EP1540416A2 - Systeme pour appliquer des marques a un support optique - Google Patents

Systeme pour appliquer des marques a un support optique

Info

Publication number
EP1540416A2
EP1540416A2 EP03756837A EP03756837A EP1540416A2 EP 1540416 A2 EP1540416 A2 EP 1540416A2 EP 03756837 A EP03756837 A EP 03756837A EP 03756837 A EP03756837 A EP 03756837A EP 1540416 A2 EP1540416 A2 EP 1540416A2
Authority
EP
European Patent Office
Prior art keywords
coating
color
wavelengths
optical media
ofthe
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP03756837A
Other languages
German (de)
English (en)
Other versions
EP1540416A4 (fr
Inventor
Jeffrey L. Conroy
Andrei Smuk
Robert Afzal
Dana Lewis
Allison Berube
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Spectra Systems Corp
Original Assignee
Spectra Systems Corp
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 Spectra Systems Corp filed Critical Spectra Systems Corp
Publication of EP1540416A2 publication Critical patent/EP1540416A2/fr
Publication of EP1540416A4 publication Critical patent/EP1540416A4/fr
Withdrawn legal-status Critical Current

Links

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
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B23/00—Record carriers not specific to the method of recording or reproducing; Accessories, e.g. containers, specially adapted for co-operation with the recording or reproducing apparatus ; Intermediate mediums; Apparatus or processes specially adapted for their manufacture
    • G11B23/38—Visual features other than those contained in record tracks or represented by sprocket holes the visual signals being auxiliary signals
    • G11B23/40—Identifying or analogous means applied to or incorporated in the record carrier and not intended for visual display simultaneously with the playing-back of the record carrier, e.g. label, leader, photograph
    • 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
    • G11B7/254—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of protective topcoat layers
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/26—Apparatus or processes specially adapted for the manufacture of record carriers
    • G11B7/266—Sputtering or spin-coating layers
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/26—Apparatus or processes specially adapted for the manufacture of record carriers
    • G11B7/268—Post-production operations, e.g. initialising phase-change recording layers, checking for defects
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
    • G11B7/242—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers
    • G11B7/244—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only
    • G11B7/246—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only containing dyes
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • 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
    • G11B7/2534—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of substrates comprising resins polycarbonates [PC]
    • 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
    • G11B7/258—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 reflective layers

