WO2006118266A1 - Support d’enregistrement optique, cible de mouchetage, et colorant chélate azo-métallique - Google Patents

Support d’enregistrement optique, cible de mouchetage, et colorant chélate azo-métallique Download PDF

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Publication number
WO2006118266A1
WO2006118266A1 PCT/JP2006/309023 JP2006309023W WO2006118266A1 WO 2006118266 A1 WO2006118266 A1 WO 2006118266A1 JP 2006309023 W JP2006309023 W JP 2006309023W WO 2006118266 A1 WO2006118266 A1 WO 2006118266A1
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Prior art keywords
group
recording
alkyl group
dye
recording medium
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PCT/JP2006/309023
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English (en)
Japanese (ja)
Inventor
Naoyuki Uchida
Hiroyuki Hoshino
Atsushi Komura
Naoki Koda
Akihiko Imagawa
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Mitsubishi Kagaku Media Co., Ltd.
Furuya Metal Co., Ltd.
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Application filed by Mitsubishi Kagaku Media Co., Ltd., Furuya Metal Co., Ltd. filed Critical Mitsubishi Kagaku Media Co., Ltd.
Publication of WO2006118266A1 publication Critical patent/WO2006118266A1/fr

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    • 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
    • G11B7/004—Recording, reproducing or erasing methods; Read, write or erase circuits therefor
    • G11B7/0045—Recording
    • G11B7/00455—Recording involving reflectivity, absorption or colour changes
    • 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
    • G11B7/2407—Tracks or pits; Shape, structure or physical properties thereof
    • G11B7/24085—Pits
    • 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
    • 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
    • G11B7/2467—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 azo-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
    • G11B7/246—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
    • G11B7/247—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 methine or polymethine dyes
    • G11B7/2472—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 methine or polymethine dyes cyanine

Definitions

  • Optical recording media Optical recording media, sputtering targets, and azo metal chelate dyes
  • the present invention relates to an optical recording medium that can be recorded and reproduced by a laser beam, and to a sputtering target and an azo metal chelate dye used in the optical recording medium. More specifically, the present invention has good recording characteristics at a wide recording linear velocity.
  • the present invention also relates to an optical recording medium for high-density recording or high-speed recording that has excellent light resistance, and a sputtering target and an azo metal chelate dye used for the optical recording medium.
  • optical recording media having a recording layer containing an organic dye such as CD-R and DVD-R
  • optical recording media having a recording layer containing an organic dye are relatively inexpensive and compatible with optical recording media dedicated to reproduction. In particular, it is widely used.
  • current optical recording media have a recording layer made of an alloy thin film layer, an organic dye-containing thin film layer, or the like on a transparent disk substrate, and a reflective layer on the opposite side of the substrate through the recording layer. It has a laminated structure having a protective layer covering these recording layers and reflective layers, and performs recording / reproduction with a laser beam through a substrate.
  • a metal or alloy thin film is generally used (see Patent Document 1), and gold, silver, a silver alloy or the like is often used among them.
  • Silver, which is the center of these alloys, has been put to practical use because it is relatively inexpensive and provides high reflectivity.
  • Patent Document 2 describes a reflective layer containing a silver-copper alloy or a silver-paradium mu copper alloy.
  • Patent Document 3 describes that a reflective layer is provided with an alloy thin film containing less than 40% silver on copper.
  • Patent Document 4 describes a copper alloy reflective layer and target containing Ag and Ti. While doing so, they Each of these is an optical recording medium having a low linear velocity recording speed of less than 2. OmZs. Further, the present invention relates to an optical recording medium having a low recording density.
  • Patent Document 1 Japanese Patent Publication No. 7-105065
  • Patent Document 2 JP-A-4-49539
  • Patent Document 3 Japanese Patent Laid-Open No. 4-364240
  • Patent Document 4 International Publication No. WO2002Z021524 Pamphlet
  • an object of the present invention is an optical recording medium for high-density recording or high-speed recording, has good recording characteristics at a wide recording linear velocity, and is excellent in “practical” light resistance.
  • An optical recording medium is provided.
  • Another object of the present invention is to provide an optical recording medium suitable for high-speed recording. Another object of the present invention is to provide a sputtering target for producing a reflection layer of an optical recording medium excellent in light resistance and recording characteristics.
  • Another object of the present invention is to provide a predetermined organic dye used in a recording layer of an optical recording medium suitable for high-speed recording.
  • the present inventors have found the following items and completed the present invention.
  • the dye retention before and after the light resistance test when the organic dye forming the recording layer is formed as a single layer is 80% or more, more preferably 90% or more in the recording layer used in the low-speed recording medium.
  • the composition of the dye is adjusted so that it is 70% or less, which is not good enough for practical use.
  • a reflective layer having a composition that is a differential value of reflectivity R with respect to the wavelength of the reflective layer in air dRZd (% / nm) force is 3 or less in the wavelength range of 300 nm to 500 nm. It has been found that by these combinations, an excellent optical recording medium can be obtained not only at high speed recording but also at a wide recording linear velocity, and excellent in “practical” light resistance.
  • the gist of the present invention is to have a recording layer made of an organic dye and a reflective layer containing a metal on a substrate having concentric or spiral grooves, and the shortest mark length is less than 0. Or 35.
  • the track pitch of the guide groove on the substrate is 0. or less
  • the groove width is 0. or less
  • the thickness of the recording layer in the groove Is less than 70 nm
  • the organic dye single layer forming the recording layer has a dye retention power defined by the following definition of the light irradiation condition shown in ISO-105-B02.
  • the present invention resides in an optical recording medium.
  • Another gist of the present invention is that a recording layer containing at least an organic dye and a reflective layer containing a metal are provided on a substrate having concentric or spiral grooves, and the shortest mark length is In an optical recording medium on which recording is performed at a recording linear velocity of 35.
  • the recording layer contains an azo compound represented by the following general formula (1) and Zn as an organic dye.
  • the optical recording medium comprises at least an azo metal chelate dye composed of the above metal ions.
  • R 1 is a hydrogen atom or an ester group represented by CO R 3 (where R 3 is
  • a linear or branched alkyl group or a cycloalkyl group is represented. ).
  • R 2 represents a linear or branched alkyl group.
  • At least one of X 1 and X 2 is an NHSO Y group (where Y is a straight chain substituted with at least two fluorine atoms or
  • R 4 and R 5 each independently represents a hydrogen atom, a linear or branched alkyl group, or a linear or branched alkoxy group.
  • R 6 , R 7 , R 8 and R 9 each independently represent a hydrogen atom or an alkyl group having 1 or 2 carbon atoms.
  • the NHSO Y basic force H + is removed.
  • Another aspect of the present invention is that the reflection of the optical recording medium having a recording layer containing at least an organic dye and a reflective layer containing a metal on a substrate having concentric or spiral grooves.
  • a sputtering target for use in the production of a layer characterized in that it has at least a material force represented by the following composition B.
  • X represents at least one element selected from the group consisting of Zn, Al, Pd, In, Sn, Cr, and Ni, provided that the total amount of Cu, Ag, and X is 100 at% or less.
  • Another aspect of the present invention is to provide a substrate having concentric or spiral grooves, An organic recording medium having a recording layer containing at least an organic dye and a reflective layer containing a metal, wherein the shortest mark length is less than 0, or 35.
  • An azo metal chelate dye used as a dye comprising an azo compound represented by the above general formula (1) and a metal ion of Zn.
  • the present invention has excellent recording characteristics at a wide recording linear velocity, and has excellent "practical" light resistance.
  • An optical recording medium is provided.
  • an optical recording medium suitable for high-speed recording is provided.
  • a sputtering target for producing a reflective layer of an optical recording medium having excellent light resistance and recording characteristics.
  • the present invention also provides an azo metal chelate dye used for a recording layer of an optical recording medium suitable for high-speed recording.
  • FIG. 1 is a cross-sectional view schematically showing a configuration of an optical recording medium according to an embodiment of the present invention.
  • FIGS. 2 (a) and 2 (b) are cross-sectional views schematically showing a configuration of an optical recording medium according to an embodiment of the present invention.
  • Fig. 3 is a graph showing the wavelength distribution of the refractive index (n) of the main metal material, and Fig. 3 (b) is the wavelength of the extinction coefficient (k) of the main metal material.
  • (C) is a graph showing the wavelength distribution of reflectance in air calculated for a reflective layer (thickness 120 nm) formed using main metal materials.
  • FIGS. 4 (a) to 4 (d) are diagrams showing the measurement results of recording characteristics and “practical” light resistance of the optical recording media of Example 2 and Comparative Example 1.
  • Fig. 4 (a) is a graph showing the measurement result of the recording power margin
  • Fig. 4 (b) is a graph showing the measurement result of the asymmetry margin
  • Fig. 4 (c) is a measurement result of the bottom jitter before and after the light resistance test.
  • Fig. 4 (d) is a graph showing the measurement results before and after the PImax light resistance test.
  • FIGS. 5 FIGS.
  • FIGS. 5 (a) to (d) are diagrams showing measurement results of recording characteristics and “practical” light resistance of the optical recording media of Example 3 and Comparative Example 2
  • Fig. 5 (a) is a graph showing the measurement result of the recording power margin
  • Fig. 5 (b) is a graph showing the measurement result of the asymmetry margin
  • Fig. 5 (c) shows the measurement result of the bottom jitter before and after the light resistance test
  • Fig. 5 (d) is a graph showing the measurement results before and after the PImax light resistance test.
  • FIGS. 6 (a) and 6 (b) are diagrams showing measurement results of the recording characteristics of the optical recording media of Example 4 and Comparative Example 3, and FIG. 6 (a) shows the recording power.
  • Figure 6 (b) is a graph showing the measurement result of the asymmetry margin.
