WO1999018571A1 - Optic storage medium - Google Patents

Optic storage medium Download PDF

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Publication number
WO1999018571A1
WO1999018571A1 PCT/EP1998/006100 EP9806100W WO9918571A1 WO 1999018571 A1 WO1999018571 A1 WO 1999018571A1 EP 9806100 W EP9806100 W EP 9806100W WO 9918571 A1 WO9918571 A1 WO 9918571A1
Authority
WO
WIPO (PCT)
Prior art keywords
storage medium
optical storage
dye
medium according
layer
Prior art date
Application number
PCT/EP1998/006100
Other languages
German (de)
French (fr)
Inventor
Reiner Vesper
Hartmut LÖWER
Raimund Zimmermann
Wilfried Haese
Original Assignee
Bayer Aktiengesellschaft
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bayer Aktiengesellschaft filed Critical Bayer Aktiengesellschaft
Priority to KR1020007003682A priority Critical patent/KR20010024430A/en
Priority to IL13487298A priority patent/IL134872A0/en
Priority to AU10266/99A priority patent/AU1026699A/en
Priority to CA002305147A priority patent/CA2305147A1/en
Priority to EP98952645A priority patent/EP1023724A1/en
Priority to BR9812868-0A priority patent/BR9812868A/en
Priority to JP2000515272A priority patent/JP2001519581A/en
Publication of WO1999018571A1 publication Critical patent/WO1999018571A1/en
Priority to NO20001746A priority patent/NO20001746D0/en

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Classifications

    • 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
    • G11B7/252—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers
    • G11B7/253—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of substrates
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
    • G11B7/242—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers
    • G11B7/244—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only
    • G11B7/246—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only containing dyes
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G—PHYSICS
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    • 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
    • G11B2007/24618—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 two or more dyes in two or more different layers, e.g. one dye absorbing at 405 nm in layer one and a different dye absorbing at 650 nm in layer two
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    • G11B2220/25—Disc-shaped record carriers characterised in that the disc is based on a specific recording technology
    • G11B2220/2537—Optical discs
    • G11B2220/2545—CDs
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    • 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
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    • 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
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    • 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
    • G11B7/2475—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 merocyanine
    • G—PHYSICS
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    • 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
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    • G11B7/248—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 porphines; azaporphines, e.g. phthalocyanines
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    • 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
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    • G11B7/2534—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of substrates comprising resins polycarbonates [PC]
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    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
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    • G11B7/2535—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of substrates comprising resins polyesters, e.g. PET, PETG or PEN
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    • 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
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    • G11B7/2538—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of substrates comprising resins polycycloolefins [PCO]
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    • 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
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    • G11B7/254—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of protective topcoat layers
    • G11B7/2542—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of protective topcoat layers consisting essentially of organic resins
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    • 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
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Definitions