Definitions

  • This invention relates, to a method and apparatus for rapid production of high quality images upon the read out side of optical media.
  • Optical media includes a variety of supplementary information that is in addition to the data recorded in the optical media.
  • the supplementary information is frequently presented in elaborate form, consistent with the marketing, advertising or other goals of the manufacturer.
  • the supplementary information may be included in various fashions, such as through the use of stick on labels, inks or through other techniques.
  • Labeling or markings are typically applied to the "non-read" side of a disc, such as a CD ROM or a DVD, for indicating information such as the source ofthe disc and a listing of the information recorded thereon.
  • a disc such as a CD ROM or a DVD
  • markings on the non-readout side of optical media permits the use of a variety of marking technologies, ranging from simple to complex. Placement of markings on the read-side of optical media, particularly in the area where data is recorded, is a greater challenge, as the markings can interfere with the use ofthe optical media.
  • any advantages are limited. That is, for example, the markings are visible only under certain conditions, and complicated or expensive manufacturing processes are called for to produce finished product. Furthermore, the degree of control, or complexity of the marking may be less than desired for effective advertising or other information bearing schemes.
  • this patent discloses use of dispersing agents, which indicate inhomogeneity, a property that would cause laser scatter in an optical media readout system.
  • the initiators disclosed in this patent are sensitive to visible light and require the use of an oxygen barrier layer to affect adequate curing.
  • Use of an oxygen barrier layer is a substantial hindrance to the application of these materials to quantities of optical disc, as manufacturing environments do not typically provide for a dark and / or oxygen free environment. Further such additional steps present economic and production burdens that would serve to limit use ofthe marking system.
  • a need also exists to provide a system for manufacturing optical media or disks that addresses the foregoing need for enhanced marking, identification, authentication and encoding capabilities.
  • aspects of the invention include, but are not limited to: applying certain materials as a coating, or coatings, onto an optical media; curing the coatings with a first light, such as ultraviolet (UV) light; addressing each of the coatings with certain wavelengths of a second light, such as UV, infrared (IR), or near infrared (MR); and using selective exposure of the coatings to the certain wavelengths of second light to record an image in the collective appearance ofthe coatings.
  • a first light such as ultraviolet (UV) light
  • addressing each of the coatings with certain wavelengths of a second light such as UV, infrared (IR), or near infrared (MR)
  • MR near infrared
  • Aspects ofthe invention include application ofthe coating, or coatings, and the marking upon the read side or the non-read side of the optical media, without loss, or substantial loss, ofthe functionality ofthe media.
  • Further aspects of the invention include a single or multi-color image, or marking, formed in the collective appearance ofthe coatings, where the marking may be produced in a form that is tiansmissive, or substantially tiansmissive of wavelengths of interest.
  • the marking is tiansmissive to readout wavelengths used in the readout ofthe optical media marked with the color image.
  • aspects of the invention may further include, but are not limited to, the use of coatings that absorb or reflect light at predetermined wavelengths, the use of multiple markings, and the use ofthe markings as security measures.
  • Further aspects of the invention include providing for the use ofthe read side of the optical media for marking with advertising, branding, and other markings normally associated with the non-readout side ofthe media.
  • aspects of the apparatus involved in the production of coated optical media suited for receipt of a marking as disclosed herein include, but are not limited to, integrated optical media production equipment, where the integrated equipment incorporates appropriate modifications in support of the embodiments described herein.
  • apparatus may involve use of manual or semi-automated techniques for generation of coated optical media, and the markings thereon.
  • Further aspects of the invention also include use of examination and inspection techniques for qualifying and or controlling various facets of optical media production.
  • manufacturing may include processes for assessing the optical quality of the coating prior to marking.
  • manufacturing may involve examining aspects of a statistically significant portion of finished product for quality.
  • a CCD camera and processor, or equivalent apparatus may be employed to image and compare the appearance of various features in a production marking to data records describing the desired appearance quality ofthe respective features.
  • Figure 1 is a cross-sectional diagram of a prior art optical media
  • Figure 2 is a cross-sectional diagram of an optical media having a coating in accordance with the teachings herein
  • Figure 3 depicts an absorbance curve for a color fonner in a coating formulation
  • Figure 4 compares background color formation in various compositions
  • Figure 5 depicts absorbance spectra for two photoacid generators
  • Figure 6 depicts a UV absorption spectra for a first photoinitiator
  • Figure 7 depicts a UV absorption spectra for a second photoinitiator
  • Figure 8 depicts a line spectrum for a medium pressure iron-doped lamp
  • Figure 9 depicts a line spectrxim for a gallium iodide lamp
  • Figure 10 depicts a line spectrum for a xenon gas filled lamp
  • Figure 11 depicts transmission curves for various filters
  • Figure 12 depicts absorbance peaks at 540 nm for various concentrations of a color former
  • Figure 13 depicts absorbance peaks at 540 nm for various concentrations of triphenyl sulfonium triflate
  • Figure 14 average color decrease in a first environmental study
  • Figure 15 depicts reductions in surface tension as a function of concentrations of various wetting agents;
  • Figure 16 depicts average absorbance of various formulations after environmental testing;
  • Figure 17 depicts average decrease in optical density for various formulations after environmental testing
  • Figure 18 depicts a storage case laden with filter paper
  • Figure 19 depicts fading in color resulting from TEA exposure
  • Figure 20 depicts the development of color as a function of exposure wavelength
  • Figure 21 depicts development of color in samples containing UV absorbers
  • Figure 22 depicts the effect of adding UV absorbers on color generation
  • Figure 23 depicts color formation in UV stabilized formulations
  • Figure 24 depicts color formation in a particular sample of a UV stabilized formulation
  • Figure 25 depicts results of a study adjusting ratios of color former and photoacid generators
  • Figure 26 depicts color level and sensitivity as a function of photoacid generator concentration and film thickness
  • Figure 27 depicts the absorbance of a CN-120 based formulation
  • Figure 28 compares absorbance spectra for various UV absorbers
  • Figure 29 depicts color formation times for combinations having various photoacid generators
  • Figure 30 depicts aspects of color generation as a function of photoacid generator
  • Figure 31 depicts color formation as a function of illumination type
  • Figure 32 depicts color formation as a function of UV absorber
  • Figure 33 depicts color formation as a function of illumination fluence
  • Figure 34 depicts color formation as a function of additives for enhancement;
  • Figure 35 depicts color formation in a buffered system;
  • Figure 36 depicts film thickness as a function of spin speed
  • Figure 37 depicts film thickness and optical density as a function of spin speed
  • Figure 38 depicts film thickness and optical density as a function of spin speed
  • Figure 39 depicts color formation for varying ratios of photoacid generator to color former
  • Figure 40 depicts a cross section of an optical media having a color forming layer and a overcoat layer
  • Figure 41 depicts optical density for two coatings
  • Figure 42 depicts color formation as a function of time one geometry
  • Figure 44 depicts residual sensitivity in a two coating system
  • Figure 45 depicts lightfastness in exposed areas
  • Figure 46 depicts color development from environmental testing
  • Figure 47 depicts environmental color retention
  • Figure 48 depicts fading from an amine study
  • Figure 49 depicts film thickness as a function of spin speed
  • Figure 50 depicts viscosity as a function of temperature
  • Figure 51 depicts a shear rate profile
  • Figure 52 depicts a shear stress and shear rate profile
  • Figure 53 depicts viscosity for a constant shear rate
  • Figure 54 depicts color formation for a set of photoacid generators and color formers
  • Figure 55 depicts color formation for a set of photoacid generators and color formers
  • Figure 56 depicts color formation for a set of photoacid generators and color formers
  • Figure 57 depicts color formation for a set of photoacid generators and color formers
  • Figure 58 depicts a comparison of light sources
  • Figure 59 depicts a comparison of light sources
  • Figure 60 depicts color formation as a function of fluence
  • Figure 61 depicts residual sensitivity of coating with various UV absorbers
  • Figure 62 depicts the optical density of exposed regions as a function of UN absorber
  • Figure 63 is a cross section of an optical media having multiple layers applied over the reflective layer
  • Figure 64 is a cross section of an optical media having multiple layers applied over the reflective layer
  • Figure 65 is a cross section of an optical media having multiple layers applied over the reflective layer
  • Figure 66 is a graph depicting absorbance curves for orange and red color foiming layers
  • Figure 67 is a graph depicting absorbance curves for a multicolor embodiment'
  • Figure 68 is a graph depicting absorbance where only a top color forming layer is exposed
  • Figure 69 is a graph depicting absorbance in a multi-color system having a UN blocking layer
  • Figure 70 is a partial view of photomask showing a shading technique
  • Figure 71 depicts markings on an optical media formed by illumination with a marking lamp
  • Figure 72 depicts an inspection apparatus for evaluating markings
  • Figure 73 depicts aspects ofthe inspection apparatus; " [0096] Figure 74 depicts test data for an uncoated disk;
  • Figure 75 depicts test data for a coated disk
  • Figure 76 depicts test data for a coated disk with at least one image recorded thereon
  • Figure 77 depicts aspects of one embodiment for a production system for application of a single color forming layer
  • Figure 78 depicts aspects of another embodiment for marking an optical media
  • Figure 79 depicts aspects of a production system for applying a two coating system
  • Figure 80 depicts an apparatus for applying multiple coatings
  • Figure 81 depicts an apparatus for manual curing of a coating on an optical media
  • Figure 82 depicts an offline marking system for marking coated optical media
  • Figure 83 depicts test data for an optical media produced in a production system.
  • the teachings herein describe a coating, or a series of coatings, for application of at least one gray scale, single color or a multi-color marking to an optical media such as a CD (compact disc) or a DVD (digital versatile disc). Also disclosed are aspects of a system for the production of optical media characterized by these markings. Aspects of the invention include, but are not limited to: applying certain materials as a coating, or coatings, onto an optical media; exiling the coatings with a first light, such as ultraviolet (UV) light; addressing each of he coatings with certain wavelengths of a second light, such as UN, and using selective exposure of the coatings to the certain wavelengths of second light to record an image in the collective appearance of the coatings. Additional layers of coatings may be added, and aspects of the process repeated, as warranted. Further aspects of the teachings herein include techniques for the inspection of coated optical media, and production thereof.
  • the optical media marked in accordance with the teachings herein are produced in a mass production environment.
  • the disclosure herein is directed toward accommodation to the demands of a mass production environment.
  • mass production environments typically demand minimal production time, and therefore require quick curing and image formation.
  • some of the embodiments disclosed herein may be further modified to accommodate other production models, such as single unit production, and make take advantage of longer curing times, or alternative imaging techniques. Such modified embodiments are considered to be a part ofthe teachings herein, and described by the appended claims.
  • Color Enhancing Additives 13 Spin Coating, Film Thickness and Optical Density.
  • the coating as disclosed herein, is suited for incorporation into various components of optical media. It is recognized that a variety of optical media exist, and that many have a slmcture that differs, at least partially, from other optical media. Therefore, this disclosure teaches what are to be considered non-limiting embodiments of incoiporating a coating into an optical media. That is, this disclosure does not provide an exhaustive disclosure of incorporation ofthe coating into optical media.
  • Figure 1 discloses aspects of an exemplary optical media.
  • a prior art optical media 8 is shown.
  • the optical media 8 includes various layers, which may be referred to herein as "components" of the optical media 8.
  • the substrate layer 16 is molded with pits 5 and lands 6 (data features), and is typically formed of polycarbonate or similar transmissive plastic material.
  • a reflective layer 14 is deposited on the data features to enable readout by an interrogating laser.
  • a protective layer 12 is one component that is typically included to ensure the integrity ofthe reflective layer 14 and is typically formed of a UN curable acrylate coating or similar material.
  • the disc maybe read through the substrate layer 16, as indicated by the directional arrow in Figure 1. Typically, printing or other indicia are placed over the protective layer 12.
  • FIG. 2 provides an illustration o the cross section of an optical media 10 with a first and introductory embodiment of a coating 100 applied thereon.
  • the optical media 10 includes a reflecting (reflective) layer 14 and a substrate layer 16.
  • the substrate layer 16 is formed of polycarbonate, while the reflecting layer 14 is metallized (has a reflective metal applied thereon). It is recognized that aspects of the reflecting layer 14 and a substrate layer 16 are typically dictated by the specifications for the optical media 10, and therefore are generally not discussed further herein.
  • the discs 10 typically contain pits 5 and lands 6 as data features.
  • the coating 100 is applied over the substrate 16 ofthe optical media 8.
  • aspects of the substrate layer 16 maybe adjusted to account for subsequent preparation of the coating 100.
  • the substrate layer 16 may be installed with a reduced thickness as determined by reference to a manufacturer's specification for the type of optical media 8. Subsequent installation ofthe coating 100 is then used to increase the thickness ofthe optical media 10 to meet the desired thickness specification.
  • the coating 100 contains color foiming materials necessary for generation of a color image.
  • the color forming materials may be configured in a variety of ways, to be discussed further herein.
  • the color fo ⁇ ning materials may be used to develop a gray scale, single color, or multi-color marking.
