EP0480278B1 - Utilisation de colorants d'anthraquinones pour l'impression par transfert thermique - Google Patents

Utilisation de colorants d'anthraquinones pour l'impression par transfert thermique Download PDF

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Publication number
EP0480278B1
EP0480278B1 EP91116652A EP91116652A EP0480278B1 EP 0480278 B1 EP0480278 B1 EP 0480278B1 EP 91116652 A EP91116652 A EP 91116652A EP 91116652 A EP91116652 A EP 91116652A EP 0480278 B1 EP0480278 B1 EP 0480278B1
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EP
European Patent Office
Prior art keywords
alkyl
thermal transfer
transfer printing
anthraquinone dyes
dyes
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Expired - Lifetime
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EP91116652A
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German (de)
English (en)
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EP0480278A1 (fr
Inventor
Ruediger Dr. Sens
Karl-Heinz Dr. Etzbach
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BASF SE
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BASF SE
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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
    • B41M5/3852—Anthraquinone or naphthoquinone dyes
    • 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
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/913—Material designed to be responsive to temperature, light, moisture
    • 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
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/914—Transfer or decalcomania

Definitions

  • the present invention relates to the use of anthraquinone dyes of the general formula I. for thermal transfer printing, in which R has the following meaning: Alkyl, alkoxyalkyl, aryloxyalkyl, alkanoyloxyalkyl, alkoxycarbonyloxyalkyl or alkoxycarbonylalkyl groups, each of which can contain up to 20 C atoms and whose C chain can be interrupted by one to four oxygen atoms in ether function; C5-C8-cycloalkyl groups or a phenyl group, which can each carry C1-C4-alkyl or C1-C4-alkoxy as substituents, and specifically a method for transferring these anthraquinone dyes by diffusion from a support to a plastic-coated substrate using a thermal head.
  • the main heat source used is a thermal head with which short heating impulses lasting a fraction of a second can be emitted.
  • a transfer sheet which contains the dye to be transferred together with one or more binders, a carrier material and possibly other auxiliaries such as release agents or crystallization-inhibiting substances is heated from the rear by the thermal head.
  • the dye diffuses from the transfer sheet into the surface coating of the substrate, e.g. into the plastic layer of a coated paper.
  • the main advantage of this method is that the amount of color transferred and thus the color gradation can be specifically controlled via the energy to be delivered to the thermal head.
  • the three subtractive primary colors yellow, magenta and cyan, possibly also black, are generally used in thermal transfer printing.
  • the dyes used for optimum color recording must have the following properties: easy thermal transferability, low tendency to migrate within or from the surface coating of the recording medium at room temperature, high thermal and photochemical stability and resistance to moisture and chemicals, no tendency to crystallize when the Transfer sheet, a suitable color for subtractive color mixing, a high molar absorption coefficient and easy technical accessibility.
  • the invention was therefore based on the object of finding suitable cyan dyes for thermal transfer printing which come closer to the required property profile than the dyes previously used.
  • a method for the transfer of anthraquinone dyes by diffusion from a support onto a plastic-coated substrate using a thermal head was found, which is characterized in that a support is used for this purpose, on which one or more of the anthraquinone dyes I are located.
  • anthraquinone dyes I themselves are known per se (for example CH-A-148686 and CH-A-222704) or can be obtained by known methods, for example by the following synthesis scheme:
  • Suitable alkyl radicals R are, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, sec-pentyl, tert-pentyl, hexyl, 2-methyl pentyl, heptyl, octyl , 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl and branched radicals of this type, the alkyl radicals having up to 12 C atoms being preferred and those having 6 C atoms are particularly preferred.
  • alkanoyloxyalkyl, alkoxycarbonyloxyalkyl and alkoxycarbonylalkyl groups are also suitable as radical R: - (CH2) 2-O-CO-CH3, - (CH2) 2-O-CO-C4H9, - (CH2) 2-O-CO-C6H13, - (CH2) 4-O-CO-C12H25 and - ( CH2) 5-O-CO-C4H9; - (CH2) 2-O-CO-O-CH3, - (CH2) 2-O-CO-O-C4H9, - (CH2) 2-O-CO-O-C5H11, - (CH2) 3-O- CO-O-C6H13 and - (CH2) 6-O-CO-O-C2H5; - (CH2) 2-CO-O-CH3, - (CH2) 2-CO-O-C3H7, - (CH2) 2-CO-O-C4H9 and - (CH2) 6-CO-O-CH2-CH ( C2H5)
  • the C chain of the radicals R already listed can in each case be interrupted by one to four oxygen atoms in ether function; Examples for this are: - [(CH2) 2-O] 2-CH3, - [(CH2) 2-O] 2-C3H7, - [(CH2) 2-O] 2-C4H9, - [(CH2) 4-O] 2- C2H5, - [(CH2) 2-CH (CH3) -O] 2-C2H5, - [(CH2) 2-O] 3-C4H9, - [(CH2) 2-O] 4-CH3, - [(CH2 ) 3-O] 4-C6H13 and - [(CH2) 2-O] 2 - [(CH2) 3-O] 2-C2H5; - [(CH2) 2-O] 2-Ph, - (CH2) 3-O- (CH2) 2-O-Ph, - [(CH2) 2-O] 3-Ph and - [(CH2) 2- O] 3-Ph-3-CH3; - (CH2) 2-O-CO- (CH2) 2-O