  • FIGS. 7 (a) to 7 (d) are diagrams showing the recording characteristics and “practical” light resistance measurement results of the optical recording medium of Comparative Example 4, and FIG. Fig. 7 (b) is a graph showing the measurement result of the recording power margin, Fig. 7 (b) is a graph showing the measurement result of the asymmetry margin, Fig. 7 (c) is a graph showing the measurement result of the bottom jitter before and after the light resistance test, and Fig. 7 (d) ) Is a graph showing the measurement results before and after the PImax light resistance test.
  • FIG. 8 is a graph showing the wavelength distribution of the reflectance of a single metallic reflective layer used in each example and comparative example.
  • FIGS. 9A to 9D are graphs showing the d RZ values of the single metallic reflective layer used in each example and comparative example.
  • Fig. 9 (a) shows a single Cu reflective layer (Example 1)
  • Fig. 9 (b) shows a single Au reflective layer (Example 2)
  • Fig. 9 (c) shows a single Ag reflective layer (Comparative Example 1).
  • FIG. 9 (d) shows the values of the single A1 reflective layer (Example 5), respectively.
  • FIG. 10 shows the reflectivity of CuAg and CuAg Pd obtained in Example 6.
  • 12. 8 is a graph showing the measurement results of 12. 9 0.7 together with the measurement results of Ag, Au, and Cu obtained in Example 5.
  • Fig.11 [Fig.11] Fig.11 (a) and Fig.11 (b) show the dRZd values of CuAg and CuAg Pd, respectively.
  • FIG. 12 is a graph showing the relationship between the Ag content obtained in Example 6 and the maximum value of dRZd ⁇ in the wavelength region of 300 to 500 nm.
  • Figure 13 shows the relationship between the X value (Ag content) and the bottom jitter value in Cu Ag when light resistance is assumed to have a nearly linear correlation with the Ag content. It is a graph.
  • FIGS. 14 (a) and 14 (b) are graphs showing the results of the light resistance test in Examples 6 to 8, and FIG. 14 (a) shows the xenon irradiation time, the jitter value, and the like.
  • Fig. 14 (b) is a graph showing the relationship between xenon irradiation time and PI error.
  • Fig. 15 Fig. 15 (a) and Fig. 15 (b) are both graphs showing the results of storage stability tests at high temperatures and high humidity in Examples 6 to 8, and Fig. 15 (a) shows jitter values.
  • Figure 15 (b) is a graph showing the PI error over time.
  • the present invention first, on a substrate having concentric or spiral grooves, at least a recording layer made of an organic dye and a reflective layer containing a metal, and the shortest mark length is less than 0.4 ⁇ m. Or 35.
  • the track pitch of the guide groove on the substrate is 0.8 m or less
  • the groove width is 0.4 ⁇ m or less
  • first optical recording medium of the present invention It is 70% or less in scale 5 (light resistance test), and the differential value dRZd (% Znm) of reflectance R with respect to wavelength ⁇ in the air of the reflective layer is in the wavelength range of 300 nm to 500 nm.
  • optical recording medium characterized by 3 or less (hereinafter sometimes referred to as “first optical recording medium of the present invention”).
  • the present inventors have intensively studied to provide an optical recording medium for high-density recording or high-speed recording and having good recording characteristics at a wide recording linear velocity.
  • “high density recording” in the present invention is premised on recording with a minimum mark length of less than 0.4 m. This is because the problem to be solved by the present invention is a particularly remarkable force in an optical recording medium that is densified by shortening the recording mark and narrowing the track pitch. In “high density recording”, it is important to reduce the formation of excessive recording areas.
  • high-speed recording means recording at a recording linear velocity of 35.
  • OmZs or more for example, DV D, the DVD speed is 1 ⁇ , that is, the linear velocity of 3.5mZs is 10 times or more. (Recording at rotational speed).
  • the recording of the first optical recording medium of the present invention corresponds to "high-speed recording”
  • the above-mentioned “high-density recording” that is, the minimum mark length of less than 0.4 m is always required. It does not have to be a record of. However, even in this case, the shortest mark length is usually less than 0.5 m, preferably 0.44 / zm. In the following, it is desirable to perform recording at a density in the range of 0.4 m or less.
  • dye layer there are suitable dyes or combinations of dyes as dyes used in the recording layer (dye layer). That is, using a dye having a dye retention of 70% or less after the light resistance test of a single recording layer, or mixing a "dye having poor light resistance” and a “dye having good light resistance” Mixing so that the dye retention before and after the light resistance test of the recording layer is 70% or less.
  • the present inventors further investigated the new problem.
  • the differential value dRZd (% Znm) of the reflectance R with respect to the wavelength of the reflective layer in the air is set to 3 or less in the wavelength range of 300 nm to 500 nm.
  • I was able to solve this problem. That is, “practical” light resistance can be improved.
  • the “practical” light resistance in the present invention means that the light resistance of a single recording layer is not good enough, but it is
  • a recording layer made of at least an organic dye and a reflective layer containing a metal are provided, and the shortest mark length is 0. Or 35.
  • the groove width on the substrate is 0. or less, and the recording layer thickness in the groove is 70 nm or less.
  • dRZd % Znm
  • % Znm the differential value of reflectance R with respect to the wavelength of the reflective layer in the air is in the wavelength range of 300 nm to 500 nm. It is characterized by being 3 or less.
  • “dye retention” means the ratio of absorbance before and after the light resistance test at the maximum absorption wavelength of the coating film of the organic dye single layer forming the recording layer in the wavelength region of 300 to 800 nm, that is, ⁇ (Absorbance after test) / (Absorbance before test) ⁇ X 100 (%).
  • the track pitch can be increased to 0.8 ⁇ m or less, and a sufficient push-pull signal amplitude can be secured. Therefore, as described above, when recording is performed by rotating the disk at high speed, it is possible to stably track the groove.
  • the groove width is usually not less than 0, more preferably not less than 0, in order to ensure a sufficient push-pull signal amplitude.
  • the track pitch is usually 0.2 ⁇ m or more, preferably 0.4 ⁇ m or more.
  • the recording layer thickness in the groove is 70 nm or less, formation of an excessive recording portion is suppressed, and good “high density recording” and “high speed recording” with less crosstalk are possible. It becomes.
  • the film thickness of the recording layer in the groove is usually 5 nm or more, more preferably lOnm or more, and further preferably 20 nm or more.
  • the recording laser light irradiation time for recording the shortest mark length 3T mark in the example of the present embodiment
  • the bottom jitter minimum jitter value
  • This “recording the shortest mark length with a shortened pulse so that the irradiation time is less than 8 ns” means, for example, that the rise time of the semiconductor laser in the DVD wavelength region is around 4 ns. How severe the recording conditions are.
  • the irradiation pulse width of the laser for 3T mark length recording used in each of the examples and comparative examples described later is 7.9 ns for 10 ⁇ speed recording (35 mZs) and 16 ⁇ speed recording (56. OmZs), respectively. And 6.5ns.
  • “good recording is possible at a wide recording linear velocity” means 3.5. From mZs to approximately 70mZs (for DVD, for example, 1x speed recording of DVD (3.5mZs) to about 20x speed recording (70mZs)) can be recorded without bottom jitter exceeding 9%, or commercially available This means that the reproduction apparatus has an error rate that is good enough to cause no reproduction problems.
  • the jitter value is a good index for evaluating the recording quality. For example, in the currently known range, it is usually 8.0% or less, more preferably 7% or less, more preferably 6 in 3.5mZs to 28mZs (for example, 1x speed recording to 8x speed recording in DVD). In general, it is determined to be particularly good when recording capable of obtaining a bottom jitter of less than% is possible.
  • optical mode recording is known to have a high reaction rate, and in principle, the reaction can be terminated in the order of fsec to psec. If the reaction is completed in this time order, it is highly possible that interference between adjacent marks does not occur in consideration of the rotational speed force of the disc.
  • the above "dye having poor light resistance” corresponds to a state force excited by light, a probable force of causing a so-called “non-radiative transition", and a dye compound.
  • (1) not only has a strong absorption band that is considered to involve ⁇ - ⁇ * transitions or charge transfer transitions in the vicinity of the recording / reproducing wavelength, but also has a lot of spatial configurations and good flatness.
  • structural dyes Examples of this are ⁇ - ⁇ * transitions that are likely to occur, many of which emit fluorescent light, and include a number of organic dyes.
  • suitable optical disks include the following specific cyanine dyes. It is done.
  • metal chelate dyes have been said to have good light resistance.
  • metal chelate dyes (2) metal chelate dyes whose central metal tends to be desorbed by light due to their light binding properties are “light resistance”. Is considered to fall under "inferior pigment”. (2) is the case where the central metal ion, like zinc, does not have an empty d orbital in the outermost d orbital that should be involved in the coordination bond, or there are few empty d orbitals (this In the invention, for example, Zn 2+ has a 3d lc> electron configuration because 2 electrons can be taken from the electron configuration 3d 1G 4s 2 of Zn (by ionic ion).) Covalent metal-ligand bonding Power is reduced.
  • the central metal of such a metal chelate dye having a poor light resistance is a metal having few or no vacant d orbitals due to ions.
  • the ligand has a molecular orbital in which MLCT (metaH: o-ligand charge transfer) is likely to occur (for example, the ligand has an empty anti-bonding orbital). It is also preferable.
  • the magnitude of the contribution of the optical mode in the decomposition of these dyes can also be estimated based on whether or not fluorescence is emitted. That is, it is considered that dyes that emit fluorescence tend to have a large contribution of optical modes in decomposition.
  • the covalent bond (strong coordination) between the ligand and the central metal ion is small because the central metal ion has d 9 or d lc> electron configuration, but the structure selection energy force is close to SO. It can also be thought to be related to something.
  • the “structure selection energy” described above was in accordance with KF Puncell et al, Inorganic Chemistry, 1977, p.550.
  • a dye compound having a high probability of non-radiative transition occurs in the "dye having good light resistance" in the "dye having good light resistance".
  • a dye compound having a high probability of non-radiative transition occurs in such a dye compound.
