WO2002029801A1 - Colored data storage media - Google Patents

Colored data storage media Download PDF

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Publication number
WO2002029801A1
WO2002029801A1 PCT/US2001/026275 US0126275W WO0229801A1 WO 2002029801 A1 WO2002029801 A1 WO 2002029801A1 US 0126275 W US0126275 W US 0126275W WO 0229801 A1 WO0229801 A1 WO 0229801A1
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WO
WIPO (PCT)
Prior art keywords
storage media
substrate
group
foregoing
copolymers
Prior art date
Application number
PCT/US2001/026275
Other languages
French (fr)
Inventor
Curtis R. Cradic
Steven Richard Peak
Connie J. Bland
Steven Frederick Hubbard
Original Assignee
General Electric Company A Corporation Of The State Of New York
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 General Electric Company A Corporation Of The State Of New York filed Critical General Electric Company A Corporation Of The State Of New York
Priority to KR10-2003-7004547A priority Critical patent/KR20040005827A/en
Priority to JP2002533293A priority patent/JP2004511061A/en
Priority to AU2001285209A priority patent/AU2001285209A1/en
Priority to EP20010964344 priority patent/EP1325498B1/en
Priority to AT01964344T priority patent/ATE543181T1/en
Publication of WO2002029801A1 publication Critical patent/WO2002029801A1/en

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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G83/00Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
    • GPHYSICS
    • G11INFORMATION STORAGE
    • G11BINFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00Recording 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
    • G11B7/24Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/241Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
    • G11B7/252Record 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
    • G11B7/253Record 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
    • G11B7/2533Record 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
    • GPHYSICS
    • G11INFORMATION STORAGE
    • G11BINFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00Recording 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
    • G11B7/24Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/241Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
    • G11B7/242Record 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
    • G11B7/243Record 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 inorganic materials only, e.g. ablative layers
    • G11B7/2433Metals or elements of groups 13, 14, 15 or 16 of the Periodic System, e.g. B, Si, Ge, As, Sb, Bi, Se or Te
    • GPHYSICS
    • G11INFORMATION STORAGE
    • G11BINFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00Recording 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
    • G11B7/24Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/241Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
    • G11B7/242Record 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
    • G11B7/244Record 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
    • G11B7/246Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only containing dyes
    • G11B7/247Record 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
    • G11B7/2472Record 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
    • GPHYSICS
    • G11INFORMATION STORAGE
    • G11BINFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00Recording 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
    • G11B7/24Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/241Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
    • G11B7/242Record 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
    • G11B7/244Record 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
    • G11B7/246Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only containing dyes
    • G11B7/248Record 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
    • GPHYSICS
    • G11INFORMATION STORAGE
    • G11BINFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00Recording 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
    • G11B7/24Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/241Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
    • G11B7/252Record 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
    • GPHYSICS
    • G11INFORMATION STORAGE
    • G11BINFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00Recording 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
    • G11B7/24Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/241Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
    • G11B7/252Record 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
    • G11B7/253Record 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
    • G11B7/2533Record 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
    • G11B7/2534Record 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]
    • GPHYSICS
    • G11INFORMATION STORAGE
    • G11BINFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00Recording 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
    • G11B7/24Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/241Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
    • G11B7/252Record 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
    • G11B7/254Record 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
    • G11B7/2542Record 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
    • GPHYSICS
    • G11INFORMATION STORAGE
    • G11BINFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00Recording 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
    • G11B7/24Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/241Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
    • G11B7/252Record 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
    • G11B7/254Record 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
    • G11B7/2548Record 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 inorganic materials
    • GPHYSICS
    • G11INFORMATION STORAGE
    • G11BINFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00Recording 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
    • G11B7/24Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/241Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
    • G11B7/252Record 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
    • G11B7/257Record 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 layers having properties involved in recording or reproduction, e.g. optical interference layers or sensitising layers or dielectric layers, which are protecting the recording layers
    • G11B7/2578Record 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 layers having properties involved in recording or reproduction, e.g. optical interference layers or sensitising layers or dielectric layers, which are protecting the recording layers consisting essentially of inorganic materials
    • GPHYSICS
    • G11INFORMATION STORAGE
    • G11BINFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00Recording 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
    • G11B7/24Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/241Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
    • G11B7/252Record 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
    • G11B7/258Record 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 reflective layers
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/31504Composite [nonstructural laminate]
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/31504Composite [nonstructural laminate]
    • Y10T428/31507Of polycarbonate

