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EP0441208A1 - Use of azo-dyes for thermal transfer printing - Google Patents

Use of azo-dyes for thermal transfer printing Download PDF

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Publication number
EP0441208A1
EP0441208A1 EP91101022A EP91101022A EP0441208A1 EP 0441208 A1 EP0441208 A1 EP 0441208A1 EP 91101022 A EP91101022 A EP 91101022A EP 91101022 A EP91101022 A EP 91101022A EP 0441208 A1 EP0441208 A1 EP 0441208A1
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Prior art keywords
alkyl
substituents
carry
alkoxy
phenyl
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EP91101022A
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German (de)
French (fr)
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EP0441208B1 (en
Inventor
Volker Bach
Karl-Heinz Etzbach
Sabine Gruettner
Helmut Reichelt
Ruediger Sens
Gunther Lamm
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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
    • B41M5/388—Azo 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 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.
  • Thermal transfer printing generally uses the three subtractive primary colors yellow, magenta and cyan, possibly also black, with the dyes used for optimal 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 is stored, a suitable color for the subtractive color mixing, a high molar absorption coefficient and easy technical accessibility.
  • magenta dyes previously used cannot convince. This also applies, for example, to the azo dyes described in US Pat. No. 4,764,178 and recommended for thermal transfer, which are similar to azo dyes I and have coupling components based on aniline, tetrahydroquinoline, aminoquinoline or julolidine.
  • azo dyes I themselves are known per se or by known methods, e.g. according to the older German patent application P 38 33 443.7, according to O. Annen et al., Rev. Prog. Coloration 17, 72-85 (1987) or M.A. Weaver and L. Shuttleworth, Dyes and Pigments 3, 81-121 (1982).
  • the invention was therefore based on the object of finding suitable red and blue dyes for thermal transfer printing which come closer to the required property profile than the dyes known hitherto.
  • a method for transferring azo 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 azo dyes I defined at the outset are located.
  • Suitable alkyl radicals R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 11 , R 12 , R 13 , R 15 or R 16 are especially methyl, ethyl, propyl, Isopropyl and butyl, as well as isobutyl, sec-butyl and tert-butyl.
  • the radicals R 1 , R 2 , R 3 , R 5 , R 6 , R 7 , R 8 , R 15 or R 16 are, for example, pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, 2-methylpentyl, heptyl, To name octyl, 2-ethylhexyl and the isomer mixture isooctyl and cyclohexyl.
  • R 1 , R 2 , R 3 , R 5 , R 6 , R 7 , R 8 , R 15 or R 16 are, for example, nonyl and decyl and their isomer mixtures isononyl and isodecyl.
  • undecyl, dodecyl, tridecyl and its isomer mixture isotridecyl, tetradecyl, pentadecyl are also suitable as radicals R 1 , R 2 or R 3 , and hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl as radicals R 2 and R 3 .
  • alkoxyalkyl groups those which contain up to 8 carbon atoms are also suitable as radicals R 8 and those with up to 12 carbon atoms are also suitable as radicals R 15 or R 16 .
  • Preferred alkoxy groups as R 2 , R 3 , R 8 , R "or R 12 are, for example: methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy and sec-butoxy.
  • R 8 in particular R 2 or R 3, are furthermore, for example, pentyloxy, isopentyloxy, neopentyloxy, hexyloxy, octyloxy and 2-ethylhexyloxy.
  • radicals R 2 or R 3 are, for example, nonyloxy or decyloxy, and also undecyloxy, dodecyloxy, tridecyloxy, tetradecyloxy and pentadecyloxy.
  • R 8 radicals can also be alkylthio groups, such as methylthio, ethylthio and 2-cyanoethylthio, in addition propylthio, isopropylthio, butylthio, pentylthio, hexylthio, heptylthio, octylthio, 2-ethylhexylthio, 2-ethoxycarbonylethylthio and especially 2-methoxycarbonyl.
  • radicals R 1 are C 1 -C 8 -alkyl, including in particular methyl and isopropyl, cyclohexyl, phenyl, which can also carry methoxy, sulfonamido or chlorine as substituents, and also benzyl.
  • Preferred radicals R 1 are also thien-3-yl and especially thien-2-yl, furan-3-yl and especially furan-2-yl as well as pyrid-2-yl, pyrid-4-yl and especially pyrid-3- yl.
  • radicals R 2 or R 3 of the alkyl radicals mentioned are those with up to 12 C atoms, especially methyl, ethyl and propyl, of the cyanoalkyl and alkoxy radicals mentioned those with up to 10 C atoms.
  • Particularly preferred radicals R 2 or R 3 have the formula Ila with methyl or ethyl as the radical R 4 '.
  • the dyes I to be used according to the invention are distinguished from the red and blue dyes with coupling components based on aniline, which have been used for thermal transfer printing to date, by the following properties: easier thermal transferability, improved migration properties in the recording medium at room temperature, higher thermal stability, higher lightfastness, better resistance to moisture and chemicals, better solubility in the manufacture of the printing ink, higher color strength and easier technical accessibility.
  • the azo dyes I show a significantly better color purity, in particular in dye mixtures, and give improved black prints.
  • the transfer sheets required as dye donors for the thermal transfer printing process according to the invention are prepared as follows:
  • the azo dyes I are in an organic solvent such as isobutanol, methyl ethyl ketone, methylene chloride, chlorobenzene, toluene, tetrahydrofuran or mixtures thereof, with one or more binders and possibly other auxiliaries such as release agents or crystallization-inhibiting substances are processed into a printing ink which preferably contains the dyes in a molecularly dispersed solution. The printing ink is then applied to an inert support and dried.
  • Suitable binders for the use of azo dyes I according to the invention are all materials which are soluble in organic solvents and which are known to serve for thermal transfer printing, i.e. Cellulose derivatives such as methyl cellulose, hydroxypropyl cellulose, cellulose acetate or cellulose acetobutyrate, especially ethyl cellulose and ethyl hydroxyethyl cellulose, starch, alginates, alkyd 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 and ethyl hydroxyethyl cellulose, starch, alginates, alkyd resins such as polyvinyl alcohol or polyvinyl pyrrolidone, and especially polyvinyl acetate and poly
  • 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 e.g. Gum arabic into consideration.
  • binders 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 are described in EP-A-216 483.
  • the thickness of the dye carrier is generally 3 to 30 microns, preferably 5 to 10 microns.
  • the substrate to be printed e.g. Paper
  • a plastic that absorbs the dye during the printing process.
  • Polymeric materials whose glass transition temperature Tg is between 50 and 100 ° C., i.e. e.g. Polycarbonates and polyester. Further details can be found in EP-A-227 094, EP-A-133 012, EP-A-133 011, JP-A-199 997/1986 or JP-A-283 595/1986.
  • a thermal head is used for the process according to the invention, which can be heated to temperatures of up to 300 ° C., so that the dye transfer takes place in a maximum time of 15 msec.
  • transfer sheets were made from polyester film of 6 to 10 ⁇ m in the usual way Starch produced, which was provided with an approximately 5 pm thick transfer layer of a binder B, each containing approximately 0.25 g of azo dye I.
  • the weight ratio of binder to dye was 4: 1, unless otherwise stated in the tables below.
  • 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 1200 ° 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 is also listed.
  • EC ethyl cellulose
  • PVB polyvinyl butyrate
  • VY Vylon.

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

Abstract

Use of azo dyes I <IMAGE> for thermal transfer printing, having the following meaning of the substituents: R<1> = H; C1-C15-alkyl, which can carry phenyl or phenoxy as substituents; cyclohexyl which can carry C1-C5-alkyl, C1-C5-alkoxy or halogen as substituents; phenyl which can carry C1-C5-alkyl, C1-C5-alkoxy, sulphonamido or halogen as substituents; thienyl which can carry C1-C5-alkyl or halogen as substituents, furanyl or pyridyl; a radical II [-W-O]n-R<4>     II where W = identical or different C2-C6-alkylene; n = 1 to 6; R<4> = C1-C4-alkyl or phenyl or benzyl which can both carry C1-C4-alkyl or C1-C4-alkoxy as substituents; R<2> and R<3> = H; alkyl, alkoxy, alkoxyalkyl, alkanoyloxyalkyl, alkoxycarbonyloxyalkyl, alkoxycarbonylalkyl, haloalkyl, hydroxyalkyl or cyanoalkyl each having up to 15 C atoms, which can carry phenyl, C1-C4-alkylphenyl, C1-C4-alkoxyphenyl, halophenyl, benzyloxy, C1-C4-alkylbenzyloxy, C1-C4-alkoxybenzyloxy, halobenzyloxy, halogen, hydroxyl or cyano as substituents; cyclohexyl which can carry C1-C15-alkoxy or halogen as substituents, phenyl which can carry C1-C15-alkyl, C1-C15-alkoxy, benzyloxy or halogen as substituents; a radical II; D = a radical of a diazo component III D-NH2 III.

Description

Die vorliegende Erfindung betrifft die Verwendung von Azofarbstoffen der allgemeinen Formel I

Figure imgb0001
für den Thermotransferdruck, in der die Substituenten folgende Bedeutung haben:

