 實施例52 C52 L-64 Co 392 98 〇 實施例53 C53 L-65 Co 393 94 〇 實施例54 C54 L-66 Co 390 98 〇 實施例55 C55 L-67 Co 390 97 〇 實施例56 C56 L.48 Co 395 97 〇 實施例57 C57 L-69 Co 391 97 〇 實施例58 C58 L-71 Co 396 100 〇 實施例59 C59 L-72 Co 397 99 〇 實施例60 C60 L-73 Co 394 96 〇 實施例61 C61 L-74 Co 390 100 〇 實施例62 C62 L-75 Co 393 100 〇 實施例63 C63 L-76 Co 389 100 〇 實施例64 C64 L-77 Co 400 99 〇 實施例65 C65 L-78 Co 395 97 〇 實施例66 C66 L-79 Co 391 100 〇 實施例67 C67 L-80 Co 401 99 〇 實施例68 C68 L-81 Co 395 98 〇 實施例69 C69 L-82 Co 392 100 〇 實施例70 C70 L-83 Co 401 100 〇 實施例71 C71 L-85 Co 401 95 〇 實施例72 C72 L-99 Co 379 100 〇 實施例73 C73 L-100 Co 386 99 〇 91 100105051 201137051 [表 2a] 實施例 化合物No. 配位基 (例示化合物） 過渡金屬 λ max (nm) 耐光性 (%) 溶解性 實施例74 C74 L-101 Co 415 90 〇 實施例75 C75 L-101 Fe 388 57 〇 實施例76 C76 L-102 Co 421 70 〇 實施例77 C77 L-107 Co 390 74 〇 實施例78 C78 L-108 Co 391 87 〇 實施例79 G79 L-109 Co 390 77 〇 實施例80 C80 L-110 Co 390 88 〇 實施例81 C81 L-111 Co 415 94 〇 實施例82 C82 L-112 Co 396 74 〇 實施例83 C83 L-114 Co 367 84 〇 實施例84 G84 L-119 Co 373 87 〇 實施例85 C85 L-120 Co 383 91 〇 實施例86 C86 L-130 Co 387 96 〇 實施例87 C87 L-131 Co 403 83 〇 實施例88 C88 L-133 Co 404 96 〇 實施例89 C89 L-134 Co 400 97 〇 實施例90 C90 L-135 Co 390 97 〇 實施例91 C91 L-136 Co 396 95 〇 實施例92 C92 L-137 Co 408 93 〇 實施例93 C93 L-140 Co 409 84 〇 實施例94 C94 L-140 Fe 386 74 〇 實施例95 C95 L-164 Co 394 90 〇 實施例96 C96 L-163 Co 394 81 〇 實施例97 C97 L-165 Co 398 90 〇 實施例98 C98 L-166 Co 390 87 〇 實施例99 C99 L-168 Co 459 88 〇 實施例100 C100 L-138 Co 400 92 〇 92 100105051 201137051 [表 2b] 實施例 化合物 No. 配位基 (例示化合物） 過渡金屬 A max (nm) 耐光性 (%) 溶解性 實施例101 C101 L-295 Co 393 90 〇 實施例102 C102 L-296 Co 392 91 〇 實施例103 C103 L-267 Co 369 97 〇 實施例104 C104 L-297 Co 394 96 〇 實施例105 C105 L-265 Co 393 92 〇 實施例106 C106 L-298 Co 401 67 〇 實施例107 C107 L-299 Co 393 90 〇 實施例108 C108 L-266 Co 389 98 〇 實施例109 G109 L-265 Ni 372 52 〇 實施例110 C110 L-300 Co 395 86 〇 實施例111 cm L-255 Co 392 92 〇 實施例112 C112 L-253 Co 393 93 〇 實施例113 C113 L-252 Co 395 92 〇 實施例114 C114 L-301 Co 388 96 〇 實施例115 C115 L-302 Co 422 89 〇 實施例116 C116 L-303 Co 393 92 〇 實施例117 C117 L-311 Co 389 93 〇 實施例118 C118 L-310 Co 394 95 〇 實施例119 C119 L-307 Co 413 91 〇 實施例120 C120 L-312 Co 404 93 〇 實施例121 C121 L-356 Co 389 71 〇 [記錄評估] {實施例122} &lt;光學記錄媒體之特性評估&gt; 在厚1,1mm、執距0.32μηι、溝寬度180nm、溝深度45nm 的聚碳酸酯製基板上，利用藏鐘設置厚70nm的AgBi〇.2Nd〇.5 反射膜。接著，將化合物Cl依對TFP(2,2,3,3-四氟-1-丙醇) 成為0.7重量％濃度的方式進行混合之溶液，利用旋塗法進 行塗佈，於70°C進行25分鐘乾燥，藉此便設置記錄層。另 93 100105051 201137051 外’以空氣為參考(reference)所測得於470nm的吸光度係 0.24。然後，在該記錄層上，利用濺鍍將厚20nm的Ιη203 阻障層予以成膜。再壓接厚100μηι的Lintec公司製BD-R 用覆蓋片（商品名Opteria)，便製得光學記錄媒體。 針對所獲得光學記錄媒體，依照以下所示方法施行光學記 錄媒體的特性評估。 (光學記錄媒體的特性評估） 使用雷射波長405nm、NA(開口數）0.85的測試機 (PULSTEC 公司製 ODU-1000)，依線速度 9.834m/s(2X 記錄 速度。記錄速度IX係4.917m/s)、最短標記長149nm施行 隨機形態（使用1-7PP調變）記錄，求取最佳記錄功率RW。 又，再生係設為線速度4.917m/s ’並依BD-R評估基準的The wavelength of the double wave of LiSrAlF6 crystal (basic oscillation wavelength: 860 nm) is 43 〇 nm and the like. Among these, it is particularly preferable to use blue laser light having a center wavelength of 405 nm. Among the absorption wavelengths and absorbances of optical recording media, from the viewpoint of film thickness and high sensitivity to lasers, it is preferable that the absorption spectrum of the chelating chelate compound in acetonitrile is the largest in the present invention. The absorption wavelength (Xmax) is 380 to 500 nm, and the OD coefficient of Imax is usually 3 Å or more, preferably 35 or more, and particularly preferably 40 or more. [IV-2. Optical recording device used in the present invention] The basic structure of the recording device used in the recording method of the present invention can be the same as that of the conventional optical recording device. For example, the focus servo method and the track feeding method can be applied to a conventionally known method. The spot that focuses the focus position of the beam is, for example, irradiated to the inter-groove portion of the cover layer as shown in Fig. 1, and the tracking groove portion can be tracked by the tracking device. Push-pull signals are usually utilized. For example, when recording is performed on the inter-groove portion shown in Fig. 1, the focused recording-reproducing light beam causes the main component dye of the recording layer to start to heat up and heat, and causes deterioration (expansion, decomposition, sublimation, melting, etc.). When the mark long modulation recording is performed, the power (recording power) of the recording and reproducing light beam is made to be strong and weakly modulated in accordance with the standard &amp; length. In addition, the mark length modulation method is not particularly limited, and can be applied to 100105051 83 201137051 EFM modulation (CD) and EFM+ modulation which are commonly used in the Run-Length-Limited code (Run-Length-Limited code). Change (DVD), 1-7PP modulation (blue light), etc. However, in the recording/reproducing system premised on the HtoL polarity signal, when the LtoH recording is performed, the polarity of the recording data signal is reversed in advance in accordance with the polarity of the recording signal of the mark and the interval. Accordingly, the recorded signal is apparently equivalent to the HtoL polarity signal. Usually, in the mark portion, the recording power is set to the high level Pw, and between the marks (interval), the low level Ps is set. Ps/Pw is usually set to 0.5 or less. Ps is a single-shot irradiation that does not cause the deterioration of the recording layer, and can be used to preheat the recording layer before Pw. A well-known recording pulse strategy can also be suitably applied to the recording method and recording apparatus of the present invention. For example, the recording power Pw corresponding to the recording mark portion can be used for intermittent irradiation in a shorter period of time, and the complex power level can be modulated, and after Pw irradiation, the irradiation for a certain time until the ps is lower than the Ps. Recording strategy such as power level Pb. [IV-3. Recording sensitivity] The oxime chelating compound of the present invention having an oxime ligand represented by the above general formula (1) or (II) is excellent in recording laser sensitivity. Specifically, after the optical recording medium described in FIG. 1 or FIG. 2 was produced, a tester (ODU-IOOO manufactured by PULSTEC Co., Ltd.) having a laser wavelength of 405 nm and NA = 0.85 was used, and the linear velocity was 9.834 m/s (2X recording). Speed. Recording speed IX is 4.917m/s), shortest mark length is 149nm, and when recording in random form (using 1-7PP modulation), 100105051 84 201137051 meets the residual value of the same test machine for regeneration. Hereinafter, the optimum power Rw is preferably 8.0 mW or less, preferably 7.0 mW or less. The reason for the excellent sensitivity of the chelating chelating compound is as follows, and the hydrazine-integrating complex compound having a hydrazine ligand represented by the above-mentioned general formula (1) can have a salt structure. The cation can function as a laser sensitivity site. [IV-4. Reflectance of Recording Section] The recording method of the optical ray of the present invention is characterized in that the reflectance of the simple portion is higher than that of the unrecorded portion before the recording. . In order to make the reflectance of the recording portion higher than the reflectance of the unrecorded portion, the coating coloring matter has a -quantity or more in the (four)-wavelength wavelength. It is preferable to have a groove shape described in the examples and the like. If such == use U&gt;Wt0High which is different from the conventional recording mechanism. It has been recorded, and the light information recording and reproduction of density is entered. EXAMPLES The invention is illustrated by the following examples. The following examples are set forth below for the purpose of the present invention, and are not limited to the evaluation of [solubility and light resistance] {Example 1} Using the compound C1 shown in Table la, the following solubility test was carried out. 100105051 85 201137051 &lt;Solubility test&gt; The coating solvent was 2,2,3,3-tetrafluoropropanol, and the concentration of the compound C1 was 1.0% by weight, and the system was subjected to atmospheric pressure for 3 minutes. After the sound wave was placed, it was dropped on a filter paper (Toyo Filter Paper Co., Ltd., filter paper rN 〇 5c), and dried at room temperature for 24 hours, and visually observed whether or not there was a crystal residue of undissolved components on the filter paper. The judgment criteria were as follows: 〇: no undissolved residue was observed X: a large amount of undissolved residue No undissolved residue was observed in the compound C1, and it was found that the solubility was excellent. Next, film absorption spectrum measurement and light resistance test were carried out. &lt;Light resistance test&gt; The compound C1 was dissolved in 2,2,3,3-tetrafluoropropanol at a concentration of 1.0% by weight. After the fine dirt was removed by filtration, the obtained solution was dropped to a diameter of 120 mm and thick. On a 1.2 mm injection-molded polycarbonate substrate, coating was carried out by a spin coating method (4900 rpm). (: After drying for 30 minutes, a coating film having a film thickness of about 50 nm was obtained. The coating film was irradiated with a 550 W/m 2 irradiation intensity for 40 