+

US20020170461A1 - Thermochromic ink composition - Google Patents

Thermochromic ink composition Download PDF

Info

Publication number
US20020170461A1
US20020170461A1 US10/143,707 US14370702A US2002170461A1 US 20020170461 A1 US20020170461 A1 US 20020170461A1 US 14370702 A US14370702 A US 14370702A US 2002170461 A1 US2002170461 A1 US 2002170461A1
Authority
US
United States
Prior art keywords
thermochromic
ink composition
substrate
thermochromic ink
printed
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.)
Abandoned
Application number
US10/143,707
Inventor
Rajendra Mehta
Richard Shields
Aurelia Kalman
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.)
Individual
Original Assignee
Individual
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 Individual filed Critical Individual
Priority to US10/143,707 priority Critical patent/US20020170461A1/en
Publication of US20020170461A1 publication Critical patent/US20020170461A1/en
Abandoned legal-status Critical Current

Links

Images

Classifications

    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]

Definitions

  • thermochromic ink composition which is provided on a security document, and more particularly, to a thermochromic ink composition, which, when applied to selected areas of a substrate, provides enhanced adhesion of toners which are subsequently printed onto those areas of the substrate with a non-impact printing device.
  • thermochromic inks typically comprise an electron-donating chromogenic substance, an electron-accepting substance, and a solvent which undergo a reversible color change in response to a change in the ambient temperature, for example, from ambient to freezing or from ambient to elevated temperatures.
  • the color change which takes place may be a change from one color to another, from colored to colorless, or from colorless to colored.
  • Thermochromic inks have frequently been used to provide security features on documents such as checks and other business forms. For example, documents may be provided with an area or areas which will change color upon exposure to a temperature change such that the authenticity of the document may be verified or so that anti-copy protection is provided.
  • thermochromic inks are often subsequently imaged with non-impact printers such as laser, ink jet, and ion deposition printers or impact printers to provide variable or non-variable information.
  • non-impact printers such as laser, ink jet, and ion deposition printers or impact printers to provide variable or non-variable information.
  • non-impact printers such as laser, ink jet, and ion deposition printers or impact printers
  • thermochromic ink which may be printed on a document as well as a need for providing good toner adhesion to indicia subsequently printed by non-impact printers onto areas previously printed with the thermochromic ink.
  • thermochromic ink composition which is applied to a security document by a letter press printing method and which provides enhanced toner adhesion when areas of the document containing the thermochromic ink are subsequently printed by a non-impact printing device such as a laser printer.
  • a security document which comprises a substrate having first and second surfaces in which a thermochromic ink composition is applied to a least a portion of the first or second surface.
  • the ink composition provides a color change in response to a change in temperature.
  • the thermochromic ink composition also provides enhanced adhesion for toner particles which are subsequently printed on the substrate.
  • thermochromic ink composition preferably comprises a thermochromic aqueous slurry and an ink vehicle, where the thermochromic aqueous slurry preferably comprises particles of an encapsulated thermochromic pigment dispersed in a water-based slurry.
  • the ink vehicle is selected from the group consisting of 1) a phenolic modified rosin and an oil compatible with the rosin, 2) at least one styrene maleic anhydride resin and a glycol, or 3) an acrylic resin varnish.
  • the ink vehicle comprises a phenolic modified rosin and an oil compatible with the rosin.
  • the rosin has preferably been modified with formaldehyde and pentaerythritol.
  • the oil is preferably selected from the group consisting of tall oil, linseed oil, and combinations thereof.
  • the thermochromic ink composition preferably comprises from about 20 to 45% by weight of the thermochromic aqueous slurry, from about 25 to 50% by weight of the phenolic modified rosin, from about 25 to 45% by weight tall oil, and from about 0 to 25% by weight linseed oil.
  • thermochromic ink composition preferably comprises from about 20 to 45% by weight of the thermochromic aqueous slurry, from about 20 to 50% by weight phenolic modified rosin, and from about 20 to 45% by weight tall oil.
  • the composition preferably further comprises from about 1 to 25% weight linseed oil.
  • the ink vehicle comprises at least one styrene maleic anhydride resin and a glycol.
  • the thermochromic ink composition preferably comprises from about 15 to 45% by weight of the thermochromic aqueous slurry and from about 30 to 75% by weight of the ink vehicle.
  • the ink composition preferably further comprises from about 1 to 10% by weight triethanolamine, and from about 1 to 10% by weight propylene glycol.
  • the ink vehicle comprises an acrylic resin varnish.
  • the thermochromic ink composition preferably comprises from about 15 to 25% by weight of a styrene maleic anhydride resin/glycol vehicle, 30 to 50% by weight of the acrylic resin varnish, from about 20 to 45% by weight of the thermochromic aqueous slurry, and from about 10 to 30% by weight linseed oil.
  • the ink composition preferably further comprises from about 1 to 6% by weight triethanolamine, and from about 1 to 5% by weight soybean oil.
  • thermochromic ink composition is preferably provided on a security document by applying the composition onto at least a portion of the first and second surface of a substrate. Toner is then printed over at least a portion of the area of the first or second surface containing the thermochromic ink composition.
  • the thermochromic ink composition is applied to the substrate by a letterpress printing process.
  • thermochromic ink composition of the present invention thus provides a dual function in that it provides a color change in response to a change in temperature as well as providing enhanced adhesion of toner particles to a substrate.
  • thermochromic ink composition for use on security documents which provides a color change in response to a change in temperature and which also provides enhanced toner adhesion when the substrate is subsequently printed with a non-impact printing device.
  • FIG. 1 is a front elevation view of a security document which has been printed with the thermochromic ink composition of the present invention.
  • thermochromic ink composition of the present invention may be applied to security documents such as checks, money orders, negotiable certificates or other documents of value as well as business forms, or other documents in which it is desirable to provide a color change for authentication or other purposes.
  • thermochromic ink composition preferably comprises a) a thermochromic aqueous slurry, and b) an ink vehicle selected from the group consisting of 1) a phenolic modified rosin and an oil compatible with the rosin, 2) at least one styrene maleic anhydride resin and a glycol, or 3) an acrylic resin varnish. While not wishing to be bound to any specific theory or mechanism, it is believed that the enhanced toner adhesion provided by the ink composition results from the use of an ink vehicle containing either a phenolic modified rosin, a maleic anhydride resin, or an acrylic resin.
  • the preferred ink vehicle for use in the present invention comprises a phenolic modified rosin (modified with formaldehyde and pentaerythritol) and an oil which is compatible with the rosin.
  • a preferred phenolic modified rosin is available from Akzo Nobel Resins, Mendham, New Jersey, under the designation SPR-10.
  • Suitable compatible oils include tall oil and linseed oil.
  • the tall oil is preferable a tall oil fatty acid ester available from Arizona Chemical, Panama City, Fla., under the designation SYLFAT® 9012.
