EP0490225B1 - Utilisation de colorants anthraquinoniques pour l'impression par transfert thermique - Google Patents

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

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Publication number
EP0490225B1
EP0490225B1 EP91120731A EP91120731A EP0490225B1 EP 0490225 B1 EP0490225 B1 EP 0490225B1 EP 91120731 A EP91120731 A EP 91120731A EP 91120731 A EP91120731 A EP 91120731A EP 0490225 B1 EP0490225 B1 EP 0490225B1
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Prior art keywords
carry
substituents
alkyl
alkoxy
phenyl
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EP91120731A
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German (de)
English (en)
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EP0490225A1 (fr
Inventor
Karl-Heinz Dr. Etzbach
Rüdiger Dr. Sens
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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 main heat source used is a thermal head with which short heating pulses 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, for example 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.
  • Thermal transfer printing generally uses the three subtractive primary colors yellow, magenta and cyan, possibly also black, whereby 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 as well as resistance to moisture and chemicals, no tendency to crystallize when storing the transfer sheet, a suitable color for the subtractive color mixture, 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.
  • the anthraquinone dyes I themselves are known per se or can be obtained by known methods (EP-A-56 492 and DE-A-34 26 093).
  • the ring A is preferably unsubstituted, but can also carry up to two of the following substituents: chlorine, bromine, mercapto and preferably hydroxy and amino, in addition C1-C8-alkylamino such as pentyl-, hexyl-, heptyl- and octylamino and especially C1 -C4 alkylamino such as methyl, ethyl, propyl, isopropyl and butylamino.
  • substituents chlorine, bromine, mercapto and preferably hydroxy and amino
  • C1-C8-alkylamino such as pentyl-, hexyl-, heptyl- and octylamino
  • C1 -C4 alkylamino such as methyl, ethyl, propyl, isopropyl and butylamino.
  • Suitable radicals R1 or R2 are nitro and mercapto, especially hydrogen and very particularly hydroxy and amino.
  • R 1 or R 2 are alkoxy, alkylthio and especially alkylamino groups which contain up to 20, preferably up to 8, C atoms and whose C chain can additionally be interrupted by ether oxygen atoms;
  • Ph phenyl
  • R1 or R2 may also be phenoxy, phenylthio and phenylamino groups; Examples include: -O-Ph, -O-Ph-2-CH3, -O-Ph-4-CH3, -O-Ph-2-O-CH3 and -O-Ph-4-O-CH3; -S-Ph, -S-Ph-2-CH3, -S-Ph-4-CH3, -S-Ph-2-O-CH3 and -S-Ph-4-O-CH3; -NH-Ph, -NH-Ph-2-CH3, -NH-Ph-4-CH3, -NH-Ph-2-O-CH3 and -NH-Ph-4-O-CH3.
  • the radical R3 is particularly suitable for the oxdiazole derivatives of the formula IIa, the thiazole derivatives of the formula IId and the thiadiazole derivatives of the formula IIe.
  • Suitable alkyl radicals R4 are, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, sec-pentyl, tert-pentyl, hexyl, 2-methylpentyl, heptyl, Octyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl and branched residues of this type.
  • the C chain of the alkyl radicals R4 mentioned can be interrupted by oxygen atoms in ether function.
  • Examples include the following radicals, in addition to the oxaalkyl groups already listed for the radicals R 1 or R 2: - (CH2) 2-O-CH3, - (CH2) 2-O-C2H5, - (CH2) 2-O-C3H7, - (CH2) 2-O-C4H9, - (CH2) 3-O-CH3, - (CH2) 3-O-C2H5, - (CH2) 3-O-C3H7, - (CH2) 3-O-C4H9, -CH2-CH (CH3) -O-CH3, -CH2-CH (CH3) - O-C2H5, -CH2-CH (CH3) -O-C3H7, -CH2-CH (CH3) -O-C4H9, - (CH2) 4-O-CH3, - (CH2) 4-O-C2H5, - ( CH2) 4-O-C4H9,
  • radical R4 are alkylthio groups such as the examples mentioned for the radicals R1 or R2.
  • radicals R5, R8, R6 or R7 in addition to the cycloalkyl and phenyl groups mentioned for R4, the alkyl groups also listed there are particularly suitable.
  • radicals R6 or R7 are especially alkoxycarbonyl groups, the C chain of which can be interrupted by ether oxygen atoms, and also cycloalkyloxycarbonyl and phenoxycarbonyl groups; Examples of these groups are as follows: -CO-O-C6H13, -CO-O-C10H21 and -CO-O-C11H23; -CO-O - [(CH2) 2-O] 3-C3H7, -CO-O - [(CH2) 2-O] 3-C4H9, -CO-O - [(CH2) 3-O] 2-C4H9 and -CO-O - [(CH2) 3-O] 3-C4H9; -CO-O-C6H11 and -CO-O-Ph.