Definitions

  • the present disclosure relates to data storage media, and especially relates to fluorescent, plastic data storage media.
  • Optical, magnetic and magneto-optic media are primary sources of high performance storage technology which enables high storage capacity coupled with a reasonable price per megabyte of storage.
  • Use of optical media has become widespread in audio, video, and computer data applications in such formats as compact disk (CD), digital versatile disk (DVD) including multi-layer structures like DVD-5, DND-9, and multi-sided formats such as DND-10, and DND-18, magneto- optical disk (MO), and other write-once and rewritable formats such as CD-R, CD- RW, DND-R, DND-RW, DND+RW, DVD-RAM.
  • data are encoded onto a substrate into a digital data series.
  • pre-recorded media such as CD
  • the data are typically pits and grooves formed on the surface of a plastic substrate through a method such as injection molding, stamping or the like.
  • the data are encoded by laser, which illuminates an active data layer that undergoes a phase change, thus producing a series of highly-reflecting or non-reflective regions making up the data stream.
  • a laser beam first travels through a plastic substrate before reaching the data layer. At the data layer, the beam is either reflected or not, in accordance with the endcoded data. The laser light then travels back through the plastic and into an optical detector system where the data are interpreted.
  • the media comprises: a substrate comprising colorant and plastic, wherein the substrate has a transmissivity of less than about 85% at a readback laser wavelength, when traversing a 1.2 mm thick colored subtrate (disk).
  • the media comprises: a substrate comprising a fluorescent colorant and plastic, wherein the substrate has a fluorescent color emission wavelength which is not equal to the readback laser wavelength.
  • the present invention relates to data storage media, namely, colored optical data storage media and methods for making the same.
  • the colored media has, at the readback laser wavelength, a transmissivity of light of about 85% or less, with about 70% to about 85% preferred, about 75% to about 80% also preferred, and about 75% to about 85% especially preferred, when traversing a 1.2 mm thick colored substrate (disk).
  • the media if fluorescent, the media preferably emits light at a wavelength which does not inhibit data retrieval.
  • the fluorescent media can comprise a substrate which has a transmissivity, at the readback laser wavelength, exceeding 68%, with about 70% to about 95% preferred, about 70% to about 95% more preferred, and about 70% to about 85% especially preferred, when traversing a 1.2 mm thick substrate (disk).
  • these storage media can comprise a substrate comprising a plastic and a colorant which does not inhibit data retrieval.
  • a colorant which does not inhibit data retrieval.
  • up to about 10 weight percent (wt%) colorant can be used, with up to about 5 wt% preferred, up to - about 1 wt% colorant more preferred, and less than about 0.5 wt% or so colorant especially preferred, based upon the total weight of the substrate.
  • any plastic that exhibits appropriate properties and can be employed.
  • the plastic should be capable of withstanding the subsequent processing parameters (e.g., application of subsequent layers) such as sputtering (i.e., temperatures up to and exceeding about 200°C (typically up to or exceeding about 300°C) for magnetic media, and temperatures of about room temperature (about 25 °C) up to about 150°C for magneto-optic media). That is, it is desirable for the plastic to have sufficient thermal stability to prevent deformation during the deposition steps.
  • appropriate plastics include thermoplastics with glass transition temperatures greater than about 150°C, with greater than about 200°C preferred (e.g., polyetherimides, polyetheretherketones, polysulfones, polyethersulfones, polyetherethersulfones, polyphenylene ethers, polyimides, high heat polycarbonates, etc.); with materials having glass transition temperatures greater than about 250°C more preferred, such as polyetherimide in which sulfonedianiline or oxydianiline has been substituted for m-phenylenediamine, among others, as well as polyimides, such as Probimide (or the dry powder equivalent, Matrimid 5218, from Ciba Geigy Chemical); combinations comprising at least one of the foregoing plastics, and others.
  • thermoplastics with glass transition temperatures greater than about 150°C, with greater than about 200°C preferred
  • materials having glass transition temperatures greater than about 250°C more preferred such as polyetherimide in which sulfonedianiline or
  • thermosets it is possible for thermosets to be used in the application provided the thermoset possess sufficient flow under the stamping conditions to permit formation of the desired surface features.
  • a plastic homopolymer, copolymer, or blend
  • polymer blends such as those described in U.S. Patent No. 5,534,602 (to Lupinski and Cole, 1996), may be employed in the preparation of the coating solution.
  • polymer blends provide, selectively, variable glass transition temperatures of about 190°C to about 320°C.
  • plastics include, but are not limited to, amorphous, crystalline and semi-crystalline thermoplastic materials: polyvinyl chloride, polyolefms (including, but not limited to, linear and cyclic polyolefins and including polyethylene, chlorinated polyethylene, polypropylene, and the like), polyesters (including, but not limited to, polyethylene terephthalate, polybutylene terephthalate, polycyclohexylmethylene terephthalate, and the like), polyamides, polysulfones (including, but not limited to, hydrogenated polysulfones, and the like), polyimides, polyether imides, polyether sulfones, polyphenylene sulfides, polyether ketones, polyether ether ketones, ABS resins, polystyrenes (including, but not limited to, hydrogenated polystyrenes, syndiotactic and atactic polystyrenes, polycyclohexyl
  • R 1 is an aromatic organic radical and, more preferably, a radical of the formula (II):
  • each of A 1 and A 2 is a monocyclic divalent aryl radical and Y 1 is a bridging radical having one or two atoms which separate A from A .
  • one atom separates A ! from A 2 .
  • radicals of this type are -O-, -S-, -S(O)-, -S(O 2 )-, -C(O)-, methylene, cyclohexyl-methylene, 2-[2,2,l]-bicycloheptylidene, ethylidene, isopropylidene, neopentylidene, cyclohexylidene, cyclopentadecylidene, cyclododecylidene, and adamantylidene.
  • the bridging radical Y 1 can be a hydrocarbon group or a saturated hydrocarbon group such as methylene, cyclohexylidene or isopropylidene.
  • Polycarbonates can be produced by the interfacial reaction of dihydroxy compounds in which only one atom separates A 1 and A 2 .
  • dihydroxy compound includes, for example, bisphenol compounds having general formula (El) as follows:
  • R a and R b each represent a halogen atom or a monovalent hydrocarbon group and may be the same or different; p and q are each independently integers from 0 to 4; and X 8 represents one of the groups of formula (IN):
  • R c and R d each independently represent a hydrogen atom or a monovalent linear or cyclic hydrocarbon group and R e is a divalent hydrocarbon group.
  • dihydroxy compounds include dihydric phenols and the dihydroxy-substituted aromatic hydrocarbons disclosed by name or formula (generic or specific) in U.S. Patent 4,217,438, which is incorporated herein by reference.
  • a nonexclusive list of specific examples of the types of bisphenol compounds that may be represented by formula (IE) includes the following: l,l-bis(4-hydroxyphenyl) methane; l,l-bis(4- hydroxyphenyl) ethane; 2,2-bis(4-hydroxyphenyl) propane (hereinafter "bisphenol A” or "BPA”); 2,2-bis(4-hydroxyphenyl) butane; 2,2-bis(4-hydroxyphenyl) octane; 1,1- bis(4-hydroxyphenyl) propane; l,l-bis(4-hydroxyphenyl) n-butane; bis(4- hydroxyphenyl) phenylmethane; 2,2-bis(4-hydroxy-l-methylphenyl) propane; 1,1- bis(4-hydroxy-t-butylphenyl) propane; bis(hydroxyaryl) alkanes such as 2,2-bis(4- hydroxy-3-bromophenyl) propane; l,l-bis(4
  • polycarbonates resulting from the polymerization of two or more different, dihydric phenols or a copolymer of a dihydric phenol with a glycol or with a hydroxy- or acid-terminated polyester or with a dibasic acid or with a hydroxy acid or with an aliphatic diacid in the event a carbonate copolymer rather than a homopolymer is desired for use.
  • useful aliphatic diacids have from 2 to about 40 carbons.
  • a preferred aliphatic diacid is dodecandioic acid.
  • Polyarylates and polyester-carbonate resins or their blends can also be employed.
  • Branched polycarbonates are also useful, as well as blends of linear polycarbonate and a branched polycarbonate. The branched polycarbonates may be prepared by adding a branching agent during polymerization.
  • branching agents are well known and may comprise polyfunctional organic compounds containing at least three functional groups which may be hydroxyl, carboxyl, carboxylic anhydride, haloformyl and mixtures comprising at least one of the foregoing.
  • Specific examples include trimellitic acid, trimellitic anhydride, trimellitic trichloride, tris-p-hydroxy phenyl ethane, isatin-bis- phenol, tris-phenol TC (l,3,5-tris((p-hydroxyphenyl)isopropyl)benzene), tris-phenol PA (4(4(1, l-bis(p-hydroxyphenyl)-ethyl) alpha,alpha-dimethyl benzyl)phenol), 4- chloroformyl phthalic anhydride, trimesic acid and benzophenone tetracarboxylic acid, and the like.
  • the branching agents may be added at a level of about 0.05 to about 2.0 weight percent. Branching agents and procedures for making branched polycarbonates are described in U.S. Patent. Nos. 3,635,895 and 4,001,184 which are incorporated by reference. All types of polycarbonate end groups are herein contemplated.
  • Preferred polycarbonates are based on bisphenol A, in which each of A 1 and A 2 is p-phenylene and Y l is isopropylidene.
  • the weight average molecular weight of the polycarbonate is about 5,000 to about 100,000, more preferably about 10,000 to about 65,000, and most preferably about 15,000 to about 35,000.
  • concentration of Fries product present in the polycarbonate it is of particular interest to determine the concentration of Fries product present in the polycarbonate. As noted, the generation of significant Fries product can lead to polymer branching, resulting in uncontrollable melt behavior.
  • the terms "Fries” and “Fries product” denote a repeating unit in polycarbonate having the formula (V):
  • X a is a bivalent radical as described in connection with Formula (III) supra.
  • the polycarbonate composition may also include various additives ordinarily incorporated in resin compositions of this type.
  • additives are, for example, fillers or reinforcing agents; heat stabilizers; antioxidants; light stabilizers; plasticizers; antistatic agents; mold releasing agents; additional resins; blowing agents; and the like, as well as combinations comprising at least one of the foregoing additives.
  • fillers or reinforcing agents include glass fibers, asbestos, carbon fibers, silica, talc and calcium carbonate.
  • heat stabilizers examples include triphenyl phosphite, tris-(2,6-dimethylphenyl)phosphite, tris-(mixed mono-and di- nonylphenyl)phosphite, dimethylbenene phosphonate and trimethyl phosphate.
  • antioxidants include octadecyl-3-(3,5-di-tert-butyl-4- hydroxyphenyl)propionate, and pentaerythrityl-tetrakis[3-(3 ,5-di-tert-butyl-4- hydroxyphenyl)propionate].
  • Examples of light stabilizers include 2-(2-hydroxy-5- methylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)-benzotriazole and 2- hydroxy-4-n-octoxy benzophenone.
  • plasticizers include dioctyl-4,5- epoxy-hexahydrophthalate, tris-(octoxycarbonylethyl)isocyanurate, tristearin and epoxidized soybean oil.
  • Examples of the antistatic agent include glycerol monostearate, sodium stearyl sulfonate, and sodium dodecylbenzenesulfonate.
  • mold releasing agents include stearyl stearate, beeswax, montan wax and paraffin wax.
  • other resins include but are not limited to polypropylene, polystyrene, polymethyl methacrylate, and polyphenylene oxide. Combinations of any of the foregoing additives may be used. Such additives may be mixed at a suitable time during the mixing of the components for forming the composition.
  • the color is imparted to the substrate with a colorant (e.g., dye, pigment, or the like).
  • a colorant e.g., dye, pigment, or the like.
  • the amount and type of colorant is chosen to avoid producing a substrate having contaminants (i.e., by-products) which produce data readout errors, and to attain the desired color., while controlling transmissivity, at the readback laser wavelength, to greater than about 68%, when traversing a 1.2 mm thick colored substrate (disk).
  • the substrate may be fluorescent, that is, emit light at a particular wavelength.