  • the absorbed light is mainly converted into thermal energy.
  • a metal chelate dye is, for example, an azo metal chelate dye which is a first transition element (3d transition element) having an empty d orbital in the d orbital of the central metal ion or capable of forming an empty d orbital.
  • hybrid orbitals are formed through the overlap of empty d orbitals of metal ions and orbitals of ligands, and the covalent bondability of metal ligands makes it possible to form a chelate structure that is stable even in the excited state. There is a high possibility of being formed. That is, it is considered that the ligand does not release the coordination bond force even by photoexcitation.
  • Examples of the "dye having inferior light resistance" include a azo complex having Zn as a central metal, or a cyanine dye containing no quencher.
  • an azo complex having Cu or Ni as a central metal may be used, but an azo complex having Zn as a central metal is particularly preferable.
  • Examples of such dyes include metal chelate dyes that coordinate two azo compounds described below with respect to one Zn element.
  • the "dye having poor light resistance” in the present invention is preferably a single composition of the dye and having a dye retention of 70% or less as defined in the present invention.
  • Dye retention power small within this range Since it is a “dye having inferior light resistance”, it is preferable because it may be excellent in characteristics at high-speed recording or high-density recording for the reasons described above.
  • the “dye having good light resistance” in the present invention is preferably a single composition of the dye and having a dye retention rate of more than 70% as defined in the present invention. More preferably, it is 80% or more, and still more preferably 85% or more.
  • examples of azo complexes include azo metal chelate dyes comprising an azo compound represented by the following general formula (1) and a metal ion of Zn ( Hereinafter, “Dye (1)” is suitably used.
  • R 1 is a hydrogen atom or an ester group represented by CO R 3 (where R 3 is
  • a linear or branched alkyl group or a cycloalkyl group is represented. ).
  • R 2 represents a linear or branched alkyl group.
  • At least one of X 1 and X 2 is NHSO Y group (where Y is at least 2
  • R 4 and R 5 each independently represents a hydrogen atom, a linear or branched alkyl group, or a linear or branched alkoxy group.
  • R 6 , R 7 , R 8 and R 9 each independently represent a hydrogen atom or an alkyl group having 1 or 2 carbon atoms.
  • R 3 is preferably a straight chain or branched chain having 1 to 8 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, or a sec-butyl group.
  • a cycloalkyl group having 3 to 8 carbon atoms such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group.
  • a straight chain alkyl group having 1 or 2 carbon atoms such as a methyl group or an ethyl group; a cyclohexane having 3 or more and 6 or less carbon atoms such as a cyclopentyl group or a cyclohexyl group, because steric hindrance is small.
  • R 2 is preferably a linear alkyl group having 1 to 8 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group; an isopropyl group, a sec-butyl group, and an isobutyl group.
  • Y represents a linear or branched alkyl group substituted with at least two fluorine atoms.
  • the linear or branched alkyl group is preferably a linear or branched alkyl group having 1 to 6 carbon atoms, and more preferably a linear alkyl group having 1 to 3 carbon atoms.
  • R 4 and R 5 are preferably a hydrogen atom, a linear alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 8 carbon atoms.
  • R 4 and R 5 are more preferably a hydrogen atom, an alkyl group having 1 or 2 carbon atoms, or an alkoxy group having 1 or 2 carbon atoms.
  • the alkyl group and alkoxy group are preferably unsubstituted.
  • R 4 and R 5 are particularly preferably a hydrogen atom, a methyl group, an ethyl group, or a methoxy group.
  • R 6 , R 7 , R 8 and R 9 each independently represents a hydrogen atom or an alkyl group having 1 or 2 carbon atoms. It is preferable to use a hydrogen atom or an alkyl group having 1 or 2 carbon atoms because the absorbance and refractive index can be easily adjusted to predetermined values.
  • the hydrogen atom bonded to the carbon atom may be substituted with another substituent (for example, a halogen atom), but is preferably an unsubstituted alkyl group.
  • the alkyl group having 1 or 2 carbon atoms include a methyl group and an ethyl group. From the viewpoint of ease of synthesis and three-dimensional structure, R 6 , R 8 , and R 9 are most preferably a hydrogen atom.
  • azo compound (ligand) of the general formula (1) constituting the dye (1) include
  • examples of cyanine dyes preferable as the “dye having poor light resistance” include cyanine dyes represented by the following general formula (2) (hereinafter, referred to as “dye (2)” as appropriate).
  • ring A and ring B may each independently have a substituent, and represent a benzene ring or a naphthalene ring.
  • R 1C) and R 11 each independently represents an alkyl group having 1 to 5 carbon atoms which may have a substituent.
  • R 12 , R 13 , R 14 and R 15 each independently represents an alkyl group having 1 to 5 carbon atoms which may have a substituent.
  • R 16 represents a hydrogen atom, a halogen atom, a cyano group or an alkyl group having 1 to 5 carbon atoms which may have a substituent.
  • Q— stands for anti-on. Counter-on includes BF-, PF-, metal complexes, etc.
  • R 1C) and R 11 have 1 to 5 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, sec-butyl, etc. It is a straight chain or branched alkyl group. Particularly preferred is a straight-chain alkyl group having 1 or 2 carbon atoms such as a methyl group or an ethyl group because of its small steric hindrance.
  • the hydrogen atom of the alkyl chain may be substituted with fluorine or a substituent described later.
  • R 12 , R 13 , R 14 , and R 15 are preferably straight-chain alkyl groups having 1 to 5 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group; an isopropyl group, Examples thereof include branched alkyl groups having 3 to 5 carbon atoms such as sec-butyl group, isobutyl group and t-butyl group.
  • the hydrogen atom of the alkyl chain may be substituted with fluorine or a substituent described later.
  • R 16 is preferably a hydrogen atom; a halogen atom such as CI and Br; a cyano group; a methyl group; It is a straight chain or branched alkyl group having 1 to 5 carbon atoms, such as a ru group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, and a sec-butyl group. When an alkyl group is used, the hydrogen atom of the alkyl chain may be substituted with a substituent described later.
  • Aromatic or heterocyclic aryl groups having 1 to 12 carbon atoms (carbocyclic or heterocyclic aryl groups having 1 to 12 carbon atoms),
  • a dialkylamino group having 1 to 6 carbon atoms having 1 to 6 carbon atoms
  • a thioalkyl group having 1 to 6 carbon atoms having 1 to 6 carbon atoms
  • a trialkylsilyl group having 1 to 6 carbon atoms having 1 to 6 carbon atoms
  • R 1G and R 16 are preferably substituted on the alkyl group.
  • Aromatic or heterocyclic aryl groups having 1 to 12 carbon atoms (carbocyclic or heterocyclic aryl groups having 1 to 12 carbon atoms),
  • a dialkylamino group having 1 to 6 carbon atoms having 1 to 6 carbon atoms
  • Nitro group A thioalkyl group having 1 to 6 carbon atoms
  • a trialkylsilyl group having 1 to 6 carbon atoms having 1 to 6 carbon atoms
  • the substituent is preferably a carbocyclic or heterocyclic aryl group having 1 to 12 carbon atoms. More preferred is a carbocyclic aryl group having 6 to 12 carbon atoms. From the viewpoint of recording characteristics, a benzene ring is more preferable.
  • the surface power of recording characteristics is also most preferable. It is preferable to substitute the hydrogen of the alkyl chain with a benzene ring in a part of the alkyl group used for R 12 to R 16 .
  • examples of the method of using a benzene ring as a substituent include the following combinations (1) to ( ⁇ ). Considering steric hindrance and the like, it is preferable to use a combination of (iii) and (
  • R 12 and R 13 are alkyl groups, hydrogen in one or both alkyl chains of R 12 and R 13 is substituted with a benzene ring.
  • R ′′ and R 15 are alkyl groups, hydrogen in one or both of R 14 and R 15 is substituted with a benzene ring.
  • R 16 is an alkyl group
  • the hydrogen of the alkyl chain of R 16 is substituted with a benzene ring.
  • Specific examples of the dye (2) include compounds having the structure shown below.
  • any one of the above “dyes having poor light resistance” in the recording layer may be used alone, or two or more may be used in any combination.
  • only one or two or more of the above-described dye (1) may be used, or only one or two or more of the above-described dye (2) may be used.
  • Any one or more of 1) and the above-described dye (2) may be used in combination as appropriate.
  • another "dye having poor light resistance" may be used in combination.
  • a transition metal other than Zn for example, V, Cr, Mn, Fe, Co, Ni, Cu
  • a metal-containing azo complex is preferred, and the central metal ion forming a coordination bond is preferably a divalent ion.
  • At least one azo compound selected from the group consisting of compound forces represented by the following general formulas (3), (4), (5), and (6), and a 3d transition element excluding Zn Azo metal chelate dyes (hereinafter referred to as azo metal chelate dyes having azo compounds corresponding to the respective general formulas, “Dye (3)”, “Dye (4)”, “Dye ( 5) ”and“ dye (6) ”.
  • R 17 represents an alkyl group having 1 to 6 carbon atoms which may have a substituent.
  • R 21 to R 27 in general formulas (3) and (4) and R 18 and R 19 in general formulas (5) and (6) each independently have a hydrogen atom or a substituent. It represents a straight, branched or cyclic alkyl group having 1 to 6 carbon atoms. R 18 and R 19 may combine with each other to form a ring.
  • X 1 and X 2 are an NHS OY group (where Y is substituted with at least two fluorine atoms) Linear or branched
  • the azo compounds represented by), (4), (5) and (6) form a coordinate bond with a metal ion.
  • R 17 is preferably a straight chain or branched chain having 1 to 6 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, sec-butyl, etc. It is an alkyl group.
  • R 18 and R 19 are preferably a methyl group, an ethyl group, an isopropyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, a hexyl group, and the like. And a linear or branched alkyl group. R 18 and R 19 may combine with each other to form a cyclic alkyl group such as a cyclic cyclohexyl group.
