EP0097220B1 - The stabilization of leucomethylene blue dyes on a printing substrate - Google Patents

The stabilization of leucomethylene blue dyes on a printing substrate Download PDF

Info

Publication number
EP0097220B1
EP0097220B1 EP83101757A EP83101757A EP0097220B1 EP 0097220 B1 EP0097220 B1 EP 0097220B1 EP 83101757 A EP83101757 A EP 83101757A EP 83101757 A EP83101757 A EP 83101757A EP 0097220 B1 EP0097220 B1 EP 0097220B1
Authority
EP
European Patent Office
Prior art keywords
printing substrate
acid
substrate
printing
leucomethylene blue
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP83101757A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0097220A2 (en
EP0097220A3 (en
Inventor
Paul Lewis Gendler
Annette Bronkesh Jaffe
Robert James Twieg
William Emmett Bernier
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.)
International Business Machines Corp
Original Assignee
International Business Machines 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 International Business Machines Corp filed Critical International Business Machines Corp
Publication of EP0097220A2 publication Critical patent/EP0097220A2/en
Publication of EP0097220A3 publication Critical patent/EP0097220A3/en
Application granted granted Critical
Publication of EP0097220B1 publication Critical patent/EP0097220B1/en
Expired 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
    • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
    • B41M5/337—Additives; Binders
    • B41M5/3375—Non-macromolecular compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M1/00—Inking and printing with a printer's forme
    • B41M1/26—Printing on other surfaces than ordinary paper
    • B41M1/36—Printing on other surfaces than ordinary paper on pretreated paper, e.g. parchment, oiled paper, paper for registration purposes
    • 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
    • B41M5/124—Duplicating or marking methods; Sheet materials for use therein using pressure to make a masked colour visible, e.g. to make a coloured support visible, to create an opaque or transparent pattern, or to form colour by uniting colour-forming components
    • B41M5/128—Desensitisers; Compositions for fault correction, detection or identification of the layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/20—Duplicating or marking methods; Sheet materials for use therein using electric current

Definitions

  • This invention relates to substrates for printing on which leucomethylene blue dyes have been stabilized against background formation by the addition of an additive material.
  • Leucomethylene blue dyes find widespread application in color printing technologies such as thermal printing, pressure printing and electrolytic printing.
  • One common problem with the different leuco dyes used in these technlogies is their spontaneous conversion to the dye form by ambient conditions.
  • many methods involving protection of the leuco dyes have been used, such as encapsulation and the use of stilt layers. Such methods have given some success in various printing technologies, but they are not applicable to electrochromic printing, where the mechanism requires an aqueous electrolyte layer to be in intimate contact with the colour-forming agent. It is in electrochromic printing that the present invention finds its most particularly useful application.
  • Electrochromic printing is well known in the art. The present state of electrochromic printing is referenced by US-A-4,211,616 and EP-A-47367, along with the art cited therein.
  • EP-A-47367 discloses a substrate for electrochromic recording characterised in that the substrate comprises paper containing a water soluble leuco methylene blue compound containing a sulphonated aromatic or sulphonated aliphatic moiety.
  • EP-A-0056096 which forms part of the prior art according to Artcle 54(3) and (4) EPC for all designated contracting states, discloses in Example 2 a paper substrate which is coated sequentially with an aqueous solution containing two leuco dyes followed by three coatings of aqueous electrolyte solution.
  • the first solution contains 1 % potassium iodide (leuco dye), 1 % o-sulfobenzoylleucomethylene blue (leuco dye), 0.1% ascorbic acid, 1% oxalic acid, and adjusted to pH 2.3.
  • the electrolyte solution contains 9% ammonium bromide, 10% potassium bromide 1.4% potassium dihydrogen phosphate, and adjusted to pH 7.
  • EP-A-0058855 which also forms part of the prior art according to Article 54(3) and (4) EPC for all contracting states, discloses a printing substrate manufactured from inter alia a coating formulation comprising a leuco dye/electrolyte dispersion in water which consists of 1.0% benzoyl leuco-methylene blue, 4.5% NH 4 Br and 5% Kbr.
  • a dye stabiliser is used in the coating formulation; this stabiliser is 0.1% ascorbic acid.
  • an electrochromic printing substrate comprising a leucomethylene blue dye characterised in that the substrate also includes a stabilising amount of an additive selected from the group, consisting of citric acid, aspartic acid, malonic acid, oxalic acid, tartaric acid, ketomalonic acid monohydrate, glucose and methionine, as sole stabilising agent.
  • paper is treated with an aqueous solution containing from about.5 to 5% by weight of a leuco dye. Generally about 1 % by weight is the most preferred level.
  • the solution also contains a stabilizer in an amount which is, at minimum equal to the molar amount of the dye. The stabilizer may be present up to about 5% by weight concentration. In most instances the solution will also contain bromide ions in an amount of from 1 % to 30% by weight, generally about 15% by weight.
  • the paper contains approximately 10 mg of leuco dye for each standard size page of 215x280 mm (8-1/2x11 inch) dimensions.
  • the operative additives do, however, have a community of physical and mechanical properties. They are all solids which are soluble in water and they all contain an oxygen atom doubly bonded to a carbon atom.
  • the experimental results obtained using the additives of the present invention are summarized in the following table I, showing results obtained with o-sulfobenzoylleucomethylene blue (o-SBLMB) as the substrate leucodye.
  • the most preferred additive is malonic acid.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Color Printing (AREA)
EP83101757A 1982-06-18 1983-02-23 The stabilization of leucomethylene blue dyes on a printing substrate Expired EP0097220B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US38983382A 1982-06-18 1982-06-18
US389833 1995-02-15

