TW584850B - Method for recording optical data and optical data-recording medium - Google Patents

Abstract

The invention provides a method for recording optical data being able to carry out the recordation and reproduction in high density by using a laser light having a short wave of length less than 450 nm, and provides an optical data-recoding medium having an excellent recording property and stability of recording data being able to preserve in long term under high temperature and high humidity as well as being able to be utilized in aforesaid optical data recording method. The method for recording optical data according to the invention comprises carrying out an optical recordation of recording an optical data on an optical recording medium by exposing under laser light having a short wave of length less than 450 nm, which is characterized in that the recording layer of aforesaid optical data-recording medium comprises a phthalocyanine derivate. Additionally, the invention further comprises an optical data-recording medium which is characterized in that it utilizes aforesaid method for recording optical data.

Description

584850584850

五、發明說明（1 ) [發明的技術領域] 本發明和使用雷射光實施資訊之記錄及再生的光資訊記 錄方法、及該光資訊記錄方法使用之光資訊記錄媒體相關 〇 [先前技藝] 大家都知道可以利用雷射光實施一次資訊記錄的光資訊 記錄媒體（光碟）。此光碟又稱爲再記錄型CD(所謂CD-R) ，其代表性構造爲在透明圓盤狀基板上依照有機色素構成 之記錄層、金等金屬構成之光反射層、以及樹脂製保護層 之順序層疊而成之構造。利用對CD-R照射近紅外線之雷 射光（通常爲780nm附之之波長的雷射光）來實施對此CD-R之資訊記錄，記錄層之照射部分會吸收該光而使局部之 溫度上昇，產生物理或化學變化（例如，凹陷之產生），以 改變光學特性來記錄資訊。另一方面，資訊之讀取（再生） 也是照射具有和記錄用雷射光相同波長之雷射光，利用檢 測出記錄層之光學特性已改變部分（記錄部分）及未改變部 分（未記錄部分）間的反射率差異，來再生資訊。 近年來，要求具有更高記錄密度之光資訊記錄媒體。爲 了滿足此要求，而提出再記錄型數位多功能光碟（所謂 DVD-R)之光碟（例如，「日經NEWS MEDIA」別冊「DVD 」、1 995年發行）。此DVD-R之構造上，係在以追縱照射 之雷射光爲目的之導引槽（預溝紋）只有CD-R —半以下V. Description of the Invention (1) [Technical Field of the Invention] The present invention relates to an optical information recording method for recording and reproducing information using laser light, and an optical information recording medium used by the optical information recording method. [Previous technology] Everyone It is known that an optical information recording medium (disc) can be used to perform information recording once with laser light. This optical disc is also called a re-recordable CD (the so-called CD-R), and its typical structure is a recording layer made of an organic pigment on a transparent disc-shaped substrate, a light reflecting layer made of metal such as gold, and a protective layer made of resin. The structure is stacked in order. CD-R is irradiated with near-infrared laser light (usually laser light with a wavelength of 780nm) to perform information recording on this CD-R. The irradiated part of the recording layer will absorb the light and increase the local temperature. Generate physical or chemical changes (for example, the creation of depressions) to change optical characteristics to record information. On the other hand, the reading (reproducing) of information also irradiates laser light having the same wavelength as the laser light for recording, and detects when the optical characteristic of the recording layer has changed (recorded portion) and the unchanged portion (unrecorded portion). Difference in reflectivity to reproduce information. In recent years, an optical information recording medium having a higher recording density has been required. In order to meet this requirement, a re-recording type digital versatile disc (so-called DVD-R) is proposed (for example, "Nikkei NEWS MEDIA" separate volume "DVD", issued in 995). The structure of this DVD-R is that the guide groove (pre-groove) for the purpose of tracking laser light is only CD-R—less than half

584850 五、發明說明（2) (0.74〜0.8//m)的透明圓盤狀基板上，形成由色素構成之 記錄層；通常在該記錄層上會設有光反射層，以及必要時 會設置保護層，然後，將具有前述構造之2片碟片、或將 和該碟片相同形狀之圓盤狀保護基板，以黏結劑貼附於該 記錄層之內側。而DVD-R之資訊的記錄、再生，則是照 射可見雷射光（通常爲630nm〜680nm之波長範圍的雷射光） ，即可實現比CD-R具有更高密度的記錄。 最近，網際網路等之網路及高視覺電視急速普及。又， HDTV(高解析度電視）之播放行程亦十分緊湊，故對記錄 媒體更進一步要求能更便宜、更簡便、及大容量之影像資 訊記錄。以DVD-R而言，雖然已大致確保其某種程度之 大容量記錄媒體的地位，然而，卻無法斷言其已具有可充 份對應將來要求之大記錄容量。因此，不斷開發利用比 DVD_R更短之波長的雷射光來提升記錄密度並具有更大記 錄容量的光碟。例如，日本特開平4-74690號公報、日本 特開平7-304256號公報、日本特開平7-3〇4257號公報、 曰本特開平8-127174號公報、日本特開平11-53758號公 報、日本特開平U—334204號公報、日本特開平n_ 3342〇5號公報、日本特開平u_3342〇6號公報、日本特開 平11-334207號公報、日本特開2〇〇〇_43423號公報、日本 特開2000-1 085 1 3號公報、日本特開2〇〇卜1135〇4號公報 、曰本特開2000- 1 49320號公報、日本特開2〇〇〇- 1 588 1 8 號公報、日本特開2000-228028號公報中，就針對具有含 -4- 584850 五、發明說明（3) 有機色素之記錄層的光資訊記錄媒體，提出從記錄層側朝 光反射層側照射波長530nm以下之雷射光，執行資訊之記 錄及再生的記錄再生方法。具體而言，就是對使用波如菲 啉化合物、偶氮系色素、金屬偶氮系色素、蝰酞酮系色素 、三甲基酞青色素、二氰基乙烯基苯構造色素、香豆基化 合物、及萘酞菁化合物等當做記錄層之色素的光碟，照射 藍光（波長430nm、488nm)或藍綠色（波長515nm)的雷射光 ，執行資訊之記錄及再生的資訊記錄再生方法。 又，從和目前之CD-R系統的互換性觀點，故提出可以 2種不同波長區域之雷射光實施記錄及再生的光記錄媒體 。例如，日本特開2000- 1 41 900號公報、日本特開2000-1 5 8 8 1 6號公報、日本特開2000-1 8 547 1號公報、日本特開 2000-289342號公報、日本特開2000-309 1 65號公報中， 則是混合使用CD-R使用之色素及DVD-R使用之色素，而 爲可以任一種雷射光都可實施記錄及讀取之記錄媒體。 然而，依據本發明者進行之檢討，前述公報記載之光碟 ，以波長450tim以下之短波長雷射光照射執行資訊記錄時 ，其反射率及調變度等記錄特性並無法達到可以達到滿足 之水準，另外，其儲存安定性方面亦非十分充分，故有改 良之必要。尤其是’則述公報記載之光碟中，照射波長 405nm附近之雷射光時，其記錄特性亦會降低。 [發明所欲解決之問題] 本發明就是爲了解決前述傳統技術之問題點，本發明之 584850 五、發明說明（4) 第1課題，就是可以利用波長45 0nm以下之短波長雷射光 一亦即，高泛用性之波長405nm附近之半導體雷射光的照 射，實施資料之高密度記錄及再生，而且，提供具有優良 記錄特性之光資訊記錄方法及光資訊記錄媒體。 本發明之第2課題，就是利用針對高溫及高濕度設計安 定記錄層，提供可長期儲存記錄資訊之光資訊記錄方法及 光資訊記錄媒體。 本發明之第3課題，就是提供可以波長45 Onm以下之短 波長雷射光及傳統CD-R使用之波長750〜850nm雷射光 二者皆可執行記錄及再生，具有優良泛用性之光資訊記錄 方法及光資訊記錄媒體。 [解決問題之機構] 本發明利用下列方式達成前述目的。 亦即，本發明爲利用波長45Onm以下之雷射光照射將資 訊記錄於光資訊記錄媒體的光資訊記錄方法，且爲具有前 述光資訊記錄媒體之記錄層含有酞菁衍生物之特徵的光資 訊記錄方法。 又，本發明之特徵爲使用於前述光資訊記錄方法之光資 訊記錄媒體。 [發明之實施形態] <光資訊記錄方法> 本發明之光資訊記錄方法’以恒定線性速度（CD格式時 爲1.2〜1.4m/秒）或常數角速率旋轉，並從基板側或保護 584850 五、發明說明（5) 層側照射半導體雷射光等之記錄用光。因爲此光之照射， 記錄層之局部的溫度會因吸收該光而上昇，產生物理或化 學變化（例如，產生坑等），利用改變其光學特性來記錄資 訊。在本發明中，採用具有390〜450nm範圍之振盪波長 的半導體雷射光。較佳之光源爲具有中心振盪波長390〜 4 15nm範圍之振盪波長的藍紫色半導體雷射光、以及以導 光體元件使中心振盪波長850nm之紅外半導體雷射光成爲 一半波長之中心振盪波長405〜425nm的藍紫色SHG雷射 光。而以記錄密度之觀點，尤以藍紫色半導體雷射光爲佳 。以如前面所述之方式記錄的資訊之再生，以和前述相同 之恒定線性速度進行旋轉，同時從基板側或保護層側照射 半導體雷射光，然後檢測該反射光。 <光資訊記錄媒體> 本發明之光資訊記錄媒體係前述光資訊記錄方法使用之 光資訊記錄媒體，該光資訊記錄媒體之記錄層含有酞菁衍 生物。 該酞菁衍生物具有700nm附近之主吸收帶及340η附近 之副吸收帶。利用此酞菁衍生物做爲記錄層乏記錄材料， 可得到對波長450nm以下之短波長雷射光亦可提供高反射 率及高調變度之良好記錄再生特性的光資訊記錄媒體。 此外，此光資訊記錄媒體同時對波長7 5 0〜8 5 0 nm之雷 射光亦具有高反射率及高調變度的良好記錄再生特性。 又，該酞菁衍生物因爲具有特定之取代基，形成熱力學584850 V. Description of the invention (2) (0.74 ~ 0.8 // m) on the transparent disc-shaped substrate, a recording layer composed of pigments is formed; usually a light reflection layer will be provided on the recording layer, and if necessary, it will be provided. The protective layer is then attached to the inside of the recording layer with an adhesive using two discs having the aforementioned structure or a disk-shaped protective substrate having the same shape as the disc. The DVD-R records and reproduces information by irradiating visible laser light (usually in the wavelength range of 630nm to 680nm) to achieve higher density recording than CD-R. Recently, networks such as the Internet and high-vision television have spread rapidly. In addition, the playback schedule of HDTV (high-resolution television) is also very compact, so the recording medium is further required to be cheaper, simpler, and large-capacity video information records. In the case of DVD-R, although it has generally secured its status as a large-capacity recording medium, it cannot be said that it already has a large recording capacity that can adequately meet future requirements. Therefore, optical discs with a shorter wavelength than DVD_R are used to increase the recording density and have a larger recording capacity. For example, Japanese Unexamined Patent Publication No. 4-74690, Japanese Unexamined Patent Publication No. 7-304256, Japanese Unexamined Patent Publication No. 7-30404257, Japanese Unexamined Patent Publication No. 8-127174, Japanese Unexamined Patent Publication No. 11-53758, Japanese Patent Laid-Open No. U-334204, Japanese Patent Laid-Open No. 3342405, Japanese Patent Laid-Open No. u_3342〇6, Japanese Patent Laid-Open No. 11-334207, Japanese Patent Laid-Open No. 2000-43423, Japan Japanese Patent Laying-Open No. 2000-1 085 1 3, Japanese Patent Laying-Open No. 2000-1351 04, Japanese Patent Laying-Open No. 2000-1 49320, Japanese Patent Laying-Open No. 2000- 1 588 1 8, Japanese Patent Laid-Open No. 2000-228028 proposes to irradiate a light-emitting layer with a wavelength of 530 nm or less from the recording layer side toward the light reflection layer side for an optical information recording medium having a recording layer containing -4- 584850 5. Invention Description (3) Organic pigment The laser beam performs recording and reproduction methods of recording and reproducing information. Specifically, the use of wave-like compounds such as phenanthroline compounds, azo-based pigments, metal azo-based pigments, phthalophthalone-based pigments, trimethylphthalocyanine pigments, dicyanovinylbenzene structural pigments, and coumarin-based compounds An optical disc, such as a naphthalocyanine compound, and a pigment used as a recording layer, irradiates blue light (wavelength 430nm, 488nm) or blue-green (wavelength 515nm) laser light to perform information recording and reproduction information recording and reproduction methods. Furthermore, from the viewpoint of interchangeability with the current CD-R system, an optical recording medium capable of recording and reproducing laser light in two different wavelength regions has been proposed. For example, Japanese Patent Laid-Open No. 2000-1 41 900, Japanese Patent Laid-Open No. 2000-1 5 8 8 16, Japanese Patent Laid-Open No. 2000-1 8 547 1, Japanese Patent Laid-Open No. 2000-289342, and Japanese Patent No. In Japanese Laid-Open Publication No. 2000-309 1 65, a pigment used in a CD-R and a pigment used in a DVD-R are mixed, and a recording medium that can perform recording and reading with any kind of laser light is used. However, according to the review conducted by the present inventors, when the optical discs described in the aforementioned bulletin were irradiated with short-wavelength laser light having a wavelength of 450 tim or less to perform information recording, the recording characteristics such as reflectance and modulation degree could not reach a satisfactory level. In addition, its storage stability is not very sufficient, so it is necessary to improve. In particular, in the optical disc described in the "Gazette", when laser light having a wavelength of around 405 nm is irradiated, its recording characteristics are also deteriorated. [Problems to be Solved by the Invention] The present invention is to solve the problems of the aforementioned conventional technology. 584850 of the present invention V. Description of the invention (4) The first problem is to use short-wavelength laser light with a wavelength of 4500 nm or less. High-use semiconductor laser light with a wavelength of around 405nm is used for high-density recording and reproduction of data. Furthermore, it provides optical information recording methods and optical information recording media with excellent recording characteristics. The second subject of the present invention is to provide a light information recording method and an optical information recording medium capable of storing recorded information for a long time by designing a stable recording layer for high temperature and high humidity. The third subject of the present invention is to provide both short-wavelength laser light with a wavelength below 45 Onm and laser light with a wavelength of 750 to 850nm used by conventional CD-R. Both can perform recording and reproduction, and has excellent general-purpose optical information recording. Method and optical information recording medium. [Mechanism for Solving Problems] The present invention achieves the foregoing objects by the following means. That is, the present invention is an optical information recording method for recording information on an optical information recording medium by irradiating with laser light having a wavelength of 45 nm or less, and is an optical information recording having the characteristics that the recording layer of the optical information recording medium contains a phthalocyanine derivative. method. The present invention is also characterized by an optical information recording medium used in the aforementioned optical information recording method. [Embodiment of the invention] < Optical information recording method > The optical information recording method of the present invention 'rotates at a constant linear velocity (1.2 to 1.4m / sec in the CD format) or a constant angular rate, and is protected from the substrate side or 584850 V. Description of the invention (5) The layer side is irradiated with semiconductor laser light and other recording light. Because of the irradiation of this light, the local temperature of the recording layer will rise due to the absorption of this light, resulting in physical or chemical changes (for example, pits, etc.). Information is recorded by changing its optical characteristics. In the present invention, a semiconductor laser light having an oscillation wavelength in a range of 390 to 450 nm is used. The preferable light source is a blue-violet semiconductor laser light having a central oscillation wavelength in the range of 390 to 4 15 nm, and a light guide element that makes the infrared semiconductor laser light with a central oscillation wavelength of 850 nm to be half of the central oscillation wavelength of 405 to 425 nm Blue-purple SHG laser light. From the viewpoint of recording density, blue-violet semiconductor laser light is preferred. The information recorded in the manner described above is reproduced, rotated at the same constant linear speed as described above, while radiating semiconductor laser light from the substrate side or the protective layer side, and then detecting the reflected light. < Optical information recording medium > The optical information recording medium of the present invention is an optical information recording medium used in the aforementioned optical information recording method, and a recording layer of the optical information recording medium contains a phthalocyanine derivative. This phthalocyanine derivative has a main absorption band near 700 nm and a side absorption band near 340η. By using the phthalocyanine derivative as a recording material lacking recording material, an optical information recording medium capable of providing short-wavelength laser light with a wavelength of 450 nm or less and providing good recording and reproduction characteristics with high reflectance and high modulation degree can be obtained. In addition, this optical information recording medium also has good recording and reproduction characteristics for laser light with a wavelength of 750 to 850 nm, with high reflectance and high modulation. In addition, the phthalocyanine derivative has a specific substituent group and forms thermodynamics.

