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WO2004042704A2 - Incorporation de reperes dans des supports optiques - Google Patents

Incorporation de reperes dans des supports optiques Download PDF

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Publication number
WO2004042704A2
WO2004042704A2 PCT/US2003/035390 US0335390W WO2004042704A2 WO 2004042704 A2 WO2004042704 A2 WO 2004042704A2 US 0335390 W US0335390 W US 0335390W WO 2004042704 A2 WO2004042704 A2 WO 2004042704A2
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WO
WIPO (PCT)
Prior art keywords
optical media
color
layer
marking
formulation
Prior art date
Application number
PCT/US2003/035390
Other languages
English (en)
Other versions
WO2004042704A3 (fr
Inventor
Jeffrey L. Conroy
Robert S. Afzal
Allison Berube
Nabil M. Lawandy
Dana Lewis
Thomas Pizzuti
Andrei Smuk
Original Assignee
Spectra Systems Corporation
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 Corporation filed Critical Spectra Systems Corporation
Priority to EP03781782A priority Critical patent/EP1558969A4/fr
Priority to AU2003287540A priority patent/AU2003287540A1/en
Publication of WO2004042704A2 publication Critical patent/WO2004042704A2/fr
Publication of WO2004042704A3 publication Critical patent/WO2004042704A3/fr

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Classifications

    • 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
    • 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
    • G11B7/2403—Layers; Shape, structure or physical properties thereof
    • G11B7/24035—Recording layers
    • G11B7/24038—Multiple laminated recording layers