  • R 2 is preferably a hydrogen atom; a straight or straight chain having 1 to 6 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, and a hexyl group.
  • R 2 is particularly preferably a hydrogen atom.
  • R 21 and R 27 are preferably hydrogen atoms; carbon numbers such as methyl group, ethyl group, isopropyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, and hexyl group. 1 or more and 6 or less linear or branched alkyl group;
  • X 1 , X 2 , and Y may be the same as those of the azo compound represented by the general formula (1)
  • Aromatic or heterocyclic aryl groups having 1 to 12 carbon atoms (carbocyclic or heterocyclic aryl groups having 1 to 12 carbon atoms),
  • a dialkylamino group having 1 to 6 carbon atoms having 1 to 6 carbon atoms
  • Nitro group A thioalkyl group having 1 to 6 carbon atoms
  • a trialkylsilyl group having 1 to 6 carbon atoms having 1 to 6 carbon atoms
  • any of the above “dyes having good light resistance” may be used alone, or two or more thereof may be used in any combination.
  • only one or two or more of the dyes (3), (4), (5) and (6) described above may be used.
  • (4), (5) and (6) a plurality of them may be used alone or in combination of two or more.
  • another "light-resistant dye” may be used in combination.
  • the light resistance index of a dye whose effect is clear on the recording characteristics is as follows. That is, when using together the “dye having poor light resistance” and the “dye having good light resistance” constituting the recording layer, the mixing ratio of these dyes is controlled as follows.
  • the dye retention rate of the recording layer single layer is the light irradiation condition shown in ISO 105-B02, that is, Wool
  • the light resistance is better than this value, the sufficient optical mode is not exhibited in the decomposition, so that the contribution of the heat mode (pyrolysis reaction) in the decomposition of the dye is large. It may not be possible to improve the characteristics.
  • the dye retention of the single recording layer is determined by the method described in the following example even when the bonded disc is peeled off at the bonded portion and the disc slice having the substrate and the dye that appears. It is possible to evaluate.
  • the combination of the above-described dyes suitable for high-speed recording may deteriorate the light resistance of the disk.
  • a transition metal chelate compound eg, acetyl acetyltonate chelate
  • a metal compound and the like may contain a recording sensitivity improver.
  • the metal compound means a compound in which a metal such as a transition metal is contained in the compound in the form of atoms, ions, clusters, etc., for example, an ethylenediamine complex, an azomethine complex, a phenol hydroxylamine complex.
  • Organometallics such as phenantorphine complex, dihydroxyazobenzene complex, dioxime complex, nitrosaminophenol complex, pyridyltriazine complex, acetylylacetonate complex, metaorthocene complex, and volphiline complex Compounds are listed. Although it does not specifically limit as a metal atom, It is preferable that it is a transition metal.
  • the present inventors have studied to improve "practical" light resistance without using aggressive additives.
  • a reflective layer is used in which the differential value (dR / d ⁇ ) of the reflectance R with respect to the wavelength in the air at a wavelength of 300 nm ⁇ ⁇ ⁇ 500 nm is (dRZd ⁇ ) ⁇ 3.
  • the inventors have obtained the knowledge that the light resistance of the recording layer can be improved.
  • Examples of the reflective layer that satisfy the conditions to be applied include at least one element selected from Cu, Au, and A1 forces (hereinafter, sometimes referred to as "specific element"), and in the reflective layer.
  • Specific element examples include a reflective layer in which the total ratio of these specific elements is 50 at% or more. If this ratio is less than 50 at%, there is a possibility that (dRZc) ⁇ 3 in the above wavelength range may not be satisfied, and therefore sufficient light resistance may not be obtained.
  • elements other than the above-mentioned specific elements in the powerful reflective layer preferably Ag, Cr, Ni, Pt, Ta, Pd, Mg, Se, Hf, V, Nb, Ru, W, Mn, Re, Fe And at least one element selected from the group consisting of Co, Rh, Ir, Cd, Ga, In, Si, Ge, Te, Pb, Po, Sn, Bi, Ti, Zn, Zr, and rare earth metals.
  • the ratio of these elements in the reflective layer is preferably 100 at% together with the ratio of the specific elements. It is preferable to adjust the type of elements other than the specific element and the amount of the elements to satisfy (dRZd X) ⁇ 3.
  • a reflective layer having a reflectance in air of 20% to 70% at 300 nm to 500 nm is preferable.
  • the reflective layer satisfying the strong requirements improves the light resistance of the recording layer is considered as follows.
  • the light resistance test (ISO-105-B02) for optical disks, which is generally performed, is a test method that assumes exposure to sunlight. It is known that the intensity of sunlight reaches saturation at 300 nm to 500 nm, particularly 400 nm to 500 nm. Also, since the energy of light particles is proportional to the frequency of light, the energy of light particles is also Higher than the energy of long wavelength light particles. Since light particles with high energy have a higher probability of exceeding the threshold for breaking the binding of the dye, it is desirable that the light of this wavelength is not excessively absorbed by the dye in order to improve the light resistance of the disk.
  • a reflective layer having a low reflectance in this wavelength range it is preferable to use a reflective layer having a low reflectance in this wavelength range. Therefore, if a reflective layer having a low reflectance in the above wavelength range is used, the amount of multiple reflected light between the dye recording layer and one reflective layer is reduced, so that deterioration of the recording layer having a dye having poor light resistance is suppressed. It is thought that In this way, the “practical” light resistance can be further improved.
  • Fig. 3 (a) is a graph showing the wavelength distribution of the refractive index (n) of the main metal material
  • Fig. 3 (b) is the wavelength distribution of the extinction coefficient (k) of the main metal material
  • FIG. 3 (c) is a graph showing the wavelength distribution of reflectance in air calculated for a reflective layer (thickness 120 nm) formed using main metal materials.
  • the film thickness of the reflective layer of 120 nm is a film thickness at which the reflectance is sufficiently saturated.
  • the reflectance “in the air” means the ratio of the return light intensity to the incident light intensity when the incident light is directly irradiated onto the film surface of the reflective layer through the air.
  • FIG. 3 (a) shows that the refractive index (n) of Au, Cu, and Al is larger in the region of 350 nm to 500 nm than Ag that is generally used as a reflective layer.
  • the refractive index (n) of Au and Cu is around 1 stably in this wavelength range.
  • the reflectivity of Au and Cu is 30% to 70%, which is quite small compared to Ag.
  • Examples of the reflective layer that satisfy the conditions to be applied include at least one element selected from Cu, Au, and A1 forces (hereinafter sometimes referred to as "specific element"), and in the reflective layer.
  • Specific element an element selected from Cu, Au, and A1 forces
  • Examples include a reflective layer in which the total ratio of these specific elements is 50 at% or more. If this ratio is less than 50 at%, the preferred reflectance range may not be satisfied.
  • the ratio of these elements in the reflective layer is preferably 100 at% in combination with the ratio of the specific elements.
  • the recording layer is made of organic pigment
  • the recording speed dependency such as recording sensitivity and jitter becomes very remarkable as compared with a recording film medium made of metal or semiconductor. Therefore, as a condition required for a reflection layer of a medium having an organic dye as a recording layer, a reflection layer having a high reflectance of a certain value or higher and higher heat conduction is desired.
  • the metal reflective film having a high reflectance means that the reflective layer is a reflective layer in which the real part n of the refractive index at the recording wavelength is not more than a certain value and the imaginary part k is large.
  • the refractive index of the reflective layer for obtaining a practical reflectance is 0.0 ⁇ ⁇ 1.0 and k> 2.0.
  • the thermal conductivity is high!
  • the above reflectivity is high!
  • the bottom line of the waveform tends to be inclined rather than horizontal (hereinafter sometimes referred to as waveform distortion).
  • waveform distortion may cause the bottom jitter to deteriorate.
  • bottom jitter at high speed recording may be bad or vice versa.
  • the present inventors have found that this waveform distortion is related to the temperature distribution in the film thickness direction of the recording layer, which optimizes the combination of the film thickness of the recording layer and the reflective layer, the optical constant, and the thermal conductivity of the reflective layer. As a result, it is considered that good recording is possible at a wide recording linear velocity of 3.5 mZs to 35. Om / s and eventually 3.5 mZs to approximately 70 mZs. RU
  • the recording mark waveform may be improved in a wide recording linear velocity range by having a reflection layer that can use the recording laser light without waste in a thermal optical manner.
  • the above-mentioned "reflective layer is mainly composed of copper, gold, and aluminum” means that the reflective layer is made of copper, gold, or aluminum alone, or any of copper, gold, and aluminum. This means that it contains 50 atomic% or more of the combination of two or more. In order to optimize weather resistance, film structure, and optical properties, it is preferable to contain elements other than copper and gold.
  • Examples of such elements include Al, Ag, Cr, Ni, Pt, Ta, Pd, Mg, Se, Hf, V, Nb, Ru, W, Mn, Re, Fe, Co, Rh, Ir, Examples include the group consisting of Cd, Ga, In, Si, Ge, Te, Pb, Po, Sn, Bi, Ti, Zn, Zr and rare earth metals.
  • the content of these elements is preferably 0.1 to 40 atomic%.
  • a material containing such an element for example, CuAg, CuZrAg and the like are preferable.
  • dRZd (% / m) of reflectance of 3 or less with respect to the wavelength in air at a wavelength of 300 nm to 500 nm.
  • the differential value of the reflectance of pure silver at ⁇ 500 nm exceeds 5 at the maximum, which is not preferable for practical light resistance, but for example, even if it is a metal reflective film containing silver, the composition ratio of silver is reduced.
  • the dRZd X value of the present invention can be 3 or less.
  • the wavelength is 300 ⁇ ! 35 m / s for the first time by combining a reflective layer with a reflectance dRZd (% Znm) of 3 or less and a recording layer containing a dye with poor light resistance at a wavelength in the air of ⁇ 500 nm.