  • the linseed oil is preferably an alkali refined linseed oil obtained from Degen Oil Chemical, Jersey City, N.J., under the designation P-1037 Supreme Linseed oil.
  • An alternative ink vehicle which is suitable for use in the present invention comprises at least one styrene maleic anhydride resin and a glycol.
  • Preferred styrene maleic anhydride resin vehicles are commercially available from Kustom Blending, Inc., Florence, Ky. under the designations KS-153 and KS-100.
  • Such vehicles comprise styrene maleic anhydride resins dissolved in glycol with a small amount of amine.
  • the KS-100 vehicle further includes urea.
  • the ink composition preferably further includes an amount of propylene glycol and optionally, an amine, preferably triethanolamine.
  • thermochromic composition of the present invention is an acrylic resin varnish.
  • a preferred acrylic resin varnish is commercially available from Ron Ink under the designation “Laser Safe Sheet-fed Varnish-24809 MQ5” and includes an acrylic resin, an aliphatic oil, a pigment or filler, wax, and soybean oil.
  • the ink composition preferably further includes an amount of the styrene-maleic anhydride resin vehicle described above, an amine, and an oil such as linseed oil and/or soybean oil.
  • thermochromic aqueous slurry included in the ink composition may be obtained from a number of commercial suppliers and preferably comprises particles of an encapsulated thermochromic pigment dispersed in a water-based slurry.
  • a preferred thermochromic aqueous slurry for use in the present invention is commercially available from Neil Brothers Ltd., Birmingham, United Kingdom, under the designation AQ Type 25 or AQ Type 42.
  • the aqueous slurry may be formulated so as to provide a variety of color changes.
  • the thermochromic aqueous slurry provides a reversible color change from colored to colorless which occurs at a temperature range of between about 85° F. and 125° F.
  • the color change may be from a first color to a second color.
  • a non-thermochromic yellow dye with a thermochromic red slurry
  • the color appears orange at ambient temperature, then changes to yellow at elevated temperatures.
  • blue thermochromic slurry with a non-thermochromic yellow dye
  • a color change will occur from green to yellow.
  • blue thermochromic slurry with a non-thermochromic red dye
  • the color change will be from purple to red.
  • thermochromic aqueous slurries can be mixed with non-thermochromic dyes as described above to cause a color to color change. Such slurries include blue, gray, pink, red, orange and purple.
  • thermochromic ink composition is preferably made by first preparing the ink vehicle, then adding the pre-mixed thermochromic aqueous slurry to the ink vehicle.
  • a solution of phenolic modified rosin is prepared at 52-53% concentration in a tall oil fatty acid ester.
  • the liquid tall oil fatty acid ester is added to a kettle at room temperature and then heated to 135-140° C. while the phenolic modified rosin is slowly added with stirring. Once in solution, the hot mixture is filtered through 150 micron mesh and cooled.
  • the thermochromic aqueous slurry is then added to the resin solution while mixing, which solution is preferably warmed to about 55° C.
  • thermochromic ink composition is generally applied to a document substrate by any suitable letterpress printing process.
  • Letterpress processes permit greater quantities of ink to be applied to a substrate than lithographic processes, resulting in more vibrant, contrasting color responses.
  • the composition may be applied in selected areas which can form blocks of color, or they may be applied so as to form images, numbers, letters, symbols, or other indicia.
  • the composition may be selectively printed on the surface of stock papers during the manufacturing process, and may be applied to one or both sides of the substrate.
  • the substrate may comprise any suitable paper substrate including bond papers, calendared papers, safety papers, and opaque white papers.
  • a security document 10 is illustrated in the form of a check comprising a substrate 12 having a first surface 14 , with selected portions which have been printed with the thermochromic ink composition of the present invention.
  • the ink has been printed as the company name and address 16 , and in areas 18 and 20 which may be subsequently printed with the check amount and payee information.
  • the thermochromic ink composition in areas 18 and 20 , the information subsequently printed using toner in those areas with a non-impact printer will exhibit increased adhesion to the substrate.
  • the authenticity of the document may be verified in those areas by subjecting the document to a change in temperature so that a color change can be observed.
  • thermochromic ink composition may be printed on selected portions of a document in a number of patterns, depending on the desired application. It should be appreciated that may different combinations for placement of the ink composition on a security document are possible and are within the scope of this invention.
  • thermochromic ink composition of the present invention provides areas of a document with enhanced toner adhesion when printed by non-impact printing devices, it should be appreciated that the document surface is also receptive to being printed by a variety of conventional impact printing devices using ink or transfer ribbons.
  • thermochromic ink compositions prepared using an ink vehicle comprising a phenolic modified resin and an oil in accordance with the present invention: Formula 1 Weight % Phenolic modified rosin 1 35.6 Tall oil fatty acid ester 2 31.8 Thermochromic aqueous slurry 3 32.6
  • Formula 1 above was tested to determine its toner adhesion enhancing capabilities on a 20# bond substrate.
  • the substrate was printed with a Lexmark 4039 printer using conventional toner available from Lexmark.
  • the tapes used for the test were 3M 811 removable tape and 3M 610 permanent tape.
  • the tape was applied over the toner images in areas containing the thermochromic ink as well as uncoated imaged areas.
  • the tape was smoothed down with a 1 pound roller (force of about 1 lb/in. 2 ) and removed after about 5 seconds of adhesion. Toner transfer to the tape was then observed subjectively. It was clear that less toner was removed in areas containing the thermochromic ink than in those areas which did not contain the ink.
  • thermochromic ink compositions prepared using a styrene maleic anhydride resin ink vehicle in accordance with the present invention: Formula 1 Weight % KS-153 1 41.67 KS-100 2 13.89 Propylene glycol 6.66 Thermochromic aqueous slurry 3 26.67 Sucrose acetate isobutyrate 4 11.11
  • thermochromic ink composition prepared using an ink vehicle comprising an acrylic resin varnish in accordance with the present invention: Formula 1 Weight % KS-153 1 17.09 24809 MQ5 2 25.10 Thermochromic aqueous slurry 3 25.65 Linseed oil 25.13 Triethanolamine 4.27 Soy bean oil 1.71 Slip Dispersion 4 1.05
  • Formula 1 above was tested to determine its toner adhesion enhancing capabilities on the following cellulosic substrates: 24# bond from International Paper; 24# bond from Union Camp, and 20# bond from Unisource.
  • the first substrate was printed using a Xerox Docutec printer.
  • the second substrate was printed with a Lexmark 4039.
  • the third substrate was printed using a Hewlett Packard Laserjet 6HP printer using conventional toner in cartridges available from the respective printer companies.
  • the tapes used for the test were 3M811 (standard Scotch Magic Tape®) and 3M610 permanent tape.
  • the tape was applied over tone images in areas containing the thermochromic ink as well as over uncoated imaged areas.
  • the tape was smoothed down with a force of about 1 lb/in. 2 and removed after about 5 seconds of adhesion. Toner transfer to the tape was then observed subjectively. Estimated toner transfer of coated areas in all samples was less than 2% transfer. In addition, it was observed that less toner was removed in areas containing the thermochromic ink than in uncoated areas.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)