  • the invention relates to a writable, optical storage medium, in particular in the form of a single or multiple writable compact disk (CD) with a specific carrier layer.
  • a writable, optical storage medium in particular in the form of a single or multiple writable compact disk (CD) with a specific carrier layer.
  • Conventional writable optical storage media in particular CD-Rs, in which the data is recorded and read using laser light, are made up of a transparent support, a recording layer made of a metal such as e.g. Te, Bi or Mn or a dye such as e.g. a cyanine, merocyanine, phthalocyanine or azo dye, a metallic reflection layer and optionally a protective layer.
  • the data is recorded by irradiating laser light through the transparent support.
  • the recording layer is deformed, sublimed, evaporated or modified at the irradiated points, so that depressions are formed if necessary.
  • a free space is often also formed between the recording layer and the adjacent layer.
  • a reflective metal layer made of Au, Ag, Al or Cu and, in turn, a protective layer are usually applied to the writable layer.
  • the reading is carried out by irradiation with a laser light of lower energy, also through the transparent support.
  • the contrast between the light reflected by the depressions and the light reflected by the other parts of the storage medium is read as an electrical signal.
  • Usual non-writable CDs do not have any of the writable layers listed above, but only depressions corresponding to the data to be played back, which are already formed on the carrier, e.g. through press molding. Apart from that, the structure is relatively similar.
  • CD-Rs A problem with known CD-Rs is the relatively high sensitivity of the recording layer. Exposure to heat and radiation can lead to the recording layer changing and the CD-Rs being no longer writable and / or no longer readable. So some manufacturers give that Recommendation not to expose CD-Rs to direct sunlight. Device manufacturers advise not to play CD-Rs in DVD players, as it is feared that the shorter wavelength of the laser used in the DVD player could damage the CD-Rs. The stored information can then only be read incorrectly, which are measured with the aid of electronic test equipment and 'r-rate is specified as a block Erro among others.
  • the block error rate summarizes the total number of incorrect information blocks and should be as small as possible. If the block error rate exceeds 220, the data carrier does not meet specifications.
  • the block error rate is determined with a CD test player. For more information see W. Schild "Errors from the player, errors from the record", from Funkschau 23/1988. It is also possible that the CD-Rs have been changed so much that they can no longer be read or written to.
  • the present invention has for its object to provide writable optical storage media and in particular writable CDs, which have improved stability and thus durability.
  • a writable optical storage medium which comprises a protective layer, one or more writable layers, optionally a light-reflecting layer and at least one carrier layer, and which is characterized in that the carrier layer contains at least one dye so that it has a transmission of at least 70% for the wavelength of the laser used for writing and / or reading and for all other wavelengths of visible light which are at least 100 nm shorter than the wavelength of the laser light has an absorption of at least 70% .
  • the carrier layer preferably contains at least two dyes, particularly preferably three dyes, in order to obtain the desired absorption characteristic.
  • the dye (s) is preferably selected from the group of the anthraquinone and pyrazolone dyes.
  • Makrolexgelb 3G® pyrazolone dye, Color Index, Part 1: Solvent Yellow 93
  • Makrolexrot 5B® anthraquinone dye, Color Index, Part 1, Solvent Red 52, Part 2 No. 68210
  • Hytherm Blue E® anthraquinone dye, Color Index Part 1 Solvent Blue 101
  • the material for the backing layer is not critical, there are no specific restrictions.
  • the carrier layer consists of material usually used for optical storage media and in particular CD-Rs, in particular of the polymers transparent for the laser light used for writing and / or reading, such as poly (co) carbonates, polymethyl methacrylates, poly-4-methylpentene-1, amorphous cyclic polyolefins, polyesters, epoxy resins, polyacrylates, in particular poly (co) carbonate is used. It can have information signals in the form of depressions and / or control signals and / or guide grooves, i.e. it can be an optionally formatted carrier with or without information signals. If necessary, it can be surface-treated in the usual way.
  • the dye (s) are incorporated in the carrier material in the usual way, e.g. by compounding the dyes with or by applying the dyes to the carrier material granules.
  • the dye can preferably also be added as a masterbatch.
  • the concentration of the dye (s) in the carrier material is preferably 0.1 to 1.4% by weight, preferably 0.3-0.8% by weight.
  • the carrier is made from the dye-containing material in the usual way. shaped, e.g. by injection molding or embossing.
  • carrier layers they preferably consist of the same polymer material.
  • the dye (s) can be incorporated in a single or in several carrier layers.
  • the writable layer (s) that may be provided is / are preferably the customary, sensitive dye layer (s) (cf., for example, EP-A 353 392, 488 231 and 410 879). They consist of one or more organic dyes such as phthalocyanines, merocyanines, cyanines, indodicarbocyanines, azulenes and azo dyes. These are applied, for example, as a solution in a solvent in the customary manner, for example by spin coating. As a solvent, for example Diacetone alcohol, fluorinated alcohols such as. B. tetrafluoropropanol, butanol or mixtures thereof.
  • a solvent for example Diacetone alcohol, fluorinated alcohols such as. B. tetrafluoropropanol, butanol or mixtures thereof.
  • the dyes of the writable layer (s) are different from the dyes of the backing layer. Cyanine dyes are particularly preferred.
  • the reflective layer optionally provided preferably consists of a metal with a reflection of more than 80% at the laser light wavelength used, e.g. Au, Ag, AI, Cu or an alloy thereof. It can e.g. by deposition from the gas phase such as vacuum deposition, sputtering, ion-plating or similar techniques.
  • the protective layer consists of a resin with excellent impact resistance, usually an epoxy resin, polyacrylate resin, or silicone hard resin. The protective layer is usually formed by applying the resin by spin coating followed by UV radiation for curing. But it can also consist of a soft material such as a polyurethane resin.
  • the layer thicknesses of the individual layers are preferably 0.5-1.2 mm (carrier), up to 200 nm (writable layer), up to 200 nm (reflective layer) and 5-200 ⁇ m (protective layer).
  • the wavelength of the laser for writing and / or reading is preferably 760-800 nm, particularly preferably 775-785 nm or 620-660 nm, particularly preferably 635-650 nm.
  • the relative viscosity of the polycarbonate is measured using a 0.5% solution of the polycarbonate in methylene chloride at 25 ° C. Examples:
  • polycarbonate granulate 99.6224% by weight polycarbonate granulate, Makrolon CD 2005 from Bayer AG, a polycarbonate from bisphenol-A with tert-butylphenol end groups with an average solution viscosity of 1.20 (measured in
  • the dyes are thoroughly mixed with the granules in a closed vessel and the mixture is then compounded on a Werner Pfleiderer ZSK 53 twin-screw kneader at a melt temperature of approx. 240 ° C.
  • CD-R blanks are produced on a CD injection molding machine with CD-R stamper, which have a thickness of 1.2 mm and an outer diameter of 120 mm.
  • the CD-R production takes place at a melt temperature of 330 ° C, a mold temperature of 100 ° C and a cycle time of 10 seconds.
  • the CD-R stamper has a spirally arranged pre-groove with an average width of 75 nm, an average Depth of 180 nm with a track spacing of 1.6 ⁇ m
  • Fig. 1 shows that the material has a high absorption at wavelengths below 700 nm (measurement geometry: 0 ° / diffuse). Comparative example
  • Analog CD-R blanks are produced for comparison, although no dyes are added to the substrate material Makrolon CD 2005.
  • Fig. 2 shows that the material has high transmission in the entire range of visible light (measurement geometry: 0 ° / diffuse).
  • a layer of dye is then applied to the CD-R blanks.
  • the cyanine dye OM57 from Fuji is used as the dye in conjunction with the Quencher Kayasorb IRG-022 from NipponKayaku Co.
  • the ratio of dye to quencher is 20: 1.
  • the dye / quencher was applied from diacetone alcohol solution by means of spin coating, the conditions being chosen so that an average dye layer thickness of 150 nm results.
  • the CD-Rs obtained, those according to the invention or those from the comparative test, are subsequently written in a Hyundai CD-R 100 burner with 4 times the write / read speed.
  • the block error rate (BLER) of the CD-Rs is then measured using an ISEDD test player from the engineering office for environmental technology and measurement technology, Bielefeld, in which a Philips and a Sony player are integrated.
  • CD-R 60 59 according to the invention
  • the CD-Rs according to the invention and the comparison CD-Rs are then subjected to an exposure test in accordance with ISO 4892-2.
  • the exposure was carried out through the substrate material onto the CD-R dye layer under the following test conditions:
  • Atlas Xenon- WOM light source XENON lamp 6.5KW (from Atlas)
  • the comparison CD-R shows a significant increase in BLER after only about 10 hours of exposure. After about 20 hours of exposure, the BLER was at a value of about 500, i.e. H. far out of specification.
  • the CD-R according to the invention shows no increase in BLER up to practically 50 hours of exposure.