  • a reflective layer with a reflectance dRZd (% Znm) of 3 or less and a recording layer containing a dye with poor light resistance at a wavelength in the air of ⁇ 500 nm.
  • the reflective layer contains at least one element selected from Cu, Au and A1 force, and the total ratio of the elements is 50 atomic% in the reflective layer (“atomic%” is described as “at%”) In some cases, it is preferable to set the above.
  • Cu, Au, and A1 Cu and A1 are preferred at least from the viewpoint of reflectivity.
  • the island-like structure of the sputtered film grows during the high-temperature and high-humidity test and the temperature rising process during recording, and the smoothness of the film may be reduced. result However, the fact that the jitter of the recorded portion is sometimes lowered is remarkable.
  • the reflective layer is preferably a thin film containing at least a Cu alloy represented by the following composition (A).
  • X represents at least one element selected from the group consisting of Zn, Al, Pd, In, Sn, Cr, and Ni.
  • third element species when X is referred to as “third element species”, (However, the total amount of Cu, Ag, and X is 100at% or less.)
  • the Cu content is usually 50 at% or more, preferably 65 at% or more, more preferably 80 at% or more, and usually 97 at% or less, preferably 95 at% or less. More preferably, it is in the range of 90 at% or less.
  • the content of! /, Ag is usually 3 at% or more, preferably 5 at% or more, and usually 50 at% or less, preferably 30 at% or less. .
  • the Ag content should be 50 at% or less. It is preferable that in addition, as supported by the examples described later, the organic dye layer that can withstand high-speed recording as described in the present invention is used as the recording layer, and the effect of improving sufficient light resistance by combining with the reflective layer is further improved. In order to ensure it, it is preferable that the Ag content is 30 at% or less.
  • the content of X is usually 0.05 at% or more, preferably 0.1 at% or more, and usually 10 at% or less, preferably 5 at% or less.
  • the total of them satisfies the above range.
  • the content of the third element species X is preferably 0.05 at% or more. In order to stabilize and easily obtain a sufficient effect, it is more preferably set to 0.3 lat% or more. In particular, Zn has a low melting point, and therefore the amount may not be sputtered when the target is sputtered. Therefore, it is considered preferable that the composition is more than 0.3 lat% as a more stable composition.
  • the content of the third element species X is preferably 10 at% or less. If it is 10 &% or less, it is easy to secure a high reflectance. In order to easily ensure a sufficiently high reflectance, the content of the third element species X is more preferably 5 at% or less.
  • the third element species X has little influence on (dRZd). In other words, the third element species X is preferable for ensuring fine adjustment of the reflectance and storage stability of the reflective layer, rather than being preferable for the light resistance improvement effect of the present invention. .
  • Zn, Al, Pd, In, and Sn are more preferable.
  • Zn, A1, and Pd are preferable because sufficient reflectance can be easily secured.
  • Zn was found to have a higher reflectivity even if the addition amount is small, as determined by the present inventors.
  • O In and Sn are also the same as Zn, Al and Pd described above. The power of ⁇ can be expected.
  • Zn, In, and Sn form an O component that attacks a Cu alloy and ZnO, In 2 O, and SnO that are conductive oxides.
  • These conductive oxides ZnO, InO, and SnO are n-type semiconductors, and generate a contact potential difference with Cu.
  • oxygen ions (0 2_ ) are more likely to be attracted to the Zn, In, and Sn sides than Cu, and it is considered that Cu oxides are delayed.
  • a thin film (reflective layer) containing at least a Cu alloy having high reflectivity and excellent storage stability as described above is used.
  • the third element species X when Zn (melting point: 419.6 ° C, boiling point: 907 ° C) is selected as the third element species X, it is about 0.01 to 2.5 at% higher than the above-mentioned composition (A). It is preferable to contain Zn in the sputtering target. This is because low melting point 'low boiling point elements are easy to volatilize. Although there is a method of suppressing volatilization by making the distance between the target and the substrate during sputtering closer than other places, in order to obtain a predetermined reflective layer more stably and without waste, the sputtering target must be It is particularly preferable that the composition (B) is satisfied. If the composition of the reflective layer and the composition of the target are made the same or close to each other so that the composition (B) can be seen, it becomes easy to produce a reflective layer having the composition (A).
  • X represents at least one element selected from the group consisting of Zn, Al, Pd, In, Sn, Cr, and Ni, provided that the total amount of Cu, Ag, and X is 100 at% or less.
  • the preferable content range of Cu, Ag, and the third element species X is the same as that of the composition (A) described as the composition of the reflective layer.
  • the melting point of X is 66.4 ° C for A1, Pd force 550 ° C, 2 31.97 ° C for Sn, and 156.6 ° C for In, in addition to Zn described above. Yes (See Iwanami Science Dictionary 5th Edition, Iwanami Shoten, 1998)
  • Patent Document WO 2002Z021524 the following processes are possible. That is, in a high frequency melting furnace, Cu and Ag are put into a crucible at a predetermined ratio, melted in a vacuum, and after the Cu and Ag are sufficiently dissolved, the third element species X is added. Alternatively, Cu, Ag, and third element species X may be put in a crucible at a predetermined ratio in a high-frequency melting furnace and vacuum-melted.
  • both Cu and Ag may be added at a predetermined ratio.
  • Zn it is preferable to add it after Cu and Ag are sufficiently dissolved. This is because the composition tends to become the specified value due to volatilization when initially charging with high vapor pressure V and Zn.
  • the melting temperature in the furnace is set to about 1100 ° C to 1200 ° C
  • the material of the crucible is C, Al 2 O, MgO or ZrO.
  • the melt is cooled in a vertical mold and solidified to produce an ingot.
  • the ingot is removed from the vertical mold and cooled to room temperature.
  • the uppermost feeder part of the ingot is cut and removed, and the ingot is rolled by a compressor to produce a plate-like alloy.
  • the plate-like alloy is cut into a product shape, the front surface of the product is polished, and finally the Cu alloy of the present invention is used. This sputtering target is produced.
  • the melting point of the main element (Cu in the above sputtering target) and the melting point of the additive element are usually separated by several hundred ° C! /, It is a case that is extremely high. If Ti with a melting point of 1668 ° C is added to a molten main element Cu (approximately 1000 ° C), alloying progresses due to solid diffusion, but the rate is slow and uniform yield is difficult to alloy well. It is. If the ratio of Cu and Ti is 1: 1, the melting point is 960 ° C due to the correlation. Therefore, it is possible to easily alloy the molten main element. However, there are some that do not require parent alloying even if their melting points differ greatly. It is Pd as X. Even if Pd (melting point: 1554 ° C) is added to Ag at a molten metal temperature of 1100 ° C without being mother alloyed, alloying proceeds easily due to the high diffusion rate.
  • the organic dye to be contained in the recording layer of the optical recording medium using the reflective layer is not particularly limited.
  • organic dyes include macrocyclic azanulene dyes (phthalocyanoine dyes, naphthalocyanine dyes, porphyrin dyes, etc.), polymethine dyes (cyanine dyes, merocyanine dyes, squalium dyes, etc.), anthraquinone dyes, azulene dyes.
  • azo metal chelate dyes and metal-containing indoor-phosphorus dyes are examples of such organic dyes.
  • azo metal chelate dyes or phthalocyanine dyes are preferable to use in consideration of various factors such as productivity, performance, and performance.
  • the azo metal chelate dyes include azo metal chelate dyes comprising the above-mentioned azo compound having a predetermined structure and Ni and Zn metal ions.
  • the reflection layer exhibits a predetermined effect when used in combination with a recording layer containing a “dye having poor light resistance”.
  • the refractive index (n) after recording generally decreases, so the refractive index (n) of the recording layer before recording is high, and the absorption is smaller than a certain amount. This is a necessary condition to ensure sufficient signal amplitude after recording. .
  • the reflective layer is thin, the transmitted light increases and the components that do not contribute to the signal increase. Therefore, the reflective layer needs to have a film thickness of a certain thickness or more.
  • the refractive index (n) at the recording / reproducing wavelength is 11 ⁇ 1.4, and the extinction coefficient (k W ⁇ 0.3 at the recording / reproducing wavelength) is set in the groove.
  • the film thickness (d) of the film satisfies 0.05 ⁇ (nd / ⁇ ) ⁇ 0.3, and if the reflective layer is not used as a translucent film, The thickness (d) preferably satisfies 50nm ⁇ d ⁇ 250nm
  • the upper limit of n is usually 4.0, and the lower limit of k is usually 0.01.
  • the recording layer and the reflective layer satisfy the optical constants and film thicknesses described above, the high reflectivity at the recording / reproducing light wavelength and sufficient signal amplitude after recording necessary for recording by the drive are obtained. be able to.
  • the first optical recording medium of the present invention is not particularly limited as long as it has the above-described recording layer and reflective layer on a substrate, but is preferably a preferred configuration.
  • a configuration in which a recording layer and a reflective layer are sandwiched between two substrates as represented by the configuration shown in FIGS. 1 (a) and (b), and a configuration shown in FIG. 1 (c).
  • the present invention can also be applied to a single-sided two-layer type configuration as shown in FIGS. 2 (a) and 2 (b).
  • FIGS. 1 (a) to 1 (c) and FIGS. 2 (a) and 2 (b) are schematic cross-sectional views showing the layer structure of the optical recording medium according to the embodiment of the present invention.
  • the optical recording medium 100 shown in Fig. 1 (a) includes a substrate (1) 101, a recording layer (1) 102, a reflective layer (1) 103, a protective coat layer (1) 104, and an adhesive layer. 105, a protective coat layer (2) 106, a reflective layer (2) 107, a recording layer (2) 108, and a substrate (2) 109 are laminated in this order.