Abstract

A thermochromic ink composition is provided for use on security documents such as checks which provides a reversible color change in response to heat. The ink composition includes a thermochromic aqueous slurry and an ink vehicle comprising either a phenolic modified rosin and a compatible oil, a styrene maleic anhydride resin and a glycol, or an acrylic resin varnish. The ink composition is printed on at least a portion of a substrate using letterpress printing methods and provides enhanced adhesion to toner when applied to areas of a substrate which are subsequently printed with a non-impact printing device such as a laser printer.

Description

    CROSS REFERENCE TO RELATED APPLICATIONS
  • This application is a division of U.S. patent application Ser. No. 09/498,669 filed Feb. 7, 2000.[0001]
    • BACKGROUND OF THE INVENTION
  • This invention relates to a thermochromic ink composition which is provided on a security document, and more particularly, to a thermochromic ink composition, which, when applied to selected areas of a substrate, provides enhanced adhesion of toners which are subsequently printed onto those areas of the substrate with a non-impact printing device. [0002]
  • The use of thermochromic inks in the art is known. Such inks typically comprise an electron-donating chromogenic substance, an electron-accepting substance, and a solvent which undergo a reversible color change in response to a change in the ambient temperature, for example, from ambient to freezing or from ambient to elevated temperatures. The color change which takes place may be a change from one color to another, from colored to colorless, or from colorless to colored. Thermochromic inks have frequently been used to provide security features on documents such as checks and other business forms. For example, documents may be provided with an area or areas which will change color upon exposure to a temperature change such that the authenticity of the document may be verified or so that anti-copy protection is provided. [0003]
  • Documents printed with thermochromic inks are often subsequently imaged with non-impact printers such as laser, ink jet, and ion deposition printers or impact printers to provide variable or non-variable information. However, a problem has existed with providing images on security documents with non-impact printers as it has been difficult to achieve satisfactory toner bonding on paper products used to make such security documents. And, because of the lack of strong adherence of toner to paper, documents printed by non-impact printers are often subject to deliberate alteration by counterfeiters. It would be desirable to be able to provide thermochromic inks on a document as well as to be able to add additional printed information with a non-impact printer while avoiding the problem of inadvertent or intentional toner removal to provide an added security feature. [0004]
  • Accordingly, there is still a need in the art for a thermochromic ink which may be printed on a document as well as a need for providing good toner adhesion to indicia subsequently printed by non-impact printers onto areas previously printed with the thermochromic ink. [0005]
    • SUMMARY OF THE INVENTION
  • The present invention meets that need by providing a thermochromic ink composition which is applied to a security document by a letter press printing method and which provides enhanced toner adhesion when areas of the document containing the thermochromic ink are subsequently printed by a non-impact printing device such as a laser printer. [0006]
  • According to one aspect of the present invention, a security document is provided which comprises a substrate having first and second surfaces in which a thermochromic ink composition is applied to a least a portion of the first or second surface. The ink composition provides a color change in response to a change in temperature. The thermochromic ink composition also provides enhanced adhesion for toner particles which are subsequently printed on the substrate. [0007]
  • The thermochromic ink composition preferably comprises a thermochromic aqueous slurry and an ink vehicle, where the thermochromic aqueous slurry preferably comprises particles of an encapsulated thermochromic pigment dispersed in a water-based slurry. The ink vehicle is selected from the group consisting of 1) a phenolic modified rosin and an oil compatible with the rosin, 2) at least one styrene maleic anhydride resin and a glycol, or 3) an acrylic resin varnish. [0008]
  • In one embodiment of the invention, the ink vehicle comprises a phenolic modified rosin and an oil compatible with the rosin. The rosin has preferably been modified with formaldehyde and pentaerythritol. The oil is preferably selected from the group consisting of tall oil, linseed oil, and combinations thereof. In one embodiment, the thermochromic ink composition preferably comprises from about 20 to 45% by weight of the thermochromic aqueous slurry, from about 25 to 50% by weight of the phenolic modified rosin, from about 25 to 45% by weight tall oil, and from about 0 to 25% by weight linseed oil. In an alternative embodiment, the thermochromic ink composition preferably comprises from about 20 to 45% by weight of the thermochromic aqueous slurry, from about 20 to 50% by weight phenolic modified rosin, and from about 20 to 45% by weight tall oil. The composition preferably further comprises from about 1 to 25% weight linseed oil. [0009]
  • In an alternative embodiment of the invention, the ink vehicle comprises at least one styrene maleic anhydride resin and a glycol. In this embodiment, the thermochromic ink composition preferably comprises from about 15 to 45% by weight of the thermochromic aqueous slurry and from about 30 to 75% by weight of the ink vehicle. The ink composition preferably further comprises from about 1 to 10% by weight triethanolamine, and from about 1 to 10% by weight propylene glycol. [0010]
  • In yet another alternative embodiment of the invention, the ink vehicle comprises an acrylic resin varnish. In this embodiment, the thermochromic ink composition preferably comprises from about 15 to 25% by weight of a styrene maleic anhydride resin/glycol vehicle, 30 to 50% by weight of the acrylic resin varnish, from about 20 to 45% by weight of the thermochromic aqueous slurry, and from about 10 to 30% by weight linseed oil. The ink composition preferably further comprises from about 1 to 6% by weight triethanolamine, and from about 1 to 5% by weight soybean oil. [0011]
  • The thermochromic ink composition is preferably provided on a security document by applying the composition onto at least a portion of the first and second surface of a substrate. Toner is then printed over at least a portion of the area of the first or second surface containing the thermochromic ink composition. Preferably, the thermochromic ink composition is applied to the substrate by a letterpress printing process. [0012]
  • The thermochromic ink composition of the present invention thus provides a dual function in that it provides a color change in response to a change in temperature as well as providing enhanced adhesion of toner particles to a substrate. [0013]
  • Accordingly, it is a feature of the present invention to provide a thermochromic ink composition for use on security documents which provides a color change in response to a change in temperature and which also provides enhanced toner adhesion when the substrate is subsequently printed with a non-impact printing device. Other features and advantages of the invention will be apparent from the following description, the accompanying drawing, and the appended claims. [0014]
    • BRIEF DESCRIPTION OF THE DRAWINGS
  • FIG. 1 is a front elevation view of a security document which has been printed with the thermochromic ink composition of the present invention.[0015]
    • DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
  • The thermochromic ink composition of the present invention may be applied to security documents such as checks, money orders, negotiable certificates or other documents of value as well as business forms, or other documents in which it is desirable to provide a color change for authentication or other purposes. [0016]
  • The thermochromic ink composition preferably comprises a) a thermochromic aqueous slurry, and b) an ink vehicle selected from the group consisting of 1) a phenolic modified rosin and an oil compatible with the rosin, 2) at least one styrene maleic anhydride resin and a glycol, or 3) an acrylic resin varnish. While not wishing to be bound to any specific theory or mechanism, it is believed that the enhanced toner adhesion provided by the ink composition results from the use of an ink vehicle containing either a phenolic modified rosin, a maleic anhydride resin, or an acrylic resin. [0017]
  • The preferred ink vehicle for use in the present invention comprises a phenolic modified rosin (modified with formaldehyde and pentaerythritol) and an oil which is compatible with the rosin. A preferred phenolic modified rosin is available from Akzo Nobel Resins, Mendham, New Jersey, under the designation SPR-10. Suitable compatible oils include tall oil and linseed oil. The tall oil is preferable a tall oil fatty acid ester available from Arizona Chemical, Panama City, Fla., under the designation SYLFAT® 9012. The linseed oil is preferably an alkali refined linseed oil obtained from Degen Oil Chemical, Jersey City, N.J., under the designation P-1037 Supreme Linseed oil. [0018]
  • An alternative ink vehicle which is suitable for use in the present invention comprises at least one styrene maleic anhydride resin and a glycol. Preferred styrene maleic anhydride resin vehicles are commercially available from Kustom Blending, Inc., Florence, Ky. under the designations KS-153 and KS-100. Such vehicles comprise styrene maleic anhydride resins dissolved in glycol with a small amount of amine. The KS-100 vehicle further includes urea. When such vehicles are used, the ink composition preferably further includes an amount of propylene glycol and optionally, an amine, preferably triethanolamine. [0019]
