WO2009139216A1 - 光ディスク記録媒体の製造方法 - Google Patents
光ディスク記録媒体の製造方法 Download PDFInfo
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- WO2009139216A1 WO2009139216A1 PCT/JP2009/054459 JP2009054459W WO2009139216A1 WO 2009139216 A1 WO2009139216 A1 WO 2009139216A1 JP 2009054459 W JP2009054459 W JP 2009054459W WO 2009139216 A1 WO2009139216 A1 WO 2009139216A1
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- layer
- recording
- recording medium
- curable resin
- recording layer
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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
- G11B7/26—Apparatus or processes specially adapted for the manufacture of record carriers
- G11B7/263—Preparing and using a stamper, e.g. pressing or injection molding substrates
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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
- G11B7/26—Apparatus or processes specially adapted for the manufacture of record carriers
-
- 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
- G11B7/2403—Layers; Shape, structure or physical properties thereof
- G11B7/24035—Recording layers
- G11B7/24038—Multiple laminated recording layers
Definitions
- the present invention relates to an optical disk recording medium manufacturing method for manufacturing an optical disk recording medium having a plurality of recording layers on which information is recorded by pits as an optical disk recording medium at low cost.
- optical disc recording media which is one of the optical information recording methods, has become more information with the spread of personal computers, the start and spread of terrestrial digital broadcasting, and the acceleration of the spread of high-definition televisions to ordinary homes. Is required to be recordable. Therefore, there is a demand for an increase in recording density of optical disc recording media.
- An optical disk recording medium is formed by forming a recording layer, for example, a recording film or a dielectric layer laminated on a substrate. Then, reading or writing of an information signal with respect to the optical disc recording medium is performed by irradiating a recording layer having a recording film with laser light.
- the recording density of the optical disk recording medium can be increased by reducing the diameter of the light spot collected on the recording film.
- the light spot diameter is limited by the wavelength ( ⁇ ) of the light source and the numerical aperture (NA) of the objective lens, and is proportional to ⁇ / 2NA.
- the wavelength is shortened from 830 nm of a CD which is a first generation optical disc recording medium to 650 nm in a DVD (Digital Versatile Disc). Further, with respect to the NA, the NA, which is a first generation optical disc recording medium, is increasing to about 0.45 and about 0.60 for DVD.
- BD Blu-ray Disk: registered trademark, hereinafter referred to as BD
- BD Blu-ray Disk: registered trademark, hereinafter referred to as BD
- This BD is an optical disk recording medium that uses a technique for further increasing the recording density, which is a technique for further increasing the recording density in combination with increasing the recording density by reducing the light spot diameter.
- a BD as a large-capacity optical disk recording medium is configured by laminating a metal thin film, a dielectric film or the like on an uneven surface on a 1.1 mm thick substrate and providing a protective layer with a thickness of about 0.1 mm.
- An optical disk recording medium manufacturing method having a plurality of recording layers and known as BD is described in, for example, Patent Document 1 below, and is generally performed as follows.
- a manufacturing method of an optical disc recording medium having two recording layers will be described with reference to FIG.
- a metal thin film, a thin film material capable of thermal recording, or the like is formed on a molding resin substrate 200 having a concavo-convex pattern to be pits or guide grooves on one side and having a thickness of about 1.1 mm.
- the first recording layer L0 is formed.
- a spacer layer 201 having a thickness of several ⁇ m to several tens of ⁇ m separating adjacent recording layers is formed on the first recording layer L0 on the molding resin substrate 200.
- the spacer layer 201 is made of, for example, an ultraviolet curable resin.
- the transparent stamper 203 having a concavo-convex pattern such as pits or guide grooves on one side is pressed on the spacer layer 201, and the spacer layer 201 is cured by irradiating ultraviolet rays from the upper surface of the transparent stamper 203.
- the pits and the concave / convex pattern 201 a of the guide groove are transferred onto the spacer layer 201.
- a metal thin film having a predetermined transmittance with respect to the wavelength of the laser beam to be recorded / reproduced on the concave / convex pattern 201a of the pit or guide groove transferred onto the spacer layer 201, or A thin film material capable of thermal recording is formed to form the second recording layer L1.
- a protective layer 202 that protects the second recording layer L1 is formed on the second recording layer L1.
- an optical disc recording medium having two recording layers is formed.
- the second recording layer described above is taken into consideration while taking into account interlayer crosstalk during signal recording / reproduction. This is possible by repeating the formation process several times and laminating a plurality of recording layers in order.
- the multilayer optical disc recording medium configured as described above is required to form a laminated recording layer within a range of 0.1 mm in order to reduce the influence of signal deterioration due to the tilt of the disc.
- the first recording layer L0 and the second recording layer L1 are formed on the first recording layer L0 through a spacer of several microns to several tens of microns.
- the protective layer 202 is configured.
- the optical disk recording medium having the multilayer recording layer is required to be able to perform uniform recording and reading from the innermost periphery to the outermost periphery of the molding resin substrate 200.
- homogeneity and uniformity of the optical properties and physical shape of the spacer layer 201 set between the first recording layer L0 and the second recording layer L1 are required.
- an inexpensive method for producing an optical disk recording medium is expected.
- optical disc recording media are expected to retain the recorded information for a long period of time because the purpose of long-term storage is an important purpose of use. For this reason, a multilayer structure capable of maintaining good recording characteristics even in a high temperature and high humidity environment or a low temperature environment is required.
- the transparent stamper 203 (FIG. 15B) having a concavo-convex pattern such as pits and guide grooves on one side used in the above-described conventional method for manufacturing an optical disk recording medium having two recording layers is often transparent. It is made of resin. An optical disk recording medium having two recording layers uses one transparent stamper, whereas an optical disk recording medium on which n recording layers are formed uses n ⁇ 1 transparent stampers. And this transparent stamper cannot be reused. For this reason, the cost is increased in the conventional stamper process. Therefore, in the manufacture of an inexpensive optical disk recording medium, improvement of the stamper process has been demanded.
- an object of the present invention is to provide an optical disc recording medium manufacturing method capable of manufacturing an inexpensive optical disc recording medium.
- a transfer substrate is prepared, and an ultraviolet curable resin layer is formed on the transfer substrate.
