Classifications

• • G—PHYSICS
  • G11—INFORMATION STORAGE
  • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
  • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
  • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
  • G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
  • G11B7/252—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers
  • G11B7/253—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of substrates
  • G11B7/2533—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of substrates comprising resins
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F8/00—Chemical modification by after-treatment
  • C08F8/04—Reduction, e.g. hydrogenation
• • G—PHYSICS
  • G11—INFORMATION STORAGE
  • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
  • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
  • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
  • G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
  • G11B7/252—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers
  • G11B7/253—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of substrates
  • G11B7/2533—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of substrates comprising resins
  • G11B7/2536—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of substrates comprising resins polystyrene [PS]

Definitions

• Transparent plastics such as aromatic polycarbonate, polymethyl methacrylate or polystyrene can be used as the substrate for optical data storage media.
• Addition copolymers of ethylene and a norbornene derivative or a tetracyclododecene derivative as well as hydrogenated products of ring-opened metathesis polymers from norbornene or tetracyclododecene are also suitable.
• Aromatic polycarbonates have very good mechanical properties and heat resistance, but they have too high birefringence and water absorption.
• Polystyrene has too high birefringence and too low heat resistance.
• Polymethyl methacrylate has too high water absorption and insufficient dimensional stability.
• Addition copolymers of ethylene and a non-polar norbornene or tetracyclododecene have low birefringence and almost no water absorption.
• asymmetrical optical data carriers e.g. CD, MO,
• Swelling of the substrate layers can lead to mechanical stresses, in particular at interfaces to information and protective layers, which cause the information layers to detach from substrate layers more quickly.
• the invention relates to substrates based on homo- and / or copolymers of vinylcyclohexane, comonomers being selected from at least one of the group of olefins, acrylic acid derivatives, maleic acid derivatives, vinyl ethers and vinyl esters or mixtures thereof from at least 2 comonomers, the moment of inertia of the substrate in general from 280 to 50 g-cm 2 , particularly preferably from 260 to 100 g-cm 2 , very particularly preferably from 250 to 150 g-cm 2 , determined according to torsional vibration, and the specific density from 1 to 0.8 g-cm 3 , preferably 0.98 to 0.90 g-cm 3 .
• the invention furthermore relates to an optical substrate which, in particular in the case of high-focusing optics (high numerical aperture> 45), shows very little interference due to birefringence, characterized in that the path difference of the light which falls on the substrate depends on the angle of incidence in the case of vertical and of it deviating angles up to 27 °, a difference in the path difference in general from 0 to 60 nm, preferably from 0 to 50 nm, very particularly preferably from 0 to 40 nm.
• the substrates according to the invention are distinguished by high dimensional stability, high transparency, low birefringence and high heat resistance and are therefore extremely suitable as substrate material for optical data storage media.
• the substrates are particularly suitable for the production of optical
• Vibrations of the data carrier are reduced in comparison to the data carriers currently used, for example polycarbonate.
• the saturation water absorption of a blank according to the invention of the optical storage medium is generally less than 0.5%, preferably less than 0.2%, very particularly preferably less than 0.1%, in particular less than 0.06%, measured in accordance with DIN 53 495.
• the material has a high modulus of elasticity. This is associated with a high flexural strength, which in turn allows the construction of dimensionally stable substrate plates. Thinner substrate thicknesses allow higher data densities, since optics with high numerical aperture NA and low laser wavelength ⁇ become less critical (spot diameter ⁇ ⁇ / NA, G. Bonwkuis, J. Braat, A. Huijser, J. Pasman, G. van
• the optical transmission is greater than 89% for wavelengths greater than 400 nm.
• the material is therefore a preferred optical material for short and long-wave light, in particular for wavelengths from 300 to 800 nm.
• Substrates with low differences in path difference depending on the angle of incidence of the light are particularly suitable for improving the optoelectronic write-in and read-out signals and are ideal substrates for readable, writable and rewritable data carriers.