  • Another alternative ink vehicle which may be used in the thermochromic composition of the present invention is an acrylic resin varnish. A preferred acrylic resin varnish is commercially available from Ron Ink under the designation “Laser Safe Sheet-fed Varnish-24809 MQ5” and includes an acrylic resin, an aliphatic oil, a pigment or filler, wax, and soybean oil. When such a vehicle is used, the ink composition preferably further includes an amount of the styrene-maleic anhydride resin vehicle described above, an amine, and an oil such as linseed oil and/or soybean oil. [0020]
  • The thermochromic aqueous slurry included in the ink composition may be obtained from a number of commercial suppliers and preferably comprises particles of an encapsulated thermochromic pigment dispersed in a water-based slurry. A preferred thermochromic aqueous slurry for use in the present invention is commercially available from Neil Brothers Ltd., Birmingham, United Kingdom, under the designation AQ Type 25 or AQ Type 42. The aqueous slurry may be formulated so as to provide a variety of color changes. Preferably, the thermochromic aqueous slurry provides a reversible color change from colored to colorless which occurs at a temperature range of between about 85° F. and 125° F. Depending on the dyes included in the thermochromic slurry, the color change may be from a first color to a second color. For example, by adding a non-thermochromic yellow dye with a thermochromic red slurry, the color appears orange at ambient temperature, then changes to yellow at elevated temperatures. By mixing blue thermochromic slurry with a non-thermochromic yellow dye, a color change will occur from green to yellow. By mixing blue thermochromic slurry with a non-thermochromic red dye, the color change will be from purple to red. A variety of other thermochromic aqueous slurries can be mixed with non-thermochromic dyes as described above to cause a color to color change. Such slurries include blue, gray, pink, red, orange and purple. [0021]
  • The thermochromic ink composition is preferably made by first preparing the ink vehicle, then adding the pre-mixed thermochromic aqueous slurry to the ink vehicle. In a preferred method, a solution of phenolic modified rosin is prepared at 52-53% concentration in a tall oil fatty acid ester. The liquid tall oil fatty acid ester is added to a kettle at room temperature and then heated to 135-140° C. while the phenolic modified rosin is slowly added with stirring. Once in solution, the hot mixture is filtered through 150 micron mesh and cooled. The thermochromic aqueous slurry is then added to the resin solution while mixing, which solution is preferably warmed to about 55° C. [0022]
  • The thermochromic ink composition is generally applied to a document substrate by any suitable letterpress printing process. Letterpress processes permit greater quantities of ink to be applied to a substrate than lithographic processes, resulting in more vibrant, contrasting color responses. The composition may be applied in selected areas which can form blocks of color, or they may be applied so as to form images, numbers, letters, symbols, or other indicia. The composition may be selectively printed on the surface of stock papers during the manufacturing process, and may be applied to one or both sides of the substrate. The substrate may comprise any suitable paper substrate including bond papers, calendared papers, safety papers, and opaque white papers. [0023]
  • With reference to the drawing, it must be appreciated that Patent Office requirements for solid black line drawings on a white surface make illustration of some of the subtleties of our invention relating to different colors difficult by the required Patent Office drawings alone. Reference to the following detailed description of the illustration will make full appreciation of the drawing and our invention possible. [0024]
  • Referring now to FIG. 1, a [0025] security document 10 is illustrated in the form of a check comprising a substrate 12 having a first surface 14, with selected portions which have been printed with the thermochromic ink composition of the present invention. The ink has been printed as the company name and address 16, and in areas 18 and 20 which may be subsequently printed with the check amount and payee information. By providing the thermochromic ink composition in areas 18 and 20, the information subsequently printed using toner in those areas with a non-impact printer will exhibit increased adhesion to the substrate. In addition, the authenticity of the document may be verified in those areas by subjecting the document to a change in temperature so that a color change can be observed. For example, heat from a finger held on a portion of the thermochromic ink printed document for a few seconds may be sufficient to initiate a reversible color change to verify authenticity. Other potential uses for the thermochromic ink composition of the present invention will be apparent to those skilled in the art. The thermochromic ink composition may be printed on selected portions of a document in a number of patterns, depending on the desired application. It should be appreciated that may different combinations for placement of the ink composition on a security document are possible and are within the scope of this invention.
  • While the thermochromic ink composition of the present invention provides areas of a document with enhanced toner adhesion when printed by non-impact printing devices, it should be appreciated that the document surface is also receptive to being printed by a variety of conventional impact printing devices using ink or transfer ribbons. [0026]
  • In order that the invention may be more readily understood, reference is made to the following examples which are intended to illustrate the invention, but not limit the scope thereof. [0027]
    • EXAMPLE 1
  • The following formulas illustrate thermochromic ink compositions prepared using an ink vehicle comprising a phenolic modified resin and an oil in accordance with the present invention: [0028]
    Formula 1 Weight %
    Phenolic modified rosin1 35.6
    Tall oil fatty acid ester2 31.8
    Thermochromic aqueous slurry3 32.6
  • [0029]
    Formula 2 Weight %
    Phenolic modified rosin1 36.9
    Tall oil fatty acid ester2 24.6
    Alkali refined linseed oil3 7.5
    Thermochromic aqueous slurry4 31.0
  • Formula 1 above was tested to determine its toner adhesion enhancing capabilities on a 20# bond substrate. The substrate was printed with a Lexmark 4039 printer using conventional toner available from Lexmark. The tapes used for the test were 3M 811 removable tape and 3M 610 permanent tape. The tape was applied over the toner images in areas containing the thermochromic ink as well as uncoated imaged areas. The tape was smoothed down with a 1 pound roller (force of about 1 lb/in.[0030] 2) and removed after about 5 seconds of adhesion. Toner transfer to the tape was then observed subjectively. It was clear that less toner was removed in areas containing the thermochromic ink than in those areas which did not contain the ink.
    • Example 2
  • The following formulas illustrate thermochromic ink compositions prepared using a styrene maleic anhydride resin ink vehicle in accordance with the present invention: [0031]
    Formula 1 Weight %
    KS-1531 41.67
    KS-1002 13.89
    Propylene glycol 6.66
    Thermochromic aqueous slurry3 26.67
    Sucrose acetate isobutyrate4 11.11
  • [0032]
    Formula 2 Weight %
    KS-1531 71
    Thermochromic aqueous slurry2 24
    Triethanolamine  5
  • [0033]
    Formula 3 Weight %
    KS-1531 63
    Propylene glycol  4
    Thermochromic aqueous slurry2 26
    Triethanolamine  3
    Slip dispersion3
    • EXAMPLE 3
  • The following formula illustrates a thermochromic ink composition prepared using an ink vehicle comprising an acrylic resin varnish in accordance with the present invention: [0034]
    Formula 1 Weight %
    KS-1531 17.09
    24809 MQ52 25.10
    Thermochromic aqueous slurry3 25.65
    Linseed oil 25.13
    Triethanolamine 4.27
    Soy bean oil 1.71
    Slip Dispersion4 1.05
  • Formula 1 above was tested to determine its toner adhesion enhancing capabilities on the following cellulosic substrates: 24# bond from International Paper; 24# bond from Union Camp, and 20# bond from Unisource. The first substrate was printed using a Xerox Docutec printer. The second substrate was printed with a Lexmark 4039. The third substrate was printed using a Hewlett Packard Laserjet 6HP printer using conventional toner in cartridges available from the respective printer companies. [0035]
  • The tapes used for the test were 3M811 (standard Scotch Magic Tape®) and 3M610 permanent tape. The tape was applied over tone images in areas containing the thermochromic ink as well as over uncoated imaged areas. The tape was smoothed down with a force of about 1 lb/in.[0036] 2 and removed after about 5 seconds of adhesion. Toner transfer to the tape was then observed subjectively. Estimated toner transfer of coated areas in all samples was less than 2% transfer. In addition, it was observed that less toner was removed in areas containing the thermochromic ink than in uncoated areas.
  • While certain representative embodiments and details have been shown for purposes of illustrating the invention, it will be apparent to those skilled in the art that various changes in the methods and apparatus disclosed herein may be made without departing from the scope of the invention, which is defined in the appended claims.[0037]