- a nickel stamper having a desired concavo-convex pattern is pressed and applied to the ultraviolet curable resin layer, and at the same time, ultraviolet rays are irradiated from the transfer substrate side to form the concavo-convex pattern on the ultraviolet curable resin layer.
- a recording layer is formed on the ultraviolet curable resin layer on which the uneven pattern is formed.
- an ultraviolet curable resin layer is formed on the recording layer formed in the previous stage, and a nickel stamper having a desired uneven pattern is pressed and applied to the ultraviolet curable resin layer.
- the optical disk recording medium of the present invention is manufactured.
- a plurality of recording layers are formed on a transfer substrate in descending order of light transmittance. Therefore, the ultraviolet curable resin layer can be efficiently cured even when irradiated with ultraviolet rays from the back side of the transfer substrate. Further, since the nickel stamper is used, the stamper can be repeatedly used in the stamper process.
- an optical disc recording medium having a multi-layer recording layer can be UV-cured from the high transmittance side of the configuration, so that the recording layer can be freely designed and has good process consistency. It can be manufactured at low cost.
- FIG. 1 It is a schematic sectional block diagram (the 1) of the principal part of the optical disk recording medium formed in the 1st and 2nd embodiment of this invention. It is a schematic sectional block diagram (the 2) of the principal part of the optical disk recording medium formed in the 1st and 2nd embodiment of this invention.
- A, B, C are manufacturing process diagrams (part 1) of an optical disk recording medium according to the first embodiment of the present invention.
- D, E, F are manufacturing process diagrams (part 2) of the optical disc recording medium according to the first embodiment of the present invention.
- G, H, I are manufacturing process diagrams (part 3) of the optical disc recording medium according to the first embodiment of the present invention.
- FIG. J, K, L are manufacturing process diagrams (part 4) of the optical disc recording medium according to the first embodiment of the present invention.
- FIG. M is a manufacturing process diagram (part 5) for an optical disc recording medium according to the first embodiment of the present invention.
- FIG. N is a manufacturing process diagram (No. 6) of an optical disc recording medium according to the first embodiment of the invention.
- FIG. O, P, Q are manufacturing process diagrams (part 7) of the optical disc recording medium according to the first embodiment of the present invention.
- R, S, T are manufacturing process diagrams (part 8) of the optical disc recording medium according to the first embodiment of the present invention.
- It is a schematic plane block diagram of the press blade type
- FIG. 12 is a cross-sectional configuration diagram along line AA of the press blade mold shown in FIG. 11.
- FIG. 12 is a cross-sectional configuration diagram along line AA of the press blade mold shown in FIG. 11.
- a and B are manufacturing process diagrams of an optical disk recording medium according to a second embodiment of the present invention.
- a to E are schematic manufacturing process diagrams of an optical disc recording medium in a conventional example.
- FIG. 1 shows a schematic cross-sectional configuration of a main part of an optical disk recording medium formed in the first embodiment of the present invention.
- the optical disc recording medium formed in the present embodiment is an optical disc recording medium having four recording layers.
- FIG. 1 shows a part of a cross section of an optical disk recording medium in which four recording layers are formed on a disk-shaped molding resin substrate 1 having a thickness of 1.1 mm and an outer diameter of about 120 mm. .
- An optical disk recording medium includes a first recording layer L0, a spacer layer 51, a second recording layer L1, a molding substrate (hereinafter referred to as molding resin substrate) 1 made of 1.1 mm thick resin, The spacer layer 52, the third recording layer L2, the spacer layer 53, the fourth recording layer L3, the cover layer 61, and the hard coat layer 71 are sequentially laminated.
- FIG. 2 shows the cross-sectional configuration of the optical disk recording medium shown in FIG. 1 in more detail.
- the first recording layer L0 is formed by laminating a reflective film 12, a first dielectric film 13, a recording film 14, and a second dielectric film 15 from the molding resin substrate 1 side.
- the second recording layer L1 is formed by laminating a reflective film 22, a first dielectric film 23, a recording film 24, and a second dielectric film 25 from the molding resin substrate 1 side.
- the third recording layer L2 is formed by laminating a reflective film 32, a first dielectric film 33, a recording film 34, and a second dielectric film 35 from the molding resin substrate 1 side.
- the fourth recording layer L3 is formed by laminating a reflective film 42, a first dielectric film 43, a recording film 44, and a second dielectric film 45 from the molding resin substrate 1 side.
- the recording films 14, 24, 34, 44 are recording films made of a write-once phase change material, and are designed so that the signal amount from each layer at the time of reading is equal. That is, the magnitude relationship between the light transmittances of the first recording layer L0 to the fourth recording layer L3 in the optical disc recording medium of the present embodiment is L0 ⁇ L1 ⁇ L2 ⁇ L3.
- the thicknesses of the first and second dielectric films 13, 15, 23, 25, 33, 35, 43, and 45 used for the first recording layer L0 to the fourth recording layer L3 are preferably 3 nm to 100 nm. And is determined in consideration of optical characteristics and thermal characteristics.
- the material of the first and second dielectric films 13, 15, 23, 25, 33, 35, 43, and 45 is preferably a material having a low absorption capacity with respect to the wavelength of the recording / reproducing laser.
- a material having an extinction coefficient K value of 0.2 or less is preferable.
- An example of such a material is a ZnS—SiO 2 mixture (preferably a molar ratio of 4: 1).
- a known material conventionally used as a material for the dielectric film of an optical disk recording medium can also be used.
- Examples of the material of the first and second dielectric films 13, 15, 23, 25, 33, 35, 43, 45 include Al, Si, Ta, Ti, Zr, Nb, Mg, B, Zn, Pb, Use of nitrides, oxides, carbides, fluorides, sulfides, nitride oxides, nitrided carbides, acid carbides, etc. of elements such as metals such as Ca, La and Ge, and metalloids, and the use of these as main components and materials it can.
- AlN X (0.5 ⁇ X ⁇ 1), AlN, Al 2 O 2-X (0 ⁇ X ⁇ 1), Al 2 O 3 , Si 3 N 4-X (0 ⁇ X ⁇ 1), Si 3 N 4 -X , SiO X (1 ⁇ X ⁇ 2), SiO 2 , SiO, MgO, Y 2 O 3 , MgAl 2 O 4 , TiO X (1 ⁇ X ⁇ 2), TiO 2 , BaTiO 3 , StTiO 4 , Ta 2 O 5-X (0 ⁇ X ⁇ 1), Ta 2 O 5 , GeO X (1 ⁇ X ⁇ 2), SiC, ZnS, PbS, Ge—N, Ge—N—O, Si— N—O, CaF 2 , LaF, MgF 2 , NaF, ThF 4 or the like can be used.