  • the coating 100 does not interfere, or substantially interfere, with the readout ofthe optical media 10. That is, the coating 100 and any markings recorded in the coating 100, do not appreciably absorb or scatter light at the readout wavelength ofthe optical media readout laser. Likewise, the thickness and other aspects of the coating 100 do not substantially interfere with the readout mechanism. Accordingly, the coating 100 may be applied to the "play" side 16 or "non- play" side 12 ofthe optical media 10 depicted in Figure 2.
  • the coating 100 contains what can be referred to as two "sets" of photosensitive materials.
  • One set of photosensitive materials provides for curing ofthe coating 100 once the coating 100 is in place. That is, exposure to one set of wavelengths provides for curing of the first set of photosensitive materials.
  • a second set of photosensitive materials in the coating 100 exhibits optical changes upon adequate exposure to a separate set of wavelengths.
  • the coating 100 may contain photoinitiators to initiate crosslinking.
  • the coating 100 may include, but is not limited to, compounds such as photoacid or photobase generators, acid or base sensitive dyes, leucodyes, metal chelates, fluorescent dyes, or laser dyes.
  • the coating 100 may be colored or colorless to the eye, and may be fluorescent under certain electromagnetic radiation. Fluorescent emission wavelengths may include, but are not limited to, a wavelength in the visible region.
  • Commonly used readout light wavelengths for the optical media 10 include 408nm, 440nm, 630nm, 650nm, and 780nm, while other readout wavelengths are possible.
  • the coating 100 may include materials that are photosensitive to any band of wavelengths (also referred to as a "set of wavelengths").
  • the photosensitive materials may be responsive to UV-A, UN-B, UN-C, VIS (visible wavelengths), short wavelength infrared (IR), IR, or long wavelength IR.
  • VIS visible wavelengths
  • IR short wavelength infrared
  • IR IR
  • long wavelength IR long wavelength IR
  • optical media 8 are referred to herein in general terms, such as “CD” or “DVD.” However, it is considered that optical media 8 encompass many different media formats.
  • the many formats of optical media 8 include: DVD 5, DVD 9, DVD 10, DVD 14, DVD 18, DVD-R, DVD-RW, CD-Audio, CD-Video, CD-R, CD- RW, CD-ROM, CD-ROM/XA, CD-i, CD-Extra, CD-Photo, Super-Audio CD, Mini- Disc a hybrid format, which may include any one or more of the foregoing, Blu-Ray, and others. It is recognized that this is not an exhaustive list, and should therefore only be considered illustrative of the variety of optical media formats that may benefit from the use of this invention.
  • SR-494 is an ethoxylated (4) pentaerythritol tetraacrylate
  • SR-238 is a 1,6 hexanediol diacrylate having a low viscosity, fast curing monomer with low volatility, a hydrophobic backbone, and good solvency for use in free radical polymerization
  • ESACURE KTO-46 is a stable liquid mixture of trimethylbeiizoyldiphenylphosphine oxide, ⁇ -hydroxyketones, and benzophenone derivatives.
  • ESACURE KTO-46 is a liquid photoinitiator that can be incorporated by simply stirring into a resin system, and is insoluble in water and is soluble in most common organic solvents and monomers. KTO-46 may also be referred to as including ESACURE KIP-150 and ESACURE TZT.
  • ESACURE KIP-150 being an: oligo [2-hydroxy-2-methyl-l-[4-(l-methylvinyl) phenyl] propanone]; and ESACURE TZT being an eutectic liquid mixture of: 2,4,6 trimethylbenzophenone and 4 methylbenzophenone.
  • ESACURE KTO-46, ESACURE KIP-150 and ESACURE TZT are produced by Lamberti Spa, Gallarate-Va, Italy.
  • SR-494 and SR-238 are products of Sartomer Corporation of Exton, PA.
  • KTO-46 is also marketed by Sartomer Corporation as SARCURE-1135 (therefore, KTO-46 and SR-1135 are used interchangeably herein).
  • SR-285 is tetiahydrofurfuryl acrylate that is a low viscosity, polar, monofunctional monomer, which contains a cyclic group, and promotes adhesion to numerous substrates; and SR-9021 is a highly propoxylated (5.5) glyceryl triacrylate, that is a low skin irritation trifunctional monomer offering low viscosity, good flexibility, fast curing, and excellent hardness.
  • SR-285 and SR-9021 are products of Sartomer Corporation of Exton, PA.
  • SR-494 and SR-9021 were selected for use in the coating base due to high functionality, low surface tension, fast surface and through cure response, adhesion, and hardness. These components were also considered advantageous as alkoxylation reduced a propensity to irritate skin.
  • SR-238 and SR-285 were skin irritants, but did offer desirable solvation of additives and swell polycarbonate for good adhesion.
  • SR-238 and SR-285 also exhibit low viscosity, which provided an opportunity to tailor the viscosity of the coating base.
  • KTO-46 was selected for use as a photoinitiator, as KTO-46 is considered to be substantially sensitive to long wavelengths of ultraviolet light (i.e., above about 320 nm up to about 400 nm).
  • the coating 100 is applied by spin coating.
  • the edges ofthe optical media 10 occasionally exhibited coverage that was less than desired. It was determined that this was due to the high surface tension of the lacquer (coating base). Therefore, wetting agents were added to the coating base to improve substrate wetting and lower the surface tension were.
  • Exemplary systems for spin-coating formulations onto the substrate 16 include those available from Headway Research, hie. of Garland, TX. Aspects of a system used herein for applying formulations by spin-coating processes includes: controls for adjusting formulation temperature, controls for varying spin speeds in increments, with a maximum spin speed of at least 10,000 (10K) rpm. Systems may further include aspects such as environmental controls for controlling ambient gases, as well as formulation recovery apparatus for recycling unused formulation. Other systems may be used for spin coating, and may further be integrated into mass production apparatus.
  • One model suited for applications of the formulations herein, at least in small batches, is model PWM32-PS-R790 Spinner System, used for aspects of testing as described herein. As systems for spin coating are known, these systems are generally only described firrther herein in terms of application ofthe coating 100, and requirements thereof.
  • composition of a total often formulations is shown.
  • the first coating base is shown as the Control, with subsequent formulations shown as mixtures 1-9. Quantities of each component in each of the ten compositions are expressed in weight percent ofthe total mixture.
  • formulations including wetting agents exhibited reduced surface tension over formulations without a wetting agent. This was considered to be advantageous since formulations having lower surface tensions should coat the substrate 16 better than those formulations with higher surface tension. It was noted that after the addition of 0.3% BYK-333 and after 0.05% BYK-307, the surface tension of the formulation did not change significantly. Therefore, formulations 3 and 7 were tested physically by spincoating the coating base onto various discs 10 and inspecting the edges o the substrate 10. Upon inspection, formulation 3 was found to coat the discs 10 the best while increasing the surface slip significantly. It was noted that the viscosities ofthe various formulations did not change drastically between samples 1 through 9. As a result, formulation 3 was selected as a preferred coating base.
  • SR-9021 could be used interchangeably with SR-9020, since both had similar properties. This was considered to be advantageous since SR-9020 offers higher thermal stability than SR-9021. Therefore, SR-9020 was substituted into formulation 3.
  • SR-9020 is a 3 mole propoxylated glyceryl triacrylate, that is a trifiinctional monomer offering low viscosity, good flexibility, fast curing, and excellent hardness.
  • SR-9020 is a product of Sartomer Corporation.
  • formulations 10 and 14 were significantly harder than the control (formulation 3) while still exhibiting similar viscosities.
  • Formulations 10 and 14 were then subjected to a number of tests, which made up a New Formulation Screening Test shown in Table 5. In preferred embodiments, each formulation must pass this screening to be considered as a possible base for the coating 100. Table 5 shows the tests involved as well as the criteria.
  • Photoacid generators are added to develop the color in the coating 100 once exposed to wavelengths of light. This process involves generation of acid by the PAG when exposed to the wavelengths of light.
  • an acid sensitive color former CF
  • the PAG is sensitive to ultraviolet light.
  • Coating base samples were made by mixing the original control formulation (45% SR-494, 45% SR-238, and 10% KTO/46). This mixture was added at 94% to a 3% concentration of COPIKEM 16 Red (a color former) and a 3% concentration of each ofthe photoacid generators to be investigated.
  • the lacquers were spun coat onto blank, un-metallized polycarbonate substrate 16 for 15 seconds at 4K rpm. Each disc 10 was then placed under a pulsing XENON lamp with a double paned window glass filter for 5 seconds. The resultant disc 10 had a coating that was clear, dry, and hard. A portion of the disc 10 was then exposed for 5 seconds. Another portion ofthe disc 10 was exposed for 10 seconds.
  • Table 8 shows the results for three photoacid generators (PAG).
  • the three PAG were incorporated in the modified coating base formulation 10 (94% of 32.35% SR-494, 32.35% SR-9020, 15%SR-285, 10%SR-238, 10% KTO/46, and .3% BYK- 333).
  • a 3% concentration of each photoacid generators was mixed with the color former PERGASCRIPT Red I-6B.
  • the comparative solubility for of the three photoacid generators being (4-tert-butylphenyl) diphenyl sulfonium triflate is more soluble than (4- methylphenyl) diphenyl sulfonium triflate and is more soluble than triphenylsulfonium triflate.
  • PERGASCRIPT Red I-6B is proprietary, this is not presented herein. However, further herein, various color formers suited for use with the teachings herein are presented.
  • Table 9 shows the results of a first set of experiments with varying amoiints of photoinitiators. Each sample was prepared by spincoating, then cured by illumination with a XENON lamp with a window glass filter for five seconds. The samples were then exposed under the XENON lamp for ten seconds. Each entry in Table 9 is given in the weight percentage ofthe photoinitiator as a part ofthe 94% coating base. The degree of cure was established by attempting physical smudging of the coating, with the scale for the degree of curing as follows: E (excellent) > G (good) > D (decent) > P (poor). Table 9
  • DAROCUR 4265 is a mixture of 50 % 2,4,6-Trimethylbenzoyl-diphenyl- phosphineoxide and 50 % 2-Hydroxy-2-methyl-l-phenyl-propan-l-one.
  • IRGACURE 369 is 2-Benzyl-2-dimethylamino-l-(4-morpholinophenyl)-butanone-l, which is a highly efficient UV curing agent which is used to initiate the photopolymerisation of chemically prepolymers - e.g. acrylates - in combination with mono- or multifunctional monomers.
  • IRGACURE 819 is Bis(2,4,6-trimethylbenzoyl)-phenylphosphineoxide, which is a versatile photoinitiator for radical polymerization of unsaturated resins upon UV light exposure. It is especially suited for white pigmented formulations, the curing of glass fiber reinforced polyester/styrene systems and for clear coatings subjected to outdoor use in combinations with light stabilizers. Thick section curing is also possible with this photoinitiator. All three are products of Ciba Specialty Chemicals of Basle, Switzerland, and Tarrytown, NY.
  • CN-384 In order to further improve samples 20 and 21, CN-384, an amine synergist was added at 0.5% and 1%, respectively. These new additions succeeded in producing a very clear cured coating. However, at 1%, the exposed areas were not intense enough. Unfortunately, with the addition of CN-384, it was found that the exposed areas of the discs 10 exhibited considerable fading after about twenty four hours at room temperature. (CN-384 is a difunctional amine coinitiator which, when used in conjunction with a photosensitizer such as benzophenone, promotes rapid curing under UV light. Additional benefits include reduced odors, both at press side and in the cured film, and reduced blooming. CN-384 is a product of Sartomer Corporation of Exton, PA).
  • IRGACURE 2959 is l-[4-(2-Hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-l- propane-1-one, which is a liighly efficient non-yellowing radical photoinitiator for the UV curing of systems comprising of unsaturated monomers and prepolymers. It is especially suited where low odor is required and for use in water-borne systems based on acrylate or unsaturated polyester resins.
  • SARCURE 1124 is isopropyl thioxanthone, a photoimtiator that is used in combination with a suitable coinitiator, e.g., ethyl 4- (dimethylamino) benzoate (SARCURE SRI 125), to initiate UV free radical polymerization.
  • SARCURE SRI 124 is used in inks, varnishes, and decorative coatings.
  • ESACURE KFP100F is a liquid mixture of about 70% Oligo [2-hydroxy-2-methyl-l-[ 4- (1-methylvinyl) phenyl] propanone and about 30% 2-hydroxy-2-methyl-l -phenyl propan-1-one.
  • both exiling and imaging are completed using wavelengths of ultraviolet light. It is recognized that other formulations than those disclosed herein may exhibit better response at other wavelengths, and therefore use of wavelengths specified herein on only exemplary.
  • deep UV light wavelengths below about 320 nm
  • photoacid generators are available which operate in this area and because deep UV light is not typically found at high intensities in natural illumination (sunlight, fluorescent or incandescent lighting). This tends to provide for a more durable image under ambient conditions when in use.
  • the absorbance spectra of two commercially available photoacid generators having little absorption above 290 nm is depicted in Figure 5.
  • photoinitiators There are a number of commercially available photoinitiators whose primary absorption bands lie at wavelengths greater than 300 nm. Most notably, the phosphine oxide functionalized photoinitiators such as LUCIRIN TPO from BASF Corporation of Charlotte NC, (the main component in KTO46) and IRGACURE 819, whose spectra are shown in Figures 6 and 7, respectively. Other photoinitiators may be used which also exhibit absorption for wavelengths above about 300 nm. It should also be noted that these initiators are ofthe direct fragmentation type of unimolecular initiators.
  • Bimolecular initiators typically consist of a sensitizing molecule capable of absorbing light and transferring it to a synergist molecule capable of foiniing a radical upon the energy transfer.
  • One ofthe most common sensitizers to absorb visible light is ITX, or isopropyltbioxanthone.
  • ITX is commonly used with an amine synergist such as ethyl-p-dimethyl amino benzoate (EDAB) or octyl-p-dimethyl amino benzoate (ODAB). Both EDAB and ODAB are capable of forming radicals upon energy transfer from the ITX. These components are not considered appropriate for use in the coating for two reasons.
  • the ITX sensitizer also sensitizes the photoacid to visible light, thereby eliminating the spectral resolution between curing and writing. (To some extent this also happens when using certain unimolecular photoinitiators such as IRGACURE 819, which also causes a slight sensitization ofthe photoacid generate to long wave UV light).
  • typical synergists such as amines (and to a lesser extent alkoxylated monomers such as SR-494, SR-9020, SR-9021) significantly reduce or even eliminate color formation or image stability through neutralization ofthe acid generated by tlie photoacid generator.
  • CW sources such as metal and metal halide arc lamps (from Honle UV America, Inc of Marlboro, MA), as well as pulsed arc lamps such a XENON gas arc lamps (Xenon Corporation, of Woburn MA).
  • One advantage of using light filters, or other techniques is that a narrow band of wavelengths may be produced, or that unwanted wavelengths may be substantially removed. Such techniques provide for better resolution (separation of curing and imaging wavelengths), thus increasing the availability or selection of photoinitiators and photoacid generators and combinations thereof.
  • a typical mercury vapor lamp produces a spectrum that is predominately a line spectrum.