Claims (5)

What is claimed is:
1. A security document comprising a substrate having first and second surfaces; said substrate having a thermochromic ink composition applied to at least a portion of said first or second surface, said thermochromic ink composition comprising a thermochromic aqueous slurry and an ink vehicle; wherein said thermochromic ink composition provides enhanced adhesion for toner particles printed thereon.
2. A security document as claimed in claim 1 wherein said ink vehicle is selected from the group consisting of: 1) a phenolic modified rosin and an oil compatible with said rosin, or 2) at least one styrene maleic anhydride resin and a glycol, or 3) an acrylic resin varnish.
3. A method of applying a thermochromic ink composition comprising an encapsulated thermochromic pigment and an ink vehicle, said method comprising the steps of:
a) providing a substrate having first and second surfaces,
b) applying said thermochromic ink composition onto at least a portion of said first or second surface of said substrate; and
c) printing tone over at least a portion of the area of said first or second surface containing said thermochromic ink composition.
4. The method of claim 3 wherein said thermochromic ink composition is applied to said substrate by a letterpress printing process.
5. The method of claim 3 wherein said thermochromic ink composition provides enhanced adhesion of said toner to said substrate.
US10/143,707 2000-02-07 2002-05-10 Thermochromic ink composition Abandoned US20020170461A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US10/143,707 US20020170461A1 (en) 2000-02-07 2002-05-10 Thermochromic ink composition

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US09/498,669 US6413305B1 (en) 2000-02-07 2000-02-07 Thermochromic ink composition
US10/143,707 US20020170461A1 (en) 2000-02-07 2002-05-10 Thermochromic ink composition

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
US09/498,669 Division US6413305B1 (en) 2000-02-07 2000-02-07 Thermochromic ink composition

Publications (1)

Publication Number Publication Date
US20020170461A1 true US20020170461A1 (en) 2002-11-21

Family

ID=23982013

Family Applications (2)

Application Number Title Priority Date Filing Date
US09/498,669 Expired - Fee Related US6413305B1 (en) 2000-02-07 2000-02-07 Thermochromic ink composition
US10/143,707 Abandoned US20020170461A1 (en) 2000-02-07 2002-05-10 Thermochromic ink composition

Family Applications Before (1)

Application Number Title Priority Date Filing Date
US09/498,669 Expired - Fee Related US6413305B1 (en) 2000-02-07 2000-02-07 Thermochromic ink composition

Country Status (1)

Country Link
US (2) US6413305B1 (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080290178A1 (en) * 2007-05-25 2008-11-27 Target Brands, Inc. Transaction card with thermochromic feature
USD685854S1 (en) * 2012-05-22 2013-07-09 Dolphin Organics LLC Label
US8652996B2 (en) 2011-12-31 2014-02-18 Sanford, L.P. Irreversible thermochromic pigment capsules
US8664156B2 (en) 2011-12-31 2014-03-04 Sanford, L.P. Irreversible thermochromic ink compositions
US8709973B2 (en) 2011-12-31 2014-04-29 Sanford, L.P. Irreversible thermochromic ink compositions
US8865621B2 (en) 2012-08-06 2014-10-21 Sanford, L.P. Irreversible color changing ink compositions

