EP0830256A2 - Zeitliche markierung,uv-strahlungsdetektion und druck unter verwendung von uv-löschbaren farbmitteln - Google Patents

Zeitliche markierung,uv-strahlungsdetektion und druck unter verwendung von uv-löschbaren farbmitteln

Info

Publication number
EP0830256A2
EP0830256A2 EP96917030A EP96917030A EP0830256A2 EP 0830256 A2 EP0830256 A2 EP 0830256A2 EP 96917030 A EP96917030 A EP 96917030A EP 96917030 A EP96917030 A EP 96917030A EP 0830256 A2 EP0830256 A2 EP 0830256A2
Authority
EP
European Patent Office
Prior art keywords
colorant
ultraviolet radiation
mutable
substrate
transorber
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.)
Ceased
Application number
EP96917030A
Other languages
English (en)
French (fr)
Inventor
Ronald Sinclair Nohr
John Gavin Macdonald
Jeffrey Dean Lindsay
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.)
Kimberly Clark Worldwide Inc
Kimberly Clark Corp
Original Assignee
Kimberly Clark Worldwide Inc
Kimberly Clark 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 Kimberly Clark Worldwide Inc, Kimberly Clark Corp filed Critical Kimberly Clark Worldwide Inc
Priority to EP01104021A priority Critical patent/EP1123811A3/de
Priority to EP01104058A priority patent/EP1123814A2/de
Priority to EP01104036A priority patent/EP1123812A2/de
Priority to EP01104057A priority patent/EP1132119A3/de
Priority to EP01104037A priority patent/EP1123813A2/de
Publication of EP0830256A2 publication Critical patent/EP0830256A2/de
Ceased 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
    • B41M5/46—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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M3/00—Printing processes to produce particular kinds of printed work, e.g. patterns
    • B41M3/14—Security printing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M3/00—Printing processes to produce particular kinds of printed work, e.g. patterns
    • B41M3/14—Security printing
    • B41M3/142—Security printing using chemical colour-formers or chemical reactions, e.g. leuco-dye/acid, photochromes
    • 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
    • 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
    • B41M5/267—Marking of plastic artifacts, e.g. with laser
    • 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
    • B41M5/28—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using thermochromic compounds or layers containing liquid crystals, microcapsules, bleachable dyes or heat- decomposable compounds, e.g. gas- liberating
    • B41M5/282—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using thermochromic compounds or layers containing liquid crystals, microcapsules, bleachable dyes or heat- decomposable compounds, e.g. gas- liberating using thermochromic compounds
    • B41M5/284—Organic thermochromic compounds
    • 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
    • B41M7/0009—Obliterating the printed matter; Non-destructive removal of the ink pattern, e.g. for repetitive use of the support
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B43—WRITING OR DRAWING IMPLEMENTS; BUREAU ACCESSORIES
    • B43M—BUREAU ACCESSORIES NOT OTHERWISE PROVIDED FOR
    • B43M11/00—Hand or desk devices of the office or personal type for applying liquid, other than ink, by contact to surfaces, e.g. for applying adhesive
    • B43M11/06—Hand-held devices
    • B43M11/08—Hand-held devices of the fountain-pen type
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C65/00—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
    • C07C65/32—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing keto groups
    • C07C65/38—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing keto groups having unsaturation outside the aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
    • C08B37/0009—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid alpha-D-Glucans, e.g. polydextrose, alternan, glycogen; (alpha-1,4)(alpha-1,6)-D-Glucans; (alpha-1,3)(alpha-1,4)-D-Glucans, e.g. isolichenan or nigeran; (alpha-1,4)-D-Glucans; (alpha-1,3)-D-Glucans, e.g. pseudonigeran; Derivatives thereof
    • C08B37/0012—Cyclodextrin [CD], e.g. cycle with 6 units (alpha), with 7 units (beta) and with 8 units (gamma), large-ring cyclodextrin or cycloamylose with 9 units or more; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
    • C08B37/0009—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid alpha-D-Glucans, e.g. polydextrose, alternan, glycogen; (alpha-1,4)(alpha-1,6)-D-Glucans; (alpha-1,3)(alpha-1,4)-D-Glucans, e.g. isolichenan or nigeran; (alpha-1,4)-D-Glucans; (alpha-1,3)-D-Glucans, e.g. pseudonigeran; Derivatives thereof
    • C08B37/0012—Cyclodextrin [CD], e.g. cycle with 6 units (alpha), with 7 units (beta) and with 8 units (gamma), large-ring cyclodextrin or cycloamylose with 9 units or more; Derivatives thereof
    • C08B37/0015—Inclusion compounds, i.e. host-guest compounds, e.g. polyrotaxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/16—Writing inks
    • C09D11/17—Writing inks characterised by colouring agents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/32—Inkjet printing inks characterised by colouring agents
    • C09D11/328—Inkjet printing inks characterised by colouring agents characterised by dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/36—Inkjet printing inks based on non-aqueous solvents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/50—Sympathetic, colour changing or similar inks
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/004—Reflecting paints; Signal paints
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/0825—Developers with toner particles characterised by their structure; characterised by non-homogenuous distribution of components
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/087—Binders for toner particles
    • G03G9/08775—Natural macromolecular compounds or derivatives thereof
    • G03G9/08777—Cellulose or derivatives thereof
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/09—Colouring agents for toner particles
    • G03G9/0906—Organic dyes
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/09—Colouring agents for toner particles
    • G03G9/0926—Colouring agents for toner particles characterised by physical or chemical properties
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/097—Plasticisers; Charge controlling agents
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
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    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/097—Plasticisers; Charge controlling agents
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
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    • G03G9/08—Developers with toner particles
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
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    • G03G9/08—Developers with toner particles
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    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09B—EDUCATIONAL OR DEMONSTRATION APPLIANCES; APPLIANCES FOR TEACHING, OR COMMUNICATING WITH, THE BLIND, DEAF OR MUTE; MODELS; PLANETARIA; GLOBES; MAPS; DIAGRAMS
    • G09B3/00—Manually or mechanically operated teaching appliances working with questions and answers
    • G09B3/02—Manually or mechanically operated teaching appliances working with questions and answers of the type wherein the student is expected to construct an answer to the question which is presented or wherein the machine gives an answer to the question presented by a student
    • G09B3/04—Manually or mechanically operated teaching appliances working with questions and answers of the type wherein the student is expected to construct an answer to the question which is presented or wherein the machine gives an answer to the question presented by a student of chart form
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F3/00—Labels, tag tickets, or similar identification or indication means; Seals; Postage or like stamps
    • G09F3/02—Forms or constructions
    • G09F3/0291—Labels or tickets undergoing a change under particular conditions, e.g. heat, radiation, passage of time
    • G09F3/0294—Labels or tickets undergoing a change under particular conditions, e.g. heat, radiation, passage of time where the change is not permanent, e.g. labels only readable under a special light, temperature indicating labels and the like
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F7/00—Signs, name or number plates, letters, numerals, or symbols; Panels or boards
    • 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
    • B41M7/0081—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock using electromagnetic radiation or waves, e.g. ultraviolet radiation, electron beams