- the film thicknesses of the recording films 14, 24, 34 and 44 used for the first recording layer L0 to the fourth recording layer L3 are preferably in the range of 5 nm to 30 nm, for example, about 15 nm.
- a phase change material that undergoes an irreversible state change upon irradiation with laser light can be used.
- a chalcogen compound or a single chalcogen can be used.
- the chalcogen compound for example, an eutectic material of Sb and Te can be used, and preferably, an eutectic material of Sb and Te to which an additive element such as Ge is added can be used.
- the amount of the additive element in the recording films 14, 24, 34, and 44 is preferably 10 atm% or less.
- the thickness of the reflective films 12, 22, 32, and 42 used in the first recording layer L0 to the fourth recording layer L3 is preferably 3 nm or more, and more preferably in the range of 5 nm to 60 nm.
- the material of the reflective films 12, 22, 32, 42 for example, metal or semimetal can be used.
- the material of the reflective films 12, 22, 32, and 42 is preferably selected in consideration of reflectivity and thermal conductivity.
- the reflective films 12, 22, 32, and 42 have reflectivity with respect to the wavelength of the recording / reproducing laser beam and have a thermal conductivity.
- the material of the reflective films 12, 22, 32, 42 is specifically illustrated, simple substance such as Al, Ag, Au, Ni, Cr, Ti, Pd, Co, Si, Ta, W, Mo, Ge, Or the alloy which has these as a main component can be mentioned.
- Al-based, Ag-based, Au-based, Si-based, and Ge-based materials are particularly preferable from the viewpoint of practicality.
- the alloy for example, Al—Ti, Al—Cr, Al—Cu, Al—Mg—Si, Ag—Pd—Cu, Ag—PdTi, Si—B and the like are preferably used.
- the thickness of the reflective films 12, 22, 32, and 42 is set to a thickness that does not allow light to pass through, for example, 50 nm or more, the reflectance can be increased and heat can be easily released.
- the thickness of the reflective films 12, 22, 32, and 42 is set to an appropriate thickness, for example, about 10 nm, heat escape can be secured while increasing the transmittance.
- the reflective films 12, 22, 32, and 42 are not limited to a single layer structure, and may have a laminated structure in which, for example, two layers (reflective layers) made of metal or metalloid are laminated. It is also possible to have a multilayer structure having more than one layer. This facilitates optical design and facilitates balance with thermal characteristics.
- a barrier layer made of a SiN film or the like may be provided between the dielectric layer and the reflective layer.
- the spacer layers 51, 52, and 53 are formed by spin-coating a light-transmitting material having ultraviolet sensitivity (hereinafter referred to as an ultraviolet curable resin) that forms a multilayer structure of an optical disk recording medium, and is cured by irradiation with ultraviolet rays. Be placed.
- an ultraviolet curable resin a light-transmitting material having ultraviolet sensitivity
- the arrangement and film thickness of this spacer are set for the purpose of suppressing interlayer crosstalk.
- the cover layer 61 is formed for the purpose of protecting the optical disk recording medium.
- the recording / reproducing of the information signal is performed, for example, by condensing the laser beam through the cover layer 61 onto the recording layer for recording the information signal.
- the cover layer 61 for example, an ultraviolet gland curable resin, an ultraviolet curable resin and a polycarbonate sheet, or an adhesive layer and a polycarbonate sheet can be used.
- the cover layer 61 is set to be 100 ⁇ m on the 1.1 mm molding resin substrate 1 including the multilayer recording layer.
- the hard coat layer 71 protects the recording / reproduction quality of information signals from mechanical shocks and scratches on the optical disk recording medium, as well as from fingerprints when handling by the user.
- an ultraviolet curable resin such as a mixture of fine silica powder to improve mechanical strength, a solvent type, or a solventless type can be used. It has a mechanical strength and has a thickness of 1 ⁇ m to several ⁇ m in order to repel oil and fat such as fingerprints.
- a transfer substrate (hereinafter, transfer resin substrate) 10 made of resin is prepared.
- the transfer resin substrate 10 can be a light transmissive resin substrate such as polycarbonate, ZEONOR, ZEONEX, and is formed by, for example, injection molding.
- the plate thickness is 0.5 mm to 1.1 mm, and the diameter is a disk shape having a diameter of about ⁇ 120 mm.
- a central hole 2 having a diameter of about ⁇ 15 mm is formed at the center of the transfer resin substrate 10.
- the transfer resin substrate 10 is carried into a spin coater, and an ultraviolet curable resin is applied to the transfer resin substrate 10 by a spin coat method in order to form the cover layer 61.
- the transfer resin substrate 10 is placed on a turntable of a spin coater (not shown). Then, a desired coating solution is supplied from the dispenser onto the transfer resin substrate 10 and the rotating portion is rotated at a high speed to uniformly spread the coating solution on the transfer resin substrate 10, thereby forming a desired film. Form a film.
- the central portion of the transfer resin substrate 10 is the origin, an appropriate amount of the ultraviolet curable resin is supplied to a position having a radius of 15 mm via a dispenser.
- the rotating part of the spin coater rotates at a low speed of 60 rpm while the ultraviolet curable resin is being supplied.
- the UV curable resin is completely supplied after 5 to 10 seconds, and the rotation of the rotating part is accelerated to 3000 rpm and stops after 5 seconds.
- the transfer resin substrate 10 coated with the ultraviolet curable resin is transported to the UV exposure unit and irradiated with UV light from the back surface of the transfer resin substrate 10 with a flash lamp, whereby the ultraviolet curable resin is cured and the cover layer 61 is cured. Is formed as a film.
- the fourth recording layer L3 is a layer having the highest light transmittance among the recording layers formed in this embodiment.
- the cover layer 61 may be used as it is, or an ultraviolet curable resin for the spacer layer may be newly formed.
- an ultraviolet curable resin for the spacer layer is used, and the spacer layer 61 a is formed on the upper surface of the cover layer 61.