  • R1 Wasserstoff; C1-C15-Alkylgruppen, die Phenyl oder Phenoxy als Substituenten tragen können; eine Cyclohexylgruppe, die Ci-C5-Alkyl, Ci-Cs-Alkoxy oder Halogen als Substituenten tragen kann; eine Phenylgruppe, die C1-C5-Alkyl, C1-C5-Alkoxy, Sulfonamido oder Halogen als Substituenten tragen kann; eine Thienylgruppe, die C1-C5-Alkyl oder Halogen als Substituenten tragen kann, eine Furanyl- oder Pyridylgruppe; einen Rest der allgemeinen Formel II
    Figure imgb0002
    in der w gleiche oder verschiedene C2-Cs-Alkylengruppen bezeichnet, n 1 bis 6 bedeutet und R4 für eine C1-C4-Alkylgruppe oder eine Phenyl- oder Benzylgruppe steht, die beide jeweils C1-C4-Alkyl oder C1-C4-Alkoxy als Substituenten tragen können;
  • R2, Rs Wasserstoff; Alkyl-, Alkoxy-, Alkoxyalkyl-, Alkanoyloxyalkyl-, Alkoxycarbonyloxyalkyl-, Alkoxycarbonylalkyl-, Halogenalkyl- , Hydroxyalkyl- oder Cyanoalkylgruppen, die jeweils bis zu 15 C-Atome enthalten können und Phenyl, C1-C4-Alkylphenyl, Ci-C4-Alkoxyphenyl, Halogenphenyl, Benzyloxy, C1-C4-Alkylbenzyloxy, C1-C4-Alkoxyben- zyloxy, Halogenbenzyloxy, Halogen, Hydroxy oder Cyano als Substituenten tragen können; eine Cyclohexylgruppe, die C1-C14-Alkyl, C1-C14-Alkoxy oder Halogen als Substituenten tragen kann; eine Phenylgruppe, die C1-C15-Alkyl, C1-C15-Alkoxy, Benzyloxy oder Halogen als Substituenten tragen kann; einen Rest der oben angegebenen Formel II; D den Rest einer Diazokomponente III
    Figure imgb0003
    sowie speziell ein Verfahren zur Übertragung dieser Azofarbstoffe durch Diffusion von einem Träger auf ein mit Kunststoff beschichtetes Substrat mit Hilfe eines Thermokopfes.
The present invention relates to the use of azo dyes of the general formula I.
Figure imgb0001
 for thermal transfer printing, in which the substituents have the following meaning:
  • R 1 is hydrogen; C 1 -C 15 alkyl groups which can carry phenyl or phenoxy as substituents; a cyclohexyl group which can carry Ci-C 5 alkyl, C i -C s alkoxy or halogen as a substituent; a phenyl group which can carry C 1 -C 5 alkyl, C 1 -C 5 alkoxy, sulfonamido or halogen as substituents; a thienyl group which may carry C 1 -C 5 alkyl or halogen as a substituent, a furanyl or pyridyl group; a radical of the general formula II
    Figure imgb0002
     in which w denotes the same or different C 2 -C s alkylene groups, n denotes 1 to 6 and R 4 represents a C 1 -C 4 alkyl group or a phenyl or benzyl group, both of which are each C 1 -C 4 alkyl or can carry C 1 -C 4 alkoxy as substituents;
  • R2, R s hydrogen; Alkyl, alkoxy, alkoxyalkyl, alkanoyloxyalkyl, alkoxycarbonyloxyalkyl, alkoxycarbonylalkyl, haloalkyl, hydroxyalkyl or cyanoalkyl groups, each of which can contain up to 15 C atoms and phenyl, C 1 -C 4 alkylphenyl, C i - C 4 -alkoxyphenyl, halophenyl, benzyloxy, C 1 -C 4 -alkylbenzyloxy, C 1 -C 4 -alkoxybenzyloxy, halobenzyloxy, halogen, hydroxy or cyano can carry as substituents; a cyclohexyl group which can carry C 1 -C 14 alkyl, C 1 -C 14 alkoxy or halogen as substituents; a phenyl group which can carry C 1 -C 15 alkyl, C 1 -C 15 alkoxy, benzyloxy or halogen as substituents; a radical of formula II given above; D the rest of a diazo component III
    Figure imgb0003
     and specifically a process for the transfer of these azo dyes by diffusion from a support to a plastic-coated substrate using a thermal head.

Die Technik des Thermotransferdrucks ist allgemein bekannt; als Wärmequelle kommt neben Laser und IR-Lampe vor allem ein Thermokopf zur Anwendung, mit dem kurze Heizimpulse der Dauer von Bruchteilen einer Sekunde abgegeben werden können.The technique of thermal transfer printing is well known; In addition to the laser and IR lamp, the main heat source used is a thermal head with which short heating impulses lasting a fraction of a second can be emitted.

Bei dieser bevorzugten Ausführungsform des Thermotransferdrucks wird ein Transferblatt, das den zu übertragenden Farbstoff zusammen mit einem oder mehreren Bindemitteln, einem Trägermaterial und eventuell weiteren Hilfsmitteln wie Trennmitteln oder kristallisationshemmenden Stoffen enthält, von der Rückseite her durch den Thermokopf erhitzt. Dabei diffundiert der Farbstoff aus dem Transferblatt in die Oberflächenbeschichtung des Substrates, z.B. in die Kunststoffschicht eines beschichteten Papiers.In this preferred embodiment of thermal transfer printing, 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.

Der wesentliche Vorteil dieses Verfahrens besteht darin, daß über die an den Thermokopf abzugebende Energie die übertragene Farbmenge und damit die Farbabstufung gezielt gesteuert werden kann.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.

Beim Thermotransferdruck werden allgemein die drei subtraktiven Grundfarben Gelb, Magenta und Cyan, gegebenenfalls zusätzlich Schwarz, verwendet, wobei die eingesetzten Farbstoffe für eine optimale Farbaufzeichnung folgende Eigenschaften aufweisen müssen: leichte thermische Transferierbarkeit, geringe Neigung zur Migration innerhalb oder aus der Oberflächenbeschichtung des Aufnahmemediums bei Raumtemperatur, hohe thermische und photochemische Stabilität sowie Resistenz gegen Feuchtigkeit und Chemikalien, keine Tendenz zur Kristallisation bei Lagerung des Transferblattes, einen geeigneten Farbton für die subtraktive Farbmischung, einen hohen molaren Absorptionskoeffizienten und leichte technische Zugänglichkeit.Thermal transfer printing generally uses the three subtractive primary colors yellow, magenta and cyan, possibly also black, with the dyes used for optimal 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 is stored, a suitable color for the subtractive color mixing, a high molar absorption coefficient and easy technical accessibility.

Diese Anforderungen sind gleichzeitig nur sehr schwer zu erfüllen. Insbesondere können die bislang verwendeten Magentafarbstoffe nicht überzeugen. Dies trifft beispielsweise auch für die in der US-A-4 764 178 beschriebenen und für den Thermotransfer empfohlenen Azofarbstoffe zu, die den Azofarbstoffen I ähneln und Kupplungskomponenten auf Anilin-, Tetrahydrochinolin-, Aminochinolin- oder Julolidinbasis aufweisen.At the same time, these requirements are very difficult to meet. In particular, the magenta dyes previously used cannot convince. This also applies, for example, to the azo dyes described in US Pat. No. 4,764,178 and recommended for thermal transfer, which are similar to azo dyes I and have coupling components based on aniline, tetrahydroquinoline, aminoquinoline or julolidine.

Die Azofarbstoffe I selbst sind an sich bekannt oder nach bekannten Methoden, z.B. nach der älteren deutschen Patentanmeldung P 38 33 443.7, nach O. Annen et al., Rev. Prog. Coloration 17, 72-85 (1987) oder M.A. Weaver und L. Shuttleworth, Dyes and Pigments 3, 81-121 (1982), erhältlich.The azo dyes I themselves are known per se or by known methods, e.g. according to the older German patent application P 38 33 443.7, according to O. Annen et al., Rev. Prog. Coloration 17, 72-85 (1987) or M.A. Weaver and L. Shuttleworth, Dyes and Pigments 3, 81-121 (1982).

Der Erfindung lag daher die Aufgabe zugrunde, für den Thermotransferdruck geeignete Rot- und Blaufarbstoffe zu finden, die dem geforderten Eigenschaftsprofil näherkommen als die bisher bekannten Farbstoffe.The invention was therefore based on the object of finding suitable red and blue dyes for thermal transfer printing which come closer to the required property profile than the dyes known hitherto.

Demgemäß wurde die Verwendung der eingangs definierten Azofarbstoffe I für den Thermotransferdruck gefunden.Accordingly, the use of the azo dyes I defined at the outset was found for thermal transfer printing.

Außerdem wurde ein Verfahren zur Übertragung von Azofarbstoffen durch Diffusion von einem Träger auf ein mit Kunststoff beschichtetes Substrat mit Hilfe eines Thermokopfes gefunden, welches dadurch gekennzeichnet ist, daß man hierfür einen Träger verwendet, auf dem sich ein oder mehrere der eingangs definierten Azofarbstoffe I befinden.In addition, a method for transferring azo 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 azo dyes I defined at the outset are located.

Weiterhin wurden bevorzugte Ausführungsformen dieses Verfahrens gefunden, welche dadurch gekennzeichnet sind, daß man hierzu Farbstoffe der Formel la

Figure imgb0004
verwendet, in der die Substituenten folgende Bedeutung haben:

  • R" C1-Cg-Alkylgruppen, die Phenyl oder Phenoxy als Substituenten tragen können; eine Cyclohexylgruppe; eine Phenylgruppe, die C1-C4-Alkyl, C1-C4-Alkoxy oder Chlor als Substituenten tragen kann; eine Thienylgruppe; einen Rest der allgemeinen Formellla
    Figure imgb0005
    in der p für 0 oder 1 und q für 1 bis 4 stehen und R4' eine Ci-C4-Alkyl-, Phenyl- oder Benzylgruppe bezeichnet;
  • R2',R3' C1-C12-Alkyl-, C1-C10-Alkoxy- oder C1-C10-Cyanoalkylgruppen; einen Rest der oben angegebenen Formel Ila; D' den Rest einer Diazokomponente 111, die aus der Anilin-, Phenylazoanilin-, Aminothiophen-, Phenylazoaminothiophen-, Aminothiazol-, Phenylazoaminothiazol-, Aminoisothiazol-, Aminobenzisothiazol-, Aminothiadiazol-, Aminoisothiadiazol-, Aminooxazol-, Aminooxadiazol-, Aminodiazol-, Aminotriazol- oder Aminopyrrolreihe stammt.
Furthermore, preferred embodiments of this process have been found, which are characterized in that dyes of the formula Ia
Figure imgb0004
 used in which the substituents have the following meaning:
  • R "is C 1 -Cg alkyl groups which may have phenyl or phenoxy as substituents; a cyclohexyl group; a phenyl group which may have C 1 -C 4 alkyl, C 1 -C 4 alkoxy or chlorine as substituents; a thienyl group; a rest of the general formula la
    Figure imgb0005
     in which p is 0 or 1 and q is 1 to 4 and R 4 ' denotes a C 1 -C 4 -alkyl, phenyl or benzyl group;
  • R 2 ', R 3 ' C 1 -C 12 alkyl, C 1 -C 10 alkoxy or C 1 -C 10 cyanoalkyl groups; a radical of the formula Ila given above; D 'is the remainder of a diazo component 111 which consists of the aniline, phenylazoaniline, aminothiophene, phenylazoaminothiophene, aminothiazole, phenylazoaminothiazole, aminoisothiazole, aminobenzisothiazole, aminothiadiazole, aminoisothiadiazole, aminooxadiazole, aminooxaziazole, aminooxaziazole Aminotriazole or aminopyrrole series comes from.