Definitions

  • This invention relates to a method and apparatus for rapid production of high quality images in various components 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 optical disc, such as a Compact Disc (CD) or a Digital Versatile Disc (DVD), for indicating information such as the source of the disc and a listing of the information recorded thereon.
  • a optical disc such as a Compact Disc (CD) or a Digital Versatile Disc (DVD)
  • the placement of markings on the non-readout side of optical media permits the use of a variety of marking technologies, ranging f om 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 of the optical media.
  • the ink would likely cause scatter of a readout light (laser), thus inhibiting readout of the data features.
  • a readout light laser
  • the disclosed use of an infrared (IR) laser to impart the image implies the ink would interfere with a normal data readout process since CD and DND media use near-IR lasers in the readout mechanism.
  • 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.
  • Patents disclosing colorforming coatings include U.S. Patent No. 4,552,830, entitled “Carbonylic Halides as Activators for Phototropic Compositions", issued November 12, 1985 to Reardon et al. and U.S. Patent No. 4,343,885, entitled “Phototropic Photosensitive Compositions Containing Fluoran Colorformer", issued August 10, 1982 to Reardon. Both patents disclose compositions useful for the production of photoresist films for the electronics industry. These compositions are disclosed as contaiiiing a polymerizable, crosslinkable or curable component with a photoinitiator, a colorformer, and an activator; where the composition becomes insoluble and change color under the influence of actinic radiation.
  • 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 of the marking system.
  • Non-limiting examples of existing embodiments of optical media are provided in Figs. 1-8.
  • a prior art optical media 8 is depicted as a compact disc (CD).
  • the CD 8 includes a substrate 17 (typically formed of polycarbonate), a metallized layer 14 (also referred to as a reflecting layer 14), and a protective layer 12.
  • a label is disposed on a label side 7, over the protective layer 12, which is typically formed of a UV curable acrylic.
  • a readout light penetrates the readout side 2 to provide a readout signal for interpreting data features known as pits 5 and lands 6.
  • FIGs. 2-8 Aspects of other embodiments of optical media 8 are presented in Figs. 2-8.
  • FIG. 2 depicts an optical media 8 as a single sided / single layer embodiment of a Digital Versatile Disc (DVD).
  • DVD 8 includes substrate layers 17, reflective layers 14, and a bonding layer 15.
  • the structure shown in Fig. 2 correlates to aspects of optical media 8 commonly referred to as "DVD-5.”
  • Fig. 3 depicts another embodiment of a prior art optical media 8, where a single sided / dual layer embodiment of a DVD is shown.
  • the reflective layer 14 includes a semi-reflective layer 14-1 and a substantially reflective layer 14-2.
  • the substrate layer 17 includes a first substrate layer 17-1, and a second substrate layer 17-2.
  • This structure correlates to aspects of optical media 8 commonly referred to as "DVD-9.” hi this embodiment, two layers of data features are provided on the one side of the DVD 8.
  • Other examples of prior art optical media 8 include a dual sided / single layer DVD, as shown in Fig. 4. This structure correlates to aspects of optical media 8 commonly referred to as “DVD- 10.” A dual sided / dual layer embodiment of a DVD 8 is shown in Fig. 5. This structure correlates to aspects of optical media 8 commonly referred to as "DVD- 18.”
  • This embodiment of a DVD includes two sides, each with a dual layer format. Both layers of each side are manufactured on a single polycarbonate substrate layer 17, and subsequently bonded together at the bonding layer 15.
  • DVD-18 has the largest capacity of the family but is the most difficult and complex to manufacture. A unique stamper is needed to create each of the four substrate layers 17.
  • DVD-14 is a related format in which only one half of the disc 8 is a dual layer disc 8. This format contains approximately 14 gigabytes of data. DVD-14 is slightly easier to manufacture than a DVD- 18, since one side is a DVD-5.
  • Further examples of optical media 8 include a hybrid SACD, as shown in Fig. 6; a hybrid DVD, as shown in Fig. 7; and, a DVD Plus, as shown in Fig. 8.
  • Combination disc formats for example combining DVD-ROM on one side with DVD-RAM on the other, are known.
  • Such discs 8 are double sided discs and are read from both sides.
  • Hybrid SACD is a format developed by Philips and Sony and combines a SACD (i.e., physically a DVD layer) with a CD layer. Both layers are read from the same side, which means that the SACD layer must be reflective for a red laser but will transmit an infra red CD laser.
  • Such discs can be played on both a CD player (which will read the CD layer) and a SACD player.
  • Hybrid DVD is a similar format to the hybrid SACD with a conventional DVD data layer over a CD data layer.
  • DVD Plus refers to a disc comprising a CD bonded to a DVD substrate. The resulting disc allows both DVD and CD data to be read from one disc, like a hybrid DVD, but the disc is read from both sides. Neither format is commonly available as yet.
  • Each format of optical media 8 is described by certain specifications. For example, for the CD shown in Fig. 1, the specification thickness for the substrate layer 17 is 1.2 mm, while the pits 5 are separated by about 125 nm from the lands 6. In DVD, as shown in Figs.2-5, the substrate layers 17 are typically 0.6 mm thick.
  • optical media 8 This cursory examination of these popular (but few) embodiments of optical media 8 serves to point out that a variety of layers exist within the various formats for optical media 8. These layers each contain a certain amount of material selected for providing certain properties, such as clarity and rigidity. One skilled in the art can surmise that the various layers may be constructed of an assortment of materials, while providing for the functionality of the optical media 8.
  • disc-molding materials examples include PLEXIGLAS VOD- 100 produced by Elf Atochem of North America Inc., Philadelphia, PA which is a grade of acrylic thermoplastic specially designed for optical disc manufacturing; a similar material is ACRYLITE DQ501 from CYRO Industries, Rockaway, NJ; another product is Polycyclohexylethylene (PCHE), from Dow Plastics, Midland, MI, which is a saturated cyclic hydrocarbon that is derived from styrene monomer, and said to have exceptional optical purity and clarity, with a refractive index of 1.51 and high light transmittance across the full spectrum, including the blue-green range.
  • Further non-limiting examples of disc-molding materials are LEXAN products from General Electric of Pittsfield, MA, which include models OQ1040L, OQ1050 and OQ1030L.
  • optical media 8 call for advanced marking schemes. This need is growing rapidly with changes in optical media technology and growing demand. For example, the advent of dual sided optical media 8 necessitates the development of a marking scheme that does not interfere, or substantially interfere, with a readout laser.
  • Such a scheme should provide enhanced marking, identification, authentication and encoding capabilities for optical media.
  • the scheme should provide for rapid production of images, text, or other optically encoded information on the label and/or read side of the optical media.
  • the scheme should further provide for markings that are robust and durable in environments where optical media may be used.
  • Method and apparatus for imparting images upon the readout and/or non-readout side of optical media such as CDs and DVDs are disclosed.
  • 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, preferably with a first light, such as long wave ultraviolet (UV) light; addressing each of the coatings with certain wavelengths of a second light, such as short wave UV; 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.
  • a first light such as long wave ultraviolet (UV) light
  • addressing each of the coatings with certain wavelengths of a second light such as short wave UV
  • UV light for the curing and imaging steps ensures that the techniques provide for a marking that is non-interfering with data read out, since most current and future optical disc formats utilize IR, NIR, or visible wavelengths for laser readout, and since UV curable materials are used in most of these formats. Accordingly, it is preferred that curing and imaging wavelengths make use of wavelengths in the UV region of the spectrum.
  • aspects of the invention include application of the coating, (or coatings), upon the read side or the non-read side of the optical media. Further aspects of the invention include application of a gray scale, single-color or multi-color image, (referred to as a "marking"), formed in the collective appearance of the coatings.
  • the coatings and the markings do not interfere, or substantially interfere, with the use of the optical media.
  • the coatings and the markings are transmissive, or substantially transmissive of wavelengths of interest, such as the ' wavelengths used by a readout laser for the optical media.
  • 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 of the markings as security measures. Further aspects of the invention include providing for the use of the read side of the optical media for marking with advertising, branding, and other markings normally associated with the non-readout side of the media.
  • an optical media having at least one layer that includes a formulation formed of at least one set of photosensitive color forming materials, wherein the at least one set of photosensitive color forming materials is adapted for forming at least one marking upon exposure to a source of marking light; wherein, upon formation, the at least one marking is apparent in at least a readout area of the optical media and substantially non- interfering with a readout light for the optical media.
  • an optical media having a first layer formed of photosensitive color forming materials for forming a marking in response to illumination with a marking light, and a second layer disposed over the first layer and comprised of a material absorptive of the marking light; wherein, the marking is apparent in at least a readout area of the optical media and is substantially non-interfering with a readout light for the optical media.
  • an optical media having at least one layer includes at least one set of photosensitive color forming materials, wherein the at least one set of photosensitive color forming materials exhibits at least one marking in a readout area of the optical media that is substantially non-interfering with a readout light for the optical media.
  • a method for producing an optical media includes selecting a formulation having at least one set of photosensitive color forming materials, wherein the at least one set of photosensitive color forming materials is adapted for forming at least one marking upon exposure to a source of marking light, wherein the at least one marking, upon formation, appears in at least a readout area of the optical media and is substantially non-interfering with a readout light for the optical media; and, applying the formulation in at least a portion of at least one layer of the optical media.
  • an optical media having at least one first layer formed of about 0.3 weight percent of a polyether modified poly-dimethyl-siloxane; about 10 weight percent of a stable liquid mixture of trimetliylbenzoyldiphenylphosphine oxide, ⁇ -hydroxyketones, and benzophenone derivatives; about 10 weight percent of a 1,6 hexanediol diacrylate; about 15 weight percent of tefrahydrofurfuryl acrylate; about 32.35 weight percent of ethoxylated (4) pentaerythritol tetraacrylate; about 32.35 weight percent of a highly propoxylated (5.5) glyceryl triacrylate; about 3 weight percent of triphenylsulfonium triflate and a color former having a wavelength absorbance peak of about 540 nm.
  • Another optical media disclosed herein has a protective layer formed of a formulation having of at least one set of photosensitive color forming materials, wherein the at least one set of color forming materials is adapted for forming at least one marking upon exposure to a source of marking light; wherein, upon formation, the at least one marking is apparent in the optical media.
  • Another optical media disclosed herein has a bonding layer formed of a formulation having at least one set of photosensitive color forming materials, wherein the at least one set of color forming materials is adapted for forming at least one marking upon exposure to a source of marking light; wherein, upon formation, the at least one marking is apparent in the optical media.
  • FIG. 1 depicts aspects of a prior art optical media known as a compact disc
  • FIGs.2-5 depict aspects of prior art optical media known as a DVD
  • Fig. 6 depicts aspects of a prior art optical media known as a hybrid SACD;
  • Fig. 7 depicts aspects of a prior art optical media known as a hybrid DVD;
  • FIG. 8 depicts aspects of a prior art optical media known as a DVD Plus