hours under the conditions of a temperature of 58 ° C and a humidity of 50% RH. The dye residual ratio is obtained from the absorbance before and after the irradiation of the maximum wavelength. The absorption maximum wavelength (Xmax) before irradiation is 368 nm, and the light resistance (dye residual ratio) is 92%. Here, the calculation formula of the above-described dye residual ratio is used. The system is as follows: 100105051 86 201137051 Residue rate of pigment (%) = (absorbance of absorption maximum wavelength after xenon lamp irradiation) / (absorbance of absorption maximum wavelength before xenon lamp irradiation) χ 1 〇〇 {Examples 2 to 73} In addition to compound C1 The same test as in Example 施 was carried out except that the compounds C2 to C73 shown in Table la to lc were changed. The evaluation results are shown in Tables 1 to 1 c. {Example 74} &lt;Solubility Test&gt; The following solubility test was carried out using the compound C74 shown in Table 2a. The coating solvent was 2,2,3,3-tetrafluoropropanol, and the concentration of the compound C74 was 0.7% by weight at 40 to 50 〇C. Next, after performing ultrasonic treatment under normal pressure, place at room temperature After 30 minutes, it was dropped on a filter paper (Toyo Filter Paper Co., Ltd., No. 5C), and dried at room temperature for 24 hours, and visually observed whether or not there was a crystal residue of undissolved components on the filter paper. As follows: 〇: No undissolved residue was observed X: Undissolved residue A large amount of compound C74 was observed, and no undissolved residue was observed, and it was found to be excellent in solubility. Next, film absorption spectrum measurement and light resistance test were carried out. &lt;Light resistance test &gt; Compound C74 was dissolved in 2,2,3,3-tetrapropanol 100105051 87 201137051 at a concentration of 0.7% by weight, and fine dirt was removed by filtration, and then the obtained solution was dropped to a diameter of 120 mm and a thickness of 0.6 mm. The injection-molded polycarbonate substrate was applied by a spin coating method (4900 rpm), and dried at 80 ° C for 30 minutes to obtain a coating film having a film thickness of about 30 nm. The coating film was allowed to stand at room temperature. Under the condition of humidity of 30 to 60% RH, after irradiating the xenon lamp for 550 W/m2 for 40 hours, 'the residual ratio of the dye before and after the irradiation according to the maximum absorption wavelength is obtained. The maximum absorption wavelength (Xmax) before irradiation is 415. The light resistance (pigment residual ratio) was 90%. {Examples 75 to 121} The same test as in Example 74 was carried out except that the compound C74 was changed to the compounds C75 to C121 shown in Tables 2a and 2b. The evaluation results are shown in Tables 2a and 2b. Further, the ligands of the compounds shown in Tables 1 to 2 and Tables 2a and 2b are as follows: the case where the transition metal is a transition metal is a divalent cation and the case of a trivalent cation. Both are 2 : 1 (that is, in general formula (1), a = 2). 100105051 88 201137051 [Table la] Example Compound Ligand Transition Metal A max Light Resistance Solubility No. (Ex. Compound) (nm) (%) Example 1 Cl Ll Co 368 92 〇 Example 2 C2 L-2 Co 372 85 〇 Example 3 C3 L-3 Co 388 99 〇 Example 4 C4 L-4 Co 370 78 〇 Example 5 C5 L-5 Co 396 100 〇 Example 6 C6 L-6 Co 392 100 〇 Example 7 C7 L-7 Co 377 73 〇 Example 8 C8 L-9 Co 369 92 〇 Example 9 C9 L-10 Co 369 92 〇 Example 10 CIO L-ll Co 371 89 〇 Example 11 C11 L-12 Co 381 91 〇 Example 12 C12 L-13 Co 367 94 〇 Example 13 C13 L-14 Co 368 90 〇 Example 14 C14 L-15 Co 375 86 〇 Example 15 C15 L-16 Co 391 87 〇 Example 16 C16 L-17 Co 368 89 〇 Example 17 C17 L-18 Co 373 95 〇 Example 18 C18 L-19 Co 370 96 〇 Example 19 C19 L-21 Co 370 97 〇 Example 20 C20 L-22 Co 371 96 Example 21 C21 L-23 Co 371 96 〇 Example 22 C22 L-24 Co 367 93 〇 Example 23 C23 L-25 Co 372 92 〇 Example 24 C24 L-26 Co 388 99 〇 Example 25 C25 L -27 Co 389 96 〇89 100105051 201137051 [Table lb] Example Compound Ligand Transition Metal λ max Photochromic Solubility No. (Ex. Compound) (nm) (%) Example 26 C26 L-28 Co 371 95 〇Example 27 C27 L-29 Co 366 78 〇 Example 28 C28 L-30 Co 384 98 〇 Example 29 C29 L-31 Co 370 91 〇 Example 30 C30 L-32 Co 371 94 〇 Example 31 C31 L-33 Co 373 76 〇 Example 32 C32 L-37 Co 370 95 〇 Example 33 C33 L-43 Co 383 94 〇 Example 34 C34 L-44 Co 383 92 〇 Example 35 C35 L-45 Co 388 92 〇 Example 36 C36 L-46 Co 392 99 〇 Example 37 C37 L-47 Co 387 98 〇 Example 38 C38 L-48 Co 386 100 〇 Example 39 C39 L-49 Co 370 96 〇 Example 40 C40 L-50 Co 370 95 〇 Example 41 C41 L-51 Co 369 96 〇 Example 42 C42 L-52 Co 370 94 〇 Example 43 C43 L-53 Co 399 98 〇 Example 44 C44 L-55 Co 365 99 〇 Example 45 C45 L-56 Co 367 97 〇 Example 46 C46 L-58 Co 368 97 〇 Example 47 C47 L-59 Co 390 100 〇 Example 48 C48 L-60 Co 391 99 〇 Example 49 C49 L-61 C o 391 98 〇Example 50 C50 L-62 Co 392 97 〇90 100105051 201137051 [Table lc] Example compound ligand transition metal λ max Light resistance Solubility No. (Example compound) (nm) (%) Implementation Example 51 C51 L-63 Co 394 99 〇 Example 52 C52 L-64 Co 392 98 〇 Example 53 C53 L-65 Co 393 94 〇 Example 54 C54 L-66 Co 390 98 〇 Example 55 C55 L-67 Co 390 97 〇 Example 56 C56 L.48 Co 395 97 〇 Example 57 C57 L-69 Co 391 97 〇 Example 58 C58 L-71 Co 396 100 〇 Example 59 C59 L-72 Co 397 99 〇Example 60 C60 L-73 Co 394 96 〇 Example 61 C61 L-74 Co 390 100 〇 Example 62 C62 L-75 Co 393 100 〇 Example 63 C63 L-76 Co 389 100 〇 Example 64 C64 L-77 Co 400 99 〇 Example 65 C65 L-78 Co 395 97 〇 Example 66 C66 L-79 Co 391 100 〇 Example 67 C67 L-80 Co 401 99 〇 Example 68 C68 L-81 Co 395 98 〇 Example 69 C69 L-82 Co 392 100 〇 Example 70 C70 L-83 Co 401 100 〇 Example 71 C71 L-85 Co 401 95 〇 Example 72 C72 L-99 Co 379 100 〇 Example 73 C7 3 L-100 Co 386 99 〇91 100105051 201137051 [Table 2a] Example Compound No. Ligand (exemplified compound) Transition metal λ max (nm) Light resistance (%) Solubility Example 74 C74 L-101 Co 415 90 〇 Example 75 C75 L-101 Fe 388 57 〇 Example 76 C76 L-102 Co 421 70 〇 Example 77 C77 L-107 Co 390 74 〇 Example 78 C78 L-108 Co 391 87 〇 Example 79 G79 L-109 Co 390 77 〇 Example 80 C80 L-110 Co 390 88 〇 Example 81 C81 L-111 Co 415 94 〇 Example 82 C82 L-112 Co 396 74 〇 Example 83 C83 L-114 Co 367 84 Example 84 G84 L-119 Co 373 87 〇 Example 85 C85 L-120 Co 383 91 〇 Example 86 C86 L-130 Co 387 96 〇 Example 87 C87 L-131 Co 403 83 〇 Example 88 C88 L -133 Co 404 96 〇 Example 89 C89 L-134 Co 400 97 〇 Example 90 C90 L-135 Co 390 97 〇 Example 91 C91 L-136 Co 396 95 〇 Example 92 C92 L-137 Co 408 93 〇 Example 93 C93 L-140 Co 409 84 〇 Example 94 C94 L-140 Fe 386 74 〇 Example 95 C95 L-164 Co 394 90 〇 Example 96 C96 L-163 Co 394 81 〇 Example 97 C97 L-165 Co 398 90 〇 Example 98 C98 L-166 Co 390 87 〇 Example 99 C99 L-168 Co 459 88 〇 Example 100 C100 L-138 Co 400 92 〇92 100105051 201137051 [ Table 2b] Example Compound No. Ligand (exemplified compound) Transition metal A max (nm) Light resistance (%) Solubility Example 101 C101 L-295 Co 393 90 〇 Example 102 C102 L-296 Co 392 91 Example 103 C103 L-267 Co 369 97 〇 Example 104 C104 L-297 Co 394 96 〇 Example 105 C105 L-265 Co 393 92 〇 Example 106 C106 L-298 Co 401 67 〇 Example 107 C107 L -299 Co 393 90 〇Example 108 C108 L-266 Co 389 98 〇Example 109 G109 L-265 Ni 372 52 〇Example 110 C110 L-300 Co 395 86 〇Example 111 cm L-255 Co 392 92 〇 Example 112 C112 L-253 Co 393 93 〇 Example 113 C113 L-252 Co 395 92 〇 Example 114 C114 L-301 Co 388 96 〇 Example 115 C115 L-302 Co 422 89 〇 Example 116 C116 L- 303 Co 393 92 〇Example 117 C117 L-311 Co 389 93 〇Example 118 C118 L-310 Co 394 95 〇Implementation 119 C119 L-307 Co 413 91 〇Example 120 C120 L-312 Co 404 93 〇Example 121 C121 L-356 Co 389 71 〇[Record evaluation] {Example 122} &lt;Evaluation of characteristics of optical recording medium&gt; On a polycarbonate substrate having a thickness of 1,1 mm, a pitch of 0.32 μm, a groove width of 180 nm, and a groove depth of 45 nm, an AgBi〇.2Nd〇.5 reflection film having a thickness of 70 nm was provided by a bell. Next, a solution in which the compound Cl was mixed with a concentration of 0.7% by weight of TFP (2,2,3,3-tetrafluoro-1-propanol) was applied by spin coating and dried at 70 ° C. Drying was carried out for 25 minutes, whereby the recording layer was set. Another 93 100105051 201137051 The absorbance at 470 nm measured by air reference is 0.24. Then, on the recording layer, a 20 nm thick barrier layer of Mn 203 was formed by sputtering. An optical recording medium was produced by pressure-bonding a cover sheet (trade name: Opteria) of BD-R manufactured by Lintec Co., Ltd. having a thickness of 100 μm. With respect to the obtained optical recording medium, the characteristic evaluation of the optical recording medium was carried out in accordance with the method shown below. (Evaluation of characteristics of optical recording medium) A tester (ODU-1000 manufactured by PULSTEC Co., Ltd.) having a laser wavelength of 405 nm and NA (number of openings) of 0.85 was used, and the linear velocity was 9.834 m/s (2X recording speed. Recording speed IX was 4.917 m). /s), the shortest mark length 149nm is applied in a random pattern (using 1-7PP modulation) to obtain the best recording power RW. In addition, the regeneration system is set to a linear velocity of 4.917 m/s ′ and is based on the BD-R evaluation standard.