Definitions

  • Gaming tickets typically comprise a cardboard or paper substrate printed with the win/loss status and a layer of metahzed, opaque overprinting covering the printed win/loss status.
  • the player, after purchasing the ticket, must remove the metahzed coating by scraping the metahzed coating with a coin or the like to reveal the status. This is an inconvenient and messy process.
  • opaque temporary marking for concealing information printed on documents such as gaming tickets.
  • ultraviolet radiation can cause permanent damage to the eyes and skin.
  • arc welders must wear protective gear to prevent exposure to the ultraviolet radiation emitted during arc welding. Accordingly, there is a need for an inexpensive and convenient means for indicating the degree of exposure to ultraviolet radiation.
  • the ultraviolet radiation transorber absorb ultraviolet radiation at a wavelength of from about 4 to about 400 nanometers. More particularly, it is desirable that the ultraviolet transorber absorb ultraviolet radiation at a wavelength of 125 to 325 nanometers.
  • a particularly suitable form of ultraviolet radiation is incoherent, pulsed ultraviolet radiation emitted from a dielectric barrier discharge excimer lamp.
  • the present invention further encompasses an erasable price marking for pricing goods comprising a substrate and indicia on the substrate surface visually indicating a price and defined by the mutable colorant composition of the present invention. Upon irradiation with ultraviolet radiation, the ultraviolet radiation transorber of the mutable colorant composition interacts with the colorant to irreversibly mutate the colorant and thereby render the colorant substantially colorless so that the indicia become invisible.
  • This invention further encompasses an ultraviolet light exposure indicator comprising a substrate and a film on the substrate comprising the mutable colorant composition of the present invention.
  • the film has a mutable colorant density across the area of the film extending from a region having a first amount of mutable colorant to a region having a second amount of mutable colorant greater than the first amount, so that when the indicator is irradiated with a dosage of ultraviolet radiation, die indicator provides an indication of the dosage of ultraviolet radiation to which the indicator is exposed.
  • the substrate is an adhesive strip so that the indicator can be conveniently attached to a surface of concern such as an arc welder's helmet.
  • the present invention also encompasses colored articles for printing and methods for printing articles.
  • the colored article of the present invention includes a substrate comprising a matrix and the mutable colorant composition of the present invention dispersed in or on the matrix.
  • the mutable colorant composition is in the matrix when the matrix is a polymer.
  • Suitable articles include a variety of items such as plastic containers, plastic films, and paper. Contoured or glossy plastic containers are particularly suitable articles, as are transparent films for use in making transparencies or shdes for visual projection.
  • Figure 2 illustrates an ultraviolet radiation transorber/ mutable colorant/ molecular includant complex wherein me mutable colorant is Victoria Pure Blue BO (Basic Blue 7), the ultraviolet radiation transorber is IRGACURE 184
  • Figure 3 is a perspective view of a book marked with a photoerasable price marking made according to an embodiment of the present invention.
  • FIG. 5 is a gaming ticket made in accordance with an embodiment of the present invention.
  • Figure 8 is a plan view of a felt tip maker of the present invention.
  • the wick and fibrous material containing the photoerasable dye are illustrated with hidden lines.
  • Figure 14 is an illustration of several 222 nanometer excimer lamps arranged in four parallel columns wherein the twelve numbers represent the locations where twelve intensity measurements were obtained approximately 5.5 centimeters from the excimer lamps.
  • the method comprises irradiating a composition containing a mutable colorant and a radiation transorber with radiation at a dosage level sufficient to mutate the colorant.
  • the present invention further relates to a method of stabilizing a colorant comprising associating the modified photoreactor described above with the colorant.
  • the photoreactor may be associated with a wavelength-selective sensitizer, or the photoreactor may be associated with a molecular includant, or both.
  • composition and such variations as “colored composition” are used herein to mean a colorant, and a radiation transorber.
  • the radiation transorber may contain any conventional photoreactor or a photoreactor modified as described below.
  • the composition may further include a molecular includant.
  • the radiation transorber may contain an aylketoalkene stabilizer as the wavelength-selective sensitizer.
  • the wavelength-selective sensitizer may optionally be the arylketoalkene stabilizer as described below.
  • the term "compound” is intended to include a single material or a mixture of two or more materials. If two or more materials are employed, it is not necessary that all of them absorb radiation of the same wavelength.
  • a radiation transorber is comprised of a photoreactor and a wavelength selective sensitizer. The radiation transorber has the additional property of making the colorant with which die radiation transorber is associated hght stable to sunhght or artificial hght.
  • the term "derivatized molecular includant” is used herein to mean a molecular includant having more an two leaving groups covalently coupled to each molecule of molecular includant.
  • the term “leaving group” is used herein to mean any leaving group capable of participating in a bimolecular nucleophihc substitution reaction.
  • the term “artificial light” is used herein to mean light having a relatively broad bandwidth that is produced from conventional light sources, including, but not limited to, conventional incandescent hght bulbs and fluorescent hght bulbs.
  • the term “ultraviolet radiation” is used herein to mean electromagnetic radiation having wavelengths in the range of from about 4 to about 400 nanometers.
  • the colorant is associated with the functionalized molecular includant.
  • the term "associated" in its broadest sense means that the colorant is at least in close proximity to the functionalized molecular includant.
  • the colorant may be maintained in close proximity to the functionahzed molecular includant by hydrogen bonding, van der Waals forces, or the like.
  • the colorant may be covalently bonded to the functionahzed molecular includant, although this normally is neither desired nor necessary.
  • the colorant may be at least partially included within the cavity of the functionalized molecular includant.
  • Examples 1, 2, 6, and 7 disclose one or more methods of preparing and associating colorants and ultraviolet radiation transorbers to cyclodextrins.
  • the efficiency of energy transfer from the ultraviolet radiation transorber to the colorant is, at least in part, a function of the number of ultraviolet radiation transorber molecules which are attached to the molecular includant.
  • the present invention also provides a method of making a functionahzed molecular includant.
  • the method of making a functionahzed molecular includant involves me steps of providing a derivatized ultraviolet radiation transorber having a nucleophihc group, providing a derivatized molecular includant having more than two leaving groups per molecule, and reacting the derivatized ultraviolet radiation transorber with the derivatized molecular includant under conditions sufficient to result in the covalent coupling of an average of more than two ultraviolet radiation transorber molecules to each molecular includant molecule.
  • the derivatized ultraviolet radiation transorber may be 2-[/?-(2-methyl-2- mercaptomethylpropionyl)phenoxy]ethyl 1 ,3-dioxo-2-isoindoline- acetate.
  • the derivatized ultraviolet radiation transorber may be 2-mercaptomethyl-2-methyl-4'-[2-[p-(3- oxobutyl)phenoxy]ethoxy]propiophenone.
  • the derivatized ultraviolet radiation transorber and the derivatized molecular includant are selected to cause the covalent coupling of the ultraviolet radiation transorber to the molecular includant by means of a bimolecular nucleophilic substitution reaction.
  • the nucleophilic group of the derivatized ultraviolet radiation transorber may be any nucleophilic group capable of participating in a bimolecular nucleophilic substitution reaction, provided, of course, that the reaction results in the covalent coupling of more than two molecules of the ultraviolet radiation transorber to the molecular includant.
  • the nucleophilic group generally will be a Lewis base, i.e., any group having an unshared pair of electrons.
  • the group may be neutral or negatively charged. Examples of nucleophilic groups include, by way of illustration only, aliphatic hydroxy, aromatic hydroxy, alkoxides, carboxy, carboxylate, amino, and mercapto.
  • the leaving group of the derivatized molecular includant may be any leaving group capable of participating in a bimolecular nucleophilic substitution reaction, again provided that the reaction results in the covalent coupling of more man two molecules of the ultraviolet radiation transorber to the molecular includant.
  • leaving groups include, also by way of illustration only, p-toluenesulfonates (tosylates),
  • bromobenzenesulfonates brosylates
  • p-nitrobenzenesulfonates nosylates
  • methanesulfonates meylates
  • oxonium ions alkyl perchlorates
  • ammonioalkane sulfonate esters betylates
  • alkyl fluorosulfonates trifluoromethanesulfonates (triflates), nonafluorobutanesulfonates (nonaflates), and 2,2,2- trifluoroethanesulfonates (tresylates).
  • the reaction of the derivatized ultraviolet radiation transorber with the derivatized molecular includant is carried out in solution.
  • the choice of solvent depends upon the solubilities of the two derivatized species.
  • a particularly useful solvent is N,N-dimemylformamide (DMF).
  • reaction conditions such as temperature, reaction time, and the like generally are matters of choice based upon the natures of the nucleophihc and leaving groups. Elevated temperatures usually are not required.