  • Fig. 9 depicts an optical media having a coating
  • Figs. 10A-E depicts exemplary embodiments of target layers in a DVD
  • Fig. 11 depicts an absorbance curve for a color former in a coating formulation
  • Fig. 12 compares background color formation in various compositions
  • Fig. 13 depicts absorbance spectra for two photoacid generators
  • Fig. 14 depicts a UV absorption spectra for a first photoinitiator
  • Fig. 15 depicts a UV abso ⁇ tion spectra for a second photoinitiator
  • Fig. 16 depicts a line spectrum for a medium pressure iron-doped lamp
  • Fig. 17 depicts a line spectrum for a gallium iodide lamp
  • Fig. 18 depicts a line spectrum for a xenon gas filled lamp
  • Fig. 19 depicts transmission curves for various filters
  • Fig. 20 depicts absorbance peaks at 540 nm for various concentrations of a color former
  • Fig. 21 depicts absorbance peaks at 540 nm for various concentrations of triphenyl sulfonium triflate
  • Fig. 22 average color decrease in a first environmental study
  • Fig. 23 depicts reductions in surface tension as a function of concentrations of various wetting agents
  • Fig. 24 depicts average absorbance of various formulations after environmental testing
  • Fig. 25 depicts average decrease in optical density for various formulations after environmental testing
  • Fig.26 depicts a storage case laden with filter paper
  • Fig.27 depicts fading in color resulting from TEA exposure
  • Fig.28 depicts the development of color as a function of exposure wavelength
  • Fig.29 depicts development of color in samples containing UV absorbers
  • Fig.30 depicts the effect of adding UV absorbers on color generation
  • Fig.31 depicts color formation in UV stabilized formulations
  • Fig.32 depicts color formation in a particular sample of a UV stabilized formulation
  • Fig. 33 depicts results of a study adjusting ratios of color former and photoacid generators
  • Fig. 34 depicts color level and sensitivity as a function of photoacid generator concentration and film thickness
  • Fig.35 depicts the absorbance of a CN-120 based formulation
  • Fig.36 compares absorbance spectra for various UV absorbers
  • Fig. 37 depicts color formation times for combinations having various photoacid generators
  • Fig.38 depicts aspects of color generation as a function of photoacid generator
  • Fig. 39 depicts color formation as a function of illumination type
  • Fig. 40 depicts color formation as a function of UV absorber
  • Fig. 41 depicts color formation as a function of illumination fluence
  • Fig. 42 depicts color formation as a function of additives for enhancement
  • Fig. 43 depicts color formation in a buffered system
  • Fig. 44 depicts film thickness as a function of spin speed
  • Fig. 45 depicts film thickness and optical density as a function of spin speed
  • Fig. 46 depicts film thickness and optical density as a function of spin speed
  • Fig. 47 depicts color formation for varying ratios of photoacid generator to color former
  • Fig. 48 depicts optical density for two coatings
  • Fig. 49 depicts color formation as a function of time one geometry
  • Fig. 50 depicts absorbance spectra for three embodiments of overcoat layers
  • Fig. 51 depicts residual sensitivity in a two coating system
  • Fig. 52 depicts lightfastness in exposed areas; [0083 Fig. 53 depicts color development from environmental testing; [0084 Fig. 54 depicts environmental color retention; [0085 Fig.55 depicts fading from an amine study; [0086 Fig. 56 depicts film thickness as a function of spin speed; [0087 Fig. 57 depicts viscosity as a function of temperature; [0088 Fig. 58 depicts a shear rate profile; [0089 Fig. 59 depicts a shear stress and shear rate profile; [0090 Fig. 60 depicts viscosity for a constant shear rate; [0091 Fig.
  • Fig. 61 depicts color formation for a set of photoacid generators and color formers; [0092 Fig. 62 depicts color fonnation for a set of photoacid generators and color formers; [0093 Fig. 63 depicts color formation for a set of photoacid generators and color formers; [0094 Fig. 64 depicts color formation for a set of photoacid generators and color formers; [0095 Fig. 65 depicts a comparison of light sources; [0096 Fig. 66 depicts a comparison of light sources; [0097 Fig. 67 depicts color formation as a function of fluence; [0098 Fig. 68 depicts residual sensitivity of coating with various UV absorbers; [0099 Fig. 69 depicts the optical density of exposed regions as a function of UV absorber;
  • Fig. 70 is a cross section of an optical media having multiple layers applied over the reflective layer
  • Fig. 71 is a cross section of an optical media having multiple layers applied over the reflective layer
  • Fig. 72 is a cross section of an optical media having multiple layers applied over the reflective layer
  • Fig. 73 is a graph depicting absorbance curves for orange and red color fomiing layers
  • Fig. 74 is a graph depicting absorbance curves for a multicolor embodiment
  • Fig. 75 is a graph depicting absorbance where only a top color forrning layer is exposed;
  • Fig. 76 is a graph depicting absorbance in a multi-color system having a UV blocking layer;
  • Fig.77 depicts a system for curing the coating
  • Fig. 78 depicts markings on an optical media formed by illumination with a marking lamp
  • Fig. 79 depicts test data for an uncoated disk
  • Fig. 80 depicts test data for a coated disk
  • Fig. 81 depicts test data for a coated disk with at least one image recorded thereon;
  • Fig. 82 depicts test data for an optical media produced in a production system
  • Fig. 83 depicts spectra of various formulations applied to the label side of an optical media.
  • optical media including a coating, or a series of coatings, incorporated for retention of at least one gray scale, single color or a multi-color marking into the readout area of the optical media, without interference, or substantial interference with the functionality of the optical media.
  • 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, preferably with a first light, such as ultraviolet (UV) light; addressing each of the coatings with certain wavelengths of a second light, such as UV, 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.
  • a first light such as ultraviolet (UV) light
  • UV ultraviolet
  • optical media are referred to herein in general terms, as “CD” or “DVD”, however, it is considered that existing formats for optical media 8 are presently available, or in development.
  • 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, Blu-Ray, Mini-Disc any hybrid of the foregoing, and others.
  • Examples of further formats or structures for optical media include those disclosed in U.S. Patents No. 5,452,282 and the Continuation-in-part thereof, U.S.
  • Patent No. 6,011,767 entitled “Optical Data Storage Disc” as well as U.S. Patent No. 6,160,789, entitled “Optical Data Storage Disc with a Visible Holographic Image and Method for its Manufacture.”
  • the foregoing list should therefore only be considered illustrative of the variety of optical media 8 that may support or benefit from the use of the teachings herein, and is therefore neither exhaustive or limiting.
  • a coating 100 is applied to a prior art optical media 8, such as a CD, to produce a coated optical media 10.
  • the optical media 10 contains layers as are contained in prior art optical media 8.
  • the optical media 10 contains the CD substrate layer 17 (also referred to as a "polycarbonate layer"), a metallized layer 14 and a protective layer 12.
  • the addition of the coating 100 presents a modification to the manufacturer's specification for the format for the optical media 8. More specifically, and by way of example, it is realized that the additional coating 100 increases the thickness of the optical media 8.
  • the increased thickness although a modification to the specification for the fonnat (in this case a CD), does not interfere, or substantially interfere, with the functionality of the optical media 10.
  • the addition of the coating 100 is a permissible modification or an insubstantial deviation from the architecture for the format.
  • various compensation techniques may be used.
  • the thickness of the CD substrate layer 17 is reduced during the molding process to account for addition of the coating 100, and produce a disc 10 which remains in specification.
  • a particular format may be characterized by structures (a physical design) that are common to other formats.
  • the teachings herein are not limited to a particular design for an optical media 8. Therefore, the layers or components of a given format are occasionally refened to herein in generic terms. These terms include designations such as, "layer” "structure” and “component.” Further, in some instances, a particular layer may be refened to in more specific terms.
  • the term “formulation” generally means the composition of materials applied to an optical media for purposes of foiming a visually perceptible contrast within areas of the optical media, thus forming a marking.
  • the formulation may contain materials that are refened to as "color forming,” although some embodiments may use color subtractive processes for creating an image. Other embodiments produce images that only appear within the gray scale. Therefore, these materials may also be refened to as “contrast forming.”
  • color forming and “contrast forming” are therefore interchangeable herein, and refer to the ability of a formulation to form a visually perceptible marking.
  • At least one formulation of at least one energy sensitive color forming material is applied to an optical media 10.
  • the formulation is applied as an integral part of the structure within the optical media 10.
  • the substrate layer 17 that typically appears in an optical media 8 (and it typically formed of polycarbonate) is targeted for addition of the formulation.
  • Other layers may be targeted for replacement or augmentation with a formulation according to aspects as disclosed herein.
  • target layer is used generally to refer to any layer within an optical media 8 that is, or may be, replaced or augmented by the incorporation of a formulation as disclosed herein.
  • a formulation is said to be used "in" a target layer
  • the formulation may actually be layered in the target layer, used in place of materials conventionally used in a target layer, or in conjunction with the materials conventionally used in a target layer. That is, in this latter example, the formulation may replace a portion of the target layer, or be mixed with materials used in the target layer.
  • a number of factors may govern the composition and/or use of a formulation in any given target layer.
  • the design criteria for a specific structure of an optical media 8 may dictate certain thickness, clarity or hardness requirements.
  • Other factors may include the operational wavelength for the readout laser.
  • Commonly used readout light wavelengths for optical media 8 include 408 nm, 440 nm, 630 nm, 650 nm, and 780 nm, while other readout wavelengths are possible.
  • wavelengths of light and “wavelength” refer to appropriate wavelengths used for performance of a technique, or to achieve an effect.
  • long wave or short wave ultraviolet (UV) may be used to cure a target layer, to create a marking in a target layer, or to view a marking
  • wavelengths of light include bands or sets of wavelengths, which may be refened to as one of: UV-A, UN-B, UN-C, UN, visible (VIS), near infrared (MR), infrared (J-R) and longwave infrared (LIR). Further classifications may be applied.
  • wavelengths may include any appropriate form of actinic radiation where that form is useful for achieving the desired affect.
  • the wavelength chosen for a specific purpose is dependent upon various factors such as, and not limited to, the composition of the formulation and the being non-interfering with the laser readout of the optical media. It should be understood that although certain prefened formulations are disclosed herein, with use of a specific wavelengths of UV, one may select wavelength as appropriate to achieve an intended purpose, while remaining within the teachings herein.
  • Curing of a target layer is typically achieved using a first set of wavelengths of light.
  • use of a first light is not limiting.
  • application of a formulation by way of compounding techniques may simply require adequate cooling of the target layer to provide for setting the formulation materials in the target layer.
  • the formulation is cooled to an ambient temperature.
  • the energy source used to form a marking may include any wavelength of light or combination of wavelengths of light deemed appropriate to form an image in the target layer.
  • a particle beam e.g., an e-beam
  • the energy source may include any wavelength of light or combination of wavelengths of light deemed appropriate to form an image in the target layer.
  • a particle beam e.g., an e-beam
  • Optical changes are initiated in a target layer through the selective and controlled exposure to wavelengths of light, preferably UV wavelengths which are non-interfering with laser readout.
  • a formulation may be used in a single target layer or multiple target layers may be used. Where multiple target layers are used, each one may be sensitive to the same or a different energy source.