  • the spectrum in Figure 8 shows the output from a medium pressure iron-doped mercury lamp typically used for UV curing lacquers applied to of optical media 10. Once can see how the majority ofthe output comes from discrete lines associate with electronic transition of the lamp dopant.
  • the preferred method for exiling the coating consists of using the KTO-46 photoinitiator with a combination of a XENON bulb and an L37 filter glass.
  • Typical mercury line lamps did not produce an intensity of light that was adequate in comparison to the XENON lamps, where both were outfitted with an L37 filter.
  • the XENON lamps were selected for curing ofthe coating 100.
  • filtering of wavelengths for curing could also be performed through the use of cold mirror technology, where a mirror which selectively reflected a portion ofthe UV spectrum and allowed the visible and infrared portions to pass would thus provide only the desired wavelengths.
  • This technique would provide a benefit of reducing thermal loading in the coating 100, as well and the thermal management required to cool an absorptive filter.
  • Another approach that is considered useful for curing would be to use different types of glasses with different UV transmission as the bulb material, thereby keeping the thennal load in the lamp housing. This is a well known approach used by most bulb manufacturers including Xenon Corporation, which offers five bulb types that differ only in the type of glass used.
  • oxygen inhibition is known, and described by Crivello and K. Dietliker (see chapter 2 page 83).
  • oxygen reacts with the free radical and forms peroxy radicals by reaction with the photoinitiator, monomer or propagating chain radical.
  • the reactivity of the peroxy radicals is insufficient to continue the free radical polymerization process, leading to chain termination and resulting in an under cured system.
  • Methods to overcome oxygen inhibition include (1) adding more photoinitiator or (2) increasing curing time. As the photoimtiator selected is relatively expensive, option (2) is considered to be preferable over option (1).
  • a -iurther solution to the oxygen-inhibition problem is to replace the ambient air environment with an inert gas, such as nitrogen.
  • an inert gas such as nitrogen.
  • nitrogen an inert gas
  • This enables all the free radicals produced by UV exposure to be used in the polymerization process.
  • a purge gas such as nitrogen
  • a further method of overcoming oxygen inhibition is to use photoinitiators which are less reactive with oxygen. These initiators tend to require shorter UV light to work ( ⁇ 320 nm).
  • the photoinitiators may include the sensitizing molecule and a synergist described earlier. As described earlier, the sensitizers also sensitize the photoacid generators to visible light. This has a propensity to reduce the spectral resolution between the bands of wavelengths for curing and for writing.
  • Typical synergists such as amines (and to a lesser extent alkoxylated monomers such as SR-494, SR-9020, SR-9021), significantly reduce or even eliminate color formation or image stability through neutralization of the acid generated by the photoacid generator. Therefore, this technique is not preferred for use with the coating 100.
  • a preferred method to overcome oxygen inhibition is to increase the intensity of the curing light, such as using a high intensity pulsed source, such as the model RC- 747 lamp available from Xenon Corporation of Woburn MA.
  • a high intensity pulsed source such as the model RC- 747 lamp available from Xenon Corporation of Woburn MA.
  • the energy of each flash of light is so intense that very high concentrations of free radicals are created. This approach produces enough free radicals so that the oxygen at the surface of the coating 100 is depleted and additional free radicals are available for curing.
  • energy intensity is an important factor to provide for instantaneous curing. More information on the effect of light intensity on curing and overcoming oxygen inhibition may be obtained by reference to a technical paper "Secrets of the Dark,” produced by Fusion UV Systems, Inc. of Gaithersburg, MD.
  • pulsed light has proven advantageous for curing ofthe coating 100 disclosed herein, because it provides high intensity light in a region ofthe spectrum that is compatible with the color formation process. Furthermore, use of pulsed light has reduced the oxygen inhibition problem greatly, so that nitrogen environments or excessive amounts of photoinitiators are not required while keeping curing time to as short a time as possible.
  • the base formulation of the coating 100 was then changed to formulation 3 (0.3% BYK-333, 10% KTO/46, 10% SR-238, 15% SR-285, 32.35% SR-494, and 32.35% SR-9020).
  • the color formers that worked well were then tested again to ensure the color formation was the same. Color formation differed only slightly with the results shown in Table 13.
  • Tables 14 and 15 show that in the 3% color former, 3% photoacid generator and 94%o base coating (formulation control or formulation 3, respectively) the intensity of some colors was higher than others. The intensity of the colors, however, was not fixed. It was considered that it should be possible to increase the color intensity through various methods, such as increasing the concentration ofthe photoacid generator and/or color former, and by adding color enhancers.
  • FIG. 13 depicts effects in color intensity after increasing the amount of photoacid generator (in this experiment, triphenylsulfonium triflate was used) i the coating 100.
  • Figure 13 shows that the combination using 6% photoacid generator, 3% color former, and 91% coating base formulation, with an exposure time of 10 seconds, produced the most color. It may also be possible to increase the optical density (OD), in this case by adding more than the 6%> photoacid generator. However, with 9% photoacid generator, the color intensity exhibited a marked decrease. For that reason, it might prove favorable to test concentrations of triphenylsulfonium triflate (TPST) between 6% and 9%. Overall, it appears that adding more color former than photoacid generator produces preferable results, and is more economic.
  • TPST triphenylsulfonium triflate
  • test results shown in Figure 14 demonstrate that some formulations retain their color better than others in the presence of temperature and hximidity. Specifically, the addition of non-alkoxylated monomers such as SR-355 (formulation 14), CN-983 (formulation 45), and SR-368 (formulation 46) all increase performance. This could be as a result of decreased alkoxy content (decreased hydrophilicity), and increased Tg or crosslink density.
  • TPST triphenylsulfonium triflate
  • a second set of formulations were designed and prepared to expand upon the previous observations.
  • the second set is described in Table 15. All base components were added and mixed before the addition ofthe photoacid generator and color former. Components SR-368, CN-983 and CN-120 were liquefied on a hot plate prior to addition. Once the base components were mixed and homogeneous, 3% photoacid generator was added to each batch. Formulations 53, 55 and 57 would not go in to solution and these batches were discarded. Components ofthe formulation based on the base coating formulation 10 did not dissolve as readily as others, but these did eventually go in to solution. Once all of the photoacid generator was dissolved, the color former was added to an amount of 3% total weight for each batch. All formulations went in to solution without difficulty, and there were no mixing issues with the addition of color former. Each formulation was then filtered through a 5 micron nylon syringe filter. Initially, all formulations had a pale to light rose or yellow color.
  • SR-506 is isobornyl acrylate, which is an excellent reactive diluent for oligomers.
  • CN-120 is a difunctional bisphenol A based epoxy acrylate. Both are products of Sartomer Corporation.
  • Formulation 59 based on bisphenol A diacrylate and SR-355 (Di-TMPTA), was considered to exhibit the best performance from the group tested.
  • a coating 100 formed from formulation 59 should be highly crosslinked, high Tg, film with no alkoxylation. All the remaining formulations contained significant amount of alkoxylated monomers which lead to lower Tg's, hydrophilicity, and possibly basic environments. Accordingly, a third set of formulations was designed to explore the CN- 120 formulation and the effect of alkoxylation on image stability.
  • CN-132 is a low viscosity aliphatic diacrylate oligomer, and is a product of Sartomer Corporation.
  • formula 61 was selected for further development because it gave an excellent combination of cure speed, film hardness, and outstanding image stability.
  • the CN-120 and SR-368 monomers were difficult to work with, so liquid versions CN-120-B60 (60% CN-120 in SR-238) and SR-368D (approximately 85% SR- 368 in TMPTA) were substituted for ease of handling and subsequent manufacturing.
  • SR-368D is tris (2-hydroxy ethyl) isocyanurate triacrylate, and is a clear liquid triazin compound which is used in free radical polymerization.
  • CN120B60 is a difunctional bisphenol A based epoxy acrylate blended with 40% SR-238, hexane diol diacrylate. CN120B60 provides a good balance of water properties and high reactivity. Both are products of Sartomer Corporation.
  • the disks 10 could then be measured to reveal the amount of fading.
  • Five disks 10 having a coating base including SR-9021 were spun coat, cured, and exposed for 10 seconds with L37 filter and nitiogen. Absorbance curves for each of the disks 10 were collected. The disks 10 were then put into storage cases 180 where filter paper 181 was placed in the open cornel's and center, as Figure 18 shows.
  • Figure 18 depicts a typical storage case 180 for an optical media wherein the grey areas denote locations where filter paper 181 was placed. One hundred ⁇ L of triethyl amine was deposited onto each section of the filter paper 181. Each case 180 was then closed and put into a dark drawer for 2 hours, after which time absorbance curves were taken to determine the amount of fading that had taken place.
  • a test fixture consisting of a four foot long two-bulb fluorescent lamp fixture was fabricated.
  • the lamp used was a Philips ECON-O-WATT F40-CW 37 watt, from Philips Lighting Co. of NJ.
  • the fluence produced was approximately 250mw/m 2 in the UV-A band, as measured by commercially available equipment.
  • a set of discs 10 were prepared using formulation 10, based upon SR-9020. The discs 10 were cured and left unexposed to imaging wavelengths.
  • the discs 10 were then set under the fluorescent light fixture with a portion of each disc 10 covered by a 2" x 2" filter glass to determine which wavelengths of light led to the greatest color fonnation.
  • the discs 10 were then exposed to develop about 0.2 AU in an uncovered region.
  • the most damaging wavelengths appear to have been below about 370 nm, with wavelengths below about 320 nm being the most problematic. This seemed to indicate that the UVB portion ofthe spectrum was the bandwidth where UN protection would be most beneficial.
  • Figure 20 depicts results of illuminations, where UV-30, L-37, L-38, L-39, L-40 and L-42 denotes model names for commercially available UV filters from HOYA Corporation of Tokyo Japan.
  • the name ofthe cutoff filter describes the 50% transmission point.
  • the UV-30 filter which is rated for wavelengths at 300 mn, has a 50% transmission point at 300 nm. It is recognized that the 50% transmission point is approximate and can move slightly with thickness, so a thin piece of a L-37 filter might look very similar to a thick piece of UV-36, etc. So, while a 1 mm thick L-37 is generally preferred for applications herein, (having about 50% transmission at 370 nm), a thicker UV-36 filter can also work well, as well as a UV-34 filter in addition to some ofthe other filters. UV-32 is considered to be at about the lower limit, and above UN- 39, curing becomes slow. Therefore, preferred cutoff filters provide for 50% transmission between about 320 nm to about 380 nm, and, most preferably, between about 340 nm to about 370 nm.
  • UV absorbers were added to samples ofthe formulation to see if color formation would slow or cease when the samples were subjected to ambient room light.
  • the UN absorbers used were TI ⁇ UNI ⁇ 327, TI ⁇ UVI ⁇ 171, TI ⁇ UVI ⁇ 213, and TI ⁇ UNI ⁇ 571.
  • TI ⁇ UVF 327 is 2,4-di-tert-bu tyl-6-(5-chlorobenzotria zol-2-yl) phenol;
  • TI ⁇ UVI ⁇ 171 is (2-(2H- benzotriazol-2-yl)-6-dodecyl-4 ⁇ methyl-phenol);
  • TI ⁇ UVI ⁇ 213 is a mixture of reaction products of methyl 3-(3-(2H-benzotraizole-2-yl)-5-t-butyl-4-hydroxyphenyl) proprionate / PEG 300; and
  • TINUVIN 571 is branched and linear 2-(2H-benzotriazol-2-yl)-6- dodecyl-4-methylpl ⁇ enol.
  • the TINUVIN products are produced by Ciba Specialty Chemicals.
  • each of the samples of TINUVIN were in liquid form, with the exception of TINUVIN 327 which was a powder. Testing was performed by adding one percent of each UV absorber to formulation 10, except one sample was made with 5% TINUVIN 171. However, since the point ofthe UV absorbers was to slow color formation, another step was performed to ensure that each sample could still produce enough color when imaged. Figure 21 shows that the samples produced adequate color. In fact, samples incorporating UV absorbers produced more color than the sample without any UV absorbers (denoted as MC9020 in Figure 21). Color formation in the sample containing 5% TINUVIN 171 was not confirmed, but a quick check was performed after 10 seconds of exposure, and showed that the absorbance at 540 nm was 0.40 OD.
  • Figure 22 shows some types of TINUVIN work better than others but the comparative difference at 1% concentration is rnmimal.
  • the sample containing 5% concentration of TINUVIN 171 exhibited better performance at reducing the color formation, but the difference was considered to be only a moderate effect.
  • Use of the 5% concentration also caused a significant increase in the writing time required to produce an image. Attempts were made to prepare a formulation containing 10% of TINUVIN 171, however, the materials bloomed after curing (displayed color formation without exposure to an imaging light).
  • the sample containing a 5% concentration of TINUV ⁇ N 171 showed the same effect after a longer time.
  • TINUVIN 171 was ruled out as most likely not being a good candidate for use as a UV absorber.
  • UN absorbers were tested in what was becoming the preferred formulation, one based upon C ⁇ -120 and SR-368. A series of three UN absorbers were used at 5% loading as shown in Table 18. Discs 10 were coated with formulation 80-82 by spincoating at a speed of 6K rpm, cured for two seconds about one inch away from the lamp, in a nitrogen environment. The discs 10 were exposed through a L37 filter for ten seconds, also about one inch away from the lamp. These discs 10 were compared to the base 9020 formulation without stabilization.
  • UV-24 is the shortened name for CYASORB UV-24, which is 2,2'-dihydroxy- 4-methoxybenzophenone.
  • UV-531 is tlie shortened name for CYASORB UV-531 FLAKE, which is 2-Hydroxy-4- «-octoxybenzophenone. Both are products of Cytec Corporation of Stamford, CT.
  • MC80 is the shortened name for UVESTUL MC80, which is octyl methoxycinnamate, and is a product of BASF Corporation of Japan.
  • Results of a study shows that the thickness ofthe coating 100 plays a role in color formation and light sensitivity, fri the study, samples of a formulation were coated onto discs 10 by spincoating at 4K rpm and 6K rpm. This resulted in coatings 100 of different thicknesses.
  • Discs 10 were cured for two seconds, about one inch away from the lamp, in a nitrogen environment. Exposed regions were imaged for ten seconds, also at about one inch away from the XE ⁇ O ⁇ lamp.
  • Control samples based on a formulation including SR-9020 were produced using spincoating at 4K rpm. The control samples were exposed for 10 seconds at a distance of five inches from the lamp (since higher fluence was detennined to cause fading in the formulation including SR-9020).
  • TPST was considered to be the simplest and shortest UV absorbing sulfonium- based photoacid generator available.