  • the reaction temperature may be in a range of from about 0°C to around ambient temperature, i.e., to 20°-25°C.
  • the preparation of the functionahzed molecular includant as described above generally is carried out in the absence of the colorant.
  • the colorant may be associated with the derivatized molecular includant before reacting the derivatized ultraviolet radiation transorber with the derivatized molecular includant, particularly if a degree of substitution greater than about three is desired.
  • the degree of substitution is about three, it is believed that the association of the colorant with the functionahzed molecular includant still may permit the colorant to be at least partially included in a cavity of the functionalized molecular includant.
  • steric hindrance may partially or completely prevent the colorant from being at least partially included in a cavity of the functionalized molecular includant. Consequently, die colorant may be associated with the derivatized molecular includant which normally will exhibit little, if any, steric hindrance. In this instance, the colorant will be at least partially included in a cavity of the derivatized molecular includant.
  • the above-described bimolecular nucleophihc substitution reaction then may be carried out to give a colored composition of the present invention in which the colorant is at least partially included in a cavity of the functionalized molecular includant.
  • the present invention provides compositions comprising a colorant which, in the presence of a radiation transorber, is mutable when exposed to a specific wavelength of radiation, while at the same time, provides light stability to the colorant with respect to sunlight and artificial light.
  • die mutated colorant will be stable, i.e., not appreciably adversely affected by radiation normally encountered in the environment, such as natural or artificial light and heat.
  • a colorant rendered colorless will remain colorless indefinitely.
  • the dye may be an organic dye.
  • Organic dye classes include, by way of illustration only, triarylmethyl dyes, such as Malachite Green Carbinol base ⁇ 4-(dimethylamino)- ⁇ -[4- (dimethylan ino)phenyl]- ⁇ -phenylbenzene-methanol ⁇ , Malachite
  • thiazine dyes such as Methylene Green, zinc chloride double salt [3,7-bis(dimethylamino)-6-nitrophenothiazin-5-ium chloride, zinc chloride double salt]
  • oxazine dyes such as Lumichrome (7,8- dimediylalloxazine); naphthahmide dyes, such as Lucifer Yellow
  • azoic diazo dyes such as Fast Blue BB salt (Azoic Diazo No. 20; 4-benzoylamino-2,5- diethoxybenzene diazonium chloride, zinc chloride double salt); phenylenediamine dyes, such as Disperse Yellow 9 [N-(2,4- dinitrophenyl)-l,4-phenylenediamine or Solvent Orange 53]; diazo dyes, such as Disperse Orange 13 [Solvent Orange 52; 1- pheny lazo-4-(4-hydroxyphenylazo)naphthalene] ; anthraquinone dyes, such as Disperse Blue 3 [Celhton Fast Blue FFR; 1- memyl_J ⁇ no-4-(2-hydroxyethylamino)-9,10-anthraquinone], Disperse Blue 14 [Celhton
  • the present invention includes unique compounds, namely, radiation transorbers, that are capable of absorbing narrow ultraviolet wavelength radiation, while at the same time, imparting hght-stability to a colorant with which the compounds are associated.
  • the compounds are synthesized by combining a wavelength-selective sensitizer and a photoreactor.
  • the photoreactors oftentimes do not efficiently absorb high energy radiation.
  • die resulting compound is a wavelength specific compound that efficiently absorbs a very narrow spectrum of radiation.
  • the wavelength-selective sensitizer may be covalently coupled to the photoreactor.
  • the wavelength-selective sensitizer may be selected from the group consisting of phthaloylglycine and 4- (4-oxyphenyl)-2-butanone.
  • the photoreactor may be selected from the group consisting of l-[4-(2- hydroxyethoxy)phenyl]-2-hydroxy-2-methylpropan- 1-one and cyclohexyl-phenyl ketone ester.
  • Other photoreactors are listed by way of example, in the detailed description below regarding the improved stabihzed composition of the present invention.
  • the ultraviolet radiation transorber may be 2-[p-
  • the ultraviolet radiation transorber may be 2-hydroxy-2-methyl-4'-2-[p-(3- oxobutyl)phenoxy]propiophenone.
  • the colorant and the ultraviolet radiation transorber have been described as separate compounds, they can be part of the same molecule. For example, they can be covalently coupled to each other, either directly, or indirectly through a relatively small molecule, or spacer. Alternatively, the colorant and ultraviolet radiation transorber can be covalently coupled to a large molecule, such as an oligomer or a polymer.
  • the colorant and ultraviolet radiation transorber may be associated with a large molecule by van der Waals forces, and hydrogen bonding, among other means.
  • the composition further comprises a molecular includant.
  • the cavity in the molecular includant can be a tunnel through the molecular includant or a cave-like space or a dented-in space in the molecular includant.
  • the cavity can be isolated or independent, or connected to one or more other cavities.
  • the dielectric barrier discharge lamp produces radiation having a narrow bandwidth, i.e., the half width is of the order of approximately 5 to 100 nanometers.
  • the radiation will have a half width of the order of approximately 5 to 50 nanometers, and more desirably will have a half width of the order of 5 to 25 nanometers.
  • the half width will be of the order of approximately 5 to 15 nanometers.
  • the amount or dosage level of ultraviolet radiation that the colorant of the present invention is exposed to will generally be that amount which is necessary to mutate the colorant.
  • the amount of ultraviolet radiation necessary to mutate the colorant can be determined by one of ordinary skill in the art using routine experimentation.
  • Power density is the measure of the amount of radiated electromagnetic power traversing a unit area and is usually expressed in watts per centimeter squared (W/cm 2 ).
  • the power density level range is between approximately 5 mW/cm and 15 mW/cm , more particularly 8 to 10 mW/cm 2 .
  • the dosage level typically is a function of the time of exposure and the intensity or flux of the radiation source which irradiates die colored composition.
  • nanometer excimer lamps located approximately 5 to 6 centimeters from the colorant, wherein the lamps are arranged in four parallel columns approximately 30 centimeters long. It is to be understood that the arrangement of the lamps is not critical to this aspect of the invention. Accordingly, one or more lamps may be arranged in any configuration and at any distance which results in the colorant mutating upon exposure to the lamp's ultraviolet radiation. One of ordinary skill in the art would be able to determine by routine experimentation which configurations and which distances are appropriate. Also, it is to be understood tiiat different excimer lamps are to be used with different ultraviolet radiation transorbers.
  • Such free radical- generating compounds typically are hindered ketones, some examples of which include, but are not hmited to: benzildimethyl ketal (available commercially as IRGACURE 651, Ciba-Geigy Co ⁇ oration, Hawthorne, New York); 1-hydroxycyclohexyl phenyl ketone (IRGACURE 500); 2-methyl-l-[4-
  • Benzoin n-butyl ether (2-Butoxy- 1 ,2-diphenylethanone) (ESACURE EB1 , Fratelh Lamberti); mixture of benzoin butyl ethers (TRIGONAL 14, Akzo); Benzoin iso-butyl ether (2- Isobutoxy-l,2-diphenylethanone) (VICURE 10, Stauffer); blend of benzoin n-butyl ether and benzoin isobutyl ether (ESACURE EB1 , Fratelh Lamberti); mixture of benzoin butyl ethers (TRIGONAL 14, Akzo); Benzoin iso-butyl ether (2- Isobutoxy-l,2-diphenylethanone) (VICURE 10, Stauffer); blend of benzoin n-butyl ether and benzoin isobutyl ether (ESACURE
  • this embodiment of the present invention provides a stabihzing arylketoalkene which, when associated with a colorant, stabilizes the colorant. Therefore, the above arylketoalkene can be used as an additive to any colorant composition. For example, as the arylketoalkene compound is poorly water soluble, it can be directly added to solvent or oil colorant compositions. Additionally, the arylketoalkene compound can be added to other colorant compositions that contain additives enabhng the solubihzation of the compound therein.
  • the arylketoalkene stabihzing compounds can be solubihzed in an aqueous solution by a variety of means.
  • One means of solubihzing the arylketoalkene stabihzing compound of the present invention is to attach the compound to a large water soluble molecule, such as a cyclodextrin, as described in Examples 28 through 31.
  • a large water soluble molecule such as a cyclodextrin
  • a cyclodextrin such as described in Examples 28 through 31.
  • between about 1 and 12 arylketoalkene molecules can be attached to a cyclodextrin molecule. More desirably, between about 4 to about 9 arylketoalkene molecules are attached to a cyclodextrin molecule.
  • the colored composition of the present invention can be utilized on or in any substrate. If one desires to mutate the colored composition that is present in a substrate, however, the substrate should be substantially transparent to the ultraviolet radiation which is employed to mutate the colorant. That is, the ultraviolet radiation will not significantly interact with or be absorbed by the substrate. As a practical matter, the composition typically will be placed on a substrate, with the most common substrate being paper. Other substrates, including, but not hmited to, woven and nonwoven webs or fabrics, films, and the like, can be used, however.
  • thermoplastic polymers include, but are not limited to: end-capped polyacetals, such as poly(oxymethylene) or polyformaldehyde, poly(trichloroacetaldehyde), ⁇ oly(n-valeraldehyde), poly(acetaldehyde), poly(propionaldehyde), and the hke; acrylic polymers, such as polyacrylamide, poly(acrylic acid), poly(methacrylic acid), poly(eti ⁇ yl acrylate), poly(methyl methacrylate), and the hke; fluorocarbon polymers, such as poly(tetrafluoroethylene), perfluorinated ethylenepropylene copolymers, ethylenetetrafluoroethylene copolymers, poly-
  • chlorotrifluoroethylene ethylene-chlorotrifluoroethylene copolymers, poly(vinylidene fluoride), poly(vinyl fluoride), and the hke