  • Each color forming target layer contains at least one formulation. Selective or controlled exposure is typically achieved using known techniques. Examples include the use of a positive or negative photomask, a direct writing laser, or an electronic photomask (such as an LCD display).
  • a color forming formulation is used within at least one target layer of the optical media, where the color forming layer provides for development, or dissipation, of a primary color.
  • each one of the multiple layers is preferably associated with at least one color related to an additive or subtractive color schemes.
  • each layer may provide for the appearance of red, green or blue (RGB); alternatively, each layer may provide for the subtraction of cyan, magenta, yellow or black (CMYK).
  • RGB red, green or blue
  • CYK cyan, magenta, yellow or black
  • a color forming layer is applied to an optical media in conjunction with an overcoat layer.
  • the "two coat system” provides certain versatility not available in the "single coat system” where only layers of color forming formulations are used.
  • an overcoat is applied which contains photoabsorptive materials.
  • the overcoat provides protection of the color forming layer from UV in ambient light, thereby improving aspects of the appearance of a marking. For example, use of UV absorbers may limit growth of background color due to exposure to ambient light, and therefore the longevity of a marking.
  • the terms "marking,” and "image” refer to the optical changes formed in the target layer as a result of exposure to the energy source.
  • the marking may be used as "label.”
  • the image may include any form of marking within the contemplation of one forming the image.
  • a marking may include, without limitation, a bar code, text, graphics, alphanumeric characters, and symbols.
  • the "content" of the marking may contain any content within the contemplation of one making the marking.
  • content may include, without limitation, instructional, promotional, advertising, branding, authentication, identification, serialization, and/or other types of information.
  • the markings may be best viewed from the read side. In others, the markings are best viewed from the non-readout side. Some markings may be viewed equally as well from both sides.
  • FIG. 3 a prior art version of a single sided, dual layer optical media 8 is depicted.
  • One example of an optical media 8 using this type of construction is the format refened to as "DVD-9", and as shown in Fig. 3.
  • the readout side 2 the optical media 8 shown in Fig. 3, a DVD-9, includes a first substrate layer 17-1, a semi- reflective layer 14-1, a bonding layer 15, a reflective layer 14-2, a second substrate layer 17-2, and a label side 7.
  • Figs. 10A-E collectively refened to as Fig. 10, provide an introduction to use of coatings in an optical media 10, such as the single sided, dual layer optical media 8 depicted in Fig. 3.
  • FIG. 10A an optical media 10 of thickness T is shown.
  • the substrate layer 17-1 is designated as a target layer for incorporation of the coating 100.
  • the coating 100 includes two layers, a single color forming layer 101 and an over coat layer 102. h one embodiment, the first substrate layer 17-1 is manufactured to a reduced thickness 111, to account for augmentation with the coating 100 and production of a coated optical media 10.
  • the entire bonding layer 15 has been replaced by the inco ⁇ oration of a single color forming layer 101.
  • the color forming layer 101 has been inco ⁇ orated without an overcoat layer 102.
  • the remaining portions of the optical media 10 are constructed in accordance with the specifications of the prior art.
  • the bonding layer 15 provides a target layer for inco ⁇ oration of an overcoat layer 102 and a color forming layer 101, where the remaining portion of the bonding layer 15 uses prior art materials (such as UV curable acrylates).
  • Fig. 10D depicts a variation of the embodiment depicted in Fig. IOC.
  • a further embodiment is presented in Fig. 10E.
  • Fig. 10E is discussed further herein.
  • One skilled in the art will recognize that the foregoing embodiments of target layers introduce aspects of combinations that can include a large number of variations. Accordingly, these foregoing embodiments are illustrative and not limiting of the invention.
  • formulations are robust to the retention of a color selected and developed during the manufacturing process, and are robust to the physical demands of the application. That is, each formulation is substantially color fast under normal conditions, and substantially durable to normal wear.
  • a fonnulation is composed of materials that are disbursed in a polymeric matrix or other suitable equivalent. In some embodiments, the materials are disbursed in an ultraviolet (UV) curable polymer.
  • UV ultraviolet
  • Formulations may be applied through any technique that is appropriate for the optical media 10.
  • a fonnulation is applied by spin-coating.
  • the step of spin coating the formulation onto the optical media 10 occurs during the mass production of the optical media 10 and preferably follows traditional steps for the manufacture of an optical media 8.
  • a formulation could be included in one target layer, while a surface relief pattern having continuous variations defining a holographic image is inco ⁇ orated into another layer.
  • a fonnulation is used in combination with, or as an overlay to, a surface relief pattern having continuous variations and defining a holographic image. In these embodiments, the combination appears on the non-readout side. Accordingly, one can understand that the teachings herein may be used with a variety of techniques for manufacture of optical media 10.
  • ti e coating 100 contains what can be refened to as two "sets" of photosensitive materials.
  • One set of photosensitive materials provides for curing of the 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.
  • the coating 100 may include materials that are photosensitive to any band of wavelengths (also refened to as a "set of wavelengths").
  • the photosensitive materials may be responsive to UV-A, UV-B, or UV-C wavelengths.
  • having two sets of photosensitive materials provides for use of two sets wavelengths to initiate the changes in the coating 100 as described herein. It is considered that other fonnulations, not discussed herein, may advantageously make use of wavelength separation over the spectrum of useful wavelengths. Accordingly, the teachings herein are not limited to the exemplary embodiments herein, which merely provide one example of a system for applying markings to optical media.
  • coating is taken to mean an application of formulation as disclosed herein. That is, although techniques may be used for application of a formulation as a coating, such as by spin coating, inco ⁇ oration of formulations are not meant to be limited to coating techniques. Other non-limiting examples of application of one or more formulations include use of compounding techniques, where a formulation is inco ⁇ orated into other materials, which are applied to the optical media. In general, it is considered that the term “coating” applies to materials included in an optical media in accordance with the teachings herein. [00147] A. Single Coating Development
  • SR-494 is an ethoxylated (4) pentaerythritol tefraacrylate
  • 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 trimemylbenzoyldiphenylphosphine oxide, ⁇ -hydroxyketones, and benzophenone derivatives.
  • ESACURE KTO-46 is a liquid photoinitiator that can be inco ⁇ orated by simply stining into a resin system, and is insoluble in water and is soluble in most common organic solvents and monomers. KTO-46 may also be refened to as including ESACURE KIP- 150 and ESACURE TZT.
  • ESACURE KTP-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 KTP-150 and ESACURE TZT are produced by Lamberti Spa, Gallarate-Na, Italy.
  • SR-494 and SR-238 are products of Sartomer Co ⁇ oration of Exton, PA.
  • KTO-46 is also marketed by Sartomer Co ⁇ oration as SARCURE-1135 (therefore, KTO-46 and SR-1135 are used interchangeably herein).
  • SR-285 is tetrahydrofurfuryl 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 Co ⁇ oration 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 i itate skin.
  • SR-238 and SR-285 were skin mitants, 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 of the optical media 10 occasionally exl ibited 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 17 include those available from Headway Research, Inc. 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 confrolling 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 further herein in terms of application of the coating 100, and requirements thereof.
  • Formulations were made with all of the new components (Table 1) to see how they affected the performance of the coating 100.
  • Wetting agents were included in the new formulations to improve distribution of the formulations over the discs 10.
  • the wetting agents tested were BYK-307 and BYK-333, both agents being polyether modified poly-dimethyl- siloxanes, and exhibiting similar properties for reducing surface tension.
  • BYK-307 and BYK- 333 are products of BYK-Chemie, of Wesel Germany, and distributed in the US by BYK- Chemie USA, of Wallingford, Connecticut. Table 2 shows the formulations and results.
  • 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 of the total mixture.
  • 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 frifunctional monomer offering low viscosity, good flexibility, fast curing, and excellent hardness.
  • SR-9020 is a product of Sartomer Co ⁇ oration.
  • the components given in Table 3 are trade names of the Sartomer Co ⁇ oration used for: propoxylated (3) glyceryl triacrylate (SR-9020); ethoxylated (3) trimethylolpropane triacrylate (SR-454); tris (2-hydroxyetl ⁇ yl) isocyanurate triacrylate (SR-368); di- trimethylolpropane tefraacrylate (SR-355); and, urethane acrylate (CN-983).
  • SR-9020 propoxylated (3) glyceryl triacrylate
  • SR-454 ethoxylated (3) trimethylolpropane triacrylate
  • SR-368 tris (2-hydroxyetl ⁇ yl) isocyanurate triacrylate
  • SR-355 di- trimethylolpropane tefraacrylate
  • CN-983 urethane acrylate
  • 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 prefened 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 tiie 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.
  • 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 of the disc 10 was exposed for 10 seconds. This produced a red color on the clear disc 10 with intensities varying between the different portions of the disc 10.
  • absorbance curves were recorded on a spectrometer.
  • the spectrometer used was a UV/NIS model called LAMBDA 2, produced by Perkin Elmer Co ⁇ oration, of Boston, MA.
  • Table 8 shows the results for three photoacid generators (PAG).
  • the three PAG were inco ⁇ orated 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 amounts 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 of the photoinitiator as a part of the 94%o 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-dimetl ⁇ ylamino-l-(4-mo ⁇ holinophenyl)-butanone-l, which is a highly efficient UN 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)-phenylphospl ineoxide, which is a versatile photoinitiator for radical polymerization of unsaturated resins upon UN 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, ⁇ Y.
  • C ⁇ -384 is a difunctional amine coinitiator which, when used in conjunction with a photosensitizer such as benzophenone, promotes rapid curing under UN 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 Co ⁇ oration of Exton, PA).
  • IRGACURE 2959 is l-[4-(2-Hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-l- propane-1-one, which is a highly efficient non-yellowing radical photoinitiator for the UN 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 photoinitiator that is used in combination with a suitable coinitiator, e.g., ethyl 4-(dimethylamino) benzoate (SARCURE SRI 125), to initiate UN free radical polymerization.
  • SARCURE SRI 124 is used in inks, varnishes, and decorative coatings.
  • ESACURE KIP 100F is a liquid mixture of about 70% Oligo [2-hydroxy-2-methyl-l-[ 4-(l-methylvinyl) phenyl] propanone and about 30% 2-hydroxy-2- methyl-1 -phenyl propan-1-one.
  • both curing 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 UN light wavelengths below about 320 nm
  • photoacid generators are available which operate in this area and because deep UN 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 abso ⁇ tion above 290 nm are depicted in Fig. 13.
  • photoinitiators There are a number of commercially available photoinitiators whose primary abso ⁇ tion bands lie at wavelengths greater than 300 nm. Most notably, the phospliine oxide functionalized photoinitiators such as LUCIRI ⁇ TPO from BASF Co ⁇ oration of Charlotte ⁇ C, (the main component in KTO46) and IRGACURE 819, whose spectra are shown in Figs. 14 and 15, respectively. Other photoinitiators may be used which also exhibit abso ⁇ tion for wavelengths above about 300 nm. It should also be noted that these initiators are of the direct fragmentation type of clearlynolecular initiators.