- an ultraviolet curable resin is applied by spin coating to form a film.
- the central portion of the transfer resin substrate 10 is the origin, an appropriate amount of the ultraviolet curable resin is supplied to a position having a radius of 15 mm via a dispenser.
- the rotating part of the spin coater rotates at a low speed of 60 rpm, for example, while the ultraviolet curable resin is supplied.
- the UV curable resin is supplied, for example, after 5 to 10 seconds, and the rotating part is accelerated to 8000 rpm, stops after 5 seconds, and is applied to a desired thickness.
- the spacer layer 61a is shown to be thicker than the cover layer 61. In practice, however, the thickness of the cover layer 61 is approximately 55 ⁇ m.
- the film is formed to 1 to 3 ⁇ m.
- the transfer resin substrate 10 is conveyed to a transfer portion having a nickel stamper having a desired uneven pattern.
- the nickel stamper is pressed against the cover layer 61 or the ultraviolet curable resin (spacer layer 61a) formed on the cover layer 61 in this embodiment.
- a spacer layer 61a having a concavo-convex pattern 3a is formed by irradiating UV from the back surface of the transfer resin substrate 10 with a flash lamp.
- the transfer resin substrate 10 provided with the concave / convex pattern 3a on the spacer layer 61a is carried into a sputtering apparatus to form a fourth recording layer L3.
- the fourth recording layer L3 is the recording layer having the highest light transmittance among the recording layers formed in the present embodiment example.
- the fourth recording layer L3 is formed in the order of the second dielectric film 45, the recording film 44, the first dielectric film 43, and the reflective film 42 in a vacuum. .
- the fourth recording layer L3 is formed by these laminated films.
- the second dielectric film 45, the recording film 44, the first dielectric film 43, and the reflective film 42 are formed at desired positions using a mask.
- the diameter is in the range of 40 mm to 118 mm.
- the spacer layer 53 is formed by applying an ultraviolet curable resin on the fourth recording layer L3 for the purpose of forming an uneven pattern having pits and guide grooves on the resin layer.
- the ultraviolet curable resin is applied and formed by spin coating.
- the central portion of the transfer resin substrate 10 is the origin, an appropriate amount of the ultraviolet curable resin is supplied to the transfer resin substrate 10 at a radius of 15 mm via the dispenser.
- the rotating part of the spin coater rotates at a low speed of 60 rpm, for example, while the ultraviolet curable resin is supplied.
- the UV curable resin is supplied after 5 to 10 seconds, for example, and the rotating part is accelerated to 4000 rpm, stops after 5 seconds, and is applied to a desired thickness.
- the transfer resin substrate 10 on which the spacer layer 53 made of an ultraviolet curable resin is formed is transported to a transfer portion having a nickel stamper having an uneven pattern of a desired shape.
- the uneven pattern 53 a is formed on the spacer layer 53.
- UV irradiation is performed from the back surface of the transfer resin substrate 10 with a flash lamp to form the spacer layer 53 having the uneven pattern 53a.
- the fourth recording layer L3 is formed on the light irradiation side of the spacer layer 53 in the previous stage, but the fourth recording layer L3 transmits the light of the flash lamp to the spacer layer 53. To do. Therefore, a desired uneven pattern 53 a is formed on the spacer layer 53 even by UV irradiation from the back side of the transfer resin substrate 10.
- the transfer resin substrate 10 provided with the concavo-convex pattern 53a on the spacer layer 53 is carried into a sputtering apparatus, and a third recording layer L2 is formed.
- the third recording layer L2 is the recording layer having the second highest light transmittance among the recording layers formed in the present embodiment example.
- the third recording layer L2 is formed in vacuum in the order of the second dielectric film 35, the recording film 34, the first dielectric film 33, and the reflective film 32. Then, the third recording layer L2 is formed by these laminated films. Further, in this sputtering method, the second dielectric film 35, the recording film 34, the first dielectric film 33, and the reflective film 32 are formed at desired positions using a mask.
- the diameter is in the range of 40 mm to 118 mm.
- a spacer layer is formed by applying an ultraviolet curable resin on the third recording layer L2 of the transfer resin substrate 10 for the purpose of forming an uneven pattern having pits and guide grooves. 52 is formed.
- the spacer layer 52 is formed by applying an ultraviolet curable resin by spin coating.
- an appropriate amount of the ultraviolet curable resin is supplied to a radius of 15 mm via a dispenser.
- the rotating part of the spin coater rotates at a low speed of, for example, 60 rpm, completes the supply after 5 to 10 seconds, is accelerated to 5000 rpm, and stops after 5 seconds. And applied to a desired thickness.
- the transfer resin substrate 10 is transported to a transfer portion having a nickel stamper having a concavo-convex pattern having pits and guide grooves, and a concavo-convex pattern 52 a is formed on the spacer layer 52. Also in this case, simultaneously with pressing the nickel stamper, UV irradiation is performed from the back surface of the transfer resin substrate 10 with a flash lamp. Then, the UV curable resin is cured by UV irradiation, and the spacer layer 52 in which the uneven pattern 52a is formed is formed.
- the fourth recording layer L3 and the third recording layer L2 are formed on the light irradiation side of the spacer layer 52 in the previous stage, but the fourth recording layer L3 and the third recording layer L3 are formed.
- the recording layer L2 transmits the light from the flash lamp to the spacer layer 52. For this reason, a desired uneven pattern 52 a is formed in the spacer layer 52 even by ultraviolet irradiation from the back surface side of the transfer resin substrate 10.
- the transfer resin substrate 10 provided with the concavo-convex pattern 52a on the spacer layer 52 is carried into a sputtering apparatus to form a second recording layer L1.
- the second recording layer L1 is the recording layer having the third highest light transmittance among the recording layers formed in the present embodiment example.
- the second recording layer L1 is formed in a vacuum continuously in the order of the second dielectric film 25, the recording film 24, the first dielectric film 23, and the reflective film 22. Then, the second recording layer L1 is formed by these laminated films. Further, in this sputtering method, the second dielectric film 25, the recording film 24, the first dielectric film 23, and the reflective film 22 are formed at desired positions using a mask. It is formed in a range of 118 mm.