584850 五、發明說明（6) 上相當安定之非晶相。因此，光資訊記錄媒體在儲存時， 記錄層不會產生結晶化等之相轉換’因此’本發明之光資 訊記錄媒體具有優良之儲存安定性。 以下，爲本發明光資訊記錄媒體之實施形態的詳細說明 〇 本發明之光資訊記錄媒體所使用之酞菁衍生物最好爲下 述一般式（I)所示之化合物。 [化1] 一般式（I): RV R02584850 V. Description of the invention (6) A fairly stable amorphous phase. Therefore, when the optical information recording medium is stored, the recording layer does not undergo phase conversion such as crystallization. Therefore, the optical information recording medium of the present invention has excellent storage stability. The following is a detailed description of embodiments of the optical information recording medium of the present invention. The phthalocyanine derivative used in the optical information recording medium of the present invention is preferably a compound represented by the following general formula (I). General formula (I): RV R02

R阳R阼 一般式（I)中，Ral〜Ral及RW〜RP分別代表獨立之氫 原子、鹵原子、氰基、硝基、甲醯基、羧基、磺基、碳原 子數1至20之烷基、碳原子數6至14之芳基、碳原子數 7至15之芳烷基、碳原子數1至1〇之異環基、碳原子數 1至20之烷氧基、碳原子數6至14之烯丙氧基、碳原子 數2至21之醯基、碳原子數1至20之烷基碾基、碳原子 數6至20之芳基碾基、碳原子數1至25之氨基甲醯基、 584850 五、發明說明（7) 碳原子數〇至32之氨磺醯基、碳原子數2至21之烷氧醯 基、碳原子數7至15之烷氧羰基、碳原子數2至21之醯 胺基、碳原子數1至20之磺醯胺基、及碳原子數0至36 之氨基，Μ代表具有2個氫原子、金屬、金屬氧化物、或 配位之金屬。 一般式（I)中之Ral〜Ra8最好非全部爲氫原子，又，Ral 〜Ra2之任一方、Ra3〜Ra4之任一方、Ra5〜Ra6之任一方 、7〜Ra8之任一方、合計4個取代基最好非同時爲氫原 子，此時，RW〜RW最好全部爲氫原子。 一般式（I)中，Ral〜Ral及RW〜RP之實例爲氫原子、 鹵原子、羧基、磺基、碳原子數1至16之烷基、碳原子 數6至10之芳基、碳原子數1至16之烷氧基、碳原子數 6至10之烯丙氧基、碳原子數1至16之碾基、碳原子數 2至20之氨磺醯基、碳原子數2至17之烷氧醯基、碳原 子數7至11之烷氧羰基、碳原子數2至18之醯胺基、以 及碳原子數1至18之磺醯胺基，較佳者爲氫原子、鹵原 子、羧基、磺基、碳原子數1至16之烷基、碳原子數6 至10之烯丙氧基、碳原子數1至14之烷基颯基、碳原子 數6至14之芳基碾基、碳原子數2至16之氨磺醯基、碳 原子數2至13之烷氧醯基、碳原子數2至14之醯胺基、 及碳原子數1至14之磺醯胺基，更佳者〜Rd爲氫原 子、鹵原子、磺基、碳原子數8至16之烷基、碳原子數1 至12之楓基、碳原子數1至12之氨磺醯基、碳原子數2 584850 五、發明說明（8) 至12之醯胺基、及碳原子數1至12之搞醯肢基’尺心〜& "則爲氫原子、鹵原子，最佳則是R α 1〜R α 1之至少其一 爲磺基、碳原子數1至10之suifony1基、及碳原子數1 至10之氨磺醯基，而RM〜則爲氫原子。 一般式（I)中，Ral〜Ral及〜亦可具取代基，而 取代基之實例如下所示。 如碳原子數1至20之鏈狀或環狀的烷基（例如’甲基、 乙基、異丙基、環己基）、碳原子數6至18之烯丙氧基（例 如，苯基、氯苯基、2,4-二-t-戊基苯基、1-萘基）、碳原子 數7至18之芳烷基（例如，苄基、甲氧苄基）、碳原子數2 至20之鏈烯基（例如，乙烯基、2-甲基乙烯基）、碳原子數 2至20之炔基（例如，乙炔基、2-甲基乙炔基、苯基乙炔 基）、鹵原子（例如，F、Cl、Br、I)、氰基、羥基、羧基、 碳原子數2至20之醯基（例如，乙醯基、苯醯基、水楊醯 基、三甲基乙醯基）、碳原子數1至20之烷氧基（例如，甲 氧基、丁氧基、環己基羥基）、碳原子數6至20之烯丙氧 基（例如，苯氧基、1-萘氧基、甲苯醯基）、碳原子數1至 20之烷基硫代氨基（例如，甲硫基、丁硫基、苯甲硫基、 3 -甲氧基丙硫基）、碳原子數6至20之嫌丙基硫基（例如， 苯基硫基、4 -氯苯基硫基）、碳原子數1至20之院基珮基（ 例如，甲硫醯基、丁烷醯基）、碳原子數6至20之芳基碾 基（例如，苯亞磺醯基、對甲苯磺醯基）、碳原子數1至1 7 之氨基甲醯基（例如，無取代之氨基甲醯基、甲基氨基甲 -10- 五、發明說明（9) 醯基、乙基氨基甲醯基、η-丁基氨基甲醯基、二甲基氨基 甲醯基）、碳原子數1至16之醯胺基（例如，乙醯胺基、苯 甲醯胺基）、及碳原子數2至10之醯醯氧基（例如，乙酸基 、苯醯氧基）、碳原子數2至10之烷氧醯基（例如，甲氧羰 基、乙酯基）、5或6個異環基（例如，吡啶基、硫茂基、 呋喃基、硫氮雜茂基、二氮雜茂基、吡唑啉基等芳香族異 環基；吡咯烷環基、氮己環基、對氧氯己環基、吡喃環基 、吡喃環基、二噁烷環基、二硫雜環戊烷環基等異環基） 〇 一般式（I)中，Ral〜Ral及〜R〃8之取代基應爲如碳 原子數1至16之鏈狀或環狀的烷基、碳原子數6至14之 烯丙氧基、碳原子數7至15之芳烷基、碳原子數1至16 之烷氧基、碳原子數6至14之烯丙氧基、鹵原子、碳原 子數2至17之烷氧醯基、碳原子數1至10之氨基甲醯基 、及碳原子數1至10之醯胺基，而其中較佳者爲碳原子 數1至10之鏈狀或環狀的烷基、碳原子數7至13之芳烷 基、碳原子數6至10之烯丙氧基、碳原子數1至10之烷 氧基、碳原子數6至10之烯丙氧基、氯原子、碳原子數2 至11之烷氧醯基、碳原子數1至7之氨基甲醯基、及碳 原子數1至8之醯胺基。 更好則是碳原子數1至8之鏈狀或環狀的烷基、碳原子 數7至11之芳烷基、碳原子數1至8之烷氧基、碳原子 數3至9之烷氧醯基、苯基及氯原子，最好是碳原子數1 -11- 584850 五、發明說明（1〇) 至6之院氧基。 一般式（I)中，Μ應爲金屬，其中又以鋅、鎂、銅、鎳、 或鈀較佳，更好爲銅或鎳，最好則是銅。 爲了提高記錄材料之重要特性--C/N(載波雜訊比），以一 般式⑴表示之化合物的分子量應爲L300以下，U00以 下更好，且，此時，Ral、Ra2、Ra3、Ra4、R〇:5、R〇:6、r a7、或所代表之取代基最好爲氮磺醯基或磺醯基，其 中，〜Ra2之任一方、Ra3〜Ra4之任一方、Ra5〜Ra6 之任一方、R"7〜之任一方、合計4個取代基最好爲同 一磺醯基。 一般式（I)所代表之化合物，亦可在任意位置鏈結而形成 聚合物，此時之各單位可以相同或不同，又，亦可鏈結於 聚苯乙烯、聚甲基丙烯酸酯、聚乙烯醇、纖維素等之聚合 物鏈。 本發明光資訊記錄媒體使用之一般式（I)所代表的酞菁衍 生物，可單獨使用特定之介電質，亦可混合使用複種不同 構造者。尤其是，爲了防止記錄層之結晶化，最好使用取 代基之取代位置不同的異構物混合物。 本發明之光資訊記錄媒體的記錄層，係吸收記錄用之雷 射光的能量，利用科學或物理之分解、變質來形成記錄標 記（坑）。此記錄標記在再生時會檢測反射率之變化部位。 消耗係數（k)係光能量吸收量相關之光學物性，執行記錄時 ，並非只和記錄層吸收之雷射光能量相關，亦和記錄再生 •12- 584850 五、發明說明（11 ) 時檢測之反射率相關。折射率（n)和記錄標記之光學尺寸（ 反射率之變化量）相關。因記錄用之雷射光的輸出有其數 mW至數十mW之現實範圍’故記錄用化合物之基本骨架 亦有其適當的消耗係數（k)及折射率（η)之範圍。 本發明之光資訊記錄媒體時，含有一般式（1)代表之化合 物的記錄層折射率（η)及消耗係數（k)，應配合記錄用雷射 光之波長，位於1.〇<η<1·9、0.03<k<0.30之範圍內，最好 則是位於1·5<η<1·9、0.04<k<0.15之範圍內。又，此折射 率（η)及消耗係數（k)以如旋轉分析法（橢圓對稱）即可檢測。 下述表1至4中，是本發明使用之酞菁衍生物的良好具 體實例，然而，本發明並不限於此。 表1至4中，例如，Rx/Ry(x及y代表αΐ至α8、石1至 /3 8之任一）之標記代表Rx或Ry之任一方，所以，具有此 標記之化合物爲取代位置異構體之混合物。又，無取代時 ，亦即以氫原子取代時，則省略標記。 -13- 584850 五、發明說明（12) [表1] 裘1 N 〇. 取代基位置及取代基 M (I 一 1) ReA/Re2, RaVRa4> RfiS/Rafi, Ra7/Rfl8 Cu (T 一 2) ~so2n (C.,Hia- /) 2 W2、RW4，WRW、Ru?/RJg C u (I 一 3) -S02NH (2-5~bu loxy-5 —i*-amy 1 pheny 1) Rttl/R°2. RuVRl,\ RaVRoH C u- (I 一 4) -SOoNII (CII2) aO (-2, 4-d 1 - r~amy 1 — phenyl) Ra7/Rc,,-SOsH RaL/lH ReVRu、R W6、Ra7/Re， N i. (I - 5) 一 S02N (3 — methoxypropy】）2 RttVR"2. R0VRo\ RflVRoB N i (I 一 6) —S O 2 NM e (cyclohexyl) RaVRtf4> Ra7/RrtR N i (I 一 7) -SOuN (3 - 7 - p. r ο ρ 〇 x y p h e n y 1 ) 2 Rul/Ra^ R"VRe4, R'VR**16. Rn7/RrtH P d CI 一 8) 一 SO 2 Nil (2 - / — amyl oxy — carbonyl phenyl) Rel/Re' WR1*4，RcVRaS、Ra7/R “ Pd (I 一 9) 一 S02NH(2，4, 6 — trimethyl — phenyl) Rff1/Krt2、Re:1/T? “、WRaii、Ra>/Raa Co (I 一 10) — S02 (4—morphol Ino) RrtVR"2、RuVRe' Ra5VRaH、RaVReti F e (T 一 11) ~S02N (C2He) (4-i.】uoropheny】） Rrt,/Rfr2. R"VRa\ RrtVRKi? C u (I 一 12〕 -so2nh (CHJ 3n (C2Hs), Rn]/Rn\ RaVRa\ R-'VR^, R^/R^ C u (I - 13) —SOz (2 — ；7- propox y phenyl) Rai/RaK Ra3/Re4> Ra0/Rart, R,l7/Ray> N L (I 一 ]4) —S O 2 (2-77-butoxy — 5-i — btity] -phenyl) Rtt[/Ra2^ RaVRaR> R^/R"8 Co 一 S .O 2 ( 2 —τη cthoxycarbony】 -phenyl) -14- 584850 五、發明說明（13)[表2] 表2In the general formula (I), Ral ~ Ral and RW ~ RP respectively represent an independent hydrogen atom, a halogen atom, a cyano group, a nitro group, a methylamino group, a carboxyl group, a sulfo group, and a carbon number of 1 to 20. Alkyl group, aryl group having 6 to 14 carbon atoms, aralkyl group having 7 to 15 carbon atoms, heterocyclic group having 1 to 10 carbon atoms, alkoxy group having 1 to 20 carbon atoms, carbon number 6 to 14 allyloxy, 2 to 21 carbon atoms, alkyl 1 to 20 carbon atoms, aryl 6 to 20 carbon atoms, 1 to 25 carbon atoms Carbamate group, 584850 V. Description of the invention (7) Ammoniasulfonyl group having 0 to 32 carbon atoms, alkoxyfluorenyl group having 2 to 21 carbon atoms, alkoxycarbonyl group having 7 to 15 carbon atoms, carbon atom Amidino groups of 2 to 21, sulfonamido groups of 1 to 20 carbon atoms, and amino groups of 0 to 36 carbon atoms, M represents a metal having 2 hydrogen atoms, a metal, a metal oxide, or a coordination metal . Ral ~ Ra8 in general formula (I) is preferably not all hydrogen atoms, and any one of Ral ~ Ra2, any one of Ra3 ~ Ra4, any one of Ra5 ~ Ra6, any one of 7 ~ Ra8, a total of 4 The substituents are preferably non-simultaneous hydrogen atoms. In this case, RW ~ RW are preferably all hydrogen atoms. In the general formula (I), examples of Ral ~ Ral and RW ~ RP are a hydrogen atom, a halogen atom, a carboxyl group, a sulfo group, an alkyl group having 1 to 16 carbon atoms, an aryl group having 6 to 10 carbon atoms, and a carbon atom. Alkoxy groups of 1 to 16, allyloxy groups of 6 to 10 carbon atoms, aryl groups of 1 to 16 carbon atoms, sulfamoyl groups of 2 to 20 carbon atoms, 2 to 17 carbon atoms Alkoxyfluorenyl group, alkoxycarbonyl group with 7 to 11 carbon atoms, fluorenylamino group with 2 to 18 carbon atoms, and sulfonamido group with 1 to 18 carbon atoms, preferably a hydrogen atom, a halogen atom, Carboxyl, sulfo, alkyl with 1 to 16 carbons, allyloxy with 6 to 10 carbons, alkylfluorenyl with 1 to 14 carbons, aryl 6 to 14 carbons Sulfamoyl groups with 2 to 16 carbon atoms, alkoxyfluorenyl groups with 2 to 13 carbon atoms, fluorenilyl groups with 2 to 14 carbon atoms, and sulfonamido groups with 1 to 14 carbon atoms, more Preferably, Rd is a hydrogen atom, a halogen atom, a sulfo group, an alkyl group having 8 to 16 carbon atoms, a maple group having 1 to 12 carbon atoms, an amidosulfonyl group having 1 to 12 carbon atoms, and 2 carbon atoms. 