Limit Equalizer mode 施行 Jitter 評估。 結果，最佳記錄功率PW係6,8mW，Jitter值係7.5%。 {實施例123〜187} 除將化合物C1變更為表3a〜3c所示化合物C2〜C121之 外，其餘均施行與實施例122同樣的試驗。 评估結果如表3 a〜3 c所不。 100105051 94 201137051 [表 3a] 實施例 化合物No. 配位基 (例示化合物） 過渡金屬 Pw (mW) Jitter (%) 實施例122 Cl L-l Co 6.8 7.5 實施例123 C2 L-2 Co 6.3 5.9 實施例124 C5 L-5 Co 7.3 6.2 實施例125 C6 L-6 Co 7.3 6.7 實施例126 C7 L-7 Co 6.8 6.3 實施例127 C8 L-9 Co 6.2 6.0 實施例128 CIO L-ll Co 7.0 7.5 實施例129 C12 L-13 Co 7.3 6.7 實施例130 C20 L-22 Co 6.8 6.2 實施例131 G22 L-24 Co 6.9 6.1 實施例132 C24 L-26 Co 7.7 7.0 實施例133 C27 L-29 Co 7.3 6.7 實施例134 C33 L-43 Co 7.3 6.3 實施例135 C34 L-44 Co 7.3 6.4 實施例136 C36 L-46 Co 7.3 6.4 實施例137 C38 L-48 Co 7.3 6.8 實施例138 C39 L-49 Co 7.3 6.7 實施例139 C40 L-50 Co 7.0 6.5 實施例140 C41 L-51 Co 7.3 7.6 實施例141 C42 L-52 Co 7.5 7.4 實施例142 C49 L-61 Co 7.0 6.2 實施例143 C52 L-64 Co 7.0 6.3 實施例144 C53 L-65 Co 7.0 6.2 實施例145 C59 L-72 Co 6.9 6.2 實施例146 C60 L-73 Co 7.6 6.4 95 100105051 201137051 [表 3b] 實施例 化合物No. 配位基 (例示化合物） 過渡金屬 Pw (mW) Jitter (%) 實施例147 C61 L-74 Co 7.3 6.0 實施例148 C62 L-75 Co 7.5 5.8 實施例149 C63 L-76 Co 7.3 6.2 實施例150 C64 L-77 Co 7.0 6.1 實施例151 C67 L-80 Co 7.3 6.4 實施例152 C70 L-83 Co 6.2 6.2 實施例153 C74 L-101 Co 7.5 5.8 實施例154 C75 L-101 Fe 7.5 6.2 實施例155 C76 L-102 Co 7.5 6.2 實施例156 C77 L-107 Co 6.3 6.3 實施例157 C78 L-108 Co 6.8 7.2 實施例158 C80 L-110 Co 7.8 6.8 實施例159 C81 L-111 Co 7.2 7.5 實施例160 C82 L-112 Co 7.5 7.2 實施例161 C85 L-120 Co 7.5 7.6 實施例162 C87 L-131 Co 7.0 7.0 實施例163 C89 L-134 Co 7.5 7.5 實施例164 C91 L-136 Co 7.5 7.2 實施例165 C92 L-137 Co 7.6 7.7 實施例166 C95 L-164 Co 7.4 6.6 實施例167 C96 L-163 Co 7.6 7.4 實施例168 C97 L-165 Co 7.3 7.3 實施例169 C98 L-166 Co 7.3 7.5 實施例170 C99 L-168 Co 7.8 7.4 96 100105051 201137051 [表 3c] 實施例 化合物No. 配位基 (例示化合物） 過渡金屬 Pw (mW) Jitter (%) 實施例171 C101 L-295 Co 6.6 5.7 實施例172 C102 L-296 Co 6.6 5.7 實施例173 C103 L-267 . Co 7.0 6.0 實施例174 C104 L-297 Co 5.9 6.1 實施例175 C105 L-265 Co 6.3 6.1 實施例176 C106 L-298 Co 6.6 6.1 實施例177 C107 L-299 Co 6.4 6.7 實施例178 C108 L-266 Co 6.6 6.8 實施例179 C109 L-265 Ni 6.3 7.1 實施例180 C110 L-300 Co 6.4 7.1 實施例181 cm L-255 Co 7.2 7.1 實施例182 C112 L-253 Co 6.8 7.2 實施例183 C113 L-252 Co 7.0 7.3 實施例184 C114 L-301 Co 7.5 7.4 實施例185 C115 L-302 Co 7.1 7.4 實施例186 C116 L-303 Co 7.0 7.5 實施例187 C121 L-356 Co 6.3 6.8 表中的化合物均係λ max為350nm〜530nm，其中較佳者 係360nm〜500nm範圍，可使用於為達高密度記錄的利用所 欲波長350nm〜530nm雷射光之記錄。 再者，使用各例示化合物的光學記錄媒體之記錄機制，均 屬於Low To High型，最佳記錄功率Rw係在8mW以下。 又，此時的光學記錄媒體之Jitter係8%以下的良好結果。 [化合物合成例] 以下，針對例示化合物中，Cl、C2、及C5的合成方法進 行說明，而關於其他化合物亦施行同樣的合成。 {實施例188} 97 100105051 201137051 &lt;醯肼配位基(L-2)之合成&gt; [化 39]Limit Equalizer mode Performs a Jitter assessment. As a result, the optimum recording power PW was 6,8 mW, and the Jitter value was 7.5%. {Examples 123 to 187} The same test as in Example 122 was carried out except that the compound C1 was changed to the compounds C2 to C121 shown in Tables 3a to 3c. The evaluation results are shown in Tables 3 a to 3 c. 100105051 94 201137051 [Table 3a] Example Compound No. Ligand (exemplified compound) Transition metal Pw (mW) Jitter (%) Example 122 Cl Ll Co 6.8 7.5 Example 123 C2 L-2 Co 6.3 5.9 Example 124 C5 L-5 Co 7.3 6.2 Example 125 C6 L-6 Co 7.3 6.7 Example 126 C7 L-7 Co 6.8 6.3 Example 127 C8 L-9 Co 6.2 6.0 Example 128 CIO L-ll Co 7.0 7.5 Example 129 C12 L-13 Co 7.3 6.7 Example 130 C20 L-22 Co 6.8 6.2 Example 131 G22 L-24 Co 6.9 6.1 Example 132 C24 L-26 Co 7.7 7.0 Example 133 C27 L-29 Co 7.3 6.7 Example 134 C33 L-43 Co 7.3 6.3 Example 135 C34 L-44 Co 7.3 6.4 Example 136 C36 L-46 Co 7.3 6.4 Example 137 C38 L-48 Co 7.3 6.8 Example 138 C39 L-49 Co 7.3 6.7 Example 139 C40 L-50 Co 7.0 6.5 Example 140 C41 L-51 Co 7.3 7.6 Example 141 C42 L-52 Co 7.5 7.4 Example 142 C49 L-61 Co 7.0 6.2 Example 143 C52 L-64 Co 7.0 6.3 Example 144 C53 L-65 Co 7.0 6.2 Example 145 C59 L-72 Co 6.9 6.2 Example 146 C60 L-73 Co 7.6 6.4 95 100105051 201137051 [Table 3b] Example Compound No. Ligand (exemplified compound) Transition metal Pw (mW) Jitter (%) Example 147 C61 L-74 Co 7.3 6.0 Example 148 C62 L-75 Co 7.5 5.8 Example 149 C63 L-76 Co 7.3 6.2 Example 150 C64 L-77 Co 7.0 6.1 Example 151 C67 L-80 Co 7.3 6.4 Example 152 C70 L-83 Co 6.2 6.2 Example 153 C74 L-101 Co 7.5 5.8 Example 154 C75 L-101 Fe 7.5 6.2 Example 155 C76 L-102 Co 7.5 6.2 Example 156 C77 L-107 Co 6.3 6.3 Example 157 C78 L-108 Co 6.8 7.2 Example 158 C80 L-110 Co 7.8 6.8 Example 159 C81 L-111 Co 7.2 7.5 Example 160 C82 L-112 Co 7.5 7.2 Example 161 C85 L-120 Co 7.5 7.6 Example 162 C87 L-131 Co 7.0 7.0 Example 163 C89 L-134 Co 7.5 7.5 Example 164 C91 L-136 Co 7.5 7.2 Example 165 C92 L-137 Co 7.6 7.7 Example 166 C95 L-164 Co 7.4 6.6 Example 167 C96 L-163 Co 7.6 7.4 Example 168 C97 L-165 Co 7.3 7.3 Example 169 C98 L-166 Co 7.3 7.5 Example 170 C99 L-168 Co 7.8 7.4 96 100105051 201137051 [Table 3c] Example Compound No. Ligand (Exemplary Compound) Transition Gold Pw (mW) Jitter (%) Example 171 C101 L-295 Co 6.6 5.7 Example 172 C102 L-296 Co 6.6 5.7 Example 173 C103 L-267 . Co 7.0 6.0 Example 174 C104 L-297 Co 5.9 6.1 Example 175 C105 L-265 Co 6.3 6.1 Example 176 C106 L-298 Co 6.6 6.1 Example 177 C107 L-299 Co 6.4 6.7 Example 178 C108 L-266 Co 6.6 6.8 Example 179 C109 L-265 Ni 6.3 7.1 Example 180 C110 L-300 Co 6.4 7.1 Example 181 cm L-255 Co 7.2 7.1 Example 182 C112 L-253 Co 6.8 7.2 Example 183 C113 L-252 Co 7.0 7.3 Example 184 C114 L-301 Co 7.5 7.4 Example 185 C115 L-302 Co 7.1 7.4 Example 186 C116 L-303 Co 7.0 7.5 Example 187 C121 L-356 Co 6.3 6.8 The compounds in the table are all λ max of 350 nm to 530 nm, of which 360 nm is preferred. The 500 nm range allows for the recording of laser light with a desired wavelength of 350 nm to 530 nm for high density recording. Further, the recording mechanism of the optical recording medium using each of the exemplified compounds belongs to the Low To High type, and the optimum recording power Rw is 8 mW or less. Moreover, the Jitter of the optical recording medium at this time has a good result of 8% or less. [Compound Synthesis Example] Hereinafter, a method for synthesizing Cl, C2, and C5 in an exemplary compound will be described, and the same synthesis will be carried out for other compounds. {Example 188} 97 100105051 201137051 &lt;Synthesis of anthracene ligand (L-2)&gt; [Chem. 39]