- a spacer layer 51a is formed on the second recording layer L1 so as to be approximately half the predetermined thickness.
- the ultraviolet curable resin to be the spacer layer 51a is applied and formed on the second recording layer L1 on the transfer resin substrate 10 by spin coating.
- an appropriate amount of UV curable resin is supplied to the transfer resin substrate 10 at a radius of 15 mm via a dispenser.
- the rotating unit of the spin coater is rotated at a low speed of 60 rpm, for example.
- the supply of the ultraviolet curable resin is completed, for example, after 5 to 10 seconds, and the rotating unit is accelerated to 8000 rpm and stopped after 5 seconds. Thereby, the spacer layer 51a made of the ultraviolet curable resin is applied to a desired thickness.
- FIG. 7M a notch portion for peeling transfer, which is necessary in a later step, is formed in the multilayer film on the transfer resin substrate 10 formed as described above using a press blade mold 300.
- FIG. 11 shows a schematic plan configuration of the press blade mold 300
- FIG. 12 shows a cross-sectional configuration along the line AA in FIG.
- the press blade mold 300 is formed by embedding an inner peripheral blade 303 and an outer peripheral blade 304 in a disc-shaped base 301.
- An opening 302 is formed at the center of the disk-shaped pedestal 301 and is used for alignment with the center hole 2 of the transfer resin substrate 10.
- the inner peripheral blade 303 and the outer peripheral blade 304 are made of hardened steel, and the end surfaces are formed into knife edges.
- the pedestal 301 is made of, for example, metal or plastic. In the present embodiment, notches are formed at the inner and outer format of the optical disk recording medium and at positions where the area is removed.
- FIGS. 13A and 13B show the layout of a recording layer of, for example, a BD write-once type, rewritable type, and read-only type.
- FIG. 13A is a schematic plan configuration of a BD
- FIG. 13B is a cross-sectional configuration along the line AA in FIG. 13A.
- the structure of the optical disk recording medium is roughly divided into a BCA (Burst Cutting Area) 101, a lead-in zone 102, a data area 103, a lead-out zone 104, an outer zone (Outer- Zone) 105.
- BCA Band Cutting Area
- the structure after the first recording layer has the same layout except for BCA101.
- the inner peripheral edge 303 of the press blade mold 300 is configured on the inner side of the innermost peripheral BCA 101 in the optical disk recording medium, and the outer peripheral edge 304 is the outermost peripheral lead in the optical disk recording medium.
- the outer zone 104 is formed outside.
- the press blade mold 300 is mounted on a simple press machine, and the transfer resin substrate 10 is fixed to the press stage 401. Then, the optical disk recording medium having a multi-layered recording layer manufactured through the above-described steps is aligned with reference to the center hole 2, and the press blade mold 300 is pressed to a predetermined pressure and depth. By doing so, as shown in FIG. 8N, the notch portions 91 and 92 for peeling transfer are formed.
- the inner peripheral blade 303 forms an inner peripheral notch 91
- the outer peripheral blade 304 forms an outer peripheral notch 92.
- the notches 91 and 92 are formed at least to a depth reaching the transfer resin substrate 10.
- the innermost notch 91 is formed in the range of diameter ⁇ 20 mm to diameter 40 mm, more preferably diameter ⁇ 24 mm to ⁇ 35 mm, with the central portion of the transfer resin substrate 10 as the origin.
- the outermost notch 92 is preferably formed in the range of a diameter ⁇ 119 mm to a diameter ⁇ 119.5 mm with the central portion of the transfer resin substrate 10 as the origin.
- the innermost notch 91 and the outermost notch 92 have respective films such as the second recording layer L1 to the fourth recording layer L3 of the optical disk recording medium in their cross sections. It is important not to. That is, the phase change recording material constituting the recording film of the optical disk recording medium is not covered with the cross section of the notches 91 and 92 and is continuously covered with the ultraviolet curable resin as the structure. As a result, even when exposed to a high temperature and high humidity environment or maintained in a low temperature environment, good recording characteristics are maintained over a long period of time.
- the second recording layer L1 to the fourth recording layer L3 are formed in a diameter range of 40 mm to 118 mm.
- the second recording layer L 1 to the second recording layer L 1 to the second recording layer L in the cross section of the notches 91, 92 are formed. No. 4 recording layer L3 is not exposed.
- a molding resin substrate 1 is prepared in which a concavo-convex pattern 5 is provided by injection molding and a center hole 4 having a diameter of about 15 mm is formed in the center.
- the concavo-convex pattern 5 is required to be in the same direction as the concavo-convex patterns of the second recording layer L1 to the fourth recording layer L3 to be bonded later.
- the molding resin substrate 1 is preferably made of a material having a thickness of 1.1 mm and a diameter of ⁇ 120 mm, such as polycarbonate, ZEONOR, and ZEONEX, which can be molded, has high light transmittance, and has low water absorption.
- the molding resin substrate 1 provided with the concavo-convex pattern 5 is carried into a sputtering apparatus to form a first recording layer L0.
- the first recording layer L0 is formed in vacuum in the order of the second dielectric film 15, the recording film 14, the first dielectric film 13, and the reflective film 12. Thereby, the first recording layer L0 made of a laminated film is formed.
- a step of forming the concave / convex pattern 5 for the first recording layer L0 on the transfer resin substrate 10 side by forming the first recording layer L0 on the molding resin substrate 1 side. Can be reduced.
- a spacer layer 51b is formed on the first recording layer L0 with a thickness approximately half of the predetermined thickness.
- the spacer layer 51b is formed by applying an ultraviolet curable resin on the first recording layer L0 by spin coating.
- an appropriate amount of the ultraviolet curable resin is supplied to the radius 15 mm position on the molding resin substrate 1 through the dispenser. The At this time, while the ultraviolet curable resin is supplied, the rotating part of the spin coater is rotated at a low speed of 60 rpm.
- the supply of the ultraviolet curable resin is completed after 5 to 10 seconds, and the rotating part is accelerated to 8000 rpm and stopped after 5 seconds.
- the spacer layer 51b applied to have a desired thickness for example, a thickness of several ⁇ m, is formed on the first recording layer L0.
- the transfer resin substrate 10 having the notch portions 91 and 92 for release transfer formed in the steps shown in FIGS. 3A to 8N, and the steps shown in FIGS. 9O to 9Q.