  • the colorant is a fluorescent material which has a fluorescent color emission wavelength which is not equal to the readback laser wavelength, and preferably different by at least about 10 nanometers (nm) (i.e., higher or lower) than the readback laser wavelength, with a difference of about 15 nm or greater preferred, and about 20 nm or greater especially preferred.
  • the substrate have a transmissivity at the readback laser frequency, of greater than about 70% when traversing a 1.2 mm thick colored substrate (disk).
  • Some possible fluorescent colorants include:
  • the decorative layer which is disposed on a side of the disk opposite a data storage layer or in between data storage layers which are read from opposite sides of the disk, can be any color or design, such as a design which optionally includes sparkle, i.e., visual effects which scatter the incident light (such as glass or metal (in the form of flakes, chips, particles, powder, and the like, as well as combinations comprising at least one of the foregoing forms, with flakes preferred), titanium dioxide (TiO 2 ), mica, fiberglass, angular metamerism materials such as, ChromaFlair Gold/Silver 080, ChromaFlair Cyan/Purple 230 (commercially available from Flex Products, Santa Rosa, California), among other materials, as well as combinations comprising at least one of the foregoing visual effects.
  • sparkle i.e., visual effects which scatter the incident light
  • titanium dioxide TiO 2
  • mica titanium dioxide
  • fiberglass angular metamerism materials
  • ChromaFlair Gold/Silver 080 ChromaF
  • the composition may optionally include various additives ordinarily incorporated in resin compositions of this type.
  • additives may include antioxidants, heat stabilizers, anti-static agents (terra alkylammonium benzene sulfonate salts, terra alkylphosphonium benzene sulfonate salts, and the like), mold releasing agents (pentaerythritol tetrastearate; glycerol monstearate, and the like), and the like, and combinations comprising at least one of the foregoing.
  • the substrate can comprise about 0.01 to about 0.1 wt% of a heat stabilizer; about 0.01 to about 0.2 wt% of an antistatic agent; and about 0.1 to about 1 wt% of a mold releasing agent; based upon the total weight of the substrate.
  • antioxidants include, for example, organophosphites, e.g., tris(nonyl-phenyl)phosphite, tris(2,4-di-t-butylphenyl)phosphite, bis(2,4-di-t- butylphenyl)pentaerythritol diphosphite, distearyl pentaerythritol diphosphite and the like; alkylated monophenols, polyphenols and alkylated reaction products of polyphenols with dienes, such as, for example, tetrakis[methylene(3,5-di-tert-butyl-4- hydroxyhydrocinnamate)] methane, 3,5-di-tert-butyl-4-hydroxyhydrocinnamate octadecyl, 2,4-di-tert-butylphenyl phosphite, and the like; butylated reaction products of
  • UN absorbers comprise: UN absorbers; stabilizers such as light and thermal stabilizers (e.g., acidic phosphorous- based compounds); hindered phenols; zinc oxide and/or zinc sulfide particles; lubricants (mineral oil, and the like), plasticizers, dyes (quinines, azobenzenes, and the like); among others, as well as combinations comprising at least one of the foregoing additives.
  • stabilizers such as light and thermal stabilizers (e.g., acidic phosphorous- based compounds); hindered phenols; zinc oxide and/or zinc sulfide particles; lubricants (mineral oil, and the like), plasticizers, dyes (quinines, azobenzenes, and the like); among others, as well as combinations comprising at least one of the foregoing additives.
  • stabilizers such as light and thermal stabilizers (e.g., acidic phosphorous- based compounds); hindered phenols; zinc oxide and
  • catalyst(s) may also be employed, namely in the extruder or other mixing device.
  • the catalyst typically assists in controlling the viscosity of the resulting material.
  • Possible catalysts include tetraalkylammonium hydroxide, tetraalkylphosphonium hydroxide and the like, with diethyldimethylammonium hydroxide and tetrabutylphosphonium hydroxide preferred.
  • the catalyst(s) can be employed alone or in combination with quenchers such as acids, such as phosphoric acid, and the like. Additionally, water may be injected into the polymer melt during compounding and removed as water vapor through a vent to remove residual volatile compounds.
  • Data storage media can be produced by first forming the plastic using a conventional reaction vessel capable of adequately mixing various precursors, such as a single or twin screw extruder, kneader, blender, or the like.
  • the precursors can either be premixed with the colorant (e.g., in a pellet, powder, and/or liquid form) and simultaneously fed through a hopper into the extruder, or the colorant can be optionally added in the feed throat or through an alternate injection port of the injection molding machine or other molding.
  • the extruder should be maintained at a sufficiently high temperature to melt the plastic precursors without causing decomposition thereof.
  • temperatures of about 220°C to about 360°C can be used, with about 260°C to about 320°C preferred.
  • the residence time in the extruder should be controlled to minimize decomposition. Residence times of up to about 2 minutes (min) or more can be employed, with up to about 1.5 min preferred, and up to about 1 min especially preferred.
  • the mixture Prior to extrusion into the desired form (typically pellets, sheet, web, or the like, the mixture can optionally be filtered, such as by melt filtering and/or the use of a screen pack, or the like, to remove undesirable contaminants or decomposition products.
  • the plastic composition can be formed into the data storage media using various molding and/or processing techniques.
  • Possible molding techniques include injection molding, film casting, extrusion, press molding, blow molding, stamping, and the like.
  • additional processing such as electroplating, coating techniques (spin coating, spray coating, vapor deposition, screen printing, painting, dipping, and the like), lamination, sputtering, and combinations comprising at least one of the foregoing processing techniques, among others conventionally known in the art, may be employed to dispose desired layers on the colored substrate.
  • An example of a polycarbonate data storage media comprises an injection molded colored polycarbonate substrate which may optionally comprise a hollow (bubbles, cavity, and the like) or filled (metal, plastics, glass, ceramic, and the like, in various forms such as fibers, spheres, particles, and the like) core. Disposed on the substrate are various layers including: a data layer, dielectric layer(s), a reflective layer(s), and/or a protective layer, as well as combinations comprising at least one of the foregoing layers. These layers comprise conventional materials and are disposed in accordance with the type of media produced.
  • the layers may be protective layer, dielectric layer, data storage layer, dielectric layer, and then the reflective layer disposed in contact with the substrate, 5 with an optional decorative layer disposed on the opposite side of the substrate.
  • the layers may be optional decorative layer, protective layer, reflective layer, dielectric layer, and data storage layer, with a subsequent dielectric layer in contact with the substrate. It is understood that the form of the media is not limited to disk-shape, but may be any shape which can be 10 accommodated in a readout device.
  • the data storage Iayer(s) may comprise any material capable of storing retrievable data, such as an optical layer, magnetic layer, or a magneto-optic layer.
  • the data layer has a thickness of up to about 600 Angstroms (A) or so, with a thickness up to about 300A preferred.
  • Possible data storage layers include, but are 15 not limited to, oxides (such as silicone oxide), rare earth element - transition metal alloy, nickel, cobalt, chromium, tantalum, platinum, terbium, gadolinium, iron, boron, others, and alloys and combinations comprising at least one of the foregoing, organic dye (e.g., cyanine or phthalocyanine type dyes), and inorganic phase change compounds (e.g., TeSeSn, InAgSb, and the like).
  • oxides such as silicone oxide
  • rare earth element - transition metal alloy nickel, cobalt, chromium, tantalum, platinum, terbium, gadolinium, iron, boron, others, and alloys and combinations comprising at least one of the foregoing
  • organic dye e.g., cyanine or phthalocyanine type dyes
  • inorganic phase change compounds e.g., TeSeSn, InAgSb, and the like.
  • the protective layer(s), which protect against dust, oils, and other contaminants, can have a thickness of greater than about 100 microns ( ⁇ ) to less than about 10 A, with a thickness of about 300 or less preferred in some embodiments, and a thickness of about 100 A or less especially preferred.
  • the thickness of the protective layer(s) is usually determined, at least in part, by the type of read/write
  • Possible protective layers include anti-corrosive materials such as gold, silver, nitrides (e.g., silicon nitrides and aluminum nitrides, among others), carbides (e.g., silicon carbide and others), oxides (e.g., silicon dioxide and others), polymeric materials (e.g., polyacrylates or polycarbonates), carbon film (diamond, diamond-like carbon, and the
  • Possible dielectric layers include nitrides (e.g., silicon nitride, aluminum nitride, and others); oxides (e.g., aluminum oxide); carbides (e.g., silicon carbide); and combinations comprising at least one of the foregoing materials, among other materials compatible within the environment and preferably not reactive with the surrounding layers.
  • the reflective layer(s) should have a sufficient thickness to reflect a sufficient amount of energy (e.g., light) to enable data retrieval.
  • the reflective layer(s) can have a thickness of up to about 70 ⁇ A or so, with a thickness of about 300 A to about 600 A generally preferred.
  • Possible reflective layers include any material capable of reflecting the particular energy field, including metals (e.g., aluminum, silver, gold, titanium, and alloys and mixtures comprising at least one of the foregoing metals, and others).
  • lubrication layer In addition to the data storage layer(s), dielectric layer(s), protective layer(s) and reflective layer(s), other layers can be employed such as lubrication layer and others.
  • Useful lubricants include fluoro compounds, especially fluoro oils and greases, and the like.
  • Colored pellets were prepared by mixing low viscosity polycarbonate resin powder (melt flow at 250°C of 11 grams per 10 minutes (ASTM-D1238); molecular weight of about 17,700 grams per mole (g/mol) measured on GPC) with colorants specified in the Table. Formulations also included mold release agent (0.02 wt% glycerol monostearate) and Doverphos (S-9228); Bis(2,4- dicumylphenyl)pentaerythritol diphosphate antioxidant at 0.02 wt%). The blends were melted in a 30 millimeter (mm) twin-screw extruder, passed through a die, cooled, and pelletized.
  • mm millimeter
  • Resulting pellets were injection molded into 1.2 mm thick compact disk substrates using a Krauss Maffei 80/190°C Marathon Series, CD Liner, w/Non- Open Mold. Processing conditions as follows: Barrel Zone Temperature of about 250 to about 330°C; Mold Temperatures set to 45°C; Injection Speed Profile of about 20 millimeters per second (mm/s) to about 65 mm s, 4 stages; Holding Pressure profile of about 150 bar to about 550 bar, 5 stages; Holding Pressure Time of about 0.05 to about 0.25 seconds, 5 stages; Cooling Time set for 2.5 seconds; Clamp Tonnage set for 400 kN; Injection pressure set at 1795 bar; Injection Position Profile of about 17.0 mm to about 4.5 mm, 4 stages.
  • Block Error Rate is a measure of the number of blocks of data that have at least one occurrence of erroneous data. BLER is the combination of El 1+E21+E31+E12+E22+E32 errors.
  • a Block Error Rate below about 220 pulses is typically required in industry, with below 100 preferred, and below 50 especially preferred.
  • Pellets were also injection molded into 1.2 mm thick colored substrate (disk) and placed in spectrophotometer to determine the absorbance at 780 nanometers (nm), (i.e., the wavelength of the optical disk tester. If the disc is not readable by the tester an error message is given such as: "Unable to Retrieve NTOC (IFB)". Which means that the tester could not establish the "Volume Table of Contents", this information shows the layout of the program material on the disc.
  • IOB Unable to Retrieve NTOC
  • TRM amount of light transmitted through the substrate
  • the visual effects can be disposed between two substrates with reflective and data layers disposed between the visual effects and the substrate, optionally, adhesives can be used for bonding.
  • adhesives can be used for bonding.