Abstract

The invention relates to an inscribable optic storage medium comprising a protective layer, one or more inscribable layers, optionally a reflecting layer and at least one support layer. The support layer has at least one colorant with at least 70 % transmission at the laser wavelength used for writing and/or reading, and with at least 70 % absorption at all other wavelengths of visible light which are at least 100 nm shorter than the wavelength of the laser light.

Description

Optisches SpeichermediumOptical storage medium
Die Erfindung betrifft ein beschreibbares, optisches Speichermedium, insbesondere in Form einer ein- oder mehrfach beschreibbaren Compact Disk (CD) mit einer spezifischen Trägerschicht.The invention relates to a writable, optical storage medium, in particular in the form of a single or multiple writable compact disk (CD) with a specific carrier layer.
Übliche beschreibbare, optische Speichermedien, insbesondere CD-Rs, bei denen die Datenaufzeichnung und Ablesung mit Hilfe von Laserlicht erfolgt, sind aufgebaut aus einem transparenten Träger, einer Aufzeichnungsschicht aus einem Metall wie z.B. Te, Bi oder Mn oder einem Farbstoff wie z.B. einem Cyanin-, Merocyanin-, Phthalocyanin-, oder Azo-Farbstoff, einer metallischen Reflexionsschicht sowie gegebenenfalls einer Schutzschicht. Die Datenaufzeichnung erfolgt durch Bestrahlen mit Laserlicht durch den transparenten Träger. Dadurch wird die Aufzeichnungschicht an den bestrahlten Punkten deformiert, sublimiert, verdampft oder modifiziert, so daß sich gegebenenfalls Vertiefungen bilden. Häufig bildet sich auch ein freier Raum zwischen der Aufzeichnungsschicht und der benachbarten Schicht. Auf der beschreibbaren Schicht ist üblicherweise eine reflektierende Metallschicht aus Au, Ag, AI oder Cu und wiederum darauf eine Schutzschicht aufgebracht. Die Ablesung erfolgt durch Bestrahlen mit einem Laserlicht geringerer Energie ebenfalls durch den transparenten Träger. Der Kontrast zwischen dem von den Vertiefungen reflektierten Licht und dem von den übrigen Partien des Speichermediums reflektierten Licht wird als elektrisches Signal abgelesen.Conventional writable optical storage media, in particular CD-Rs, in which the data is recorded and read using laser light, are made up of a transparent support, a recording layer made of a metal such as e.g. Te, Bi or Mn or a dye such as e.g. a cyanine, merocyanine, phthalocyanine or azo dye, a metallic reflection layer and optionally a protective layer. The data is recorded by irradiating laser light through the transparent support. As a result, the recording layer is deformed, sublimed, evaporated or modified at the irradiated points, so that depressions are formed if necessary. A free space is often also formed between the recording layer and the adjacent layer. A reflective metal layer made of Au, Ag, Al or Cu and, in turn, a protective layer are usually applied to the writable layer. The reading is carried out by irradiation with a laser light of lower energy, also through the transparent support. The contrast between the light reflected by the depressions and the light reflected by the other parts of the storage medium is read as an electrical signal.
Übliche nicht beschreibbare CDs (ROM-Typ, read-only-memory) weisen keine, vorstehend aufgeführte beschreibbare Schicht auf, sondern nur den wiederzugebenden Daten entsprechende Vertiefungen, die bereits auf dem Träger ausgebildet sind, z.B. durch Pressformen. Davon abgesehen ist der Aufbau relativ ähnlich.Usual non-writable CDs (ROM-type, read-only-memory) do not have any of the writable layers listed above, but only depressions corresponding to the data to be played back, which are already formed on the carrier, e.g. through press molding. Apart from that, the structure is relatively similar.
Für eine genauere Erläuterung s. A. B. Marchant, Optical Recording (1990).For a more detailed explanation see. A. B. Marchant, Optical Recording (1990).
Ein Problem bei bekannten CD-Rs stellt die relativ hohe Empfindlichkeit der Aufzeichnungsschicht dar. Wärmeeinwirkung und Einwirkung von Strahlung können dazu führen, daß sich die Aufzeichnungsschicht verändert und die CD-Rs nicht mehr beschreibbar und/oder nicht mehr lesbar sind. So geben einige Hersteller die Empfehlung, CD-Rs nicht dem direkten Sonnenlicht auszusetzen. Gerätehersteller raten, CD-Rs nicht in DVD-Spielern abzuspielen, da befürchtet wird, daß die kürzere Wellenlänge des im DVD-Spieler verwendeten Lasers die CD-Rs schädigen könnte. Die gespeicherten Informationen sind dann nur noch fehlerhaft ablesbar, was mit Hilfe von elektronischen Testgeräten gemessen werden und u. a. als Block-Erro'r-Rate angegeben wird.A problem with known CD-Rs is the relatively high sensitivity of the recording layer. Exposure to heat and radiation can lead to the recording layer changing and the CD-Rs being no longer writable and / or no longer readable. So some manufacturers give that Recommendation not to expose CD-Rs to direct sunlight. Device manufacturers advise not to play CD-Rs in DVD players, as it is feared that the shorter wavelength of the laser used in the DVD player could damage the CD-Rs. The stored information can then only be read incorrectly, which are measured with the aid of electronic test equipment and 'r-rate is specified as a block Erro among others.