Bevorzugte Diazokomponenten III sind:

  • - Anilinderivate der allgemeinen Formel Illa
    Figure imgb0006
  • - Phenylazoanilinderivate der allgemeinen Formel Illb
    Figure imgb0007
  • - Aminothiophenderivate der allgemeinen Formel Illc
    Figure imgb0008
  • - Phenylazoaminothiophenderivate der allgemeinen Formel Illd
    Figure imgb0009
  • - Aminothiazolderivate der allgemeinen Formel Ille
    Figure imgb0010
  • - Phenylazoaminothiazolderivate der allgemeinen Formel Illf
    Figure imgb0011
  • - Aminoisothiazolderivate der allgemeinen Formel Illg
    Figure imgb0012
  • - Aminobenzisothiazolderivate der allgemeinen Formeln Illh und Illi
    Figure imgb0013
  • - Aminothiadiazolderivate der allgemeinen Formel Illk
    Figure imgb0014
  • - Aminoisothiadiazolderivate der allgemeinen Formel IIII
    Figure imgb0015
  • - Aminopyrrolderivate der allgemeinen Formel Illm
    Figure imgb0016
Preferred diazo components III are:
  • - Aniline derivatives of the general formula Illa
    Figure imgb0006
  • - Phenylazoaniline derivatives of the general formula Illb
    Figure imgb0007
  • - Aminothiophene derivatives of the general formula Illc
    Figure imgb0008
  • - Phenylazoaminothiophene derivatives of the general formula Illd
    Figure imgb0009
  • - Aminothiazole derivatives of the general formula Ille
    Figure imgb0010
  • - Phenylazoaminothiazole derivatives of the general formula Illf
    Figure imgb0011
  • - Aminoisothiazole derivatives of the general formula Illg
    Figure imgb0012
  • - Aminobenzisothiazole derivatives of the general formulas Illh and Illi
    Figure imgb0013
  • - Aminothiadiazole derivatives of the general formula Illk
    Figure imgb0014
  • - Aminoisothiadiazole derivatives of the general formula IIII
    Figure imgb0015
  • - Aminopyrrole derivatives of the general formula Illm
    Figure imgb0016

Dabei haben die Substituenten folgende Bedeutung:

  • R5, R6, R7 Wasserstoff, Chlor, Brom, Nitro- oder Cyanogruppen; Alkyl-, Alkoxyalkyl-, Alkanoyloxyalkyl- oder Alkoxycarbonylalkylgruppen, die jeweils bis zu 10 C-Atome enthalten können; einen Rest der Formel II; Reste der Formeln -CO-OR15, -CO-NR15R16, -SO-OR15, -SO2-OR15 oder -SO2-NR15R16 in denen
  • R15 und R16 Alkyl oder Alkoxyalkyl, die jeweils bis zu 10 C-Atome enthalten können, und R16 zusätzlich Wasserstoff bedeuten;
  • R5 weiterhin einen in 3-Stellung durch C1-C8-Alkoxy substituierten Oxadiazolrest;
  • R6 weiterhin Reste der Formeln -CO-R17 oder -CO-OR17 in denen
  • R17 für Phenyl, das C1-C8-Alkyl als Substituenten tragen kann, steht; einen Rest der allgemeinen Formel IV
    Figure imgb0017
    in der X Cyano, -CO-OR15 oder -CO-NR15R16 bedeutet;
  • R8 Wasserstoff, Chlor, eine Cyano- oder Thiocyanatogruppe, Alkyl-, Alkoxy-, Alkylthio- oder Alkoxyalkylgruppen, die jeweils bis zu 10 C-Atome enthalten können; 2-(C1 -C2-Alkoxycarbonyl)ethylthiogruppen; eine 2-(Pyrrolid-1-yl)ethylgruppe; C5-C6-Cycloalkyl- oder -Cycloalkylthiogruppen; eine Phenylgruppe, die C1-C4-Alkyl, C1-C4-Alkoxy, Benzyloxy oder Phenylthio als Substituenten tragen kann, Ar-C1-C4-alkyl-, Ar-C1-C4-alkoxy- oder Ar-C1-C4-alkylthiogruppen; Thienyl- oder Pyridylgruppen, die Ci-C4-Alkyl als Substituenten tragen können; einen Rest der Formel II; Reste der Formeln -CO-OR15, -CO-NR15R16, -SO-OR15 oder -SO2-OR15
  • R9 Wasserstoff, Chlor, Brom, eine Nitro-, Cyano-, Thiocyanato- oder Phenylgruppe; Reste der Formeln -CO-OR15 oder -CO-NR15R16
  • R10 Wasserstoff, Chlor, Brom, eine Nitro-, Cyano- oder Formylgruppe; Reste der Formeln -CO-OR15 oder -CO-NR15R16 einen Rest der Formel IV
  • R11, R12 Wasserstoff, Chlor, Brom, Nitro- oder Cyanogruppen; C1-C4-Alkyl- oder C1-C4-Alkoxygruppen; Reste der Formeln -CO-OR15 oder -CO-NR15R16
  • R13 Wasserstoff, Chlor, Brom oder C1-C4-Alkylgruppen
  • R14 Wasserstoff oder eine Cyanogruppe; Reste der Formeln -CO-OR15 oder -CO-NR15R16
  • R18 eine Cyano- oder Formamidgruppe;
  • R19 eine Methyl- oder Phenylgruppe; X Wasserstoff, Chlor oder eine Nitrogruppe; Y Wasserstoff oder eine Cyanogruppe.
The substituents have the following meaning:
  • R 5 , R 6 , R 7 are hydrogen, chlorine, bromine, nitro or cyano groups; Alkyl, alkoxyalkyl, alkanoyloxyalkyl or alkoxycarbonylalkyl groups, each of which can contain up to 10 carbon atoms; a radical of formula II; Residues of the formulas -CO-OR 15 , -CO-NR 15 R 16 , -SO-OR 15 , -SO 2 -OR 15 or -SO 2 -NR 15 R 16 in which
  • R 15 and R 16 are alkyl or alkoxyalkyl, each of which can contain up to 10 carbon atoms, and R 16 is additionally hydrogen;
  • R 5 is furthermore an oxadiazole radical substituted in the 3-position by C 1 -C 8 alkoxy;
  • R 6 furthermore radicals of the formulas -CO-R 17 or -CO-OR 17 in which
  • R 17 represents phenyl which can carry C 1 -C 8 alkyl as a substituent; a radical of the general formula IV
    Figure imgb0017
     in which X is cyano, -CO-OR 15 or -CO-NR 15 R 16 ;
  • R 8 is hydrogen, chlorine, a cyano or thiocyanato group, alkyl, alkoxy, alkylthio or alkoxyalkyl groups, each of which can contain up to 10 carbon atoms; 2- (C 1 -C 2 alkoxycarbonyl) ethylthio groups; a 2- (pyrrolid-1-yl) ethyl group; C 5 -C 6 cycloalkyl or cycloalkylthio groups; a phenyl group which can carry C 1 -C 4 alkyl, C 1 -C 4 alkoxy, benzyloxy or phenylthio as substituents, Ar-C 1 -C 4 -alkyl-, Ar-C 1 -C 4 -alkoxy- or Ar-C 1 -C 4 alkylthio groups; Thienyl or pyridyl groups which can carry C 1 -C 4 -alkyl as substituents; a radical of formula II; Residues of the formulas -CO-OR 15 , -CO-NR 15 R 16 , -SO-OR 15 or -SO 2 -OR 15
  • R 9 is hydrogen, chlorine, bromine, a nitro, cyano, thiocyanato or phenyl group; Radicals of the formulas -CO-OR 15 or -CO-NR 15 R 16
  • R 10 is hydrogen, chlorine, bromine, a nitro, cyano or formyl group; Residues of the formulas -CO-OR 15 or -CO-NR 15 R 16 are a radical of the formula IV
  • R 11 , R 12 are hydrogen, chlorine, bromine, nitro or cyano groups; C 1 -C 4 alkyl or C 1 -C 4 alkoxy groups; Radicals of the formulas -CO-OR 15 or -CO-NR 15 R 16
  • R13 is hydrogen, chlorine, bromine or C 1 -C 4 alkyl groups
  • R14 is hydrogen or a cyano group; Radicals of the formulas -CO-OR 15 or -CO-NR 15 R 16
  • R 18 is a cyano or formamide group;
  • R 19 is a methyl or phenyl group; X is hydrogen, chlorine or a nitro group; Y is hydrogen or a cyano group.

Geeignete Alkylreste R1, R2, R3, R4, R5, R6, R7, R8, R11, R12, R13, R15 oder R16 sind dabei vor allem Methyl, Ethyl, Propyl, Isopropyl und Butyl, daneben auch Isobutyl, sec.-Butyl und tert.-Butyl.Suitable alkyl radicals R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 11 , R 12 , R 13 , R 15 or R 16 are especially methyl, ethyl, propyl, Isopropyl and butyl, as well as isobutyl, sec-butyl and tert-butyl.

Als Reste Rl, R2, R3, R5, R6, R7, R8, R15 oder R16 sind außerdem z.B. Pentyl, Isopentyl, Neopentyl, tert.-Pentyl, Hexyl, 2-Methylpentyl, Heptyl, Octyl, 2-Ethylhexyl und das Isomerengemisch Isooctyl und Cyclohexyl zu nennen.The radicals R 1 , R 2 , R 3 , R 5 , R 6 , R 7 , R 8 , R 15 or R 16 are, for example, pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, 2-methylpentyl, heptyl, To name octyl, 2-ethylhexyl and the isomer mixture isooctyl and cyclohexyl.

Reste R1, R2, R3, R5, R6, R7, R8, R15 oder R16 sind weiterhin beispielsweise Nonyl und Decyl sowie ihre Isomerengemische Isononyl und Isodecyl. Daneben eignen sich als Reste R1, R2 oder R3 auch Undecyl, Dodecyl, Tridecyl und sein Isomerengemisch Isotridecyl, Tetradecyl, Pentadecyl, sowie als Reste R2 und R3 zusätzlich Hexadecyl, Heptadecyl, Octadecyl, Nonadecyl und Eicosyl.R 1 , R 2 , R 3 , R 5 , R 6 , R 7 , R 8 , R 15 or R 16 are, for example, nonyl and decyl and their isomer mixtures isononyl and isodecyl. In addition, undecyl, dodecyl, tridecyl and its isomer mixture isotridecyl, tetradecyl, pentadecyl are also suitable as radicals R 1 , R 2 or R 3 , and hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl as radicals R 2 and R 3 .

