EP0728073B1 - Transfer printing medium - Google Patents

Transfer printing medium Download PDF

Info

Publication number
EP0728073B1
EP0728073B1 EP94930625A EP94930625A EP0728073B1 EP 0728073 B1 EP0728073 B1 EP 0728073B1 EP 94930625 A EP94930625 A EP 94930625A EP 94930625 A EP94930625 A EP 94930625A EP 0728073 B1 EP0728073 B1 EP 0728073B1
Authority
EP
European Patent Office
Prior art keywords
curable
ink
prepolymer
transfer printing
printing medium
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP94930625A
Other languages
German (de)
French (fr)
Other versions
EP0728073A1 (en
Inventor
Frank A. Meneghini
John S. Deeken
John J. Drake
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Markem Imaje Corp
Original Assignee
Markem Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Markem Corp filed Critical Markem Corp
Publication of EP0728073A1 publication Critical patent/EP0728073A1/en
Application granted granted Critical
Publication of EP0728073B1 publication Critical patent/EP0728073B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
    • B41M5/42—Intermediate, backcoat, or covering layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/382—Contact thermal transfer or sublimation processes
    • B41M5/38207—Contact thermal transfer or sublimation processes characterised by aspects not provided for in groups B41M5/385 - B41M5/395
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/382—Contact thermal transfer or sublimation processes
    • B41M5/392—Additives, other than colour forming substances, dyes or pigments, e.g. sensitisers, transfer promoting agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M7/00—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock
    • B41M7/009—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock using thermal means, e.g. infrared radiation, heat
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
    • B41M5/46—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography characterised by the light-to-heat converting means; characterised by the heat or radiation filtering or absorbing means or layers
    • B41M5/465—Infrared radiation-absorbing materials, e.g. dyes, metals, silicates, C black