Die Block-Error-Rate gibt summarisch die Gesamtzahl fehlerhafter Informationsblöcke an und soll möglichst klein sein. Überschreitet die Block-Error-Rate den Wert 220, ist der Datenträger nicht spezifikationsgerecht. Die Block-Error-Rate wird mit einem CD- Testspieler ermittelt. Für nähere Angaben s. W. Schild "Fehler vom Player, Fehler von der Platte", aus Funkschau 23/1988. Es ist auch möglich, daß die CD-R so stark verändert sind, daß sie überhaupt nicht mehr gelesen oder beschrieben werden können.The block error rate summarizes the total number of incorrect information blocks and should be as small as possible. If the block error rate exceeds 220, the data carrier does not meet specifications. The block error rate is determined with a CD test player. For more information see W. Schild "Errors from the player, errors from the record", from Funkschau 23/1988. It is also possible that the CD-Rs have been changed so much that they can no longer be read or written to.
Der vorliegenden Erfindung liegt die Aufgabe zugrunde, beschreibbare optische Speichermedien und insbesondere beschreibbare CDs bereitzustellen, die eine verbesserte Stabilität und damit Lebensdauer besitzen.The present invention has for its object to provide writable optical storage media and in particular writable CDs, which have improved stability and thus durability.
Diese Aufgabe wird erfindungsgemäß dadurch gelöst, daß ein beschreibbares optisches Speichermedium zur Verfügung gestellt wird, das eine Schutzschicht, eine oder mehrere beschreibbare Schichten, gegebenenfalls eine lichtreflektierende Schicht und mindestens eine Trägerschicht umfaßt, und das dadurch gekennzeichnet ist, daß die Trägerschicht mindestens einen Farbstoff enthält, so daß sie bei der zum Beschreiben und/oder Ablesen verwendeten Wellenlänge des Lasers eine Transmission von mindestens 70 % aufweist und bei allen anderen Wellenlängen des sichtbaren Lichts, die mindestens 100 nm kürzer sind als die Wellenlänge des Laserlichts eine Absorption von mindestens 70 % aufweist. Bevorzugt enthält die Trägerschicht mindestens zwei Farbstoffe, besonders bevorzugt drei Farbstoffe, um die gewünschte Absorptionscharakteristik zu erhalten.This object is achieved in that a writable optical storage medium is made available which comprises a protective layer, one or more writable layers, optionally a light-reflecting layer and at least one carrier layer, and which is characterized in that the carrier layer contains at least one dye so that it has a transmission of at least 70% for the wavelength of the laser used for writing and / or reading and for all other wavelengths of visible light which are at least 100 nm shorter than the wavelength of the laser light has an absorption of at least 70% . The carrier layer preferably contains at least two dyes, particularly preferably three dyes, in order to obtain the desired absorption characteristic.
Bevorzugt wird der/die Farbstoffe ausgewählt aus der Gruppe der Anthrachinon- und Pyrazolonfarbstoffe. Besonders bevorzugt sind Makrolexgelb 3G® (Pyrazolonfarbstoff, Colour Index, Teil 1 : Solvent Yellow 93), Makrolexrot 5B® (Anthrachinonfarbstoff, Colour Index, Teil 1, Solvent Red 52, Teil 2 Nr. 68210) und Hytherm Blue E® (Anthrachinonfarbstoff, Colour Index Teil 1 Solvent Blue 101).The dye (s) is preferably selected from the group of the anthraquinone and pyrazolone dyes. Makrolexgelb 3G® (pyrazolone dye, Color Index, Part 1: Solvent Yellow 93), Makrolexrot 5B® (anthraquinone dye, Color Index, Part 1, Solvent Red 52, Part 2 No. 68210) and Hytherm Blue E® (anthraquinone dye, Color Index Part 1 Solvent Blue 101).