Alkylreste R2 oder R3 können auch Phenyl als Substituenten tragen; beispielsweise sind hier zu nennen (dabei bedeutet Ph = Phenyl):

  • -CH2-Ph, -CH(CH3)-Ph, -(CH2)2-Ph, -(CH2)4-CH(CH3)-Ph-3-CH3, -(CH2)3-CH(C4H9)-Ph-3-CH3, -(CH2)6-Ph-4-0-CH3, -CH(C2Hs)-(CH2)3-Ph-3-0-C2H5 und -CH(C2H5)-(CH2)3-Ph-3-Cl.
Alkyl radicals R 2 or R 3 can also carry phenyl as substituents; For example, here are to be mentioned (where Ph = phenyl):
  • -CH 2 -Ph, -CH (CH 3 ) -Ph, - (CH 2 ) 2 -Ph, - (CH 2 ) 4 -CH (CH 3 ) -Ph-3-CH 3 , - (CH 2 ) 3 -CH (C 4 H 9 ) -Ph-3-CH 3 , - (CH 2 ) 6 -Ph-4-0-CH 3 , -CH (C 2 Hs) - (CH 2 ) 3 -Ph-3-0-C 2 H 5 and -CH (C 2 H 5 ) - (CH 2 ) 3 -Ph-3-Cl.

Weiterhin eignen sich z.B. folgende Halogen-, Hydroxy- und Cyanoalkylgruppen als Reste R2 oder R3:

  • -(CH2)5-Cl, -CH(C4H9)-(CH2)3-Cl oder -(CH2)4-CF3; -(CH2)2-CH(CH3)-OH, -(CH2)2-CH(C4H9)-OH oder -CH(C2H5)-(CH2)9-OH; -(CH2)2-CN, -(CH2)3-CN, -CH2-CH(CH3)-CH(C2Hs)-CN, -(CH2)6-CH(C2H5)-CN und -(CH2)3-CH(CH3)-(CH2)2-CH(CH3)-CN.
The following halogen, hydroxyl and cyanoalkyl groups are also suitable as radicals R 2 or R 3 :
  • - (CH 2 ) 5 -Cl, -CH (C 4 H 9 ) - (CH 2 ) 3 -Cl or - (CH 2 ) 4 -CF 3 ; - (CH 2 ) 2 -CH (CH 3 ) -OH, - (CH 2 ) 2 -CH (C 4 H 9 ) -OH or -CH (C 2 H 5 ) - (CH 2 ) 9 -OH; - (CH 2 ) 2 -CN, - (CH 2 ) 3 -CN, -CH 2 -CH (CH 3 ) -CH (C 2 Hs) -CN, - (CH 2 ) 6 -CH (C 2 H 5 ) -CN and - (CH 2 ) 3 -CH (CH 3 ) - (CH 2 ) 2 -CH (CH 3 ) -CN.

Handelt es sich bei den Resten R1, R2, R3, R5, R6, R7, R15 oder R16 um Alkoxyalkylgruppen der bevorzugten Formel II, so sind geeignete Gruppen W beispielsweise 1,2- und 1,3-Propylen, 1,2-, 1,3-, 1,4-und 2,3-Butylen, Pentamethylen, Hexamethylen und 2-Methylpentamethylen, besonders Ethylen, und Reste R4 vor allem Methyl, Ethyl, Propyl, Butyl sowie Benzyl und Phenyl, die beide Substituenten wie Methyl-(oxy), Ethyl(oxy), Propyl(oxy) und Butyl (oxy) tragen können. Besonders bevorzugte Gruppen II sind z .B.:

  • -(CH2)2-O-CH3, -(CH2)2-0-C2Hs, -(CH2)2-O-C3H7, -(CH2)2-O-C4H9, -(CH2)2-O-CH2-CH(CH3)-CH3, -(CH2)2-O-Ph, -(CH2)2-0-CH2-Ph, -[(CH2)2-O]2-CH3, -[(CH2)2-O]2-C2H5, -[(CH2)2-O]2-Ph, -[(CH2)2-O]2-Ph-4-O-C4H9, -[(CH2)2-O]3-C4H9, -[(CH2)2-0]3-Ph, -[(CH2)2-O]3-Ph-3-C4H9, -[(CH2)2-O]4-CH3, -(CH2)3-O-(CH2)2-O-CH3, -(CH2)3-O-(CH2)2-O-C2H5, -(CH2)3-0-(CH2)2-0-Ph, -(CH2)3-O-[(CH2)2-O]2-CH3 und -(CH2)3-O-[(CH2)2-O]2-C2H5.
If the radicals R 1 , R 2 , R 3 , R 5 , R 6 , R 7 , R 15 or R 16 are alkoxyalkyl groups of the preferred formula II, suitable groups W are, for example, 1,2- and 1,3 -Propylene, 1,2-, 1,3-, 1,4-and 2,3-butylene, pentamethylene, hexamethylene and 2-methylpentamethylene, especially ethylene, and radicals R 4 especially methyl, ethyl, propyl, butyl and benzyl and phenyl, which can carry both substituents such as methyl (oxy), ethyl (oxy), propyl (oxy) and butyl (oxy). Examples of particularly preferred groups II are:
  • - (CH 2 ) 2 -O-CH 3 , - (CH 2 ) 2 -0-C 2 Hs, - (CH 2 ) 2 -OC 3 H 7 , - (CH 2 ) 2 -OC 4 H 9 , - (CH 2 ) 2 -O-CH 2 -CH (CH 3 ) -CH 3 , - (CH 2 ) 2 -O-Ph, - (CH 2 ) 2 -0-CH 2 -Ph, - [(CH 2 ) 2 -O] 2 -CH 3 , - [(CH 2 ) 2 -O] 2 -C 2 H 5 , - [(CH 2 ) 2 -O] 2 -Ph, - [(CH 2 ) 2 -O ] 2 -Ph-4-OC 4 H 9 , - [(CH 2 ) 2 -O] 3 -C 4 H 9 , - [(CH 2 ) 2 -0] 3 -Ph, - [(CH 2 ) 2 -O] 3 -Ph-3-C 4 H 9 , - [(CH 2 ) 2 -O] 4 -CH 3 , - (CH 2 ) 3 -O- (CH 2 ) 2 -O-CH 3 , - (CH 2 ) 3 -O- (CH 2 ) 2 -OC 2 H 5 , - (CH 2 ) 3 -0- (CH 2 ) 2 -0-Ph, - (CH 2 ) 3 -O - [(CH 2 ) 2 -O] 2 -CH 3 and - (CH2) 3 -O - [(CH 2 ) 2 -O] 2 -C 2 H 5 .

Als weitere bevorzugte Gruppen II sind beispielsweise zu nennen:

  • -(CH2)3-O-CH3, -(CH2)3-O-C2H5, -(CH2)3-0-C3H7, -(CH2)3-O-C4H9, -(CH2)3-0-Ph, -[(CH2)3-O]2-CH3, -[(CH2)3-0-]2-C2Hs, -CH2-CH(CH3)-O-CH3, -CH2-CH(CH3)-0-C2Hs, -CH2-CH(CH3)-O-C3H7, -CH2-CH(CH3)-O-C4H9, -CH2-CH(CH3)-O-Ph, -(CH2)4-O-CH3, -(CH2)4-O-C2H5, -(CH2)4-O-C4H9, -(CH2)4-O-CH2-CH(C2H5)-C4H9, -(CH2)4-O-Ph, -(CH2)4-O-CH2-Ph-2-O-C2H5, -(CH)4-O-C6H10-2-C2H5, -[(CH2)4-O]2-CH3, -[(CH2)4-O]2-C2H5, -[(CH2)2-CH(CH3)-O]2-C2H5, - (CH2)5-O-CH3, -(CH2)5-0-C2Hs, -(CH2)5-O-C3H7, -(CH2)s-0-Ph, -(CH2)2-CH(C2H5)-O-CH2-Ph-3-O-C4H9, -(CH2)2-CH(C2H5)-O-CH2-Ph-3-Cl, -(CH2)6-O-C4H9, -(CH2)6-O-Ph-4-O-C4H9, -(CH2)3-CH(CH3)-CH2-O-C4H9, -(CH2)3-O-(CH2)4-O-CH3, -(CH2)3-O-(CH2)4-O-C2H5, -(CH2)4-O-(CH2)3-O-CH3 und -(CH2)4-O-CH2)3-O-C2H5.
Examples of further preferred groups II are:
  • - (CH 2 ) 3 -O-CH 3 , - (CH 2 ) 3 -OC 2 H 5 , - (CH 2 ) 3 -0-C 3 H 7 , - (CH 2 ) 3 -OC 4 H 9 , - (CH 2 ) 3 -0-Ph, - [(CH 2 ) 3 -O] 2 -CH 3 , - [(CH 2 ) 3 -0-] 2 -C 2 Hs, -CH 2 -CH (CH 3 ) -O-CH 3 , -CH 2 -CH (CH 3 ) -0-C 2 Hs, -CH 2 -CH (CH 3 ) -OC 3 H 7 , -CH 2 -CH (CH 3 ) -OC 4 H 9 , -CH 2 -CH (CH 3 ) -O-Ph, - (CH 2 ) 4 -O-CH 3 , - (CH 2 ) 4 -OC 2 H 5 , - (CH 2 ) 4 -OC 4 H 9 , - (CH 2 ) 4 -O-CH 2 -CH (C 2 H 5 ) -C 4 H 9 , - (CH 2 ) 4 -O-Ph, - (CH 2 ) 4 -O-CH 2 -Ph-2-OC 2 H 5 , - (CH) 4 -OC 6 H 10 -2-C 2 H 5 , - [(CH 2 ) 4 -O] 2 -CH 3 , - [(CH 2 ) 4 -O] 2 -C 2 H 5 , - [(CH 2 ) 2 -CH (CH 3 ) -O] 2 -C 2 H 5 , - (CH 2 ) 5 -O-CH 3 , - (CH 2 ) 5 -0-C 2 Hs, - (CH 2 ) 5 -OC 3 H 7 , - (CH 2 ) s-0-Ph, - (CH 2 ) 2 -CH (C 2 H 5 ) -O-CH 2 -Ph-3-OC 4 H 9 , - (CH 2 ) 2 -CH (C 2 H 5 ) -O-CH 2 -Ph-3-Cl, - (CH 2 ) 6 -OC 4 H 9 , - (CH 2 ) 6 -O-Ph-4-OC 4 H 9 , - (CH 2 ) 3 -CH (CH 3 ) -CH 2 -OC 4 H 9 , - (CH 2 ) 3 -O- (CH 2 ) 4 -O-CH 3 , - (CH 2 ) 3 -O- (CH 2 ) 4 -OC 2 H 5 , - (CH 2 ) 4 -O- (CH 2 ) 3 -O-CH 3 and - ( CH 2 ) 4 -O-CH 2 ) 3 -OC 2 H 5 .