584850 V. Amino groups of invention description (8) to 12, and The number of atoms from 1 to 12 is "Central ~" & " is a hydrogen atom, a halogen atom, and most preferably, at least one of R α 1 to R α 1 is a sulfo group, and the carbon number is 1 to Suifony 1 group of 10 and sulfamoyl group having 1 to 10 carbon atoms, and RM ~ are hydrogen atoms. In the general formula (I), Ral ~ Ral and ~ may also have a substituent, and examples of the substituent are shown below. Such as a chain or cyclic alkyl group having 1 to 20 carbon atoms (for example, 'methyl, ethyl, isopropyl, cyclohexyl), an allyloxy group having 6 to 18 carbon atoms (for example, phenyl, Chlorophenyl, 2,4-di-t-pentylphenyl, 1-naphthyl), aralkyl groups having 7 to 18 carbon atoms (eg, benzyl, methoxybenzyl), 2 to carbon atoms 20 alkenyl (eg, vinyl, 2-methylvinyl), alkynyl having 2 to 20 carbon atoms (eg, ethynyl, 2-methylethynyl, phenylethynyl), halogen atom ( For example, F, Cl, Br, I), cyano, hydroxy, carboxyl, fluorenyl having 2 to 20 carbon atoms (for example, ethynyl, phenylfluorenyl, salicylfluorenyl, trimethylacetamyl), carbon Alkoxy groups with 1 to 20 atoms (for example, methoxy, butoxy, cyclohexylhydroxyl), allyloxy groups with 6 to 20 carbon atoms (for example, phenoxy, 1-naphthyloxy, toluene Fluorenyl), alkylthioamino groups having 1 to 20 carbon atoms (for example, methylthio, butylthio, benzylthio, 3-methoxypropylthio), and 6 to 20 carbon atoms Propylthio (for example, phenylthio, 4-chlorophenyl Radicals), aminyl radicals having 1 to 20 carbon atoms (for example, methylthio, butanesulfenyl), aryl radicals having 6 to 20 carbon atoms (for example, phenylsulfinyl, p-toluene) Sulfonyl), carbamoyl groups having 1 to 17 carbon atoms (for example, unsubstituted carbamoyl groups, methylcarbamoyl-10-) 5. Description of the invention (9) fluorenyl groups, ethylcarbamoyl groups Group, η-butylcarbamoyl group, dimethylcarbamoyl group), amidino group having 1 to 16 carbon atoms (eg, ethylamino, benzamidine), and 2 carbon atoms Fluorenyl to 10 (for example, acetate, phenylfluorenyl), alkoxyfluorenyl (for example, methoxycarbonyl, ethyl), 2 or 10 carbon atoms, 5 or 6 heterocyclic groups ( For example, aromatic heterocyclic groups such as pyridyl, thiocene, furanyl, thioazacenyl, diazacenyl, and pyrazolinyl; pyrrolidinyl, azahexyl, p-chlorochlorohexyl, pyridine Heterocyclic groups such as pyranyl, pyranyl, dioxane, dithiocyclopentane, etc.) In general formula (I), the substituents of Ral ~ Ral and ~ R〃8 should be as follows 1 to 16 carbon atoms Or cyclic alkyl group, allyloxy group with 6 to 14 carbon atoms, aralkyl group with 7 to 15 carbon atoms, alkoxy group with 1 to 16 carbon atoms, allyl group with 6 to 14 carbon atoms An oxygen group, a halogen atom, an alkoxyfluorenyl group having 2 to 17 carbon atoms, a carbamoyl group having 1 to 10 carbon atoms, and a fluorenylamino group having 1 to 10 carbon atoms, and among them, a carbon atom is preferred Chain or cyclic alkyl group of 1 to 10, aralkyl group of 7 to 13 carbon atoms, allyloxy group of 6 to 10 carbon atoms, alkoxy group of 1 to 10 carbon atoms, carbon atom Allyloxy groups of 6 to 10, chlorine atoms, alkoxyfluorenyl groups of 2 to 11 carbon atoms, carbamoyl groups of 1 to 7 carbon atoms, and fluorenylamino groups of 1 to 8 carbon atoms. More preferably, it is a chain or cyclic alkyl group having 1 to 8 carbon atoms, an aralkyl group having 7 to 11 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, and an alkane having 3 to 9 carbon atoms. Oxyfluorenyl, phenyl and chlorine atoms are preferably 1-11 to 584850 carbon atoms. V. Oxygen groups of the invention description (10) to 6. In the general formula (I), M should be a metal. Among them, zinc, magnesium, copper, nickel, or palladium is preferred, copper or nickel is more preferred, and copper is most preferred. In order to improve the important characteristics of the recording material-C / N (Carrier-to-Noise Ratio), the molecular weight of the compound expressed by the general formula ⑴ should be less than L300, and preferably less than U00. At this time, Ral, Ra2, Ra3, Ra4 , R0: 5, R0: 6, r a7, or the substituent represented by azosulfonyl or sulfonyl is preferred. Among them, any one of ~ Ra2, any of Ra3 ~ Ra4, Ra5 ~ Ra6 Either one of R " 7 ~, and a total of four substituents are preferably the same sulfofluorenyl group. The compound represented by general formula (I) can also be linked at any position to form a polymer. At this time, the units can be the same or different, and can also be linked to polystyrene, polymethacrylate, poly Polymer chains of vinyl alcohol, cellulose, etc. The phthalocyanine derivative represented by the general formula (I) used in the optical information recording medium of the present invention may use a specific dielectric material alone, or may use a mixture of a plurality of different structures. In particular, in order to prevent crystallization of the recording layer, it is preferable to use a mixture of isomers having different substituent substitution positions. The recording layer of the optical information recording medium of the present invention absorbs the energy of the laser light used for recording, and uses scientific or physical decomposition and deterioration to form a recording mark (pit). This recording mark detects a change in reflectance during reproduction. Consumption coefficient (k) refers to the optical physical properties related to the amount of absorbed light energy. When recording is performed, it is not only related to the laser light energy absorbed by the recording layer, but also to recording and reproduction. • 12-584850 V. Reflection detected during the description of the invention (11) Rate related. The refractive index (n) is related to the optical size (amount of change in reflectance) of the recording mark. Since the output of the laser light for recording has a realistic range of several mW to several tens of mW ', the basic skeleton of the recording compound also has a range of appropriate consumption coefficient (k) and refractive index (η). In the optical information recording medium of the present invention, the refractive index (η) and the consumption coefficient (k) of the recording layer containing the compound represented by the general formula (1) should match the wavelength of the laser light used for recording, and are located at 1.0. ≪ η < 1 · 9, 0.03 < k < 0.30, and preferably 1.5 < η < 1,9, 0.04 < k < 0.15. The refractive index (η) and the consumption coefficient (k) can be detected by a rotation analysis method (elliptical symmetry), for example. The following Tables 1 to 4 are good specific examples of the phthalocyanine derivative used in the present invention, however, the present invention is not limited thereto. In Tables 1 to 4, for example, the mark of Rx / Ry (x and y represent any of αΐ to α8, stone 1 to / 3 8) represents either Rx or Ry. Therefore, the compound having this mark is a substitution position A mixture of isomers. When there is no substitution, that is, when a hydrogen atom is substituted, the label is omitted. -13- 584850 V. Description of the invention (12) [Table 1] Qiu 1 N 〇. Substituent position and substituent M (I-1) ReA / Re2, RaVRa4 > RfiS / Rafi, Ra7 / Rfl8 Cu (T-1 2 ) ~ so2n (C., Hia- /) 2 W2, RW4, WRW, Ru? / RJg C u (I-3) -S02NH (2-5 ~ bu loxy-5 —i * -amy 1 pheny 1) Rttl / R ° 2. RuVRl, \ RaVRoH C u- (I-4) -SOoNII (CII2) aO (-2, 4-d 1-r ~ amy 1 — phenyl) Ra7 / Rc ,,-SOsH RaL / lH ReVRu , R W6, Ra7 / Re, N i. (I-5)-S02N (3 — methoxypropy)) 2 RttVR " 2. R0VRo \ RflVRoB N i (I-6) —SO 2 NM e (cyclohexyl) RaVRtf4 > Ra7 / RrtR N i (I-7) -SOuN (3-7-p. R ο ρ 〇xypheny 1) 2 Rul / Ra ^ R " VRe4, R'VR ** 16. Rn7 / RrtH P d CI-1 8) Mono SO 2 Nil (2-/ — amyl oxy — carbonyl phenyl) Rel / Re 'WR1 * 4, RcVRaS, Ra7 / R "Pd (I-9)-S02NH (2,4, 6 — trimethyl — phenyl) Rff1 / Krt2, Re: 1 / T? ", WRaii, Ra > / Raa Co (I-10) — S02 (4—morphol Ino) RrtVR " 2, RuVRe 'Ra5VRaH, RaVReti F e (T-11) ~ S02N (C2He ) (4-i.】 Uoropheny】) Rrt, / Rfr2. R & quo t; VRa \ RrtVRKi? C u (I-12) -so2nh (CHJ 3n (C2Hs), Rn) / Rn \ RaVRa \ R-'VR ^, R ^ / R ^ C u (I-13) --SOz ( 2 —; 7- propox y phenyl) Rai / RaK Ra3 / Re4 > Ra0 / Rart, R, l7 / Ray > NL (I 一) 4) —SO 2 (2-77-butoxy — 5-i — btity]- phenyl) Rtt [/ Ra2 ^ RaVRaR > R ^ / R " 8 Co -S .O 2 (2 —τη cthoxycarbony] -phenyl) -14- 584850 V. Description of the invention (13) [Table 2] Table 2