Das Material für die Trägerschicht ist nicht kritisch, es gibt keine spezifischen Einschränkungen. Die Trägerschicht besteht aus üblicherweise für optische Speichermedien und insbesondere CD-Rs verwendetem Material, insbesondere aus dem für das zum Beschreiben und/oder Ablesen verwendete Laserlicht transparenten Polymeren, wie Poly(co)carbonaten, Polymethylmethacrylaten, Poly-4-methylpenten-l, amorphe cyclische Polyolefine, Polyester, Epoxiharzen, Polyacrylaten, insbesondere wird Poly(co)carbonat verwendet. Sie kann Informationssignale in Form von Vertiefungen und/oder Kontrollsignale und/oder Führungsrillen aufweisen, d.h. sie kann ein gegebenenfalls formatierter Träger mit oder ohne Informationssignale sein. Gegebenenfalls kann sie auf übliche Weise oberflächenbehandelt sein.The material for the backing layer is not critical, there are no specific restrictions. The carrier layer consists of material usually used for optical storage media and in particular CD-Rs, in particular of the polymers transparent for the laser light used for writing and / or reading, such as poly (co) carbonates, polymethyl methacrylates, poly-4-methylpentene-1, amorphous cyclic polyolefins, polyesters, epoxy resins, polyacrylates, in particular poly (co) carbonate is used. It can have information signals in the form of depressions and / or control signals and / or guide grooves, i.e. it can be an optionally formatted carrier with or without information signals. If necessary, it can be surface-treated in the usual way.
Der/die Farbstoffe werden auf übliche Art und Weise in das Trägermaterial eingearbeitet, z.B. durch Compoundieren der Farbstoffe mit oder durch Aufbringen der Farbstoffe auf das Trägermaterial-Granulat. Vorzugsweise kann die Farbstoffzugabe auch als Masterbatch erfolgen.The dye (s) are incorporated in the carrier material in the usual way, e.g. by compounding the dyes with or by applying the dyes to the carrier material granules. The dye can preferably also be added as a masterbatch.
Die Konzentration des/der Farbstoffe im Trägermaterial beträgt bevorzugt 0,1 bis 1,4 Gew-%, vorzugsweise 0,3 - 0,8 Gew-%. Der Träger wird aus dem farbstoffhaltigen Material auf übliche Weise. geformt, z.B. durch Spritzguß oder Prägen.The concentration of the dye (s) in the carrier material is preferably 0.1 to 1.4% by weight, preferably 0.3-0.8% by weight. The carrier is made from the dye-containing material in the usual way. shaped, e.g. by injection molding or embossing.
Falls mehrere Trägerschichten vorgesehen werden, so bestehen sie bevorzugt aus demselben Polymer-Material. Der/die Farbstoffe können in diesem Fall in einer einzigen oder in mehreren Trägerschichten eingearbeitet sein.If several carrier layers are provided, they preferably consist of the same polymer material. In this case, the dye (s) can be incorporated in a single or in several carrier layers.
Die gegebenenfalls vorgesehene(n) beschreibbare(n) Schicht(en) ist/sind bevorzugt die üblichen, sensitiven Farbstoffschicht(en) (vgl. z. B. EP-A 353 392, 488 231 und 410 879). Sie bestehen aus einem oder mehreren organischen Farbstoffen wie Phthalocyaninen, Merocyaninen, Cyaninen, Indodicarbocyaninen, Azulenen und Azo- Farbstoffen. Diese werden z.B. als Lösung in einem Lösungsmittel in üblicher Weise wie z.B. durch spin-coating aufgetragen. Als Lösemittel werden beispielsweise Diacetonalkohol, fluorierte Alkohole wie z. B. Tetrafluorpropanol, Butanol oder auch Gemiche daraus verwandt.The writable layer (s) that may be provided is / are preferably the customary, sensitive dye layer (s) (cf., for example, EP-A 353 392, 488 231 and 410 879). They consist of one or more organic dyes such as phthalocyanines, merocyanines, cyanines, indodicarbocyanines, azulenes and azo dyes. These are applied, for example, as a solution in a solvent in the customary manner, for example by spin coating. As a solvent, for example Diacetone alcohol, fluorinated alcohols such as. B. tetrafluoropropanol, butanol or mixtures thereof.
Die Farbstoffe der einschreibbaren Schicht(en) sind von den Farbstoffen der Trägerschicht verschieden. Besonders bevorzugt sind Cyaninfarbstoffe. Die gegebenenfalls vorgesehene reflektierende Schicht besteht bevorzugt aus einem Metall mit einer Reflexion von mehr als 80% bei der verwendeten Laserlichtwellenlänge wie z.B. Au, Ag, AI, Cu oder einer Legierung daraus. Sie kann z.B. durch Ablagerung aus der Gasphase wie Vakuumablagerung, Sputtering, ion- plating oder ähnliche Techniken aufgebracht werden. Die Schutzschicht besteht aus einem Harz mit hervorragender Schlagfestigkeit, üblicherweise einem Epoxiharz, Polyacrylatharz, oder Silikon-Hartharz. Die Schutzschicht wird üblicherweise durch Auftragen des Harzes durch Spin-Coating gefolgt von UV-Bestrahlung zum Härten gebildet. Sie kann aber auch aus einem weichen Material wie beispielsweise einem Polyurethanharz bestehen.The dyes of the writable layer (s) are different from the dyes of the backing layer. Cyanine dyes are particularly preferred. The reflective layer optionally provided preferably consists of a metal with a reflection of more than 80% at the laser light wavelength used, e.g. Au, Ag, AI, Cu or an alloy thereof. It can e.g. by deposition from the gas phase such as vacuum deposition, sputtering, ion-plating or similar techniques. The protective layer consists of a resin with excellent impact resistance, usually an epoxy resin, polyacrylate resin, or silicone hard resin. The protective layer is usually formed by applying the resin by spin coating followed by UV radiation for curing. But it can also consist of a soft material such as a polyurethane resin.