Families Citing this family (77)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000025260A1 (en) 1998-10-23 2000-05-04 Coinstar, Inc. Coin-discriminator voucher anti-counterfeiting method and apparatus
US6644696B2 (en) * 1998-10-23 2003-11-11 Coinstar, Inc. Coin-discriminator voucher anti-counterfeiting method and apparatus
US6413305B1 (en) * 2000-02-07 2002-07-02 The Standard Register Company Thermochromic ink composition
JP3658272B2 (en) † 2000-04-07 2005-06-08 大日本インキ化学工業株式会社 Printing ink composition
US20030200725A1 (en) * 2001-06-29 2003-10-30 Aloisi Robert J. Packaging material and products comprising indicia-former which changes from a first visual condition to a second visual condition and indicates a characteristic of the package contents
US6972780B2 (en) * 2002-01-25 2005-12-06 Intel Corporation System and method of printing on thermochromic film
US6783991B1 (en) * 2002-02-06 2004-08-31 The Standard Register Company Reversible and reusable authentication system for secure documents
US20050097046A1 (en) 2003-10-30 2005-05-05 Singfield Joy S. Wireless electronic check deposit scanning and cashing machine with web-based online account cash management computer application system
US20050112768A1 (en) * 2003-11-26 2005-05-26 Thomas Evans Method of authenticating tagged polymers
US7094364B2 (en) * 2003-11-26 2006-08-22 General Electric Company Method of authenticating polymers, authenticatable polymers, methods of making authenticatable polymers and authenticatable articles, and articles made there from
US7169615B2 (en) * 2003-11-26 2007-01-30 General Electric Company Method of authenticating polymers, authenticatable polymers, methods of making authenticatable polymers and authenticatable articles, and articles made there from
US20090266991A1 (en) * 2003-11-26 2009-10-29 Sabic Innovative Plastics Ip B.V. Method of authenticating tagged polymers
US20050110978A1 (en) * 2003-11-26 2005-05-26 Radislav Potyrailo Method of authenticating articles, authenticatable polymers, and authenticatable articles
BRPI0609139A2 (en) * 2005-03-19 2010-02-23 Dystar Textilfarben Gmbh & Co safety kit and safety paint
US8092866B2 (en) * 2005-03-22 2012-01-10 World Wide Lines, Inc. Thermochromatic pigment covered article and method of making the same
US20070129463A1 (en) * 2005-12-05 2007-06-07 Zeying Ma Pigment-based ink formulations including dispersants and binders and methods of making same
US8799147B1 (en) 2006-10-31 2014-08-05 United Services Automobile Association (Usaa) Systems and methods for remote deposit of negotiable instruments with non-payee institutions
US7873200B1 (en) 2006-10-31 2011-01-18 United Services Automobile Association (Usaa) Systems and methods for remote deposit of checks
US8351677B1 (en) 2006-10-31 2013-01-08 United Services Automobile Association (Usaa) Systems and methods for remote deposit of checks
US8708227B1 (en) 2006-10-31 2014-04-29 United Services Automobile Association (Usaa) Systems and methods for remote deposit of checks
US7876949B1 (en) 2006-10-31 2011-01-25 United Services Automobile Association Systems and methods for remote deposit of checks
US7885451B1 (en) 2006-10-31 2011-02-08 United Services Automobile Association (Usaa) Systems and methods for displaying negotiable instruments derived from various sources
US10380559B1 (en) 2007-03-15 2019-08-13 United Services Automobile Association (Usaa) Systems and methods for check representment prevention
US8959033B1 (en) 2007-03-15 2015-02-17 United Services Automobile Association (Usaa) Systems and methods for verification of remotely deposited checks
US8433127B1 (en) 2007-05-10 2013-04-30 United Services Automobile Association (Usaa) Systems and methods for real-time validation of check image quality
US8538124B1 (en) 2007-05-10 2013-09-17 United Services Auto Association (USAA) Systems and methods for real-time validation of check image quality
US9058512B1 (en) 2007-09-28 2015-06-16 United Services Automobile Association (Usaa) Systems and methods for digital signature detection
US9898778B1 (en) 2007-10-23 2018-02-20 United Services Automobile Association (Usaa) Systems and methods for obtaining an image of a check to be deposited
US9892454B1 (en) 2007-10-23 2018-02-13 United Services Automobile Association (Usaa) Systems and methods for obtaining an image of a check to be deposited
US8358826B1 (en) 2007-10-23 2013-01-22 United Services Automobile Association (Usaa) Systems and methods for receiving and orienting an image of one or more checks
US9159101B1 (en) 2007-10-23 2015-10-13 United Services Automobile Association (Usaa) Image processing
US7996316B1 (en) * 2007-10-30 2011-08-09 United Services Automobile Association Systems and methods to modify a negotiable instrument
US8046301B1 (en) * 2007-10-30 2011-10-25 United Services Automobile Association (Usaa) Systems and methods to modify a negotiable instrument
US7996315B1 (en) * 2007-10-30 2011-08-09 United Services Automobile Association (Usaa) Systems and methods to modify a negotiable instrument
US7996314B1 (en) * 2007-10-30 2011-08-09 United Services Automobile Association (Usaa) Systems and methods to modify a negotiable instrument
US8001051B1 (en) * 2007-10-30 2011-08-16 United Services Automobile Association (Usaa) Systems and methods to modify a negotiable instrument
US8320657B1 (en) 2007-10-31 2012-11-27 United Services Automobile Association (Usaa) Systems and methods to use a digital camera to remotely deposit a negotiable instrument
US8290237B1 (en) 2007-10-31 2012-10-16 United Services Automobile Association (Usaa) Systems and methods to use a digital camera to remotely deposit a negotiable instrument
US7900822B1 (en) 2007-11-06 2011-03-08 United Services Automobile Association (Usaa) Systems, methods, and apparatus for receiving images of one or more checks
US7896232B1 (en) 2007-11-06 2011-03-01 United Services Automobile Association (Usaa) Systems, methods, and apparatus for receiving images of one or more checks
US7821453B2 (en) * 2007-12-20 2010-10-26 Sarnoff Corporation Distributed iterative multimodal sensor fusion method for improved collaborative localization and navigation
US10380562B1 (en) 2008-02-07 2019-08-13 United Services Automobile Association (Usaa) Systems and methods for mobile deposit of negotiable instruments
US8351678B1 (en) 2008-06-11 2013-01-08 United Services Automobile Association (Usaa) Duplicate check detection
US8422758B1 (en) 2008-09-02 2013-04-16 United Services Automobile Association (Usaa) Systems and methods of check re-presentment deterrent
US10504185B1 (en) 2008-09-08 2019-12-10 United Services Automobile Association (Usaa) Systems and methods for live video financial deposit
US7962411B1 (en) 2008-09-30 2011-06-14 United Services Automobile Association (Usaa) Atomic deposit transaction
US8275710B1 (en) 2008-09-30 2012-09-25 United Services Automobile Association (Usaa) Systems and methods for automatic bill pay enrollment
US7974899B1 (en) 2008-09-30 2011-07-05 United Services Automobile Association (Usaa) Atomic deposit transaction
US7885880B1 (en) 2008-09-30 2011-02-08 United Services Automobile Association (Usaa) Atomic deposit transaction
US8391599B1 (en) 2008-10-17 2013-03-05 United Services Automobile Association (Usaa) Systems and methods for adaptive binarization of an image
US7949587B1 (en) 2008-10-24 2011-05-24 United States Automobile Association (USAA) Systems and methods for financial deposits by electronic message
US7970677B1 (en) 2008-10-24 2011-06-28 United Services Automobile Association (Usaa) Systems and methods for financial deposits by electronic message
US8388024B2 (en) * 2009-01-27 2013-03-05 The Standard Register Company Double mailer intermediate
US8452689B1 (en) 2009-02-18 2013-05-28 United Services Automobile Association (Usaa) Systems and methods of check detection
US10956728B1 (en) 2009-03-04 2021-03-23 United Services Automobile Association (Usaa) Systems and methods of check processing with background removal
FR2947842B1 (en) * 2009-07-10 2014-05-09 Sarl Imprimerie Papeterie De Montchapet SECURE PRINTING PAPER AND METHOD OF OBTAINING
US8542921B1 (en) 2009-07-27 2013-09-24 United Services Automobile Association (Usaa) Systems and methods for remote deposit of negotiable instrument using brightness correction
US9779392B1 (en) 2009-08-19 2017-10-03 United Services Automobile Association (Usaa) Apparatuses, methods and systems for a publishing and subscribing platform of depositing negotiable instruments
US8977571B1 (en) 2009-08-21 2015-03-10 United Services Automobile Association (Usaa) Systems and methods for image monitoring of check during mobile deposit
US8699779B1 (en) 2009-08-28 2014-04-15 United Services Automobile Association (Usaa) Systems and methods for alignment of check during mobile deposit
US20110240723A1 (en) * 2010-03-31 2011-10-06 David Yost Double Postcard and Intermediate Form For Same
US9129340B1 (en) 2010-06-08 2015-09-08 United Services Automobile Association (Usaa) Apparatuses, methods and systems for remote deposit capture with enhanced image detection
US9790390B2 (en) 2010-11-02 2017-10-17 Standard Register, Inc. Thermochromic ink and document printed therewith
US10380565B1 (en) 2012-01-05 2019-08-13 United Services Automobile Association (Usaa) System and method for storefront bank deposits
US10552810B1 (en) 2012-12-19 2020-02-04 United Services Automobile Association (Usaa) System and method for remote deposit of financial instruments
US9742711B2 (en) 2013-03-15 2017-08-22 Sorenson Ip Holdings, Llc Communication systems and related methods for notifying devices having a plurality of unique identifiers about missed communications
CN103254691A (en) * 2013-04-07 2013-08-21 上海欣渊文化用品有限公司 Reversible temperature change erasable neutral ink composition and its manufacturing method
FR3005436B1 (en) 2013-05-13 2016-01-01 Fasver METHOD AND DEVICE FOR SECURELY PROTECTING AN OFFICIAL DOCUMENT AND OFFICIAL DOCUMENT SO PROTECTED
US11138578B1 (en) 2013-09-09 2021-10-05 United Services Automobile Association (Usaa) Systems and methods for remote deposit of currency
US9286514B1 (en) 2013-10-17 2016-03-15 United Services Automobile Association (Usaa) Character count determination for a digital image
JP6334340B2 (en) 2014-09-12 2018-05-30 株式会社東芝 Forgery and alteration prevention medium, forgery and alteration prevention medium creation device, and forgery and alteration prevention medium creation method
US10402790B1 (en) 2015-05-28 2019-09-03 United Services Automobile Association (Usaa) Composing a focused document image from multiple image captures or portions of multiple image captures
US11359137B2 (en) 2017-05-03 2022-06-14 University Of South Florida Microencapsulated thermochromic materials and uses thereof
US11030752B1 (en) 2018-04-27 2021-06-08 United Services Automobile Association (Usaa) System, computing device, and method for document detection
GB2595495B (en) 2020-05-28 2025-04-16 Alphabond Tech Ltd Composition
US11900755B1 (en) 2020-11-30 2024-02-13 United Services Automobile Association (Usaa) System, computing device, and method for document detection and deposit processing
US12211095B1 (en) 2024-03-01 2025-01-28 United Services Automobile Association (Usaa) System and method for mobile check deposit enabling auto-capture functionality via video frame processing