Daneben sind z.B. folgende Alkoxyalkylgruppen geeignet:

  • -(CH2)8-O-CH3, -(CH2)8-O-C4H9, -(CH2)8-O-CH2-Ph-3-C2H5, -(CH2)4-CH(C)-(CH2)3-O-CH2-Ph-3-CH3 und -(CH2)3-CH(C4H9)-O-CH2-Ph-3-CH3.
The following alkoxyalkyl groups are also suitable:
  • - (CH 2 ) 8 -O-CH 3 , - (CH 2 ) 8 -OC 4 H 9 , - (CH 2 ) 8 -O-CH 2 -Ph-3-C 2 H 5 , - (CH 2 ) 4 -CH (C) - (CH 2 ) 3 -O-CH 2 -Ph-3-CH 3 and - (CH 2 ) 3 -CH (C 4 H 9 ) -O-CH 2 -Ph-3-CH 3rd

Von den oben aufgeführten Alkoxyalkylgruppen sind solche, die bis zu 8 C-Atome enthalten, auch als Reste R8 und solche mit bis zu 12 C-Atomen auch als Reste R15 oder R16 geeignet.Of the alkoxyalkyl groups listed above, those which contain up to 8 carbon atoms are also suitable as radicals R 8 and those with up to 12 carbon atoms are also suitable as radicals R 15 or R 16 .

Als Reste R2, R3, R8, R" oder R12 bevorzugte Alkoxygruppen sind beispielsweise zu nennen: Methoxy, Ethoxy, Propoxy, Isopropoxy, Butoxy, Isobutoxy und sec.-Butoxy.Preferred alkoxy groups as R 2 , R 3 , R 8 , R "or R 12 are, for example: methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy and sec-butoxy.

Reste R8, besonders R2 oder R3 sind weiterhin z.B. Pentyloxy, Isopentyloxy, Neopentyloxy, Hexyloxy, Octyloxy und 2-Ethylhexyloxy.R 8 , in particular R 2 or R 3, are furthermore, for example, pentyloxy, isopentyloxy, neopentyloxy, hexyloxy, octyloxy and 2-ethylhexyloxy.

Als Reste R2 oder R3 eignen sich außerdem beispielsweise Nonyloxy oder Decyloxy, daneben noch Undecyloxy, Dodecyloxy, Tridecyloxy, Tetradecyloxy und Pentadecyloxy.Also suitable as radicals R 2 or R 3 are, for example, nonyloxy or decyloxy, and also undecyloxy, dodecyloxy, tridecyloxy, tetradecyloxy and pentadecyloxy.

Reste R8 können auch Alkylthiogruppen sein wie bevorzugt Methylthio, Ethylthio und 2-Cyanoethylthio, daneben Propylthio, Isopropylthio, Butylthio, Pentylthio, Hexylthio, Heptylthio, Octylthio, 2-Ethylhexylthio, 2-Ethoxycarbonylethylthio und besonders 2-Methoxycarbonylthio.R 8 radicals can also be alkylthio groups, such as methylthio, ethylthio and 2-cyanoethylthio, in addition propylthio, isopropylthio, butylthio, pentylthio, hexylthio, heptylthio, octylthio, 2-ethylhexylthio, 2-ethoxycarbonylethylthio and especially 2-methoxycarbonyl.

Als Reste R2 oder R3 geeignete Alkanoyloxyalkyl-, Alkoxycarbonyloxyalkyl- und Alkoxycarbonylalkylgruppen sind beispielsweise:

  • -(CH2)2-O-CO-CH3, -(CH2)3-O-CO-(CH2)7-CH3, -(CH2)2-0-CO-(CH2)3-Ph-2-0-CH3, -CH(CH2-Ph-3-CH3)-O-CO-C4H9 und -(CH2)4-O-CO-(CH2)4-CH(C2H5)-OH;
  • - (CH2)2-O-CO-O-CH3, -(CH2)3-O-CO-O-(CH2)7-CH3, -CH(C2H5)-CH2-O-CO-O-C4H9, -(CH2)4-O-CO-O-(CH2)2-CH(CH3)-O-Ph-3-CH3 und -(CH2)5-O-CO-O-(CH2)5-CN;
  • -(CH2)2-CO-O-CH3, -(CH2)3-CO-O-(C4H9, -(CH2)3-CH(CH3)-CH2-CO-O-C4H9, -(CH2)3-CH(C4H9)-CH2-CO-O-C2H5, -(CH2)2-CO-0-(CH2)s-Ph, -(CH2)4-CO-O-(CH2)4-Ph-4-C4H9, -(CH2)3-CO-O-(CH2)4-O-Ph-3-O-CH3, -(CH2)2-CH(CH2OH)-(CH2)2-CO-O-C2H5, -CH(C2H5)-CH2-CO-O-(CH2)4-OH und -(CH2)3-CO-O-(CH2)6-CN.
Examples of alkanoyloxyalkyl, alkoxycarbonyloxyalkyl and alkoxycarbonylalkyl groups which are suitable as R 2 or R 3 are:
  • - (CH 2 ) 2 -O-CO-CH 3 , - (CH 2 ) 3 -O-CO- (CH 2 ) 7 -CH 3 , - (CH 2 ) 2 -0-CO- (CH 2 ) 3 -Ph-2-0-CH 3 , -CH (CH 2 -Ph-3-CH 3 ) -O-CO-C 4 H 9 and - (CH 2 ) 4 -O-CO- (CH 2 ) 4 - CH (C 2 H 5 ) -OH;
  • - (CH 2 ) 2 -O-CO-O-CH 3 , - (CH 2 ) 3 -O-CO-O- (CH 2 ) 7 -CH 3 , -CH (C 2 H 5 ) -CH 2 - O-CO-OC 4 H 9 , - (CH 2 ) 4 -O-CO-O- (CH 2 ) 2 -CH (CH 3 ) -O-Ph-3-CH 3 and - (CH 2 ) 5 - O-CO-O- (CH 2 ) 5 -CN;
  • - (CH 2 ) 2 -CO-O-CH 3 , - (CH 2 ) 3 -CO-O- (C 4 H 9 , - (CH 2 ) 3 -CH (CH 3 ) -CH 2 -CO-OC 4 H 9 , - (CH 2 ) 3 -CH (C 4 H 9 ) -CH 2 -CO-OC 2 H 5 , - (CH2) 2-CO-0- (CH2) s-Ph, - (CH 2 ) 4 -CO-O- (CH 2 ) 4 -Ph-4-C 4 H 9 , - (CH 2 ) 3 -CO-O- (CH 2 ) 4 -O-Ph-3-O-CH 3 , - (CH 2 ) 2 -CH (CH 2 OH) - (CH 2 ) 2 -CO-OC 2 H 5 , -CH (C 2 H 5 ) -CH 2 -CO-O- (CH 2 ) 4 -OH and - (CH 2 ) 3 -CO-O- (CH 2 ) 6 -CN.

Phenyl- und Cyclohexylreste, die als Reste R1, R2 oder R3 enthalten sein können, sind beispielsweise folgende:

  • -Ph, -Ph-3-CH3, -Ph-4-(CH2)io-CH3, -Ph-3-(CH2)5-CH(CH3)-CH3, Ph-4-O-C4H9, -Ph-4-(CH2)5-CH(C2H5)-CH3, -Ph-4-0-CH2-Ph und -Ph-4-CI, sowie im Falle von R1 besonders -Ph-3-SO2-N(CH3)-CH3 und -Ph-3-SO2-N((CH2)2-O-CH3)-(CH2)2-O-CH3;
  • -C6H1o-4-CH3, -C6H10-4-C10H21, -C6H10-3-O-C4H9, -C6H10-3-O-(CH2)4-CH(C2H5)-CH3 und -C6H10-4-Cl.
Phenyl and cyclohexyl radicals which may be present as R 1 , R 2 or R 3 are, for example, the following:
  • -Ph, -Ph-3-CH 3 , -Ph-4- (CH 2 ) io-CH 3 , -Ph-3- (CH 2 ) 5 -CH (CH 3 ) -CH 3 , Ph-4-OC 4 H 9 , -Ph-4- (CH 2 ) 5 -CH (C 2 H 5 ) -CH 3 , -Ph-4-0-CH 2 -Ph and -Ph-4-CI, as well as in the case of R 1 especially -Ph-3-SO 2 -N (CH 3 ) -CH 3 and -Ph-3-SO 2 -N ((CH 2 ) 2 -O-CH 3 ) - (CH 2 ) 2 -O-CH 3 ;
  • -C 6 H 1 o-4-CH3, -C 6 H 10 -4-C 10 H 21 , -C 6 H 10 -3-OC 4 H 9 , -C 6 H 10 -3-O- (CH 2 ) 4 -CH (C 2 H 5 ) -CH 3 and -C 6 H 10 -4-Cl.

Handelt es sich bei den Resten R5, R6, R7, R8, R9, R10, R11, R12 oder R14 um Gruppierungen der Formeln -CO-OR15 oder -CO-NR15R16, so sind besonders geeignet

  • -CO-O-CH3, -CO-O-C2H5, -CO-O-C3H7, -CO-O-C4H9, -CO-N(CH3)-CH3 und -CO-N(C2H5)-C2H5,
  • daneben beispielsweise auch
  • -CO-O-C5H11, -CO-O-C6H13, -CO-N(C3H7)-C3H7 und -CO-N(C4H9)-C4H9.
If the radicals R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 or R 14 are groupings of the formulas -CO-OR 15 or -CO-NR 15 R 16 , so are particularly suitable
  • -CO-O-CH 3 , -CO-OC 2 H 5 , -CO-OC 3 H 7 , -CO-OC 4 H 9 , -CO-N (CH 3 ) -CH 3 and -CO-N (C 2 H 5 ) -C 2 H 5 ,
  • besides, for example
  • -CO-OC 5 H 11 , -CO-OC 6 H 13 , -CO-N (C 3 H 7 ) -C 3 H 7 and -CO-N (C 4 H 9 ) -C 4 H 9 .

Gruppierungen der Formeln -SO-OR15 oder SO2-OR15, die als Reste R5, R6, R7 oder R8 eingesetzt werden können, sind z.B.

  • -SO-O-CH3, -SO-O-C2H5, -SO-O-C3H7, -S02-0-CH3, -SO2-O-C2H5, -SO2-O-C3H7.
Groupings of the formulas -SO-OR 15 or SO 2 -OR 15 , which can be used as R 5 , R 6 , R 7 or R 8 , are, for example
  • -SO-O-CH 3 , -SO-OC 2 H 5 , -SO-OC 3 H 7 , -S0 2 -0-CH 3 , -SO 2 -OC 2 H 5 , -SO 2 -OC 3 H 7 .