Die Schichtdicken der einzelnen Schichten betragen bevorzugt 0,5 - 1,2 mm (Träger), bis zu 200 nm (beschreibbare Schicht), bis 200 nm (reflektierende Schicht) und 5 - 200 μm (Schutzschicht).The layer thicknesses of the individual layers are preferably 0.5-1.2 mm (carrier), up to 200 nm (writable layer), up to 200 nm (reflective layer) and 5-200 μm (protective layer).
Die Wellenlänge des Lasers zum Beschreiben und/oder Ablesen beträgt bevorzugt 760- 800 nm, besonders bevorzugt 775-785 nm bzw. 620-660 nm, besonders bevorzugt 635- 650 nm.The wavelength of the laser for writing and / or reading is preferably 760-800 nm, particularly preferably 775-785 nm or 620-660 nm, particularly preferably 635-650 nm.
Die folgenden Beispiele verdeutlichen die Erfindung weiter.The following examples further illustrate the invention.
Die relative Viskosität des Polycarbonats wird mit Hilfe einer 0,5 % Lösung des Polycarbonats in Methylenchlorid bei 25°C gemessen. Beispiele:The relative viscosity of the polycarbonate is measured using a 0.5% solution of the polycarbonate in methylene chloride at 25 ° C. Examples:
Erfindungsgemäßes Beispiel:Example according to the invention:
Als Trägermaterial wird folgende Mischung hergestellt:The following mixture is produced as carrier material:
99,6224 Gew. % Polycarbonatgranulat, Makrolon CD 2005 der Bayer AG, ein Polycarbonat aus Bisphenol-A mit tert.-Butylphenol-Endgruppen einer mittleren Lösungsviskosität von 1.20 (gemessen in99.6224% by weight polycarbonate granulate, Makrolon CD 2005 from Bayer AG, a polycarbonate from bisphenol-A with tert-butylphenol end groups with an average solution viscosity of 1.20 (measured in
Methylenchlorid bei 25°C und einer Konzentration von 0,5g inMethylene chloride at 25 ° C and a concentration of 0.5 g in
100ml Methylenchlorid) 0,06513 Gew.-% Pyrazolonfarbstoff Macrolexgelb 3G (geführt im Colour Index, Teil 1 , als Solvent Yellow 93), Bayer AG100 ml methylene chloride) 0.06513% by weight pyrazolone dye Macrolexgelb 3G (listed in the Color Index, Part 1, as Solvent Yellow 93), Bayer AG
0, 19746 Gew.-% Anthrachinonfarbstoff Macrolexrot 5B (geführt im Colour Index,0, 19746% by weight of anthraquinone dye Macrolexrot 5B (listed in the Color Index,
Teil 1, als Solvent Red 52), Bayer AG 0, 11501 Gew.-% Anthrachinonfarbstoff Hythermblue E (geführt im Colour Index als Solvent Blue 101),Part 1, as Solvent Red 52), Bayer AG 0, 11501% by weight anthraquinone dye Hythermblue E (listed in the Color Index as Solvent Blue 101),
Die Farbstoffe werden mit dem Granulat in einem geschlossenen Gefäß intensiv durchmischt und die Mischung danach auf einem Zwei-Schnecken-Kneter des Typs Werner Pfleiderer ZSK 53 bei einer Massetemperatur von ca. 240°C compoundiert.The dyes are thoroughly mixed with the granules in a closed vessel and the mixture is then compounded on a Werner Pfleiderer ZSK 53 twin-screw kneader at a melt temperature of approx. 240 ° C.
Anschließend werden auf einer CD-Spritzgießmaschine mit CD-R-Stamper CD-R- Rohlinge hergestellt, die eine Dicke von 1,2 mm und einen Außendurchmesser von 120 mm aufweisen. Die CD-R-Herstellung erfolgt dabei bei einer Massetemperatur von 330°C, einer Werkzeugtemperatur von 100°C und einer Zykluszeit von 10 sec. Der CD- R-Stamper weist ein spiralförmig angeordnetes Pregroove mit einer mittleren Breite von 75 nm, einer mittleren Tiefe von 180 nm mit einem Spurabstand von 1,6 μm aufSubsequently, CD-R blanks are produced on a CD injection molding machine with CD-R stamper, which have a thickness of 1.2 mm and an outer diameter of 120 mm. The CD-R production takes place at a melt temperature of 330 ° C, a mold temperature of 100 ° C and a cycle time of 10 seconds. The CD-R stamper has a spirally arranged pre-groove with an average width of 75 nm, an average Depth of 180 nm with a track spacing of 1.6 μm
An den CD-R-Rohlingen wird die Transmission gemessen. Fig. 1 zeigt, daß das Material bei Wellenlängen unterhalb von 700 nm eine hohe Absorption aufweist (Meßgeometrie: 0°/diffus). VergleichsbeispielThe transmission is measured on the CD-R blanks. Fig. 1 shows that the material has a high absorption at wavelengths below 700 nm (measurement geometry: 0 ° / diffuse). Comparative example
