EP0258856B1 - Dye transfer method - Google Patents

Dye transfer method Download PDF

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Publication number
EP0258856B1
EP0258856B1 EP87112630A EP87112630A EP0258856B1 EP 0258856 B1 EP0258856 B1 EP 0258856B1 EP 87112630 A EP87112630 A EP 87112630A EP 87112630 A EP87112630 A EP 87112630A EP 0258856 B1 EP0258856 B1 EP 0258856B1
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Prior art keywords
alkyl
alkoxy
phenyl
hydrogen
ethyl
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German (de)
French (fr)
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EP0258856B2 (en
EP0258856A2 (en
EP0258856A3 (en
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Bernhard Dr. Albert
Karl-Heinz Dr. Etzbach
Ruediger Dr. Sens
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BASF SE
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BASF SE
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    • 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
    • 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
    • B41M5/3854—Dyes containing one or more acyclic carbon-to-carbon double bonds, e.g., di- or tri-cyanovinyl, methine
    • 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
    • Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
    • Y10S8/92—Synthetic fiber dyeing
    • Y10S8/922—Polyester fiber

Definitions

  • a transfer sheet which contains a sublimable dye, optionally together with a binder on a support, is heated from the back with a heating head with short (duration: fractions of a second) heating pulses, the dye subliming or evaporating and on a recording medium is transferred.
  • the main advantage of this method is that it is easy to control the amount of dye to be transferred (and thus the color gradation) by adjusting the energy to be delivered to the heating head.
  • JP-A 159091/1985 describes dyes of the formula in which R is alkyl, aralkyl, aryl or a 5- / 6-membered carbocyclic ring means described for this purpose.
  • JP-A 30392/1985 are dyes of the formula known in which R, R1 and R 2 are allyl, alkyl, alkoxyalkyl and XH, methyl.
  • JP-A 239292/1985 uses dyes of the formula for the transfer described.
  • R 1 is 1-8 C, alkyl
  • R 2 is H or methyl
  • D is Quinone derivatives of the formula in which R and R 1 denotes methyl, ethyl, propyl or butyl are described for this application in JP-A 229 786/1985.
  • the invention had for its object to provide dyes which are easily sublimable or evaporable under the conditions of a thermal head, which do not undergo thermal and photochemical decomposition, which can be processed into printing inks and which meet the color requirements.
  • the dyes should be easily accessible technically.
  • the dyes used in the process according to the invention are distinguished by better sublimability, in some cases higher light fastness or by higher resistance to chemical substances.
  • R 1 and R 2 include, for example: C 1 -C 4 -alkyl such as CH 3 , C 2 Hs, n-propyl, isopropyl, n-butyl, isobutyl, tertiary-butyl; C 1 - to C 4 alkoxy such as methoxy, ethoxy, propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, tertiary-butyloxy; Ci to C 4 alkylthio such as methylthio, ethyl and butyl hio and halogen such as bromine, preferably chlorine and fluorine.
  • R1 can also form a heterocyclic ring together with R, so that can correspond to the following formulas: and
  • C i - to C 6 alkyl which may be mentioned in detail, for example: methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-pentyl, i-pentyl, n-hexyl, i-hexyl.
  • C 1 -C 4 -alkoxy in the alkoxy-bearing substituents are: methoxy, ethoxy, n- and i-propoxy and n- and i-butoxy.
  • Halogen is suitable as a substituent on C 1 -C 6 -alkyl, bromine, chlorine, preferably fluorine.
  • C 2 - to Cs-alkanoyl examples include acetyl, propionyl, butanoyl and pentanoyl.
  • R 'and R can also be phenyl which is optionally substituted by methyl or methoxy, C 5 -C 6 -cycloalkyl or benzyl.
  • Dimethylamino, diethylamino or N-ethyl-N-exthoxyethylamino are, except when R 1 and R 2 are hydrogen.
  • the dyes (I) are synthesized by known processes or processes known per se.
  • Azo dyes (I) with were synthesized by the method described in DE-A 31 08 077 and 35 29 831.
  • Dyes of the type were developed according to the method of Mc Kusick et al., J. Am. Chem. Soc. (1958), 80, 2806 described process by reacting the corresponding aniline derivatives with tetracyanoethylene.
  • the dyes are in a suitable solvent, e.g. Chlorobenzene or isobutanol processed with a binder to form a printing ink.
  • a suitable solvent e.g. Chlorobenzene or isobutanol processed with a binder to form a printing ink.
  • the printing ink is applied to the inert carrier using a doctor blade and the dyeing is air-dried.
  • binders come e.g. Ethyl cellulose, polysulfones or polyethersulfones into consideration.
  • Inert carriers are e.g. Tissue paper, blotting paper or glassine paper as well as plastic films with good heat resistance, e.g. optionally metal-coated polyester, polyamide or polyimide.
  • the thickness of the carrier is preferably 3 to 30 microns. Further suitable carrier materials, binders and solvents for the production of the printing inks are described in DE-
  • the transfer takes place by means of a thermal head, which must deliver sufficient heating power so that the dye is transferred within a few milliseconds.
  • the paper layer (donor) coated with the dye to be tested is placed with the dye layer on an 80 ⁇ m thick polyester film (receiver) and pressed on.
  • the encoder / receiver is then wrapped with aluminum foil and heated between two heated plates for 30 seconds.
  • the amount of dye migrated into the PES film is determined photometrically. If the logarithm of the absorbance A of the colored polyester films measured at different temperatures (range: 100 to 200 ° C) is plotted against the associated reciprocal absolute temperature, straight lines are obtained, from the slope of which the activation energy A E T for the transfer experiment is calculated:
  • the temperature T * [ ° C] is additionally taken from the plots at which the extinction A of the colored polyester film reaches the value 1.
  • the dyes specified in Tables 1 to 6 were processed according to Al) or All) and the dye-coated supports obtained according to B) were tested for the sublimation behavior.
  • the table shows the color shade on polyester as well as the thermal transfer parameters T * and ⁇ ET.