  • Bimolecular initiators typically consist of a sensitizing molecule capable of absorbing light and transfening it to a synergist molecule capable of forming a radical upon the energy transfer.
  • One of the most common sensitizers to absorb visible light is ITX, or isopropylthioxanthone.
  • 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 of the photoacid generate to long wave UN 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 of the acid generated by the photoacid generator.
  • 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 Fig. 16 shows the output from a medium pressure iron- doped mercury lamp typically used for UN curing lacquers applied to of optical media 10. Once can see how the majority of the output comes from discrete lines associate with electronic transition of the lamp dopant.
  • These lamps typically work well for UN curing because the major lines are compatible with the photoinitiators used in UN curing systems.
  • Another popular lamp is the pulse XE ⁇ O ⁇ gas filled lamp, such as those made by XE ⁇ O ⁇ Co ⁇ oration of Woburn MA.
  • the spectrum for these lamps are much more "blackbody” in nature, with a spectrum derived from the color temperature of the plasma fonned in the lamp during the pulse.
  • a typical spectrum from a XE ⁇ O ⁇ RC-747 gas filled lamp is depicted in Fig. 18.
  • the prefened method for curing the coating consists of using the KTO-46 photoinitiator with a combination of a XE ⁇ O ⁇ bulb and an L37 filter glass.
  • Typical mercury line lamps did not produce an intensity of light that was adequate in comparison to the XE ⁇ O ⁇ lamps, where both were outfitted with an L37 filter.
  • the XE ⁇ O ⁇ lamps were selected for curing of the coating 100.
  • 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 tem ination and resulting in an under cured system.
  • Methods to overcome oxygen inhibition include (1) adding more photoinitiator or (2) increasing curing time. As the photoinitiator selected is relatively expensive, option (2) is considered to be preferable over option (1).
  • a further 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.
  • This enables all the free radicals produced by UN exposure to be used in the polymerization process.
  • a purge gas such as nitrogen
  • the expense of using a purge gas must therefore be weighed against various other requirements, such as the cure time, and desired end product.
  • a furtl er method of overcoming oxygen inhibition is to use photoinitiators which are less reactive with oxygen. These initiators tend to require shorter UN 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.
  • a prefened 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 Co ⁇ oration of Woburn MA.
  • a high intensity pulsed source such as the model RC-747 lamp available from Xenon Co ⁇ oration of Woburn MA.
  • the energy of each flash of light is so intense that very high concentrations of free radicals are created.
  • pulsed light has proven advantageous for curing of the coating 100 disclosed herein, because it provides high intensity light in a region of the spectrum that is compatible with the color formation process. Furtliennore, use of pulsed light has reduced the oxygen inhibition problem greatly, so tiiat nitrogen environments or excessive amounts of photoinitiators are not required while keeping curing time to as short a time as possible.
  • Tables 14 and 15 show that in the 3% color former, 3% photoacid generator and 94% base coating (fonnulation 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 of the photoacid generator and/or color former, and by adding color enhancers.
  • Fig. 21 depicts effects in color intensity after increasing the amount of photoacid generator (in this experiment, triphenylsulfonium triflate was used) in the coating 100.
  • Fig. 21 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.
  • OD optical density
  • TPST triphenylsulfonium triflate
  • Fig.22 The test results shown in Fig.22 demonstrate that some formulations retain their color better than others in the presence of temperature and humidity. Specifically, the addition of non- alkoxylated monomers such as SR-355 (formulation 14), CN-983 (fonnulation 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. The use of the tert butyl derivative of triphenylsulfonium triflate (TPST) or higher concentrations of the photoacid generator did not impact performance significantly.
  • 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 of the 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 of the 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.
  • 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 Co ⁇ oration.
  • This study also evaluated changing the wetting agent from BYK-333 to a crosslinkable siloxane.
  • Several candidate reactive wetting agents were examined, including three RAD products from TEGO (RAD 2250, RAD 2200N, RAD2100). The performance of these products was examined using formulation 48. TEGO RAD 2200N was selected as it gave the best surface tension reduction and clarity performance. Results of the examination are shown in Fig. 23.
  • TEGO RAD 2250 and RAD 2200N are each a crosslinkable silicone polyether acrylate, while TEGO RAD 2100 is a crosslinkable silicone acrylate.
  • TEGO products are available from Tego Chemie Service GmbH, and distributed in the United States by Degussa Tego Coating & Ink Additives of Hopewell, NA.
  • 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 fonned from fonnulation 59 should be highly crosslinked, high Tg, film with no alkoxylation. All the remaining fonnulations 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 Co ⁇ oration.
  • TOTAL 100 100 100 100 ⁇ oo
  • ⁇ oo 100 100 100 100 100 100 100 100 100
  • SR-368D is tris (2-hydroxy ethyl) isocyanurate triacrylate, and is a clear liquid triazin compound which is used in free radical polymerization.
  • C ⁇ 120B60 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.
  • Fig. 26 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.
  • test fixture consisting of a four foot long two-bulb fluorescent lamp fixture was fabricated.
  • the lamp used was a Philips ECON-O- ATT 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 formation.
  • 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 of the spectrum was the bandwidth where UN protection would be most beneficial.
  • Fig. 28 depicts results of illuminations, where UN-30, L-37, L-38, L-39, L-40 and L-42 denotes model names for commercially available UN filters from HOYA Corporation of Tokyo Japan.
  • the name of the cutoff filter describes the 50% transmission point.
  • the UN-30 filter which is rated for wavelengths at 300 nm, has a 50% transmission point at 300 nm. It is recognized that the 50% fransmission 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 UN-36, etc. So, while a 1 mm thick L-37 is generally prefened for applications herein, (having about 50% fransmission at 370 nm), a thicker UN-36 filter can also work well, as well as a UN- 34 filter in addition to some of the other filters.
  • UN-32 is considered to be at about the lower limit, and above UN-39, curing becomes slow. Therefore, prefened 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.
  • photoabsorptive materials were added to samples of the formulation to see if color fonnation would slow or cease when the samples were subjected to ambient room light.
  • the photoabsorptive materials selected for testing were UN absorbers.
  • the UN absorbers used were TI ⁇ UNI ⁇ 327, TI ⁇ UNI ⁇ 171, T1 ⁇ UNI ⁇ 213, and TI ⁇ UNI ⁇ 571.
  • TI ⁇ UNI ⁇ 327 is 2,4-di- tert-bu tyl-6-(5-chlorobenzotria zol-2-yl) phenol;
  • TI ⁇ UNI ⁇ 171 is (2-(2H-benzotriazol-2-yl)-6- dodecyl-4-- methyl-phenol);
  • TI ⁇ UNI ⁇ 213 is a mixture of reaction products of methyl 3-(3- (2H-benzotraizole-2-yl)-5-t-butyl-4-hydroxyphenyl) proprionate / PEG 300; and
  • TI ⁇ UNI ⁇ 571 is branched and linear 2-(2H-benzotriazol-2-yl)-6-dodecyl-4-methylphenol.
  • the TI ⁇ UNI ⁇ products are produced by Ciba Specialty Chemicals.
  • TI ⁇ UNI ⁇ were in Jiquid form, with the exception of- TI ⁇ UNI ⁇ 327 which was a powder. Testing was perfonned by adding one percent of each UN absorber to fonnulation 10, except one sample was made with 5% TI ⁇ UNI ⁇ 171. However, since the point of the UN absorbers was to slow color formation, another step was performed to ensure that each sample could still produce enough color when imaged. Fig. 29 shows that the samples produced adequate color. In fact, samples incorporating UN absorbers produced more color than the sample without any UN absorbers (denoted as MC9020 in Fig. 29). Color formation in the sample containing 5% TESfUNr ⁇ 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.
  • Fig. 30 depicts effects of adding UN absorbers as determined in an accelerated fluorescent light study.
  • Fig. 30 shows some types of TI ⁇ UNI ⁇ work better than others but the comparative difference at 1%> concentration is minimal.
  • the sample containing 5% concenfration of TI ⁇ UNI ⁇ 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 TINUNiN 171 however, the materials bloomed after curing (displayed color formation without exposure to an imaging light).
  • the sample containing a 5% concentration of TINUNIN 171 showed the same effect after a longer time. Therefore, TINUNIN 171 was ruled out as most likely not being a good candidate for use as a UN absorber.
  • UN absorbers were tested in what was becoming the prefened 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 fonnulation 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.
  • UN-531 is the shortened name for CYASORB UN-531 FLAKE, which is 2-Hydroxy-4- «-octoxybenzophenone. Both are products of Cytec Corporation of Stamford, CT.
  • MC80 is the shortened name for UNI ⁇ UL MC80, which is octyl methoxycinnamate, and is a product of BASF Corporation of Japan.
  • the UV stabilized formulations exhibited slower color formation times with lower ultimate colors for equivalent UV dose compared to unstabilized formulations. Results are depicted in Fig. 31. However the longer color formation time (or higher fluence) was considered to be outside of the required cycle time for the manufacturing specification. Furthermore, the high fluence rates required to write into these coatings caused some undesired physical deformations (such as shrinkage and warp), as well as differences in the properties, i)f the coating between exposed and unexposed areas. As an example, the color formation time of formulation 81 is shown in Fig. 32. Even at about one inch away from the XENON lamp, exposure times of more than ten seconds were required to obtain color formation greater than 0.5 AU.
  • Results of a study shows that the thickness of the coating 100 plays a role in color formation and light sensitivity.
  • 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 XENON lamp.
  • Confrol 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 determined to cause fading in the formulation including SR-9020).
  • TPST was considered to be the simplest and shortest UN absorbing sulfonium-based photoacid generator available.
  • Diphenyl iodonium hexafluorophosphate (DPI HXFP) was also considered to be a simple short UN absorbing photoacid generator.
  • the absorbance spectra, of these two photoacid generators, shown in Fig. 13, have a maximum at approximately 200nm, with a tail into the mid-UN.
  • 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 refened to as a "set of wavelengths.”
  • FIG. 37 shows the color formation curves for each formulation prepared. The samples shown in Fig. 37 were exposed at a distance of one inch from the XE ⁇ O ⁇ lamp. Some photoacid generators demonstrated faster color formation (writing) times than TPST, most notably the 4-phenoxy derivative. [00259] While these different photoacid generators provided for different writing speeds and color density, a more important performance parameter was considered to be whether or not the photoacid generators would provide for increased writing speed or color density without increased susceptibility to fluorescent and sunlight exposure.
  • a weak base was examined.
  • weak bases included acetic acid and sodium salt. Unfortunately, these compounds were not very soluble in acrylates, and only 0.1% loading was achieved. However, even at this low loading, an effect was observed.
  • the salt did act as a buffer, but it also reduced the rate of color formation and the overall color of the coating as well.- Aspects of the use of buffers are depicted in Fig. 43.
  • Formulations 58 (375 cps) and 61 (504 cps) were coated at incrementing spin speeds 5-1 OK. Optical Density and film thickness detenninations were performed, and the results are shown in Fig. 46. As expected, the more viscous formulation 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. That is, varying film thickness has a beneficial aspect of permitting an end user to dispense a minimum amount of material needed for a given color density, thereby providing for reduced costs and reducing light sensitivity.
  • FIG. 47 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
  • the first step in development of the color forming coating 100 was to evaluate the properties that could be divided between the color forming 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 quickly without nifrogen, 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 formulations produced the best environmental results, but exhibited higher optically denser for the color forming wavelengths than all of the aliphatic formulations such as fonnulations 1 and 9.