  • the anthraquinone dyes I to be used according to the invention are distinguished from the cyan dyes previously used for thermal transfer printing by the following properties: easier thermal transferability despite the relatively high molecular weight, improved migration properties in the recording medium at room temperature, higher lightfastness, better resistance to moisture and chemicals, better solubility the production of the printing ink, higher color strength, higher color purity and easier technical accessibility.
  • the dyestuffs I possibly in combination with other classes of dyestuffs, give neutral, strong black prints.
  • the transfer sheets required as dye donors for the thermal transfer printing process according to the invention are prepared as follows:
  • the anthraquinone dyes I are dissolved in an organic solvent, e.g. Isobutanol, methyl ethyl ketone, methylene chloride, chlorobenzene, toluene, tetrahydrofuran or mixtures thereof, processed with one or more binders and possibly other auxiliaries such as release agents or crystallization inhibitors to give a printing ink which preferably contains the dyes in molecularly dispersed solution.
  • the printing ink is then applied to an inert support and dried.
  • Suitable binders are all materials which are soluble in organic solvents and are known to serve for thermal transfer printing, for example cellulose derivatives such as methyl cellulose, hydroxypropyl cellulose, cellulose acetate or cellulose acetobutyrate, especially ethyl cellulose, ethyl hydroxyethyl cellulose and cellulose acetate hydrogen phthalate, starch, Alginates, alkyd resins and vinyl resins such as polyvinyl alcohol or polyvinyl pyrrolidone, and especially polyvinyl acetate and polyvinyl butyrate.
  • cellulose derivatives such as methyl cellulose, hydroxypropyl cellulose, cellulose acetate or cellulose acetobutyrate, especially ethyl cellulose, ethyl hydroxyethyl cellulose and cellulose acetate hydrogen phthalate
  • starch Alginates
  • alkyd resins and vinyl resins such as polyvinyl alcohol or polyvinyl pyrrolidone, and
  • polymers and copolymers of acrylates or their derivatives such as polyacrylic acid, polymethyl methacrylate or styrene acrylate copolymers, polyester resins, polyamide resins, polyurethane resins or natural resins such as, for example, gum arabic can be used.
  • binders absorb the dye after the printing ink has dried in the form of a transparent film without visible crystallization.
  • binders are ethyl cellulose or ethyl hydrooxyethyl cellulose of medium to small viscosity settings. Binder mixtures are often recommended, e.g. those made of ethyl cellulose and polyvinyl butyrate in a weight ratio of 2: 1.
  • the weight ratio of binder to dye is usually 8: 1 to 1: 1, preferably 5: 1 to 2: 1.
  • Inert carrier materials are, for example, tissue paper, blotting paper or glassine paper and films made of heat-resistant plastics such as polyesters, polyamides or polyimides, these films also being able to be metal-coated.
  • the inert carrier can also be coated with a lubricant on the side facing the thermal head in order to prevent the thermal head from sticking to the carrier material.
  • Suitable lubricants are, for example, silicones or polyurethanes, as described in EP-A-216 483 or EP-A-227 095.
  • the thickness of the dye carrier is generally 3 to 30 microns, preferably 5 to 10 microns.
  • the substrate to be printed for example paper, must itself be coated with a binder that absorbs the dye during the printing process.
  • a binder that absorbs the dye during the printing process.
  • Polymeric materials whose glass transition temperature are preferably used for this purpose T g is between 50 and 100 ° C, for example polycarbonates and polyester. Further details are EP-A-227 094, EP-A-133 012, EP-A-133 011, EP-A-111 004, JP-A-199 997/1986, JP-A-283 595/1986, JP-A-237 694/1986 or JP-A-127 392/1986.
  • a thermal head which can be heated to temperatures up to over 300 ° C., so that the dye transfer takes place in a time of at most 15 ms.
  • transfer sheets were made in a conventional manner from 8 ⁇ m thick polyester film, which was provided with an approximately 5 ⁇ m thick transfer layer made from a binder B, each of which contained 0.5 g of anthraquinone dye I.
  • the weight ratio of binder to dye was 2: 1 in each case.
  • the substrate to be printed consisted of paper approximately 120 ⁇ m thick, which was coated with an 8 ⁇ m thick plastic layer (Hitachi Color Video Print Paper).
  • the coated side of the encoder and slave was placed on top of one another, wrapped with aluminum foil and heated to a temperature between 70 and 80 ° C. for two minutes between two heating plates. With similar samples, this process was repeated three times at a higher temperature between 80 and 120 ° C.
  • the amount of dye diffused into the plastic layer of the receiver is proportional to the optical density, which was determined as absorbance A photometrically after the respective heating to the temperatures given above.
  • the temperature T * at which the extinction reaches 1, ie, the transmitted light intensity, can also be taken from the application is one tenth of the incident light intensity.
  • binder B used in each case.
  • EC ethyl cellulose
  • EHEC ethyl hydroxyethyl cellulose
  • PVB polyvinyl butyrate