Abstract

The colored data storage media comprises a substrate comprising colorant and plastic, wherein the substrate has a transmissivity of about 85% or less, at a readback laser wavelength, when traversing 1.2 mm thick colored substrate (disk). Alternatively, the storage media comprises: a substrate comprising a fluorescent colorant and plastic, wherein the substrate has a fluorescent color emission wavelength which is not equal to the readback laser wavelength.

Description

COLORED DATA STORAGE MEDIA
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims the benefit of the filing date of U.S. Provisional Application Serial No. 60/236,434, filed on September 29, 2000, which is hereby incorporated by reference.
TECHNICAL FIELD
[0002] The present disclosure relates to data storage media, and especially relates to fluorescent, plastic data storage media.
BACKGROUND
[0003] Optical, magnetic and magneto-optic media are primary sources of high performance storage technology which enables high storage capacity coupled with a reasonable price per megabyte of storage. Use of optical media has become widespread in audio, video, and computer data applications in such formats as compact disk (CD), digital versatile disk (DVD) including multi-layer structures like DVD-5, DND-9, and multi-sided formats such as DND-10, and DND-18, magneto- optical disk (MO), and other write-once and rewritable formats such as CD-R, CD- RW, DND-R, DND-RW, DND+RW, DVD-RAM. In these and other formats, data are encoded onto a substrate into a digital data series. In pre-recorded media, such as CD, the data are typically pits and grooves formed on the surface of a plastic substrate through a method such as injection molding, stamping or the like.
[0004] In recordable and rewritable media, the data are encoded by laser, which illuminates an active data layer that undergoes a phase change, thus producing a series of highly-reflecting or non-reflective regions making up the data stream. In these formats, a laser beam first travels through a plastic substrate before reaching the data layer. At the data layer, the beam is either reflected or not, in accordance with the endcoded data. The laser light then travels back through the plastic and into an optical detector system where the data are interpreted.
[0005] It is well known in the art that, due to the sensitivity of the optical readout system, the amount of absoiption of the light by the media should be minimized. Consequently, the plastic in the optical media is a colorless, transparent material having good birefringence properties, such as polycarbonate. Although media formats have been introduced which read data from the top-side of a substrate, the vast majority of playback systems are only compatible with media requiring the laser to travel through the substrate twice. Hence, the transparency to the laser is a requirement and colorless materials are typically used to maximize transparency at the laser wavelength.
[0006] The widespread use of colorless, transparent materials makes product differentiation difficult, except by costly printing methods on the top surface of the optical media. Furthermore, in the cases where printed decorations cover one entire surface of a disk, the covered surface is unusable for data storage.
[0007] What is needed in the art are colored plastic compositions for use as optical media.
BRIEF SUMMARY
[0008] The colored data storage media overcomes the above described drawbacks and deficiencies. In one embodiment, the media comprises: a substrate comprising colorant and plastic, wherein the substrate has a transmissivity of less than about 85% at a readback laser wavelength, when traversing a 1.2 mm thick colored subtrate (disk).
[0009] In another embodiment, the media, comprises: a substrate comprising a fluorescent colorant and plastic, wherein the substrate has a fluorescent color emission wavelength which is not equal to the readback laser wavelength. DETAILED DESCRIPTION
[0010] The present invention relates to data storage media, namely, colored optical data storage media and methods for making the same. In one embodiment, the colored media has, at the readback laser wavelength, a transmissivity of light of about 85% or less, with about 70% to about 85% preferred, about 75% to about 80% also preferred, and about 75% to about 85% especially preferred, when traversing a 1.2 mm thick colored substrate (disk). Alternatively, if fluorescent, the media preferably emits light at a wavelength which does not inhibit data retrieval. The fluorescent media can comprise a substrate which has a transmissivity, at the readback laser wavelength, exceeding 68%, with about 70% to about 95% preferred, about 70% to about 95% more preferred, and about 70% to about 85% especially preferred, when traversing a 1.2 mm thick substrate (disk).
[0011] Typically, these storage media can comprise a substrate comprising a plastic and a colorant which does not inhibit data retrieval. Generally, up to about 10 weight percent (wt%) colorant can be used, with up to about 5 wt% preferred, up to - about 1 wt% colorant more preferred, and less than about 0.5 wt% or so colorant especially preferred, based upon the total weight of the substrate.
[0012] In theory, any plastic that exhibits appropriate properties and can be employed. However, the plastic should be capable of withstanding the subsequent processing parameters (e.g., application of subsequent layers) such as sputtering (i.e., temperatures up to and exceeding about 200°C (typically up to or exceeding about 300°C) for magnetic media, and temperatures of about room temperature (about 25 °C) up to about 150°C for magneto-optic media). That is, it is desirable for the plastic to have sufficient thermal stability to prevent deformation during the deposition steps. For magnetic media, appropriate plastics include thermoplastics with glass transition temperatures greater than about 150°C, with greater than about 200°C preferred (e.g., polyetherimides, polyetheretherketones, polysulfones, polyethersulfones, polyetherethersulfones, polyphenylene ethers, polyimides, high heat polycarbonates, etc.); with materials having glass transition temperatures greater than about 250°C more preferred, such as polyetherimide in which sulfonedianiline or oxydianiline has been substituted for m-phenylenediamine, among others, as well as polyimides, such as Probimide (or the dry powder equivalent, Matrimid 5218, from Ciba Geigy Chemical); combinations comprising at least one of the foregoing plastics, and others.
[0013] Additionally, it is possible for thermosets to be used in the application provided the thermoset possess sufficient flow under the stamping conditions to permit formation of the desired surface features. As various applications may require polymers with different glass transition temperatures, it may be advantageous to be able to adjust the glass transition temperature of a plastic (homopolymer, copolymer, or blend) to achieve a film with the desired glass transition temperature. To this end, polymer blends, such as those described in U.S. Patent No. 5,534,602 (to Lupinski and Cole, 1996), may be employed in the preparation of the coating solution. In this example, polymer blends provide, selectively, variable glass transition temperatures of about 190°C to about 320°C.
[0014] Some possible examples of plastics include, but are not limited to, amorphous, crystalline and semi-crystalline thermoplastic materials: polyvinyl chloride, polyolefms (including, but not limited to, linear and cyclic polyolefins and including polyethylene, chlorinated polyethylene, polypropylene, and the like), polyesters (including, but not limited to, polyethylene terephthalate, polybutylene terephthalate, polycyclohexylmethylene terephthalate, and the like), polyamides, polysulfones (including, but not limited to, hydrogenated polysulfones, and the like), polyimides, polyether imides, polyether sulfones, polyphenylene sulfides, polyether ketones, polyether ether ketones, ABS resins, polystyrenes (including, but not limited to, hydrogenated polystyrenes, syndiotactic and atactic polystyrenes, polycyclohexyl ethylene, styrene-co-acrylonitrile, styrene-co-maleic anhydride, and the like), polybutadiene, polyacrylates (including, but not limited to, polymethylmethacrylate, methyl methacrylate-polyimide copolymers, and the like), polyacrylonitrile, polyacetals, polycarbonates, polyphenylene ethers (including, but not limited to, those derived from 2,6-dimethylphenol and copolymers with 2,3,6-trimethylphenol, and the like), ethylene- vinyl acetate copolymers, polyvinyl acetate, liquid crystal polymers, ethylene-tetrafluoroethylene copolymer, aromatic polyesters, polyvinyl fluoride, polyvinylidene fluoride, polyvinylidene chloride, Teflons, as well as thermosetting resins such as epoxy, phenolic, alkyds, polyester, polyimide, polyurethane, mineral filled silicone, bis-maleimides, cyanate esters, vinyl, and benzocyclobutene resins, in addition to blends, copolymers, mixtures, reaction products and composites comprising at least one of the foregoing plastics.
[0015] As used herein, the terms "polycarbonate", "polycarbonate composition", and "composition comprising aromatic carbonate chain units" includes compositions having structural units of the formula (I):
O 1— O — " — O (I)
[0016] in which at least about 60 percent of the total number of R1 groups are aromatic organic radicals and the balance thereof are aliphatic, alicyclic, or aromatic radicals. Preferably, R1 is an aromatic organic radical and, more preferably, a radical of the formula (II):
A1 — Y1 — A2 (jj)
[0017] wherein each of A1 and A2 is a monocyclic divalent aryl radical and Y1 is a bridging radical having one or two atoms which separate A from A . In an exemplary embodiment, one atom separates A! from A2. Illustrative, non-limiting examples of radicals of this type are -O-, -S-, -S(O)-, -S(O2)-, -C(O)-, methylene, cyclohexyl-methylene, 2-[2,2,l]-bicycloheptylidene, ethylidene, isopropylidene, neopentylidene, cyclohexylidene, cyclopentadecylidene, cyclododecylidene, and adamantylidene. The bridging radical Y1 can be a hydrocarbon group or a saturated hydrocarbon group such as methylene, cyclohexylidene or isopropylidene.
[0018] Polycarbonates can be produced by the interfacial reaction of dihydroxy compounds in which only one atom separates A1 and A2. As used herein, the term "dihydroxy compound" includes, for example, bisphenol compounds having general formula (El) as follows:
Figure imgf000007_0001
[0019] wherein Ra and Rb each represent a halogen atom or a monovalent hydrocarbon group and may be the same or different; p and q are each independently integers from 0 to 4; and X8 represents one of the groups of formula (IN):
Rc Re
— C— or — ϊ—
R (IN)
[0020] wherein Rc and Rd each independently represent a hydrogen atom or a monovalent linear or cyclic hydrocarbon group and Re is a divalent hydrocarbon group.
[0021] Some illustrative, non-limiting examples of suitable dihydroxy compounds include dihydric phenols and the dihydroxy-substituted aromatic hydrocarbons disclosed by name or formula (generic or specific) in U.S. Patent 4,217,438, which is incorporated herein by reference. A nonexclusive list of specific examples of the types of bisphenol compounds that may be represented by formula (IE) includes the following: l,l-bis(4-hydroxyphenyl) methane; l,l-bis(4- hydroxyphenyl) ethane; 2,2-bis(4-hydroxyphenyl) propane (hereinafter "bisphenol A" or "BPA"); 2,2-bis(4-hydroxyphenyl) butane; 2,2-bis(4-hydroxyphenyl) octane; 1,1- bis(4-hydroxyphenyl) propane; l,l-bis(4-hydroxyphenyl) n-butane; bis(4- hydroxyphenyl) phenylmethane; 2,2-bis(4-hydroxy-l-methylphenyl) propane; 1,1- bis(4-hydroxy-t-butylphenyl) propane; bis(hydroxyaryl) alkanes such as 2,2-bis(4- hydroxy-3-bromophenyl) propane; l,l-bis(4-hydroxyphenyl) cyclopentane; and bis(hydroxyaryl) cycloalkanes such as l,l-bis(4-hydroxyphenyl) cyclohexane; and the like as well as combinations comprising at least one of the foregoing. [0022] It is also possible to employ polycarbonates resulting from the polymerization of two or more different, dihydric phenols or a copolymer of a dihydric phenol with a glycol or with a hydroxy- or acid-terminated polyester or with a dibasic acid or with a hydroxy acid or with an aliphatic diacid in the event a carbonate copolymer rather than a homopolymer is desired for use. Generally, useful aliphatic diacids have from 2 to about 40 carbons. A preferred aliphatic diacid is dodecandioic acid. Polyarylates and polyester-carbonate resins or their blends can also be employed. Branched polycarbonates are also useful, as well as blends of linear polycarbonate and a branched polycarbonate. The branched polycarbonates may be prepared by adding a branching agent during polymerization.
[0023] These branching agents are well known and may comprise polyfunctional organic compounds containing at least three functional groups which may be hydroxyl, carboxyl, carboxylic anhydride, haloformyl and mixtures comprising at least one of the foregoing. Specific examples include trimellitic acid, trimellitic anhydride, trimellitic trichloride, tris-p-hydroxy phenyl ethane, isatin-bis- phenol, tris-phenol TC (l,3,5-tris((p-hydroxyphenyl)isopropyl)benzene), tris-phenol PA (4(4(1, l-bis(p-hydroxyphenyl)-ethyl) alpha,alpha-dimethyl benzyl)phenol), 4- chloroformyl phthalic anhydride, trimesic acid and benzophenone tetracarboxylic acid, and the like. The branching agents may be added at a level of about 0.05 to about 2.0 weight percent. Branching agents and procedures for making branched polycarbonates are described in U.S. Patent. Nos. 3,635,895 and 4,001,184 which are incorporated by reference. All types of polycarbonate end groups are herein contemplated.
[0024] Preferred polycarbonates are based on bisphenol A, in which each of A1 and A2 is p-phenylene and Yl is isopropylidene. Preferably, the weight average molecular weight of the polycarbonate is about 5,000 to about 100,000, more preferably about 10,000 to about 65,000, and most preferably about 15,000 to about 35,000. [0025] In monitoring and evaluating polycarbonate synthesis, it is of particular interest to determine the concentration of Fries product present in the polycarbonate. As noted, the generation of significant Fries product can lead to polymer branching, resulting in uncontrollable melt behavior. As used herein, the terms "Fries" and "Fries product" denote a repeating unit in polycarbonate having the formula (V):
Figure imgf000009_0001
[0026] wherein Xa is a bivalent radical as described in connection with Formula (III) supra.
[0027] The polycarbonate composition may also include various additives ordinarily incorporated in resin compositions of this type. Such additives are, for example, fillers or reinforcing agents; heat stabilizers; antioxidants; light stabilizers; plasticizers; antistatic agents; mold releasing agents; additional resins; blowing agents; and the like, as well as combinations comprising at least one of the foregoing additives. Examples of fillers or reinforcing agents include glass fibers, asbestos, carbon fibers, silica, talc and calcium carbonate. Examples of heat stabilizers include triphenyl phosphite, tris-(2,6-dimethylphenyl)phosphite, tris-(mixed mono-and di- nonylphenyl)phosphite, dimethylbenene phosphonate and trimethyl phosphate. Examples of antioxidants include octadecyl-3-(3,5-di-tert-butyl-4- hydroxyphenyl)propionate, and pentaerythrityl-tetrakis[3-(3 ,5-di-tert-butyl-4- hydroxyphenyl)propionate]. Examples of light stabilizers include 2-(2-hydroxy-5- methylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)-benzotriazole and 2- hydroxy-4-n-octoxy benzophenone. Examples of plasticizers include dioctyl-4,5- epoxy-hexahydrophthalate, tris-(octoxycarbonylethyl)isocyanurate, tristearin and epoxidized soybean oil. Examples of the antistatic agent include glycerol monostearate, sodium stearyl sulfonate, and sodium dodecylbenzenesulfonate. Examples of mold releasing agents include stearyl stearate, beeswax, montan wax and paraffin wax. Examples of other resins include but are not limited to polypropylene, polystyrene, polymethyl methacrylate, and polyphenylene oxide. Combinations of any of the foregoing additives may be used. Such additives may be mixed at a suitable time during the mixing of the components for forming the composition.
[0028] The color is imparted to the substrate with a colorant (e.g., dye, pigment, or the like). The amount and type of colorant is chosen to avoid producing a substrate having contaminants (i.e., by-products) which produce data readout errors, and to attain the desired color., while controlling transmissivity, at the readback laser wavelength, to greater than about 68%, when traversing a 1.2 mm thick colored substrate (disk). Contrary to conventional belief, the substrate may be fluorescent, that is, emit light at a particular wavelength. In this embodiment, the colorant is a fluorescent material which has a fluorescent color emission wavelength which is not equal to the readback laser wavelength, and preferably different by at least about 10 nanometers (nm) (i.e., higher or lower) than the readback laser wavelength, with a difference of about 15 nm or greater preferred, and about 20 nm or greater especially preferred. Here it is further preferred that the substrate have a transmissivity at the readback laser frequency, of greater than about 70% when traversing a 1.2 mm thick colored substrate (disk).
