Embodiments of the invention generally relate to optical discs rendered unreadable after a limited number of plays.
Conventional optical discs have reached widespread acceptance as a low-cost, reliable storage medium for digital information including music, video, and data. One of the traditional advantages of optical discs is their ability to be played thousands of times without degrading the digital information. However, in some applications, this aspect of the conventional optical disc represents a disadvantage by allowing the digital information to be used or copied more than the creator of the digital information desires. Although some discs have been provided with features to frustrate unlimited use, these discs have typically only temporarily rendered the disc unreadable. Further, known discs that are rendered permanently unusable have generally been rendered unreadable in response to time, such as by oxidation after the removal of a barrier layer. Such discs do not provide optimum qualities of rendering a disc permanently unreadable in response to the number of uses.
Some embodiments of the invention include a limited play optical disc comprising a substrate having machine-readable information encoding features and a coating comprising a tellurapyrylium dye irreversibly bleachable by light. In such embodiments, the information encoding features are machine-readable prior to bleaching of the dye, which may be activated by light. The bleached dye, however, alters the disc to inhibit further reading of the information encoding features. The dye can be bleached by a number of readings of the disc, as, for example, by exposure to light associated with reading of the disc. Embodiments of the optical discs have a relatively short effective life, limited by the number of times the disc is played (e.g. one, two, three or more times). Embodiments of the invention also include methods of making and using a limited play optical disc.
a) shows information encoding features in accordance with some embodiments of the invention.
b) shows an enlarged view of a portion of
c) shows a read pattern in accordance with some embodiments of the invention.
The following detailed description should be read with reference to the drawings, in which like elements in different drawings are numbered identically. The drawings, which are not necessarily drawn to scale, depict selected embodiments and are not intended to limit the scope of the invention. Several forms of the embodiments will be shown and described, and other forms will be apparent to those skilled in the art. It will be understood that embodiments shown in drawings and described are merely for illustrative purposes and are not intended to limit the scope of the embodiments as defined in the claims that follow.
Optical discs enable 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, for example, compact disc (CD), compact disc read only memory (CD ROM), digital versatile disc (DVD) including multi-layer structures like DVD-5, DVD-9, and multi-sided formats such as DVD-10, and DVD-18, magneto-optical disc (MO), other write-once and re-writable formats such as CD-R, CD-RW, DVD-R, DVD-RW, DVD+RW, DVD-RAM, high definition optical discs such as Blu-ray and HD DVD, volumetric playback structures, and the like.
During use, the reading beam (sometimes referred to herein as an incident beam) 18 passes through the substrate 10, is reflected by the reflective layer 14, and passes out through the substrate 10 and the information encoding features as a reflected beam for detection by a reading device. In some embodiments the reading device is selected from the group consisting of a disc drive, CD player, and DVD player. The reading device may include an optical source, such as a laser, that directs the reading beam against the disc 4. A detector senses returning radiation (i.e., the reflected beam) from the disc 4.
As shown in
a)-(c), adapted from The Compact Disc Handbook by K. C. Pohlmann, A-R Editions, Inc., Madison, Wis., 1992, show the information encoding features being read on a typical optical disc. As an example,
Upon sufficient exposure to the reading beam, the dye in the coating 20 undergoes a change in index of refraction to sharply reduce the information encoding feature contrast, resulting in unrecoverable data. As shown in
Embodiments of the optical discs have a relatively short effective life, limited by the number of times the disc is played (e.g. one, two, three, five or more times). In some embodiments the disc is read more than once before further reading is inhibited. In some embodiments the disc is read more than twice before further reading is inhibited. Further, the dyes are useful for rendering the disc permanently unreadable after a limited number of uses. The number of times the disc is read before permanent bleaching may be pre-determined by the selection of dye and the presence or absence of bleaching accelerators. The dye coating may be of a sufficient thickness and sensitivity to bleach in response to the laser intensity typically emitted from a standard disc reader, in contrast to dye coatings having a thickness and sensitivity that can only be activated in response to the typically higher intensity lasers utilized in disc writers.
In some embodiments, the dye irreversibly bleachable by light is selected from the group consisting of tellurapyrylium dyes. Generally, tellurapyrylium dyes include aromatic, benzenoid-like heterocycles consisting of a tellurium atom bearing a positive charge in a six-membered ring with three double bonds. Tellurapyrylium dyes have a +2 oxidation state where the tellurium atom is conjugated with the carbon π-framework and a +4 oxidation state of the tellurium atom. In the +4 oxidation state, the tellurium atom is not conjugated to the carbon π-framework and the tellurapyrylium dyes with a +4 oxidation state of the tellurium atom have significantly shorter wavelengths of absorption (λmax) than tellurapyrylium dyes with a +2 oxidation state of the tellurium atom. Embodiments of the invention utilize a change in oxidation state at the tellurium atom of a tellurapyrylium dye to cause a loss of a chromophore at the wavelengths of emission of the read laser of a reading device or to cause a large change in refractive index at the wavelengths of emission of the read laser of the reading device.