  • the addition of an overcoat 102 might be used to enhance the stability of the image in heat/humidity testing, non-CN-120 formulation were again examined, with a goal of decreasing writing times and decreasing shrinkage.
  • 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 UN transmissive coating.
  • Formulations Ol and O2 contained a SR-238 and SR-368 combination to provide for good adhesion and cure, with C ⁇ -120 in formulation O2 for additional hardness and UN opacity.
  • UN absorber UN-24 was used at 10% loading.
  • An immediate observation was that, as before, the photoacid generator was minimally soluble in the alkoxylated monomer SR-9021. (As may be apparent, formulations designated with a "C" indicate a fonnulation for the color fonning layer 101, while an "O" designation indicate a formulation for the overcoat layer 102.)
  • Sample discs 10 were prepared by spin coating color forming layers 101 with formulations Cl, C2, and C3 onto substrate 17 at 4K ⁇ m, curing in a nitrogen environment, through a L37 UN 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 UN filter with a "D" bulb at about one inch from the lamp for 3 seconds.
  • a candidate two layer coating 100 was designed. These formulations are presented in Table 20.
  • the color forming layer 101 was modified to decrease the concenfration 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 fonning layer 101 did not appear to form any noticeable color from the curing of the topcoat 102.
  • tiie UN stabilizing layer and color forming layer 101 allows the efficient use of shorter UN wavelengths ( ⁇ 320 nm) for color formation. This allows for efficient exposure of the color forming layer 101 using these wavelengths, then shielding 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 of the high shrinkage, UN absorbing C ⁇ - 120.
  • Formulation C6 was a modification to Formulation C5, where SR-368 was used in place of SR-494. It was theorized that this substitution would decrease the alkoxylation content and lead to a harder but still low slrinkage film 101 or color forming layer 101.
  • Formulation C7 was a modified formulation containing C ⁇ -120, SR-368, SR-238 designed to meet adhesion requirements.
  • 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 shrinkage without sacrificing hardness and scratch resistance.
  • Overcoats 102 were formulated using both 10% and 20% UN-24. The 20% loadings noticeably affected the viscosity.
  • the color coat formulations were applied by spin coating at 4K ⁇ m and then cured in ambient air at about one inch under the lamp, using the L37 filter for 2 seconds. It was noted that the discs 10 cured with a varying amount of "pinkness.” The pinkness ranged from no color for C5, to very slight color for C6, to slight color for C7. It was hypothesized that this most likely tracked the optical density of the coatings, since C7 had the highest aromatic content, C6 contained SR-368 which absorbs some UV, and C5 was the most UV transmissive of the coatings.
  • 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).
  • CN965 is an aliphatic polyester based urethane diacrylate oligomer. It is a flexible oligomer offering good weatherability.
  • 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
  • C ⁇ 120M50 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%.
  • 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.
  • Fig. 51 Residual sensitivity of the coatmg 100 is shown in Fig. 51.
  • the samples break up into two main groups depending on photoacid generator concentration. It was noted that in both cases, Overcoat (O13) appeared to provide better UN protection than Overcoat (O14).
  • the formulation C13 appeared to have the least residual sensitivity and appeared to provide the best optical density ratio for unexposed areas to exposed areas. Further, it was noted that the results for this ratio may, however, include some bias. This bias may result from not exposing the C14 formulation for an adequately long time so as to more fully develop the ultimate color, and thereby effectively reducing the developed color of the C14 formulations.
  • the coatings 101 with the highest amounts of photoacid generators and color formers retained a larger amount of their color upon prolonged light exposure. This effect is shown in Fig. 52.
  • Environmental testing at 70°C and 90% relative humidity showed that acid migration from the topcoat to the bottom coat is possible. Results are provided in Fig. 53. A clear split in the level of background color is seen in the formulations which do not contain acid (Overcoat O14) and the acid containing coating (Overcoat O13). Therefore, the utility of the acid in the amine/ink test will have to be confirmed before SB-520 or equivalents are included in the formulation. If necessary, a trade-off/ optimization study may be perfonned to minimize color development form this topcoat 102 while still imparted ink resistance.
  • 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 of the filter paper 181 and sealing the discs 10 in a storage case 180. This led to complete destruction of the 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 the 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 DND.
  • the test was repeated with 10 ⁇ l of concentrated ammonium hydroxide.
  • the disc 10 without the overcoat 102 deteriorated within an hour, as before. However, this time the disc 10 with the overcoat 102 formed from the O14 formulation retarded the fading by a few hours.
  • the disc 10 with the overcoat 102 formed from the O13 formulation was essentially unchanged and only showed signs of fading near the middle of the disc 10 after a day.
  • Metalized substrate 17 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 of the formulations tested in the quantitative study are presented in Table 25.
  • the formulations were applied to the substrate 17 by spin-coating at 4K rpm for 10 seconds.
  • the disks 10 produced were cured under the L-37 UN filter, in a nitrogen environment, and using the XE ⁇ O ⁇ 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.
  • 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 DND cases 180 and exposed to lO ⁇ l of ammomum 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 Fig.55.
  • 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 foiniulations. Each formulation was then spun coat onto borosilicate glass discs from 2K-10K ⁇ m in intervals of IK ⁇ m. 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 deteimine the thickness of the film 101 in two different areas on the disc. Fig.
  • the lacquer for the color coating can be dispensed at different temperatures. Accordingly, the viscosity as a function of temperature was determined. Niscosity 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 LNDN-III+CP rheometer and spindle CPE-40 at 4.75 ⁇ m. The viscosity and temperature profile is shown in Fig. 57 for color coat C6. As expected, the viscosity of the lacquer decreases with increasing temperature.
  • Fig. 58 shows that the bottom layer 101, (containing fonnulation c6), viscosity was nearly constant with increasing shear rates. However, with increased time of shearing, the viscosity increased.
  • the increasing shear curve implied ti e fonnulation is a Newtonian fluid. However, the decreasing curve implied the fluid rheology is time dependent.
  • Another type of graph that shows how the fluid behaves is a shear stress and shear rate profile is provided in Fig. 59. In Fig. 59, the linear relationship between shear stress and shear rate confirms that the fluid is Newtonian, in both shearing directions.
  • the HO ⁇ LE "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 HO ⁇ LE lamp being available from Honle UN America, Inc., of Marlboro, MA.
  • Figs. 61-64 illustrate the effect of photoacid generator to color fonner ratio on color formations. Looking at each different photoacid generator concentration as a set, it appeared that a general trend is followed. Figs. 61-64 show that color formation in samples having a ratio (or equivalent thereof) of 2:3.5 perform better than samples having ratios of 2:3, -which perform better than samples having ratios of 2:4.
  • the HO ⁇ LE "H” bulb performed best on a fluence basis for the combined UNA UNB levels, as shown in Fig. 65. However, it should be noted that the HO ⁇ LE did put out more UNB than either XE ⁇ O ⁇ bulb. When only the UNB levels were used to plot the curves, as shown in Fig. 66, the HO ⁇ LE lamp showed less of an advantage, but still appeared to be superior to the XE ⁇ O ⁇ bulbs. At any level, the HO ⁇ LE and "C" bulbs are superior lb the "D" bulb. Finally, the HO ⁇ LE "H” bulb was used to perform long exposures to examine the maximum useful fluences for imaging the coatings. As seen in Fig. 67, a typical formulation begins to reach a maximum after about 5 kJ/m 2 of UNB exposure. In some embodiments, a full spectrum of UN is used to cure the overcoat 102.
  • Overcoat (Ol) fonnulations were made with various UN absorbers at 10% concenfration.
  • the various absorbers used are shown in Table 28.
  • TI ⁇ UNI ⁇ -327 did not go into solution, and the fonnulation using TINUNIN-R796 crystallized after 24 hours.
  • TINUNIN- R796 is 2-(2'hydroxy-5'methacryloxyethylphenyl)-2H-benzotriazole, and is a reactive UN absorber capable of crosslinking into the coating.
  • Niscosity was measured for each of the formulations and optical density was measured on both cured and exposed regions of the 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 Fig. 68. It was noted that the UNA composition had almost no effect on the lightfastness of the exposed areas of the disks 10, as shown in Fig. 69.
  • Fig. 9 a review of the two embodiments of a coating 100 thus far is provided.
  • Fig. 9 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 UN absorbers).
  • Fig. 10 provides a second embodiment, wherein components are separated into two layers 101, 102.
  • the coating 100 is formed of a color forming layer 101 and an overcoat 102 (with the exception of Fig. 10B).
  • components of the color forming layers 101 are advantageously separated from components in the overcoat 102, thus providing for improved performance in regards to some of the properties of the coating 100.
  • the removal of UN absorbers from the color fonning layer 101 and attendant use of the UN absorbers in the over coat layer 102 provides for selection of more robust UN absorbers that do not interfere with the imaging process.
  • UN absorbers are but one example of image enhancing agents that may be used in an over coat layer 102.
  • Other non-limiting examples include materials that limit the effects of humidity, or enhance color (as described elsewhere herein).
  • Figs. 70-72 In a further embodiment, shown in Fig. 70, three layers 301, 302, 303 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 Fig. 70 is formed so that the first layer 301, the second layer 302, and the third layer 303 are applications of fonnulations for single layer embodiments.
  • each layer 301, 302, 303 produces a distinct color, such as one of red, green, and blue.
  • a coating 100 containing four layers 401, 402, 403, 404 is shown.
  • the first layer 401 is a color fonning layer 101
  • the second layer 402 is a protective overcoat 102
  • the third layer 403 is also a color fonning layer 101
  • the fourth layer 404 is another protective overcoat 102.
  • each of the first layer 401, the second layer 402, and the third layer 403 are color forming layers 101
  • the fourth layer 404 is a protective overcoat 102.
  • the color formed in each of the first three layers 401, 402, 403 may conespond to a primary color, such that upon completion of imaging, a multi-color image is apparent.
  • a further embodiment of a coating 100 a six layer embodiment, 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 conespond to a specific color, such as one of the primary colors. Imaging of each of the layers 501, 503, 505 provides for the collective appearance of a multi-color image.
  • At least a portion of the target layer materials is used. That is, in Figs. 70-72, a portion of the substrate layer 17 contains polycarbonate, without any color forming materials.
  • compositions used in the color forming layers 301, 401, 501 include materials having properties that might degrade the underlying metalized layer 14.
  • at least a portion of the polycarbonate is retained as a barrier layer to protect the metalized layer 14 from acids in the color forming materials that could lead to oxidation (change in the reflectivity) of the metalized layer 14.
  • a metallized disc was spun coat at 4000 ⁇ m 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 ⁇ m 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 photomask 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.
  • Spectra of the orange and red formulations were taken. These samples were spun coat on clear polycarbonate discs at 4000 ⁇ m and cured and exposed as described above. Also, spectra of the different combination of layered colors were taken, whether the disc 10 was layered with a first coat of orange or red, and then with the other color on top.
  • Fig. 73 depicts the spectra of a red disc 10 and an orange disc 10, where each color has been evaluated separately.