  • Diphenyl iodonium hexafluorophosphate (DPI HXFP) was also considered to be a simple short UV absorbing photoacid generator.
  • the absorbance spectra, of these two photoacid generators, shown in Figure 5, have a maximum at approximately 200nm, with a tail into the mid-UV.
  • UV-A are generally between about 320 nm to about 400 nm; UV-B wavelengths are generally about 270 nm to about 320 nm, and UV-C wavelengths are generally below about 270 nm. These bands of wavelengths, and other bands of wavelengths, may also be referred to as a "set of wavelengths.”
  • FIG. 29 shows the color formation curves for each formulation prepared. The samples shown in Figure 29 were exposed at a distance of one inch from the XENON lamp. Some photoacid generators demonstrated faster color formation (writing) times than TPST, most notably the 4-phenoxy derivative.
  • Formulations 58 (375 cps) and 61 (504 cps) were coated at incrementing spin speeds 5-1 OK. Optical Density and film thickness determinations were performed, and the results are shown in Figure 38. As expected, the more viscous fonnulation produced a thicker film. Also of interest is that both of these more viscous formulations produced a more linear response of film thickness to spin speed. In the finished product, methods for controlling color may include controlling exposure time or varying the formulation, however, it is considered that will be less attractive that varying film thickness will typically be preferable.
  • FIG 39 shows the relation ship between photoacid generator (TPST) and color former (PERGASCRIPT I-6B) concentrations and optical densities for a constant film thickness. Optical densities were measured on discs 10 cured for 2 seconds, in a nitrogen environment at about one inch from the lamp. These samples were then exposed at one inch from the lamp, for the indicated times.
  • TPST photoacid generator
  • PERGASCRIPT I-6B color former
  • Figure 40 depicts a cross section of an embodiment of an optical media 10.
  • the disc 10 contains pits 5 and land 6 as data features.
  • the disc 10 is formed of a substiate 16 and includes a reflective layer 14.
  • the color forming coating 100 as described in the foregoing, it shown as being formed of two components.
  • the first component ofthe color forming coating 100 is the color forming layer 101.
  • the second component ofthe color forming coathig 100 is the overcoat 102.
  • the first step in development ofthe color forming coating 100 was to evaluate the properties that could be divided between the color foiming layer 101 and the overcoat layer 102 to provide for simplified formulations.
  • adhesion to polycarbonate, good color formation, photoacid generator and color former solubility, were desired.
  • overcoat 102 good curing to a hard mar resistant surface, high optical density in the UV, and adhesion to the underlying color forming layer 101 were desired.
  • Both layers 101, 102 would ideally cure quicldy without nitrogen, be low shrinkage, and work together to increase environmental stability of the image (i.e., resistance to the influence of heat, humidity or the introduction of additional chemicals).
  • the CN-120-based fonnulations produced the best environmental results, but exhibited higher optically denser for the color foiming wavelengths than all of the aliphatic formulations such as formulations 1 and 9, .
  • the addition of an overcoat 102 might be used to enliance the stability of the image in heaxVhxiimdity testing, non-CN-120 formulation were again examined, with a goal of decreasing writing times and decreasing slirinkage.
  • Formulations Cl and C2 contained reduced CN-120 content and increased SR- 368 content for increased clarity in the UV and decreased shrinkage for adhesion.
  • Formulation C3 contained SR-9021 and SR-368 to provide for a low shrinkage, high adhesion, fast curing, and UV tiansmissive coating.
  • Formulations Ol and O2 contained a SR-238 and SR-368 combination to provide for good adhesion and cure, with CN-120 in formulation O2 for additional hardness and UV opacity.
  • UV absorber UV-24 was used at 10% loading.
  • An immediate observation was that, as before, tlie photoacid generator was minimally soluble in the alkoxylated monomer SR- 9021. (As may be apparent, formulations designated with a "C" indicate a formulation for the color forming layer 101, while an "O" designation indicate a formulation for the overcoat layer 102.)
  • Sample discs 10 were prepared by spm coating color forming layers 101 with formulations Cl, C2, and C3 onto substrate 16 at 4K rpm, curing in a nitrogen environment, through a L37 UV filter with a "D" bulb, at a distance of about one inch, for three seconds. Imaging through a quartz mask was performed at about five inches from the lamp for 10 seconds.
  • the overcoat layers 102 (formulations Ol and O2) were applied over the color forming layer 101 by spincoating at 2.5K rpm.
  • the overcoat layers 102 were cured in a nitrogen environment, using a L37 UV filter with a "D" bulb at about one inch from the lamp for 3 seconds.
  • Color forming layers 101 made of formulations C2 and C3 wet and spun nicely, while formulation Cl did not perform as well. Both formulations Ol and O2 for the overcoat layer 102 wet nicely and coated all the color forming layer 101 well. All finished discs 10 were mar resistant to a plastic pen tip.
  • a tape pull test utilizing a 2.5 mm spacing blade was performed using SCOTCH tape as a light adhesive tape. (PERMACEL #99 did not adhere well enough to the coating to be used). Color forming layer 101 formed of formulation Cl failed, while color forming layers 101 formed of formulations C2 and C3 passed the test. Both overcoat layers 102 (Ol and O2) adhered to the color forming layers 101 without any problems. When adhesion ofthe overcoat layer 102 was problematic, it was noted that failures occurred at the interface of the polycarbonate layer 16 and the color forming layer 101 (as expected).
  • a candidate two layer coating 100 was designed. These formulations are presented i Table 20.
  • the color forming layer 101 was modified to decrease the concentration of CN-120 and to increase transparency and adhesion.
  • the photoacid generator to color former ratio was increased to 3:4.5 to increase writing speed and color intensity.
  • the overcoat layer 102 was a formulation of SR-368 and SR-238.
  • the overcoat 102 was then cured at about one inch from the lamp for 1.5 seconds without nitrogen and without the use of a filter, thus giving the full spectrum of lamp radiation to enhance surface cure.
  • the underlying color forming layer 101 did not appear to form any noticeable color from the curing ofthe topcoat 102.
  • the 3:4.5 photoacid generator to color former ratio proved to be high and lead to very strong color. Optical densities of approximately 0.8 were achieved in short times at 5 VA inches on the XENON "D" bulb.
  • UV stabilizing layer and color forming layer 101 allows the efficient use of shorter UV wavelengths ( ⁇ 320 nm) for color formation. This allows for efficient exposure ofthe color forming layer 101 using these wavelengths, then sWelding the layer 101 from these and wavelengths found in typical illumination such as sunlight and fluorescent lighting.
  • Formulation C5 was the previous SR-9021 based formulation 3 (Table 14) which had excellent properties but failed environment testing. It was considered that an overcoat 102 might improve the environmental stability of a color forming layer 101 which used formulation C3, and provide enough protection to avoid the use ofthe high shrinkage, UN absorbing C ⁇ -120.
  • Formulation C6 was a modification to Formulation C5, where SR-368 was used in place of SR-494.
  • Formulation C7 was a modified formulation containing C ⁇ -120, SR-368, SR-238 designed to meet adhesion requirements. It was considered that a color forming layer 101 containing formulation C7 should pass environmental testing with ease, albeit at the expense of writing time and shrinkage. It was expected that formulation O3 would yield a hard, UN absorbing overcoat which may have shrinkage issues, due to the C ⁇ -120. Formulation O4 was predominantly formed of SR- 368, with use of SR-339 as the diluent for added UN absorption.
  • Formulation O5 was a SR-9021 based overcoat with C ⁇ -120 added for hardness. Formulation O5 was devised with the hope that the SR-9021 would manage slirihkage without sacrificing hardness and scratch resistance. Overcoats 102 were formulated using both 10% and 20% UV- 24. The 20% loadings noticeably affected the viscosity.
  • Imaging was performed at about 4" from the lamp, with the "D" bulb for 10 seconds, through a chrome-on-quartz mask. Top coats 102 were applied by spin coating at 4K rpm and cured at about one inch from the lamp, using a "D" bulb with full spectrum. Curing was for 1.5 seconds (for the 10% UVA set) or 2.0 seconds (for the 20% UVA set).
  • Formulation C7 outperformed the other coatings 101 even without an overcoat 102. Results are depicted in Figure 42. [00265] Regarding overcoat 102 applications having 10% loading, each sample appeared to remain stable in terms of adhesion and hardness. Further, a trend of underlying image stability was noted in regard to the lc undercoated samples. That is, formulation O3 performed better than O4, which performed much better than O5, which performed better that no overcoat 102. This again tracks with the lack of alkoxylation and potentially the glass transition temperature and hydrophobicity ofthe coating 100.
  • CN965 is an aliphatic polyester based urethane diacrylate oligomer. It is a flexible oligomer offering good weatherabihty.
  • CN966B85 is an aliphatic polyester based urethane diacrylate oligomer blended with 15% SR238, hexanediol diacrylate.
  • CN981B88 is an aliphatic polyester/polyether based urethane diacrylate oligomer blended with 12%> SR238, hexanediol diacrylate monomer. All three are products of Sartomer Corporation.
  • SR-339, 2-phenoxyethyl acrylate is a low volatility monofunctional, aromatic monomer which offers good adhesion properties.
  • CN120M50 is a difunctional bisphenol A based epoxy acrylate blended with 50% SR-339, phenoxy ethyl acrylate. CN120M50 provides a good balance of water properties and high reactivity.
  • SB520M35 is a moderately functional, carboxylic acid containing acrylate oligomer blended in SR- 339, phenoxy ethyl acrylate monomer. Reactive solids are 100% 0 .
  • SB520M35 offers a fast cure rate, excellent adhesion to metals and plastics, and good wetting and flow characteristics. SB520M35 also contains carboxylic acid functionality, which leads to improved amine fading resistance. These three acrylates are products of Sartomer Corporation.
  • a large piece of filter paper 181 was used to replace the insert, and 1 ml of TEA was distributed around the filter paper 181. This test failed to induce any fading in the pattern of images in the coating 101. It was then thought that perhaps a more volatile and mobile base was needed, such as ammonia.
  • a first attempt at this test consisted of placing a 200 ⁇ l drop of concentrated ammonium hydroxide in the middle ofthe filter paper 181 and sealing the discs 10 in a storage case 180. This led to complete destruction ofthe images on all discs 10, with or without any overcoating. The amount of ammonium hydroxide used proved to be excessive and practically was most likely well beyond what would be encountered in a package. Accordingly, a second test was performed using 25 ⁇ l of ammonium hydroxide.
  • the discs 10 without an overcoat 102 and the overcoat 102 without acid were both completely faded (the overcoat may have been slightly better), while tlie overcoat 102 containing acid did retain most of its original color, except for the areas closest to the ammonium hydroxide spot (which were around the stacking ring). Over the next several hours, these discs 10 also deteriorated significantly from the inner ring radially outward. Again, the amount of ammonium hydroxide used may have been excessive when compared to the environment of a typical optical media package 180, such as for a CD or a DVD.
  • Metalized substrate 16 were coated using the color coating formulation containing a photoacid generator to color former ration of 2.0%> TPST:3.5% CF.
  • the components for each ofthe formulations tested in the quantitative study are presented in Table 25.
  • Tl e formulations were applied to the subsfrate 16 by spin-coating at 4K rpm for 10 seconds.
  • the disks 10 produced were cured under the L-37 UV filter, in a nitrogen environment, and using the XENON D-bulb for 2 seconds at a distance of about one inch. Each disk 10 was then exposed under the D-bulb for 10 seconds at a four inch distance to produce color.
  • a topcoat 102 was manually applied to each disk 10 using various formulations on the HEADWAY. This topcoat 102 was cured under the D-bulb for 3 seconds at a distance of one inch. Table 25
  • Optical density of each disk 10 was measured using an Ocean Optics Spectrometer. The absorbance at 540nm was measured. The disks 10 were placed into individual DVD cases 180 and exposed to lO ⁇ l of ammonium hydroxide. The ammonium hydroxide was placed in the center of a piece of filter paper 181 that had been fixed to the inside cover of each case 180. The cases 180 were closed and left to sit. Periodically, each disk 10 was removed from each case 180, and optical density measurements were performed to evaluate the loss of color. Resulting data is presented in Figure 48.
  • a modified version of the formulation for the color forming layer 101 was prepared by diluting the formulation with 30% by weight of a 5% KTO-46 in SR-238 diluent. Film thickness versus spin speed curves were generated for both formulations. Each formulation was then spun coat onto borosilicate glass discs from 2K-10K rpm in intervals of IK rpm. The color forming layer 101 on the discs 10 was then cured for two seconds under L37 with the Xenon D bulb in a nitrogen atmosphere. Tape was then applied to the disc 10 to remove the coating and then tested on the WYKO to determine tlie thickness of the film 101 in two different areas on the disc.
  • Figure 49 shows the results ofthe average film thickness for each spin speed. This experiment shows that the original color coat, C6, has a greater film thickness when applied using spin speeds (S.S.) from about 2K-5K rpm. After that, however, tlie two samples proved to be very similar.
  • the lacquer for the color coating can be dispensed at different temperatures. Accordingly, the viscosity as a function of temperature was determined. Viscosity measurements were performed a temperature range of about 25°C to about 50°C in intervals of about 5°C. Measurements were performed with the Brookfield LNDV-III+CP rheometer and spindle CPE-40 at 4.75 rpm. The viscosity and temperature profile is shown in Figure 50 for color coat C6. As expected, the viscosity ofthe lacquer decreases with increasing temperature.
  • HONLE "H” bulb was a continuous wave mercury vapor solution with a line spectrum quite different from a xenon lamp, and it was considered that testing this lamp could prove informative.
  • the HONLE lamp being available from Honle UV America, Inc., of Marlboro, MA.
  • Figures 54-57 illustrate the effect of photoacid generator to color former ratio on color formations. Looking at each different photoacid generator concentration as a set, it appeared that a general trend is followed. This trend is shown in Figure 54, and is considered to indicate that color formation in samples having a ratio (or equivalent thereof) of 2:3.5 performs better than ratios of 2:3, which perform better than ratios of 2:4.
  • the HONLE "H” bulb performed best on a fluence basis for the combined UVA/UVB levels, as shown in Figure 58. However, it should be noted that the HONLE did put out more UVB than either XENON bulb. When only the UVB levels were used to plot the curves, as shown in Figure 59, the HONLE lamp showed less of an advantage, but still appeared to be superior to the XENON bulbs. At any level, the HONLE and "C" bulbs are superior to the "D" bulb. Finally, the HONLE "H” bulb was used to perform long exposures to examine the maximum useful fluences for imaging the coatings.