Ο 在刚mUS形燒瓶中，將3氮基-n乙基·6經基-4•甲基吼 定_ 1.78g 一曱基甲酿按i、及醋酸針，於⑽^ 進行數小日杨紐拌。似確認反麟點後，過遽 所析出的沉澱’獲得淡綠色針狀結晶。在·㈤燒杯中，於 擾拌所獲得沉殿全量及乙醇8_中，添加水編1及m鹽 酸㈣，過㈣析出的―，獲得淡灰色粉末⑷。構造係利 用1HNMR進行確認。產率約6〇%。 [化 40]Ο In a mUS-shaped flask, 3 nitric acid-nethyl·6 via benzyl-4•methyl hydrazine _ 1.78g 曱 曱 甲 按 i i 、 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及New mix. It seems that after confirming the anti-colon point, the precipitate precipitated by the ’ is obtained as a pale green needle crystal. In the (5) beaker, add the water 1 and m hydrochloric acid (4) and the (4) precipitated to obtain the light gray powder (4) in the total amount of the temple and the ethanol 8_. The structure was confirmed by 1H NMR. The yield is about 6%. [40]

在100ml莊形燒瓶中，使化合物⑷〇 ^、 P(TCI公司製)〇.46g、及曱醇2_進行數小時加熱回流後， 過濾所析出的沉殿，獲得檸檬色粉末(醯肼配位基(L_2))。構 造係利用1HNMR進行確認。產率約90%。 〈例示化合物(C2)之合成〉 100105051 98 201137051 [化 41]In a 100 ml-shaped flask, the compound (4) 〇^, P (manufactured by TCI), 46 g, and decyl alcohol 2, were heated and refluxed for several hours, and then the precipitated precipitate was filtered to obtain a lemon color powder. Bit base (L_2)). The structure was confirmed by 1H NMR. The yield is about 90%. <Synthesis of Exemplary Compound (C2)> 100105051 98 201137051 [Chem. 41]