No. 取代基位置及取代基 M (I — 15) Ral/Ra2, Rft7/RrtB 一 S02 (CH2)…（2-ch loro-4 —r-amy 1 pheny ί) C u (I — 16) R0l/Re2，RftVRe1，Rtt5/Ra6. Ro7/Rfl8 —S02 (CH2) 2C02C4H3 — / Pd (I -17) Rci/Re2、RttVRa4、Rrt7/Rffil -S02 (cyclohexyl) Cu Cl -1 8) Rtf3/R°\ RaS/Ra6s R^VR08 -S02 (4 - (2 — 5 — biitoxy ~ b e η z o y i a m i π o) phenyl} N i (I 一 1 9) Rel/Rtt2、RtfVR “、WR “ -50^(2. 6-dLchloro —4~me thoxyphenyl) P d (I -2 0) WRW、R*W1、ReVRW 一 S〇2CH (Me) CO，CH2 -CH (C2HJ C,Hu~/7 M g (1 一 2 1) R，丨丨/R“·、k"3/R“、R W6、Rtf7/R “ ~S02 (2 - (2 — el*hoxyerhoxy) -phenyl} ~ C 2Hr Z n (1 一 2 2) Ku】/Ru2、Ruvnw5/Re<1、Rw7/Rtf8 ~S02N (CII.CH.OMe) 2 C υ π -2 3) RqL/Ru2> Rft7/RrtK 一〇CH2CH (C2HR) C4H0 - J3 N i (I -2 4) Rnl/Rft2, RnVRnR • 0 CHM e (phenyl) Z n (I 一 2 5 ) R"1、R"2、Ra：1、R“、RttS，R “、卩07、R “ -0 C Η ( 5 ~ b u t y 1) 2 C τι (I -2 6) R"1, Re2、Ra3、1?°4, K。·' RoG、Rf、K°8 -OCH2CH2OCaH7~ / S i C 1 2 (I -27) Ra]/Ra2, R,inXRa\ ReVRttR, Ro7//Rifl —ί — a n y 1 R“/R“、R<3VF·、WRaH、 N i ~ C 1 -15- 584850 五、發明說明（14) [表3] 表3No. Substituent positions and substituents M (I — 15) Ral / Ra2, Rft7 / RrtB-S02 (CH2) ... (2-ch loro-4 —r-amy 1 pheny ί) C u (I — 16) R0l / Re2, RftVRe1, Rtt5 / Ra6. Ro7 / Rfl8 —S02 (CH2) 2C02C4H3 — / Pd (I -17) Rci / Re2, RttVRa4, Rrt7 / Rffil -S02 (cyclohexyl) Cu Cl -1 8) Rtf3 / R ° \ RaS / Ra6s R ^ VR08 -S02 (4-(2 — 5 — biitoxy ~ be η zoyiami π o) phenyl} N i (I-1 9) Rel / Rtt2, RtfVR ", WR" -50 ^ (2. 6-dLchloro —4 ~ me thoxyphenyl) P d (I -2 0) WRW, R * W1, ReVRW-S〇2CH (Me) CO, CH2 -CH (C2HJ C, Hu ~ / 7 M g (1-2 1) R ， 丨 丨 / R "·, k " 3 / R", R W6, Rtf7 / R "~ S02 (2-(2 — el * hoxyerhoxy) -phenyl} ~ C 2Hr Z n (1-2 2 ) Ku】 / Ru2, Ruvnw5 / Re < 1, Rw7 / Rtf8 ~ S02N (CII.CH.OMe) 2 C υ π -2 3) RqL / Ru2 > Rft7 / RrtK 1CH2CH (C2HR) C4H0-J3 N i (I -2 4) Rnl / Rft2, RnVRnR • 0 CHM e (phenyl) Z n (I-2 5) R " 1, R " 2, Ra: 1, R ", RttS, R", 卩 07, R "-0 C Η (5 ~ buty 1) 2 C τι (I -2 6) R " 1, Re2, Ra3, 1? 4, K. 'RoG, Rf, K ° 8 -OCH2CH2OCaH7 ~ / S i C 1 2 (I -27) Ra] / Ra2, R, inXRa \ ReVRttR, Ro7 // Rifl —ί — any 1 R “/ R ", R < 3VF ·, WRaH, Ni ~ C 1 -15- 584850 5. Explanation of the invention (14) [Table 3] Table 3