Definitions

  • This invention relates to laser-induced transfer printing.
  • irradiation of an ink-bearing carrier with laser light causes the ink to transfer from the carrier to a surface, e.g., the surface of a microelectronic device, audio cassette, computer diskette, or syringe body.
  • a surface e.g., the surface of a microelectronic device, audio cassette, computer diskette, or syringe body.
  • JP-A-03/244 588 describes a transfer recording material that includes an image-forming element containing a compound containing an ethylenic unsaturated double bond, a photopolyemrization initiator, and a coloring agent.
  • the image-forming element includes a filler, such as carbon black.
  • the invention provides a laser-induced transfer printing method comprising the steps of
  • the invention also provides a transfer printing medium comprising a carrier to which is applied a curable laser-transferrable ink having one or more layers, said ink comprising:
  • Preferred embodiments correspond to claims 12 to 23.
  • the transfer medium is capable of converting laser energy to heat.
  • the ink includes (a) at least one colorant; (b) at least one polymerization initiator; and (c) at least one curable prepolymer.
  • colorant it is meant any additive that imparts color to the ink, including the colors white and black. Colorants include both dyes and pigments, as well as metallized coatings.
  • prepolymer it is meant any species capable of being polymerized following either thermal or photochemical initiation to form a polymer.
  • the ink transfers to a surface of interest and cures in one step upon application of laser energy.
  • at least one of the polymerization initiators is a thermal polymerization initiator and at least one of the prepolymers is thermally curable.
  • at least one of the polymerization initiators is a photoinitiator and at least one of the prepolymers is photochemically curable.
  • One example of a preferred prepolymer is an epoxy-functionalized prepolymer.
  • a second example is an epoxy-functionalized prepolymer combined with a vinyl ether-functionalized prepolymer.
  • a third example is an epoxy-functionalized prepolymer combined with an acrylate-functionalized prepolymer.
  • a fourth example includes the acrylate-functionalized prepolymers themselves.
  • a fifth example is a blocked isocyanate-functionalized prepolymer and a sixth example is a blend of a vinyl ether-functionalized prepolymer and a maleate- or maleimide-functionalized prepolymer.
  • At least one of the ink layers may be a curable size coat that includes a polymerization initiator and a curable prepolymer.
  • the size coat is used in combination with a color coat layer.
  • the color coat is non-curable and includes a colorant and a thermoplastic film-forming resin.
  • the color coat is curable and includes a colorant, a polymerization initiator, and a curable prepolymer.
  • the polymerization initiators and prepolymers found in the respective layers may be the same as, or different from, each other.
  • the invention features a laser-induced transfer printing method using the above-described transfer printing medium.
  • the method includes the steps of irradiating the particular transfer printing medium with laser light of a predetermined wavelength to transfer the ink from the carrier to a surface of interest, and curing the ink to adhere the ink to the surface of interest.
  • the transfer and cure of the ink may be effected in a single step through irradiation with said laser light. Cure may also be effected in a separate step subsequent to transfer.
  • the invention provides transfer printing media featuring curable inks that adhere well to the surface on which they are deposited following laser irradiation.
  • the inks transfer cleanly from the supporting carrier and cure rapidly; in some cases, transfer and cure are effected in a single step. It is not necessary to add a separate self-oxidizing material such as nitrocellulose in order to effect transfer.
  • a separate self-oxidizing material such as nitrocellulose in order to effect transfer.
  • the ability to use non-curable layers e.g., non-curable color coats
  • curable layers e.g., curable size coats
  • the invention features a transfer printing medium capable of converting laser energy to heat in which a curable laser-transferrable ink having one or more layers is deposited on a carrier.
  • the carrier must have sufficiently low surface energy to permit transfer of the ink. It also must not melt or otherwise deform upon laser irradiation.
  • suitable carriers include flexible plastic films such as polyethylene, polypropylene, and polyester.
  • the transfer medium is capable of converting laser energy to heat to promote transfer of the ink from the carrier to the surface of interest.
  • one or more thermal convertors different from said colorant and not carbon black are incorporated into the carrier, the ink, or both.
  • the thermal convertors different from said colorant and not carbon black may be separate additives or may be part of the prepolymer.
  • the amount of convertor ranges from about 0.25 to about 30% by weight (based upon the total solids content of the ink).
  • the particular convertor is selected based upon the particular laser energy used for irradiation.
  • the preferred convertors are, polyethylene glycol (e.g., PEG 3000 commercially available from Union Carbide), talc (e.g., Nytal® 400 commercially available from R.T. Vanderbilt), and PPZ, a phosphotriazine commercially available from Idemitsu Petrochemicals Co. Ltd; PPZ may also function as a prepolymer.
  • the preferred convertors are IR99, IRA 980, and IR165, all of which are proprietary dyes commercially available from Glendale Protective Technologies, IR dye 14,617 (a proprietary dye commercially available from Eastman Kodak), and Projet® 900NP (a proprietary dye commercially available from ICI).
  • the preferred convertors are IR dye 14,617 and IRA 980.
  • the inks may have one or more layers, with particular ingredients (e.g., prepolymer, polymerization initiator, etc.) being present in any of the layers.
  • a one layer ink referred to here as a "one-pass” coating
  • a two layer ink referred to here as a "two-pass” coating
  • a color coat which may be curable or non-curable
  • the inks are curable, adhesion upon transfer to a surface of interest is improved.
  • the advantage of the size coat (which is transferred with the color coat upon laser irradiation) is that adhesion is further enhanced, thereby making it possible to use even a non-curable color coat.
  • the inks contain one or more curable prepolymers, with the total amount of curable prepolymer ranging from 25 to 95% by weight (based upon the total solids content of the ink).
  • Curable prepolymers useful in the invention have two or more functional groups available for crosslinking (which occurs either simultaneously with transfer upon application of laser radiation or following laser irradiation in a separate thermal or photochemical cure step).
  • One class of suitable curable prepolymers includes epoxy-functionalized prepolymers such as bisphenol A diglycidyl ether (commercially available from Shell Oil under the designation Epon® 001) and epoxy-functionalized novolac resins (e.g., Epon® 164 commercially available from Shell Oil). Lower molecular epoxides such as UVR6110 (a liquid diepoxide commercially available from Union Carbide) may be added as well.
  • Epon® 001 bisphenol A diglycidyl ether
  • Epon® 164 commercially available from Shell Oil
  • Lower molecular epoxides such as UVR6110 (a liquid diepoxide commercially available from Union Carbide) may be added as well.
  • a second class of suitable curable prepolymers includes these epoxy-functionalized prepolymers in combination with one or more vinyl ether-functionalized prepolymers which co-cure with the epoxy-functionalized prepolymers.
  • suitable vinyl ether-functionalized prepolymers include bisphenol A-divinyl ether adduct; 2,4-toluene diisocyanate/hydroxybutyl vinyl ether adduct; cyclohexyl divinyl ether commercially available from GAF or ISI Products; vinyl ethyl ether, vinyl isobutyl ether, vinyl octadecyl ether, polyethylene glycol divinyl ether, polytetrahydrofuran/350/divinyl ether, and trimethylol propane trivinyl ether, all of which are commercially available from BASF; Rapi/cure® divinyl ether/3, Rapi/cure® cyclohexyl vinyl ether, Rapi/cure® PEPC, and
  • a third class of suitable curable prepolymers includes the above-described epoxy-functionalized prepolymers in combination with one or more acrylate-functionalized prepolymers.
  • acrylate-functionalized prepolymers include RDX 29522 and Ebecryl® 639 (both of which are commercially available from Radcure); Sartomer® 351 (commercially available from Sartomer); and NR440 (commercially available from Zeneca Resins).
  • a fourth class of suitable curable prepolymers includes the acrylate-functionalized prepolymers themselves without the epoxy-functionalized prepolymers.
  • a fifth class of suitable curable prepolymers includes blocked isocyanate-functionalized prepolymers.
  • Examples include B1299 (commercially available from Huls) and BL4165A (commercially available from Miles).
  • a sixth class of suitable curable prepolymers includes the above-described vinyl ether-functionalized prepolymers in combination with maleate- or maleimide-functionalized prepolymers.
  • maleate-functionalized prepolymers include 89-8902 (commercially available from Cargil Products); and Astrocure® 78HV and Astrocure® 78LV (both of which are commercially available from Zircon).
  • maleimide-functionalized prepolymers include BMI/S/M/20/TDA (commercially available from Mitsui Toatsu Chemical, Inc.
  • Non-curable layers may be used in combination with one or more curable layers.
  • a non-curable color coat may be combined with an overlying curable size coat.
  • Suitable non-curable resins are thermoplastic film-forming resins. Examples include acrylic resins such as Rhoplex® B85 (an acrylic dispersion commercially available from Rohm & Haas) and Amsco® 3011 (an acrylic dispersion available from Rohm & Haas); urethane resins such as QW-16 (a urethane dispersion useful as a film-former that is commercially available from K.J. Quinn); phenoxy resins such as PKHW 35 (commercially available from Union Carbide); and combinations thereof.