- the molding resin substrate 1 provided with the first recording layer L0 and the spacer layer 51b is bonded and pressed onto the spacer layer 51a with the center holes 2 and 4 as a reference.
- the ultraviolet curable resin constituting the spacer layers 51a and 51b is in an uncured state.
- ultraviolet rays are irradiated from the transfer resin substrate 10 side to bond and cure, and then the transfer resin substrate 10 is peeled off, and a laminated film having a plurality of recording layers is transferred to the molding resin substrate 1 side.
- the fourth recording layer L3, the third recording layer L2, and the second recording layer L1 are formed on the light irradiation side in the previous stage.
- These second recording layer L1 to fourth recording layer L3 are formed on the transfer resin substrate 10 on the light irradiation side in order of increasing light transmittance. Therefore, the fourth recording layer L3, the third recording layer L2, and the second recording layer L1 transmit the light from the flash lamp to the spacer layers 51a and 51b at the joint portions. For this reason, the spacer layers 51a and 51b are bonded and cured by UV irradiation from the transfer resin substrate 10 side. As a result, as shown in FIG. 10S, the laminated film formed on the transfer resin substrate 10 is transferred onto the molding resin substrate 1.
- a hard coat material mainly composed of an ultraviolet curable resin is applied to a multilayer optical disk recording medium on the molding resin substrate 1 by a spin coating method, and then irradiated with ultraviolet rays. Harden.
- the central hole 2 is strictly controlled so that the hard coat material is not applied.
- the multilayer film from the first recording layer L0 to the fourth recording layer L3 and the end face for peeling off the cover layer 61 are protected by the hard coat layer 71 that has been cured.
- a multilayer optical disk recording medium is completed.
- the light intensity of the reproduction signal from the outermost surface on the reading side is required to be several percent of the incident light.
- the reflectance is required to be increased.
- Each layer is designed so that the amount of light reaching the outermost surface on the reading side is substantially the same.
- the recording layer has a high light transmittance, that is, in the present embodiment example, the recording layer is formed on the transfer resin substrate 10 from the fourth recording layer L3 side. It is possible to efficiently cure the ultraviolet rays. For this reason, since light irradiation can be efficiently performed from the transfer resin substrate 10 side, a nickel stamper can be used. Since a nickel stamper that can be used repeatedly can be used instead of the transparent resin stamper that can be used only once, the cost can be reduced in the stamper process. Further, in this embodiment, the use of a nickel stamper allows the uneven pattern to be efficiently transferred to the ultraviolet curable resin layer. For example, the recording layer has a high degree of freedom in design and good process consistency. In addition, since the recording layer is formed so as not to be exposed in the cross section of the notch, it is resistant to changes with time, and a high-quality optical disc recording medium can be manufactured.
- the first recording layer L0 is formed on the molding resin substrate 1, and then bonded to the transfer resin substrate 10 on which the second recording layer L1 to the fourth recording layer L3 are formed. It was set as the structure made to do.
- the present embodiment is not limited to this, and the first recording layer L0 may be formed on the transfer resin substrate 10 side following the formation of the second recording layer L1. In this case, only the transfer spacer layer is formed on the molding resin substrate 1, and the laminated film on the transfer resin substrate 10 on which the first recording layer L0 to the fourth recording layer L4 are formed is formed. What is necessary is just to transcribe
- FIG. 14 shows the shape during the process of the optical disc recording medium having a four-layer structure according to the second embodiment of the present invention. Since the optical disk recording medium formed in this embodiment is the same as the optical disk recording medium shown in FIGS.
- the transfer resin substrate 20 has an outer diameter of 122 to 128 mm, preferably 124 mm to 126 mm, a thickness of 0.1 mm to 1.1 mm, preferably 0.4 mm to 0.6 mm, and has no central hole. This is an example of a disk shape.
- This embodiment is the same as the first embodiment except that the transfer resin substrate 20 does not have a central hole, and is formed by the same method as the first embodiment.
- FIG. 14A is a process diagram of a stage corresponding to FIG. 4F in the manufacturing process in the first embodiment. In FIG. 14A, parts corresponding to those in FIG.
- a first recording layer such as a reflective film, a dielectric film, and a recording film is formed on a molding resin substrate having a center hole (through hole) of about 15 mm in the center
- an ultraviolet curable resin that serves as a spacer layer is spun.
- the ultraviolet curable resin to be applied cannot be arranged at the center.
- a cap processed with metal is fitted as a means for closing the central hole in the central portion, and UV curable resin is supplied to a position substantially equivalent to the central portion on the substrate, so that the coating film thickness is made uniform
- the measures such as measuring are taken.
- a process similar to that of the first embodiment of the present invention is performed while holding an ineffective portion as a recording medium exceeding ⁇ 120 mm by the transfer resin substrate 20 having no central hole in the center. You can go through.
- the ultraviolet curable resin is used for the transfer resin substrate 20 both when the cover layer 61 is formed and when the spacer layers 51a, 52, 53, and 61a are formed. It becomes possible to apply to the central portion, and the film thickness distribution by the spin coating method is remarkably improved.
- the coating film thickness is determined by the viscosity of the resin, the number of rotations at the time of spin coating, and the friction coefficient of the recording layer interface in contact with the resin.
- a method of moving far-infrared rays on the transfer resin substrate 20 during coating rotation at a predetermined speed is also known, but its control is complicated. Even with such a method, maintaining the physical shape of the outermost peripheral portion well requires a lot of labor.
- the transfer resin substrate 20 is a substrate having a diameter larger than 120 mm, for example, a substrate having a diameter of 124 mm, and the optical disk recording medium is multilayered in the same process as in the first embodiment. Then, after the cutting process of the transfer resin substrate 20, that is, through the steps shown in FIGS. 7 and 8, as shown in FIG. 14B, the opening of the central hole 94 and the ineffective portion of the outer peripheral portion are cut. By doing so, it is possible to stably secure a region where the film thickness distribution of the recording film is good. Also in this embodiment example, after that, in the same process as the process shown in FIG. 9 to FIG. 10 in the first embodiment, the transfer to the molding resin substrate 1 and the application of the hard coat material are good. An optical disc recording medium having four recording layers is completed.