(L-2)(L-2)

在100ml茄形燒瓶中裝入醯肼配位基(L-2)0.83g及曱醇 30ml，接著添加三乙胺0.34ml、與醋酸鈷四水合物0.3g的 曱醇5ml溶液。經數小時加熱回流後，過濾、所析出的沉殿， 獲得橙色粉末(例示化合物(C2))。產率約50%。 {實施例189} &lt;醯肼配位基(L-1)之合成&gt; [化 42]Into a 100 ml eggplant-shaped flask, 0.83 g of an oxime ligand (L-2) and 30 ml of decyl alcohol were placed, followed by a solution of 0.34 ml of triethylamine and a solution of 0.3 g of decyl alcohol of cobalt acetate tetrahydrate. After heating under reflux for several hours, the precipitated precipitate was filtered to obtain an orange powder (exemplified compound (C2)). The yield is about 50%. {Example 189} &lt;Synthesis of anthracene ligand (L-1)&gt; [Chem. 42]

0 + Br^〇Et \ 在100ml茄形燒瓶中，於溴醋酸乙酯（TCI公司製）334g的 二氯曱烷50ml溶液中，添加N-曱基咪唑（TCI公司 製）1.80g，於室溫下進行1小時攪拌後，過濾所析出的沉澱， 獲得白色光澤結晶（c)。構造係利用1HNMR進行確認。產率 約 90%。 [化 43] 100105051 99 2011370510 + Br^〇Et \ In a 100 ml eggplant-shaped flask, 1.80 g of N-mercaptoimidazole (manufactured by TCI Co., Ltd.) was added to a solution of 334 g of bromoacetic acid ethyl ester (manufactured by TCI) in 50 ml of dichloromethane. After stirring for 1 hour at a temperature, the precipitate precipitated was filtered to obtain a white luster crystal (c). The structure was confirmed by 1H NMR. The yield is about 90%. [化43] 100105051 99 201137051

在100ml莊形燒瓶中’將化合物(c)〇 5g、耕一水合物〇.5g 及甲醇8ml進行8小時加熱回流，過濾所獲得沉澱，獲得白 色光澤結晶（d)。構造係利用1HNMR進行確認。產率約90%。 [化 44]In a 100 ml-shaped flask, 5 g of the compound (c), 5 g of hydrazine monohydrate, and 8 ml of methanol were heated under reflux for 8 hours, and a precipitate obtained by filtration was obtained to obtain a white colored crystal (d). The structure was confirmed by 1H NMR. The yield is about 90%. [化44]

(d) (a) (L~1) 在100ml祐形燒瓶中，將化合物⑷〇 3g、化合物(a)29g及 甲醇50m卜於70°C施行數小時加熱授拌，過濾所獲得沉澱， 獲得黃色粉末（醯肼配位基(L-1))。構造係利用ihnmr進行 確認。產率約60%。 &lt;例示化合物（C1)之合成&gt; [化 45](d) (a) (L~1) In a 100 ml flask, 3 g of the compound (4), 29 g of the compound (a), and 50 m of methanol were heated at 70 ° C for several hours, and the precipitate was obtained by filtration. Yellow powder (醯肼 ligand (L-1)). The structure was confirmed by ihnmr. The yield is about 60%. &lt;Synthesis of exemplified compound (C1)&gt; [Chem. 45]

(C1) 在l〇0ml茄形燒瓶中，攪拌醯肼配位基(L-l)〇.3g及曱醇 20m1，並於其中添加醋酸鈷四水合物O.lg的曱醇5ml溶液。 於70〇C加熱攪拌數小時後，濃縮反應溶液，經冷卻至室溫， 100105051 100 201137051 過濾所析出的橙色沉澱(例示化合物(Cl))。產率約60%。 {實施例190} &lt;醯肼配位基(L-5)之合成&gt; [化 46](C1) In a 10 ml eggplant-shaped flask, a hydrazine ligand (L-1) 〇.3 g and a sterol 20 ml were stirred, and a 5 ml solution of decyl alcohol of cobalt acetate tetrahydrate O.lg was added thereto. After heating and stirring at 70 ° C for several hours, the reaction solution was concentrated, and the precipitated orange precipitate (exemplified compound (Cl)) was filtered by cooling to room temperature, 100105051 100 201137051. The yield is about 60%. {Example 190} &lt;Synthesis of anthracene ligand (L-5)&gt; [Chem. 46]

在300ml茄形燒瓶中，將4-氟苯曱酸乙酯（TCI公司 製）18.5g、咪唑(TCI公司製）11.2g、碳酸鉀29.7g、及二曱亞 砜100m卜於120°C進行2小時加熱攪拌。利用TLC確認反 應終點後，再利用醋酸乙酯進行萃取，並依管柱色層分析進 行精製，獲得白色光澤結晶（e)。構造係利用1HNMR進行確 認。產率約60%。 [化 47]In a 300 ml eggplant-shaped flask, 18.5 g of ethyl 4-fluorobenzoate (manufactured by TCI Co., Ltd.), 11.2 g of imidazole (manufactured by TCI Co., Ltd.), 29.7 g of potassium carbonate, and 100 μm of disulfoxide at 120 ° C were used. Stir and heat for 2 hours. After confirming the reaction end point by TLC, extraction was carried out using ethyl acetate, and purification was carried out by column chromatography to obtain white luster crystals (e). The structure was confirmed by 1H NMR. The yield is about 60%. [化47]

在300ml茄形燒瓶中，將化合物(e)6.15g、三氟曱磺酸曱 酯20.2g及丙酮100m卜於60°C進行4小時加熱攪拌。過濾 所析出的結晶，獲得膚色沉澱(f)。產率約100%。 [化 48] 100105051 101 201137051In a 300 ml eggplant-shaped flask, 6.15 g of the compound (e), 20.2 g of yttrium trifluorosulfonate and 100 ml of acetone were heated and stirred at 60 ° C for 4 hours. The precipitated crystals were filtered to obtain a skin color precipitate (f). The yield is about 100%. [化48] 100105051 101 201137051

Tfo- '0-0- COOEtTfo- '0-0- COOEt

Tfcr CONHNHj (f) (β) 在100ml另5形燒瓶中’將化合物（f) i 79g、肼一水合物 0.5g、及甲醇6ml進行8小時加熱回流，過濾所獲得的沉澱， 獲得白色光澤結晶（g)。產率約90%。 [化 49]Tfcr CONHNHj (f) (β) In a 100 ml other 5-shaped flask, '79 g of compound (f) i, 0.5 g of hydrazine monohydrate, and 6 ml of methanol were heated under reflux for 8 hours, and the obtained precipitate was filtered to obtain white luster crystals. (g). The yield is about 90%. [化49]

TfO ^n-^^-CONHNHj + ho y (β) (a) 在200ml茄形燒瓶中’將化合物(g)〇 6g、化合物⑷〇 38g 及曱醇50ml，於70°C進行數小時加熱攪拌，過濾所獲得的 沉澱，獲得黃色粉末（醯肼配位基(L_5))。產率約6〇%。 &lt;例示化合物（C5)之合成&gt; [化 50]TfO ^n-^^-CONHNHj + ho y (β) (a) In a 200 ml eggplant-shaped flask, '6 g of compound (g), 38 g of compound (4) and 50 ml of decyl alcohol were heated and stirred at 70 ° C for several hours. The precipitate obtained was filtered to obtain a yellow powder (anthracene ligand (L_5)). The yield is about 6%. &lt;Synthesis of exemplified compound (C5)&gt; [Chem. 50]

