EP0761466A1 - Elément donneur de colorant stabilisé, utilisé pour le transfert thermique de colorant - Google Patents

Elément donneur de colorant stabilisé, utilisé pour le transfert thermique de colorant Download PDF

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Publication number
EP0761466A1
EP0761466A1 EP96420277A EP96420277A EP0761466A1 EP 0761466 A1 EP0761466 A1 EP 0761466A1 EP 96420277 A EP96420277 A EP 96420277A EP 96420277 A EP96420277 A EP 96420277A EP 0761466 A1 EP0761466 A1 EP 0761466A1
Authority
EP
European Patent Office
Prior art keywords
dye
stabilizer
layer
donor element
molecular weight
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.)
Granted
Application number
EP96420277A
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German (de)
English (en)
Other versions
EP0761466B1 (fr
Inventor
Richard Cornelius Van Hanehem
James Paul Muehlbauer
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.)
Eastman Kodak Co
Original Assignee
Eastman Kodak Co
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
Priority claimed from US08/632,818 external-priority patent/US5620941A/en
Application filed by Eastman Kodak Co filed Critical Eastman Kodak Co
Publication of EP0761466A1 publication Critical patent/EP0761466A1/fr
Application granted granted Critical
Publication of EP0761466B1 publication Critical patent/EP0761466B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • B41M5/382—Contact thermal transfer or sublimation processes
    • B41M5/385—Contact thermal transfer or sublimation processes characterised by the transferable dyes or pigments
    • B41M5/39—Dyes containing one or more carbon-to-nitrogen double bonds, e.g. azomethine
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/382—Contact thermal transfer or sublimation processes
    • B41M5/392—Additives, other than colour forming substances, dyes or pigments, e.g. sensitisers, transfer promoting agents