Citations (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4028118A (en) * 1972-05-30 1977-06-07 Pilot Ink Co., Ltd. Thermochromic materials
US4421560A (en) * 1981-04-08 1983-12-20 Pilot Ink Company Ltd. Thermochromatic materials
US4425161A (en) * 1980-11-27 1984-01-10 Yutaka Shibahashi Thermochromic materials
US4851282A (en) * 1986-03-01 1989-07-25 Matsui Shikiso Chemical Co., Ltd. Thermochromic particle containing linear material
US5401060A (en) * 1993-06-14 1995-03-28 Wallace Computer Services, Inc. Document with heat and pressure sensitive chromogentic composition thereon
US5405932A (en) * 1991-11-04 1995-04-11 Hoechst Ag Oil-soluble, phenolic resin-modified natural resinic acid esters, processes for their preparation and their use as self-gelling printing ink resins
US5490956A (en) * 1992-10-26 1996-02-13 Pilot Ink Co., Ltd. Thermochromic opaque composition, laminate member employing the same, and three-dimensional member employing said laminate member and capable of concealing and revealing the interior
US5585425A (en) * 1994-03-25 1996-12-17 The Pilot Ink Co., Ltd. Thermochromic opaque/transparent composition, laminate member employing the same, and three-dimensional member employing said laminate member and capable of concealing and revealing the interior
US5591255A (en) * 1993-12-29 1997-01-07 Chromatic Technologies, Inc. Thermochromic ink formulations, nail lacquer and methods of use
US5636874A (en) * 1994-04-05 1997-06-10 Micro Format, Inc. Temperature sensitive security document
US5698296A (en) * 1989-04-18 1997-12-16 The Standard Register Company Business document having security features
US5826915A (en) * 1995-02-17 1998-10-27 Wallace Computer Services, Inc. Method of using thermochromic material on security documents and product
US5873604A (en) * 1995-05-25 1999-02-23 Verify First Technologies, Inc. Document security system having thermo-activated pantograph and validation mark
US5902389A (en) * 1997-03-27 1999-05-11 Arizona Chemical Company Rosin-based resin ink vehicles
US5997849A (en) * 1993-12-29 1999-12-07 Chromatic Technologies, Inc. Thermochromic ink formulations, nail lacquer and methods of use
US6358596B1 (en) * 1999-04-27 2002-03-19 The Standard Register Company Multi-functional transparent secure marks
US6396927B1 (en) * 1995-05-25 2002-05-28 Verify First Technologies, Inc. Variable density verification
US6413305B1 (en) * 2000-02-07 2002-07-02 The Standard Register Company Thermochromic ink composition
US6607813B2 (en) * 2001-08-23 2003-08-19 The Standard Register Company Simulated security thread by cellulose transparentization