在1〇_茄形燒瓶中，攪拌醯肼配位基(L-5)0.5g及曱醇 30m卜並在其中添加醋酸飴四水合物〇叫的甲醇㈣溶 液。於70 C進行數小時加熱槐拌後，；農縮反應溶液，並冷 卻至至，過濾所析出的橙色沉澱，獲得例示化合物（C5)。 100105051 102 201137051 產率約60%。 [比較例1] 使用日本專利特開2008-195915所記載的下述化合物 (h)，施行與實施例122同樣的記錄評估’雖信號振幅可觀 測，但卻屬於無法進行Jitter評估程度的低記錄品質。 [化 51]In a 1 〇 eggplant-shaped flask, 0.5 g of a ruthenium ligand (L-5) and 30 m of decyl alcohol were stirred, and a methanol (tetra) solution of yttrium acetate tetrahydrate was added thereto. After heating and kneading at 70 C for several hours, the reaction solution was thawed and cooled, and the precipitated orange precipitate was filtered to obtain the exemplified compound (C5). 100105051 102 201137051 The yield is about 60%. [Comparative Example 1] Using the following compound (h) described in JP-A-2008-195915, the same recording evaluation as in Example 122 was carried out. Although the signal amplitude was observable, it was a low record incapable of performing Jitter evaluation. quality. [化 51]

OMe C〇2+ _ 2 (產業上之可利用性） 本發明的醯肼螯合錯合化合物係當使用為光學記錄媒體 之記錄層形成用色素時，對塗佈溶劑的溶解性及耐光性均優 異，且有用於作為能因應使用藍色雷射光的高速光記錄（特 別係BD-R)之記錄媒體。 另外，2010年2月16日所提出申請的日本專利申請案 2010-031438號之說明書、申請專利範圍、圖式及摘要等全 部内容，均爰引於本案中，並融入為本發明的說明書揭示。 【圖式簡單說明】 100105051 103 201137051 圖1係顯示本發明實施形態的光學記錄媒體之層構成一 例的示意剖視圖。 圖2係顯示本發明實施形態的光學記錄媒體之層構成另 一例的示意剖視圖。 【主要元件符號說明】 20 光學記錄媒體 21 基板 22 反射層 23 記錄層 24 阻障層 25 覆蓋層 26 覆蓋層溝間部 27 覆蓋層溝部 28 記錄再生光光束 29 物鏡 30 記錄再生光光束入射面 31 靠近記錄再生光光束入射面之一側的導溝部 32 遠離記錄再生光光束入射面之一側的導溝部 100 光學記錄媒體 101 基板 102 反射層 103 記錄層 100105051 104 201137051 104 107 108 111 112 113 114 115 121 122 阻障層 記錄再生光光束 物鏡 中間層 半透明反射層 記錄層 阻障層 覆蓋層 L1層 L0層 100105051 105OMe C 〇 2+ _ 2 (Industrial Applicability) The ruthenium chelating compound of the present invention is a solubility in a coating solvent and light resistance when a dye for recording layer formation on an optical recording medium is used. Both are excellent, and are used as a recording medium capable of high-speed optical recording (especially BD-R) capable of using blue laser light. In addition, the contents of the specification, the scope of the application, the drawings and the abstract of the Japanese Patent Application No. 2010-031438, filed on Feb. 16, 2010, are hereby incorporated by reference in . [Brief Description of the Drawings] 100105051 103 201137051 Fig. 1 is a schematic cross-sectional view showing an example of a layer configuration of an optical recording medium according to an embodiment of the present invention. Fig. 2 is a schematic cross-sectional view showing another example of a layer configuration of an optical recording medium according to an embodiment of the present invention. [Description of main component symbols] 20 Optical recording medium 21 Substrate 22 Reflecting layer 23 Recording layer 24 Barrier layer 25 Covering layer 26 Covering layer groove portion 27 Covering layer groove portion 28 Recording and reproducing light beam 29 Objective lens 30 Recording and reproducing light beam incident surface 31 The guide groove portion 32 near one side of the incident surface of the recording and reproducing light beam is away from the guide groove portion 100 on the side of the incident surface of the recording and reproducing light beam. Optical recording medium 101 Substrate 102 Reflecting layer 103 Recording layer 100105051 104 201137051 104 107 108 111 112 113 114 115 121 122 barrier layer recording and reproducing light beam objective lens intermediate layer semi-transparent reflective layer recording layer barrier layer coating layer L1 layer L0 layer 100105051 105

Claims (1)