  • Such an optical recording medium 100 includes a substrate (1) 101, a recording layer (1) 102, a reflective layer (1) 103, a protective coating layer (1) 104, a bonding disk 11 and a substrate ( 2) 109, recording layer (2) 108, reflective layer (2) 107, protective coating layer (2) 106, laminating disk 12 in this order, protective coating layer (1) 104 and protective coating layer (2)
  • Adhesive layer 105 with 106 facing each other It is configured by pasting together.
  • the substrate (2) 109 side force is also applied to the recording layer (1) 102 by irradiating the laser beam 110, and the recording layer (2) 108 by irradiating the laser beam 111 from the substrate (1) 101 side. In this case, information recording / reproduction is performed.
  • the optical recording medium 200 shown in FIG. 1 (b) includes a substrate (1) 201, a reflective layer (1) 202, a protective coat layer (1) 203, an adhesive layer 204, and a protective coat layer (2 ) 205, a reflective layer (2) 206, a recording layer 207, and a substrate (2) 208 are stacked in this order.
  • Such an optical recording medium 200 includes a dummy disk 21 in which a substrate (1) 201, a reflective layer (1) 202, and a protective coat layer (1) 203 are laminated in this order, a substrate (2) 208, a recording layer 207, a reflective layer
  • the bonding disk 22 having the layer (2) 206 and the protective coating layer (2) 205 laminated in this order is bonded to the protective coating layer (1) 203 and the protective coating layer (2) 205 with the adhesive layer 204 facing each other. It is configured by pasting together. Then, information on the recording layer 207 is recorded / reproduced by irradiating the laser beam 210 with the side force of the substrate (2) 208 as well.
  • the optical recording medium 300 shown in FIG. 1 (c) has a layer structure in which a substrate 301, a reflective layer 302, a recording layer 303, a barrier layer 304, and a transparent resin layer 305 are sequentially laminated. Have.
  • information is recorded and reproduced on the recording layer 303 by irradiating the laser beam 310 not only on the substrate 301 side but also on the transparent resin layer 305 side (film surface incidence type).
  • An optical recording medium 400 shown in FIG. 2A includes a substrate (1) 401, a recording layer (1) 402, a reflective layer (1) 403, an intermediate layer 404, and a recording layer (2) 405.
  • a reflective layer (2) 406, an adhesive layer 407, and a substrate (2) 408 are sequentially laminated.
  • the optical recording medium 500 shown in FIG. 2 (b) includes a substrate (1) 501, a recording layer (1) 502, a reflective layer (1) 503, an adhesive layer (intermediate layer) 504, and a barrier layer. 508, a recording layer (2) 505, a reflective layer (2) 506, and a substrate (2) 507 are stacked in this order.
  • the substrate (1) 401 and 501 side forces are also irradiated with laser light 410 and 510, whereby the recording layers (1) 402 and 502 and the recording layers (2) 405 and 505 are irradiated. ! /, Information is recorded and played back.
  • an ultraviolet curable resin layer, an inorganic thin film, or the like may be formed on the mirror surface side of the substrate to prevent adhesion of dust or the like.
  • a print receiving layer that can be written (printed) on various printers such as ink jet and thermal transfer or various writing tools may be provided on the surface that is not the incident surface of the recording / reproducing light.
  • the material of the substrate in the optical recording medium according to the embodiment of the present invention is basically transparent in the wavelength direction of the recording light and the reproducing light in the thickness direction up to the recording layer. That's fine.
  • Examples of the material having such a transparent thickness portion include acrylic resin, methacrylic resin, polycarbonate resin, polyolefin resin (especially amorphous polyolefin), polyester resin, polystyrene resin, and the like.
  • a resin layer made of resin such as fat or epoxy resin, glass glass, or a radiation curable resin such as photocurable resin on glass. Digits can be used.
  • Injection molded polycarbonate is preferred from the viewpoints of high productivity, cost, moisture absorption resistance, and the like.
  • Amorphous polyolefin is preferred from the standpoint of chemical resistance and moisture absorption resistance.
  • a glass substrate is preferable from the viewpoint of high-speed response.
  • a resin substrate or a resin layer may be provided in contact with the recording layer, and a guide groove or pit for recording / reproducing light may be provided on the resin substrate or the resin layer.
  • Such guide grooves and pits are preferably provided at the time of forming the substrate, but can also be provided on the substrate using an ultraviolet curable resin layer.
  • the groove pitch is preferably about 0.1 to 2.0 m.
  • the groove depth is measured by AFM (atomic force microscope) and is usually 50 nm or more.
  • Red semiconductor laser light such as DVD-R, normally has a power of lOOnm or more, especially in the range of low 1x speed (hereinafter sometimes referred to as “IX”) to high speed 8 X recording speed.
  • the groove depth is 120 nm or more.
  • the groove depth is usually 200 nm or less, preferably 180 nm or less. If the groove depth is larger than the above lower limit value, the degree of modulation is low, and if the groove depth is smaller than the upper limit value, it is easy to ensure a sufficient reflectivity.
  • the groove width is measured by AFM (Atomic Force Microscope) and is usually at least 0.10 m, preferably at least 0.20 m.
  • the groove width is preferably 0.40 m or less.
  • the groove width is more preferably 0.28 m or more and 0.34 m or less.
  • the groove width is made larger than the above lower limit, it becomes easy to suppress the influence of thermal interference and obtain good jitter when recording at a high speed of 8 X or more.
  • the recording power margin is widened and the tolerance for fluctuations in laser power is increased, so that the recording characteristics and recording conditions are improved.
  • the groove width is smaller than the above upper limit value, thermal interference in the recording mark can be suppressed in low-speed recording such as IX, and a good jitter value is easily obtained.
  • Information such as address information, medium type information, recording pulse conditions, and optimum recording power can be recorded on the optical recording medium according to the embodiment of the present invention.
  • These emotions for example, the LPP (Land Pre-Pit) or ADIP (Address in Pre-groove) format described in the DVD-R and DVD + R standards may be used.
  • the recording layer material, mixing ratio, and film thickness are as described above.
  • the film thickness of the part between the grooves is smaller than the film thickness in the grooves.
  • Examples of the method for forming the recording layer include generally used thin film forming methods such as a vacuum deposition method, a sputtering method, a doctor blade method, a cast method, a spin coating method, and an immersion method.
  • the spin coating method is preferable from the viewpoint of cost.
  • the vacuum deposition method is preferable to the coating method from the viewpoint of obtaining a recording layer having a uniform thickness.
  • a treatment such as heating or application to a solvent vapor may be performed.
  • the coating solvent for forming the recording layer by a coating method is not particularly limited as long as it does not attack the substrate.
  • ketone alcohol solvents such as diacetone alcohol and 3-hydroxyl-3-methyl-2-butanone
  • cellosolve solvents such as methylcetosolve and ethylcetosolve
  • chain hydrocarbons such as n-hexane and n-octane Solvents
  • Cyclic hydrocarbon solvents such as cyclohexane, methylcyclohexane, ethylcyclohexane, dimethylcyclohexane, n-butylcyclohexane, tert-butylcyclohexane, cyclooctane; tetrafluoropropanol, ota
  • Non-fluoroalkyl alcohol solvents such as tafanolopent
  • an organic dye and recording layer components such as various additives as necessary are put in a crucible installed in a vacuum vessel, and the inside of the vacuum vessel is filled with an appropriate vacuum pump. After evacuating to about 0 — 2 to 10 — 5 Pa, the crucible is heated to evaporate the components of the recording layer, and vapor deposited on a substrate placed facing the crucible to form a recording layer.
  • the recording layer may be a near-infrared laser having a wavelength of about 770 to 830 nm, which is usually used for CD-R, or a DVD-R.
  • a recording medium with multiple wavelengths, such as a so-called blue laser of 5 nm, should be used in combination with a dye suitable for recording using each of the recording media to provide an optical recording medium that supports recording with laser light in multiple wavelength ranges. You can also.
  • dyes that can be used in combination include azo dyes or azo metal chelate dyes, cyanine dyes, squalium dyes of the same type as the azo metal chelate dyes having the specific characteristics or structures described above.
  • the thermal decomposition accelerator for the dye include metal compounds such as a metal anti-knock agent, a metamouth compound, and an acetylethylacetonate metal complex.
  • a noinder, a leveling agent, an antifoaming agent and the like can be used in combination with the recording layer of the present invention, if necessary.
  • Preferable binders include polybutyl alcohol, polyvinyl pyrrolidone, nitrocellulose, cellulose acetate, ketone series resin, acrylic series resin, polystyrene series resin, urethane series resin, polyvinyl butyral, polycarbonate, and polyolefin. Can be mentioned.
  • Examples of the method for forming the reflective layer include sputtering, ion plating, chemical vapor deposition, and vacuum vapor deposition.
  • the thickness of the reflective layer is set to the following range in consideration of recording characteristics and industrial production. That is, the thickness of the reflective layer is usually 50 nm or more, preferably 60 nm or more, while it is usually 300 nm or less, preferably 250 nm or less, more preferably 200 nm or less.
  • the roughness (particle size) of the reflective layer is preferably as small as that of a gold thin film or less from the viewpoint of weather resistance and reflectance.
  • the recording / reproducing light wavelength is short, and in the case of high-density recording, the roughness of aluminum is likely to increase. Therefore, it is necessary to improve the smoothness by alloying.
  • sputtering Another idea is to reduce the argon pressure at the time.
  • the material of the protective layer formed on the reflective layer is not particularly limited as long as it protects the reflective layer from external force.
  • the organic material include thermoplastic resin, thermosetting resin, electron beam curable resin, and UV curable resin.
  • inorganic substances include SiO, SiN, MgF, and SnO.
  • Thermoplastic resin, thermosetting resin, and the like can be formed by dissolving in an appropriate solvent, applying a coating solution, and drying.
  • the UV curable resin can be formed by preparing a coating solution as it is or by dissolving it in a suitable solvent, coating the coating solution, and curing it by irradiating with UV light.