Embodiments of the invention utilize tellurapyrylium dyes to create an optical disc that has a limited number of plays due to loss of information read by the read laser of a reading device. Without intending to be bound by theory, it appears the primary means of accomplishing the loss of chromophore or the change in refractive index is the coupling of a photochemical reaction induced by the read laser with a chemical change in oxidation state at the tellurium atom of the tellurapyrylium dye. For example, the photochemical generation of singlet oxygen caused by the tellurapyrylium dyes absorbing the wavelengths of light emitted by the read laser and transferring this energy to ground state oxygen to produce singlet oxygen. Singlet oxygen then reacts with the tellurium atom of the tellurapyrylium dye to give the Te(IV) oxidation state and a new dye whose wavelengths of absorption and refractive index at a given wavelength have changed to render the information encoding features unreadable.
While any tellurapyrylium dye may be used, some embodiments of tellurapyrylium dyes useful in specific embodiments of the invention are tellurapyrylium dyes selected from the following classes of monomethine (compound I) or trimethine (compound II) shown below:
Upon bleaching, the dye will have an index of refraction similar to the polycarbonate, resulting in a large change in the index of refraction. For example, some tellurapyrylium dye may provide a decrease of index of refraction of more than about 0.3 (e.g., about 0.4). As another example, some tellurapyrylium dye may provide a decrease of index of refraction of more than about 0.5 (e.g., about 0.7). In some embodiments, the tellurapyrylium dye may provide a decrease of index of refraction of more than about 1 (e.g., about 1.5) before bleaching and after bleaching.
The coating may have any thickness sufficient to provide the operable change in index of refraction without obscuring the information encoding features. In some embodiments, the coating has a thickness of less than about one micron. In some embodiments, the coating has a thickness of about 50 to about 300 nanometers. In yet further embodiments, the coating has a thickness of between about 100 to about 250 nanometers. The coating thickness may be chosen to correspond with the pit depth to achieve the one-half wave phase shift discussed above.
Further, the coating may be relatively conformal with the information encoding features. Conformality can be defined as the depth of the dye coated pit divided by the depth of the undyed pit. In some embodiments, the coating is about 25% to about 100% conformal with the information encoding features, and in some embodiments may be about 35% to about 65% (e.g., 50%) conformal. In such embodiments, the resulting dye filled pit depth may be a corresponding percentage of the uncoated pit depth.
In addition, in some embodiments the coating 20 does not significantly decrease the reflectivity of the optical disc. For example, in some embodiments, the reflectively of the disc and coating is greater than about 65%. Such embodiments are useful for reflecting light to be read by a common beam reader.
The coating 20 may be placed in any suitable position on or within the disc 4. In some embodiments the coating is in apposition to the substrate and/or information encoding features. Further, the coating 20 may be in apposition to the reflective layer 14, as shown in
In some embodiments, the coating is activated in response to light having a wavelength of about three hundred nanometers to about eight hundred nanometers. In some embodiments the coating is activated in response to light having a wavelength of about four hundred nanometers to about eight hundred nanometers (e.g., about 600 nm to about 800 nm). For example, the coating may show optimal change of index of refraction at about 650 nm in embodiments where the coating is provided on a DVD. In examples where the coating is provided on a CD, the coating may have an optimal change of index of refraction at about 780 nm. An example of a dye suitable for CD applications includes 4-[3-(2,6-di-tert-butylselenopyran-4H-ylidene)propen-1-yl]-2,6-di-tert-butyltellurapyrylium tetrafluoroborate. Of course, other wavelengths may be chosen. For example, activity in wavelength ranges of about 400 to about 425 nm may be useful in Blu-ray and/or HD DVD applications. In embodiments having a substrate comprising polycarbonate, the wavelength at which the polycarbonate absorbs an unacceptable amount of the light can set the lower limit of the wavelength.
In some embodiments, the coating may include one or more additives. For example, a photobleach accelerator may be provided. Such accelerators are useful for optimizing the rate at which the dye will bleach in response to light. An example of such an accelerator includes a borate and may include an organoborate, tetra phenyl boron, and/or n-butyl triphenylboron. Other accelerators include quinones as discussed in U.S. Pat. No. 4,201,588, the relevant contents of which are hereby incorporated by reference. Generally, accelerators having a charge opposite that of the dyes form one to one salts and are used directly as such. Accordingly, a 1:1 ratio of accelerator to dye molecules may be provided. Uncharged accelerators (such as, for example, the quinones cited above or trialkylamines such as Bis-tris (2,2-bis(hydroxymethyl)-2,2′,2″-nitrilotriethanol) can be utilized in any ratio (e.g., 9:1 dye to accelerator to 1:9 dye to accelerator).