  • epoxy resins such as the condensation products of epichlorohydrin and bisphenol A
  • polyamides such as poly(6- aminocaproic acid) or poly( ⁇ -caprolactam), poly(hexamethylene adipamide), poly(hexamethylene sebacamide), poly(l l- aminoundecanoic acid), and the hke
  • polyaramides such as poly(imino-l,3-phenyleneiminoisophthaloyl) or poly(m-phenylene isophthalamide), and the hke
  • parylenes such as poly-/?-xylylene, poly (chloro- ?
  • the ether layer was dried over anhydrous magnesium sulfate.
  • the ether was removed under reduced pressure, leaving 12.7 g (87 percent) of a white crystalline powder.
  • the material was shown to be 1 -hydroxycyclohexyl 4- (2- carboxyethyl)carbonylphenyl ketone by nuclear magnetic resonance analysis.
  • a 250-ml, three-necked, round-bottomed reaction flask containing a magnetic stirring bar and fitted with a thermometer, condenser, and pressure-equahzing addition funnel equipped with a nitrogen inlet tube was charged with 10 g (9.8 mmole) of ⁇ - cyclodextrin (American Maize-Products Company, Hammond, Indiana), 31.6 g (98 mmoles) of 1 -hydroxycyclohexyl 4- (2- chloroformylethyl)carbonylphenyl ketone, and 100 ml of N,N- dimethylformamide while being continuously flushed with nitrogen.
  • the reaction mixture was heated to 50°C and 0.5 ml of triethylamine added.
  • reaction mixture was maintained at 50°C for an hour and allowed to cool to ambient temperature. In this preparation, no attempt was made to isolate the product, a ⁇ -cyclodextrin to which an ultraviolet radiation transorber had been covalently coupled (referred to hereinafter for convenience as ⁇ -cyclodextrin-transorber).
  • the eluted product was isolated by evaporating the solvent.
  • the structure of the product was verified by nuclear magnetic resonance analysis.
  • Lamp A was a 222-nanometer excimer lamp assembly organized in banks of four cylindrical lamps having a length of about 30 cm.
  • the lamps were cooled by circulating water through a centrally located or inner tube of the lamp and, as a consequence, they operated at a relatively low temperature, i.e., about 50°C.
  • the power density at the lamp's outer surface typically is in the range of from about 4 to about 20 joules per square meter (J/m ⁇ ).
  • Lamp B was a 500-watt Hanovia medium pressure mercury lamp (Hanovia Lamp Co., Newark, New Jersey). The distance from Lamp B to the sample being irradiated was about 15 cm.
  • a few drops of an N, N-dimethylformamide solution of die beta-cyclodextrin-transorber Colorant A inclusion complex were placed on a TLC plate and in a small polyethylene weighing pan. Both samples were exposed to Lamp A and were decolorized (mutated to a colorless state) in 15-20 seconds. Similar results were obtained with Lamp B in 30 seconds.
  • this example describes the preparation of a beta-cyclodextrin molecular includant having (1) a colorant at least partially included within the cavity of the cyclodextrin and associated therewith by means of hydrogen bonds and/or van der Waals forces, and (2) an ultraviolet radiation transorber covalently bonded to the cyclodextrin substantially outside of the cavity of the cyclodextrin.
  • reaction mixture was heated to 50°C and 0.5 ml of triethylamine added.
  • the reaction mixture was maintained at 50°C for an hour and allowed to cool to ambient temperature.
  • the reaction mixture then was worked up as described in Part A, above, to give 14.2 g of beta-cyclodextrin-transorber Colorant A inclusion complex, a blue-green powder.
  • Example 3 This example describes a method of preparing an ultraviolet radiation transorber, 2-[p-(2- methyllactoyl)phenoxy]ethyl 1 ,3-dioxo-2-isoindolineacetate, designated phthaloylglycine-2959.
  • This example describes a method of dehydrating the phthaloylglycine-2959 produced in Example 3.
  • the resulting reaction product had the following physical parameters:
  • This example describes the Nohr-MacDonald ehmination reaction used to dehydrate the phthaloylglycine-2959 produced in Example 3.
  • the resulting reaction product had the following physical parameters :
  • Mass spectrum m/e: 393 M +, 352, 326, 232, 160.
  • This example describes a method of producing a beta-cyclodextrin having dehydrated phthaloylglycine-2959 groups from Example 4 or 5 covalently bonded thereto.
  • reaction mixture was poured into 150 ml of weak sodium bicarbonate solution and extracted three times with 50 ml ethyl ether. The aqueous layer was then filtered to yield a white sohd comprising the beta- cyclodextrin with phthaloylglycine-2959 group attached. A yield of 9.4 g was obtained. Reverse phase TLC plate using a 50:50 DMF:acetonitrile mixture showed a new product peak compared to the starting materials.
  • the reaction is surnmarized as follows:
  • the beta- cyclodextrin molecule has several primary alcohols and secondary alcohols with which the phthaloylglycine- 2959 can react.
  • the above representative reaction only shows a single phthaloylglycine-2959 molecule for illustrative pu ⁇ oses.
  • This example describes a method of associating a colorant and an ultraviolet radiation transorber with a molecular includant. More particularly, this example describes a method of associating the colorant crystal violet with the molecular includant beta- cyclodextrin covalently bonded to the ultraviolet radiation transorber dehydrated phthaloylglycine-2959 of Example 6.
  • This example describes a method of producing the ultraviolet radiation transorber 4(4-hydroxyphenyl) butan-2-one- 2959 (chloro substituted).
  • the resulting reaction product had the following physical parameters:
  • the ultraviolet radiation transorber produced in this example, 4(4-hydroxyphenyl) butan-2-one-2959 (chloro substituted), may be associated with beta-cyclodextrin and a colorant such as crystal violet, using the methods described above wherein 4(4-hydroxyphenyl) butan-2-one-2959 (chloro substituted) would be substituted for the dehydrated phthaloylglycine- 2959.
  • Dehydroxy 2959 20 parts by weight of the hydroxy and the dehydroxy 2959 were admixed separately to one part by weight of Victoria Pure Blue
  • This example demonstrates the capability of dehydrated phthaloylglycine-2959 bound to beta-cyclodextrin to stabihze dyes against light.
  • the Victoria Pure Blue BO associated with the radiation transorber was tested to determine its capability to stabihze the associated dye against light emitted from a mercury discharge hght.
  • the Victoria Pure Blue BO alone and Victoria Pure Blue BO admixed with beta cyclodextrin were tested as controls.
  • the compositions tested were as follows:
  • Victoria Pure Blue BO included in beta cyclodextrin at a concentration of 20 mg/ml in acetonitrile.
  • the protocol for testing the stabilizing qualities of the three compositions is as follows: the dye solutions were carefully, uniformly spread on steel plates to a thickness of approximately 0.1 mm. The plates were then immediately exposed to a medium pressure 1200 watt high intensity quartz arc mercury discharge lamp (Conrad- Hanovia, Inc., Newark, New Jersey) at a distance of 30 cm from the lamp.
  • a medium pressure 1200 watt high intensity quartz arc mercury discharge lamp Conrad- Hanovia, Inc., Newark, New Jersey
  • composition number 3 the Victoria Pure Blue BO included in cyclodextrin with the radiation transorber covalently attached to the ⁇ -cyclodextrin was capable of stabihzing the dye under the mercury discharge hght.
  • the epoxide intermediate of dehydrated phthaloylglycine 2959 was prepared according to the following reaction:
  • thermometer and magnetic stirrer was placed 30.0g (0.076 mol) of the dehydrated ⁇ hthaloylglycine-2959, 70 ml methanol and 20.1 ml hydrogen peroxide (30% solution).
  • the reaction mixture was stirred and cooled in a water/ice bath to maintain a temperature in the range 15°-20° C.
  • 5.8 ml of a 6 N NaOH solution was placed in the addition funnel and the solution was slowly added to maintain the reaction mixture temperature of 15°-20° C. This step took about 4 minutes.
  • the mixture was then stirred for 3 hours at about 20°-25° C.
  • the reaction mixture was then poured into 90 ml of water and extracted with two 70 ml portions of ethyl ether.
  • the organic layers were combined and washed with 100 ml of water, dried with anhydrous MgS0 4 filtered, and the ether removed on a rotary evaporator to yield a white solid (yield 20.3g, 65%).
  • the IR showed the stretching of the C-O-C group and the material was used without further purification.
  • reaction mixture was cooled in a ice bath and 0.5 ml diisopropyl ethyl amine was added. Hydrogen sulfide was bubbled into the flask and a positive pressure maintained for 3 hours. During the last hour, the reaction mixture was allowed to warm to room temperature.
  • reaction mixture was flushed with argon for 15 minutes and then poured into 70 ml of water to which was then added 100 ml acetone. A white precipitate occurred and was filtered to yield 20.2 g (84.1%) of a white powder which was used without further purification.
  • the saturated solution was kept at a positive pressure of H 2 S.
  • the stoppers were held down by wiring and rubber bands.
  • the reaction mixture was then allowed to warm-up overnight.
  • the solution was then flushed with argon for 30 minutes and the reaction mixture poured onto 50 g of crushed ice and extracted three times (3 x 80 ml) with diethyl etiier (Aldrich Chemical Co., Milwaukee, Wisconsin).
  • a tosylated cyclodextrin was prepared according to the following reaction:
  • the degree of substitution of the white powder was determined by 13 C NMR spectroscopy
  • This example describes a method of making the wavelength-selective sensitizer, namely 4- [4' -carboxy phenyl] -3- buten-2-one as represented by the following formula:
  • Example 28 The method of Example 28 was followed except that acetone (Fisher, Optima Grade) was added first, and then the carboxybenzaldehyde was added. More particularly, 32.2 (0.21 mole) of carboxybenzaldehyde was reacted with 12.2 g (0.21 mole) of acetone in the sodium hydroxide/ethanol water mixture described in Example 28. Dilute HCl was added to bring the reaction mixture to neutral pH, yielding 37.1 g (91 %) of a pale yellow powder which was used without further purification in the following examples.
  • acetone Fisher, Optima Grade