  • an acrylate-based effect such as urethane phthalate, epoxy acrylate or polyester acrylate can be used. These materials may be used alone or in combination, or they may be used as a multilayer film instead of just one layer.
  • a coating method such as a spin coating method and a casting method, a sputtering method, a chemical vapor deposition method, and the like are used as in the recording layer.
  • a spin coating method is preferable. .
  • the thickness of the protective layer is usually 0.1 ⁇ m or more, preferably 3 m or more. On the other hand, the thickness of the protective layer is usually 100 / zm or less, preferably 30 / zm or less.
  • the laser used for recording and playback there are no particular restrictions on the laser used for recording and playback, but for example, a dye laser capable of wavelength selection over a wide range in the visible region, a helium-neon laser with a wavelength of 633 nm, and a recently developed wavelength of 680, 660, 650 High power semiconductor lasers around 635 nm, harmonic conversion YAG lasers with a wavelength of 532 nm, blue semiconductor lasers around 405 nm, and the like.
  • a semiconductor laser is preferable in terms of lightness, ease of handling, compactness, cost, and the like.
  • the optical recording medium according to the embodiment of the present invention enables high-density recording and reproduction at one wavelength or a plurality of wavelengths selected from these.
  • Recording on the optical recording medium according to the embodiment of the present invention is usually performed by irradiating a recording layer provided on both sides or one side of the substrate with laser light focused to about 1 ⁇ m.
  • the recording layer irradiated with laser light undergoes thermal changes in the recording layer, such as decomposition, heat generation, and melting. The optical characteristics change.
  • the recorded information is reproduced by irradiating a reproduction laser beam and reading the difference in reflectance between the part and the part where the optical characteristics change.
  • the azo compound represented by the above general formula (1), the metal ion of Zn, and the azo metal chelate dye which is powerful, are the optical recording media described in [I. Basic concept 1 of the present invention] (the present invention).
  • the first optical recording medium is not limited to this, and has a recording layer containing at least an organic dye and a reflective layer containing a metal on a substrate having concentric or spiral grooves, and the shortest mark length is 0.
  • an optical recording medium for recording at a recording linear velocity of 35.OmZs or more it can be widely used as an organic dye for the recording layer.
  • another optical recording medium of the present invention has a recording layer containing at least an organic dye and a reflective layer containing a metal on a substrate having concentric or spiral grooves.
  • an optical recording medium for recording at a recording linear velocity of 35 OmZs or more wherein the organic dye of the recording layer is an azo compound represented by the general formula (1)
  • a compound based on Zn and a metal ion of Zn and a powerful azo metal chelate dye this may be hereinafter referred to as “the second optical recording medium of the present invention”.
  • the second optical recording medium of the present invention According to the medium, it is possible to obtain an advantage of particularly excellent life characteristics (long-term storage stability and storage stability under high temperature and high humidity).
  • the reflective layer of the optical recording medium includes the material represented by the composition (A). According to the optical recording medium having such a configuration, it is possible to obtain the advantages that the decrease in reflectance can be suppressed to the minimum and the life characteristics are excellent.
  • composition (A) in the second optical recording medium of the present invention is also shown above. This is the same as that described in the section of [L Basic concept 1 of the present invention].
  • the sputtering target having at least the material represented by the above-mentioned composition B is also used for the reflective layer of the optical recording medium (first optical recording medium of the present invention) described in [I. Basic concept 1 of the present invention].
  • the reflective layer is formed in an optical recording medium having a recording layer containing at least an organic dye and a reflective layer containing a metal on a substrate having concentric or spiral grooves, the invention is not limited thereto. It can be used widely.
  • the sputtering target of the present invention is applied to an optical recording medium having a recording layer containing at least an organic dye and a reflective layer containing a metal on a substrate having concentric or spiral grooves.
  • a sputtering target used for forming the reflective layer which has at least the material represented by the composition B described above. According to the sputtering target of the present invention, it is possible to provide a high-quality medium that can suppress a decrease in reflectivity to a minimum and is excellent in life characteristics, and can be manufactured at a lower cost.
  • composition B in the sputtering target of the present invention is the same as those described in the above section [I. Basic concept 1 of the present invention].
  • the organic dye is a light that is an azo metal chelate dye that also has the power of the azo compound represented by the general formula (1) and the metal ions of Ni and Zn. It is particularly preferably used for forming a reflective layer of a recording medium.
  • the azo compound represented by the above general formula (1), the metal ion of Zn, and the azo metal chelate dye, which is powerful, are recorded on a substrate having concentric or spiral grooves.
  • a layer and a reflective layer containing a metal, and the shortest mark length is less than 0, or 35.
  • the azo compound represented by the above general formula (1) and the azo metal chelate dye which is composed of Zn metal ions are hereinafter referred to as “the dye of the present invention”.
  • the dye of the present invention in the above-mentioned optical recording medium for high-speed recording or high-density recording, there can be obtained an advantage that a low jitter, a low error rate, and a wide recording margin can be achieved as compared with the prior art.
  • a polycarbonate substrate having a mirror finish was prepared. Tetrafluoropropoxy O Lovro Bruno V- le concentration 1.4 wt 0/0 color containing mixture to be measured (hereinafter referred to as "TFP".) Dissolved solution with the dye layer in the following Examples and Comparative Examples Spin coating was carried out in the same manner as in the above. A small piece of the obtained dye monolayer was cut out and the wavelength dispersion of absorbance was measured using a spectrophotometer (UV-VIS). The maximum value of the obtained absorbance was used as the initial value.
  • TFP Tetrafluoropropoxy O Lovro Bruno V- le concentration 1.4 wt 0/0 color containing mixture to be measured
  • dye A an azo system represented by the following structural formula (a)
  • dye B two azo compounds represented by the following structural formula (b) and zinc (divalent ion: Zn 2+ )
  • a recording layer film thickness in the groove: 50 nm
  • the light-absorbing metal chelate pigment has an absorbance (Optical Density: Absorbance at a wavelength of 598 nm measured with air as a reference).
  • the coating solution was a TFP solution having a concentration of 1.3% by weight, and the spin coating rotation speed was 1000 rpm to 2500 rpm.
  • copper (Cu) was deposited thereon by sputtering to form a 120 nm thick Cu reflective layer.
  • the argon pressure was made lower than the well-known conditions for forming the reflective layer, and the input power was increased.
  • UV curable resin (KA YARAD manufactured by Nippon Kayaku Co., Ltd.)
  • EFM plus modulation random signal with a minimum mark length of 0.4 ⁇ m at a recording speed of 56.
  • the irradiation pulse width of the laser for recording the 3T mark length was 6.5 ns.
  • the recorded signal was reproduced using the same evaluator, and the margins (jitter recording power margin and jitter asymmetry margin) were measured.
  • the measurement result of the recording power margin is shown in the graph of Fig. 4 (a), and the measurement result of the asymmetry margin is shown in the graph of Fig. 4 (b).
  • the optical recording medium of this example using a Cu reflecting layer had an extremely good bottom jitter of 7%.
  • the asymmetry margin for which jitter is 9% or less is about 18%
  • the asymmetry margin for which jitter is 8% or less is 10% or more
  • jitter is around 8% even in the vicinity of 5% asymmetry. It was.
  • An optical recording medium was prepared in the same manner as in Example 1, except that the material of the reflective layer was changed to gold (Au) and the film thickness was changed to 90 nm. Recording and reproduction were performed on the obtained optical recording medium under the same conditions as in Example 1, and bottom jitter and PI max before and after the light resistance test were measured.
  • An optical recording medium was manufactured in the same manner as in Example 1, except that the material of the reflective layer was changed to silver (Ag) and the film thickness was changed to 120 nm. Recording and reproduction were performed on the obtained optical recording medium under the same conditions as in Example 1. Margin (recording power margin and asymmetric margin), bottom jitter before and after the light resistance test, and PI
  • the reflectance of OOnm was 4% to 96% (Fig. 8).
  • the value of dRZd ⁇ (max) in the same wavelength range was 5.6 (Fig. 9 (c)).
  • Example 1 the dye A was changed to Ni complex dye C (65 wt%) (Ni is a divalent ion: Ni 2+ ) in which two azo compounds represented by the following structural formula (c) are coordinated,
  • An optical recording medium was prepared by the same procedure except that the dye B was changed to the cyanine dye D (35% by weight) represented by the following structural formula (d).
  • the film thickness in the groove of the recording layer was 25 nm as confirmed by cross-sectional analysis using an electron microscope.
  • the film thickness of the Cu reflective layer was 120 nm as in Example 1. Recording and reproduction were performed on this optical recording medium under the same conditions as in Example 1, and margins (recording power margin and asymmetry margin), bottom jitter before and after the light resistance test, and PImax were measured.
  • the dye retention ratios of the dye single layer coating films of Dye C and Dye were 97.0% and 0%, respectively, and the dye retention ratio of the recording layer single layer was 68.2%. It was.
  • the measurement result of the recording power margin is shown in the graph of Fig. 5 (a), and the measurement result of the asymmetry margin is shown in the graph of Fig. 5 (b).
  • the power margin with a jitter of 9% or less is about lOmw and an extremely stable power margin. Is realized. Even if the asymmetry exceeds + 6.0%, it has a jitter of 9% or less, and the asymmetry margin of jitter of 9% or less shows a very wide margin of about 20%.
  • These extremely good margins mean that the thermal degradation (heat storage and thermal interference) of the recording mark is small even at extremely high speed recording of 56 mZs (16 ⁇ speed).
  • An optical recording medium was manufactured in the same manner as in Example 3 except that the material of the reflective layer was changed from copper to silver and an Ag reflective layer having a thickness of 120 nm was provided. This optical recording medium was recorded and reproduced under the same conditions as in Example 1, margin (recording power margin and asymmetry margin), bottom jitter before and after the light resistance test, and PI.
  • the recording speed was changed to 35.0 mZs (equivalent to 10 X), and the irradiation pulse width of the laser for recording the 3T mark length was changed to 7.9 ns. Recording and playback were performed under the same conditions, and margins (recording power margin and asymmetry margin) were measured.