Als Reste R5, R6 oder R7 kommen auch Gruppierungen der Formel -SO2-NR15R16 in Betracht, wie besonders

  • -S02-N(CH3)-CH3, -SO2-N((CH2)2-O-CH3)-(CH2)2-O-CH3, daneben beispielsweise auch -S02-N(C2Hs)-C2H5 und -S02-N(C3H7)-C3H7.
As radicals R 5 , R 6 or R 7 , groups of the formula -SO 2 -NR 15 R 16 are also suitable, as is particularly preferred
  • -S0 2 -N (CH 3 ) -CH 3 , -SO 2 -N ((CH 2 ) 2 -O-CH 3 ) - (CH 2 ) 2 -O-CH 3 , in addition, for example, also -S0 2 -N (C 2 Hs) -C2H5 and -S0 2 -N (C 3 H 7 ) -C 3 H 7 .

Reste R6 oder R10 können auch Gruppen der Formel IV sein wie

  • -CH = C(CN)-CN, -CH = C(CN)-CO-O-CH3, -CH = C(CN)-CO-O-C2H5, -CH = C(CN)-CO-O-C3H7, -CH = C(CN)-CO-O-C4 H9, -CH=C(CN)-N(CH3)-CH3 und -CH=C(CN)-N(C2H5)-C2H5.
R 6 or R 10 radicals can also be groups of the formula IV, such as
  • -CH = C (CN) -CN, -CH = C (CN) -CO-O-CH 3 , -CH = C (CN) -CO-OC 2 H 5 , -CH = C (CN) -CO- OC 3 H 7 , -CH = C (CN) -CO-OC 4 H 9 , -CH = C (CN) -N (CH 3 ) -CH 3 and -CH = C (CN) -N (C 2 H 5 ) -C 2 H 5 .

Von den bereits genannten Resten sind als Reste R1 besonders bevorzugt C1-C8-Alkyl, darunter besonders Methyl und Isopropyl, Cyclohexyl, Phenyl, das auch Methoxy, Sulfonamido oder Chlor als Substituenten tragen kann, und auch Benzyl. Bevorzugte Reste R1 sind weiterhin Thien-3-yl und vor allem Thien-2-yl, Furan-3-yl und besonders Furan-2-yl sowie Pyrid-2-yl, Pyrid-4-yl und besonders Pyrid-3-yl.Of the radicals already mentioned, particularly preferred radicals R 1 are C 1 -C 8 -alkyl, including in particular methyl and isopropyl, cyclohexyl, phenyl, which can also carry methoxy, sulfonamido or chlorine as substituents, and also benzyl. Preferred radicals R 1 are also thien-3-yl and especially thien-2-yl, furan-3-yl and especially furan-2-yl as well as pyrid-2-yl, pyrid-4-yl and especially pyrid-3- yl.

Als Reste R2 oder R3 sind von den genannten Alkylresten solche mit bis zu 12 C-Atomen bevorzugt, darunter besonders Methyl, Ethyl und Propyl, von den genannten Cyanoalkyl- und Alkoxyresten solche mit bis zu 10 C-Atomen. Besonders bevorzugte Reste R2 oder R3 weisen die Formel Ila auf mit Methyl oder Ethyl als Rest R4'.Preferred radicals R 2 or R 3 of the alkyl radicals mentioned are those with up to 12 C atoms, especially methyl, ethyl and propyl, of the cyanoalkyl and alkoxy radicals mentioned those with up to 10 C atoms. Particularly preferred radicals R 2 or R 3 have the formula Ila with methyl or ethyl as the radical R 4 '.

Von den oben aufgeführten Diazokomponenten D-NH2 sind die folgenden besonders bevorzugt:Of the diazo components D-NH 2 listed above, the following are particularly preferred:

  • - Anilinderivate Illa mit der eingangs definierten Bedeutung der Reste R5, R6 und R7 - Aniline derivatives Illa with the meaning of the radicals R 5 , R 6 and R 7 defined at the outset
  • - Aminothiophenderivate IIlc mit folgender Bedeutung der Reste R8, R9 und R10:
    • R8 Wasserstoff, Chlor; Alkyl-, auch Alkoxy- oder Alkoxyalkylgruppen, die jeweils bis zu 8 C-Atome enthalten können; eine Phenylgruppe, die C1-C4-Alkyl oder C1-C4-Alkoxy als Substituenten tragen kann, oder eine Benzylgruppe; einen Rest der Formel -CO-OR15;
    • R9 eine Cyanogruppe; Reste der Formeln -CO-OR15 oder auch -CO-NR15R16;
    • R10 eine Cyano-, Nitro- oder Formylgruppe; einen Rest der Formel IV
    - aminothiophene derivatives IIlc with the following meaning of the radicals R 8 , R 9 and R 10 :
    • R 8 is hydrogen, chlorine; Alkyl, also alkoxy or alkoxyalkyl groups, each of which can contain up to 8 carbon atoms; a phenyl group which may carry C 1 -C 4 alkyl or C 1 -C 4 alkoxy as a substituent, or a benzyl group; a radical of the formula -CO-OR 15 ;
    • R 9 is a cyano group; Radicals of the formulas -CO-OR 15 or also -CO-NR 15 R 16 ;
    • R 10 is a cyano, nitro or formyl group; a radical of formula IV
  • - Aminothiazolderivate Ille mit folgender Bedeutung der Reste R8 und R10:
    • R8 Wasserstoff, Chlor; C1-C8-Alkylgruppen; eine Phenylgruppe, die C1-C4-Alkyl oder C1-C4-Alkoxy als Substituenten tragen kann, oder eine Benzylgruppe; einen Rest der Formel -CO-OR15;
    • R10 eine Cyano-, Nitro- oder Formylgruppe; einen Rest der Formel -CO-OR15
    Aminothiazole derivatives Ille with the following meaning of the radicals R 8 and R 10 :
    • R 8 is hydrogen, chlorine; C 1 -C 8 alkyl groups; a phenyl group which may carry C 1 -C 4 alkyl or C 1 -C 4 alkoxy as a substituent, or a benzyl group; a radical of the formula -CO-OR 15 ;
    • R 10 is a cyano, nitro or formyl group; a radical of the formula -CO-OR 15
  • - Aminoisothiazolderivate Illg mit folgender Bedeutung der Reste R8 und R9:
    • R8 Chlor; Alkyl-, Alkoxy-, Alkythio- oder Alkoxyalkylgruppen, die jeweils bis zu 8 C-Atome enthalten können; eine Phenylgruppe, die C1-C4-Alkyl oder C1-C4-Alkoxy als Substituenten tragen kann, eine Benzyl- oder Benzyloxygruppe;
    • R9 eine Cyano- oder Nitrogruppe; einen Rest der Formel -CO-OR15
    - Aminoisothiazole derivatives Illg with the following meaning of the radicals R 8 and R 9 :
    • R 8 chlorine; Alkyl, alkoxy, alkythio or alkoxyalkyl groups, each of which can contain up to 8 carbon atoms; a phenyl group which may carry C 1 -C 4 alkyl or C 1 -C 4 alkoxy as a substituent, a benzyl or benzyloxy group;
    • R 9 is a cyano or nitro group; a radical of the formula -CO-OR 15
  • - Aminothiadiazolderivate Illk und Aminoisothiadiazolderivate IIII mit folgender Bedeutung des Restes R8:
    • R8 Wasserstoff, Chlor, eine Cyano- oder Thiocyanatogruppe; Alkyl-, Alkoxy-, Alkylthio- oder Alkoxyalkylgruppen, die jeweils bis zu 8 C-Atome enthalten können; 2-(C, -C2-Alkoxycarbonyl)ethylthiogruppen; eine Phenylgruppe, die C1-C4-Alkyl oder C,-C4-Alkoxy als Substituenten tragen kann, eine Benzyl- oder Benzyloxygruppe; Reste der Formeln -CO-OR1s, -SO-OR15 oder -SO2-OR15.
    - aminothiadiazole derivatives Illk and aminoisothiadiazole derivatives IIII with the following meaning of the radical R 8 :
    • R 8 is hydrogen, chlorine, a cyano or thiocyanato group; Alkyl, alkoxy, alkylthio or alkoxyalkyl groups, each of which can contain up to 8 carbon atoms; 2- (C, -C 2 alkoxycarbonyl) ethylthio groups; a phenyl group which may carry C 1 -C 4 alkyl or C, -C 4 alkoxy as a substituent, a benzyl or benzyloxy group; Residues of the formulas -CO-OR 1s , -SO-OR 15 or -SO 2 -OR 15 .

Die erfindungsgemäß zu verwendenden Farbstoffe I zeichnen sich gegenüber den bisher für den Thermotransferdruck eingesetzten Rot- und Blaufarbstoffen mit Kupplungskomponenten auf Anilinbasis durch folgende Eigenschaften aus: leichtere thermische Transferierbarkeit, verbesserte Migrationseigenschaften im Aufnahmemedium bei Raumtemperatur, höhere thermische Stabilität, höhere Lichtechtheit, bessere Resistenz gegen Feuchtigkeit und Chemikalien, bessere Löslichkeit bei der Herstellung der Druckfarbe, höhere Farbstärke sowie leichtere technische Zugänglichkeit.The dyes I to be used according to the invention are distinguished from the red and blue dyes with coupling components based on aniline, which have been used for thermal transfer printing to date, by the following properties: easier thermal transferability, improved migration properties in the recording medium at room temperature, higher thermal stability, higher lightfastness, better resistance to moisture and chemicals, better solubility in the manufacture of the printing ink, higher color strength and easier technical accessibility.

Zudem zeigen die Azofarbstoffe I eine deutlich bessere Farbtonreinheit, insbesondere in Farbstoffmischungen, und ergeben verbesserte Schwarz-Drucke.In addition, the azo dyes I show a significantly better color purity, in particular in dye mixtures, and give improved black prints.

Die für das erfindungsgemäße Thermotransferdruckverfahren benötigten als Farbstoffgeber fungierenden Transferblätter werden folgendermaßen präpariert: Die Azofarbstoffe I werden in einem organischen Lösungsmittel, wie Isobutanol, Methylethylketon, Methylenchlorid, Chlorbenzol, Toluol, Tetrahydrofuran oder deren Mischungen, mit einem oder mehreren Bindemitteln sowie eventuell weiteren Hilfsmitteln wie Trennmitteln oder kristallisationshemmendenStoffen zu einer Druckfarbe verarbeitet, welche die Farbstoffe vorzugsweise molekular-dispers gelöst enthält. Die Druckfarbe wird anschließend auf einen inerten Träger aufgetragen und getrocknet.The transfer sheets required as dye donors for the thermal transfer printing process according to the invention are prepared as follows: The azo dyes I are in an organic solvent such as isobutanol, methyl ethyl ketone, methylene chloride, chlorobenzene, toluene, tetrahydrofuran or mixtures thereof, with one or more binders and possibly other auxiliaries such as release agents or crystallization-inhibiting substances are processed into a printing ink which preferably contains the dyes in a molecularly dispersed solution. The printing ink is then applied to an inert support and dried.