  • the amount of non-curable prepolymer in the ink ranges from about 15 to about 35% by weight (based upon the total solids content of the ink).
  • the inks also contain a polymerization initiator in an amount ranging from about 0.1 to 5% by weight (based upon the total solids content of the ink).
  • the initiator (which typically is a free radical or cationic initiator) may be a photochemical initiator or a thermal initiator; in some cases, the same initiator can act as both a thermal and a photochemical initiator.
  • layers containing photochemical initiators may be combined with layers containing thermal initiators.
  • some initiators may be used in conjunction with accelerators such as benzpinacol, copper(II)salts (e.g., copper benzoate), and hexaphenylethane.
  • thermal initiators In the case of thermal initiators, the initiator must exhibit good stability at ambient temperature to prevent premature curing of the prepolymer. In addition, the initiation temperature must be within the range achievable by laser irradiation.
  • suitable thermal initiators for cationic initiation include aryl sulfonium salts (e.g., the salts described in WO90/11303, hereby incorporated by reference); aryl iodonium salts (e.g., UVE 9310 and U 479, both of which are commercially available from General Electric); and ammonium salts (e.g., FC520, commercially available from 3M).
  • thermal initiators for free radical initiation include the class of compounds leading to peroxy radicals, e.g., hydroperoxides, peroxyesters, and peroxyketals; representative compounds are commercially available from Elf-Atochem. Also suitable for free radical initiation are azo polymerization initiators commercially available from Wako.
  • the initiator In the case of photochemical initiators, the initiator must also exhibit good stability at ambient temperature to prevent premature curing of the prepolymer. In addition, it must exhibit absorption maxima in regions of the electromagnetic spectrum different from the regions in which the colorant exhibits absorption maxima.
  • suitable photochemical initiators for cationic initiation include aryl sulfonium salts (e.g., UVI 6974 commercially available from Union Carbide) and aryl iodonium salts (e.g., UVE 9310 and U 479, both of which are commercially available from General Electric).
  • Another example of a suitable initiator for cationic initiation is hydroxy naphthyl imide sulfonate ester.
  • Suitable photochemical initiators for free radical initiation include CPTX and ITX (both commercially available from Ciba-Geigy), each of which is combined with methyl diethanolamine (commercially available from Aldrich Chemical Co.; lucerin® TPO (commercially available from BASF) combined with methyl diethanolamine; Darcure® 4265 (commercially available from Ciba Geigy), and Irgacure® 369 combined with ITX.
  • the ink contains one or more colorants, which may be dyes, pigments, or metallized coatings (e.g., an aluminized coating).
  • the colorant is present in an amount ranging from about 35 to 65% by weight (based upon the total solids content of the ink). The particular colorant is chosen based upon the color desired on the final printed surface.
  • Suitable colorants include pigments such as talc, TiO 2 (white), phthalogreen (GT-674-D), chrome green oxide (6099), ultramarine blue (RS-9), black oxide (BK-5099D), Kroma red (7097), and Novaperm yellow (HR-70), and dyes such as dynonicidine (2915) and Dianell orange, as well as the aforementioned metallized coatings.
  • a sensitizer may be added in an amount ranging from about 0.5 to 8% by weight (based upon the total solids content of the ink) to extend the irradiating wavelength for photoinitiation into the visible region.
  • Such sensitizers are useful, for example, where the formulation contains large amounts of TiO 2 pigment which absorbs light below 400 nm and thus competes with the initiator.
  • suitable sensitizers all of which are commercially available from Aldrich Chemical Co., include perylene, rubrene, phenothiazine, anthracene derivatives, and thioxanthones, as well as lucerin TPO (commercially available from BASF).
  • ingredients which may be added to the inks to improve the coatability, printability, print performance, and durability of the inks include various surfactants, dispersing agents, and polymer dispersions. The amount of each ingredient is selected based upon the desired properties.
  • suitable surfactants which may be anionic, cationic, or nonionic
  • suitable dispersing agents include polyacrylate salts such as Daxad® 30, a 30% aqueous solution of polysodiumacrylate commercially available from W.R. Grace.
  • suitable dispersions include Shamrock® 375 and Aquacer® 355, both of which are polyethylene wax dispersions commercially available from Diamond Shamrock.
  • the transfer medium according to the invention is prepared by combining the ink ingredients in an aqueous or organic solvent (with aqueous solvents being preferred), and then applying the resulting composition to the carrier. If a size coat is used, it is applied on top of the color coat. To facilitate coating, the total solids content of the ink is adjusted to be between 10 and 50% by weight of the ink.
  • the coated carrier is then irradiated with laser light to transfer the ink from the carrier to a desired surface, e.g., the surface of a semiconductor device.
  • Suitable lasers include CO 2 lasers (irradiation wavelength equals 10.6 ⁇ m), Nd:YAG lasers (irradiation wavelength equals 1.06 ⁇ m), and diode lasers (irradiation wavelength equals, e.g., 0.9 ⁇ m).
  • CO 2 lasers irradiation wavelength equals 10.6 ⁇ m
  • Nd:YAG lasers irradiation wavelength equals 1.06 ⁇ m
  • diode lasers irradiation wavelength equals, e.g., 0.9 ⁇ m.
  • the particular irradiation wavelength, power, and time of application parameters are selected to ensure clean transfer.
  • This example describes the preparation of a transfer medium having one-pass, thermally curable, cationically initiated, ink.
  • This example describes the preparation of a transfer medium having a two-pass, cationically initiated ink in which both the color coat and the size coat are photochemically curable.
  • Methyl ethyl ketone was added to adjust the total solids content of the size coat to 25% by weight, after which the resulting size coat was applied on top of the color coat using a #5 mayer rod.
  • the coated surface of the film was then placed in intimate contact with the surface of a molded semiconductor device.
  • a CO 2 laser was directed through the uncoated side of the carrier film to transfer the ink (color coat plus size coat) to the surface of the semiconductor device.
  • the laser dwelled on each addressed pixel for 20 ⁇ s.
  • the power output of the laser at the point of contact with the coated film was 14.5 W.
  • the device bearing the transferred image was then cured (5 minutes. at a 150°C preheat, followed by a 3.6 sec exposure to UV radiation).
  • the resulting cured printed image was found to be resistant to treatment with 1,1,1-trichloroethane (3 minutes. soak, 10 brush strokes, cycled 3 times).
  • This example describes the preparation of a transfer medium having a two-pass, cationically curable ink in which the color coat is non-curable and the size coat is thermally curable.
  • Enough ammonium hydroxide was added to adjust the pH to 8.5, after which the resulting color coat was applied to a 30,5 ⁇ m (1.2 mil) thick polypropylene carrier film at a coat weight of 69 mg/m 2 .
  • Methyl ethyl ketone was added to adjust the total solids content of the size coat to 25% by weight, after which the resulting size coat was applied on top of the color coat using a #5 mayer rod.
  • the coated surface of the film was then placed in intimate contact with the surface of a molded semiconductor device.
  • a Nd:YAG laser was directed through the uncoated side of the carrier film to transfer the ink (color coat plus size coat) to the surface of the semiconductor device.
  • the laser dwelled on each addressed pixel for 18 ⁇ s.
  • the power output of the laser at the point of contact with the coated film was 4.5 W.
  • the device bearing the transferred image was then cured (4 minutes. at 175°C).
  • the resulting cured printed image was found to be resistant to treatment with 1,1,1-trichloroethane (3 minutes. soak, 10 brush strokes, cycled 3 times).
  • This example describes the preparation of a transfer medium having a one-pass, thermally curable, cationically initiated ink in which transfer and cure takes place in a single step upon laser irradiation.
  • Methyl ethyl ketone was added to adjust the total solids content to 50% by weight, after which the resulting ink was coated onto a 30,5 ⁇ m (1.2 mil) thick polypropylene carrier film using a #10 mayer rod. The coated surface of the film was then placed in intimate contact with a glass slide. Next, a CO 2 laser was directed through the uncoated side of the carrier film to transfer the ink to the surface of the glass slide. The laser dwelled on each addressed pixel for 80 ⁇ s. After addressing, the transferred coating was removed form the glass slide and analyzed by differential scanning calorimetry. There was no evidence of residual heat of reaction, indicating that the transferred coating had cured during the transfer step.
  • This example describes the preparation of a transfer medium having a two-pass, free radical-initiated ink in which both the color coat and the size coat are photochemically curable.
  • the coated surface of the film was then placed in intimate contact with the surface of a molded semiconductor device.
  • a CO 2 laser was directed through the uncoated side of the carrier film to transfer the ink (color coat plus size coat) to the surface of the semiconductor device.
  • the laser dwelled on each addressed pixel for 20 ⁇ s.
  • the power output of the laser at the point of contact with the coated film was 14.5 W.
  • the device bearing the transferred image was then cured (5 minutes. at a 100°C preheat, followed by passage through a UV fusion oven equipped with an H bulb at a speed of 42,3 mm/s (100 inches per minute).
  • the resulting cured printed image was found to be resistant to treatment with 1,1,1-trichloroethane (3 minutes. soak, 10 brush strokes, cycled 3 times).