  • the recording speed was changed to 35.
  • OmZs equivalent to 10 X
  • the irradiation pulse width of the laser for 3T mark length recording was changed to 7.9 ns. Recording and playback were performed under the same conditions, and margins (recording power margin and asymmetry margin) were measured.
  • Example 1 “Better light resistance” Ni complex dye E (Ni is 2) in which two “azo compounds” represented by the following structural formula (e) are coordinated with “Blow light resistance” Dye B valence ions: changed to Ni 2+), a dye a and dye E 50 wt%: except for using mixed at a ratio of 50 wt%, to prepare an optical recording medium by the same procedure as the actual Example 1 .
  • the film thickness in the groove of the obtained recording layer was 30 nm.
  • the film thickness of the Cu reflective layer was 120 nm.
  • the dye retention rate of the Dye E single layer coating film was 87.3%, and the dye retention rate of this recording layer single layer was 89.0%.
  • This optical recording medium was recorded and reproduced under the same conditions as in Example 1 to obtain a margin.
  • the measurement result of the recording power margin is shown in the graph of Fig. 7 (a), and the measurement result of the asymmetry margin is shown in the graph of Fig. 7 (b).
  • the bottom jitter is 9% or more, indicating that both the power margin and asymmetry margin are extremely narrow.
  • the asymmetry margin is bad – even at a recording power as low as 5%, thermal degradation has already been observed, and the jitter has deteriorated by more than 1% compared to the bottom jitter.
  • the asymmetry margin is preferably 9% or less of jitter at 5%.
  • Example 1 For the optical recording media of Example 1, Example 3, Comparative Example 1, Comparative Example 2, and Comparative Example 4 described above, recording and reproduction were performed under the same conditions as in Example 1 except that the recording speed was changed to 1 ⁇ speed. This was done and the bottom jitter was measured. The results are shown in Table 1 below.
  • bottom jitter is required to be 9% or less.
  • the optical recording media of Example 1, Example 3, Comparative Example 1, Comparative Example 2, and Comparative Example 4 are all good, with bottom jitter of 9% or less in 1x speed recording. Recording characteristics. Nevertheless, superiority and inferiority are seen in high-speed recording as described above.
  • optical recording media of the respective examples that satisfy the provisions of the present invention exhibit good recording characteristics at very wide recording speeds such as 1 ⁇ speed, 10 ⁇ speed, and 16 ⁇ speed.
  • Example 5 The reflectivity and dRZd ⁇ of the reflective layer (A1 reflective layer single layer) made of aluminum (A1) were measured by the method described above. The results are shown in the graphs of FIG. 8 and FIG. 9 (d), respectively. As is clear from Fig. 9 (d), the dRZd value of the single A1 reflective layer was always 0.1 or less in the range of 300nm to 500nm.
  • the reflectance was measured from the surface side.
  • the sputtering conditions were the same as in Example 1.
  • Fig. 10 shows the measurement results of the reflectance of CuAg and CuAg Pd in [Example 5] etc.
  • CuAg Pd has optical properties that are clearly different from those of Cu.
  • Fig. 11 (a), (b) The force that increases the noise so that the force is also increased.
  • the reflectance R (Cu Ag) at each wavelength of Ag Cu 1 -X) g was calculated by the following formula.
  • FIG. 13 shows Cu Ag under the above assumption.
  • FIG. 5 is a graph showing the relationship between the value of X (Ag content: at%) and the bottom jitter value in (100-X) X. From Fig. 13, it is considered that the upper limit of the Ag content at which good jitter characteristics are easily obtained is approximately 30 at%.
  • Example 1 the Cu reflective layer was changed to CuAg and CuAg Pd, respectively.
  • the optical recording medium (hereinafter referred to as “CuAg DVD-R” and “CuAg” respectively)
  • Storage stability test (sometimes referred to as life test) uses a constant temperature and humidity chamber (SH-641 manufactured by ESPEC) and keeps optical recording media at 80 ° C and relative humidity 85% for 875 hours. It was done by doing.
  • SH-641 manufactured by ESPEC
  • the CuAg reflective layer or CuAg Pd reflective layer of Example 6 is the CuAg reflective layer or CuAg Pd reflective layer of Example 6
  • a sputtering target was produced in accordance with the melting method in vacuum described below.
  • the melting temperature in the furnace was 1100 to 1200 ° C.
  • the crucible is C, Al 2 O, MgO or ZrO
  • Melting of the molten metal was performed by pouring into a Fe or C cage having alumina or magnesium talc applied on the inner surface.
  • the feeder was heated to about 300 ° C to 500 ° C with a heater in advance before pouring, and the lower force was solidified unidirectionally toward the upper part.
  • the melt is cooled and solidified in a vertical mold to produce an ingot, and the ingot is rolled by a rolling mill to obtain a plate shape of 90 (mm) X 90 (mm) X 8.1 (mm) An alloy was prepared.
  • the corrected board was wire-cut into a product shape.
  • the front surface of the product was polished with water-resistant abrasive paper to adjust the surface roughness, and finally a Cu alloy sputtering target was produced.
  • the degree of vacuum was maintained at 1. 3 X 10 _2 Pa (l X 10 _4 Torr) following a high vacuum. This is because Ag and Cu are easy to contain oxygen in the molten metal, and are intended for deoxidation when the molten metal is held under reduced pressure. However, since the volatilization of Ag progresses under reduced pressure, various atmosphere adjustments were made according to the situation.
  • Table 2 shows the measurement results of the reflectivity immediately after film formation, the measurement results of the reflectivity after being held for 24 hours under high temperature and high humidity, and the measurement results of the change in reflectivity.
  • timeO indicates “Reflectance measurement result immediately after deposition”.
  • After 80 ° C 80% RH2 4 hr” indicates “Reflectance measurement results after holding at high temperature and high humidity for 24 hours”.
  • “Reflectance change” is indicated as “Measurement result of reflectivity change”.
  • the effect of improving the storage stability by the addition of the third element species X clearly appears compared with the binary system of Cu and Ag. That is, for example, Cu Ag reduces the reflectivity.
  • the total sum may be set to 10 at% or less.
  • Example 9 a sputtering target having the composition described in Table 3 below was produced. Furthermore, the following experiments were conducted to investigate the acid resistance and corrosion resistance of the sputtering target and the sputtered film. That is, a sputtered film was provided on the glass substrate as in Example 9. Then, the reflectance of the sputtered film provided on the glass substrate was measured by the same method as in Example 9, and then the H 2 S gas atmosphere having a concentration of lOOppm.
  • Table 3 shows the change rate of reflectivity between the power indicated as “change rate” and “immediately after sputter film formation” and “after exposure”.
  • the present invention can be suitably used in applications such as an optical recording medium for red semiconductor lasers such as DVD player R, an optical recording medium for blue semiconductor lasers, and the like.

Abstract

La présente invention concerne un support d'enregistrement optique pour un enregistrement haute densité ou à grande vitesse présentant des caractéristiques d’enregistrement préférables dans une grande plage de vélocités linéaires d’enregistrement et une excellente résistance à la lumière. Le support d’enregistrement optique comprend au moins une couche d’enregistrement formée d’un colorant organique et une couche réfléchissante contenant un métal placé sur un substrat présentant un sillon coaxial ou spiralé. L’enregistrement est effectué avec une longueur de marque minimale ne dépassant pas 0,4 µm ou avec une vélocité d’enregistrement linéaire supérieure ou égale à 35,0 m/s. Le sillon de guidage sur le substrat comporte un pas de piste ne dépassant pas 0,8 µm, une largeur de sillon ne dépassant pas 0,4 µm et une épaisseur de pellicule de la couche d’enregistrement dans le sillon ne dépassant pas 70 nm. La couche unique de colorant organique formant la couche d’enregistrement présente une teneur en colorant ne dépassant pas 70 % en niveau 5 sur l'échelle Blue Wool (test de résistance à la lumière) dans les conditions d'irradiation lumineuse définies dans la norme ISO-105-B02. La valeur de différenciation dR/dλ (%/nm) du rapport de réflexion R de la couche de réflexion pour la longueur d’onde λ dans l’air ne dépasse pas 3 dans la plage de longueurs d’ondes comprise entre 300 nm et 500 nm.
PCT/JP2006/309023 2005-04-28 2006-04-28 Support d’enregistrement optique, cible de mouchetage, et colorant chélate azo-métallique WO2006118266A1 (fr)

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WO2008038603A1 (fr) * 2006-09-25 2008-04-03 Mitsubishi Kagaku Media Co., Ltd. Colorant azo-chélate métallique et support d'enregistrement optique

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WO2019069984A1 (fr) * 2017-10-06 2019-04-11 三菱ケミカル株式会社 Disque optique et son procédé de fabrication

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JP2002114922A (ja) * 2000-08-04 2002-04-16 Mitsubishi Chemicals Corp アゾ金属キレート色素及びこれを用いた光学記録媒体
JP2002234258A (ja) * 2001-02-13 2002-08-20 Ricoh Co Ltd 光記録媒体
JP2004272983A (ja) * 2003-03-06 2004-09-30 Ricoh Co Ltd 光記録再生方法
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JP2002114922A (ja) * 2000-08-04 2002-04-16 Mitsubishi Chemicals Corp アゾ金属キレート色素及びこれを用いた光学記録媒体
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JP2004272983A (ja) * 2003-03-06 2004-09-30 Ricoh Co Ltd 光記録再生方法
JP2006040419A (ja) * 2004-07-28 2006-02-09 Tdk Corp 光記録媒体

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Publication number Priority date Publication date Assignee Title
WO2008038603A1 (fr) * 2006-09-25 2008-04-03 Mitsubishi Kagaku Media Co., Ltd. Colorant azo-chélate métallique et support d'enregistrement optique

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