[0029] Some possible fluorescent colorants include:
Figure imgf000010_0001
as well as other fluorescent colorants, and combinations comprising at least one of the foregoing colorants.
[0030] Further color or design may be imparted to the substrate via a decorative layer which does not comprise an absorption percentage limitation. The decorative layer, which is disposed on a side of the disk opposite a data storage layer or in between data storage layers which are read from opposite sides of the disk, can be any color or design, such as a design which optionally includes sparkle, i.e., visual effects which scatter the incident light (such as glass or metal (in the form of flakes, chips, particles, powder, and the like, as well as combinations comprising at least one of the foregoing forms, with flakes preferred), titanium dioxide (TiO2), mica, fiberglass, angular metamerism materials such as, ChromaFlair Gold/Silver 080, ChromaFlair Cyan/Purple 230 (commercially available from Flex Products, Santa Rosa, California), among other materials, as well as combinations comprising at least one of the foregoing visual effects.
[0031] In addition to the plastic and colorant, the composition may optionally include various additives ordinarily incorporated in resin compositions of this type. Such additives may include antioxidants, heat stabilizers, anti-static agents (terra alkylammonium benzene sulfonate salts, terra alkylphosphonium benzene sulfonate salts, and the like), mold releasing agents (pentaerythritol tetrastearate; glycerol monstearate, and the like), and the like, and combinations comprising at least one of the foregoing. For example, the substrate can comprise about 0.01 to about 0.1 wt% of a heat stabilizer; about 0.01 to about 0.2 wt% of an antistatic agent; and about 0.1 to about 1 wt% of a mold releasing agent; based upon the total weight of the substrate.
[0032] Some possible antioxidants include, for example, organophosphites, e.g., tris(nonyl-phenyl)phosphite, tris(2,4-di-t-butylphenyl)phosphite, bis(2,4-di-t- butylphenyl)pentaerythritol diphosphite, distearyl pentaerythritol diphosphite and the like; alkylated monophenols, polyphenols and alkylated reaction products of polyphenols with dienes, such as, for example, tetrakis[methylene(3,5-di-tert-butyl-4- hydroxyhydrocinnamate)] methane, 3,5-di-tert-butyl-4-hydroxyhydrocinnamate octadecyl, 2,4-di-tert-butylphenyl phosphite, and the like; butylated reaction products of para-cresol and dicyclopentadiene; alkylated hydroquinones; hydroxylated thiodiphenyl ethers; alkylidene-bisphenols; benzyl compounds; esters of beta-(3,5-di- tert-butyl-4-hydroxyphenyl)-propionic acid with monohydric or polyhydric alcohols; esters of beta-(5-tert-butyl-4-hydroxy-3-methylphenyl)-propionic acid with monohydric or polyhydric alcohols; esters of thioalkyl or thioaryl compounds, such as, for example, distearylthiopropionate, dilaurylthiopropionate, ditridecylthiodipropionate, and the like; amides of beta-(3,5-di-tert-butyl-4- hydroxyphenyl)-propionic acid; and the like, as well as combinations comprising at least one of the foregoing.
[0033] Other potential additives which may be employed comprise: UN absorbers; stabilizers such as light and thermal stabilizers (e.g., acidic phosphorous- based compounds); hindered phenols; zinc oxide and/or zinc sulfide particles; lubricants (mineral oil, and the like), plasticizers, dyes (quinines, azobenzenes, and the like); among others, as well as combinations comprising at least one of the foregoing additives.
[0034] In order to aide in the processing of the plastic, particularly polycarbonate, catalyst(s) may also be employed, namely in the extruder or other mixing device. The catalyst typically assists in controlling the viscosity of the resulting material. Possible catalysts include tetraalkylammonium hydroxide, tetraalkylphosphonium hydroxide and the like, with diethyldimethylammonium hydroxide and tetrabutylphosphonium hydroxide preferred. The catalyst(s) can be employed alone or in combination with quenchers such as acids, such as phosphoric acid, and the like. Additionally, water may be injected into the polymer melt during compounding and removed as water vapor through a vent to remove residual volatile compounds.
[0035] Data storage media can be produced by first forming the plastic using a conventional reaction vessel capable of adequately mixing various precursors, such as a single or twin screw extruder, kneader, blender, or the like. The precursors can either be premixed with the colorant (e.g., in a pellet, powder, and/or liquid form) and simultaneously fed through a hopper into the extruder, or the colorant can be optionally added in the feed throat or through an alternate injection port of the injection molding machine or other molding.
[0036] The extruder should be maintained at a sufficiently high temperature to melt the plastic precursors without causing decomposition thereof. For polycarbonate, for example, temperatures of about 220°C to about 360°C can be used, with about 260°C to about 320°C preferred. Similarly, the residence time in the extruder should be controlled to minimize decomposition. Residence times of up to about 2 minutes (min) or more can be employed, with up to about 1.5 min preferred, and up to about 1 min especially preferred. Prior to extrusion into the desired form (typically pellets, sheet, web, or the like, the mixture can optionally be filtered, such as by melt filtering and/or the use of a screen pack, or the like, to remove undesirable contaminants or decomposition products.
[0037] Once the plastic composition has been produced, it can be formed into the data storage media using various molding and/or processing techniques. Possible molding techniques include injection molding, film casting, extrusion, press molding, blow molding, stamping, and the like. Once the substrate has been produced, additional processing, such as electroplating, coating techniques (spin coating, spray coating, vapor deposition, screen printing, painting, dipping, and the like), lamination, sputtering, and combinations comprising at least one of the foregoing processing techniques, among others conventionally known in the art, may be employed to dispose desired layers on the colored substrate.
[0038] An example of a polycarbonate data storage media comprises an injection molded colored polycarbonate substrate which may optionally comprise a hollow (bubbles, cavity, and the like) or filled (metal, plastics, glass, ceramic, and the like, in various forms such as fibers, spheres, particles, and the like) core. Disposed on the substrate are various layers including: a data layer, dielectric layer(s), a reflective layer(s), and/or a protective layer, as well as combinations comprising at least one of the foregoing layers. These layers comprise conventional materials and are disposed in accordance with the type of media produced. For example, for a first surface media, the layers may be protective layer, dielectric layer, data storage layer, dielectric layer, and then the reflective layer disposed in contact with the substrate, 5 with an optional decorative layer disposed on the opposite side of the substrate. Meanwhile, for an optical media, the layers may be optional decorative layer, protective layer, reflective layer, dielectric layer, and data storage layer, with a subsequent dielectric layer in contact with the substrate. It is understood that the form of the media is not limited to disk-shape, but may be any shape which can be 10 accommodated in a readout device.
[0039] The data storage Iayer(s) may comprise any material capable of storing retrievable data, such as an optical layer, magnetic layer, or a magneto-optic layer. Typically the data layer has a thickness of up to about 600 Angstroms (A) or so, with a thickness up to about 300A preferred. Possible data storage layers include, but are 15 not limited to, oxides (such as silicone oxide), rare earth element - transition metal alloy, nickel, cobalt, chromium, tantalum, platinum, terbium, gadolinium, iron, boron, others, and alloys and combinations comprising at least one of the foregoing, organic dye (e.g., cyanine or phthalocyanine type dyes), and inorganic phase change compounds (e.g., TeSeSn, InAgSb, and the like).
20 [0040] The protective layer(s), which protect against dust, oils, and other contaminants, can have a thickness of greater than about 100 microns (μ) to less than about 10 A, with a thickness of about 300 or less preferred in some embodiments, and a thickness of about 100 A or less especially preferred. The thickness of the protective layer(s) is usually determined, at least in part, by the type of read/write
25. mechanism employed, e.g., magnetic, optic, or magneto-optic. Possible protective layers include anti-corrosive materials such as gold, silver, nitrides (e.g., silicon nitrides and aluminum nitrides, among others), carbides (e.g., silicon carbide and others), oxides (e.g., silicon dioxide and others), polymeric materials (e.g., polyacrylates or polycarbonates), carbon film (diamond, diamond-like carbon, and the
30 like), among others, and combinations comprising at least one of the foregoing. [0041] The dielectric layer(s), which are disposed on one or both sides of the data storage layer and are often employed as heat controllers, can typically have a thickness of up to or exceeding about 1,000A and as low as about 200A or less. Possible dielectric layers include nitrides (e.g., silicon nitride, aluminum nitride, and others); oxides (e.g., aluminum oxide); carbides (e.g., silicon carbide); and combinations comprising at least one of the foregoing materials, among other materials compatible within the environment and preferably not reactive with the surrounding layers.
[0042] The reflective layer(s) should have a sufficient thickness to reflect a sufficient amount of energy (e.g., light) to enable data retrieval. Typically the reflective layer(s) can have a thickness of up to about 70θA or so, with a thickness of about 300 A to about 600 A generally preferred. Possible reflective layers include any material capable of reflecting the particular energy field, including metals (e.g., aluminum, silver, gold, titanium, and alloys and mixtures comprising at least one of the foregoing metals, and others).
[0043] In addition to the data storage layer(s), dielectric layer(s), protective layer(s) and reflective layer(s), other layers can be employed such as lubrication layer and others. Useful lubricants include fluoro compounds, especially fluoro oils and greases, and the like.
[0044] The following examples are provided to further illustrate the present invention and not to limit the scope hereof.
EXAMPLES
[0045] Colored pellets were prepared by mixing low viscosity polycarbonate resin powder (melt flow at 250°C of 11 grams per 10 minutes (ASTM-D1238); molecular weight of about 17,700 grams per mole (g/mol) measured on GPC) with colorants specified in the Table. Formulations also included mold release agent (0.02 wt% glycerol monostearate) and Doverphos (S-9228); Bis(2,4- dicumylphenyl)pentaerythritol diphosphate antioxidant at 0.02 wt%). The blends were melted in a 30 millimeter (mm) twin-screw extruder, passed through a die, cooled, and pelletized.
[0046] Resulting pellets were injection molded into 1.2 mm thick compact disk substrates using a Krauss Maffei 80/190°C Marathon Series, CD Liner, w/Non- Open Mold. Processing conditions as follows: Barrel Zone Temperature of about 250 to about 330°C; Mold Temperatures set to 45°C; Injection Speed Profile of about 20 millimeters per second (mm/s) to about 65 mm s, 4 stages; Holding Pressure profile of about 150 bar to about 550 bar, 5 stages; Holding Pressure Time of about 0.05 to about 0.25 seconds, 5 stages; Cooling Time set for 2.5 seconds; Clamp Tonnage set for 400 kN; Injection pressure set at 1795 bar; Injection Position Profile of about 17.0 mm to about 4.5 mm, 4 stages. The resulting disks were tested for Block Error Rate on a CD Associates SL100 optical tester. Block Error Rate (BLER) is a measure of the number of blocks of data that have at least one occurrence of erroneous data. BLER is the combination of El 1+E21+E31+E12+E22+E32 errors. A Block Error Rate below about 220 pulses is typically required in industry, with below 100 preferred, and below 50 especially preferred.
[0047] Pellets were also injection molded into 1.2 mm thick colored substrate (disk) and placed in spectrophotometer to determine the absorbance at 780 nanometers (nm), (i.e., the wavelength of the optical disk tester. If the disc is not readable by the tester an error message is given such as: "Unable to Retrieve NTOC (IFB)". Which means that the tester could not establish the "Volume Table of Contents", this information shows the layout of the program material on the disc.
Figure imgf000017_0001
TRM = amount of light transmitted through the substrate
BLER = pulses fail = .Unable to retrieve Volume Table of Contents (VTOC) pass = booted
Electrical Test = did it play CD optical tester.
CI. = Color Index
R0979 - commercially available from Engelhard, Peekskill, NY
R672 - commercially available from Clariant, Charlotte, NC
R65 - commercially available from Clariant, Charlotte, NC
R663 - commercially available from Clariant, Charlotte, NC
R73 - commercially available from Bayer, Pittsburgh, PA
R513 - commercially available from Ciba, Tarrytown, NY
R887 - commercially available from Bayer, Pittsburgh, PAR882 - commercially available from Clariant, Charlotte, NC R7260 - commercially available from BASF, Mt. Olive, NJ R666 - commercially available from Rose 'Color, New Ark, NJ R203 commercially available from Cabot, Alpharetta, GA R71 - commercially available from Bayer, Pittsburgh, PA R883 - commercially available from BASF, Mt. Olive, NJ R36 - commercially available from Bayer, Pittsburgh, PA AM190 - commercially available from Flex Products, Santa Rosa, CA AM080 - commercially available from Flex Products, Santa Rosa, CA AM230 - commercially available from Flex Products, Santa Rosa, CA
[0048] An alternative technique for product differentiation, colored disks, however, have not been used for optical media substrates due to absorption of the laser light, which interferes with data readout. Furthermore, the use of optical effects, such as fluorescence, in optical media substrates has not been done because fluorescence, in which light of a given color is absorbed and re-emitted at a different color, has not been tried because fluorescent emissions may interfere with the laser readout system. Other visual effects that may scatter an incident laser beam have similarly not been explored because, until recently, optical media consisted of 1 -layer substrates, such as those in CD. Recently, the advent of DVD includes a second substrate layer which may be used for decorative purposes except in cases of multi- sided media. The use of inorganic fillers such as glass flake to produce visual effects may also alter rheological properties of a thermoplastic resin making it difficult to produce optical media substrates from such compositions.
[0049] Use of color or other visual effects in optical media substrates provides a way to differentiate brands of optical media. This differentiation can be used for increased appeal in the market, brand recognition, and can help avoid problems with unwanted duplication of data. Colored substrates can also provide an advantage of wavelength selectivity that cannot be obtained with colorless materials. [0050] Data storage media substrates comprising visual effects have not previously been produced due to the significant adverse effect on rheology imparted by the visual effects. Previously, decorative labels would be glued to a surface of the substrate. In contrast, the substrates described herein can comprise the visual effects as part of the substrate, i.e., a molded layer disposed on one side of the substrate.
Alternatively, the visual effects can be disposed between two substrates with reflective and data layers disposed between the visual effects and the substrate, optionally, adhesives can be used for bonding. These visual effects could be employed for numerous purposes including product differentiation, decoration, anti-piracy, and the like.
[0051] While preferred embodiments have been shown and described, various modifications and substitutions may be made thereto without departing from the spirit and scope of the invention. Accordingly, it is to be understood that the present invention has been described by way of illustrations and not limitation.