Patent Citations (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4028118A (en) * 1972-05-30 1977-06-07 Pilot Ink Co., Ltd. Thermochromic materials
US4425161A (en) * 1980-11-27 1984-01-10 Yutaka Shibahashi Thermochromic materials
US4421560A (en) * 1981-04-08 1983-12-20 Pilot Ink Company Ltd. Thermochromatic materials
US4851282A (en) * 1986-03-01 1989-07-25 Matsui Shikiso Chemical Co., Ltd. Thermochromic particle containing linear material
US5698296A (en) * 1989-04-18 1997-12-16 The Standard Register Company Business document having security features
US5405932A (en) * 1991-11-04 1995-04-11 Hoechst Ag Oil-soluble, phenolic resin-modified natural resinic acid esters, processes for their preparation and their use as self-gelling printing ink resins
US5490956A (en) * 1992-10-26 1996-02-13 Pilot Ink Co., Ltd. Thermochromic opaque composition, laminate member employing the same, and three-dimensional member employing said laminate member and capable of concealing and revealing the interior
US5401060A (en) * 1993-06-14 1995-03-28 Wallace Computer Services, Inc. Document with heat and pressure sensitive chromogentic composition thereon
US5997849A (en) * 1993-12-29 1999-12-07 Chromatic Technologies, Inc. Thermochromic ink formulations, nail lacquer and methods of use
US5591255A (en) * 1993-12-29 1997-01-07 Chromatic Technologies, Inc. Thermochromic ink formulations, nail lacquer and methods of use
US6139779A (en) * 1993-12-29 2000-10-31 Chromatic Technologies, Inc. Thermochromic ink formulations and methods of use
US5585425A (en) * 1994-03-25 1996-12-17 The Pilot Ink Co., Ltd. Thermochromic opaque/transparent composition, laminate member employing the same, and three-dimensional member employing said laminate member and capable of concealing and revealing the interior
US5636874A (en) * 1994-04-05 1997-06-10 Micro Format, Inc. Temperature sensitive security document
US5826915A (en) * 1995-02-17 1998-10-27 Wallace Computer Services, Inc. Method of using thermochromic material on security documents and product
US5873604A (en) * 1995-05-25 1999-02-23 Verify First Technologies, Inc. Document security system having thermo-activated pantograph and validation mark
US6396927B1 (en) * 1995-05-25 2002-05-28 Verify First Technologies, Inc. Variable density verification
US6665406B1 (en) * 1995-05-25 2003-12-16 Verify First Technologies, Inc. Variable density verification
US5902389A (en) * 1997-03-27 1999-05-11 Arizona Chemical Company Rosin-based resin ink vehicles
US6358596B1 (en) * 1999-04-27 2002-03-19 The Standard Register Company Multi-functional transparent secure marks
US6413305B1 (en) * 2000-02-07 2002-07-02 The Standard Register Company Thermochromic ink composition
US6607813B2 (en) * 2001-08-23 2003-08-19 The Standard Register Company Simulated security thread by cellulose transparentization

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080290178A1 (en) * 2007-05-25 2008-11-27 Target Brands, Inc. Transaction card with thermochromic feature
US7628336B2 (en) 2007-05-25 2009-12-08 Target Brands, Inc. Transaction card with thermochromic feature
US8652996B2 (en) 2011-12-31 2014-02-18 Sanford, L.P. Irreversible thermochromic pigment capsules
US8664156B2 (en) 2011-12-31 2014-03-04 Sanford, L.P. Irreversible thermochromic ink compositions
US8709973B2 (en) 2011-12-31 2014-04-29 Sanford, L.P. Irreversible thermochromic ink compositions
US8889590B2 (en) 2011-12-31 2014-11-18 Sanford, L.P. Irreversible thermochromic ink compositions
USD685854S1 (en) * 2012-05-22 2013-07-09 Dolphin Organics LLC Label
US8865621B2 (en) 2012-08-06 2014-10-21 Sanford, L.P. Irreversible color changing ink compositions

Also Published As

Publication number Publication date
US6413305B1 (en) 2002-07-02

Similar Documents

Publication Publication Date Title
US6413305B1 (en) Thermochromic ink composition
US5944881A (en) Tri-component security numbering ink
CN101166799B (en) Ink composition and printing method using same
US5541633A (en) Ink jet printing of concealed images on carbonless paper
CA1134980A (en) Printing inks and process for using the same
WO2004067653A2 (en) Inkjet ink sets with combinations of light dye load and dark dye load
US5814579A (en) Multicolor printing system
WO1992014615A1 (en) Non-acidic barrier coating
JP2009149788A (en) Color variable ink and printed matter
CN102341461A (en) Infrared absorbing material, method for synthesizing same, coloring composition, ink, toner, printed material, image recording method and image information detecting method
HU229854B1 (en) Inujet inks providing improved wet smudge on porous print media
US5443629A (en) Latent image ink
CA2638581C (en) Improved invisible ink and scratch pad
US20050075420A1 (en) Invisible ink
EP0326303B1 (en) Improved security for images formed by impact based systems
US5087283A (en) Sympathetic ink for ink jet printer
CN102854762A (en) System and method for producing secure toner-based images
JP3355292B2 (en) Copy protection recording method
JP3902673B2 (en) Method for inkjet printing of concealed images on carbon-free paper
US20020092441A1 (en) Phosphorescent ink composition
CN113817358B (en) Water-based flexographic printing ink and preparation method thereof, color developing ink and ink pen
JP2004151283A (en) Label for displaying thermal history
EP0688838B1 (en) Composition for forming abrasion-removable coatings
EP1564019B1 (en) Copying sheet and method for creating or enhancing copying quality of a copying sheet
JP2656827B2 (en) Desensitizing ink

Legal Events

Date Code Title Description
STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION

点击 这是indexloc提供的php浏览器服务，不要输入任何密码和下载