  • Overcoat (Ol) formulations were made with various UV absorbers at 10% concentration. The various absorbers used are shown in Table 28. TINUVIN-327 did not go into solution, and the formulation using TINUVIN-R796 crystallized after 24 hours. TENTUVIN-R796 is 2-(2'hydroxy-5 , methacryloxyethylphenyl)-2H-benzotriazole, and is a reactive UV absorber capable of crosslinking into the coating.
  • Viscosity was measured for each of the formulations and optical density was measured on both cured and exposed regions ofthe disk 10.
  • the disks 10 were placed in a light chamber and periodically removed and measured for optical density at 540 nm. Results are depicted in Figure 61. It was noted that the UVA composition had almost no effect on the lightfastness of the exposed areas of the disks 10, as shown in Figure 62.
  • the result of the foregoing development work is that a variety of formulations, and techniques for development of further fonnulations has been developed.
  • formulations and the techniques for development thereof, provide for color fomiing materials that can be cured with wavelengtiis of light, and stimulated with wavelengths of light to produce and retain images, patterns, and other desired markings.
  • These formulations may be advantageously applied over data features appearing in optical media. Most advantageously, aspects of the images may be controlled so as to avoid interference with readout apparatus used to interpret data stored in the data features. It should be recognized that the foregoing is illustrative of the formulations, and not limiting of embodiments that may be practiced. For example, it is considered that the introduction of other constituents, such as acid functionality to act as base scavengers in the overcoat 102 may further aid in the stability of image retention.
  • FIG. 2 a single layer coating is shown, wherein color forming materials are included with other components to produce a coating 100.
  • the coating 100 provides color forming attributes, as well as environmental stabilizers (such as UV absorbers) to provide for coating 100 stability during normal use.
  • Figure 40 provides a second embodiment, wherein components are separated into two layers 101, 102.
  • the coating 100 is formed of a color fonning layer 101 and an overcoat 102.
  • components ofthe color forming layers 101 are advantageously separated from components in tl e overcoat 102, thus providing for improved performance in regards to some of the properties ofthe coating 100.
  • Figures 63-65 Further, non-limiting, embodiments are presented in Figures 63-65.
  • multiple layers are employed.
  • the first layer 301 and the second layer 302 are color forming layers 101, where each color forming layer 101 produces a distinct color, such as red in the first 301, and green in the second 302.
  • the third layer 303 is deployed as an overcoat 102, which is designed to protect against environmental factors.
  • the optical media 10 shown in Figure 63 is formed so that the first layer 301, the second layer 302, and the third layer 303 are applications of formulations for single layer embodiments, h these other embodiments, each layer 301, 302, 303 produces a distinct color, such as one of red, green, and blue.
  • a coating 100 containing four layers is shown.
  • the first layer 401 is a color forming layer 101
  • the second layer 402 is a protective overcoat 102.
  • the third layer 403 is also a color forming layer 101
  • the fourth layer 404 is another protective overcoat 102.
  • each ofthe first layer 401, the second layer 402, and the third layer 403 are color forming layers 101, while the fourth layer 404 is a protective overcoat 102.
  • the color formed in each of the first three layers may correspond to a primary color, such that upon completion of imaging, a multi-color image is apparent.
  • FIG. 65 a further embodiment of a coating 100 is shown.
  • alternate layers 501, 503, 505 are color forming layers 101, while overcoat layers 102 are included as layers 502, 504, 506.
  • each of the alternate layers 501, 503, 505 correspond to a specific color, such as one ofthe primary colors. Imaging of each of the layers 501, 503, 505 provides for the collective appearance of a multi-color image.
  • a metallized disc was spun coat at 4000 rpm for 10 seconds with the orange formulation.
  • the orange formulation was then cured with the Xenon 'C bulb for 3 seconds 1" away under window glass.
  • a quartz mask was then placed over the disc 10 and exposed for 10 seconds 4" away with the same Xenon 'C bulb.
  • the resultant disc 10 had an orange image on it with a clear background.
  • the disc 10 was taken and spun coat again with the red formulation at 4000 rpm for 10 seconds on the Headway.
  • the red formulation was then cured for 3 seconds with the Xenon 'C bulb 1" away under window glass.
  • a mask 925 was placed over the disc 10 and exposed for 10 seconds 4" away with the Xenon 'C bulb.
  • the final product was a disc 10 with red and orange colored images on it with a clear background.
  • FIG. 66 depicts the spectra of a red disc 10 and an orange disc 10, where each color has been evaluated separately.
  • Figure 67 shows that when the red layer and the orange layer are exposed together, the spectrum of the color obtained is essentially the same. This is without regard for the order with which the coatings are placed.
  • Figure 68 shows that the top layer 101 in a series of layer 101 can be selectively exposed without fully developing the underlying layer. One may note the majority of the color developed in the top layer 101, while the underlying layer 101 remains relatively unexposed.
  • the selective development of the upper color layer 101 can be enhanced by adding a UV blocking layer 102 between the color forming layers 101.
  • Table 30 provides a fonnulation for a UV blocking layer. This formulation was spun coat between the orange and red color foiming layers 101. In this example, the UV blocking layer 102 allowed even better reproduction of only the single topmost color. Again, exposure of both color forming layers 101 led to the same total color regardless ofthe order in which the layers 101 were applied. Results are depicted in Figure 69.
  • the foregoing embodiments make use of coatings that include color forming layers 101, overcoat layers 102, single layers 100, and a variety of combinations thereof. As one can surmise, many combinations may be developed. These can provide for a variety of effects, such as single or multi-color images. [00327] Further, one can also surmise that staged application an imaging of layers in a coating 100 may provide certain advantages. For example, a first layer 401 may be applied and then have an image recorded therein. Subsequently, a protective overcoat layer 102 is applied as a second layer 402, and a third layer 403 is applied as a second color forming layer 101.
  • the second layer 402 is used to limit exposure ofthe first layer 401 during the imaging ofthe second color forming layer 403, by use of materials that absorb imaging wavelengths, hi this manner, one image is recorded in the first layer 401, with a second image recorded in the third layer 403. Recording of the second image proceeds without interference with aspects ofthe first image. Similar techniques may also be used with single layer formulations where color forming materials are mixed with UV (or other wavelength) absorbers. Multiple wavelengths for curing and imaging may be used. In summary, a variety of application techniques, formulations, curing and imaging techniques may be used to achieve multiple effects in the collective appearance of an image.
  • the selective irradiation of color forming materials in the coating 100 with a second light is used to record images or markings into the optical media 10.
  • wavelengths of UV are used to provide for the second light.
  • the selective irradiation may be used to provide for varying degrees of contrast with the unexposed, or lesser exposed, regions of the optical media 10. That is, varying shades within an image may be created. For example, increased UV exposure in one part ofthe coating 100 will cause greater absorption than exhibited in another part of the coating 100. Shading effects, or any other marking technique, may therefore be achieved using image creating units such as a positive, negative, or electronic photomask, a direct writing laser (a laser galvo system) or through other techniques.
  • Figure 70 depicts a magnified view of a portion of one example of a photomask 925 suited for developing a shading effect.
  • a marking be realized as a single marking (e.g. a marking in a single color forming layer 101), of through the collective appearance of a series of markings (e.g., a series of markings in various color forming layers 101).
  • One embodiment of an electromc photomask 925 makes use of a programmable liquid crystal display, which preferably exhibits a high optical density at wavelengths of about 355 nm.
  • the electronic photomask 925 is reconfigured between marking routines, thereby providing for unique markings upon each ofthe optical media 10 in a series.
  • image may be taken to mean a production of the marking, where the marking is the manifestation (i.e., record) of the image within the coating 100. It should be recognized that the two terms are closely related, and may be considered interchangeable as appropriate.
  • a marking is formed using a convention that may include, but is not limited to, incorporation of text information, such as alphanumeric characters, symbols, graphic information, such as a logo, a barcode, or any other information or symbols that may be suitable for including in the marking.
  • the marking may further include embedded information and authentication signatures, and can include at least one digital watermark or other type of covert marking.
  • the marking may appear at wavelengths above or below the band of visible wavelengths. For example, the marking may be invisible to an unaided human observer.
  • the marking is self-destructing.
  • the marking disappears when introduced to ambient environmental conditions, such as ambient lighting.
  • Use of a self-destructing marking may be particularly useful for some applications, such as in some embodiments of authentication schemes.
  • Figure 71 depicts an optical media 10 where a series of layers collectively form a coating 100 thereon, hi the embodiment shown, the optical media 10 is being produced in a production line 2000, wherein a direction of production is depicted by the dashed arrow.
  • a source of imaging wavelengths 920 is depicted, as a lamp having a photomask 925 attached thereon, and is used to generate markings in the coating 100.
  • markings 620 are produced in the first color fonning layer 401 of the coating 100.
  • Additional lamps 921, 922 may be used to produce markings 620 in the additional color forming layers 402, 403.
  • the source of imaging wavelengths 920 is a laser, h this embodiment, the lamp 920 is controlled by external apparatus, not shown here, for direct writing upon the optical media 10.
  • the source of imaging wavelengths 920 may include a direct writing laser, a pulsed UV lamp, other light sources, and any combination thereof.
  • the marking 620 may convey any desired information.
  • the marking 620 may present content that includes identification information (such as a serial number), authentication information, and or instructional information.
  • the content may also include advertising, branding, or promotional information, referred to collectively herein as "promotional information.”
  • promotional information referred to collectively herein as "promotional information.”
  • the information included in the marking 620 may include, but is not limited to, any of the foregoing types of information, or combinations.
  • the term "content” as used herein refers to content of the marking 620, and can be an image, alphanumeric text and other symbols, graphics, and combinations of images and symbols.
  • the marking 620 may contain at least one digital watermark.
  • An example of a technique for varying the contrast in a transferred image includes engaging techniques used in grayscale printing. That is, using a collection of properly sized colored shapes or patterns, on uncolored background, or alternatively, uncolored shapes or patterns on fully colored background. Regulating the size and density ofthe shapes or patterns provides for control over the visual perception of color intensity in any specific region ofthe marking.
  • Figure 70 provides an example of the technique where contrast may be established by use of a photomask.
  • Figure 70 depicts a blown up cutaway section of a corner of a photomask 925, wherein the perception of shading is established by controlling the size and orientation ofthe rectangles in the photomask 925.
  • shading may be achieved through controlling the duration, power level, or other factors, governing exposure with a UV laser 920 used for direct writing onto the optical media 10.
  • a photomask 925 is used for exposure ofthe optical media 10.
  • the photomask 925 is either placed directly in contact with the optical media 10, or used at some fixed distance from the optical media 10, such as on a lens over the lamp.
  • the second light source 920 is accordingly focused to provide for desired effects in the marking 620.
  • the replication equipment appropriately moves coated optical media 10 into ahgnment within the photomask 925 station, or marking station, to provide for high throughput.
  • the cycle time for the generation of a marking in this manner is preferably about 3 seconds or less.
  • an electronic photomask 925 such as a liquid crystal display (LCD) unit is used.
  • the electronic photomask 925 may be remotely programmed and controlled. Use of the electronic photomask 925 provides certain advantages, including but not limited to, ability to change images rapidly thus leading to increased throughput, and fewer moving parts thus providing for lower maintenance costs.
  • the coating 100 may be inspected for conformity with desired specifications. In some embodiments, inspection is optional or omitted. In one embodiment, aspects of which are shown in Figure 73, non-destructive inspection occurs at an optical inspection station 700.
  • the optical inspection station 700 may include components, such as and not limited to, a laser 710, detection equipment 715, and a suitably configured processor 720.
  • laser light is directed to the coating 100 on the optical media 10.
  • the detection equipment 715 detects reflected tight, and provides a signal to the processor 720.
  • the processor 720 makes a determination, or series of determinations, regarding characteristics ofthe coating. These characteristics may include, and are not limited to, thickness and umformity. Other characteristics include, without limitation, transmission or contrast defects, coating defects including voids, dye comets, or dye spots, as well as radial deviation, dye density, or dye edge radius defects, or other deviation from applicable industry standards.
  • the determinations are used to provide acceptance or rejection of the coated optical media 10.
  • the processor 720 provides a signal to a production line controller 730.
  • Rejected optical media 10 are appropriately sidelined from the production line 2000 by the production line controller 730 for subsequent disposition, while accepted optical media 10 progress through production, hi this embodiment, 100% of production optical media 10 are inspected.
  • certain segments ofthe production quantity may be inspected. For example, a statistically significant quantity, every other, or new batches of optical media 10 may be subjected to inspection. These optical media 10 may be sidelined from production for inspection routines, or inspection in the course of production.
  • a further inspection routine involves use of electronic imaging systems to evaluate marking quality.
  • each optical media 10, or some subset thereof may be inspected.
  • equipment such as, but not limited to, a CCD array with appropriate illumination and a suitably configured microprocessor is used as detection equipment 715.
  • An example of appropriate equipment includes VERICAM from Spectra Systems, Inc. of Buffalo, Rhode Island.
  • the detection equipment 715 may be situated over the optical media 10 in a fashion to obtain a clear view of the marking 620, with ininimal reflection or other interference.