Definitions

  • This invention relates to the use of certain stabilizers in dye-donor elements for thermal dye transfer systems, and more particularly to stabilizers for p-phenylenediamine cyan dyes in such elements.
  • thermal transfer systems have been developed to obtain prints from pictures which have been generated electronically from a color video camera.
  • an electronic picture is first subjected to color separation by color filters.
  • the respective color-separated images are then converted into electrical signals.
  • These signals are then operated on to produce cyan, magenta and yellow electrical signals.
  • These signals are then transmitted to a thermal printer.
  • a cyan, magenta or yellow dye-donor element is placed face-to-face with a dye-receiving element.
  • the two are then inserted between a thermal printing head and a platen roller.
  • a line-type thermal printing head is used to apply heat from the back of the dye-donor sheet.
  • the thermal printing head has many heating elements and is heated up sequentially in response to the cyan, magenta or yellow signal. The process is then repeated for the other two colors. A color hard copy is thus obtained which corresponds to the original picture viewed on a screen. Further details of this process and an apparatus for carrying it out are contained in U.S. patent 4,621,271.
  • the dye layer of a dye-donor element for resistive head thermal dye transfer generally comprises a polymeric binder and diffusible dyes.
  • the percentage of dye in the layer is typically quite high, in the range of 20 to 80 %.
  • the dye is usually dissolved in the binder or phase-separated into small domains.
  • the slipping layer may contain mobile lubricating oils or materials which can act as plasticizers or solvents for the dye layer. This enables the dye to become mobile, allowing changes to occur in the layer including further phase separation, migration of the dye to the surface, and even crystallization of the dye.
  • Dye may also transfer to the slipping layer.
  • U.S. Patent 4,695,287 relates to dye-donor elements for thermal dye transfer containing a p-phenylenediamine cyan dye.
  • the p-phenylenediamine cyan dye may be subject to degradation during storage, when the dye layer comes into contact with humidity from the atmosphere or when the elements are stored at elevated temperatures.
  • U.S. Patent 3,868,252 relates to the use of nitroxyl-containing polymers as oxidants in a silver halide-based color diffusion transfer process.
  • nitroxyl-containing polymers as oxidants in a silver halide-based color diffusion transfer process.
  • polymers are useful in a dye-donor element to improve raw stock keeping performance.
  • a dye-donor element for thermal dye transfer comprising a support having thereon a dye layer comprising a naphthol-p-phenylenediamine cyan dye in a polymeric binder, the dye layer also containing a stabilizer, the stabilizer comprising a compound containing a nitroxyl free radical and having a molecular weight of at least 400 or a hydroxylamine moiety and having a molecular weight of at least 330, the stabilizer being present in the amount of 5-10 mole% based on the weight of the dye.
  • n in the above compound is 8 and the compound has the following structure:
  • This compound is made using Tinuvin 770® from Ciba-Geigy as a starting material and modifying it by the procedure described in J.Phys.Chem., 97 , 1138 (1993), to create the free radical.
  • Compounds containing a hydroxylamine moiety useful in the invention can comprise, for example: wherein R 2 and R 3 each independently represents an alkyl group of from about 1 to about 15 carbon atoms.
  • both R 2 and R 3 are t-C 5 H 11 which would result in the following structure:
  • Any naphthol-p-phenylenediamine cyan dye can be used in the dye-donor employed in the invention provided it is transferable to the dye-receiving layer by the action of heat.
  • Examples of such dyes include
  • the above dyes may be employed singly or in combination.
  • the dyes may be used at a coverage of from about 0.05 to about 1 g/m 2 and are preferably hydrophobic.
  • a dye-barrier layer may be employed in the dye-donor elements of the invention to improve the density of the transferred dye.
  • Such dye-barrier layer materials include hydrophilic materials such as those described and claimed in U. S. Patent 4,716,144.
  • the dye layer of the dye-donor element may be coated on the support or printed thereon by a printing technique such as a gravure process.
  • any material can be used as the support for the dye-donor element of the invention provided it is dimensionally stable and can withstand the heat of the thermal head.
  • Such materials include polyesters such as poly(ethylene terephthalate); polyamides; polycarbonates; cellulose esters; fluorine polymers; polyethers; polyacetals; polyolefins; and polyimides.
  • the support generally has a thickness of from about 5 to about 200 ⁇ m. It may also be coated with a subbing layer, if desired, such as those materials described in U. S. Patents 4,695,288 or 4,737,486.
  • the dye in the dye-donor element of the invention is dispersed in a polymeric binder such as a cellulose derivative, e.g., cellulose acetate hydrogen phthalate, cellulose acetate, cellulose acetate propionate, cellulose acetate butyrate, cellulose triacetate or any of the materials described in U. S. Patent 4,700,207; a polycarbonate; polyvinyl acetate, poly(styrene-co-acrylonitrile), a poly(sulfone) or a poly(phenylene oxide).