Landscapes

  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Thermal Sciences (AREA)
  • Toxicology (AREA)
  • Thermal Transfer Or Thermal Recording In General (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Printing Plates And Materials Therefor (AREA)
  • Laminated Bodies (AREA)
  • Paper (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

A transfer printing medium that includes a carrier to which is applied a curable laser-transferrable ink having one or more layers. The transfer medium is capable of converting laser energy to heat. The ink includes: (a) at least one colorant; (b) at least one polymerization initiator; and (c) at least one curable prepolymer.

Description

Background of the Invention
This invention relates to laser-induced transfer printing.
In laser-induced transfer printing, irradiation of an ink-bearing carrier with laser light causes the ink to transfer from the carrier to a surface, e.g., the surface of a microelectronic device, audio cassette, computer diskette, or syringe body. By manipulating the scanning parameters of the laser beam, the ink can be deposited in a programmed pattern.
JP-A-03/244 588 describes a transfer recording material that includes an image-forming element containing a compound containing an ethylenic unsaturated double bond, a photopolyemrization initiator, and a coloring agent. The image-forming element includes a filler, such as carbon black.
Summary of the invention.
The invention provides a laser-induced transfer printing method comprising the steps of
  • (a) providing a transfer printing medium capable of converting laser energy to heat comprising a carrier to which is applied a curable laser-transferrable ink; and
  • (b) irradiating said medium with laser light of a predetermined wavelength,
    whereupon said laser light transfers said ink to a surface of interest and cures said ink to adhere said ink to the surface of interest.
    • Preferred embodiments correspond to claims 2 to 10.
    The invention also provides a transfer printing medium comprising a carrier to which is applied a curable laser-transferrable ink having one or more layers, said ink comprising:
  • (a) at least one colorant;
  • (b) at least one polymerization initiator;
  • (c) at least one curable prepolymer; and
  • (d) at least one thermal convertor different from said colorant with the proviso that said thermal convertor is not carbon black,
    said transfer medium being capable of converting laser energy to heat.
    • Preferred embodiments correspond to claims 12 to 23.
    The transfer medium is capable of converting laser energy to heat. The ink includes (a) at least one colorant; (b) at least one polymerization initiator; and (c) at least one curable prepolymer. By "colorant" it is meant any additive that imparts color to the ink, including the colors white and black. Colorants include both dyes and pigments, as well as metallized coatings. By "prepolymer" it is meant any species capable of being polymerized following either thermal or photochemical initiation to form a polymer.
    In preferred embodiments, the ink transfers to a surface of interest and cures in one step upon application of laser energy. In one preferred embodiment, at least one of the polymerization initiators is a thermal polymerization initiator and at least one of the prepolymers is thermally curable. In another preferred embodiment, at least one of the polymerization initiators is a photoinitiator and at least one of the prepolymers is photochemically curable.
    One example of a preferred prepolymer is an epoxy-functionalized prepolymer. A second example is an epoxy-functionalized prepolymer combined with a vinyl ether-functionalized prepolymer. A third example is an epoxy-functionalized prepolymer combined with an acrylate-functionalized prepolymer. A fourth example includes the acrylate-functionalized prepolymers themselves. A fifth example is a blocked isocyanate-functionalized prepolymer and a sixth example is a blend of a vinyl ether-functionalized prepolymer and a maleate- or maleimide-functionalized prepolymer.
    At least one of the ink layers may be a curable size coat that includes a polymerization initiator and a curable prepolymer. The size coat is used in combination with a color coat layer. In one preferred embodiment, the color coat is non-curable and includes a colorant and a thermoplastic film-forming resin. In another preferred embodiment, the color coat is curable and includes a colorant, a polymerization initiator, and a curable prepolymer. In the case of curable color coats used with curable size coats, the polymerization initiators and prepolymers found in the respective layers may be the same as, or different from, each other.
    In a second aspect, the invention features a laser-induced transfer printing method using the above-described transfer printing medium. The method includes the steps of irradiating the particular transfer printing medium with laser light of a predetermined wavelength to transfer the ink from the carrier to a surface of interest, and curing the ink to adhere the ink to the surface of interest. The transfer and cure of the ink may be effected in a single step through irradiation with said laser light. Cure may also be effected in a separate step subsequent to transfer.
    The invention provides transfer printing media featuring curable inks that adhere well to the surface on which they are deposited following laser irradiation. The inks transfer cleanly from the supporting carrier and cure rapidly; in some cases, transfer and cure are effected in a single step. It is not necessary to add a separate self-oxidizing material such as nitrocellulose in order to effect transfer. In addition, the ability to use non-curable layers (e.g., non-curable color coats) in combination with curable layers (e.g., curable size coats) expands the types of materials that can be used for the inks, enabling the properties of the inks to be adjusted as needed for a particular application.
    Other features and advantages of the invention will be apparent from the following description of the preferred embodiments thereof, and from the claims.
    Description of the Preferred Embodiments
    The invention features a transfer printing medium capable of converting laser energy to heat in which a curable laser-transferrable ink having one or more layers is deposited on a carrier. The carrier must have sufficiently low surface energy to permit transfer of the ink. It also must not melt or otherwise deform upon laser irradiation. Examples of suitable carriers include flexible plastic films such as polyethylene, polypropylene, and polyester.
    The transfer medium is capable of converting laser energy to heat to promote transfer of the ink from the carrier to the surface of interest. To this end, one or more thermal convertors different from said colorant and not carbon black are incorporated into the carrier, the ink, or both. The thermal convertors different from said colorant and not carbon black may be separate additives or may be part of the prepolymer.
    In the case of separately added convertors included in the ink, the amount of convertor ranges from about 0.25 to about 30% by weight (based upon the total solids content of the ink). The particular convertor is selected based upon the particular laser energy used for irradiation. In the case of CO2 lasers, the preferred convertors are, polyethylene glycol (e.g., PEG 3000 commercially available from Union Carbide), talc (e.g., Nytal® 400 commercially available from R.T. Vanderbilt), and PPZ, a phosphotriazine commercially available from Idemitsu Petrochemicals Co. Ltd; PPZ may also function as a prepolymer. In the case of Nd:YAG lasers, the preferred convertors are IR99, IRA 980, and IR165, all of which are proprietary dyes commercially available from Glendale Protective Technologies, IR dye 14,617 (a proprietary dye commercially available from Eastman Kodak), and Projet® 900NP (a proprietary dye commercially available from ICI). In the case of diode lasers, the preferred convertors are IR dye 14,617 and IRA 980.
    The inks may have one or more layers, with particular ingredients (e.g., prepolymer, polymerization initiator, etc.) being present in any of the layers. One example of ink is a one layer ink (referred to here as a "one-pass" coating) having a curable color coat that includes, in a single layer, a curable prepolymer, a polymerization initiator, and a colorant. Another example is a two layer ink (referred to here as a "two-pass" coating) having a color coat (which may be curable or non-curable) in combination with an overlying curable size coat that includes a curable prepolymer and a polymerization initiator.
    Because the inks are curable, adhesion upon transfer to a surface of interest is improved. The advantage of the size coat (which is transferred with the color coat upon laser irradiation) is that adhesion is further enhanced, thereby making it possible to use even a non-curable color coat.