- the present invention has been described in the first and second embodiments as a method for producing a four-layer optical disk recording medium, it is obvious that the present invention is effective with three or five recording layers. .
- the present invention is not limited to the write-once recording medium, and can also be applied to a method for producing a rewritable and read-only optical disk recording medium.
- the manufacturing process of the multilayer optical disk recording medium of the present invention eliminates the use of a transparent stamper, and employs a nickel stamper that can be repeatedly used tens of thousands of times or more. As a process that can be used for a long time, it can be used as a process that can be used for a long time.
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Abstract
Description
光ディスク記録媒体は、基板上に、例えば記録膜や誘電体層等が積層された記録層が形成されてなる。そして、光ディスク記録媒体に対する情報の信号の読み出し、又は書き込みは、記録膜を有する記録層にレーザ光を照射することによって行われる。
大容量の光ディスク記録媒体としてのBDは、厚み1.1mmの基板上の凹凸に金属薄膜や誘電体膜などを積層し、厚み約0.1mmの保護層を設けるなどして構成されている。
まず、図15Aに示すように、片面にピットや案内溝となる凹凸パターンを有する、厚み約1.1mmの成形用樹脂基板200上に、金属薄膜や熱記録が可能な薄膜材料などを形成し、第1の記録層L0を形成する。
次に、図15Bに示すように、隣接する記録層を隔てる数μmから、数十μmの厚みを有するスペーサー層201を、成形用樹脂基板200上の第1の記録層L0上に形成する。このスペーサー層201は例えば、紫外線硬化樹脂からなる。そして、スペーサー層201の上に、片面にピットや案内溝などの凹凸パターンを有する透明スタンパ203を押圧し、透明スタンパ203上面から、紫外線を照射して、スペーサー層201を硬化させる。これによって、図15Cに示すように、ピットや、案内溝の凹凸パターン201aが、スペーサー層201上に転写される。
続いて、図15Dに示すように、スペーサー層201の上に転写されたピットや案内溝の凹凸パターン201a上に、記録再生するレーザ光の波長に対して所定の透過率を有する金属薄膜、あるいは熱記録が可能な薄膜材料を形成し、第2の記録層L1を形成する。
そして、最後に、図15Eに示すように、第2の記録層L1を保護する保護層202を、第2の記録層L1上に形成する。
2層以上の記録層によって、多層化を図る場合は、例えば下記特許文献2に記載されているように、信号の記録再生時の層間クロストークを考慮しつつ、上述した第2の記録層の形成工程を数回繰り返し、複数の記録層を順に積層することで可能となる。
さらに、前段で形成された記録層上に、紫外線硬化樹脂層を形成し、紫外線硬化樹脂層に、所望の凹凸パターンを有するニッケルスタンパを押印加圧する。それと同時に、転写用基板側から紫外線照射することにより、紫外線硬化樹脂層に凹凸パターンを形成し、凹凸パターが形成された紫外線硬化樹脂層上に、前段で形成した記録層の光透過率よりも低い光透過率を有する、他の記録層を形成する。
また、他の記録層を形成する工程を必要に応じて複数回繰り返すことにより、順次、前段で形成される記録層よりも光透過率の低い記録層を形成していく。
そして、成形基板を準備し、転写用基板上に形成された、複数の記録層を有する積層膜を、成形基板に転写し、積層膜が転写された成形基板上に、前記積層膜を被覆するハードコート層を形成する。これらに工程により、本発明の光ディスク記録媒体が製造される。
図1に、本発明の第1の実施形態で形成される光ディスク記録媒体の、要部概略断面構成を示す。本実施形態で形成される、光ディスク記録媒体は、4層の記録層を有する光ディスク記録媒体である。図1は、厚みが1.1mm、外径が約120mmの円盤状の成形用樹脂基板1上に、4層の記録層が形成された光ディスク記録媒体の断面の一部を示したものである。
本実施形態例の光ディスク記録媒体は、1.1mm厚の樹脂からなる成形基板(以下、成形用樹脂基板)1上に、第1の記録層L0、スペーサー層51、第2の記録層L1、スペーサー層52、第3の記録層L2、スペーサー層53、第4の記録層L3、カバー層61、ハードコート層71が順に積層されて形成される。
第1の記録層L0は、成形用樹脂基板1側から、反射膜12、第1の誘電膜13、記録膜14、第2の誘電膜15が積層されて構成される。
第2の記録層L1は、成形用樹脂基板1側から、反射膜22、第1の誘電膜23、記録膜24、第2の誘電膜25が積層されて構成される。
第3の記録層L2は、成形用樹脂基板1側から、反射膜32、第1の誘電膜33、記録膜34、第2の誘電膜35が積層されて構成される。
第4の記録層L3は、成形用樹脂基板1側から、反射膜42、第1の誘電膜43、記録膜44、第2の誘電膜45が積層されて構成される。
すなわち、本実施形態例の光ディスク記録媒体における第1の記録層L0~第4の記録層L3の光透過率の大小関係は、L0<L1<L2<L3となる。
凹凸パターンを形成する樹脂層として、カバー層61をそのまま用いてもよいし、スペーサー層用の紫外線硬化樹脂を新たに成膜してもよい。図3Cに示す例においては、スペーサー層用の紫外線硬化樹脂を用いる場合であり、カバー層61の上面に、スペーサー層61aを形成している。このスペーサー層61aを形成するために、紫外線硬化樹脂を、スピンコート法により塗布して成膜する。転写用樹脂基板10の中央部を原点としたときに、紫外線硬化樹脂はディスペンサーを介して半径15mmの位置に適量供給される。このとき、スピンコート装置の回転部は、紫外線硬化樹脂が供給されている間は、例えば、60rpmの低速で回転する。紫外線硬化樹脂は、例えば、5~10秒後に供給完了し、回転部が8000rpmと加速されて5秒後に停止し、所望の厚さに塗布される。
なお、図3Cに示す概略断面構成では、スペーサー層61aを、カバー層61よりも厚く図示しているが、実際には、カバー層61の厚みが、およそ55μmなのに対して、スペーサー層61aは、1~3μmに成膜されるものである。
本実施形態例においては、光ディスク記録媒体の内周及び外周フォーマットと、そのエリアをはずした位置に、切り欠き部が形成される。
光ディスク記録媒体の構造は、大きく分けて、BCA(Burst Cutting Area)101、リードインゾーン(Lead-in Zone)102、データ領域103、リードアウトゾーン(Lead-out Zone)104、アウターゾーン(Outer-Zone)105に分かれている。BDのように、多層の記録層を有する光ディスク記録媒体の場合、第1の記録層以降の構造は、BCA101を除いて同様のレイアウトとなる。