  • the detection equipment 715 includes a number of components that work together, as illustrated in Figure 73.
  • the exemplary marking detection equipment 715 includes a user interface 845 which incorporates components such as a display 840, a keyboard 850, and a network link 860 (which may use any one or more of available communication protocols and designs); also mcluded are illumination 830, a lens/CCD system 820, memory 815, and storage 818. These various components are controlled by an integrated central processing unit 800 on board the detection equipment 715.
  • the detection equipment 715 in this case may be portable or fixed.
  • the detection equipment 715 includes a microscope laser scanner.
  • the ihumination 830 is used to provide standard lighting conditions, wherein the CCD array 820 images the marking on the optical media 10.
  • the qualities of certain features of the marking 620 are determined. For example, the color of the marking, the alignment of text with the inner or outer edges of the marking with the optical media 10, aspects of a digital watermark, or the placement of one marking 620 in relation to another marking(s) 620 are evaluated.
  • the processor 800 compares observed qualities to known or desired qualities, and provides a basis for rejection or acceptance of the optical media 10. A signal indicating acceptance or rejection can be sent to a separate production line controller 730 through the network link 860. Again, rejected optical media 10 are appropriately sidelined for subsequent disposition, while accepted optical media 10 progress through production.
  • the XIRIS PI- 1500 includes a three CCD chip camera module, top mounted with integrated light source and alignment mount; a flat panel computer screen; a vision processor unit; 8 digital inputs, 8 digital outputs; and complimentary software.
  • the optical media 10 may be inspected by destructive means.
  • operators may cut segments of the optical media 10, or otherwise damage the optical media 10 to ultimately ascertain system performance information.
  • CATS SA3 System Another system for analyzing the quality of the optical media 10 produced in accordance with the teachings herein is the CATS SA3 System, available from AudioDev USA of Woodland Hills, CA. This system tests the readability and playability of optical media by measuring numerous signals and parameters. The levels of these parameters can then be analyzed to draw conclusions about the stability of the disc manufacturing process and possible playability issues.
  • Disks 10 were coated on a HEADWAY PWM32-PS-R790 Spinner System with the HDP98 Fluid Dispenser and MA24WEA dispensing arm.
  • Formulation 3 (9021) was used (see Table 14).
  • Varying spin speeds and various coating parameters were employed to examine the effect of spin coating parameters on electrical specification ofthe disks 10. Programs using more than one, or incrementing spin speeds were tested. Preferred coating parameters were determined to use a single spin at 4K rpm for 10 seconds.
  • the spin coating program used for the HEADWAY system is presented in Table 31.
  • Figure 74 Data produced by the CATS system are included in Figure 74, wherein data from an uncoated disk 10 is shown. Note the large spikes at the end of each test are due to data ending, which is not an inherent enx-r in the disc 10 or the coating 100.
  • Figure 75 provides data for a coated disk 10 that had been cured, and had not been imaged.
  • Figure 76 provides data for a coated disk 10 that had been cured, and had been imaged.
  • Techniques for inspection include completing inspections at various stages in the manufacture ofthe optical media 10. For example, a color forming layer 101 maybe applied and cured over the reflecting layer 14 disposed upon a substrate 16, and then diverted to an inspection station 700. Upon successful inspection, in some embodiments, tlie substrate 16 is then be submitted for marking. In some other embodiments, the subsfrate 16 progresses to another station for application of the overcoat 102.
  • a production system such as one similar to the SINGULUS SKYLINE system available from Singulus Technologies of Windsor CT, is used to produce optical media 10.
  • Appropriate modifications and enhancements have been incorporated into the system to provide for and enable the embodiment described herein. Aspects of the equipment are described herein, or considered generally within the skill ofthe art, and are accordingly not described in further depth.
  • newly replicated discs 10 on a spindle come off of the replication line.
  • the coatings 100 are applied using a spin-coating process, and then cured by exposure to a first light having wavelengths in the ultraviolet (UV) region.
  • UV ultraviolet
  • At least one image 620 is transferred into the coating 100, by use of exposure to a second light 920.
  • the second light 920 employs wavelengths of UV, and a photomask 925.
  • the second light 920 is directed to the coating 100 as a controlled direct writing laser.
  • An inspection step is preferably included, either before or after the exposure to the second light 920, to ensure the coating 100 meets optical or other standards for the type of optical media 10. Production times may vary with factors, such as and not limited to, coating 100 composition, spin coating time, curing time, imaging time, and inspection time.
  • a spin coating station having: manual adjustability through use of a micrometer screw, and automatic adjustability ofthe radial position of coating material dispense nozzle(s); use of a formulation having a viscosity of about, for example, 35 cps; use of a filtering system discrinihiating against particles down to about 0.2 micrometers; recycling of the spin-off lacquer; a dispensing volume of up to about 30 ml; a dispensing speed of between about 30 to 100 RPM; acceleration of up to about 2,000 RPSS; a spin speed of up to about 5,000 RPM; and a multi stage spin-up.
  • a UV curing station imparting about 300 mW/cm2 at wavelengths of about 365 mn.
  • An optical inspection station having an ability to detect surface defects in the form of height variations of about 100 nm and lateral variations of about 200 microns.
  • a photomask station imparting about 2 W/cm2 at wavelengths of about 350 nm (where about 5 J/cm2 are delivered in about 2.5 seconds, with an additional 0.5 seconds required for handling).
  • a laser characterized as providing a total deposited fluence of about 4 J/cm2, operating at a wavelength of about 355 nm, having a pulse energy limit of less than about 0.15 J/cm2 per pulse, with an average power of about 4 watts.
  • the cycle time for installation of a marking as described herein, from beginning to end is about or less than 7.5 seconds, with each individual step taking no more than 3 seconds.
  • Figure 77 provides an illustration of a commercial production environment, referred to as an "inline" system.
  • an optical media replicator 2100 such as the SKYLINE system or an equivalent, is used to create coated optical media 10 that are characterized by at least one marking 620 in a single layer coating 100.
  • the optical media replicator 2100 accepts raw materials in a production line 2000 as appropriate (flowing hi the direction of the dashed arrow) and produces finished optical media 11 having a marking as disclosed herein, hi one embodiment, the system 2100 completes initial steps, such as applying a reflective layer 14 to a substrate 16, where prepared substrate 16 are produced using a preliminary station 2110.
  • the prelimuiary station 2110 may be tasked with other production steps, such as the formation of the substrate 16.
  • the preliminary station 2110 may scan substiate 16 for defects, and include further equipment as necessary to accomplish this task. Depiction of a preliminary station 2110 should therefore be understood as a representation that the system 2100 may incorporate additional equipment as necessary to produce a prior art optical media 8.
  • the optical media 8 progress to a spin-coating station 2120 for application of a single layer of a formulation that will form the coating 100.
  • the optical media 8 proceed to a curing station 2130, where exposure to a first light 910 cures the coating 100 as described elsewhere herein.
  • the coated optical media 10 so produced proceed to a marking station 2140.
  • the optical media 10 are exposed to wavelengths of light from a second light 920.
  • the second light 920 makes use of a photomask 925 to produce a marking 620 in the coating 100 on the optical media 10.
  • Final steps are completed in a finishing station 2150, as appropriate.
  • Final steps may include, without limitation, use of inspection equipment 700 to accept or reject each ofthe marked optical media 11.
  • Operation and other aspects ofthe production system 2100 may be governed by a system controller 2101, such as a processor 2101 executing an instruction set (software), or through other techniques, such as manual operation.
  • a system controller 2101 is an external personal computer 2101, connected to controls for the various components of the production system 2100.
  • aspects of the initial and final inspections are mingled with other production steps.
  • the optical media 10 may be inspected after each one of spin coating, curing and marking.
  • a system such as the foregoing embodiment is preferably automated, or otherwise equipped to provide for rapid mass production.
  • Figure 78 depicts aspects of one embodiment of a production system 2100 equipped for marking optical media 10 having a coating 100 with multiple color forming layers 401, 402, 403.
  • the marking station 2140 includes a series light sources as the second light 920, which is also referred to as a "marking source", "marking light”, or in other similar terms.
  • a first marking lamp 921 is used in conjunction with a first photomask 925, and imparts a marking 620 in a first color foi ing layer 401.
  • a second marking lamp 921 is used in conjunction with a second photomask 926, and imparts a marking 620 in a second color forming layer 402.
  • a third marking lamp 922 is used in conjunction with a third photomask 927, and imparts a marking 620 in a third color forming layer 403.
  • FIG. 79 One further embodiment of a production system 2100 is depicted in Figure 79.
  • the production system 2100 is designed for the production of optical media 10 using a two layer coating 100.
  • the first spin-coating station 2120 apphes a color forming layer 101.
  • the color forming layer 101 is cured at the first curing station 2130.
  • the cured color forming layer 101 is marked with a marking 620 at the imaging station, as described elsewhere herein.
  • the marked optical media 11 then progresses to a second spin coating station 2160 for application of the overcoat layer 102.
  • the overcoat layer 102 is cured at the second curing station 2170, using a second curing light 975.
  • Final inspection, or other finalizing steps, are completed in the finishing station 2150.
  • aspects of the production system 2100 can depend upon the design of tlie optical media 10, and the desired appearance of the marked optical media 11.
  • a first production system 2100 is used to apply a first color forming layer 401, cure the layer 401, and then impart an image into the layer 401.
  • a second production system 2100 applies a second color forming layer 402, cures the layer 402, and then imparts an image into the layer 402.
  • a third production system 2100 applies a third color forming layer 403, cures the layer 403, and then imparts an image into the layer 403.
  • Operation and other aspects of the production system 7700 may be governed by a system controller 7701 executing an instruction set (software), or through other techniques, such as manual operation.
  • a system controller 7701 executing an instruction set (software), or through other techniques, such as manual operation.
  • One example is an external personal computer 7701, connected to various other control systems 2101.
  • manual or semi-automated systems are used "offline" to manufacture coated optical media 10 and or marked optical media 11.
  • previously produced or commercially available optical media 8 are selected for receipt of a coating 100.
  • a coating 100, as described herein, is applied to the optical media 8.
  • the coating 100 process occurs in an environment where factors such as ambient dust or atmosphere are controlled as appropriate to limit contamination ofthe coating 100.
  • Examples of offline systems include systems such as those depicted in Figures 77-79, with the omission of the preliminary station 2110. In offline systems, steps are taken as described in the foregoing discussions to produce the coated optical media 10 and / or marked optical media 11 from existing optical media 8.
  • Figure 81 depicts an embodiment of a curing station 7800 for manual curing.
  • the coating 100 is then cured.
  • the coated optical media 10 are then cooled or otherwise conditioned as appropriate.
  • the coated optical media 10 then may enter a distribution chain, be directed to a marking station, or sidelined for subsequent marldng by the manufacturer. Marking occurs in the manner described herein, and may involve use of photomask(s) 925, and/or direct writing lasers 920.
  • the coated optical media 10 are thus in a prepared state for subsequent marking by the manufacturer, or others, such as a third party.
  • Figure 82 provides an illustration of an offline marking technique, where coated optical media 10 are used to produce marked optical media 11.
  • the unmarked or "blank” coated optical media 10 are introduced into a production line 7900.
  • the production line 7900, and equivalents thereto, are also referred to as a "station for receiving optical media 10."
  • the optical media 10 progress down the production line 7900 where an offline marking system 7901 containing at least a second light 920 is used to provide a marking 620 on the optical media 10.
  • Other components in the offline marking system 7901 may include, but are not limited to, photomask equipment, alignment devices, a station for spin coating and curing of an overcoat layer 102, and other complimentary devices.
  • a direct writing laser 920, and supporting equipment may be incorporated into the offline marking system 7901, in combination with or in place of a photomask.
  • the station for receiving optical media 7900 may simply be a tray having a fixed geometry in relation to the marking light 920.
  • Offline marking may occur at a variety of places within the distribution chain.
  • offline marking may be completed at the manufacturer ofthe optical media 10, a secondary manufacturing outlet, a commercial distributor, or by an end user.
  • prepared (coated) optical media 10 may be marked by a video rental store equipped with appropriate equipment.
  • the store operators may incorporate their own content, for example, promotional information, ownership information, or other information, such as terms of use.
  • end users may also engage in marking their own optical media 10 through use of appropriate equipment. This feature may be attractive to small producers, or as a novelty to private users.
  • additional apparatus may be used for the marking of the optical media 10 and are within the contemplation of the invention disclosed herein.
  • an end user may be provided with an inexpensive kit, such as one containing software, a few sheets of an appropriate subsfrate for use in a laser printer to produce photomasks 925 from the software, and an appropriate light source (such as an array of diodes, or a black light) for use with the laser printer produced photomask 925.
  • an inexpensive kit such as one containing software, a few sheets of an appropriate subsfrate for use in a laser printer to produce photomasks 925 from the software, and an appropriate light source (such as an array of diodes, or a black light) for use with the laser printer produced photomask 925.
  • overcoat Ol Variations on the formulation for overcoat Ol were evaluated. In these tests, the overcoat Ol formulation was made substituting a percentage of photoinitiator KTO/46 with Irgacure 819. Four formulations were made, as shown in Table 33.
  • Table 35 and Table 36 disclose preferred embodiments ofthe overcoat layer 102, and the color fonning layer 101, respectively.