Zum Vergleich werden analoge CD-R-Rohlinge hergestellt, wobei allerdings dem Substratmaterial Makrolon CD 2005 keine Farbstoffe zugesetzt werden. Fig. 2 zeigt, daß das Material im gesamten Bereich des sichtbaren Lichtes hohe Transmission aufweist (Meßgeometrie: 0°/diffus).Analog CD-R blanks are produced for comparison, although no dyes are added to the substrate material Makrolon CD 2005. Fig. 2 shows that the material has high transmission in the entire range of visible light (measurement geometry: 0 ° / diffuse).
Anschließend wird auf den CD-R-Rohlingen eine Farbstoffschicht aufgebracht. Als Farbstoff wird der Cyaninfarbstoff OM57 von Fuji in Verbindung mit dem Quencher Kayasorb IRG-022 von NipponKayaku Co. verwandt. Das Verhältnis von Farbstoff zu Quencher beträgt 20:1. Der Farbstoff/Quencherauftrag erfolgte aus Diacetonalkohol- lösung mittels Spincoating, wobei die Bedingungen so gewählt werden, daß eine mittlere Farbstoffschichtdicke von 150 nm resultiert.A layer of dye is then applied to the CD-R blanks. The cyanine dye OM57 from Fuji is used as the dye in conjunction with the Quencher Kayasorb IRG-022 from NipponKayaku Co. The ratio of dye to quencher is 20: 1. The dye / quencher was applied from diacetone alcohol solution by means of spin coating, the conditions being chosen so that an average dye layer thickness of 150 nm results.
Anschließend wird auf die Farbschicht eine 60 bis 80 nm dicke Goldschicht aufgedampft, welche wiederum mit einem ca. 10 μm dicken Schutzlack versehen wird.Then a 60 to 80 nm thick gold layer is evaporated onto the color layer, which in turn is provided with an approximately 10 μm thick protective lacquer.
Die erhaltenen CD-Rs, die erfindungsgemäßen bzw. die aus dem Vergleichsversuch, werden anschließend in einem Yamaha CD-R 100 Brenner mit 4-facher Schreib- /Lesegeschwindigkeit beschrieben. Anschließend wird die Block-Error-Rate (BLER) der CD-Rs mithilfe eines ISEDD-Testspielers des Ingenieurbüros für Umwelttechnologie und Meßtechnik, Bielefeld, in dem ein Philips- und ein Sony-Player integriert sind, gemessen.The CD-Rs obtained, those according to the invention or those from the comparative test, are subsequently written in a Yamaha CD-R 100 burner with 4 times the write / read speed. The block error rate (BLER) of the CD-Rs is then measured using an ISEDD test player from the engineering office for environmental technology and measurement technology, Bielefeld, in which a Philips and a Sony player are integrated.
Die Qualität der CD-Rs liegt auf vergleichbarem Niveau, wie nachfolgende Tabelle zeigt: Tabelle 1The quality of the CD-Rs is at a comparable level, as the following table shows: Table 1
Figure imgf000009_0001
erfindungsgemäße CD-R 60 59
Figure imgf000009_0001
CD-R 60 59 according to the invention
CD-R ohne Farbstoff imCD-R without dye in
Substratmaterial 62 64Substrate material 62 64
Die erfindungsgemäßen CD-Rs sowie die Vergleich-CD-Rs werden anschließend einem Belichtungstest nach ISO 4892-2 unterzogen. Die Belichtung erfolgte durch das Substratmaterial hindurch auf die CD-R-Farbstoffschicht unter folgenden Testbedingungen:The CD-Rs according to the invention and the comparison CD-Rs are then subjected to an exposure test in accordance with ISO 4892-2. The exposure was carried out through the substrate material onto the CD-R dye layer under the following test conditions:
Gerät: Atlas Xenon- WOM Leuchtquelle: XENON-Lampe 6.5KW (v. Atlas)Device: Atlas Xenon- WOM light source: XENON lamp 6.5KW (from Atlas)
Bestrahlungsstärke: 0,35W/(m2*nm), gemessen bei 340nmIrradiance: 0.35W / (m 2 * nm), measured at 340nm
Filterung: Pyrex / PyrexFiltering: Pyrex / Pyrex
Schwarzstandardtemperatur: 65°CBlack standard temperature: 65 ° C
Probenraumtemperatur: 42°C Rel. Luftfeuchte: 65%Sample room temperature: 42 ° C Relative humidity: 65%
Beregnungszyklus : 102/ 18minIrrigation cycle: 102 / 18min
Danach werden wiederum die Block-Error-Raten mit dem ISEED-Testspieler gemessen.Then the block error rates are measured again with the ISEED test player.
Die Vergleichs-CD-R zeigt bereits nach ca. 10 Stunden Belichtungsdauer eine signifikante Zunahme im BLER. Nach ca. 20h Belichtungsdauer lag die BLER auf einem Wert von ca. 500, d. h. weit außerhalb der Spezifikation.The comparison CD-R shows a significant increase in BLER after only about 10 hours of exposure. After about 20 hours of exposure, the BLER was at a value of about 500, i.e. H. far out of specification.
Die erfindungsgemäße CD-R zeigt bis praktisch 50 Stunden Belichtungsdauer keine Zunahme im BLER. The CD-R according to the invention shows no increase in BLER up to practically 50 hours of exposure.