  • Example 29 The method of Example 29 was followed except that 5.0 g of the 4-[4' -carboxy phenyl]-3-buten-2-one was used. More particularly, 5.0 g (0.026 mole) of the 4-[4' -carboxy phenyl]-3- buten-2-one produced in Example 30 was reacted with 3.3 g (0.026 mole) of oxalyl chloride in anyhydrous DMF at about 0°C. Next, approximately 7.1 g (0.005 mole) hydroxyethyl substimted cyclodextrin was added to the mixture (5:1 ratio) under the conditions described in Example 30 and was further processed as described therein, to produce 10.8 g of white powder. The NMR of the product showed both the aromatic protons of the 4-[4'- carboxy phenyl]-3-buten-2-one produced in Example 30 and the glucose protons of the cyclodextrin.
  • Example 30 To determine whether the 4-[4'-carboxy phenyl]-3-buten-2- one produced in Example 30 has the capability to stabihze colorants, the following experiment was conducted. Test films were made up containing 90% carbowax 4600 and 10% of a 1 part Victoria Pure Blue BO (Aldrich) to 19 parts 4-[4' -carboxy phenyl]-3-buten-2-one. The mixture was melted on a hot plate, stirred, then drawn down on metal plates (at approximately 60°C), using a #3 drawdown bar. A similar sample was made with only 1 % Victoria Pure Blue BO in 99% carbowax. The plates were exposed to a 1200 Watt Mercury medium pressure lamp for one hour, the lamp being about 2 feet from the plates. After one hour, the Victoria Pure Blue BO plate was essentially colorless, while the plate having the mixmre of Victoria Pure Blue BO and 4-[4' -carboxy phenyl]-3-buten-2-one thereon had not changed.
  • Victoria Pure Blue BO Al
  • Example 29 Another experiment to determine the colorant stabihzing capabihty of the compound produced in Example 29 was as follows. Briefly described, the compound of Example 29 was used with color inks removed from the color cartridges of a CANON BJC-600e bubble jet color printer. The ink was re ⁇ installed into the cartridges, which were installed into the ink jet printer, and color test pages were generated. The fortieth color test page was used in the present study.
  • the four cartridges were BJI-201, and the four inks (cyan, magenta, black, and yellow) were prepared as follows: (1 ) Cyan
  • Example 29 The cartridges were then refilled with the corresponding ink solutions (1 ) through (4) above. Forty pages were run off, and the fortieth page was exposed to a 1200 Watt medium pressure mercury lamp with a control sheet for nine hours.
  • the control sheet is the fortieth color test page run off using the ink compositions that were in the original ink cartridges.
  • the results of this experiment are as follows. After three hours under the 1200 Watt lamp, the control was 40 to 50% bleached, while the inks containing the compound produced in Example 29 were unchanged. After nine hours, the control was 50 to 60% bleached while the inks containing the compound of Example 29 were only about 10 to 20 % bleached. Accordingly, the compound produced in Example 29 is capable of stabihzing the dyes found in standard ink jet inks.
  • EXAMPLE 37 Another experiment to determine the colorant stabihzing capabihty of the compound produced in Example 29 is as follows. The stability of the ink solutions produced in Example 28 were studied as described below.
  • Example 29 works well as a dye stabilizer to visible and ultraviolet radiation.
  • the mutable colorant composition of the present invention has a variety of useful apphcations such as temporary marking, ultraviolet radiation indication, and printing on plastic articles. Particular embodiments of these uses are described below and are illustrated in Figures 3-12.
  • the price can be printed on labels with the colorant composition of the present invention using conventional metiiods of printing such as stamping.
  • the markings may also contain nonphotoerasable printing with non-mutable colorants to indicate a brand name or logo or the name of the seller. Such indicia would remain after photoerasing the price.
  • a written message which is to be confidentially communicated can be ove ⁇ rinted with a layer of the mutable color composition of the present invention.
  • the ove ⁇ rinting layer can be photoerased to reveal the message.
  • a particularly advantageous apphcation of this concept is to gaming tickets wherein the status of the player is concealed by a layer of opaque ove ⁇ rinting.
  • a gaming ticket 22 made according to an embodiment of the present invention is shown in Figures 5 and 6 and comprises a cardboard substrate 24, non-erasable indicia 26 printed on a surface 28 of the ticket for communicating the status of the player, and an opaque layer 30 of ove ⁇ rinting on the surface of the substrate covering the non-erasable indicia 26.
  • the gaming ticket 22 also comprises additional non-erasable indicia 32 which, in this case, indicates the particular game being played.
  • the ove ⁇ rinting layer 30 comprises the mutable colorant composition of the present invention and as such is initially opaque to conceal the stams of the player, but upon irradiation with ultraviolet radiation from a source such as a dielectric barrier discharge excimer lamp 23, irreversibly mutates and becomes substantially colorless. The ove ⁇ rinting layer 30 then becomes invisible and the stams of the player is revealed.
  • the lamp 23 can be placed conveniently at or near the place of purchase of the gaming ticket 22 so that the player can immediately find out his or her stams without the inconvenience of scratching off a coating.
  • Suitable substrates 24 for a gaming ticket or any other type of document communicating concealed information include paper, cardboard, plastic, and the like.
  • the gaming ticket 22 or other document can include non-erasable indicia of any type, but typically will be alphanumeric characters.
  • the non-erasable indicia 26 to be concealed desirably should be of the same color as the ove ⁇ rinting layer 30.
  • an ove ⁇ rinting layer 30 comprising a blue mutable colored composition in combination with non-erasable indicia 26 printed with blue non-erasable ink would be particularly secure.
  • Photoerasable Paint Still another apphcation of the mutable colorant composition of the present invention is photoerasable paints for temporary marking of a variety of substrates such as signs, particularly road signs, trees, roads, sidewalks, buildings, and terrain, for example to indicate circumstances such as “work being done”, “detours”, “dangerous conditions", and the like.
  • photoerasable paint of the present invention include use by surveyors, road and construction crews, use in crime investigations and at crime scenes, agricultural uses such as marking the divisions of fields and die crops to be planted within such boundaries, and the labeling of trees to be cut in selective lumber production programs.
  • the photoerasable paint of the present invention can be used to temporarily cover messages printed with non-erasable paint as well as to provide a new message.
  • the photoerasable paint can have a variety of colors and is stable to sunhght.
  • the photoerasable paint can be erased by irradiating the paint witii ultraviolet radiation at a dosage level sufficient to irreversibly mutate the color.
  • the photoerasable paint of the present invention allows for temporary marking and removal of that marking without the need for washing, abrasion, or chemical attack.
  • the photoerasable paint of the present invention comprises a colorant vehicle which is transparent to ultraviolet radiation and the mutable colorant composition of the present invention dispersed in the vehicle.
  • a colorant vehicle which is transparent to ultraviolet radiation
  • mutable colorant composition of the present invention dispersed in the vehicle.
  • suitable paint vehicles including latex, alkyd resins, polyurethane resins, acrylic resins, silicone resins, phenohc resins, nitrocellulose, epoxy resins, cellulose acetates and butyrates, natural oils, and the like.
  • the photoerasable paint of the present invention may also include other additives such as surfactants and solvents.
  • photoerasable paint When photoerasable paint is used to cover prior non ⁇ erasable markings, it may be desirable to increase the opacity of the photoerasable paint by adding a non-erasable pigment.
  • a titanium dioxide opacifier may be suitable for inco ⁇ oration into photoerasable paint on some surfaces where a white residual would be acceptable. It may also may be desirable under some circumstances to make a color changing paint which is possible by dispersing both a photoerasable colorant and a nonphotoerasable colorant having different colors. Upon exposure to ultraviolet hght having the appropriate wavelength and dosage, the photoerasable colorant would be colorless, leaving the non-erasable colorant and effecting a color change.
  • mutable color composition of the present invention is in writing or marking instruments such as pens and wick or felt tip markers, such as magic markers and highhghters.
  • Markers using the mutable colorant composition of the present invention allow temporary marking which can be erased by irradiation with ultraviolet hght having the appropriate wavelength and dosage.
  • highhghters using ink, including the mutable colorant composition of the present invention can be used to highlight text in books. When resale of a book is desired, the highhghting can be erased by exposing the highhghted areas to ultraviolet radiation. The highhghted areas, however, would be stable to sunhght and artificial hghting.
  • Another use of the mutable color composition of the present invention includes pens containing such a composition, wherein the notations made by the pens could be erased by irradiation thereby avoiding the need to shred high security documents, or thereby avoiding the need for chemically or mechanically removing such a composition during a recycling process.
  • the marking instrument of the present invention comprises a marking fluid including a vehicle or carrier and the mutable colorant composition of the present invention.
  • a marking fluid including a vehicle or carrier and the mutable colorant composition of the present invention.
  • suitable vehicles for marking fluid such as ink, include water, glycerol, alkylene glycols, other alcohols, and the like.
  • the marking fluid may also comprise other additives known to those skilled in the art.