Publications (3)

Publication Number Publication Date
EP0097220A2 EP0097220A2 (en) 1984-01-04
EP0097220A3 EP0097220A3 (en) 1985-05-22
EP0097220B1 true EP0097220B1 (en) 1988-06-08

Family

ID=23539902

Family Applications (1)

Application Number Title Priority Date Filing Date
EP83101757A Expired EP0097220B1 (en) 1982-06-18 1983-02-23 The stabilization of leucomethylene blue dyes on a printing substrate

Country Status (3)

Country Link
EP (1) EP0097220B1 (enrdf_load_stackoverflow)
JP (1) JPS58224788A (enrdf_load_stackoverflow)
DE (1) DE3376969D1 (enrdf_load_stackoverflow)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1767377A1 (de) 2005-09-27 2007-03-28 Wipak Walsrode GmbH & Co. KG Individuell markierbare Polymerfolie, Verfahren zu deren Herstellung und zugehörige Produkte

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU628159B2 (en) * 1989-04-07 1992-09-10 Toppan Printing Co. Ltd. Composition for reversible thermal recording medium
JP2751089B2 (ja) * 1992-11-30 1998-05-18 大日本インキ化学工業株式会社 レーザーマーキング方法及び印刷インキ
DE10025832B4 (de) * 2000-05-25 2006-07-06 Aeg Niederspannungstechnik Gmbh & Co Kg Selektiver Leitungsschutzschalter mit Sperrelement
US8754005B2 (en) 2012-08-28 2014-06-17 Kimberly-Clark Worldwide, Inc. Color-changing composition and material

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0056096A2 (en) * 1981-01-09 1982-07-21 International Business Machines Corporation Process for multi-color electrolytic printing
EP0058855A2 (en) * 1981-02-24 1982-09-01 International Business Machines Corporation Electrolytic printing method and apparatus

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1135755B (de) * 1960-02-29 1962-08-30 Dr Karlheinz Pfoertner Fuer ionisierende Strahlen empfindliches, fuer sichtbares Licht unempfindliches Material und Verfahren zu dessen Herstellung
GB1141591A (en) * 1966-01-04 1969-01-29 Agfa Gevaert Nv Recording information with silver halide emulsion or 2-component diazo-type material
GB1360581A (en) * 1971-03-30 1974-07-17 Fuji Photo Film Co Ltd Thermosensitive recording material
US4262937A (en) * 1979-05-23 1981-04-21 Minnesota Mining And Manufacturing Company Carbonless imaging system
US4315068A (en) * 1980-02-05 1982-02-09 Ricoh Co., Ltd. Photo-sensitive and heat-sensitive composition and recording element using same

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0056096A2 (en) * 1981-01-09 1982-07-21 International Business Machines Corporation Process for multi-color electrolytic printing
EP0058855A2 (en) * 1981-02-24 1982-09-01 International Business Machines Corporation Electrolytic printing method and apparatus

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1767377A1 (de) 2005-09-27 2007-03-28 Wipak Walsrode GmbH & Co. KG Individuell markierbare Polymerfolie, Verfahren zu deren Herstellung und zugehörige Produkte

Also Published As

Publication number Publication date
DE3376969D1 (en) 1988-07-14
JPS58224788A (ja) 1983-12-27
EP0097220A2 (en) 1984-01-04
EP0097220A3 (en) 1985-05-22
JPH0243639B2 (enrdf_load_stackoverflow) 1990-10-01

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