    The inks contain one or more curable prepolymers, with the total amount of curable prepolymer ranging from 25 to 95% by weight (based upon the total solids content of the ink). Curable prepolymers useful in the invention have two or more functional groups available for crosslinking (which occurs either simultaneously with transfer upon application of laser radiation or following laser irradiation in a separate thermal or photochemical cure step).
    One class of suitable curable prepolymers includes epoxy-functionalized prepolymers such as bisphenol A diglycidyl ether (commercially available from Shell Oil under the designation Epon® 001) and epoxy-functionalized novolac resins (e.g., Epon® 164 commercially available from Shell Oil). Lower molecular epoxides such as UVR6110 (a liquid diepoxide commercially available from Union Carbide) may be added as well.
    A second class of suitable curable prepolymers includes these epoxy-functionalized prepolymers in combination with one or more vinyl ether-functionalized prepolymers which co-cure with the epoxy-functionalized prepolymers. Examples of suitable vinyl ether-functionalized prepolymers include bisphenol A-divinyl ether adduct; 2,4-toluene diisocyanate/hydroxybutyl vinyl ether adduct; cyclohexyl divinyl ether commercially available from GAF or ISI Products; vinyl ethyl ether, vinyl isobutyl ether, vinyl octadecyl ether, polyethylene glycol divinyl ether, polytetrahydrofuran/350/divinyl ether, and trimethylol propane trivinyl ether, all of which are commercially available from BASF; Rapi/cure® divinyl ether/3, Rapi/cure® cyclohexyl vinyl ether, Rapi/cure® PEPC, and Rapi/cure® hydroxy butyl vinyl ether, all of which are commercially available from ISP; and Vectomers® 2010, 2031, 2032, 4010, 4020, and 4030, all of which are commercially available from Allied-Signal.
    A third class of suitable curable prepolymers includes the above-described epoxy-functionalized prepolymers in combination with one or more acrylate-functionalized prepolymers. Examples of acrylate-functionalized prepolymers include RDX 29522 and Ebecryl® 639 (both of which are commercially available from Radcure); Sartomer® 351 (commercially available from Sartomer); and NR440 (commercially available from Zeneca Resins).
    A fourth class of suitable curable prepolymers includes the acrylate-functionalized prepolymers themselves without the epoxy-functionalized prepolymers.
    A fifth class of suitable curable prepolymers includes blocked isocyanate-functionalized prepolymers. Examples include B1299 (commercially available from Huls) and BL4165A (commercially available from Miles).
    A sixth class of suitable curable prepolymers includes the above-described vinyl ether-functionalized prepolymers in combination with maleate- or maleimide-functionalized prepolymers. Examples of maleate-functionalized prepolymers include 89-8902 (commercially available from Cargil Products); and Astrocure® 78HV and Astrocure® 78LV (both of which are commercially available from Zircon). Examples of maleimide-functionalized prepolymers include BMI/S/M/20/TDA (commercially available from Mitsui Toatsu Chemical, Inc.
    One or more non-curable layers may be used in combination with one or more curable layers. For example, a non-curable color coat may be combined with an overlying curable size coat. Suitable non-curable resins are thermoplastic film-forming resins. Examples include acrylic resins such as Rhoplex® B85 (an acrylic dispersion commercially available from Rohm & Haas) and Amsco® 3011 (an acrylic dispersion available from Rohm & Haas); urethane resins such as QW-16 (a urethane dispersion useful as a film-former that is commercially available from K.J. Quinn); phenoxy resins such as PKHW 35 (commercially available from Union Carbide); and combinations thereof. The amount of non-curable prepolymer in the ink ranges from about 15 to about 35% by weight (based upon the total solids content of the ink).
    The inks also contain a polymerization initiator in an amount ranging from about 0.1 to 5% by weight (based upon the total solids content of the ink). The initiator (which typically is a free radical or cationic initiator) may be a photochemical initiator or a thermal initiator; in some cases, the same initiator can act as both a thermal and a photochemical initiator. In the case of multi-layer inks containing multiple curable layers, layers containing photochemical initiators may be combined with layers containing thermal initiators. In addition, some initiators may be used in conjunction with accelerators such as benzpinacol, copper(II)salts (e.g., copper benzoate), and hexaphenylethane.
    In the case of thermal initiators, the initiator must exhibit good stability at ambient temperature to prevent premature curing of the prepolymer. In addition, the initiation temperature must be within the range achievable by laser irradiation. Examples of suitable thermal initiators for cationic initiation include aryl sulfonium salts (e.g., the salts described in WO90/11303, hereby incorporated by reference); aryl iodonium salts (e.g., UVE 9310 and U 479, both of which are commercially available from General Electric); and ammonium salts (e.g., FC520, commercially available from 3M). Examples of suitable thermal initiators for free radical initiation include the class of compounds leading to peroxy radicals, e.g., hydroperoxides, peroxyesters, and peroxyketals; representative compounds are commercially available from Elf-Atochem. Also suitable for free radical initiation are azo polymerization initiators commercially available from Wako.
    In the case of photochemical initiators, the initiator must also exhibit good stability at ambient temperature to prevent premature curing of the prepolymer. In addition, it must exhibit absorption maxima in regions of the electromagnetic spectrum different from the regions in which the colorant exhibits absorption maxima. Examples of suitable photochemical initiators for cationic initiation include aryl sulfonium salts (e.g., UVI 6974 commercially available from Union Carbide) and aryl iodonium salts (e.g., UVE 9310 and U 479, both of which are commercially available from General Electric). Another example of a suitable initiator for cationic initiation is hydroxy naphthyl imide sulfonate ester. Examples of suitable photochemical initiators for free radical initiation include CPTX and ITX (both commercially available from Ciba-Geigy), each of which is combined with methyl diethanolamine (commercially available from Aldrich Chemical Co.; lucerin® TPO (commercially available from BASF) combined with methyl diethanolamine; Darcure® 4265 (commercially available from Ciba Geigy), and Irgacure® 369 combined with ITX.
    The ink contains one or more colorants, which may be dyes, pigments, or metallized coatings (e.g., an aluminized coating). In the case of dyes and pigments, the colorant is present in an amount ranging from about 35 to 65% by weight (based upon the total solids content of the ink). The particular colorant is chosen based upon the color desired on the final printed surface. Examples of suitable colorants include pigments such as talc, TiO2 (white), phthalogreen (GT-674-D), chrome green oxide (6099), ultramarine blue (RS-9), black oxide (BK-5099D), Kroma red (7097), and Novaperm yellow (HR-70), and dyes such as dynonicidine (2915) and Dianell orange, as well as the aforementioned metallized coatings.
    In the case of inks containing photocurable prepolymers, a sensitizer may be added in an amount ranging from about 0.5 to 8% by weight (based upon the total solids content of the ink) to extend the irradiating wavelength for photoinitiation into the visible region. Such sensitizers are useful, for example, where the formulation contains large amounts of TiO2 pigment which absorbs light below 400 nm and thus competes with the initiator. Examples of suitable sensitizers, all of which are commercially available from Aldrich Chemical Co., include perylene, rubrene, phenothiazine, anthracene derivatives, and thioxanthones, as well as lucerin TPO (commercially available from BASF).
    Other ingredients which may be added to the inks to improve the coatability, printability, print performance, and durability of the inks include various surfactants, dispersing agents, and polymer dispersions. The amount of each ingredient is selected based upon the desired properties. Examples of suitable surfactants (which may be anionic, cationic, or nonionic) include Triton® X-100 (an aryl ethoxylate commercially available from Rohm & Haas) and FC 430 (a fluoroaliphatic polymeric ester available from 3M). Examples of suitable dispersing agents include polyacrylate salts such as Daxad® 30, a 30% aqueous solution of polysodiumacrylate commercially available from W.R. Grace. Examples of suitable dispersions include Shamrock® 375 and Aquacer® 355, both of which are polyethylene wax dispersions commercially available from Diamond Shamrock.