  • Preferred anthraquinone dyes I can be found in the examples.
  • 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 which 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 phthalate, polyvinyl alcoholate, or starch, polyvinyl alcoholate, or polyvinyl alcoholate, such as polyvinyl alcoholate, or polyvinyl alcoholate, such as polyvinyl alcohol, vinyl alcohol or polyvinyl alcohol, or polyvinyl alcohol, or starch, alginyl alcohol, vinyl alcohol, polyvinyl alcoholate, or polyvinyl alcohol, such as polyvinyl alcohol, vinyl alcohol or polyvinyl alcohol, or starch, alginyl alcohol, vinyl alcohol, polyvinyl alcohol, vinyl alcohol, polyvinyl alcohol, or starch, alginyl alcohol, vinyl alcohol, polyvinyl
  • 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 hydroxyethyl 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 T g is below 150 ° C., for example modified polycarbonates and polyesters, are preferably used for this purpose. 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 * can also be taken from the application, at which the extinction reaches the value 1, i.e. the transmitted light intensity 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 de colorants d'anthraquinone de formule générale I
    Figure imgb0014
     pour l'impression par transfert thermique, dans laquelle les variables ont la signification suivante:
    le cycle A peut porter jusqu'à deux des substituants suivants: un atome de chlore ou de brome, un groupe hydroxy, mercapto, amino ou alkylamino en C₁ à C₈;
    R¹, R²:   des atomes d'hydrogène, ou des groupes nitro, hydroxy, mercapto ou amino; des groupes alcoxy, alkylthio ou alkylamino en C₁ à C₂₀ dont les chaînes d'atomes de carbone peuvent être chaque fois interrompues par 1 à 4 atomes d'oxygène et qui peuvent porter les substituants suivants: des groupes cycloalkyle en C₅ à C₇, phényle ou phénoxy qui chaque fois peuvent porter comme substituants des groupes alkyle ou alcoxy en C₁ à C₄; des groupes phénoxy, phénylthio ou phénylamino, dont le reste phényle peut porter en tant que substituants des groupes alkyle ou alcoxy en C₁ à C₄;
    R3:   un des restes de formules générales IIa à IIf
    Figure imgb0015
     dans lesquelles les substituants ont la signification suivante :
    R⁴   un atome d'hydrogène;
    un groupe alkyle ou alkylthio en C₁ à C₂₀, dont les chaînes d'atomes de carbone peuvent être à chaque fois interrompues par 1 à 4 atomes d'oxygène en fonction éther et qui peuvent porter les substituants suivants: des groupes cycloalkyle en C₅ à C₇, phényle ou phénoxy, qui chaque fois peuvent porter en tant que substituants des groupes alkyle ou alcoxy en C₁ à C₄; des groupes cycloalkyle ou cycloalkylthio en C₅ à C₇ ou un groupe phényle, qui chaque fois peuvent porter en tant que substituants des groupes alkyle ou alcoxy en C₁ à C₄;
    R⁵, R⁸   des atomes d'hydrogène;
    les groupes alkyle, cycloalkyle ou phényle correspondant à la définition de R⁴;
    R⁶, R⁷   les restes R⁵ ou R⁸;
    des groupes alcoxycarbonyle, dont les chaînes d'atomes de carbone peuvent présenter jusqu'à 20 atomes de carbone et être interrompues par 1 à 4 atomes d'oxygène en fonction éther, ces groupes alcoxycarbonyle pouvant porter les substituants suivants: des groupes cycloalkyle en C₅ à C₇, phényle ou phénoxy qui chaque fois peuvent porter des groupes alkyle ou alcoxy en C₁ à C₄ en tant que substituants; des groupes cycloalkyloxycarbonyle en C₅ à C₇ ou phénoxycarbonyle, qui chaque fois peuvent porter en tant que substituants des groupes alkyle ou alcoxy en C₁ à C₄;
    X   un atome d'hydrogène ou un groupe cyano.
  2. Procédé de transfert de colorants d'anthraquinone par diffusion d'un support sur un substrat à revêtement de matière plastique au moyen d'une tête thermique, caractérisé en ce que pour cela on utilise un support sur lequel se trouve un ou plusieurs colorants d'anthraquinone de formule I selon la revendication 1.
  3. Procédé selon la revendication 2, caractérisé en ce que l'on utilise pour cela un colorant d'anthraquinone de formule Ia
    Figure imgb0016
     dans laquelle R2' représente un groupe amino ou un groupe alkylamino en C₁ à C₈.
EP91120731A 1990-12-14 1991-12-03 Utilisation de colorants anthraquinoniques pour l'impression par transfert thermique Expired - Lifetime EP0490225B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4039923A DE4039923A1 (de) 1990-12-14 1990-12-14 Verwendung von anthrachinonfarbstoffen fuer den thermotransferdruck
DE4039923 1990-12-14