  • the marking fluid for use in writing instruments of the present invention are of conventional formulation except that conventional pigments are replaced by the mutable colorant composition of the present invention.
  • Figure 7 shows a ballpoint pen cartridge 40 comprising a reservoir 42 containing ink and an applicator 46 having a ballpoint 48 extending from one end of the reservoir.
  • the ink 44 containing the mutable colorant composition of the present invention is drawn by capillary action from the reservoir 42 through the ballpoint outlet 48 of the applicator 46 when the ballpoint is drawn across a writing surface.
  • the mutable colorant composition of the present invention is useful to indicate exposure to ultraviolet light. This is possible because the mutable colorant composition of the present invention comprises a mutable colorant that decolors upon exposure to ultraviolet light in a narrow wavelength range.
  • FIG 9 illustrates an embodiment of an ultraviolet radiation exposure indicator 70 of the present invention.
  • the indicator 70 comprises a film including die mutable colorant composition of the present invention disposed on a substrate 74.
  • the indicator 70 is in the form of a strip and the substrate desirably comprises a strip of adhesive of paper or plastic.
  • the film 72 comprises the mutable colorant composition of the present invention dispersed in a carrier or vehicle such a polymer.
  • the carrier should be transparent to ultraviolet light.
  • the film 72 has layers 76 of increasing thickness which varies from low to high across the strip. As the thickness of the film 72 increases, the mutable colorant density increases, thus forming a mutable colorant density gradient across the area of the film.
  • the mutable colorant density is the amount of mutable colorant per area of the strip. Each level of increasing thickness forms regions having differing amounts of mutable colorant.
  • the indicator 70 has thus regions of increasing colorant density. A given dose of ultraviolet radiation will decolorate at least a portion of the film
  • the substrate 74 of the indicator 70 further includes a border 78 having indicia thereon for indicating die dosage of ultraviolet radiation to which the indicator is exposed.
  • the strip will need to be calibrated to a particular source of ultraviolet radiation.
  • the indicator 70 can be attached with the adhesive substrate 74 to a surface that is exposed to ultraviolet radiations such as an arc welders helmet.
  • the printable colored article of the present invention comprises a substrate including a matrix and a mutable colorant composition dispersed in the matrix.
  • the mutable colorant composition of the present invention comprises a mutable colorant and an ultraviolet radiation transorber which, upon irradiation with ultraviolet radiation, interacts with the colorant to irreversibly mutate the colorant and render the colorant substantially colorless.
  • An image can be printed on the substrate by irradiating selected portions of the substrates with ultraviolet radiation at a wavelength and dosage level sufficient to irreversibly mutable the colorant at the selected portions.
  • the substrate may further comprise multiple mutable colorant compositions each including a mutable colorant and an ultraviolet radiation transorber.
  • Each mutable colorant has a color and the colors are different from one another before mutation.
  • Each colorant is mutable at different ultraviolet radiation wavelengtiis.
  • multi-color images can be printed on the articles corresponding to the selected portions.
  • the article is desirably printed by irradiating the substrate with incoherent, pulsed ultraviolet radiation emitted from a dielectric barrier discharge excimer lamp.
  • the substrate can be directly printed with a mask having openings corresponding to the image desired to be printed.
  • the openings in the mask direct the ultraviolet radiation to the selected portions of the substrate.
  • High resolution printing particularly on highly contoured surfaces, may require controlled sweeping of a tightly focused beam of ultraviolet radiation such as from an excimer laser.
  • electrophotography techniques can be used to irradiate the selected portions of the plastic article to create the desired image.
  • Corresponding pending U.S. Patent apphcation Serial No. 08/258,858 discloses techniques for using mutable colorants in electrophotography and is expressly inco ⁇ orated herein by reference. Photoerasing can be conducted in two or more stages or can be done simultaneously with the appropriate excimer ultraviolet lamps to achieve multicolor effects.
  • the colored article for printing can be a white sheet of paper, and the paper can also be the substrate and matrix of the article. If the paper comprises two mutable colorants, one blue before mutation and the other red before mutation, and corresponding ultraviolet radiation transorbers dispersed in the paper, selective photoerasing of the sheet of paper with ultraviolet radiation of the appropriate wavelengths could produce a sheet with regions of blue, red, violet, pu ⁇ le, and white.
  • the matrix is colored with a mutable cyan colorant, a mutable magenta colorant, and a mutable yellow colorant, each of the colorants being mutable at a different wavelength of ultraviolet radiation.
  • the matrix can take the form of a single layer comprising a mixture of all three colorants or could comprise three separate layers, each comprising a different colorant stacked one on top of the other.
  • a location exposed to radiation wavelengths capable of mutating the cyan and yellow colorant would result in the location being magenta.
  • This can be achieved by simultaneous exposure of selected portions of the substrate to ultraviolet radiation of the different wavelengths such as with three ultraviolet radiation excimer lasers or can be achieved by exposure of the substrate to ultraviolet radiation of different wavelengths in stages using three masks.
  • the article substrate may be clear, opaque, or translucent and may be colored with non-mutable (nonphotoerasable) colorants in addition to the mutable colorant so that when the mutable colorant is erased in selected portions, the selected portions have the color of the non-mutable colorant.
  • Suitable articles include a variety of items such as plastic containers, plastic films, and paper. Contoured or glossy plastic containers are particularly suitable articles as are transparent films for use in making transparencies or shdes for visual projection.
  • Suitable substrates include the article itself or a film adhered or otherwise attached to the article.
  • Suitable matrix materials which form the substrate include the polymer of the plastic container or film or can be the paper when the substrate is a sheet of paper. The matrix should transmit a sufficient amount of ultraviolet hght for mutation of the colorant. It is to be understood that the colorant composition of the present invention may be admixed with the matrix, and therefore is in the substrate, or it may be present as a layer on a surface of the substrate formed by the matrix. Colored plastic articles of the present invention alleviate the need for labels and adhesives and allow printing on contoured plastic surfaces and glossy plastic surfaces, which are not amenable to contact printing, labeling, or xerography.
  • Suitable matrix material can include a variety of polymers.
  • the matrix polymer must transmit ultraviolet light, and suitable ones include gelatin, gelatin derivatives, cellulose derivatives, polysaccharides, polyvinyl compounds, acrylamide polymers, polymers of alkylacrylates and methacrylates, acrylic acid, sulfoalkylacrylates, poly(vinylbutyral), cellulose acetate, butyrate, poly (methylmethacry late), ethylcellulose, polystyrene, poly(vinylchloride), polyiosbutylene, butadiene- styrene copolymers, vinyl chloride, polyvinyl alcohol, cellulose acetate hydrogenphthalate, and polyolefins such as polyethylene and polypropylene, and similar polymers.
  • a color plastic article comprising a plastic substrate comprising a first polymer, and a plastic first film laminated to the substrate and comprising a second polymer which transmits ultraviolet radiation, and the mutable colorant composition of the present invention dispersed in the second polymer.
  • An image can be printed on the plastic article by irradiating selected portions of the first film with ultraviolet radiation at a wavelength and dosage level sufficient to irreversibly mutate the colorant at the selected portions.
  • a transparency comprises a first film laminated to a second film, the first film comprising the mutable colorant composition of the present invention.
  • the second film can include a mutable colorant composition of another color.
  • a printed plastic bottle 90 printed in accordance with an embodiment of the present invention is illustrated in Figure 10.
  • the bottle 90 is formed by a plastic substrate 92 which includes mutable colorant composition dispersed therein and has a printed image 94 formed therein by irradiating selected portions of the substrate with ultraviolet radiation.
  • a transparency 95 printed in accordance with an embodiment of the present invention is illustrated in Figure 1 1.
  • the transparency 95 comprises a substrate 96 including a mutable colorant composition of the present invention dispersed therein and an image 98 formed therein by irradiating selected portions of the substrate with ultraviolet radiation.
  • Transparencies such as the one shown in Figure 1 1 can be made in a variety of sizes and can be used to generate banners, signs, bumper stickers, shdes, and the like.
  • the method of the present invention for producing shdes allows a presenter to change and print shdes just moments before a presentation. This process of the present invention can even be used to directly produce microfilm and microfiche materials.
  • Figure 12 illustrates an embodiment of the present invention comprising a transparency 100 printed with a plurahty of discrete images 102 on separate sections of the film 104 to form a plurality of shdes such as 35mm shdes for visual projection.
  • the printed slides are cut out of the film and mounted in shde holders.
  • multicolor shdes can be produced in accordance with this process of the present invention.