No. 取代基位置及取代基 Μ (1-28) RaL/Ra2，Ra VRa\ RaE/Ra\ R^/R^ Z n -(2t 6-d i-e thoxyphenyl) (卜 2 9) JFTVRd、RU VR"\ Rar,/Rtte Cu -SO,NHCH,CH2OC3H7- I Ru7/Ruri-S〇aH (1-30) Rn,/R“、RnW4、ReS/R“ Cu -C02CH2CH2OC2H5 Rn7/R" h-C02H (1-31) Rul/Ru2、RtfVRu4、Wid Ru7/R “ Co -C02CH (Me) CO,C3H7~/ , (1-32) Rui/RVK RaVRa\ RaVRaG. ΗσΤ/Τ?ϋβ Cu -CONHCH2CH2OC^H7- / (1-33) Rfll/Ru2、RWVR “、Τ?λ:·/Ή Pd -CON (CH2CH2OC4H9~/3) 2 R° VRofl-C02H (1-34) Rul/Ra2, RaVRa4. RaVRtf\ Rtf7/Rue Co -NHCOCH (C2Hr>) C4Hi,-i7 (1-35) Ral/Ra2. Ru3/Ra\ RuVRae, Ru7/Rui Mg -NHCO (2 —λ —buioxycarbοny 1 — phenyl) (1-3 6) Rtti/Rtt2, Ra3/Ra4. Ra'VRe\ Ra7/Rtt" P d -NHS02 (2- /-propoxypheny 1) (卜3 7) ReVRa\ RaS/R°\ Rfl7/RaB Zn -NHS02 (2~/7~butoxy—5 — r-amyl — phenyl) -16- 584850 五、發明說明（15) [表4] 表4 Ν〇· 取代基位置及取代基 Μ (I- -3 8) R a]/Rrt 2、R" :VR' RaVR“、 Ra 7/Re8， * N i so2ch, (I - _ 3 9) R 2、Ru R* VR “ C u (Ι 一- SOaCH (CH,) 2 -4 0) R W Rff S/R“. Re 7/R〃 c 11 Ο - 一 so2c, 凡一 $ -4 1) R ai/Rtt 2、R0 R W6、 Ra VRe& z n (Τ - 一 so2ch2co 2CH (CHJ 2 -4 2) al/Rff 2、Ra VR“' ReVRa\ Re VR“ c u (I - 一 S02CH (CH3) CO 2CHa -4 3) w 2, Rn VR “、 Ra5/R°\ Re 了/R “ c u - so2c (I - ' 4 4) R 2、R3 •VR “、 Ras/R“、 R WA c u (I - 一 so2n (Cr,H i i 一 ,） 2 - 4 5) R w Vr2 •VR34、 RW"、 R3 VR^ c u ~SO,CH (CH^) 2 本發明使用之酞菁衍生物係以如白井-小林共同著作、（ 株）IPC發行「酞菁衍生物-化學及機能-」（ρ·1〜62)、及C· C· Leznoff - Α. Β· P. Lever共同著作、VCH發行「酞菁之 特性及應用」（p.l〜54)等記載、引用、或類似方法所合成 〇 如前面所述，本發明之光資訊記錄媒體，基板上具有含 前述酞菁衍生物之記錄層。記錄層中之前述酞菁衍生物的 I 含有量，應爲80重量百分率以上，最好爲90重量百分率 以上，若滿8 0重量百分率時，雷射光之折射率會降低， 故調變度亦會降低。 1 584850 五、發明說明（16 ) 本發明之光資訊記錄媒體中，含有各種構成物。本發明 之光資訊記錄媒體應在形成一定軌距之導引槽的圓盤狀基 板上依序形成記錄層、光反射層、及保護層，或是在該基 板上依序形成光反射層、記錄層、及保護層。又，在形成 一定軌距之導引槽的圓盤狀基板上形成記錄層及光反射層 ，將二片前述層疊體以記錄層分別朝內之方式黏結的構成 亦可。 本發明之光資訊記錄媒體爲了達成最高記錄密度，可以 採用軌距之導引槽比CD-R或DVD-R更狹窄的基板。本發 明之光資訊記錄媒體時，前述軌距應爲0.2至0.8//m之範 圍內，位於0.2至0.5//m範圍內更好，而最好爲0.2至 〇.4//m之範圍內。 導引槽之深度應爲〇·〇1至0.18/zm之範圍內，最好能爲 0.02至0.15//m之範圍內。 以下，以依序在圓盤狀基板上形成記錄層、光反射層、 及保護層之構成物當做本發明光資訊記錄媒體之實例，說 明其製造方法。 本發明之光資訊記錄媒體的基板，可以選擇以傳統光資 訊記錄媒體基板使用之各種材料來構成。基板材料有玻璃 、聚碳酸酯、聚甲基丙烯酸等丙烯酸酯樹脂；聚氯乙烯、 氯乙烯共聚合體等氯化乙烯系樹脂、環氧樹脂、非晶聚烯 烴、及聚酯；等，可依需要倂用/又，這些材料可以薄膜 狀、或具剛性之基板方式來使用。前述材料中，從耐濕性 -18- 五、發明說明（17) 、尺寸安定性、及價格觀點而言，以聚碳酸酯爲佳。 設有記錄層側之基板表面，爲了改善平面性、提昇黏結 力、以及以防止前述記錄層變質爲目的，亦可設置底塗層 。底塗層之材料可以爲如聚甲基丙烯酸、丙烯酸·甲基丙 烯酸共聚合物、苯乙烯•順丁烯二酸酐共聚合物、聚乙烯 醇、N-羥甲基丙烯胺、苯乙烯·乙烯基甲苯共聚合物、氯 磺醯化聚乙烯、硝化纖維素、聚氯乙烯、氯化聚烯烴、聚 酯、聚醯亞胺、醋酸乙烯酯•氯乙烯共聚合物、乙烯•醋酸 乙烯酯共聚合物、聚乙烯、聚丙烯纖維、聚碳酸酯等高分 子物質；及矽烷偶合劑等表面改質劑。使前述物質溶解或 分散於適當溶劑內製成塗布液，然後，以旋轉塗布、浸塗 、擠壓塗膜等塗敷方法，在基板表面形成底塗層。底塗層 之層厚一般爲0.005至20//m範圍，最好爲0.01至10/zm 之範圍內。 記錄層之形成上，可以利用蒸鍍、噴濺、CVD、或溶劑 塗布等方法，但以溶劑塗布較佳。此時，可以依據需要， 前述色素化合物中，可以利用溶劑溶解控制劑、黏結劑等 調製塗布液，然後，將此塗布液塗敷於基板表面形成塗膜 並進行乾燥。塗布液之溶劑可以爲丁基乙酯、乳酸乙醋、 鈣化白水等酯；甲基乙基甲酮、環己酮、甲基異丁基甲酮 、等酮；二氯甲烷、1，2-二氯乙烷、氯仿等氯化羥；二甲 基甲醯胺等胺；甲基環己烷等碳氫化合物；二丁醚、二*** 、四氫呋喃、二氧雜環己烷等醚；乙醇、η-丙醇、異丙醇、 -19- 584850 五、發明說明（18 ) η-正丁醇、雙丙酮醇等醇；2,2,3,3，_四氟丙醇等氟系溶劑；甲 基溶纖劑、乙基溶纖劑、丙二醇溶纖劑等醇醚類。前述溶 劑方面，可考慮使用之色素的溶解性而單獨或組合2種以 上使用。塗布液亦可配合目的而添加氧化防止劑、UV吸 收劑、可塑劑、潤滑劑等各種添加劑。 使用黏結劑時’可以使用如明膠、纖維質、葡聚糖、松 脂、橡膠等天然有機高分子物質；聚乙烯、聚丙烯、聚苯 乙燃、聚異丁燦等碳氫系樹脂、聚氯乙嫌、多氯亞乙嫌、 聚氯乙烯•聚醋酸乙烯酯共聚合物等乙烯系樹脂、聚丙烯 酸甲酯、聚甲基丙烯酸乙酯等之丙烯樹脂、聚丙烯醇、氯 化聚乙烯、環氧樹脂、下醛樹脂、橡膠衍生物、苯酚甲醛 樹脂等熱硬化性樹脂之起始縮合物的合成有機高分子。將 黏結劑倂用爲記錄層之材料時，黏結劑之使用量一般對色 素（酞菁衍生物）爲1.01倍量至50倍量（重量比）之範圍，最 好爲0.1倍量至5倍量（重量比）之範圍內。以此方式調製 之塗布液中的色素濃度，一般爲〇.〇1至10重量百分率之 範圍，最好爲0.1至5重量百分率之範圍內。 溶劑之塗布方法爲噴霧法、旋轉塗布法、浸塗法、輥塗 抹法、葉片塗布法、滲和刮塗法、網板印染法等。記錄層 可以爲單層，亦可以爲多層。記錄層之層厚一般爲10至 500nm之範圍，若在15至300nm之範圍更佳，最好則爲 20至100nm之範圍內。 以控制雷射光照射時之記錄層熱分解行爲且提筒記錄特 -20- 五、發明說明（19) 性爲目的，可以在記錄層添加各種熱分解控制劑。例如， 歐洲專利第〇600427號之添加金屬複合物的方法十分有效 ，金屬複合物常中，以二茂金屬衍生物爲佳，最好爲二環 戊二烯亞鐵衍生物。 爲了提高記錄層之耐光性，亦可使記錄層含有各種褪色 防止劑。褪色防止劑一般採用單態氧抑制劑。單態氧抑制 劑可以使用已公開之專利說明書等刊載之物。具體而言， 如曰本特開昭58-175693號公報、日本特開昭59-81194號 公報、日本特開昭60- 1 83 87號公報、日本特開昭60-1 95 86號公報、日本特開昭60- 1 9587號公報、日本特開昭 60-35054號公報、日本特開昭60_3619〇號公報、日本特 開昭60-36 1 9 1號公報、日本特開昭60-44554號公報、日 本特開昭60-44555號公報、日本特開昭60-44389號公報 、日本特開昭60-44390號公報、日本特開昭6〇-54892號 公報、日本特開昭60-47069號公報、日本特開昭6% 2〇9995號公報、日本特開平4-25492號公報、臼本特公平 1-38680號公報、日本特公平6_26〇28號公報、德國專利 350399號說明書、以及日本化學會誌1 992年1〇月號第 1 141頁等記載者。單態氧抑制劑之實例爲以下述一般式 (II)所示之化合物。 -21 - 584850 五、發明說明（20) [化2]No. Substituent positions and substituents M (1-28) RaL / Ra2, Ra VRa \ RaE / Ra \ R ^ / R ^ Z n-(2t 6-d ie thoxyphenyl) (Bu 2 9) JFTVRd, RU VR " \ Rar, / Rtte Cu -SO, NHCH, CH2OC3H7- I Ru7 / Ruri-S〇aH (1-30) Rn, / R ", RnW4, ReS / R" Cu -C02CH2CH2OC2H5 Rn7 / R " h-C02H ( 1-31) Rul / Ru2, RtfVRu4, Wid Ru7 / R "Co -C02CH (Me) CO, C3H7 ~ /, (1-32) Rui / RVK RaVRa \ RaVRaG. ΗσΤ / Τ? Ϋβ Cu -CONHCH2CH2OC ^ H7- / (1-33) Rfll / Ru2, RWVR ", T? Λ: · / Ή Pd -CON (CH2CH2OC4H9 ~ / 3) 2 R ° VRofl-C02H (1-34) Rul / Ra2, RaVRa4. RaVRtf \ Rtf7 / Rue Co -NHCOCH (C2Hr >) C4Hi, -i7 (1-35) Ral / Ra2. Ru3 / Ra \ RuVRae, Ru7 / Rui Mg -NHCO (2 —λ —buioxycarbοny 1 — phenyl) (1-3 6) Rtti / Rtt2, Ra3 / Ra4. Ra'VRe \ Ra7 / Rtt " P d -NHS02 (2- / -propoxypheny 1) (Bu 3 7) ReVRa \ RaS / R ° \ Rfl7 / RaB Zn -NHS02 (2 ~ / 7 ~ butoxy—5 — r-amyl — phenyl) -16- 584850 V. Description of the invention (15) [Table 4] Table 4 No. · Substituent position and substituent M (I--3 8) R a] / Rrt 2. R ": VR 'RaVR ", Ra 7 / Re8, * N i so2ch, (I-_ 3 9) R 2, Ru R * VR "C u (Ι--SOaCH (CH,) 2 -4 0) RW Rff S / R". Re 7 / R〃 c 11 Ο-one so2c, where one $ -4 1) R ai / Rtt 2.R0 R W6, Ra VRe & zn (Τ-one so2ch2co 2CH (CHJ 2 -4 2) al / Rff 2.Ra VR "'ReVRa \ Re VR" cu (I-one S02CH (CH3) CO 2CHa -4 3) w 2, Rn VR ", Ra5 / R ° \ Re Le / R" cu-so2c (I-'4 4) R 2, R3 • VR ", Ras / R", R WA cu (I-one so2n (Cr, H ii a,) 2-4 5) R w Vr2 • VR34, RW ", R3 VR ^ cu ~ SO, CH (CH ^) 2 The phthalocyanine derivatives used in the present invention are commonly used in the same way as Shirai-Kobayashi Publications, co-authored by IPC "Phthalocyanine Derivatives-Chemical and Functional-" (ρ · 1 ~ 62), and C · C · Leznoff-Α. Β · P. Lever, VCH issued "Characteristics of Phthalocyanine And application "(pl ~ 54) and other methods, as described above, synthesized by reference, reference, or similar methods. As described above, the optical information recording medium of the present invention has a recording layer containing the aforementioned phthalocyanine derivative on the substrate. The I content of the aforementioned phthalocyanine derivative in the recording layer should be 80% by weight or more, preferably 90% by weight or more. If the content is 80% by weight, the refractive index of the laser light will decrease, so the modulation degree will also be Will decrease. 1 584850 V. Description of the Invention (16) The optical information recording medium of the present invention contains various structures. The optical information recording medium of the present invention should sequentially form a recording layer, a light reflecting layer, and a protective layer on a disc-shaped substrate forming a guide groove with a certain track pitch, or sequentially form a light reflecting layer on the substrate, Recording layer and protective layer. In addition, a recording layer and a light reflecting layer may be formed on a disk-shaped substrate having guide grooves of a fixed gauge, and two pieces of the aforementioned laminated body may be bonded such that the recording layers face inwardly. In order to achieve the highest recording density, the optical information recording medium of the present invention may employ a substrate with a narrower guide groove than a CD-R or DVD-R. In the optical information recording medium of the present invention, the aforementioned track gauge should be in the range of 0.2 to 0.8 // m, preferably in the range of 0.2 to 0.5 // m, and more preferably in the range of 0.2 to 0.4 // m. Inside. The depth of the guide groove should be in the range of 0.001 to 0.18 / zm, and preferably in the range of 0.02 to 0.15 // m. In the following, a structure in which a recording layer, a light reflecting layer, and a protective layer are sequentially formed on a disc-shaped substrate is taken as an example of the optical information recording medium of the present invention, and its manufacturing method is explained. The substrate of the optical information recording medium of the present invention can be selected from various materials used for the substrate of the conventional optical information recording medium. Substrate materials include acrylic resins such as glass, polycarbonate, and polymethacrylic acid; vinyl chloride resins such as polyvinyl chloride and vinyl chloride copolymers, epoxy resins, amorphous polyolefins, and polyesters; etc. It is necessary to use these materials, and these materials can be used in the form of a film or a rigid substrate. Among the aforementioned materials, polycarbonate is preferred from the viewpoints of moisture resistance -18- 5. Invention Description (17), dimensional stability, and price. The substrate surface on the recording layer side is provided. In order to improve the flatness, enhance the adhesion, and to prevent the deterioration of the foregoing recording layer, an undercoat layer may also be provided. The material of the undercoat layer may be, for example, polymethacrylic acid, acrylic acid methacrylic acid copolymer, styrene maleic anhydride copolymer, polyvinyl alcohol, N-methylol acrylamine, styrene ethylene Toluene copolymer, chlorosulfonated polyethylene, nitrocellulose, polyvinyl chloride, chlorinated polyolefin, polyester, polyimide, vinyl acetate-vinyl chloride copolymer, ethylene-vinyl acetate copolymer Polymers, polyethylene, polypropylene fiber, polycarbonate and other polymer materials; and surface modifiers such as silane coupling agents. The aforementioned substance is dissolved or dispersed in an appropriate solvent to prepare a coating solution, and then an undercoat layer is formed on the substrate surface by a coating method such as spin coating, dip coating, or extrusion coating. The thickness of the undercoat layer is generally in the range of 0.005 to 20 // m, and preferably in the range of 0.01 to 10 / zm. The recording layer can be formed by a method such as vapor deposition, sputtering, CVD, or solvent coating, but solvent coating is preferred. In this case, if necessary, the coating solution may be prepared by using a solvent dissolution control agent, a binder, or the like in the pigment compound, and then the coating solution is coated on the substrate surface to form a coating film and dried. The solvent of the coating liquid may be esters such as butyl ethyl ester, ethyl lactate, calcified white water; methyl ethyl ketone, cyclohexanone, methyl isobutyl ketone, and other ketones; methylene chloride, 1, 2-dichloro Hydroxyl chloride such as ethane and chloroform; amines such as dimethylformamide; hydrocarbons such as methylcyclohexane; ethers such as dibutyl ether, diethyl ether, tetrahydrofuran, and dioxane; ethanol, η- Propanol, isopropanol, -19-584850 V. Description of the invention (18) Alcohols such as η-n-butanol and diacetone alcohol; fluorine solvents such as 2,2,3,3, _tetrafluoropropanol; methyl Alcohol ethers such as cellosolve, ethylcellosolve, and propylene glycol cellosolve. The solvent may be used alone or in combination of two or more in consideration of the solubility of the pigment used. The coating liquid may be added with various additives such as an oxidation inhibitor, a UV absorber, a plasticizer, and a lubricant according to the purpose. When using adhesives, you can use natural organic polymer materials such as gelatin, cellulose, dextran, turpentine, rubber, etc .; hydrocarbon resins such as polyethylene, polypropylene, polystyrene, polyisobutylene, and polychloride Ethylene resin, polychloroethylene, polyvinyl chloride / polyvinyl acetate copolymers and other vinyl resins, acrylic resins such as polymethyl acrylate, polyethyl methacrylate, polypropylene alcohol, chlorinated polyethylene, Synthetic organic polymer of starting condensation products of thermosetting resins such as epoxy resin, lower aldehyde resin, rubber derivative, and phenol-formaldehyde resin. When the adhesive is used as the material of the recording layer, the amount of the adhesive is generally in the range of 1.01 to 50 times (weight ratio) for the pigment (phthalocyanine derivative), and preferably 0.1 to 5 times. Amount (weight ratio). The pigment concentration in the coating liquid prepared in this way is generally in the range of from 0.01 to 10% by weight, and preferably in the range of from 0.1 to 5% by weight. The coating method of the solvent is a spray method, a spin coating method, a dip coating method, a roll coating method, a blade coating method, a permeation and blade coating method, a screen printing method, and the like. The recording layer may be a single layer or a plurality of layers. The layer thickness of the recording layer is generally in the range of 10 to 500 nm, and more preferably in the range of 15 to 300 nm, and most preferably in the range of 20 to 100 nm. In order to control the thermal decomposition behavior of the recording layer when the laser light is irradiated and record the characteristics of the cylinder, the purpose of the invention is (19). Various thermal decomposition controlling agents can be added to the recording layer. For example, the method of adding a metal compound in European Patent No. 0600427 is very effective. In the metal compound, a metallocene derivative is preferred, and a dicyclopentadiene ferrous derivative is most preferable. In order to improve the light resistance of the recording layer, the recording layer may be made to contain various anti-fading agents. Generally, a singlet oxygen inhibitor is used as the anti-fading agent. As the singlet oxygen inhibitor, those published in published patent specifications and the like can be used. Specifically, for example, Japanese Patent Laid-Open No. 58-175693, Japanese Patent Laid-Open No. 59-81194, Japanese Patent Laid-Open No. 60- 1 83 87, Japanese Patent Laid-Open No. 60-1 95 86, Japanese Patent Laid-Open No. 60-1 9587, Japanese Patent Laid-Open No. 60-35054, Japanese Patent Laid-Open No. 60_36190, Japanese Patent Laid-Open No. 60-36 1 9 1, Japanese Patent Laid-Open No. 60-44554 Japanese Patent Laid-Open No. 60-44555, Japanese Patent Laid-Open No. 60-44389, Japanese Patent Laid-Open No. 60-44390, Japanese Patent Laid-Open No. 60-54892, Japanese Patent Laid-Open No. 60-54892 Publication No. 47069, Japanese Patent Application Laid-Open No. 2 009595, Japanese Patent Application Laid-Open No. 4-25492, Usopente No. 1-38680, Japanese Patent No. 6_26〇28, German Patent No. 350399, And the Japanese Chemical Society, October 10, 1992, page 1 141 and other recorders. Examples of singlet oxygen inhibitors are compounds represented by the following general formula (II). -21-584850 V. Description of the Invention (20) [化 2]