  • Fig. 74 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.
  • Fig. 75 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 xelatively unexposed. _ . -_--- -. _
  • the selective development of the upper color layer 101 can be enhanced by adding a UN blocking layer 102 between the color forming layers 101.
  • Table 30 provides a formulation for a UN blocking layer. This formulation was spun coat between the orange and red color fonning layers 101. In this example, the UN blocking layer 102 allowed even better reproduction of only the single topmost color. Again, exposure of both color fonning layers 101 led to the same total color regardless of the order in which the layers 101 were applied. Results are depicted in Fig. 76.
  • 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.
  • staged application and imaging of layers in a coating 100 may provide certain advantages.
  • a first layer 401 is applied and then has an image recorded therein.
  • 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 of the first layer 401 during the imaging of the 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 substantial interference with aspects of the first image.
  • Similar techniques may also be used with single layer formulations where color forming materials are mixed with UN (or other wavelength) absorbers. Multiple wavelengths for curing and imaging may be used.
  • a variety of application techniques, formulations, curing and imaging techniques may be used to achieve multiple effects in the collective appearance of the coatmg 100 upon an optical media 10.
  • a coating 100 may be used advantageously in prior art optical media 8 shown in Figs. 1-8.
  • a coating 100 to replace or lie over the acrylic protective layer 12 in the CD 8.
  • a prefened fonnulation for this application would include C13 or C14.
  • interference with the laser read out is not an issue so the use of additional color formers is possible. Therefore, the use of PERGASCRIPT Red 6B in C13 and C 14 can be replaced by a number of other colors.
  • the spectra and ratios of color formers to TPST in the C13/C14 base coat is shown in Fig. 83.
  • a color fonning layer 101 could be placed in the bonding layer 15.
  • the substrate layer 17-2 could be augmented with an over coat layer 102.
  • a related embodiment would be where the reflective layer 14 is replaced by a semi-reflective layer 14-1, and the marking 620 is read through the semi-reflective layer 14-1, as viewed from the read side 2. This embodiment has an advantage of leaving room for a conventional label on the label side 7.
  • the coating 100 is used to replace the bonding layer 15 of a DND-9, as shown in Fig. 3. For these embodiments, laser read out is still the major consideration, and formulas C13 and C 14 would be prefened.
  • the coating 100 could be used between the semi-reflective and the reflective layers. Refening to Figs. 6-8, in prefened embodiments, coatings 100 are used in the bonding (adhesive) layer 15.
  • a coating 100 in direct contact with a metal or other reflective layer 14 requires use of a protective portion (such as is shown in Figs. 70-72, where a portion of the target layer in a CD inco ⁇ orates polycarbonate), or modification to the reflective materials.
  • a protective portion such as is shown in Figs. 70-72, where a portion of the target layer in a CD inco ⁇ orates polycarbonate
  • silver or gold may be used in the reflective layer 14 to protect against degradation by the photoacid. Therefore, it is recognized tiiat in some embodiments, materials compatibility must be considered.
  • the bonding involves use of a cationic resin (which uses a photoacid as an initiator).
  • a UN curable acrylate is used to coat the reflective layer 14 before bonding.
  • intermediate steps might be required to provide for a final product 10 that properly exhibits the desired markings 620.
  • the coating 100 Prior to fonning a marking in the coating 100, the coating 100 must be appropriately inco ⁇ orated into the optical media 10. As previously discussed, the coating can be applied using compounding techniques, or other techniques such as spin coating. Where spin coating is used, the coating 100 is preferably cured by use of a first light. Fig. 77 depicts a first light 910 used for curing the coating 100 upon an optical media 10. In this example, the optical media 10 is part of a production line 7800.
  • Fig. 78 depicts aspects of apparatus for forming a marking in the coating 100.
  • the selective inadiation of color fonning materials in the coating 100 with a second light 920 is used to record images 620 (markings) into the optical media 10.
  • images 620 markings
  • wavelengths of UN are used to provide for the second light 920.
  • the optical media 10 is produced in a production line 2000.
  • Selective inadiation of the optical media 10 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 620 may be created. For example, increased UN exposure in one part of the coating 100 will cause greater abso ⁇ tion 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.
  • a marking 620 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 fonning layers 101).
  • a series of markings e.g., a series of markings in various color fonning layers 101.
  • the example provided in Fig. 78 including both types. That is, one marking 620 includes stars of a single color. Another marking 620, includes stripes having two distinct colors.
  • a four layer coating 100 has been applied to the optical media.
  • a first layer 401 provides supports the generation of color for the stars 620, while a second layer 402 and a third layer 403 support generation of colors for the stripes.
  • a fourth layer 404 is applied to stabilize the markings 620 applied to the optical media 10.
  • a 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 is reconfigured between marking routines, thereby providing for unique markings 620 upon each of the optical media 10 in a series.
  • image may be taken to mean a production of the marking, where the marking 620 is the manifestation (i.e., record) of the image witiiin the coating 100. It should be recognized that the two terms are closely related, and may be considered interchangeable as appropriate.
  • the marking 620 may convey any desired infonnation, in any desired format.
  • 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, refened to collectively herein as "promotional information.”
  • the content may include a decryption key for decryption of data stored in the optical media 10. Further embodiments may involve other arrangements of encryption information.
  • the infonnation 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.
  • the content may be presented, in non-limiting examples, as an image, alphanumeric characters, and other symbols, graphics, and combinations of images and symbols.
  • the content may be presented as a data code symbology (such as a bar code), and may present at least one digital watermark.
  • the marking 620 may appear at wavelengths above or below the band of visible wavelengths.
  • the marking 620 may be invisible to an unaided human observer.
  • the marking 620 is self-destructmg.
  • the marking 620 disappears when introduced to ambient environmental conditions, such as ambient lighting.
  • Use of a marking 620 that is self-destructing may be particularly useful for some applications, such as in some embodiments of authentication schemes.
  • An example of a technique for varying the contrast in a transfened 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 of the shapes or patterns provides for confrol over the visual perception of color intensity in any specific region of the marking.
  • the marking 620 begins to degrade, and may ultimately disappear, blend, or become substantially distorted, after the passage of "an initiating event.”
  • the marking 620 may begin to degrade and ultimately disappear after the optical media is introduced to ambient conditions, such as ambient light.
  • limited play optical media e.g., optical media that self destruct once exposed to ambient conditions.
  • an optical media 10 may include a symbol 620 indicative of readability. Examples of limited play optical media are disclosed in US Patent 6,434,109 "Machine-Readable Optical Disc with Reading-Inhibit Agent" issued August 13, 2002 to Rollhaus et al.
  • the marking 620 is transmissive, or substantially transmissive at wavelengths of interest.
  • the marking 620 is substantially transmissive (substantially non-interfering) at wavelengths for a readout laser for the optical media 10.
  • the marking 620 is substantially non-interfering with wavelengths of about 400 nm, about 440 nm, about 630 nm, about 650 nm and about 780 nm.
  • the coating 100 may be inspected for conformity with desired specifications.
  • aspects of the marking 620 are subject to inspection. In some embodiments, inspection is optional or omitted.
  • appropriate equipment includes NERICAM from Spectra Systems, Inc. of Buffalo, Rhode Island.
  • Another exemplary inspection system is the XIRIS PI- 1500, commercially available from Xiris Automation, of Burlington Ontario, Canada.
  • Another system for analyzing the quality of the optical media 10 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.
  • a single disk 10 was coated, cured and then tested on the CATS system. The same disk 10 was then imaged and tested on the CATS system a second time. There differences in the CATS test results were insubstantial. Data produced by the CATS system are included in Fig. 79, 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 enor in the disc 10 or the coating 100.
  • Fig. 80 provides data for a coated disk 10 that had been cured, and had not been imaged.
  • Fig. 81 provides data for a coated disk 10 that had been cured, and had been imaged.
  • Fig. 82 depicts testing results from the CATS SA3 system for a disk 10 coated on the Singulus SKYLINE DUPLEX machine.
  • 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 prefened embodiments of the overcoat layer 102, and the color forming layer 101, respectively. These prefened embodiments have been selected to best address various goals, such as the support of high throughput manufacturing. These are not limiting of the invention. Table 35
  • a mixture was produced which included a formulation inco ⁇ orated into materials used for construction of a substrate 17-1.
  • An exemplary embodiment depicting use of the mixture is depicted in Fig. 10E.
  • 10 grams of bisphenol A polycarbonate produced by Aldrich Chemical, with a molecular weight of about 64,000
  • 300 mg of triphenyl sulfonium triflate Aldrich Chemical Co ⁇ . of St. Louis, MO
  • 300 mg of PERGASCRIPT Red 6B were added to this mixture to form a clear and homogeneous solution.
  • the solution was then cast onto a polycarbonate slide and dried under a stream of hot air for about 1 minute.
  • the resulting film was clear and colorless, indicating a homogenous solid film.
  • the film developed intense red color upon exposure to a Xenon RC747C (operating at about 1.5 kW/m 2 , and producing wavelengths in the range of about 270nm to about 400 nm).
  • Unexposed regions of the film remained clear and colorless.
  • TPST or similar derivative such as t-butylphenyldiphenyl sulfonium triflate
  • PERGASCRIPT or another color fonner(s)
  • base materials such as polycarbonate material typically used to construct an optical media 8 via the melt.
  • Such techniques may be refened to as "direct compounding” or "compounding” techniques.
  • Compounding techniques when used in combination with other aspects of the teachings herein, such as the use of an over coat layer 102, and with certain fonnulations disclosed herein, provide for effective inco ⁇ oration of a coating 100 and markings 620 into a target layer. It is noted that other techniques are known for the forming of a photosensitive polycarbonate. However, such prior art techniques do not incoiporate such aspects as disclosed, and are therefore not suited for effective inco ⁇ oration of a coating 100 and markings 620 into a target layer of an optical media 10.
  • the direct inco ⁇ oration of a formulation into a target layer by compounding is also taken to mean the inco ⁇ oration of a coating 100 in the context provided for herein. More specifically, as discussed above, it is recognized that a target layer may be augmented or replaced by a coating 100. As such, the use of compounding techniques is but one non-limiting technique for application of a coating 100 in accordance with the teachings herein
  • disc molding materials include PLEXIGLAS NOD- 100 produced by Elf Atochem of North America Inc., Philadelphia, PA; a similar material is ACRYLITE DQ501 from CYRO Industries, Rockaway, NJ; Polycyclohexylethylene (PCHE), from Dow Plastics, Midland, MI; LEXAN products from General Electric of Pittsfield, MA, including OQ1040L, OQ1050 and OQ1030L; all of which are in addition to many other products.
  • PLEXIGLAS NOD- 100 produced by Elf Atochem of North America Inc., Philadelphia, PA
  • ACRYLITE DQ501 from CYRO Industries, Rockaway, NJ
  • PCHE Polycyclohexylethylene
  • LEXAN products from General Electric of Pittsfield, MA, including OQ1040L, OQ1050 and OQ1030L; all of which are in addition to many other products.