• the materials have a high heat resistance Tg and allow high operating and use temperatures.
• Preferred materials for deposition are metals, metal compounds and dyes.
• Particularly suitable metals are aluminum, gold, silver, copper, tin, zinc, germanium, antimony, tellurium, terbium, selenium, iron, cobalt, gadolinium and their alloys.
• Particularly suitable metal compounds are zinc oxide, silicon oxide, silicon
• Nitrogen compounds and zinc sulfide are Nitrogen compounds and zinc sulfide.
• Cyanine, phthalocyanine and azo dyes are suitable as dyes.
• These materials can be applied by spin coating and sputtering techniques.
• optical data storage media The following are examples of optical data storage media:
• MD Mini disc
• MO--7 Advanced storage magnetooptic
• MAMMOS Magnetic Amplifying Magneto Optical System
• CD-ROM Read only memory
• CDs CD, CD-R (recordable), CD-RW (rewritable), CD-I (interactive), Photo-CD
• DVD DVD, DVD-R (recordable), DVD-RAM (random access memory);
• MMVF multimedia video file system
• R 1 and R 2 are independently hydrogen or C j -CG alkyl, preferably
• R 3 and R 4 are independently hydrogen or Ci-C ⁇ alkyl, preferably C j -C 4 alkyl, especially methyl and / or ethyl, or R 3 and R 4 together represent alkylene, preferably C 3 - or C - j -alkylene (fused-on 5- or 6-membered cycloaliphatic ring), R5 is hydrogen or C ⁇ -Cg- alkyl, preferably C j -C 4 - alky 1,
• R 1 , R 2 and R 5 independently of one another in particular represent hydrogen or methyl.
• the linkage can have a small proportion of head-to-head linkage.
• the vinylcyclohexane based amorphous predominantly syndiotactic polymer can be branched via centers and e.g. have a star-shaped structure.
• comonomers can preferably be used in the polymerization of the starting polymer (optionally substituted polystyrene) and incorporated into the polymer: olefins with generally 2 to 10 carbon atoms, such as, for example, ethylene, propylene, isoprene, isobutylene, butadiene, C j -Cg- preferably C1-C4-alkyl esters of acrylic or methacrylic acid, unsaturated cycloaliphatic hydrocarbons, for example cyclopentadiene, cyclohexene, cyclohexadiene, optionally substituted norbornene, dicyclopentadiene, dihydrocyclopentadiene, optionally substituted tetracyclododecenes, ring-alkylated styrenes, vinyl-methylstyrene acids, ⁇ -methyl-styrene, divinyl , Vinyl ethers, vinyl acetate, vinyl cyanides
• Amorphous vinylcyclohexane polymers which can also be used are those having a syndiotactic diad fraction, determined by two-dimensional NMR spectroscopy, from 50.1 to 74%, preferably from 52-70%.
• Process for microstructure elucidation using 13 C- ! H Correlation spectroscopy of the methylene carbon atoms of a polymer backbone are generally known and are described, for example, by AMP Ros and O. Sudmeijer (AMP Ros, O. Sudmeijer, Int. J. Polym. Anal. Charakt. (1997), 4, 39.).
• the measurement method of the rheo-optic constant is described in EP-A 0621 297. The plane-parallel 150 to 1,000 ⁇ m specimens required for this can be melt-pressed or
• Film casting are made.
• the material can be considered to be birefringent compared to polycarbonate.
• the vinylcyclohexane (co) polymers generally have absolute molecular weights M w weight average of 1,000 to 10,000,000, preferably from 60,000 to
• the vinylcyclohexane (co) polymers particularly preferably have absolute molecular weights M w of 70,000 to 450,000 g / mol, in particular 100,000 to
• the copolymers can be present both statistically and as block copolymers.
• the polymers can have a linear chain structure and also have branching points due to Co units (for example graft copolymers).
• the branching centers contain, for example, star-shaped or branched polymers.
• the polymers according to the invention can have other geometrical forms of the primary, secondary, tertiary, optionally quaternary polymer structure, in this case its so-called helix, double helix, leaflet etc. or mixtures of these structures.
• Styrene-isoprene copolymers are particularly preferred, in particular poly (styrene block-co-isoprene) and star-shaped poly (styrene block-co-isoprene).
• Block copolymers include di-blocks, tri-blocks, multi-blocks and star-shaped block copolymers.
• VCH (co) polymers are prepared by polymerizing derivatives of styrene with the corresponding monomers by radical, anionic, cationic or metal complex initiators or catalysts and then hydrogenating the unsaturated aromatic bonds completely or partially (see, for example, WHERE
• VCH (co) polymers can also be prepared, for example, by hydrogenating aromatic polystyrenes or their derivatives in the presence of a catalyst, using as solvent an ether which has no ⁇ -hydrogen atom on one
• Has adjacent carbon atom ether function or a mixture of such ethers or a mixture of at least one of the ethers mentioned with solvents suitable for hydrogenation reactions.
• the hydrogenation of the starting polymers is carried out according to generally known methods (e.g. WO 94/21 694, WO 96/34 895, EP-A-322 731).