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Organic Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Optics & Photonics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Theoretical Computer Science (AREA)
  • Biochemistry (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Molecular Biology (AREA)
  • General Health & Medical Sciences (AREA)
  • Educational Administration (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Business, Economics & Management (AREA)
  • Inorganic Chemistry (AREA)
  • Educational Technology (AREA)
  • Photometry And Measurement Of Optical Pulse Characteristics (AREA)
  • Paints Or Removers (AREA)
  • Printing Methods (AREA)
  • Credit Cards Or The Like (AREA)
  • Pens And Brushes (AREA)
  • Ink Jet Recording Methods And Recording Media Thereof (AREA)
  • Coating Apparatus (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
EP96917030A 1995-06-05 1996-06-03 Zeitliche markierung,uv-strahlungsdetektion und druck unter verwendung von uv-löschbaren farbmitteln Ceased EP0830256A2 (de)

Priority Applications (5)

Application Number Priority Date Filing Date Title
EP01104021A EP1123811A3 (de) 1995-06-05 1996-06-03 UV-löschbares Anstrichmittel und Verfahren zur Anwendung
EP01104058A EP1123814A2 (de) 1995-06-05 1996-06-03 Verfahren und Vorrichtung zum Nachweis von UV-Bestrahlung
EP01104036A EP1123812A2 (de) 1995-06-05 1996-06-03 Gegenstand für Farbdruck und Druckverfahren
EP01104057A EP1132119A3 (de) 1995-06-05 1996-06-03 Verfahren zum Informationsverbergen und Dokument zur gesicherten Kommunikation von verbergenden Informationen
EP01104037A EP1123813A2 (de) 1995-06-05 1996-06-03 Aufzeichnungsinstrument für UV-löschbare Markierung