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  • Manufacturing Optical Record Carriers (AREA)
  • Optical Record Carriers And Manufacture Thereof (AREA)

Abstract

L'invention concerne des supports optiques comportant des repères non brouilleurs ou sensiblement non brouilleurs, avec possibilité de lecture des données à partir des supports optiques. Les supports optiques utilisent certaines formulations de revêtements chromogènes décrites dans le mémorandum descriptif. Des revêtements de protection employés pour améliorer les revêtements chromogènes sont également décrits, ainsi que des procédés d'incorporation desdits revêtements dans les supports optiques. Dans des modes de réalisation préférés, le repère est créé dans un revêtement photosensible appliqué sur les supports optiques, puis polymérisé à l'aide d'une première lumière. Une seconde lumière, qui présente une bande de longueurs d'onde sensiblement distincte de celle de la première lumière, est utilisée pour imprimer une image d'un repère dans le revêtement. Le revêtement est résistant à de nombreuses influences extérieures, telles que les conditions écologiques ambiantes ou l'usure physique.
PCT/US2003/035390 2002-11-05 2003-11-05 Incorporation de reperes dans des supports optiques WO2004042704A2 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP03781782A EP1558969A4 (fr) 2002-11-05 2003-11-05 Incorporation de reperes dans des supports optiques
AU2003287540A AU2003287540A1 (en) 2002-11-05 2003-11-05 Incorporation of markings in optical media

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
US42388802P 2002-11-05 2002-11-05
US60/423,888 2002-11-05
US43564702P 2002-12-20 2002-12-20
US60/435,647 2002-12-20
US48994503P 2003-07-22 2003-07-22
US60/489,945 2003-07-22

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WO2005010877A1 (fr) * 2003-07-29 2005-02-03 Koninklijke Philips Electronics N.V. Couche de contenu pour un support optique d'enregistrement
WO2005083712A1 (fr) * 2004-02-19 2005-09-09 Koninklijke Philips Electronics N.V. Etiquette formee sur le cote entree de laser d'un disque optique
WO2007010820A1 (fr) 2005-07-15 2007-01-25 Dainippon Ink And Chemicals, Inc. Composition de résine durcissable par exposition aux rayons uv et support optique d’enregistrement d’information
EP1860656A1 (fr) * 2005-03-18 2007-11-28 Fujifilm Corporation Disque optique et support d'enregistrement optique
WO2019231117A1 (fr) * 2018-06-01 2019-12-05 주식회사 엘지화학 Composition photopolymère
WO2024096359A1 (fr) * 2022-11-04 2024-05-10 주식회사 엘지화학 Support d'enregistrement d'hologramme, son procédé de fabrication et élément optique le comprenant
WO2024096360A1 (fr) * 2022-11-04 2024-05-10 주식회사 엘지화학 Composition de photopolymère, support d'enregistrement d'hologramme, son procédé de préparation et élément optique la comprenant

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Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005010877A1 (fr) * 2003-07-29 2005-02-03 Koninklijke Philips Electronics N.V. Couche de contenu pour un support optique d'enregistrement
WO2005083712A1 (fr) * 2004-02-19 2005-09-09 Koninklijke Philips Electronics N.V. Etiquette formee sur le cote entree de laser d'un disque optique
EP1860656A4 (fr) * 2005-03-18 2009-01-21 Fujifilm Corp Disque optique et support d'enregistrement optique
EP1860656A1 (fr) * 2005-03-18 2007-11-28 Fujifilm Corporation Disque optique et support d'enregistrement optique
US8334039B2 (en) 2005-07-15 2012-12-18 Dic Corporation Ultraviolet-curable resin composition and optical information recording medium
EP1906400A1 (fr) * 2005-07-15 2008-04-02 Dainippon Ink and Chemicals, Incorporated Composition de résine durcissable par exposition aux rayons uv et support optique d enregistrement d information
EP1906400A4 (fr) * 2005-07-15 2010-08-04 Dainippon Ink & Chemicals Composition de résine durcissable par exposition aux rayons uv et support optique d'enregistrement d'information
CN101218643B (zh) * 2005-07-15 2012-02-01 大日本油墨化学工业株式会社 紫外线固化型树脂组合物和光信息记录介质
WO2007010820A1 (fr) 2005-07-15 2007-01-25 Dainippon Ink And Chemicals, Inc. Composition de résine durcissable par exposition aux rayons uv et support optique d’enregistrement d’information
TWI419929B (zh) * 2005-07-15 2013-12-21 Dainippon Ink & Chemicals 紫外線硬化型樹脂組成物及光資訊記錄媒體
WO2019231117A1 (fr) * 2018-06-01 2019-12-05 주식회사 엘지화학 Composition photopolymère
KR20190137383A (ko) * 2018-06-01 2019-12-11 주식회사 엘지화학 염료 화합물 및 포토폴리머 조성물
KR102228538B1 (ko) * 2018-06-01 2021-03-15 주식회사 엘지화학 염료 화합물 및 포토폴리머 조성물
EP3733784A4 (fr) * 2018-06-01 2021-05-12 Lg Chem, Ltd. Composition photopolymère
US12001141B2 (en) 2018-06-01 2024-06-04 Lg Chem Ltd. Photopolymer composition
WO2024096359A1 (fr) * 2022-11-04 2024-05-10 주식회사 엘지화학 Support d'enregistrement d'hologramme, son procédé de fabrication et élément optique le comprenant
WO2024096360A1 (fr) * 2022-11-04 2024-05-10 주식회사 엘지화학 Composition de photopolymère, support d'enregistrement d'hologramme, son procédé de préparation et élément optique la comprenant

Also Published As

Publication number Publication date
WO2004042704A3 (fr) 2004-08-12
EP1558969A2 (fr) 2005-08-03
AU2003287540A8 (en) 2004-06-07
EP1558969A4 (fr) 2009-03-25
AU2003287540A1 (en) 2004-06-07

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