Claims

WHAT IS CLAIMED IS:
1. A colored data storage media, comprising:
a substrate comprising colorant and plastic, wherein the substrate has a transmissivity of about 85% or less at a readback laser wavelength when traversing a 1.2 mm thick colored substrate (disk).
2. The storage media of Claim 1 , wherein the substrate comprises up to about 5 wt% of the colorant, based upon the entire weight of the substrate.
3. The storage media of Claim 2, wherein the substrate comprises up to about 1 wt% of the colorant.
4. The storage media of Claim 3, wherein the substrate comprises less than about 0.5 wt% of the colorant.
5. The storage media of Claim 1, wherein the transmissivity is about 70% to about 85%.
6. The storage media of Claim 5, wherein the transmissivity is about 75% to about 80%.
7. The storage media of Claim 5, wherein the transmissivity is about 75% to about 85%.
8. The storage media of Claim 1, wherein the substrate further comprises visual effects selected from the group consisting of glass, metal, titanium dioxide, mica, angular metamerism materials, and combinations comprising at least one of the foregoing visual effects.
9. The storage media of Claim 8, where in the visual effects have a geometry selected from the group consisting of chips, particles, and combinations comprising at least one of the foregoing geometries.
10. The storage media of Claim 8, where in the visual effects are in the form of flakes.
11. The storage media of Claim 1 , wherein the colorant further comprises a fluorescent material having a fluorescent color emission wavelength which is not equal to the readback laser wavelength.
12. The storage media of Claim 11, wherein the fluorescent color emission wavelength is different than the readback laser wavelength by at least about ±lOnm.
13. The storage media of Claim 12, wherein the fluorescent color emission wavelength is different than the readback laser wavelength by at least about ±20nm.
14. The storage media of Claim 1, wherein the plastic is selected from the group consisting of thermoplastics and thermosets.
15. The storage media of Claim 14, wherein the thermoplastic is selected from the group consisting of polyvinyl chloride, polyolefins, polyesters, polyamides, polysulfones, polyimides, polyether imides, polyether sulfones, polyphenylene sulfides, polyether ketones, polyether ether ketones, ABS resins, polystyrenes, polybutadiene, polyacrylates, polyacrylonitrile, polyacetals, polycarbonates, polyphenylene ethers, ethylene-vinyl acetate copolymers, polyvinyl acetate, liquid crystal polymers, ethylene-tetrafluoroethylene copolymer, aromatic polyesters, polyvinyl fluoride, polyvinylidene fluoride, polyvinylidene chloride, Teflons, and blends, copolymers, mixtures, reaction products and composites comprising at least one of the foregoing thermoplastics.
16. The storage media of Claim 15, wherein the thermoplastic is selected from the group consisting of polyethylene, chlorinated polyethylene, polypropylene, polyethylene terephthalate, polybutylene terephthalate, polycyclohexylmethylene terephthalate, hydrogenated polysulfones, hydrogenated polystyrenes, syndiotactic and atactic polystyrenes, polycyclohexyl ethylene, styrene-co-acrylonitrile, styrene-co- maleic anhydride, polymethylmethacrylate, methyl methacrylate-polyimide copolymers, and blends, copolymers, mixtures, reaction products and composites comprising at least one of the foregoing thermoplastics.
17. The storage media of Claim 15, wherein the polycarbonate comprises structural units of the formula (I):
O R1— O — U — O — (I)
in which at least about 60 percent of the total number of R1 groups are aromatic organic radicals and the balance are aliphatic, alicyclic, or aromatic radicals.
18. The storage media of Claim 15, wherein the polycarbonate is produced by the interfacial reaction of dihydroxy compounds having general formula (III) as follows:
Figure imgf000023_0001
wherein Ra and Rb each, independently, represent a halogen atom or a monovalent hydrocarbon group; p and q are each independently integers from 0 to 4; and X1 represents one of the groups of formula (IN):
Rc Re
— C— or — C—
Rd (IV)
wherein Rc and Rd each independently represent a hydrogen atom or a monovalent linear or cyclic hydrocarbon group and Re is a divalent hydrocarbon group.
19. The storage media of Claim 14, wherein the fhermoset is selected from the group consisting of epoxy, phenolic, alkyds, polyester, polyimide, polyurethane, mineral filled silicone, bis-maleimides, cyanate esters, vinyl, and benzocyclobutene resins, and blends, copolymers, mixtures, reaction products and composites comprising at least one of the foregoing fhermosets.
20. A colored data storage media, comprising:
a substrate comprising a fluorescent colorant and plastic, wherein the substrate has a fluorescent color emission wavelength which is not equal to the readback laser wavelength.
21. The storage media of Claim 20, wherein the fluorescent color emission wavelength is different than the readback laser wavelength by at least about ±lOnm.
22. The storage media of Claim 21 , wherein the fluorescent color emission wavelength is different than the readback laser wavelength by at least about ±15 nm.
23. The storage media of Claim 22, wherein the fluorescent color emission wavelength is different than the readback laser wavelength by at least about ±20nm.
24. The storage media of Claim 20, wherein the plastic is selected from the group consisting of thermoplastics and fhermosets.
25. The storage media of Claim 24, wherein the thermoplastic is selected from the group consisting of polyvinyl chloride, polyolefins, polyesters, polyamides, polysulfones, polyimides, polyether imides, polyether sulfones, polyphenylene sulfides, polyether ketones, polyether ether ketones; ABS resins, polystyrenes, polybutadiene, polyacrylates, polyacrylonitrile, polyacetals, polycarbonates, polyphenylene ethers, ethylene-vinyl acetate copolymers, polyvinyl acetate, liquid crystal polymers, ethylene-tetrafluoroethylene copolymer, aromatic polyesters, polyvinyl fluoride, polyvinylidene fluoride, polyvinylidene chloride, Teflons, and blends, copolymers, mixtures, reaction products and composites comprising at least one of the foregoing thermoplastics.
26. The storage media of Claim 25, wherein the thermoplastic is selected from the group consisting of polyethylene, chlorinated polyethylene, polypropylene, polyethylene terephthalate, polybutylene terephthalate, polycyclohexylmethylene terephthalate, hydrogenated polysulfones, hydrogenated polystyrenes, syndiotactic and atactic polystyrenes, polycyclohexyl ethylene, styrene-co-acrylonitrile, styrene-co- maleic anhydride, polymethylmethacrylat'e, methyl methacrylate-polyimide copolymers, and blends, copolymers, mixtures, reaction products and composites comprising at least one of the foregoing thermoplastics.
27. The storage media of Claim 25, wherein the polycarbonate comprises structural units of the formula (I):
0 R1— O — U — 0 — (I)
in which at least about 60 percent of the total number of R1 groups are aromatic organic radicals and the balance are aliphatic, alicyclic, or aromatic radicals.
28. The storage media of Claim 27, wherein the polycarbonate is produced by the interfacial reaction of dihydroxy compounds having general formula (III) as follows:
Figure imgf000025_0001
wherein Ra and Rb each, independently, represent a halogen atom or a monovalent hydrocarbon group; p and q are each independently integers from 0 to 4; and Xa represents one of the groups of formula (IV):
Rc Re
— C C— or — C—
Rd (IV)
wherein Rc and Rd each independently represent a hydrogen atom or a monovalent linear or cyclic hydrocarbon group and Re is a divalent hydrocarbon group.
29. The storage media of Claim 24, wherein the thermoset is selected from the group consisting of epoxy, phenolic, alkyds, polyester, polyimide, polyurethane, mineral filled silicone, bis-maleimides, cyanate esters, vinyl, and benzocyclobutene resins, and blends, copolymers, mixtures, reaction products and composites comprising at least one of the foregoing thermosets.
30. The storage media of Claim 20, further comprising a layer disposed adjacent to the substrate, wherein the layer is selected from the group consisting of protective layer(s), dielectric layer(s), data storage layer(s), and reflective layer(s), and combinations comprising at least one of the foregoing layers.
31. The storage media of Claim 20, wherein the substrate has a transmissivity exceeding about 68% at a readback laser wavelength, when traversing a 1.2 mm thick colored substrate (disk).
32. The storage media of Claim 31 , wherein the substrate has a transmissivity of about 70% to about 90%.
33. The storage media of Claim 32, wherein the substrate has a transmissivity of about 70% to about 85%.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003090220A1 (en) * 2002-04-22 2003-10-30 General Electric Company Method for making limited play data storage media
US6861541B2 (en) 2002-10-30 2005-03-01 General Electric Company Method for preparation of an anthraquinone colorant composition
US6991889B2 (en) 2001-03-14 2006-01-31 General Electric Company Limited play data storage media and method for limiting access to data thereon
WO2007137889A2 (en) * 2006-05-30 2007-12-06 Evonik Röhm Gmbh Method for producing a coloured thermoplastic plastic film, film and use thereof