Embodiments of the invention also include a method for inhibiting reading of an optical disc comprising the steps of providing any of the various embodiments of optical discs described above. In some embodiments the information encoding features are stamped into the substrate and the coating is deposited onto the substrate in apposition to the information encoding features. The coating may be deposited by any suitable method (e.g., spin coating), and the dye may be suspended in solution of various suitable solvents (e.g., alcohol) to facilitate deposition. The solvent may then be evaporated to leave behind a coating containing the dye.
Some embodiments of the invention include a method for inhibiting reading of an optical disc comprising the steps of acquisitioning any of the various discs described above and reading the disc with a reading device comprising a source of light and concurrently bleaching the dye to inhibit further reading of the information encoding features. The reading device comprises a source of optical radiation to read the disc and concurrently activate the coating to inhibit further reading of the information encoding features.
Embodiments of the invention as described above may be utilized in many applications. For example, in the DVD movie rental industry, the need for the customer to return the DVD after viewing is obviated because the disc would be rendered unreadable after a pre-determined number of viewings. Another example of a suitable application includes CDs. Such coated CDs would be useful for sending promotional CDs to a target audience, who would be able to play the songs a limited number of times before deciding whether to buy the uncoated version of the CD. As another example, unauthorized software downloading and file sharing could be reduced. For discs in accordance with embodiments of the invention containing software, a user would have a limited number of plays (e.g., three) to fully download the software before the disc is rendered unreadable. Therefore, the user would be discouraged from allowing others to download the software because it would permanently lose one of the plays.
The following examples are presented for illustrative purposes and are not intended to limit the scope of the claims which follow.
The tellurapyrylium dye, 4-[(2,6-di-tert-butylthiopyran-4H-ylidene)methyl]-2,6-di-tert-butyltellurapyrylium hexafluorophosphate, shown in
In this example, the blue dye with tellurium in the +2 oxidation state is converted to a yellow dye with tellurium in the +4 oxidation state. The hue shift represents approximately a 200-nm blue shift in λmax upon oxidation with a change in the index of refraction of about 0.5.
The tellurapyrylium dye, 4-[(2,6-di-tert-butylpyran-4H-ylidene)methyl]-2,6-di-tert-butyltellurapyrylium trifluoromethanesulfonate, shown in
In this example, the blue dye with tellurium in the +2 oxidation state is converted to a yellow dye with tellurium in the +4 oxidation state. The hue shift represents approximately a 150-nm blue shift in λmax upon oxidation with a change in the index of refraction of about 0.8.
The tellurapyrylium dye, 4-[(2,6-di-tert-butylpyran-4H-ylidene)methyl]-2-tert-butyl-6-(2,6-dimethylphenyl)tellurapyrylium trifluoromethanesulfonate, shown in
In this example, the blue dye with tellurium in the +2 oxidation state is converted to a yellow dye with tellurium in the +4 oxidation state. The hue shift represents approximately a 150-nm blue shift in λmax upon oxidation with a change in the index of refraction of about 0.6.
The tellurapyrylium dye, 4-[3-(2,6-di-tert-butylpyran-4H-ylidene)propen-1-yl]-2,6-di-tert-butyltellurapyrylium chloride, shown in
In this example, the blue dye with tellurium in the +2 oxidation state is converted to a yellow dye with tellurium in the +4 oxidation state. The hue shift represents approximately a 200-nm blue shift in λmax upon oxidation with a change in the index of refraction of about 0.6.
The tellurapyrylium dye, 4-[(2,6-di-tert-butylpyran-4H-ylidene)methyl]-2-tert-butyl-6-(2,6-dimethylphenyl)tellurapyrylium trifluoromethanesulfonate, shown in
DVD-Rs having a pit depth relative to the land of 180 nanometers were spin coated with tellurapyrylium dye from pressurized canisters with 3% solids (w/v) (3 grams of dye per 100 mls of solvent). Both the coating and edge-wash solvent was 1-methoxy-2-propanol having 99+% purity. The dye coating optical properties were n=2.15-0.15i at 650 nm. The average dye coating thickness was 110 nm with 50 nm on the land. The optical density of the dye coating was 0.23 at 650 nm.
The coated discs were run in a PULSTEC optical disc tester. The wavelength of the tester laser was 650 nm. The index of refraction of the dye coating started at approximately 2.12 and decreased from there based on absorption of the laser and bleaching of the dye. Various exposures were tested to determine the amount of exposure required to render the disc unreadable after two full plays with this particular coating layer. After several runs an exposure time of about 120-200 seconds was determined to be sufficient.
Thus, embodiments of the Limited Play Optical Disc are disclosed. One skilled in the art will appreciate that the present invention can be practiced with embodiments other than those disclosed. The disclosed embodiments are presented for purposes of illustration and not limitation, and the present invention is limited only by the claims that follow.
This application claims the benefit of U.S. Provisional Patent Application Ser. No. 60/951,593, titled Limited Play Optical Discs, filed Jul. 24, 2007, which is hereby incorporated by reference.
Number | Date | Country | |
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60951593 | Jul 2007 | US |