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EP0490225A1 EP0490225A1 (fr) 1992-06-17
EP0490225B1 true EP0490225B1 (fr) 1993-09-15

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US (1) US5155089A (fr)
EP (1) EP0490225B1 (fr)
JP (1) JP3088531B2 (fr)
DE (2) DE4039923A1 (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
JP5782649B2 (ja) * 2011-08-04 2015-09-24 株式会社トヨックス 管接続構造

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3671536A (en) * 1969-03-20 1972-06-20 Basf Ag Anthraquinone dyes
EP0056492B1 (fr) * 1981-01-10 1984-12-12 BASF Aktiengesellschaft Colorants pour mélanges de cristaux liquides
JPS58215397A (ja) * 1982-06-08 1983-12-14 Sony Corp 気化性色素組成物
EP0133012B2 (fr) * 1983-07-25 1999-09-15 Dai Nippon Insatsu Kabushiki Kaisha Feuille pour utilisation en impression par thermotransfer
DE3426093A1 (de) * 1984-07-14 1986-01-23 Basf Ag, 6700 Ludwigshafen Optisches aufzeichnungsmedium und verfahren zu seiner herstellung
JPS61127392A (ja) * 1984-11-28 1986-06-14 Matsushita Electric Ind Co Ltd 昇華転写用受像体
GB8504518D0 (en) * 1985-02-21 1985-03-27 Ici Plc Thermal transfer dyesheet
JPS61284489A (ja) * 1985-06-11 1986-12-15 Dainippon Printing Co Ltd 熱転写シ−ト
GB8521327D0 (en) * 1985-08-27 1985-10-02 Ici Plc Thermal transfer printing
US4698651A (en) * 1985-12-24 1987-10-06 Eastman Kodak Company Magenta dye-donor element used in thermal dye transfer
US4695286A (en) * 1985-12-24 1987-09-22 Eastman Kodak Company High molecular weight polycarbonate receiving layer used in thermal dye transfer
US4740496A (en) * 1985-12-24 1988-04-26 Eastman Kodak Company Release agent for thermal dye transfer
JPS63246284A (ja) * 1987-03-31 1988-10-13 Sumitomo Chem Co Ltd 昇華転写型感熱記録用シアン色素
DE3812053A1 (de) * 1988-04-12 1989-10-26 Basf Ag Verfahren zur uebertragung von farbstoffen

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Publication number Publication date
DE59100384D1 (de) 1993-10-21
US5155089A (en) 1992-10-13
DE4039923A1 (de) 1992-06-17
JPH04292990A (ja) 1992-10-16
JP3088531B2 (ja) 2000-09-18
EP0490225A1 (fr) 1992-06-17

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