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6475589B1 (en) * 2001-12-17 2002-11-05 General Electric Company Colored optical discs and methods for making the same
TWM253886U (en) * 2003-02-10 2004-12-21 Yes Tek Corp Digital video and audio optical disk with colors
WO2005026247A1 (en) * 2003-09-17 2005-03-24 Ciba Specialty Chemicals Holding Inc. Laser markable polymeric compositions
US7157129B2 (en) * 2003-10-24 2007-01-02 General Electric Company Method for making highly colored DVDs
US20050112768A1 (en) * 2003-11-26 2005-05-26 Thomas Evans Method of authenticating tagged polymers
US7094364B2 (en) * 2003-11-26 2006-08-22 General Electric Company Method of authenticating polymers, authenticatable polymers, methods of making authenticatable polymers and authenticatable articles, and articles made there from
US7169615B2 (en) 2003-11-26 2007-01-30 General Electric Company Method of authenticating polymers, authenticatable polymers, methods of making authenticatable polymers and authenticatable articles, and articles made there from
US20090266991A1 (en) * 2003-11-26 2009-10-29 Sabic Innovative Plastics Ip B.V. Method of authenticating tagged polymers
JP2005346791A (en) 2004-06-01 2005-12-15 Tdk Corp Optical recording medium and its manufacturing method
US20080029933A1 (en) * 2004-06-25 2008-02-07 Mitsubishi Engineering-Plastics Corporation Aromatic Polycarbonate Resin Composition, And Substrate For Optical Information-Recording Media, Transparent Optical Article, Lighting Appliance Cover And Transparent Member For Vehicles Comprising It
US20080081210A1 (en) * 2006-09-29 2008-04-03 General Electric Company Authenticatable articles and methods therefor
WO2009096972A1 (en) * 2008-01-31 2009-08-06 Hewlett-Packard Development Company, L.P. Optical data recording medium and method, system and apparatus incorporating the same
EP2604175B1 (en) 2011-12-13 2019-11-20 EndoChoice Innovation Center Ltd. Removable tip endoscope
CN103709591A (en) * 2013-12-20 2014-04-09 苏州市双赢包装材料有限公司 Formula of phenolic resin modified plastic

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63195838A (en) * 1987-02-10 1988-08-12 Canon Inc Optical information recording carrier
US4891800A (en) * 1987-08-05 1990-01-02 Sanyo Electric Company, Ltd. Optical recording disc
EP0408271A2 (en) * 1989-07-10 1991-01-16 Sanyo Electric Co., Ltd. Optical memory medium
US5648197A (en) * 1995-01-31 1997-07-15 Victor Company Of Japan, Ltd. Optical disk
JPH1125518A (en) * 1997-07-04 1999-01-29 Teijin Ltd Optical disk
WO1999018571A1 (en) 1997-10-07 1999-04-15 Bayer Aktiengesellschaft Optic storage medium
EP1069556A1 (en) * 1999-07-13 2001-01-17 Fuji Photo Film Co., Ltd. Optical information recording medium