    The transfer medium according to the invention is prepared by combining the ink ingredients in an aqueous or organic solvent (with aqueous solvents being preferred), and then applying the resulting composition to the carrier. If a size coat is used, it is applied on top of the color coat. To facilitate coating, the total solids content of the ink is adjusted to be between 10 and 50% by weight of the ink. The coated carrier is then irradiated with laser light to transfer the ink from the carrier to a desired surface, e.g., the surface of a semiconductor device. Suitable lasers include CO2 lasers (irradiation wavelength equals 10.6µm), Nd:YAG lasers (irradiation wavelength equals 1.06µm), and diode lasers (irradiation wavelength equals, e.g., 0.9µm). The particular irradiation wavelength, power, and time of application parameters are selected to ensure clean transfer.
    In the case of some inks, laser irradiation both transfers and cures the ink simultaneously. With other inks, a separate thermal or photochemical cure is effected following transfer. The cure conditions are selected based upon the particular prepolymers and initiators used in the formulation.
    The invention will now be further described by way of the following examples.
    Example 1
    This example describes the preparation of a transfer medium having one-pass, thermally curable, cationically initiated, ink.
    The following ingredients were combined to form a laser-transferrable ink (all amounts in weight percent):
    TiO2 55.0
    Bisphenol A-DVE adduct 13.0
    35201 24.8
    PEG 3000 5.0
    Aryl sulfonium salt 2.0
    Triton® X-100 0.2
    Water was added to adjust the total solids content to 35% by weight, after which the resulting ink was coated onto 30,5 µm (1.2 mil) thick polypropylene carrier film using a #15 mayer rod. The coated surface of the film was then placed in intimate contact with the surface of a molded semiconductor device. Next, a CO2 laser was directed through the uncoated side of the carrier film to transfer the ink to the surface of the semiconductor device. The laser dwelled on each addressed pixel for 16 µs. The power output of the laser at the point of contact with the coated film was 14.5 W. The device bearing the transferred image was then placed in a forced hot air oven for 30 minutes. at 175°C to cure the ink. After curing, the transferred image was found to be resistant to treatment with 1,1,1-trichloroethane (3 minutes. soak, 10 brush strokes, cycled 3 times).
    Example 2
    This example describes the preparation of a transfer medium having a two-pass, cationically initiated ink in which both the color coat and the size coat are photochemically curable.
    The following ingredients were combined to form a photochemically curable color coat (all amounts in weight percent):
    TiO2 55.0
    2,4-toluene diisocyanate/HBVE adduct 35.8
    QW-16 (urethane dispersion) 2.0
    PPZ 5.0
    Triton® X-100 0.2
    UVI 6974 2.0
    Water was added to adjust the total solids content to 35% by weight, after which the resulting color coat was applied to a 30,5 µm (1.2 mil) thick polypropylene carrier film using a #13 mayer rod.
    The following ingredients were combined to form a photochemically curable size coat (all amounts in weight percent):
    EPON® 1001 89.1
    UVI 6110 5.45
    FC-430 2.47
    UVI 6974 1.68
    Perylene® 0.3
    PPZ 1.0
    Methyl ethyl ketone was added to adjust the total solids content of the size coat to 25% by weight, after which the resulting size coat was applied on top of the color coat using a #5 mayer rod.
    The coated surface of the film was then placed in intimate contact with the surface of a molded semiconductor device. Next, a CO2 laser was directed through the uncoated side of the carrier film to transfer the ink (color coat plus size coat) to the surface of the semiconductor device. The laser dwelled on each addressed pixel for 20 µs. The power output of the laser at the point of contact with the coated film was 14.5 W. The device bearing the transferred image was then cured (5 minutes. at a 150°C preheat, followed by a 3.6 sec exposure to UV radiation). The resulting cured printed image was found to be resistant to treatment with 1,1,1-trichloroethane (3 minutes. soak, 10 brush strokes, cycled 3 times).
    Example 3
    This example describes the preparation of a transfer medium having a two-pass, cationically curable ink in which the color coat is non-curable and the size coat is thermally curable.
    The following ingredients were combined to form a non-curable color coat (all amounts in weight percent):
    Water 54.0
    Daxad® 30 0.5
    TiO2 38.4
    Triton® X-100 0.5
    Shamrock® 375 6.2
    Rhoplex® B85 1.4 Amsco® 3011 7.7
    Enough ammonium hydroxide was added to adjust the pH to 8.5, after which the resulting color coat was applied to a 30,5 µm (1.2 mil) thick polypropylene carrier film at a coat weight of 69 mg/m2.
    The following ingredients were combined to form a photochemically curable size coat (all amounts in weight percent):
    EPON® 1001 88.2
    UVR 6110 11.6
    FC-430 3.0
    UV 479 1.6
    IR 99 0.5
    Benzpinacole® 0.47
    Methyl ethyl ketone was added to adjust the total solids content of the size coat to 25% by weight, after which the resulting size coat was applied on top of the color coat using a #5 mayer rod.
    The coated surface of the film was then placed in intimate contact with the surface of a molded semiconductor device. Next, a Nd:YAG laser was directed through the uncoated side of the carrier film to transfer the ink (color coat plus size coat) to the surface of the semiconductor device. The laser dwelled on each addressed pixel for 18 µs. The power output of the laser at the point of contact with the coated film was 4.5 W. The device bearing the transferred image was then cured (4 minutes. at 175°C). The resulting cured printed image was found to be resistant to treatment with 1,1,1-trichloroethane (3 minutes. soak, 10 brush strokes, cycled 3 times).
    Example 4
    This example describes the preparation of a transfer medium having a one-pass, thermally curable, cationically initiated ink in which transfer and cure takes place in a single step upon laser irradiation.
    The following ingredients were combined to form a laser-transferrable ink (all amounts in weight percent):
    Talc 30.0
    UVE 9310 7.0
    Copper benzoate 0.14
    EPON® 164 51.43
    CHVE5 11.43
    Methyl ethyl ketone was added to adjust the total solids content to 50% by weight, after which the resulting ink was coated onto a 30,5 µm (1.2 mil) thick polypropylene carrier film using a #10 mayer rod. The coated surface of the film was then placed in intimate contact with a glass slide. Next, a CO2 laser was directed through the uncoated side of the carrier film to transfer the ink to the surface of the glass slide. The laser dwelled on each addressed pixel for 80 µs. After addressing, the transferred coating was removed form the glass slide and analyzed by differential scanning calorimetry. There was no evidence of residual heat of reaction, indicating that the transferred coating had cured during the transfer step.
    Example 5
    This example describes the preparation of a transfer medium having a two-pass, free radical-initiated ink in which both the color coat and the size coat are photochemically curable.
    The following ingredients were combined to form a photochemically curable color coat (all amounts in weight percent):
    TiO2 65.0
    Aquacer 355 11.0
    NR 440 18.8
    PPZ 3.0
    Triton X-100 0.2
    Daracure 4265 2.0
    Water was added to adjust the total solids content to 40% by weight, after which the resulting color coat was applied to a 30,5 µm (1.2 mil) thick polypropylene carrier film using a #13 mayer rod.
    The following ingredients were combined to form a photochemically curable size coat (all amounts in weight percent):
    NR 440 78.0
    Ebecryl® 639 20.0
    Daracure® 4265 2.0
    Water was added to adjust the total solids content of the size coat to 40% by weight, after which the resulting size coat was applied on top of the color coat using a #5 mayer rod.
    The coated surface of the film was then placed in intimate contact with the surface of a molded semiconductor device. Next, a CO2 laser was directed through the uncoated side of the carrier film to transfer the ink (color coat plus size coat) to the surface of the semiconductor device. The laser dwelled on each addressed pixel for 20 µs. The power output of the laser at the point of contact with the coated film was 14.5 W. The device bearing the transferred image was then cured (5 minutes. at a 100°C preheat, followed by passage through a UV fusion oven equipped with an H bulb at a speed of 42,3 mm/s (100 inches per minute). The resulting cured printed image was found to be resistant to treatment with 1,1,1-trichloroethane (3 minutes. soak, 10 brush strokes, cycled 3 times).