Als Bindemittel für die erfindungsgemäße Verwendung der Azofarbstoffe I eignen sich alle in organischen Lösungsmitteln löslichen Materialien, die bekanntermaßen für den Thermotransferdruck dienen, also z.B. Cellulosederivate wie Methylcellulose, Hydroxypropylcellulose, Celluloseacetat oder Celluloseacetobutyrat, vor allem Ethylcellulose und Ethylhydroxyethylcellulose, Stärke, Alginate, Alkydharze wie Polyvinylalkohol oder Polyvinylpyrrolidon sowie besonders Polyvinylacetat und Polyvinylbutyrat. Daneben kommen Polymere und Copolymere von Acrylaten oder deren Derivaten wie Polyacrylsäure, Polymethylmethacrylat-oder Styrolacrylatcopolymere, Polyesterharze, Polyamidharze, Polyurethanharze oder natürliche Harze wie z.B. Gummi Arabicum in Betracht.Suitable binders for the use of azo dyes I according to the invention are all materials which are soluble in organic solvents and which are known to serve for thermal transfer printing, i.e. Cellulose derivatives such as methyl cellulose, hydroxypropyl cellulose, cellulose acetate or cellulose acetobutyrate, especially ethyl cellulose and ethyl hydroxyethyl cellulose, starch, alginates, alkyd resins such as polyvinyl alcohol or polyvinyl pyrrolidone, and especially polyvinyl acetate and polyvinyl butyrate. In addition, there are 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 e.g. Gum arabic into consideration.

Häufig empfehlen sich Mischungen dieser Bindemittel, z.B. solche aus Ethylcellulose und Polyvinylbutyrat im Gewichtsverhältnis 2 : 1.Mixtures of these binders are often recommended, e.g. those made of ethyl cellulose and polyvinyl butyrate in a weight ratio of 2: 1.

Das Gewichtsverhältnis von Bindemittel zu Farbstoff beträgt in der Regel 8 : 1 bis 1 : 1, vorzugsweise 5 : 1 bis 2: 1.The weight ratio of binder to dye is usually 8: 1 to 1: 1, preferably 5: 1 to 2: 1.

Als Hilfsmittel werden z.B. Trennmittel auf der Basis von perfluorierten Alkylsulfonamidoalkylestern oder Siliconen, wie sie in der EP-A-227 092 bzw. der EP-A-192 435 beschrieben sind, und besonders organische Additive, welche das Auskristallisieren der Transferfarbstoffe bei Lagerung und Erhitzung des Farbbandes verhindern, beispielsweise Cholesterin oder Vanillin, verwendet.As aids, e.g. Release agents based on perfluorinated alkylsulfonamidoalkyl esters or silicones as described in EP-A-227 092 or EP-A-192 435, and especially organic additives which prevent the transfer dyes from crystallizing out when the ribbon is stored and heated, for example cholesterol or vanillin used.

Inerte Trägermaterialien sind beispielsweise Seiden-, Lösch- oder Pergaminpapier sowie Folien aus wärmebeständigen Kunststoffen wie Polyestern, Polyamiden oder Polyimiden, wobei diese Folien auch metallbeschichtet sein können.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.

Der inerte Träger kann auf der dem Thermokopf zugewandten Seite zusätzlich mit einem Gleitmittel beschichtet werden, um ein Verkleben des Thermokopfes mit dem Trägermaterial zu verhindern. Geeignete Gleitmittel sind beispielsweise Silicone oder Polyurethane, wie sie in der EP-A-216 483 beschrieben sind.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 are described in EP-A-216 483.

Die Stärke des Farbstoffträgers beträgt im allgemeinen 3 bis 30 µm, bevorzugt 5 bis 10 µm.The thickness of the dye carrier is generally 3 to 30 microns, preferably 5 to 10 microns.

Das zu bedruckende Substrat, z.B. Papier, muß seinerseits mit einem Kunststoff beschichtet sein, welcher den Farbstoff beim Druckvorgang aufnimmt. Vorzugsweise verwendet man hierzu polymere Materialien, deren Glasumwandlungstemperatur Tg zwischen 50 und 100°C beträgt, also z.B. Polycarbonate und Polyester. Näheres hierzu ist den EP-A-227 094, EP-A-133 012, EP-A-133 011, JP-A-199 997/1986 oder JP-A-283 595/1986 zu entnehmen.The substrate to be printed, e.g. Paper, in turn, must be coated with a plastic that absorbs the dye during the printing process. Polymeric materials whose glass transition temperature Tg is between 50 and 100 ° C., i.e. e.g. Polycarbonates and polyester. Further details can be found in EP-A-227 094, EP-A-133 012, EP-A-133 011, JP-A-199 997/1986 or JP-A-283 595/1986.

Für das erfindungsgemäße Verfahren wird ein Thermokopf eingesetzt, der auf Temperaturen bis über 300 C aufheizbar ist, so daß der Farbstofftransfer in einer Zeit von maximal 15 msec erfolgt..A thermal head is used for the process according to the invention, which can be heated to temperatures of up to 300 ° C., so that the dye transfer takes place in a maximum time of 15 msec.

BeispieleExamples

Es wurden zunächst in üblicher Weise Transferblätter (Geber) aus Polyesterfolie von 6 bis 10 µm Stärke hergestellt, die mit einer ca. 5 pm starken Transferschicht aus einem Bindemittel B versehen war, welche jeweils ca. 0,25 g Azofarbstoff I enthielt. Das Gewichtsverhältnis Bindemittel zu Farbstoff betrug jeweils, wenn in den folgenden Tabellen nicht anders angegeben, 4 : 1.Initially, transfer sheets (donors) were made from polyester film of 6 to 10 μm in the usual way Starch produced, which was provided with an approximately 5 pm thick transfer layer of a binder B, each containing approximately 0.25 g of azo dye I. The weight ratio of binder to dye was 4: 1, unless otherwise stated in the tables below.

Das zu bedruckende Substrat (Nehmer) bestand aus Papier von ca. 120 µm Stärke, das mit einer 8 µm dicken Kunststoffschicht beschichtet war (Hitachi Color Video Print Paper).The substrate to be printed (taker) consisted of paper approximately 120 µm thick, which was coated with an 8 µm thick plastic layer (Hitachi Color Video Print Paper).

Geber und Nehmer wurden mit der beschichteten Seite aufeinander gelegt, mit Aluminiumfolie umwikkelt und für 2 min zwischen zwei Heizplatten auf eine Temperatur zwischen 70 und 80 C erhitzt. Mit gleichartigen Proben wurde dieser Vorgang dreimal bei jeweils höherer Temperatur zwischen 80 und 1200 C wiederholt.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 1200 ° C.

Die hierbei in die Kunststoffschicht des Nehmers diffundierte Farbstoffmenge ist proportional der optischen Dichte, die als Extinktion A photometrisch nach dem jeweiligen Erhitzen auf die oben angegebenen Temperaturen bestimmt wurde.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.

Die Auftragung des Logarithmus der gemessenen Extinktionswerte A gegen die zugehörige reziproke absolute Temperatur ergibt Geraden, aus deren Steigung die Aktivierungsenergie ΔET für das Transferexperiment zu berechnen ist:

Figure imgb0018
R: allg. GaskonstantePlotting the logarithm of the measured extinction values A against the associated reciprocal absolute temperature gives straight lines, from the slope of which the activation energy ΔE T for the transfer experiment can be calculated:
Figure imgb0018
 R: general gas constant

Der Auftragung kann zusätzlich die Temperatur T* entnommen werden, bei der die Extinktion den Wert 1 erreicht, d.h., die durchgelassene Lichtintensität ein Zehntel der eingestrahlten Lichtintensität beträgt. Je kleinere Werte die Temperatur T* annimmt, umso besser ist die thermische Transferierbarkeit des untersuchten Farbstoffs.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. The smaller the temperature T *, the better the thermal transferability of the investigated dye.

In den folgenden Tabellen sind die bezüglich ihres Thermotransferverhaltens untersuchten Azofarbstoffe I mit den zugehörigen Absorptionsmaxima λmax [nm] aufgeführt. Die λmax-Werte wurden in Methylenchlorid oder dem jeweils angegebenen Lösungsmittel gemessen.The azo dyes I investigated with regard to their thermal transfer behavior and the associated absorption maxima λ max [nm] are listed in the following tables. The λ max values were measured in methylene chloride or the specified solvent.

Zudem ist das jeweils verwendete Bindemittel B aufgeführt. Dabei bedeutet: EC = Ethylcellulose, PVB = Polyvinylbutyrat, MS = EC:PVB = 2:1, VY = Vylon.The binder B used in each case is also listed. Here means: EC = ethyl cellulose, PVB = polyvinyl butyrate, MS = EC: PVB = 2: 1, VY = Vylon.

Soweit die bereits erwähnten Parameter T* [°C] und ΔET [kJ/mol] gemessen wurden, sind die ermittelten Werte ebenfalls angegeben.