Abstract

L'invention concerne un système pour enregistrer une marque dans la zone de lecture d'un support optique, ladite marque ne gênant pas, ou sensiblement pas, la lecture de données du support optique. Le système de l'invention est favorable aux exigences de production commerciale. Des marques peuvent contenir un contenu si l'utilisateur du système le souhaite, notamment un texte, des images, ou d'autres articles. La marque est formée dans un revêtement photosensible qui est appliqué sur le support optique, puis traité par un premier éclairage. Un second éclairage, présentant une bande de longueurs d'ondes sensiblement différente du premier éclairage, est utilisé pour former une image de la marque dans le revêtement. Ledit revêtement résiste à de nombreuses influences externes, tels que les conditions environnementales ambiantes, et l'usure environnementale.
EP03756837A 2002-09-18 2003-09-18 Systeme pour appliquer des marques a un support optique Withdrawn EP1540416A4 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
US41215302P 2002-09-18 2002-09-18
US48994503P 2003-07-22 2003-07-22
US489945P 2003-07-22
PCT/US2003/029514 WO2004027683A2 (fr) 2002-09-18 2003-09-18 Systeme pour appliquer des marques a un support optique
US412153P 2010-11-10

Publications (2)

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EP1540416A2 true EP1540416A2 (fr) 2005-06-15
EP1540416A4 EP1540416A4 (fr) 2009-03-25

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EP03756837A Withdrawn EP1540416A4 (fr) 2002-09-18 2003-09-18 Systeme pour appliquer des marques a un support optique

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EP (1) EP1540416A4 (fr)
JP (1) JP4530273B2 (fr)
AU (1) AU2003299001A1 (fr)
CA (1) CA2499640A1 (fr)
MX (1) MXPA05003053A (fr)
WO (1) WO2004027683A2 (fr)

Families Citing this family (3)

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JP4760922B2 (ja) * 2009-01-29 2011-08-31 ソニー株式会社 光情報記録媒体
JP4632101B2 (ja) 2008-07-02 2011-02-16 ソニー株式会社 光情報記録媒体
JP5278345B2 (ja) * 2010-02-05 2013-09-04 Ｄｉｃ株式会社 光ディスク用紫外線硬化型組成物および光ディスク

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Also Published As

Publication number Publication date
WO2004027683A3 (fr) 2004-09-02
MXPA05003053A (es) 2005-05-27
CA2499640A1 (fr) 2004-04-01
EP1540416A4 (fr) 2009-03-25
WO2004027683A2 (fr) 2004-04-01
JP4530273B2 (ja) 2010-08-25
JP2005539343A (ja) 2005-12-22
AU2003299001A1 (en) 2004-04-08

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