Family Cites Families (96)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US36902A (en) * 1862-11-11 Improved spring-bed
US2139155A (en) 1937-03-15 1938-12-06 Waldo G Gernandt Fuel injection system
US3152098A (en) 1960-08-31 1964-10-06 Union Carbide Corp Colored polycarbonate resin compositions
BE621193A (en) 1961-08-09
US3423483A (en) 1965-05-28 1969-01-21 Borg Warner Fluorescent polymers
US3635895A (en) 1965-09-01 1972-01-18 Gen Electric Process for preparing thermoplastic polycarbonates
US3507951A (en) 1966-07-19 1970-04-21 Mobay Chemical Corp Colored polycarbonates and process for preparing the same
US3449415A (en) 1966-12-12 1969-06-10 Union Carbide Corp Purification of formic acid and propionic acid
US3689768A (en) 1970-06-18 1972-09-05 Masamichi Sato Electron beam recording materials
US3673146A (en) 1971-02-24 1972-06-27 Gen Electric Method for stabilizing pigmented polycarbonate resins
US4092288A (en) 1974-11-04 1978-05-30 General Electric Company Stabilized polycarbonate resin
US4001184A (en) 1975-03-31 1977-01-04 General Electric Company Process for preparing a branched polycarbonate
CA1084193A (en) 1975-10-20 1980-08-19 Arthur L. Baron Pigmented polycarbonates comprising submicron silica stabilizer
US4049614A (en) 1975-10-20 1977-09-20 Mobay Chemical Corporation Pigmented polycarbonates
DE2602364A1 (en) 1976-01-22 1977-07-28 Bayer Ag PIGMENTED ABS POLYMERISATE OR POLYAMIDE
US4190843A (en) 1976-03-19 1980-02-26 Rca Corporation Recording methods for a multilayer optical record
US4097895A (en) 1976-03-19 1978-06-27 Rca Corporation Multilayer optical record
US4023185A (en) 1976-03-19 1977-05-10 Rca Corporation Ablative optical recording medium
GB1577548A (en) 1976-09-17 1980-10-22 Gen Electric Stabilized pigmented polycarbonate composition
DE2650340A1 (en) 1976-11-03 1978-05-11 Bayer Ag PLASTICS SHOWING WHITE IN VISIBILITY
JPS5370730A (en) 1976-12-07 1978-06-23 Fujitsu Ltd Memorizing medium
US4315269A (en) 1977-08-29 1982-02-09 Rca Corporation Thick protective overcoat layer for optical video disc
US4101907A (en) 1977-08-29 1978-07-18 Rca Corporation Overcoat structure for optical video disc
US4242689A (en) 1977-09-19 1980-12-30 Rca Corporation Ablative optical recording medium
US4241355A (en) 1977-09-29 1980-12-23 Rca Corporation Ablative optical recording medium
NL7809159A (en) 1977-09-29 1979-04-02 Philips Nv INFORMATION REGISTRATION ELEMENT WITH DYE CONTAINING AUXILIARY LAYER.
US4218689A (en) 1978-01-30 1980-08-19 Rca Corporation Ablatable medium for optical recording
DE2811922A1 (en) 1978-03-18 1979-09-27 Finke Ohg Karl RESIN COLOR CONCENTRATES FOR COLORING RESINS
US4219826A (en) 1978-07-10 1980-08-26 Rca Corporation Optical recording medium
DE2835067A1 (en) 1978-08-10 1980-02-21 Bayer Ag ANTHRACHINONE DERIVATIVES
JPS5538843A (en) 1978-09-14 1980-03-18 Teijin Chem Ltd Stabilized colored polycarbonate resin composition
US4217438A (en) 1978-12-15 1980-08-12 General Electric Company Polycarbonate transesterification process
US4286957A (en) 1979-01-10 1981-09-01 Essilor International "Cie Generale D'optique" Process of integrating a photochromic substance into an ophthalmic lens and a photochromic lens of organic material
US4377389A (en) 1979-12-12 1983-03-22 Foster Grant Corporation Dip dyeing of plastic articles and the dye bath composition thereof
DE3005908A1 (en) 1980-02-16 1981-09-03 Bayer Ag, 5090 Leverkusen COLOR MATERIAL PREPARATIONS, METHOD FOR THEIR PRODUCTION AND THEIR USE FOR COLORING PLASTICS
US4444714A (en) 1980-08-26 1984-04-24 American Organics Corporation Method of coloring resin products
US4363844A (en) 1980-09-22 1982-12-14 Lewis Terry W Metallized information carrying discs
US4336545A (en) 1980-12-18 1982-06-22 Eastman Kodak Company Optical disc structure, method and apparatus physically optimized for writing and reading with a single wavelength
NL8102283A (en) 1981-05-11 1982-12-01 Philips Nv OPTICALLY READABLE INFORMATION DISC WITH A REFLECTION LAYER FORMED FROM A METAL ALLOY.
JPS57205192A (en) 1981-06-12 1982-12-16 Fuji Photo Film Co Ltd Optical information recording medium
JPS5930502A (en) 1982-08-13 1984-02-18 Nippon Telegr & Teleph Corp <Ntt> Plastic optical fiber
US4477608A (en) 1982-08-20 1984-10-16 Ciba-Geigy Corporation Compositions containing graphite
US4464487A (en) 1982-12-17 1984-08-07 The Dow Chemical Company Process for preparing additive concentrates for carbonate polymers
US4504634A (en) 1982-12-27 1985-03-12 General Electric Company Copolyester-carbonate blends exhibiting improved processability
JPS59144614A (en) 1983-02-02 1984-08-18 Kureha Chem Ind Co Ltd Conjugated yarn and its preparation
US4501876A (en) 1983-07-18 1985-02-26 E. I. Du Pont De Nemours And Company Film-forming poly(conjugated polymethine-type)dye
US4719615A (en) 1983-08-22 1988-01-12 Optical Data, Inc. Erasable optical data storage medium
DE3330767A1 (en) 1983-08-26 1985-03-14 Bayer Ag, 5090 Leverkusen HANDLING STABLES IN THE ESSENTIAL EXAMPLE OF IRON MAGNETIC PIGMENTS, METHOD FOR THEIR PRODUCTION AND THEIR USE
DE3436476A1 (en) 1984-10-05 1986-04-10 Röhm GmbH, 6100 Darmstadt METHOD FOR PRESENTING OPTICALLY READABLE INFORMATION
JPS6190343A (en) 1984-10-09 1986-05-08 Polyplastics Co Optical disk
US4650823A (en) 1985-08-16 1987-03-17 Mobay Corporation Iron oxide pigmented, polycarbonate compositions
US4640690A (en) 1985-09-13 1987-02-03 Milliken Research Corporation Colored thermoplastic resin composition containing a colorant having an alkylenoxy-substituted chromophore group
US4732570A (en) 1985-09-13 1988-03-22 Milliken Research Corporation Colored thermoplastic resin
US4812141A (en) 1985-09-13 1989-03-14 Milliken Research Corporation Colored thermoplastic resin composition
DE3537622A1 (en) 1985-10-23 1987-04-23 Bayer Ag MIXTURES OF AROMATIC POLYCARBONATES AND AROMATIC POLYESTER CARBONATES AND THEIR USE FOR THE PRODUCTION OF MOLDED BODIES, FILMS, FIBERS, FILAMENTS AND COATINGS
JPH0610684B2 (en) 1986-02-24 1994-02-09 三井石油化学工業株式会社 Light fiber
DE3727093A1 (en) 1987-08-14 1989-02-23 Basf Ag AREA-SHAPED, MULTILAYERED, LASER-OPTICAL RECORDING MATERIAL
US4998239A (en) 1987-10-07 1991-03-05 The Dow Chemical Company Optical information recording medium containing a metal alloy as a reflective material
CA1340146C (en) 1987-10-09 1998-11-24 Akira Tanaka Resin molded body for optical parts
US4812142A (en) 1987-12-01 1989-03-14 Burlington Industries, Inc. Colored polycarbonate articles with high impact resistance
DE3801576A1 (en) 1988-01-21 1989-08-03 Bayer Ag Light guide based on polycarbonate fibers and method for producing the same
GB8803416D0 (en) 1988-02-15 1988-03-16 Minnesota Mining & Mfg Polymeric polymethine dyes & optical data storage media containing same
US4983648A (en) 1988-03-09 1991-01-08 The Dow Chemical Company Preparation of additive modified thermoplastic blend
JPH0362828A (en) 1989-07-30 1991-03-18 Victor Co Of Japan Ltd Coloring method for polycarbonate resin molded product for optical member
US5051977A (en) 1989-08-30 1991-09-24 Hoechst Celanese Corp. Scanning tunneling microscope memory utilizing optical fluorescence of substrate for reading
JPH07111785B2 (en) 1990-01-19 1995-11-29 富士通株式会社 optical disk
US5240464A (en) 1990-03-09 1993-08-31 Milliken Research Corporation Organic materials having sulfonamido linked poly(oxyalkylene) moieties and their preparation
EP0463579B1 (en) 1990-06-21 1996-09-18 Fuji Photo Film Co., Ltd. Magnetic disk cartridge and method of manufacturing same
US5534602A (en) 1990-07-02 1996-07-09 General Electric Company High temperature polyether imide compositions and method for making
US6022944A (en) 1990-09-05 2000-02-08 Milliken & Company Anthraquinone and condensed anthraquinone colorants having sulfonamide linked poly(oxyalkylene) moieties and their preparation
JPH04271031A (en) 1991-01-17 1992-09-28 Pioneer Electron Corp Optical recording medium
JPH05282706A (en) * 1991-08-01 1993-10-29 Canon Inc Optical recording medium and its production and substrate for optical recording medium
DE4328656A1 (en) 1993-08-26 1995-03-02 Bayer Ag Flame retardant, stress crack resistant polycarbonate ABS molding compounds
GB9320711D0 (en) 1993-10-07 1993-11-24 Minnesota Mining & Mfg Binder for magnetic media
US5472759A (en) 1993-12-16 1995-12-05 Martin Marietta Corporation Optical volume memory
US5453100A (en) 1994-06-14 1995-09-26 General Electric Company Method for color dyeing polycarbonate
FR2725069B1 (en) 1994-09-28 1997-01-03 Digipress Sa COMPACT DISC HAVING ANTI-PIRATE MARKING, PRESSING MOLD AND METHOD FOR ANTI-PIRACING MARKING OF COMPACT DISCS
US5800573A (en) 1994-10-06 1998-09-01 Bayer Aktiengesellschaft Bulk dyeing using quinophthalone dyestuffs
JPH08124212A (en) 1994-10-27 1996-05-17 Sony Disc Technol:Kk Optical information recording medium and production thereof
US5635114A (en) 1995-08-14 1997-06-03 Hong Gilbert H Method of making thin film optical storage media
US5640382A (en) 1995-12-19 1997-06-17 Imation Corp. Dual layer optical medium having partially reflecting metal alloy layer
JPH09180261A (en) 1995-12-22 1997-07-11 Pioneer Electron Corp Pasted type optical disk
DE69634451T2 (en) 1996-03-28 2005-09-15 Idemitsu Kosan Co., Ltd. SUBSTRATE FOR DIGITAL VIDEO DISK
US6099930A (en) 1996-12-17 2000-08-08 Isotag Technology, Inc. Methods for marking digital compact discs as a means to determine its authenticity
US6117168A (en) 1996-12-31 2000-09-12 Scimed Life Systems, Inc. Multilayer liquid absorption and deformation devices
US5894069A (en) 1997-02-12 1999-04-13 Eastman Kodak Company Transferring colorant from a donor element to a compact disc
TW459020B (en) 1998-04-18 2001-10-11 Ind Tech Res Inst Novel cyanine dyes for high density optical recording disk
US6007889A (en) 1998-06-22 1999-12-28 Target Technology, Llc Metal alloys for the reflective or the semi-reflective layer of an optical storage medium
US6507550B1 (en) 1998-08-10 2003-01-14 Fuji Photo Film Co., Ltd. Optical data storage medium
DE69931704T2 (en) 1998-08-10 2007-05-10 Ovd Kinegram Ag Authenticity features for CD's
US6280808B1 (en) 1999-05-25 2001-08-28 Rohm And Haas Company Process and apparatus for forming plastic sheet
US6245118B1 (en) 1999-09-10 2001-06-12 General Electric Company Resinous compositions containing blue dye
US6214433B1 (en) 1999-10-04 2001-04-10 Dsm N.V. Radiation-curable coatings for optical discs and optical discs incorporating such coatings
US6686041B2 (en) 2000-04-28 2004-02-03 Teijin Chemicals Ltd Coloring master pellet for optical molded article and colored optical disk substrate
US6475588B1 (en) 2001-08-07 2002-11-05 General Electric Company Colored digital versatile disks
US6475589B1 (en) 2001-12-17 2002-11-05 General Electric Company Colored optical discs and methods for making the same

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63195838A (en) * 1987-02-10 1988-08-12 Canon Inc Optical information recording carrier
US4891800A (en) * 1987-08-05 1990-01-02 Sanyo Electric Company, Ltd. Optical recording disc
EP0408271A2 (en) * 1989-07-10 1991-01-16 Sanyo Electric Co., Ltd. Optical memory medium
US5648197A (en) * 1995-01-31 1997-07-15 Victor Company Of Japan, Ltd. Optical disk
JPH1125518A (en) * 1997-07-04 1999-01-29 Teijin Ltd Optical disk
WO1999018571A1 (en) 1997-10-07 1999-04-15 Bayer Aktiengesellschaft Optic storage medium
EP1069556A1 (en) * 1999-07-13 2001-01-17 Fuji Photo Film Co., Ltd. Optical information recording medium

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 012, no. 480 (P - 801) 15 December 1988 (1988-12-15) *
PATENT ABSTRACTS OF JAPAN vol. 1999, no. 04 30 April 1999 (1999-04-30) *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6991889B2 (en) 2001-03-14 2006-01-31 General Electric Company Limited play data storage media and method for limiting access to data thereon
WO2003090220A1 (en) * 2002-04-22 2003-10-30 General Electric Company Method for making limited play data storage media
US6861541B2 (en) 2002-10-30 2005-03-01 General Electric Company Method for preparation of an anthraquinone colorant composition
WO2007137889A2 (en) * 2006-05-30 2007-12-06 Evonik Röhm Gmbh Method for producing a coloured thermoplastic plastic film, film and use thereof
WO2007137889A3 (en) * 2006-05-30 2008-01-24 Evonik Roehm Gmbh Method for producing a coloured thermoplastic plastic film, film and use thereof

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