201137051 七、申請專利範圍： 1.一種醯肼螯合錯合化合物，係由下述一般式(1)所示 [化1] Mb+ (X')m [一般式(I)中， 環A係至少具有1個以上N原子的單一五員環或六員環 雜環、或由五員環及/或六員環構成的2或3環式縮合雜環； 環A係可為芳香環、亦可為非芳香環，當為芳香環的情況， 環内的1個以上1^原子形成四級化的鏽鹽，當為非芳香環 的情況，環内的1個以上N原子形成四級化的銨鹽； 環A係由作為必要原子的N、以及C、N、〇及s中之任 者以上的原子形成；構成環A的C及N係可為無取代、 亦可具有以下的取代基； C的隋况，可具有選自下述中之任一者作為取代基： 可經1個以上氟原子取代的直鏈或分支的碳數1至4之烷 基’具有直鏈或分支的碳數1至4之烷基的烷氧基；無取代、 或具有1或2個直鏈或分支的碳數1至4之烷基的醯胺基； 具有直鏈或分支的碳數1至4之烷基的烷氧羰基；氰基；苯 基；及苄基； N的情況*’可具有直鏈或分支的碳數1至4之烷基作為取 100105051 106 201137051 代基； L係表示將環A與C*連結的2價連接基L’或直接鍵結； 該2價連接基L’係可具有直鏈或分支的碳數1至4之烷基 的亞曱基、伸乙基、伸苯基、伸苯亞甲基、或伸呋喃基 (furanylene group)； . Ri係表示氫原子、或直鏈或分支的碳數1至4之烧基； Z係表示羥基或可烯醇化的羰基；從Z的羥基、Z的羰基 經烯醇化而生成的羥基、一般式(I)的醯肼部位之羰基經烯醇 化而生成的羥基、以及醯肼部位的NH基中之任一者以上部 位，脫離活性氫而形成錯合物； 環B係表示由下式(B-a)或(B-b)所示，除Z之外尚可具有 取代基的五員環或六員環芳香環或雜環；201137051 VII. Patent application scope: 1. A ruthenium chelate compound which is represented by the following general formula (1): Mb+ (X') m [General formula (I), ring A system a single five-membered or six-membered ring heterocyclic ring having at least one N atom, or a two- or three-membered fused heterocyclic ring composed of a five-membered ring and/or a six-membered ring; the ring A-system may be an aromatic ring, It may also be a non-aromatic ring. In the case of an aromatic ring, one or more 1^ atoms in the ring form a quaternary rust salt. In the case of a non-aromatic ring, one or more N atoms in the ring form a four-stage. The ammonium salt is formed of N as a necessary atom and an atom of any of C, N, 〇 and s; the C and N groups constituting the ring A may be unsubstituted or may have the following a substituent; a C condition, which may have any one selected from the group consisting of: a linear or branched alkyl group having 1 to 4 carbon atoms which may be substituted by one or more fluorine atoms has a straight chain or Alkoxy group of a branched alkyl group having 1 to 4 carbon atoms; unsubstituted, or having 1 or 2 linear or branched alkyl groups having 1 to 4 carbon atoms; having a carbon number of a straight chain or a branch 1 Alkoxycarbonyl group to alkyl group of 4; cyano group; phenyl group; and benzyl group; case of N *' may have a linear or branched alkyl group having 1 to 4 carbon atoms as a group of 100105051 106 201137051; a divalent linking group L' or a direct bond linking ring A and C*; the divalent linking group L' may have a linear or branched alkyl group having 1 to 4 carbon atoms, and a phenyl group, a phenylene group, a benzylidene group, or a furanylene group; Ri is a hydrogen atom, or a linear or branched carbon number of 1 to 4; Z is a hydroxyl group or a olefin. An alcoholized carbonyl group; a hydroxyl group formed by enolification of a hydroxyl group of Z, a carbonyl group of Z, a hydroxyl group formed by enolization of a carbonyl group of a general formula (I), and an NH group of an anthracene moiety; The above part is separated from the active hydrogen to form a complex; Ring B represents a five-membered or six-membered aromatic ring which may have a substituent other than Z, as shown by the following formula (Ba) or (Bb) Heterocycle Z (B-b)Z (B-b) (上式中，原子Bi係表示C、S、或N ; 當I為C的情況，可為無取代、亦可具有選自可經1個 以上氟原子所取代之直鏈或分支的碳數1至4之烷基、及經 基中之任一者作為取代基；亦可構成由C與0利用雙鍵連 結的羰基； 當I為S的情況，可為無取代、亦可構成由S與0利用 100105051 107 201137051 雙鍵連結的亞礙基、或硬基； 亦可具有可經1個以上 1至4之烷基作為取代 當仏為N的情況，可為無取代、 氟原子所取代之直鏈或分支的碳數 基； 原子&amp;〜B4係分別獨立表示匚、n、咬〇 當B2〜㈣的情況，可為無取代、亦0可且有選自： 可經i似上，子所取代之麵或 之烧基；經基；具有直鏈或分支的碳數15 基；具有！或2個直鍵或分支的碳之烧基的燒氣 可含有1個氧原子之三員環至七 4之烧基的胺基； 取代、或具有丨或2個直鏈或分支^脂肪族環狀胺基；無 胺基；具有直鍵或分支的碳至4之炫基的醜 J反数1至4之燒 有直鍵或分支的碳數1至4之燒基的料基；苯基；及土氛基、 之任一者作為取代基；亦可構 &quot; 基 、由…利用雙鍵連結的硫代幾基、或者由= =鏈或分支的碳數i至4之燒基所取代的N利用雙鍵連 、、、。的亞胺基’·亦可形成可經直鏈或分支的碳數丨至*之貌茂 所取代的三員環至七員環的環烧 '福燒(b_ne · 的螺環； $ 當^4為N的情況’可為無取代、亦可具有直鍵或分 支的反數1至4之烧基、具有直鏈或分支的碳數i至4 基的烷氧基、或苯基作為取代基； 疋 100105051 108 201137051 …B1〜B4中相鄰接的2個原子之取代基亦可相互鍵結， 形成縮合於環B的五員環或六員環；此情況，縮合於環B 的環係由上式(B-a)或(B-b)所示） a係表示配位基數，且為1或2 ; M係表示Co、Ni、或Fe ; b係表示Μ的價數，且為2或3 ; X係表示醋酸根離子、氯化物離子、溴化物離子、峨化物 離子、過氯酸根離子、四氟硼酸根離子、四苯基硼酸根離子、 六氟磷酸根離子、曱笨磺酸根離子、三氟甲磺酸根離子、或 雙(三氟曱磺醯基)醯亞胺離子； m係將錯合物的正電荷予以中和所必要的數目，當m為2 以上時，m個X-係可為相同、亦可為不同]。 2.—種醯肼螯合錯合化合物，係由下述一般式(II)所示： [化3](In the above formula, the atom Bi represents C, S, or N; and when I is C, it may be unsubstituted or may have a carbon number selected from a straight chain or a branch which may be substituted by one or more fluorine atoms. Any one of a 1 to 4 alkyl group and a trans group as a substituent; or a carbonyl group in which C and 0 are bonded by a double bond; and when I is S, it may be unsubstituted or may be composed of S. And a substrate or a hard group which is bonded to a double bond by using 100105051 107 201137051; or may have a substituent which may be substituted by one or more alkyl groups of 1 to 4, and may be an unsubstituted, fluorine atom. The linear or branched carbon number base; the atomic &amp; ~B4 series respectively represent 匚, n, bite when B2~(4), may be unsubstituted, also 0 and may be selected from: a substituting surface or a calcining group; a transbasic group; a carbon number having a straight chain or a branched chain of 15 groups; a burning gas having a carbon atom of ? or 2 straight bonds or branches may contain 3 oxygen atoms An amine group having a ring of 7 to 4; a substituted or fluorene or 2 linear or branched aliphatic amine group; an amine group; having a direct bond The ruthenium of the branched carbon to 4 singular group 1 to 4 is burned with a straight bond or a branched carbon number of 1 to 4; the phenyl group; and the earthy base, either as a substitute a thiol group linked by a double bond or a sulfonyl group substituted with a carbon number i to 4 of a == chain or a branch, which is substituted by a double bond, The imine group can also form a ring-ring of the three-membered ring to the seven-membered ring which can be replaced by a linear or branched carbon number of 碳 to *, (b_ne · a spiro ring; $ when ^4 The case of N' may be unsubstituted, may have a direct bond or a branch of an inverse number of 1 to 4, a straight or branched carbon number i to 4 group alkoxy group, or a phenyl group as a substituent.疋100105051 108 201137051 ...Substituents of two atoms adjacent to each other in B1 to B4 may also be bonded to each other to form a five-membered or six-membered ring condensed to ring B; in this case, a ring system condensed to ring B From the above formula (Ba) or (Bb)) a represents the number of coordination groups and is 1 or 2; M represents Co, Ni, or Fe; b represents the valence of ruthenium and is 2 or 3; X series means acetate ion, chlorination Ion, bromide ion, telluride ion, perchlorate ion, tetrafluoroborate ion, tetraphenylborate ion, hexafluorophosphate ion, sulfonate ion, triflate ion, or double Trifluorosulfonyl) ruthenium ion; m is the number necessary to neutralize the positive charge of the complex. When m is 2 or more, m X-systems may be the same or different. 2. The chelating chelate compound is represented by the following general formula (II): [Chemical 3] • 〇 η Ri2~*N-L~C*N-N R13 [一般式(II)中， Rii〜R43係分別獨立表示可經1個以上氟原子所取代之直 鏈或分支的碳數1至4之烷基、或可經直鏈或分支的碳數！ 