但，R21代表可含有取代基之光基，Q·代表陰離子。 一般式（II)中，R21—般碳已被取代之碳數1至8的烷基 ，或末取代之碳數1至6的烷基。烷基之取代基可以爲鹵 原子（例如，F、C1)、烷氧基（例如，甲氧基、乙氧基）、烷 基硫代氨基（例如，甲硫基、乙硫基）、醯基（例如，乙醯基 、丙醯基）、酸基（例如，乙酸基、丙酸基）、羥基、烷氧羰 基（例如，甲氧羰基、乙氧甲醯基）、鏈烯基（例如，乙烯基 、及芳基（例如，苯基、醯基）等。其中以鹵原子、烷氧基 、烷基硫代氨基、烷氧羰基較佳。Q·之陰離子實例則爲 C104-、AsF6·、BF4·、及 SbF6-。 表5爲一般式（II)之化合物實例。 ‘ -22- 584850 五、發明說明（21 )However, R21 represents a photo group which may contain a substituent, and Q · represents an anion. In the general formula (II), R21 is an alkyl group having 1 to 8 carbon atoms which is generally substituted with carbon, or an alkyl group having 1 to 6 carbon atoms which is unsubstituted. The substituent of the alkyl group may be a halogen atom (for example, F, C1), an alkoxy group (for example, methoxy group, ethoxy group), an alkylthioamino group (for example, methylthio group, ethylthio group), fluorene Group (e.g., ethenyl, propionyl), acid (e.g., acetate, propionyl), hydroxyl, alkoxycarbonyl (e.g., methoxycarbonyl, ethoxymethyl), alkenyl (e.g., , Vinyl, and aryl (eg, phenyl, fluorenyl), etc. Among them, halogen atoms, alkoxy groups, alkylthioamino groups, and alkoxycarbonyl groups are preferred. Examples of the anion of Q · are C104-, AsF6 ·, BF4 ·, and SbF6-. Table 5 is an example of the compound of general formula (II). '-22- 584850 V. Description of the invention (21)