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US46210595A 1995-06-05 1995-06-05
US462105 1995-06-05
PCT/US1996/008478 WO1996039302A2 (en) 1995-06-05 1996-06-03 Temporary marking, ultraviolet radiation detection, and printing, all using photoerasable colorants

Related Child Applications (5)

Application Number Title Priority Date Filing Date
EP01104058A Division EP1123814A2 (de) 1995-06-05 1996-06-03 Verfahren und Vorrichtung zum Nachweis von UV-Bestrahlung
EP01104036A Division EP1123812A2 (de) 1995-06-05 1996-06-03 Gegenstand für Farbdruck und Druckverfahren
EP01104057A Division EP1132119A3 (de) 1995-06-05 1996-06-03 Verfahren zum Informationsverbergen und Dokument zur gesicherten Kommunikation von verbergenden Informationen
EP01104037A Division EP1123813A2 (de) 1995-06-05 1996-06-03 Aufzeichnungsinstrument für UV-löschbare Markierung
EP01104021A Division EP1123811A3 (de) 1995-06-05 1996-06-03 UV-löschbares Anstrichmittel und Verfahren zur Anwendung

Publications (1)

Publication Number Publication Date
EP0830256A2 true EP0830256A2 (de) 1998-03-25

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Family Applications (6)

Application Number Title Priority Date Filing Date
EP01104037A Withdrawn EP1123813A2 (de) 1995-06-05 1996-06-03 Aufzeichnungsinstrument für UV-löschbare Markierung
EP01104021A Withdrawn EP1123811A3 (de) 1995-06-05 1996-06-03 UV-löschbares Anstrichmittel und Verfahren zur Anwendung
EP01104058A Withdrawn EP1123814A2 (de) 1995-06-05 1996-06-03 Verfahren und Vorrichtung zum Nachweis von UV-Bestrahlung
EP01104057A Withdrawn EP1132119A3 (de) 1995-06-05 1996-06-03 Verfahren zum Informationsverbergen und Dokument zur gesicherten Kommunikation von verbergenden Informationen
EP96917030A Ceased EP0830256A2 (de) 1995-06-05 1996-06-03 Zeitliche markierung,uv-strahlungsdetektion und druck unter verwendung von uv-löschbaren farbmitteln
EP01104036A Withdrawn EP1123812A2 (de) 1995-06-05 1996-06-03 Gegenstand für Farbdruck und Druckverfahren

Family Applications Before (4)

Application Number Title Priority Date Filing Date
EP01104037A Withdrawn EP1123813A2 (de) 1995-06-05 1996-06-03 Aufzeichnungsinstrument für UV-löschbare Markierung
EP01104021A Withdrawn EP1123811A3 (de) 1995-06-05 1996-06-03 UV-löschbares Anstrichmittel und Verfahren zur Anwendung
EP01104058A Withdrawn EP1123814A2 (de) 1995-06-05 1996-06-03 Verfahren und Vorrichtung zum Nachweis von UV-Bestrahlung
EP01104057A Withdrawn EP1132119A3 (de) 1995-06-05 1996-06-03 Verfahren zum Informationsverbergen und Dokument zur gesicherten Kommunikation von verbergenden Informationen

Family Applications After (1)

Application Number Title Priority Date Filing Date
EP01104036A Withdrawn EP1123812A2 (de) 1995-06-05 1996-06-03 Gegenstand für Farbdruck und Druckverfahren

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EP (6) EP1123813A2 (de)
JP (1) JPH11507600A (de)
AU (1) AU5972596A (de)
BR (1) BR9608387A (de)
CA (1) CA2219463A1 (de)
CO (1) CO4440458A1 (de)
MX (1) MX9709059A (de)
WO (1) WO1996039302A2 (de)
ZA (1) ZA964549B (de)

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FI114433B (fi) 2002-01-23 2004-10-15 Nokia Corp Otossiirtymän koodaaminen videokoodauksessa
SE525673C2 (sv) 2003-08-13 2005-04-05 Peltor Ab Indikeringsanordning för åldringsbestämning av föremål av plast samt skyddshjälm innefattande en indikeringsanordning
US7875457B2 (en) 2004-05-12 2011-01-25 Axsun Technologies, Inc. Erasable taggant distribution channel validation method and system
FR2907126B1 (fr) * 2006-10-12 2010-09-17 Soppec Dispositif de marquage de peinture, peinture incorporant un tel dispositif et procede de revelation associe
DE102008049848A1 (de) * 2008-10-01 2010-04-08 Tesa Se Mehrbereichsindikator
US8284385B2 (en) 2009-11-13 2012-10-09 Lincoln Global, Inc. Welding arc apparel with UV activated images
US9121776B2 (en) 2009-11-13 2015-09-01 Lincoln Global, Inc. Welding arc apparel with UV or thermochromic activated images
JP5871204B1 (ja) * 2014-06-17 2016-03-01 Dic株式会社 土木建築材料

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JPH0749546B2 (ja) * 1987-01-21 1995-05-31 株式会社巴川製紙所 紫外線発色性インキ
JPS63179977A (ja) * 1987-01-21 1988-07-23 Tomoegawa Paper Co Ltd 紫外線発色性塗料
JPH03134072A (ja) * 1989-10-20 1991-06-07 Tomoegawa Paper Co Ltd 紫外線変色性インキ
US5865471A (en) * 1993-08-05 1999-02-02 Kimberly-Clark Worldwide, Inc. Photo-erasable data processing forms
CN1131468A (zh) * 1993-08-05 1996-09-18 金伯利-克拉克公司 可变色组合物及其使用方法
ATE197594T1 (de) * 1994-12-20 2000-12-15 Kimberly Clark Co Verbesserte, änderbare zusammensetzung
CO4560378A1 (es) * 1995-01-17 1998-02-10 Kimberly Clark Co Composicion estabilizadora para colorantes y metodo para estabilizar a la luz un colorante

Non-Patent Citations (1)

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Title
See references of WO9639302A2 *

Also Published As

Publication number Publication date
AU5972596A (en) 1996-12-24
EP1123812A2 (de) 2001-08-16
BR9608387A (pt) 1999-05-11
EP1123811A3 (de) 2004-02-04
ZA964549B (en) 1996-12-12
CO4440458A1 (es) 1997-05-07
WO1996039302A2 (en) 1996-12-12
EP1123814A2 (de) 2001-08-16
MX9709059A (es) 1998-06-28
EP1132119A3 (de) 2004-02-04
EP1132119A2 (de) 2001-09-12
EP1123813A2 (de) 2001-08-16
CA2219463A1 (en) 1996-12-12
JPH11507600A (ja) 1999-07-06
WO1996039302A3 (en) 1997-07-17
EP1123811A2 (de) 2001-08-16

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