Claims

Patentansprüche: Claims:
1. Beschreibbares, optisches Speichermedium, umfassend eine Schutzschicht, eine oder mehrere einschreibbare Schichten, gegebenenfalls eine lichtreflektierende Schicht und mindestens eine Trägerschicht, dadurch gekennzeichnet, daß die1. Writable, optical storage medium comprising a protective layer, one or more writable layers, optionally a light reflecting layer and at least one carrier layer, characterized in that the
Trägerschicht mindestens einen Farbstoff enthält, und bei der zum Beschreiben und/oder Ablesen verwendeten Wellenlänge des Lasers eine Transmission von mindestens 70 % aufweist und bei allen anderen Wellenlängen des sichtbaren Lichts, die mindestens 100 nm kürzer sind als die Wellenlänge des Laserlichts eine Absorption von mindestens 70 % aufweist.Carrier layer contains at least one dye, and has a transmission of at least 70% at the wavelength of the laser used for writing and / or reading, and an absorption of at least at all other wavelengths of visible light that are at least 100 nm shorter than the wavelength of the laser light 70%.
2. Optisches Speichermedium nach Anspruch 1, dadurch gekennzeichnet, daß die Trägerschicht mindestens zwei Farbstoffe enthält.2. Optical storage medium according to claim 1, characterized in that the carrier layer contains at least two dyes.
3. Optisches Speichermedium nach einem der Ansprüche 1 oder 2, dadurch gekennzeichnet, daß die Transmission mindestens 80 %, vorzugsweise 85 % und die Absorption mindestens 90 %, vorzugsweise 95 % beträgt.3. Optical storage medium according to one of claims 1 or 2, characterized in that the transmission is at least 80%, preferably 85% and the absorption is at least 90%, preferably 95%.
4. Optisches Speichermedium nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß die Wellenlänge des Lasers zum Beschreiben und/oder zum4. Optical storage medium according to one of claims 1 to 3, characterized in that the wavelength of the laser for writing and / or for
Ablesen 760-800 nm, vorzugsweise 775-785 nm beträgt.Reading is 760-800 nm, preferably 775-785 nm.
5. Optisches Speichermedium nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß die Wellenlänge des Lasers zum Beschreiben und/oder zum Ablesen 620-660 nm, vorzugsweise 635-650 nm beträgt.5. Optical storage medium according to one of claims 1 to 3, characterized in that the wavelength of the laser for writing and / or reading is 620-660 nm, preferably 635-650 nm.
6. Optisches Speichermedium nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß der oder die Farbstoffe ausgewählt werden aus der Gruppe der Anthrachinon- oder Pyrazolonfarbstoffe.6. Optical storage medium according to one of claims 1 to 5, characterized in that the dye or dyes are selected from the group of anthraquinone or pyrazolone dyes.
7. Optisches Speichermedium nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß der oder die Farbstoffe ausgewählt werden aus Makrolexgelb 3G®, Makrolexrot 5B® oder Hytherm Blue E®.7. Optical storage medium according to one of claims 1 to 6, characterized characterized in that the dye or dyes are selected from Makrolexgelb 3G®, Makrolexrot 5B® or Hytherm Blue E®.
8. Optisches Speichermedium nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß die Trägerschicht 0,1-1 Gew.% Farbstoff enthält.8. Optical storage medium according to one of claims 1 to 7, characterized in that the carrier layer contains 0.1-1% by weight of dye.
9. Optisches Speichermedium nach einem der Ansprüche 1 bis 8 in Form einer ein- oder mehrfach beschreibbaren Compact Disk.9. Optical storage medium according to one of claims 1 to 8 in the form of a one or more writable compact disk.
10. Optisches Speichermedium nach Anspruch 9, dadurch gekennzeichnet, daß die beschreibbare Schicht aus einem sensitiven Farbstoff besteht, der von dem oder den Farbstoffen unterschiedlich ist. 10. Optical storage medium according to claim 9, characterized in that the writable layer consists of a sensitive dye which is different from the one or more dyes.
PCT/EP1998/006100 1997-10-07 1998-09-24 Optic storage medium WO1999018571A1 (en)

Priority Applications (8)

Application Number Priority Date Filing Date Title
KR1020007003682A KR20010024430A (en) 1997-10-07 1998-09-24 Optic Storage Medium
IL13487298A IL134872A0 (en) 1997-10-07 1998-09-24 Optic storage medium
AU10266/99A AU1026699A (en) 1997-10-07 1998-09-24 Optic storage medium
CA002305147A CA2305147A1 (en) 1997-10-07 1998-09-24 Optic storage medium
EP98952645A EP1023724A1 (en) 1997-10-07 1998-09-24 Optic storage medium
BR9812868-0A BR9812868A (en) 1997-10-07 1998-09-24 Optical storage medium
JP2000515272A JP2001519581A (en) 1997-10-07 1998-09-24 Optical storage medium
NO20001746A NO20001746D0 (en) 1997-10-07 2000-04-05 Optical storage medium

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19744162A DE19744162A1 (en) 1997-10-07 1997-10-07 Writable optical storage medium useful e.g. for compact disk
DE19744162.9 1997-10-07

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EP1395984A2 (en) * 2001-06-05 2004-03-10 Flexplay Technologies, Inc. Limited play optical devices with interstitial reactive layer and methods of making same

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BR9812868A (en) 2000-08-08
DE19744162A1 (en) 1999-04-08
AU1026699A (en) 1999-04-27
CN1273666A (en) 2000-11-15
JP2001519581A (en) 2001-10-23
KR20010024430A (en) 2001-03-26
NO20001746L (en) 2000-04-05
TW464855B (en) 2001-11-21
EP1023724A1 (en) 2000-08-02
NO20001746D0 (en) 2000-04-05
IL134872A0 (en) 2001-05-20

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