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  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Thermal Transfer Or Thermal Recording In General (AREA)

Claims (3)

  1. Utilisation, pour l'impression par thermotransfert, de colorants d'anthraquinone de formule générale I
    Figure imgb0007
     dans laquelle R a les significations suivantes:
    groupements alkyle, alcoxyalkyle, aryloxyalkyle, alcanoyloxyalkyle, alcoxycarbonyloxyalkyle ou alcoxycarbonylalkyle, qui peuvent contenir chacun jusqu'à 20 atomes de carbone et dont la chaîne carbonée peut être interrompue par 1 à 4 atomes d'oxygène dans la fonction éther; groupements cycloalkyle en C₅-C₈ ou groupement phényle, qui peuvent porter chacun des restes alkyle en C₁-C₄ ou alcoxy en C₁-C₄ en tant que substituants.
  2. Procédé pour le transfert de colorants d'anthraquinone par diffusion entre un support et un substrat enduit de matière plastique au moyen d'une tête thermique, caractérisé en ce qu'on utilise à cette fin un support sur lequel se trouvent un ou plusieurs colorants d'anthraquinone de formule I selon la revendication 1.
  3. Procédé selon la revendication 2, caractérisé en ce qu'on utillise à cette fin un colorant d'anthraquinone de formule I dans laquelle R représente des groupements alkyle en C₁-C₁₂ ou un groupement phényle qui peut porter des restes alkyle en C₁-C₄ en tant que substituants.
EP91116652A 1990-10-09 1991-09-30 Utilisation de colorants d'anthraquinones pour l'impression par transfert thermique Expired - Lifetime EP0480278B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4031984A DE4031984A1 (de) 1990-10-09 1990-10-09 Verwendung von anthrachinonfarbstoffen fuer den thermotransferdruck
DE4031984 1990-10-09

Publications (2)

Publication Number Publication Date
EP0480278A1 EP0480278A1 (fr) 1992-04-15
EP0480278B1 true EP0480278B1 (fr) 1993-09-08

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EP91116652A Expired - Lifetime EP0480278B1 (fr) 1990-10-09 1991-09-30 Utilisation de colorants d'anthraquinones pour l'impression par transfert thermique

Country Status (4)

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US (1) US5208210A (fr)
EP (1) EP0480278B1 (fr)
JP (1) JPH04270689A (fr)
DE (2) DE4031984A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4214175A1 (de) * 1992-04-30 1993-11-04 Basf Ag Verfahren zur uebertragung von anthrachinonfarbstoffen
DE4215536A1 (de) * 1992-05-12 1993-11-18 Basf Ag Cyan-Mischungen für den Farbstofftransfer

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2720661C3 (de) * 1977-05-07 1979-12-06 Hoechst Ag, 6000 Frankfurt Verfahren zum Färben oder Bedrucken von Polyesterfasern
JPS60172591A (ja) * 1984-02-17 1985-09-06 Mitsubishi Chem Ind Ltd アントラキノン系感熱転写記録用色素
JPS61262190A (ja) * 1985-05-16 1986-11-20 Sumitomo Chem Co Ltd 昇華転写体
JPH01258996A (ja) * 1988-04-11 1989-10-16 Mitsui Toatsu Chem Inc 昇華転写記録用アントラキノン系色素
JPH0727342B2 (ja) * 1990-02-27 1995-03-29 株式会社島津製作所 画像表示装置におけるコントラスト設定装置

Also Published As

Publication number Publication date
US5208210A (en) 1993-05-04
EP0480278A1 (fr) 1992-04-15
JPH04270689A (ja) 1992-09-28
DE59100363D1 (de) 1993-10-14
DE4031984A1 (de) 1992-04-16

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