Figure imgb0019
Figure imgb0020
Figure imgb0021
Figure imgb0022
Figure imgb0023
Figure imgb0024
Figure imgb0025
Figure imgb0026
Figure imgb0027
Figure imgb0028
Figure imgb0029
Figure imgb0030
Figure imgb0031
Figure imgb0032
Figure imgb0033
Figure imgb0034
Figure imgb0035
Figure imgb0036
Figure imgb0037
Figure imgb0038
 As far as the already mentioned parameters T * [° C] and ΔE T [kJ / mol] were measured, the determined values are also given.
Figure imgb0019
Figure imgb0020
Figure imgb0021
Figure imgb0022
Figure imgb0023
Figure imgb0024
Figure imgb0025
Figure imgb0026
Figure imgb0027
Figure imgb0028
Figure imgb0029
Figure imgb0030
Figure imgb0031
Figure imgb0032
Figure imgb0033
Figure imgb0034
Figure imgb0035
Figure imgb0036
Figure imgb0037
Figure imgb0038

Claims (3)

1. Verwendung von Azofarbstoffen der allgemeinen Formel I
Figure imgb0039
für den Thermotransferdruck, in der die Substituenten folgende Bedeutung haben: R1 Wasserstoff; C1-C15-Alkylgruppen, die Phenyl oder Phenoxy als Substituenten tragen können; eine Cyclohexylgruppe, die C1-C5-Alkyl, C1-C5-Alkoxy oder Halogen als Substituenten tragen kann; eine Phenylgruppe, die Ci-Cs-Alkyl, C1-Cs-Alkoxy, Sulfonamido oder Halogen als Substituenten tragen kann; eine Thienylgruppe, die C1-C5-Alkyl oder Halogen als Substituenten tragen kann, eine Furanyl- oder Pyridylgruppe; einen Rest der allgemeinen Formel II
Figure imgb0040
in der W gleiche oder verschiedene C2-C6-Alkylengruppen bezeichnet, n 1 bis 6 bedeutet und R4 für eine C1-C4-Alkylgruppe oder eine Phenyl- oder Benzylgruppe steht, die beide jeweils Ci-C4-Alkyl oder C1-C4-Alkoxy als Substituenten tragen können; R2, R3 Wasserstoff; Alkyl-, Alkoxy-, Alkoxyalkyl-, Alkanoyloxyalkyl-, Alkoxycarbonyloxyalkyl-, Alkoxycarbonylalkyl-, Halogenalkyl-, Hydroxyalkyl- oder Cyanoalkylgruppen, die jeweils bis zu 15 C-Atome enthalten können und Phenyl, C1-C4-Alkylphenyl, C1-C4-Alkoxyphenyl, Halogenphenyl, Benzyloxy, C1-C4-Alkylbenzyloxy, C1-C4-Alkoxybenzyloxy, Halogenbenzyloxy, Halogen, Hydroxy oder Cyano als Substituenten tragen können; eine Cyclohexylgruppe, die C1-C15-Alkyl, C1-C15-Alkoxy oder Halogen als Substituenten tragen kann; eine Phenylgruppe, die C1-C15-Alkyl, C1-C15-Alkoxy, Benzyloxy oder Halogen als Substituenten tragen kann; einen Rest der oben angegebenen Formel II; D den Rest einer Diazokomponente ill
Figure imgb0041
 1. Use of azo dyes of the general formula I
Figure imgb0039
 for thermal transfer printing, in which the substituents have the following meaning: R 1 is hydrogen; C 1 -C 15 alkyl groups which can carry phenyl or phenoxy as substituents; a cyclohexyl group which can carry C 1 -C 5 alkyl, C 1 -C 5 alkoxy or halogen as substituents; a phenyl group which can carry C i -C s alkyl, C 1 -C s alkoxy, sulfonamido or halogen as substituents; a thienyl group which may carry C 1 -C 5 alkyl or halogen as a substituent, a furanyl or pyridyl group; a radical of the general formula II
Figure imgb0040
 in which W denotes the same or different C 2 -C 6 alkylene groups, n denotes 1 to 6 and R 4 represents a C 1 -C 4 alkyl group or a phenyl or benzyl group, both of which are each C i -C 4 alkyl or can carry C 1 -C 4 alkoxy as substituents; R 2 , R 3 are hydrogen; Alkyl, alkoxy, alkoxyalkyl, alkanoyloxyalkyl, alkoxycarbonyloxyalkyl, alkoxycarbonylalkyl, haloalkyl, hydroxyalkyl or cyanoalkyl groups, each of which can contain up to 15 carbon atoms and phenyl, C 1 -C 4 alkylphenyl, C 1 - C 4 -alkoxyphenyl, halophenyl, benzyloxy, C 1 -C 4 -alkylbenzyloxy, C 1 -C 4 -alkoxybenzyloxy, halobenzyloxy, halogen, hydroxy or cyano can carry as substituents; a cyclohexyl group which can carry C 1 -C 15 alkyl, C 1 -C 15 alkoxy or halogen as substituents; a phenyl group which can carry C 1 -C 15 alkyl, C 1 -C 15 alkoxy, benzyloxy or halogen as substituents; a radical of formula II given above; D the rest of a diazo component ill
Figure imgb0041
 2. Verfahren zur Übertragung von Azofarbstoffen durch Diffusion von einem Träger auf ein mit Kunststoff beschichtetes Substrat mit Hilfe eines Thermokopfes, dadurch gekennzeichnet, daß man hierfür einen Träger verwendet, auf dem sich ein oder mehrere Azofarbstoffe der Formel I gemäß Anspruch 1 befinden.2. Process for the transfer of azo dyes by diffusion from a carrier onto a plastic-coated substrate with the aid of a thermal head, characterized in that a carrier is used for this purpose, on which there are one or more azo dyes of the formula I according to claim 1. 3. Verfahren nach Anspruch 2, dadurch gekennzeichnet, daß man hierzu einen Azofarbstoff der Formel la
Figure imgb0042
verwendet, in der die Substituenten folgende Bedeutung haben: R1' C1-C8-Alkylgruppen, die Phenyl oder Phenoxy als Substituenten tragen können; eine Cyclohexylgruppe; eine Phenylgruppe, die C1-C4-Alkyl, C1-C4-Alkoxy oder Chlor als Substituenten tragen kann; eine Thienylgruppe; einen Rest der allgemeinen Formel lla
Figure imgb0043
in der p für 0 oder 1 und q für 1 bis 4 stehen und R4' eine C1-C4-Alkyl-, Phenyl- oder Benzylgruppe bezeichnet; R2',R3', C1-C12-Alkyl-, C1-C10-Alkoxy- oder C1-C10-Cyanoalkylgruppen; einen Rest der oben angegebenen Formellla; D' den Rest einer Diazokomponente III, die aus der Anilin-, Phenylazoanilin-, Aminothiophen-, Phenylazoaminothiophen-, Aminothiazol-, Phenylazoaminothiazol-, Aminoisothiazol-, Aminobenzisothiazol-, Aminothiadiazol-, Aminoisothiadiazol-, Aminooxazol-, Aminooxadiazol-, Aminodiazol-, Aminotriazol- oder Aminopyrrolreihe stammt. 3. The method according to claim 2, characterized in that for this purpose an azo dye of the formula la
Figure imgb0042
 used in which the substituents have the following meaning: R 1 ' C 1 -C 8 alkyl groups which can carry phenyl or phenoxy as substituents; a cyclohexyl group; a phenyl group which can carry C 1 -C 4 alkyl, C 1 -C 4 alkoxy or chlorine as substituents; a thienyl group; a radical of the general formula IIa
Figure imgb0043
 in which p is 0 or 1 and q is 1 to 4 and R 4 'denotes a C 1 -C 4 alkyl, phenyl or benzyl group; R 2 ' , R 3' , C 1 -C 12 alkyl, C 1 -C 10 alkoxy or C 1 -C 10 cyanoalkyl groups; a remainder of the formula la given above; D 'the remainder of a diazo component III consisting of the aniline, phenylazoaniline, aminothiophene, phenylazoaminothiophene, aminothiazole, phenylazoaminothiazole, aminoisothiazole, aminobenzisothiazole, aminothiadiazole, aminoisothiadiazole, aminooxadiazole, aminooxadiazole, aminooxaziazole Aminotriazole or aminopyrrole series.
EP91101022A 1990-02-08 1991-01-26 Use of azo-dyes for thermal transfer printing Expired - Lifetime EP0441208B1 (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5256624A (en) * 1991-04-18 1993-10-26 Basf Aktiengesellschaft Transfer of methine dyes
WO1996003462A1 (en) * 1994-07-22 1996-02-08 Basf Aktiengesellschaft Azo dyes having a coupling component from the aminothiazole series

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19611351A1 (en) * 1996-03-22 1997-09-25 Basf Ag Dye mixtures containing thienyl and / or thiazole azo dyes
WO2002080152A2 (en) * 2001-03-28 2002-10-10 Bayer Aktiengesellschaft Optical data carrier that contains a heterocyclic azo dye as the light-absorbing compound in the information layer
US20080081766A1 (en) * 2006-09-29 2008-04-03 Fujifilm Corporation Image-forming method using heat-sensitive transfer system
JP2008265319A (en) * 2007-03-29 2008-11-06 Fujifilm Corp Thermal transfer ink sheet and image formation method
EP1974948A3 (en) 2007-03-29 2012-02-08 FUJIFILM Corporation Image-forming method using heat-sensitive transfer system
US8258300B2 (en) * 2008-09-29 2012-09-04 King Abdulaziz University Azo dyes

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0275381A2 (en) * 1986-11-13 1988-07-27 BASF Aktiengesellschaft Dye transfer process
US4933226A (en) * 1989-12-11 1990-06-12 Eastman Kodak Company Thermal print element comprising a magenta 3-aryl-2-arylazo-5-aminothiazole or aminothiophene dye stabilized with a cyan indoaniline dye

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60239291A (en) * 1984-05-11 1985-11-28 Mitsubishi Chem Ind Ltd Coloring matter for thermal recording
GB8504518D0 (en) * 1985-02-21 1985-03-27 Ici Plc Thermal transfer dyesheet
DE3928243A1 (en) * 1989-08-26 1991-02-28 Basf Ag MEROCYANINE-TYPE THIAZOLIC DYES AND A METHOD FOR THERMAL TRANSFER OF THESE DYES

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0275381A2 (en) * 1986-11-13 1988-07-27 BASF Aktiengesellschaft Dye transfer process
US4933226A (en) * 1989-12-11 1990-06-12 Eastman Kodak Company Thermal print element comprising a magenta 3-aryl-2-arylazo-5-aminothiazole or aminothiophene dye stabilized with a cyan indoaniline dye

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DERWENT JAPANESE PATENTS REPORT. vol. 79, no. 46, 14 Dezember 1979, LONDON GB Seite 2 CANON K.K.: "Heat-sensitive sheet for latent image production" *
PATENT ABSTRACTS OF JAPAN vol. 10, no. 109 (M-472)(2166) 23 April 1986, & JP-A-60 239291 (MITSUBISHI KASEI KOGYO K.K.) 28 November 1985, *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5256624A (en) * 1991-04-18 1993-10-26 Basf Aktiengesellschaft Transfer of methine dyes
WO1996003462A1 (en) * 1994-07-22 1996-02-08 Basf Aktiengesellschaft Azo dyes having a coupling component from the aminothiazole series
US5789560A (en) * 1994-07-22 1998-08-04 Basf Aktiengesellschaft Azo dyes with a coupling component of the aminothiazole series

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JP3001991B2 (en) 2000-01-24
JPH04357088A (en) 1992-12-10
US5158928A (en) 1992-10-27
DE4003780A1 (en) 1991-08-14
EP0441208B1 (en) 1994-05-04
DE59101521D1 (en) 1994-06-09
USRE34877E (en) 1995-03-14

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