至4之烷基(其係可經1個以上氟原子取代)所取代的苯基； L係表不將與C*連結的2價連接基L’戍直接 100105051 109 201137051 鍵結；該2價連接基L’係可具有直鏈或分支的碳數1至4 之烷基的亞甲基、伸乙基、伸苯基、伸苯亞甲基、或伸呋喃 基； 心係表示氫原子、或直鏈或分支的碳數1至4之烷基； Z係表示羥基或可烯醇化的羰基；從Z的羥基、Z的羰基 經烯醇化而生成的羥基、一般式(I)的醯肼部位之羰基經烯醇 化而生成的羥基、以及醯肼部位的NH基中之任一者以上部 位，脫離活性氫而形成錯合物； 環B係表示由下式(B-a)或(B-b)所示，除Z之外尚可具有 取代基的五員環或六員環芳香環或雜環； [化4]• 〇η Ri2~*NL~C*NN R13 [In general formula (II), Rii~R43 each independently represent a linear or branched alkyl group having 1 to 4 carbon atoms which may be substituted by one or more fluorine atoms. , or the number of carbons that can be linear or branched! a phenyl group substituted with 4 alkyl groups (which may be substituted by one or more fluorine atoms); the L system indicates that the divalent linking group L' 与 linked to C* is directly bonded to 100105051 109 201137051; The linking group L' may have a straight or branched methylene group having an alkyl group having 1 to 4 carbon atoms, an extended ethyl group, a phenylene group, a benzylidene group, or a furyl group; the heart system represents a hydrogen atom, Or a straight or branched alkyl group having 1 to 4 carbon atoms; Z series means a hydroxyl group or an enolizable carbonyl group; a hydroxyl group formed from the hydroxyl group of Z, the carbonyl group of Z by enolization, and the general formula (I) Any one or more of the hydroxyl group formed by the enolization of the carbonyl group and the NH group of the oxime moiety are decomposed from the active hydrogen to form a complex; the ring B system is represented by the following formula (Ba) or (Bb) a five-membered or six-membered aromatic ring or heterocyclic ring which may have a substituent other than Z; [Chemical 4] VE9 — HJ — \B — b) (上式中，原子Bi係表示C、S、或N ; 當^為C的情況，可為無取代、亦可具有選自可經1個 以上氟原子所取代之直鏈或分支的碳數1至4之烷基、及羥 基中之任一者作為取代基；亦可構成由C與Ο利用雙鍵連 結的羰基； 當Β!為S的情況，可為無取代、亦可構成由S與Ο利用 雙鍵連結的亞砜基、或砜基； B!為N的情況，可為無取代、亦可具有可經1個以上氟 100105051 110 201137051 原子所取代之直鏈或分支的碳數1至4之烷基作為取代基， 原子b2〜b4係分別獨立表示C、N、或〇; 當B2〜B4為C的情況，可為無取代、亦可具有選自： 可經1個以上氟原子所取代之直鏈或分支的碳數1至4 . 之烷基；羥基；具有直鏈或分支的碳數1至4之烧基的烧氧 ， 基；具有1或2個直鏈或分支的碳數1至4之烧基的胺基； 可含有1個氧原子之三員環至七員環的脂肪族環狀胺基；無 取代、或具有1或2個直鏈或分支的碳數1至4之烧基的醯 胺基；具有直鏈或分支的碳數1至4之烷基的烷氧羰基；具 有直鏈或分支的碳數1至4之烷基的烷幾基；苯基；及氰基 之任一者作為取代基；亦可構成由C與〇利用雙鍵連結的 羰基、由C與S利用雙鍵連結的硫代羰基、或者由C與可 經直鏈或分支的碳數1至4之烷基所取代的N利用雙鍵連 結的亞胺基；亦可形成可經直鏈或分支的碳數1至4之烷基 所取代的三員環至七員環的環烷、稻烷、或金剛烷的螺 環； ' 當B2〜B4為N的情況，可為無取代、亦可具有直鏈或分 • 支的碳數1至4之烷基、具有直鏈或分支的碳數1至4之烷 基的烷氧基、或苯基作為取代基； 又，中相鄰接的2個原子之取代基亦可相互鍵結， 形成縮合於環B的五員環或六員環；此情況，縮合於環b 的環係由上式(B-a)或(B-b)所示） 100105051 111 201137051 a係表示配位基數，且為1或2 ; Μ係表示Co、Ni、或Fe ; b係表示Μ的價數，且為2或3 ; X—係表示醋酸根離子、氣化物離子、溴化物離子、碘化物 離子、過氯酸根離子、四氟硼酸根離子、四苯基硼酸根離子、 六氟磷酸根離子、曱苯磺酸根離子、三氟甲磺酸根離子、或 雙(三氟曱磺醯基）醯亞胺離子； m係將錯合物的正電荷予以中和所必要的數目，當m為2 以上時，m個X·係可為相同、亦可為不同]。 3. 如申請專利範圍第1或2項之醯肼螯合錯合化合物，其 中，環B係具有選自可具有取代基之吡啶酮衍生物、嘧啶 衍生物、°比°坐咬衍生物、苯并°塞讲衍生物、及丙二酸環亞異 丙酉旨(Meldrum’sacid)衍生物之環構造。 4. 如申請專利範圍第1項之醯肼螯合錯合化合物，其中， 環A係具有選自可具有取代基之吼啶環、咪唑環、苯并咪 β坐環、喧琳環、異喧琳環、B比略11定環、π底11定環、旅讲環、咮 琳環、1,2,3,4-四氫喹琳環、1，2,3,4-四氫異喹琳環、吲哚琳 環、及吡唑環之環構造； 環Β係具有選自可具有取代基之吡啶酮衍生物、嘧啶衍 生物、吡唑啶衍生物、苯并噻讲衍生物、及丙二酸環亞異丙 酯衍生物中之任一者之環構造。 5. —種光學記錄媒體之記錄層形成用色素，係含有申請專 100105051 112 201137051 利範圍第1至4項中任一項之醯肼螯合錯合化合物。 6. —種光學記錄媒體，係至少具有基板、與在該基板上形 成的記錄層；該記錄層係使用申請專利範圍第5項之光學記 錄媒體之記錄層形成用色素形成。 7. —種光學記錄媒體之記錄方法，係對申請專利範圍第6 項之光學記錄媒體，使用波長350〜530nm的雷射光執行記 錄。 8. 如申請專利範圍第7項之光學記錄媒體之記錄方法，其 中，在執行記錄的雷射光之波長中，記錄部的反射率係較高 於記錄前及未記錄部的反射率。 100105051 113VE9 — HJ — \B — b) (In the above formula, the atom Bi represents C, S, or N; when ^ is C, it may be unsubstituted or may be selected from one or more fluorine atoms. Any one of a substituted linear or branched alkyl group having 1 to 4 carbon atoms and a hydroxyl group as a substituent; or a carbonyl group in which C and oxime are bonded by a double bond; and when Β! is S, It may be unsubstituted or may constitute a sulfoxide group or a sulfone group which is bonded by a double bond between S and oxime; and when B! is N, it may be unsubstituted or may have one or more fluorines 100105051 110 201137051 atom a substituted straight or branched alkyl group having 1 to 4 carbon atoms as a substituent, and the atoms b2 to b4 each independently represent C, N, or fluorene; and when B2 to B4 are C, it may be unsubstituted or may be And having an alkyl group having a carbon number of 1 to 4 which may be substituted by one or more fluorine atoms; a hydroxyl group; a burning oxygen having a linear or branched carbon number of 1 to 4; An amine group having 1 or 2 linear or branched carbon groups of 1 to 4; an aliphatic cyclic amine group which may contain a three-membered ring of one oxygen atom to a seven-membered ring; Or an alkoxy group having 1 or 2 linear or branched carbon groups having 1 to 4 carbon atoms; an alkoxycarbonyl group having a linear or branched alkyl group having 1 to 4 carbon atoms; having a straight chain or a branch Any one of alkoxy groups having an alkyl group having 1 to 4 carbon atoms; a phenyl group; and a cyano group as a substituent; or a carbonyl group in which C is bonded to a ruthenium by a double bond, and C and S are linked by a double bond. a thiocarbonyl group, or an imido group in which N is substituted with a linear or branched alkyl group having 1 to 4 carbon atoms by a double bond; or a linear or branched carbon number can be formed. a three-membered ring substituted with an alkyl group of 4 to a cyclohexane of a seven-membered ring, a cyclohexane, or an adamantane; 'when B2 to B4 are N, it may be unsubstituted or may have a straight chain or a branched alkyl group having 1 to 4 carbon atoms, an alkoxy group having a linear or branched alkyl group having 1 to 4 carbon atoms, or a phenyl group as a substituent; further, 2 atoms adjacent to each other The substituents may also be bonded to each other to form a five-membered or six-membered ring condensed to the ring B; in this case, the ring system condensed to the ring b is represented by the above formula (Ba) or (Bb)) 100105051 111 201137051 a Express The number of bases is 1 or 2; the lanthanide indicates Co, Ni, or Fe; the b system indicates the valence of ruthenium and is 2 or 3; X- indicates the acetate ion, vaporization ion, bromide ion, and iodine Compound ion, perchlorate ion, tetrafluoroborate ion, tetraphenylborate ion, hexafluorophosphate ion, sulfonate ion, triflate ion, or bis(trifluoromethanesulfonyl)醯imine ion; m is the number necessary to neutralize the positive charge of the complex. When m is 2 or more, m X·systems may be the same or different. 3. The chelate-chelating compound according to claim 1 or 2, wherein the ring B has a pyridone derivative, a pyrimidine derivative, a chitin derivative, which may have a substituent, A benzopyrene derivative and a ring structure of a Meldrum's acid derivative of malonate. 4. The chelate-chelating compound according to the first aspect of the patent application, wherein the ring A has an acridine ring, an imidazole ring, a benzopyrene ring, a ruthenium ring, and a different one selected from the group which may have a substituent.喧琳环, B比略11定环, π底11定环,旅讲环,咮琳环, 1,2,3,4-tetrahydroquinoline, 1,2,3,4-tetrahydroiso a ring structure of a quinoline ring, a ruthenium ring, and a pyrazole ring; the ring oxime has a pyridone derivative, a pyrimidine derivative, a pyrazole pyridine derivative, a benzothiazepine derivative, which may have a substituent, And a ring structure of any of the isopropylidene malonate derivatives. A dye for forming a recording layer for an optical recording medium, which comprises the ruthenium chelate compound according to any one of items 1 to 4 of the specification 100105051 112 201137051. An optical recording medium comprising at least a substrate and a recording layer formed on the substrate; and the recording layer is formed using a recording layer forming dye of the optical recording medium of claim 5 of the patent application. 7. A method of recording an optical recording medium, wherein the optical recording medium of claim 6 is recorded using laser light having a wavelength of 350 to 530 nm. 8. The recording method of an optical recording medium according to claim 7, wherein the reflectance of the recording portion is higher than the reflectance of the recording portion and the unrecorded portion in the wavelength of the laser light to be recorded. 100105051 113
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