• a large number of known hydrogenation catalysts can be used as catalysts.
• Preferred metal catalysts are mentioned, for example, in WO 94/21 694 or WO 96/34 896.
• Any catalyst known for the hydrogenation reaction can be used as the catalyst.
• Catalysts with a large surface area e.g.
• catalysts with a small surface area (for example> 10 m 2 / g) and large average pore diameters are also suitable, which are characterized in that 98% of the pore volume has pores with pore diameters greater than 600 ⁇ (for example approx. 1,000 - 4,000 ⁇ ) (see, for example, US-A 5,654,253, US-A 5,612,422, JP-A 03076706).
• the reaction is generally carried out at temperatures between 0 and 500 ° C., preferably between 20 and 250 ° C., in particular between 60 and 200 ° C.
• the reaction is generally carried out at pressures from 1 bar to 1000 bar, preferably 20 to 300 bar, in particular 40 to 200 bar.
• the substrates are produced from the thermoplastic molding compositions containing homopolymers and / or copolymers based on vinylcyclohexane and, if appropriate, other conventional additives, such as processing aids, stabilizers, by processing the molding compositions at temperatures above 280 ° C.
• the 40 1 autoclave is flushed with inert gas (nitrogen).
• the polymer solution and the catalyst are added (Table 1).
• the protective gas is then exposed to hydrogen several times.
• the respective hydrogen pressure is set and heated to the corresponding reaction temperature with stirring.
• the reaction pressure is kept constant after the onset of hydrogen absorption.
• the reaction time is defined by the heating of the
• the polymer solution is filtered.
• the polymer solution is stabilized with 4,000 ppm Irganox XP 420 FF (Ciba Specialty Chemicals, Basel, Switzerland), freed from the solvent at 240 ° C. and the product processed into granules.
• the granules are injection molded, e.g. Shoulder bars, optical plates and other test specimens to determine the physical properties
• the syntheses are carried out using standard inert gas techniques. 138 kg abs. Cyclohexane are placed in a 250 1 reactor. 6.3 kg abs. Styrene are at
• Example 2 22 kg of the polymer solution (Example 2) are transferred to a 40 1 autoclave under nitrogen. After adding 421.5 g of Ni-5136 P (Engelhard), the autoclave is charged with nitrogen and hydrogen several times. The reaction solution is heated to 170 ° C. at 100 bar. After the heating-up phase, the reaction is run through an automatic pressure device at 150 bar up to the pressure constant and stirred for two hours.
• the catalyst is filtered from the polymer solution.
• the polymer solution is stabilized with 4,000 ppm Irganox XP 420 FF (Ciba Geigy, Basel, Switzerland), freed from the solvent at 240 ° C and processed as granules.
• CD Rohline were manufactured on an injection molding machine from Netstal, type Diskjet 600
• CD blanks inner diameter 15 mm, outer diameter 120 mm, 1.2 mm substrate thickness
• a blank CD (CD substrate) made from a bisphenol A polycarbonate (Makrolon CD 2005, Bayer AG, Leverkusen, Germany), and as examples B and C, blank CDs made from polyvinylcyclohexane based polymers according to Examples 1 and 3, used.
• the CD blanks are on an injection molding machine from Netstal, type Diskjet
• the CD blanks according to Examples B and C show, in comparison to the common substrate material according to Comparative Example A (Table 2) for use as optical storage media of high density, the important combination of low moment of inertia, low water absorption, high dimensional stability (high modulus of elasticity), low specific density, low difference in path difference depending on the angle of incidence of light, high optical transparency for short and long wavelengths, as well as low birefringence with high heat resistance.
• Example C shows a further optimized rheo-optic constant CR, with a very small difference in the path difference as a function of the angle of incidence of the light, and has a glass temperature on the

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• Chemical & Material Sciences (AREA)
• General Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Optical Record Carriers And Manufacture Thereof (AREA)
• Graft Or Block Polymers (AREA)

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• 1999
  • 1999-05-12 DE DE19921943A patent/DE19921943A1/de not_active Withdrawn
• 2000
  • 2000-05-02 EP EP00927119A patent/EP1185981A1/de not_active Withdrawn
  • 2000-05-02 JP JP2000618975A patent/JP2003500784A/ja active Pending
  • 2000-05-02 WO PCT/EP2000/003925 patent/WO2000070607A1/de not_active Application Discontinuation
  • 2000-05-02 BR BR0010493-0A patent/BR0010493A/pt not_active IP Right Cessation
  • 2000-05-02 CA CA002373712A patent/CA2373712A1/en not_active Abandoned
  • 2000-05-02 CN CN00807452A patent/CN1363090A/zh active Pending
  • 2000-05-02 KR KR1020017014348A patent/KR20020002500A/ko not_active Application Discontinuation
  • 2000-05-02 AU AU45601/00A patent/AU4560100A/en not_active Abandoned
• 2001
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