これによって、第1の記録層L0から第4の記録層L3までの多層膜、及びカバー層61の剥離用の端面が、硬化したハードコート層71で保護される。そして、ここにおいて、多層の光ディスク記録媒体が完成する。
図14に本発明の第2の実施形態における4層構造の光ディスク記録媒体の、プロセス中の形状を示す。本実施形態例で形成される光ディスク記録媒体は、図1及び図2に示した光ディスク記録媒体と同様であるから、重複説明を省略する。本実施形態例では、転写樹脂基板20を外径が122~128mmで好ましくは124mm~126mm、厚みが0.1mm~1.1mmで好ましくは0.4mmから0.6mmであり、中心孔のない円盤状とした例である。本実施形態例は、転写用樹脂基板20が、中心孔を有さない以外は、第1の実施形態と同様であり、第1の実施形態と同様の方法で形成される。図14Aは、第1の実施形態における製造工程では、図4Fに相当する段階の工程図である。図14Aにおいて、図4Fに対応する部分には、同一符号を付し、重複説明を省略する。
本実施形態例においても、その後、第1の実施形態における図9~図10に示したプロセスと同様の工程において、成形用樹脂基板1への転写と、ハードコート材の塗布を経て、良好な4層の記録層を有する光ディスク記録媒体が完成する。
2,4・・中心孔
10・・転写用樹脂基板
12,22,32,42・・反射膜
13,23,33,43・・第1の誘電膜
14,24,34,44・・記録膜
15,25,35,45・・第2の誘電膜
61・・カバー層
71・・ハードコート層
91,92・・切り欠き部
51,52,53,61a・・スペーサー層
Claims (6)
- 転写用基板を準備する工程、
前記転写用基板表面に、紫外線硬化樹脂層を形成する工程、
前記紫外線硬化樹脂層に、所望の凹凸パターンを有するニッケルスタンパを押印加圧すると同時に、前記転写用基板裏面側から紫外線照射することにより、前記紫外線硬化樹脂層に凹凸パターンを形成し、前記凹凸パターンが形成された紫外線硬化樹脂層上に、記録層を形成する工程、
前記記録層上に、紫外線硬化樹脂層を形成し、前記紫外線硬化樹脂層に、所望の凹凸パターンを有するニッケルスタンパを押印加圧すると同時に、前記転写用基板側から紫外線照射することにより、前記紫外線硬化樹脂層に凹凸パターンを形成し、前記凹凸パターが形成された紫外線硬化樹脂層上に、前段で形成した前記記録層の光透過率よりも低い光透過率を有する、他の記録層を形成する工程、
前記他の記録層を形成する工程を、必要に応じて複数回繰り返すことにより、複数の記録層を有する積層膜を形成する工程
とを含む光ディスク記録媒体の製造方法。 - 成形基板を準備する工程、
前記転写用基板上に形成された、前記複数の記録層を有する積層膜を、成形基板に転写する工程、
前記積層膜が転写された成形基板上に、前記積層膜を被覆するハードコート層を形成する工程、
を含む請求項1記載の光ディスク記録媒体の製造方法。 - 前記積層膜を成形基板に転写する工程の前に、前記転写用基板上の前記積層膜に、前記複数の記録層の断面が露出されないように、前記転写用基板上の前記積層膜の内周部と外周部に、剥離用の切り欠き部を設ける工程、を有する
請求項2記載の光ディスク記録媒体の製造方法。 - 前記転写用基板には、ニッケルスタンパを押印加圧する工程における芯出しに用いられる中心孔が形成されている
請求項1記載の光ディスク記録媒体の製造方法。 - 前記中心孔は、前記切り欠き部を設ける工程の位置決めに用いられる
請求項4記載の光ディスク記録媒体の製造方法。 - 前記成形基板を準備する工程の後、
前記成形基板上に、記録層を1層形成する工程を有する
請求項1記載の光ディスク記録媒体の製造方法。
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2009
- 2009-03-09 KR KR1020097024930A patent/KR20110006575A/ko not_active Application Discontinuation
- 2009-03-09 WO PCT/JP2009/054459 patent/WO2009139216A1/ja active Application Filing
- 2009-03-09 CN CN200980000395A patent/CN101681654A/zh active Pending
- 2009-03-09 US US12/667,824 patent/US20100330303A1/en not_active Abandoned
- 2009-03-09 EP EP09746423A patent/EP2278585A4/en not_active Withdrawn
- 2009-04-30 TW TW098114444A patent/TW201003650A/zh unknown
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JP2007115356A (ja) * | 2005-10-21 | 2007-05-10 | Toppan Printing Co Ltd | 光ディスクおよびその製造方法 |
JP2007250055A (ja) * | 2006-03-15 | 2007-09-27 | Ricoh Co Ltd | 光記録媒体とその製造方法 |
JP2007257759A (ja) | 2006-03-24 | 2007-10-04 | Matsushita Electric Ind Co Ltd | 光情報記録媒体記録再生システム |
JP2008090950A (ja) * | 2006-10-03 | 2008-04-17 | Canon Inc | 光記録媒体の製造方法および円盤状の基板の芯出し装置 |
WO2008047803A1 (fr) * | 2006-10-18 | 2008-04-24 | Panasonic Corporation | Procédé de fabrication pour support d'enregistrement d'informations multicouche, appareil de fabrication pour support d'enregistrement d'informations multicouche et support d'enregistrement d'informations multicouche |
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Also Published As
Publication number | Publication date |
---|---|
EP2278585A4 (en) | 2011-09-21 |
US20100330303A1 (en) | 2010-12-30 |
JP4577404B2 (ja) | 2010-11-10 |
CN101681654A (zh) | 2010-03-24 |
JP2009277265A (ja) | 2009-11-26 |
TW201003650A (en) | 2010-01-16 |
EP2278585A1 (en) | 2011-01-26 |
KR20110006575A (ko) | 2011-01-20 |
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