[表5] 表5 化合物編號 R，il Q- II- 1 ch3 CIO/ II- 2 c,h5 c 1 o4- II 一 3 h-C,H7 CIO； II 一 4 n-C4H5 c i o4 I] 一 S n-CsHu c i Ο.Γ 11- 6 n-C4Hs SbFr II- 7 n-C4H9 BF,； II- 8 n - C4Hs A s F 前述單態氧抑制劑等褪色防止劑的使用量，相對於色素 (酞菁衍生物）之量，通常爲0.1至50質量百分率，若能爲 0.5至45重量百分率之範圔較佳，若能爲3至40重量百 分率之範圍則更佳，最好爲5至25重量百分率之範圍內 〇 爲了提升資訊再生時之反射率，應以鄰接記錄層方式設 置光反射層。光反射層之材料--光反射性物質應爲對雷射 光具有高反射率之物質，如Mg、Se、Y、Ti、Zr、Hf、V 、Nb、Ta、Cr、Mo、W、Μη、Re、Fe、Co、Ni、Ru、Rh 、Pd、Ir、Pt、Cu、Ag、Au、Zn、Cd、A1、Ga、In、Si、 Ge、Te、Pb、Po、Sn、Bi等金屬及半金屬、或不銹鋼。 可單獨使用此類物質，或採用2種以上之組合、或使用合 金。其中以Cr、Ni、Pt、Cu、Ag、Au、A1及不銹鋼爲佳 。若爲Au金屬、Ag金屬、A1金屬或其合金更佳，最佳則 是Ag金屬、A1金屬或其合金。光反射層可以利用蒸鍍、 -23- 584850 五、 發明說明（22) 濺 噴、或離子電鍍法等在 基 板或記錄層上形成前述 光 反射 性物質。光反射層之一般 層 厚爲10至300nm之範 圍 5 最 好 爲50至200nm之範圍內丨 0 光反射層及記錄層上， 最 好設置保護層，提供記 錄 層 等 之 物理及化學上之保護。 又 ，和製造DVD-R型光 資 訊記 錄 媒體時相同，亦即使記 錄 層向內貼合二片基板時 就 不 一 定需要設置保護層。保 護 層之材料可以爲Zn-SiC 丨2、 ZnS SiO、Si02、MgF2、Sn02 、Si3N4等無機物質、熱 可 塑 性 樹 脂、UV硬化性樹脂等 有 機物質。保護層可以使 用 黏 結 劑 ，將利用塑膠擠壓加工 獲 得之薄膜層合於反射層 上 〇 亦 可 以真空蒸鍍、噴濺、塗 布 等方法來處理。另外， 熱 可 塑 性 樹脂、熱硬化性樹脂時 將其溶解於適當的溶劑 內 調 製 成 塗布液後，實施塗布液之塗敷並使其乾燥即可 形 成 〇 UV硬化性樹脂時，可直 接 使用、或將其溶解於適 當 的 溶 劑 內調製成塗布液後，實 施 塗布液之塗敷並以UV 光 照 射 使 其硬化即可形成。這些 塗 布液中亦可配合目的添 加 帶 電 防 止劑、氧化防止劑、UV 吸收劑等各種添加劑。 保 護 層 之 一般層厚爲0.1 z/m至 1 m m的範圍內。利用前述 步 驟 可以製造基板上設有記錄 層 、光反射層、及保護層 或 者 基 板上設有光反射層、記 錄 層、及保護層的層疊體 〇 [實施例] 其次，以實施例進行本 發 明之更詳細說明，但本 發 明 並 不 限於以下之實施例。 - 24-[Table 5] Table 5 Compound No. R, il Q- II- 1 ch3 CIO / II- 2 c, h5 c 1 o4- II-3 hC, H7 CIO; II-4 n-C4H5 ci o4 I]-Sn -CsHu ci 〇.Γ 11- 6 n-C4Hs SbFr II- 7 n-C4H9 BF ,; II- 8 n-C4Hs A s F The amount of cyanine derivative) is usually 0.1 to 50% by mass. It is better if it can be in the range of 0.5 to 45% by weight. It is more preferable if it can be in the range of 3 to 40% by weight. The most preferable is 5 to 25% by weight. Within the percentage range, in order to improve the reflectance at the time of information reproduction, a light reflecting layer should be provided adjacent to the recording layer. Material of the light reflecting layer-The light reflecting material should be a material with high reflectivity to laser light, such as Mg, Se, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mη, Re, Fe, Co, Ni, Ru, Rh, Pd, Ir, Pt, Cu, Ag, Au, Zn, Cd, A1, Ga, In, Si, Ge, Te, Pb, Po, Sn, Bi and other metals and Semi-metal, or stainless steel. These substances can be used alone, or a combination of two or more, or an alloy. Among them, Cr, Ni, Pt, Cu, Ag, Au, A1 and stainless steel are preferred. Au metal, Ag metal, A1 metal, or an alloy thereof is more preferable, and Ag metal, A1 metal or an alloy thereof is most preferable. The light-reflective layer can be formed on a substrate or a recording layer by vapor deposition, -23-584850 V. Description of the Invention (22) Sputtering, or ion plating method. The general thickness of the light reflection layer is in the range of 10 to 300 nm. 5 It is preferably in the range of 50 to 200 nm. 0 It is best to provide a protective layer on the light reflection layer and the recording layer to provide physical and chemical protection of the recording layer and the like. . In addition, it is the same as when manufacturing a DVD-R optical information recording medium, and even if the recording layer is bonded to two substrates inward, a protective layer is not necessarily required. The material of the protective layer may be inorganic materials such as Zn-SiC 丨 2, ZnS SiO, SiO2, MgF2, Sn02, Si3N4, organic materials such as thermoplastic resins, and UV-curable resins. The protective layer can use an adhesive, and the film obtained by plastic extrusion processing can be laminated on the reflective layer. It can also be processed by vacuum evaporation, spraying, coating and other methods. In addition, when a thermoplastic resin or a thermosetting resin is dissolved in an appropriate solvent to prepare a coating solution, the coating solution is applied and dried to form a UV curable resin, which can be used directly, or It can be formed by dissolving it in a suitable solvent to prepare a coating liquid, then applying the coating liquid and curing it by irradiation with UV light. Various additives such as a charging inhibitor, an oxidation inhibitor, and a UV absorber can be added to these coating liquids for the purpose. The general layer thickness of the protective layer is in the range of 0.1 z / m to 1 mm. The foregoing steps can be used to manufacture a laminated body provided with a recording layer, a light reflecting layer, and a protective layer on a substrate or a light reflecting layer, a recording layer, and a protective layer on a substrate. [Examples] Next, the present invention is carried out by examples. Although it will be described in more detail, the present invention is not limited to the following examples. - twenty four-

584850 五、發明說明（23 ) [實施例1] 將化合物（1-1)溶解於2,2,3,3，-四氟丙醇，獲得記錄層形 成用塗布液（濃度：1重量百分率）。在利用射出成型形成螺 旋狀導引槽（軌距：0.4#m、槽寬：0.2//m、槽深：〇.〇8/zm)之 聚碳酸酯基板（直徑：120mm、厚度：0.6mm)的導引槽側表面 ’以旋轉塗布法實施前述塗布液之塗敷，形成記錄層（厚 度（導引槽內）：約80nm)。 其次，在記錄層上實施銀之噴濺，形成厚度約lOOnm的 光反射層。然後，在光反射層上塗敷UV硬化性樹脂 (SD318、大日本INK化學工業（株）製），照射紫外線使其 硬化，形成層厚7//m之保護層。 利用以上之步驟，可以得到本發明之光碟。 [實施例2〜17] 除了將實施例1中之化合物（1-1)變更爲表6所示之化合 物（使用量未變）以外，其餘皆相同，製造本發明之光碟。 [比較例1〜7] 除了將實施例1中之化合物（I-1)變更下面所示比較用色 素化合物A至G(使用量未變）以外，其餘皆相同，製造比 較用光碟。 [化3] 比較用色素化合物A:日本特開平7-304256號公報實施 例之化合物 -25- 584850 五、發明說明（24 )584850 V. Description of the invention (23) [Example 1] Compound (1-1) was dissolved in 2,2,3,3, -tetrafluoropropanol to obtain a coating solution for forming a recording layer (concentration: 1% by weight) . Polycarbonate substrate (diameter: 120mm, thickness: 0.6mm) with spiral guide grooves (gauge: 0.4 # m, groove width: 0.2 // m, groove depth: 0.08 / zm) formed by injection molding The guide groove side surface ′) is coated with the coating liquid by a spin coating method to form a recording layer (thickness (in the guide groove): about 80 nm). Next, a silver sputtering was performed on the recording layer to form a light reflecting layer having a thickness of about 100 nm. Then, a UV-curable resin (SD318, manufactured by Dainippon Ink Chemical Industry Co., Ltd.) was coated on the light-reflective layer, and then cured by irradiation with ultraviolet rays to form a protective layer having a layer thickness of 7 // m. With the above steps, the optical disc of the present invention can be obtained. [Examples 2 to 17] Except that the compound (1-1) in Example 1 was changed to the compound shown in Table 6 (the amount used was not changed), the rest were the same, and the optical disc of the present invention was manufactured. [Comparative Examples 1 to 7] Except that the compound (I-1) in Example 1 was changed to the comparative pigment compounds A to G shown below (the amount used was not changed), the rest were the same, and a comparative optical disc was manufactured. [Compound 3] Pigment compound A for comparison: Compound of Example of Japanese Patent Application Laid-Open No. 7-304256 -25-584850 5. Explanation of the invention (24)

[化4] 比較用色素化合物B:日本特開平8-1 27 1 74號公報實施 例1之化合物Comparative pigment compound B: Japanese Unexamined Patent Publication No. 8-1 27 1 74 Compound of Example 1

Et EtEt Et

[化5] 比較用色素化合物C:日本特開平1 1 -334207號公報實施 例1之化合物Comparative pigment compound C: Compound of Example 1 of Japanese Patent Application Laid-Open No. 1 1-334207

[化6] 比較用色素化合物D:日本特開2000-228028號公報實施 例之化合物 -26- 584850 五、發明說明（25 )[Compound 6] Pigment compound D for comparison: Compound of Example of Japanese Patent Application Laid-Open No. 2000-228028 -26-584850 5. Explanation of the invention (25)

比較用色素化合物E:日本特開200 1 -287465號公報實施 例5之化合物Comparative pigment compound E: Compound of Example 5 of JP-A-200-287465