    Claims (23)

    1. A laser-induced transfer printing method comprising the steps of
      (a) providing a transfer printing medium capable of converting laser energy to heat comprising a carrier to which is applied a curable laser-transferrable ink; and
      (b) irradiating said medium with laser light of a predetermined wavelength,
      whereupon said laser light transfers said ink to a surface of interest and cures said ink to adhere said ink to the surface of interest.
    2. The laser-induced transfer printing method of claim 1 comprising the steps of:
      (a) providing a transfer printing medium capable of converting laser energy to heat comprising a carrier to which is applied a curable laser-transferrable ink having one or more layers, said ink comprising:
      (i) at least one colorant;
      (ii) at least one polymerization initiator; and
      (iii) at least one curable prepolymer;
      (b) irradiating said medium with laser light of a predetermined wavelength to transfer said ink to a surface of interest; and
      (c) curing said ink to adhere said ink to the surface of interest.
    3. The method of claim 1 or 2 wherein the transfer and cure of said ink are effected in a single step through irradiation with said laser light.
    4. The method of claim 1 or 2 wherein the transfer and cure of said ink are effected in separate steps.
    5. The method of claim 2, 3 or 4 wherein at least one of said polymerization initiators comprises a thermal polymerization initiator and at least one of said prepolymers is thermally curable.
    6. The method of claim 2, 3, or 4 wherein at least one of said polymerization initiators comprises a photoinitiator and at least one of said prepolymers is photochemically curable.
    7. The method of claim 2, 3, or 4 wherein at least one of the layers of said ink is a curable size coat comprising a polymerization initiator and a curable prepolymer.
    8. The method of claim 2, 3, or 4 wherein at least one of the layers of said ink is a curable size coat comprising a polymerization initiator and a curable prepolymer and at least one of the layers of said ink is a non-curable color coat comprising a colorant and a thermoplastic film-forming resin.
    9. The method of claim 2, 3, or 4 wherein at least one of the layers of said ink is a curable size coat comprising a polymerization initiator and a curable prepolymer and at least one of the layers of said ink is a curable color coat comprising a colorant, a polymerization initiator, and a curable prepolymer.
    10. The method of any one of claims 2 to 9 where the transfer printing medium comprises at least one thermal convertor that is different from said colorant.
    11. A transfer printing medium comprising a carrier to which is applied a curable laser-transferrable ink having one or more layers, said ink comprising:
      (a) at least one colorant;
      (b) at least one polymerization initiator;
      (c) at least one curable prepolymer; and
      (d) at least one thermal convertor different from said colorant with the proviso that said thermal converter is not carbon black,
      said transfer medium being capable of converting laser energy to heat.
    12. The transfer printing medium of claim 11 wherein said ink is capable of transfer to a surface of interest and is capable of curing in one step upon application of laser energy.
    13. The transfer printing medium of claim 11 or 12 wherein at least one of said polymerization initiators comprises a thermal polymerization initiator and at least one of said prepolymers is thermally curable.
    14. The transfer printing medium of claim 11 or 12 wherein at least one of said polymerization initiators comprises a photoinitiator and at least one of said prepolymers is photochemically curable.
    15. The transfer printing medium of any one of claims 11 to 14 wherein at least one of said prepolymers comprises an epoxy-functionalized prepolymer.
    16. The transfer printing medium of claim 15 wherein said prepolymer further comprises a vinyl ether-functionalized prepolymer.
    17. The transfer printing medium of claim 15 wherein said prepolymer further comprises an acrylate-functionalized prepolymer.
    18. The transfer printing medium of any one of claims 11 to 14 wherein at least one of said prepolymers comprises an acrylate-functionalized prepolymer.
    19. The transfer printing medium of any one of claims 11 to 14 wherein at least one of said prepolymers comprises a blocked isocyanate-functionalized prepolymer.
    20. The transfer printing medium of any one of claims 11 to 14 wherein at least one of said prepolymers comprises a blend of a vinyl ether-functionalized prepolymer and a maleate- or maleimide-functionalized prepolymer.
    21. The transfer printing medium of claim 11 wherein at least one of the layers of said ink is a curable size coat comprising a polymerization initiator and a curable prepolymer.
    22. The transfer printing medium of claim 11 wherein at least one of the layers of said ink is a curable size coat comprising a polymerization initiator and a curable prepolymer and at least one of the layers of said ink is a non-curable color coat comprising a colorant and a thermoplastic film-forming resin.
    23. The transfer printing medium of claim 11 wherein at least one of the layers of said ink is a curable size coat comprising a polymerization initiator and a curable prepolymer and at least one of the layers of said ink is a curable color coat comprising a colorant, a polymerization initiator, and a curable prepolymer.
    EP94930625A 1993-11-09 1994-10-06 Transfer printing medium Expired - Lifetime EP0728073B1 (en)

    Applications Claiming Priority (3)

    Application Number Priority Date Filing Date Title
    US14928593A 1993-11-09 1993-11-09
    US149285 1993-11-09
    PCT/US1994/011345 WO1995013195A1 (en) 1993-11-09 1994-10-06 Transfer printing medium

    Publications (2)

    Publication Number Publication Date
    EP0728073A1 EP0728073A1 (en) 1996-08-28
    EP0728073B1 true EP0728073B1 (en) 1999-04-21

    Family

    ID=22529568

    Family Applications (1)

    Application Number Title Priority Date Filing Date
    EP94930625A Expired - Lifetime EP0728073B1 (en) 1993-11-09 1994-10-06 Transfer printing medium

    Country Status (7)

    Country Link
    EP (1) EP0728073B1 (en)
    JP (1) JPH07232480A (en)
    KR (1) KR100322459B1 (en)
    AT (1) ATE179125T1 (en)
    CA (1) CA2175588A1 (en)
    DE (1) DE69418056T2 (en)
    WO (1) WO1995013195A1 (en)