  • the binder may be used at a coverage of from about 0.1 to about 5 g/m 2 .
  • the reverse side of the dye-donor element may be coated with a slipping layer to prevent the printing head from sticking to the dye-donor element.
  • a slipping layer would comprise either a solid or liquid lubricating material or mixtures thereof, with or without a polymeric binder or a surface active agent.
  • Preferred lubricating materials include oils or semi-crystalline organic solids that melt below 100°C such as poly(vinyl stearate), beeswax, perfluorinated alkyl ester polyethers, poly(caprolactone), silicone oil, poly(tetrafluoroethylene), carbowax, poly(ethylene glycols), or any of those materials disclosed in U. S.
  • Suitable polymeric binders for the slipping layer include poly(vinyl alcohol-co-butyral), poly(vinyl alcohol-co-acetal), poly(styrene), poly(vinyl acetate), cellulose acetate butyrate, cellulose acetate propionate, cellulose acetate or ethyl cellulose.
  • the amount of the lubricating material to be used in the slipping layer depends largely on the type of lubricating material, but is generally in the range of about .001 to about 2 g/m 2 . If a polymeric binder is employed, the lubricating material is present in the range of 0.05 to 50 weight %, preferably 0.5 to 40, of the polymeric binder employed.
  • the dye-receiving element that is used with the dye-donor element of the invention usually comprises a support having thereon a dye image-receiving layer.
  • the support may be a transparent film such as a poly(ether sulfone), a polyimide, a cellulose ester such as cellulose acetate, a poly(vinyl alcohol-co-acetal) or a poly(ethylene terephthalate).
  • the support for the dye-receiving element may also be reflective such as barytacoated paper, polyethylene-coated paper, an ivory paper, a condenser paper or a synthetic paper such as DuPont Tyvek®.
  • Pigmented supports such as white polyester (transparent polyester with white pigment incorporated therein) may also be used.
  • the dye image-receiving layer may comprise, for example, a polycarbonate, a polyurethane, a polyester, polyvinyl chloride, poly(styrene-co-acrylonitrile), poly(caprolactone), a poly(vinyl acetal) such as poly(vinyl alcohol-co-butyral), poly(vinyl alcohol-cobenzal), poly(vinyl alcohol-co-acetal) or mixtures thereof.
  • the dye image-receiving layer may be present in any amount which is effective for the intended purpose. In general, good results have been obtained at a concentration of from about 1 to about 5 g/m 2 .
  • the dye-donor elements of the invention are used to form a dye transfer image.
  • Such a process comprises imagewise heating a dye-donor element as described above and transferring a dye image to a dye-receiving element to form the dye transfer image.
  • the dye-donor element of the invention may be used in sheet form or in a continuous roll or ribbon. If a continuous roll or ribbon is employed, it may have alternating areas of dyes such as sublimable cyan and/or magenta and/or yellow and/or black or other dyes. Thus, one-, two-, three- or four-color elements (or higher numbers also) are included within the scope of the invention.
  • the dye-donor element comprises a poly(ethylene terephthalate) support coated with sequential repeating areas of cyan, yellow and magenta, and the above process steps are sequentially performed for each color to obtain a three-color dye transfer image.
  • the process is only performed for a single color, then a monochrome dye transfer image is obtained.
  • Thermal printing heads which can be used to transfer dye from the dye-donor elements of the invention are available commercially.
  • a thermal dye transfer assemblage of the invention comprises
  • the above assemblage comprising these two elements may be preassembled as an integral unit when a monochrome image is to be obtained. This may be done by temporarily adhering the two elements together at their margins. After transfer, the dye-receiving element is then peeled apart to reveal the dye transfer image.
  • the above assemblage is formed three times using different dye-donor elements. After the first dye is transferred, the elements are peeled apart. A second dye-donor element (or another area of the donor element with a different dye area) is then brought in register with the dye-receiving element and the process repeated. The third color is obtained in the same manner.
  • Tinuvin 123® (Ciba-Geigy)
  • Control 13 2,4,6-tri-t-butyl phenol
  • Control 14 t-butyl hydroquinone
  • Cyan dye donor samples for incubation testing were prepared by coating onto an unsubbed 100 ⁇ m poly(ethylene terephthalate) support a dye layer containing 0.27 g/m 2 of cyan dye C-1 above and various addenda to be tested in the amounts indicated in Table 1, in a cellulose acetate propionate binder (2.5% acetyl, 45% propionyl) from a toluene, methanol, cyclopentanone (70:25:5 wt-ratio) solvent mixture.
  • Example 2 This example was similar to Example 1 to show compounds of the invention compared to various other types of free radical compounds, including nitroxyl, hydrazyl, and galvinoxyl free radical-carrying compounds.
  • the stabilizers were all used at 5 mole % of dye. The following results were obtained:
  • Example 2 This example was similar to Example 2 to show compounds of the invention compared to various other commonly used antioxidants or stabilizers. The following results were obtained:

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  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Thermal Transfer Or Thermal Recording In General (AREA)
EP19960420277 1995-08-30 1996-08-22 Elément donneur de colorant stabilisé, utilisé pour le transfert thermique de colorant Expired - Lifetime EP0761466B1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US297995P 1995-08-30 1995-08-30
US2979 1995-08-30
US632818 1996-04-16
US08/632,818 US5620941A (en) 1996-04-16 1996-04-16 Stabilizers for dye-donor element used in thermal dye transfer

Publications (2)

Publication Number Publication Date
EP0761466A1 true EP0761466A1 (fr) 1997-03-12
EP0761466B1 EP0761466B1 (fr) 1999-08-04

Family

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Family Applications (1)

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EP19960420277 Expired - Lifetime EP0761466B1 (fr) 1995-08-30 1996-08-22 Elément donneur de colorant stabilisé, utilisé pour le transfert thermique de colorant

Country Status (2)

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EP (1) EP0761466B1 (fr)
JP (1) JPH09109564A (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002042089A3 (fr) * 2000-11-21 2003-03-06 Du Pont Element d'imagerie thermique possedant une stabilite amelioree
EP1525996A3 (fr) * 2000-11-21 2005-05-11 E.I. du Pont de Nemours and Company Eléments d'imagerie thermiques possedant une stabilité améliorée

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1507826A4 (fr) 2002-05-17 2007-11-07 Othera Pharmaceuticals Inc Amelioration de l'evolution des cataractes et d'autres maladies ophtalmiques
US7825134B2 (en) 2003-05-19 2010-11-02 Othera Holding, Inc. Amelioration of cataracts, macular degeneration and other ophthalmic diseases

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2232776A1 (fr) * 1973-06-05 1975-01-03 Eastman Kodak Co
EP0227096A2 (fr) * 1985-12-24 1987-07-01 EASTMAN KODAK COMPANY (a New Jersey corporation) Elément donneur de colorant cyan utilisé pour le transfert de colorant par la chaleur
EP0312812A2 (fr) * 1987-10-23 1989-04-26 EASTMAN KODAK COMPANY (a New Jersey corporation) Elément donneur d'un stabilisant utilisé pour le transfert d'un colorant par la chaleur
US5288691A (en) * 1993-02-23 1994-02-22 Eastman Kodak Company Stabilizers for dye-donor element used in thermal dye transfer
EP0628880A2 (fr) * 1993-06-05 1994-12-14 Japat Ltd Photorécepteur

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2232776A1 (fr) * 1973-06-05 1975-01-03 Eastman Kodak Co
EP0227096A2 (fr) * 1985-12-24 1987-07-01 EASTMAN KODAK COMPANY (a New Jersey corporation) Elément donneur de colorant cyan utilisé pour le transfert de colorant par la chaleur
US4695287A (en) * 1985-12-24 1987-09-22 Eastman Kodak Company Cyan dye-donor element used in thermal dye transfer
US4695287B1 (fr) * 1985-12-24 1990-03-27 Eastman Kodak Co
EP0312812A2 (fr) * 1987-10-23 1989-04-26 EASTMAN KODAK COMPANY (a New Jersey corporation) Elément donneur d'un stabilisant utilisé pour le transfert d'un colorant par la chaleur
US5288691A (en) * 1993-02-23 1994-02-22 Eastman Kodak Company Stabilizers for dye-donor element used in thermal dye transfer
EP0628880A2 (fr) * 1993-06-05 1994-12-14 Japat Ltd Photorécepteur

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002042089A3 (fr) * 2000-11-21 2003-03-06 Du Pont Element d'imagerie thermique possedant une stabilite amelioree
EP1525996A3 (fr) * 2000-11-21 2005-05-11 E.I. du Pont de Nemours and Company Eléments d'imagerie thermiques possedant une stabilité améliorée
US7005407B2 (en) 2000-11-21 2006-02-28 E. I. Du Pont De Nemours And Company Thermal imaging elements having improved stability
AU2002225703B2 (en) * 2000-11-21 2007-04-26 E.I. Du Pont De Nemours And Company Thermal imaging elements having improved stability

Also Published As

Publication number Publication date
EP0761466B1 (fr) 1999-08-04
JPH09109564A (ja) 1997-04-28

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