[化8] 比較用色素化合物F:日本特開200 1 -287465號公報實施 例6之化合物 -27- 584850 五、發明說明（26 )Comparative pigment compound F: Japanese Unexamined Patent Publication No. 200 1-287465 Example 6 Compound -27- 584850 V. Description of the invention (26)

[化9] 比較用色素化合物G:日本特開2〇〇1_287465號公報實施 例7之化合物Comparative pigment compound G: Compound of Example 7 of JP-A No. 2000-287465

(光碟之評估1) 利用振盪波長405nm之藍紫色半導體雷射光，以線速度 3.5111/秒，將141^£?1^信號記錄於實施例1〜17及比較例 1〜7製作的各光碟上後，執行記錄信號之再生。以最適功 率檢測調變度（C/N(載波雜訊比））及槽反射率。並將這些光 碟在溫度80°C、濕度85%之強制條件下放置100日後，測 -28- 584850 五、發明説明（27 ) 量調變度’評估記錄信號之劣化情形。利用PULSTEC工 業（株）製DDU 1 000製實施記錄及記錄特性評估。評估結果 如表6所示。 表6中，調變度B爲置於強制條件前的調變度、調變度 A爲置於強制條件後的調變度。 -29- 584850 五、發明說明（28 )[表6] 表6 記錄層之色素 化合物 末記錄部之 反射率(％) C/N(dB) 調變度B 調變度A 實施例1 (1-1) 63 60 52 50 實施例2 (1-2) 64 55 55 53 實施例3 (1-7) 59 54 50 48 實施例4 (Ml) 58 59 49 48 實施例5 (1-12) 61 56 50 49 實施例6 (1-23) 60 52 50 48 實施例7 (1-27) 57 53 45 44 實施例8 (1-28) 52 53 47 42 實施例9 (1-29) 65 57 55 54 實施例10 (1-30) 59 53 48 43 實施例11 (1-32) 58 52 47 43 實施例12 (1-34) 60 52 48 45 實施例13 (1-39) 66 61 57 56 實施例14 (1-40) 65 61 56 55 實施例15 (1-43) 61 62 57 56 實施例16 (1-44) 60 51 50 48 實施例17 (1-45) 64 53 54 52 比較例1 (A) 44 43 43 結晶化：無法測量 比較例2 (B) 51 42 45 結晶化：無法測量 比較例3 (C) 48 43 45 15 比較例4 (D) 36 44 39 結晶化：無法測量 比較例5 (E) 52 44 45 40 比較例6 (F) 50 48 41 結晶化：無法測量 比較例7 (G) 39 45 40 結晶化：無法測量 -30- 584850 五、發明說明（29 ) 由表6結果可知，具有含本發明特徵之酞菁衍生物的記 錄層之光碟（實施例1〜17)，和具有含比較化合物A〜G之 記錄層的光碟（比較例1〜7)相比，對前述藍紫色半導體雷 射光具有較高反射率及高調變度，且置於強制條件下時， 調變度的變化亦很小。因此，使用本發明之酞菁衍生物， 可以獲得對短波長雷射光具有高記錄物性、且對高溫-高 濕度具有高儲存安定性的光碟。 [實施例18] 將化合物（1-3)溶解於二丁醚，獲得記錄層形成用塗布液 (濃度：1重量百分率）。在利用射出成型形成螺旋狀導引槽（ 軌距：1 ·〇 μ m、槽寬：0.4 // m、槽深：0.15 // m)之聚碳酸酯基 板（直徑：120mm、厚度：0.6mm)的導引槽側表面，以旋轉塗 布法實施前述塗布液之塗敷，形成記錄層（厚度（導引槽內）: 約 1 7 0 n m) 〇 其次，在記錄層上實施銀之噴濺，形成厚度約lOOnm的 光反射層。然後，在光反射層上塗敷UV硬化性樹脂 (SD318、大日本INK化學工業（株）製），照射紫外線使其 硬化，形成層厚7 // m之保護層。 利用以上之步驟，可以得到本發明之光碟。 (光碟之評估2) 利用振盪波長780nm之半導體雷射光，以線速度1.4m/ 秒，將14T-EFM信號記錄於實施例18製作之光碟上後， 以相同半導體雷射光執行記錄信號之再生，觀測再生信號 -31 - 584850 五、發明說明（3〇 ) 波形。此外，利用振盪波長405nm之半導體雷射光，以線 速度1.4m/秒，將14T-EFM信號記錄於同一光碟後，再以 相同之半導體雷射光實施記錄信號之再生，觀測再生信號 波形。結果，不論使用何種波長之雷射光執行記錄時，都 可觀測到同樣淸晰之再生信號波形。又，以振盪波長 780nm之半導體雷射光記錄之信號，以振盪波長405nm之 半導體雷射光再生時，可觀測到淸晰之再生信號波形。 [發明之功效] 利用本發明之光資訊記錄方法及光資訊記錄媒體，可W 解決傳統技術之問題點，且具有優良之記錄特性，同時’ 在高溫及高濕度之條件下，亦可安定而長期地儲存資訊° 此外，依據本發明之光資訊記錄方法及光資訊記錄媒體’ 適當選擇記錄層使用之酞菁衍生物，可以實現以波長 450nm以下之短波長雷射光、以及傳統CD-R用之波長 750〜8 50nm雷射光兩者進行高密度記錄及再生。 -32-(Evaluation of Optical Disc 1) Using a blue-violet semiconductor laser light with an oscillation wavelength of 405 nm, a signal of 141 ^? 1 ^ was recorded on each of the optical discs produced in Examples 1 to 17 and Comparative Examples 1 to 7 at a linear velocity of 3.5111 / sec. After that, the recording signal is reproduced. The modulation (C / N (Carrier-to-Noise Ratio)) and slot reflectivity are detected with the optimum power. These discs were placed under forced conditions of temperature 80 ° C and humidity 85% for 100 days, and then measured -28- 584850. V. INTRODUCTION (27) Measured Modulation Degree 'to evaluate the degradation of recorded signals. Records and evaluation of the recording characteristics were performed using the DDU 1,000 system manufactured by PULSTEC Industrial Co., Ltd. The evaluation results are shown in Table 6. In Table 6, the degree of modulation B is the degree of modulation placed before the compulsory condition, and the degree of modulation A is the degree of modulation placed under the compulsory condition. -29- 584850 V. Description of the invention (28) [Table 6] Table 6 Reflectance (%) C / N (dB) Modulation degree B Modulation degree A in the recording layer of the pigment compound at the end of the recording layer Example 1 (1 -1) 63 60 52 50 Example 2 (1-2) 64 55 55 53 Example 3 (1-7) 59 54 50 48 Example 4 (Ml) 58 59 49 48 Example 5 (1-12) 61 56 50 49 Example 6 (1-23) 60 52 50 48 Example 7 (1-27) 57 53 45 44 Example 8 (1-28) 52 53 47 42 Example 9 (1-29) 65 57 55 54 Example 10 (1-30) 59 53 48 43 Example 11 (1-32) 58 52 47 43 Example 12 (1-34) 60 52 48 45 Example 13 (1-39) 66 61 57 56 Implementation Example 14 (1-40) 65 61 56 55 Example 15 (1-43) 61 62 57 56 Example 16 (1-44) 60 51 50 48 Example 17 (1-45) 64 53 54 52 Comparative Example 1 (A) 44 43 43 Crystallization: Unable to measure Comparative Example 2 (B) 51 42 45 Crystallization: Unable to measure Comparative Example 3 (C) 48 43 45 15 Comparative Example 4 (D) 36 44 39 Crystallization: Unable to measure Comparative Example 5 (E) 52 44 45 40 Comparative Example 6 (F) 50 48 41 Crystallization: Unable to measure Comparative Example 7 (G) 39 45 40 Crystallization: Unable to measure -30- 584850 V. Invention (29) From the results in Table 6, it can be seen that an optical disc having a recording layer containing a phthalocyanine derivative characteristic of the present invention (Examples 1 to 17) and an optical disc having a recording layer containing comparative compounds A to G (Comparative Example 1) ~ 7) Compared with the above, the blue-violet semiconductor laser light has higher reflectivity and high modulation degree, and when placed under a forced condition, the change of the modulation degree is also small. Therefore, by using the phthalocyanine derivative of the present invention, an optical disc having high recording physical properties with respect to short-wavelength laser light and high storage stability with respect to high temperature and high humidity can be obtained. [Example 18] The compound (1-3) was dissolved in dibutyl ether to obtain a coating liquid for forming a recording layer (concentration: 1% by weight). Polycarbonate substrate (diameter: 120mm, thickness: 0.6mm) with spiral guide grooves (gauge: 1.0 μm, groove width: 0.4 // m, groove depth: 0.15 // m) formed by injection molding ) The guide groove side surface is coated with the coating solution by spin coating to form a recording layer (thickness (in the guide groove): about 170 nm) 〇 Second, a silver spray is performed on the recording layer. To form a light reflecting layer having a thickness of about 100 nm. Then, a UV-curable resin (SD318, manufactured by Dainippon Ink Chemical Industry Co., Ltd.) was coated on the light-reflective layer, and then cured by irradiation with ultraviolet rays to form a protective layer with a thickness of 7 // m. With the above steps, the optical disc of the present invention can be obtained. (Evaluation of optical disc 2) After recording the 14T-EFM signal on the optical disc produced in Example 18 at a linear velocity of 1.4 m / sec using semiconductor laser light with an oscillation wavelength of 780 nm, the recorded signal was reproduced with the same semiconductor laser light. Observe the regeneration signal -31-584850 V. Description of the invention (30) Waveform. In addition, the semiconductor laser light with an oscillation wavelength of 405 nm was used to record the 14T-EFM signal on the same optical disc at a linear velocity of 1.4 m / s, and then the recorded signal was reproduced with the same semiconductor laser light, and the waveform of the reproduced signal was observed. As a result, the same clear reproduction signal waveform can be observed regardless of the wavelength of laser light used for recording. In addition, when a signal recorded with a semiconductor laser light with an oscillation wavelength of 780 nm is reproduced with a semiconductor laser light with an oscillation wavelength of 405 nm, a clear reproduction signal waveform can be observed. [Effect of the invention] The optical information recording method and the optical information recording medium of the present invention can solve the problems of the traditional technology and have excellent recording characteristics. At the same time, it can be stable under the conditions of high temperature and high humidity. Long-term storage of information ° In addition, according to the optical information recording method and the optical information recording medium according to the present invention, the phthalocyanine derivative used in the recording layer is appropriately selected to realize short-wavelength laser light having a wavelength of 450 nm or less and conventional CD-R applications. High-density recording and reproduction are performed with both laser light having a wavelength of 750 to 8 and 50 nm. -32-

Claims (1)

584850 六、申請專利範圍 1. 一種光資訊記錄方法，係利用波長45 Onm以下之雷射光 照射而將資訊記錄於光資訊記錄媒體，其特徵爲：前述 光資訊記錄媒體之記錄層含有酞菁衍生物 (phthalocyanine) 〇 2. —種光資訊記錄媒體，其特徵爲：使用如申請專利範圍 第1項之光資訊記錄方法。 -33-584850 6. Scope of patent application 1. An optical information recording method, which records information on an optical information recording medium by irradiating with laser light having a wavelength below 45 Onm, characterized in that the recording layer of the aforementioned optical information recording medium contains a phthalocyanine derivative物 (phthalocyanine) 〇2. An optical information recording medium characterized by using the optical information recording method as described in item 1 of the scope of patent application. -33-