    Families Citing this family (26)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    US5757313A (en) * 1993-11-09 1998-05-26 Markem Corporation Lacer-induced transfer printing medium and method
    US6037968A (en) * 1993-11-09 2000-03-14 Markem Corporation Scanned marking of workpieces
    WO1996024495A1 (en) * 1995-02-10 1996-08-15 Klaus Kall Method of coating a transparent carrier plate and coated carrier plate produced according to this method
    GB9617416D0 (en) * 1996-08-20 1996-10-02 Minnesota Mining & Mfg Thermal bleaching of infrared dyes
    US5695907A (en) * 1996-03-14 1997-12-09 Minnesota Mining And Manufacturing Company Laser addressable thermal transfer imaging element and method
    US5747217A (en) * 1996-04-03 1998-05-05 Minnesota Mining And Manufacturing Company Laser-induced mass transfer imaging materials and methods utilizing colorless sublimable compounds
    US7534543B2 (en) 1996-04-15 2009-05-19 3M Innovative Properties Company Texture control of thin film layers prepared via laser induced thermal imaging
    US5725989A (en) * 1996-04-15 1998-03-10 Chang; Jeffrey C. Laser addressable thermal transfer imaging element with an interlayer
    US5998085A (en) * 1996-07-23 1999-12-07 3M Innovative Properties Process for preparing high resolution emissive arrays and corresponding articles
    US6852948B1 (en) 1997-09-08 2005-02-08 Thermark, Llc High contrast surface marking using irradiation of electrostatically applied marking materials
    US6075223A (en) * 1997-09-08 2000-06-13 Thermark, Llc High contrast surface marking
    US6238847B1 (en) 1997-10-16 2001-05-29 Dmc Degussa Metals Catalysts Cerdec Ag Laser marking method and apparatus
    JPH11180099A (en) 1997-12-18 1999-07-06 Matsushita Electric Ind Co Ltd Method for marking and resin molding with mark
    US6177151B1 (en) * 1999-01-27 2001-01-23 The United States Of America As Represented By The Secretary Of The Navy Matrix assisted pulsed laser evaporation direct write
    AU2514800A (en) * 1999-01-27 2000-08-18 United States Of America As Represented By The Secretary Of The Navy, The Matrix assisted pulsed laser evaporation direct write
    WO2000078554A1 (en) 1999-06-22 2000-12-28 Omg Ag & Co. Kg Laser marking compositions and method
    US6228543B1 (en) 1999-09-09 2001-05-08 3M Innovative Properties Company Thermal transfer with a plasticizer-containing transfer layer
    US6503316B1 (en) 2000-09-22 2003-01-07 Dmc2 Degussa Metals Catalysts Cerdec Ag Bismuth-containing laser markable compositions and methods of making and using same
    US6730376B2 (en) * 2001-02-09 2004-05-04 3M Innovative Properties Company Thermally transferable compositions and methods
    US7238396B2 (en) 2002-08-02 2007-07-03 Rieck Albert S Methods for vitrescent marking
    US7678526B2 (en) 2005-10-07 2010-03-16 3M Innovative Properties Company Radiation curable thermal transfer elements
    US7396631B2 (en) 2005-10-07 2008-07-08 3M Innovative Properties Company Radiation curable thermal transfer elements
    AU2006317160A1 (en) 2005-11-22 2007-05-31 Merck Patent Gmbh Process for a thermal transfer of a liquid crystal film using a transfer element
    DE102005057474A1 (en) * 2005-11-30 2007-05-31 Merck Patent Gmbh Method for flexible and individual marking of products, documents of value and security documents, involves introduction of security features into layer system
    US9744559B2 (en) 2014-05-27 2017-08-29 Paul W Harrison High contrast surface marking using nanoparticle materials
    DE102018111132A1 (en) * 2018-05-09 2019-11-14 Lpkf Laser & Electronics Aktiengesellschaft Use of a component in a composition, composition for laser transfer printing and laser transfer printing method

    Family Cites Families (2)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    US4812354A (en) * 1986-05-14 1989-03-14 Mitsubishi Paper Mills, Ltd. Color image recording material
    JPH03244588A (en) * 1990-02-22 1991-10-31 Canon Inc Transfer recording medium

    Also Published As

    Publication number Publication date
    DE69418056D1 (en) 1999-05-27
    CA2175588A1 (en) 1995-05-18
    KR960705689A (en) 1996-11-08
    DE69418056T2 (en) 1999-11-11
    WO1995013195A1 (en) 1995-05-18
    EP0728073A1 (en) 1996-08-28
    ATE179125T1 (en) 1999-05-15
    KR100322459B1 (en) 2002-10-04
    JPH07232480A (en) 1995-09-05

    Similar Documents

    Publication Publication Date Title
    EP0728073B1 (en) Transfer printing medium
    US5757313A (en) Lacer-induced transfer printing medium and method
    JP3085542B2 (en) Laser induced thermal transfer method
    US6736055B2 (en) Method of finishing golf balls employing direct digital-to-surface printing of indicia
    EP2167592B1 (en) Uv curable ink with improved adhesion
    DE69402656T2 (en) Process for treating an image produced by thermal transfer
    US6025017A (en) Photopolymerizable coating formulation for thermal transfer media
    US8747969B2 (en) Coated films for inkjet printing
    JP2004002668A (en) Liquid ink and printer
    US6040040A (en) Multi-layer thermal transfer media from selectively curable formulations
    CN113330077A (en) Photocurable ink composition for inkjet printing
    US20070219292A1 (en) Ink set for ink-jet recording, polymerization method and image forming method
    US7163970B2 (en) Actinic ray curable ink and printed matter utilizing the same
    JP2987534B2 (en) Thermal transfer recording sheet
    WO2021161967A1 (en) Method for manufacturing coated metal plate
    JPH09290567A (en) Liquid composition, laser marking article and marking method
    JPH1039497A (en) Direct depictive waterless lithographic printing plate
    JP2935308B2 (en) Marking composition
    US5106695A (en) Method and means for producing color proofs
    JP2003335041A (en) Image-forming method, printed matter and recorder

    Legal Events

    Date Code Title Description
    PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

    Free format text: ORIGINAL CODE: 0009012

    17P Request for examination filed

    Effective date: 19960610

    AK Designated contracting states

    Kind code of ref document: A1

    Designated state(s): AT DE GB IE IT

    17Q First examination report despatched

    Effective date: 19960819

    GRAG Despatch of communication of intention to grant

    Free format text: ORIGINAL CODE: EPIDOS AGRA

    GRAG Despatch of communication of intention to grant

    Free format text: ORIGINAL CODE: EPIDOS AGRA

    GRAH Despatch of communication of intention to grant a patent

    Free format text: ORIGINAL CODE: EPIDOS IGRA

    GRAH Despatch of communication of intention to grant a patent

    Free format text: ORIGINAL CODE: EPIDOS IGRA

    GRAA (expected) grant

    Free format text: ORIGINAL CODE: 0009210

    AK Designated contracting states

    Kind code of ref document: B1

    Designated state(s): AT DE GB IE IT

    REF Corresponds to:

    Ref document number: 179125

    Country of ref document: AT

    Date of ref document: 19990515

    Kind code of ref document: T

    REG Reference to a national code

    Ref country code: IE

    Ref legal event code: FG4D

    REF Corresponds to:

    Ref document number: 69418056

    Country of ref document: DE

    Date of ref document: 19990527

    PLBE No opposition filed within time limit

    Free format text: ORIGINAL CODE: 0009261

    STAA Information on the status of an ep patent application or granted ep patent

    Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

    26N No opposition filed
    REG Reference to a national code

    Ref country code: GB

    Ref legal event code: IF02

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: AT

    Payment date: 20020919

    Year of fee payment: 9

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: IE

    Payment date: 20021030

    Year of fee payment: 9

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: IE

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20031006

    Ref country code: AT

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20031006

    REG Reference to a national code

    Ref country code: IE

    Ref legal event code: MM4A

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: DE

    Payment date: 20081014

    Year of fee payment: 15

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: IT

    Payment date: 20081028

    Year of fee payment: 15

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: GB

    Payment date: 20081001

    Year of fee payment: 15

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: DE

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20100501

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: GB

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20091006

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: IT

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20091006