Description

Verfahren zur Übertragung von FarbstoffenProcess for the transfer of dyes

Beim Sublimations-Transferverfahren wird ein Transferblatt, welches einen sublimierbaren Farbstoff, gegebenenfalls zusammen mit einem Bindemittel auf einem Träger enthält, mit einem Heizkopf mit kurzen (Dauer: Bruchteile einer Sekunde) Heizimpulsen von der Rückseite erhitzt, wobei der Farbstoff sublimiert bzw. verdampft und auf ein Aufnahmemedium transferiert wird. Der wesentliche Vorteil dieses Verfahrens besteht darin, daß die Steuerung der zu übertragenden Farbstoffmenge (und damit die Farbabstufung) durch Einstellung der an den Heizkopf abzugebenden Energie leicht möglich ist.In the sublimation transfer process, a transfer sheet, which contains a sublimable dye, optionally together with a binder on a support, is heated from the back with a heating head with short (duration: fractions of a second) heating pulses, the dye subliming or evaporating and on a recording medium is transferred. The main advantage of this method is that it is easy to control the amount of dye to be transferred (and thus the color gradation) by adjusting the energy to be delivered to the heating head.

Allgemein wird die Farbaufzeichnung unter Verwendung der drei subtraktiven Grundfarben Gelb, Magenta und Cyan (und gegebenenfalls schwarz) durchgeführt. Um eine optimale Farbaufzeichnung zu ermöglichen, müssen die Farbstoffe folgende Eigenschaften besitzen:

  • i) leichte Sublimier- bzw. Verdampfbarkeit; im allgemeinen ist diese Anforderung bei den Cyanfarbstoffen am schwierigsten zu erfüllen;
  • ii) hohe thermische und photochemische Stabilität sowie Resistenz gegen Feuchtigkeit und chemische Stoffe;
  • iii) für subtraktive Farbmischung die geeigneten Farbtöne aufweisen;
  • iv) einen hohen molekularen Absorptionskoeffizienten aufweisen
  • v) leicht technisch zugänglich sein.
In general, the color recording is carried out using the three subtractive primary colors yellow, magenta and cyan (and possibly black). To enable optimal color recording, the dyes must have the following properties:
  • i) easy sublimability or vaporizability; in general, this requirement is the most difficult to meet with cyan dyes;
  • ii) high thermal and photochemical stability and resistance to moisture and chemicals;
  • iii) have suitable shades for subtractive color mixing;
  • iv) have a high molecular absorption coefficient
  • v) be easily technically accessible.

Die meisten der bekannten, für den thermischen Transferdruck verwendeten Farbstoffe erfüllen diese Forderungen nicht in ausreichendem Maße.Most of the known dyes used for thermal transfer printing do not sufficiently meet these requirements.

Aus dem Stand der Technik sind für diesen Zweck bereits Farbstoffe bekannt:Dyes are already known for this purpose from the prior art:

In der JP-A 159091/1985 werden Farbstoffe der Formel

Figure imgb0001
in der R Alkyl, Aralkyl, Aryl oder einen 5-/6-gliedrigen carbocyclischen Ring bedeutet für diesen Zweck beschrieben.JP-A 159091/1985 describes dyes of the formula
Figure imgb0001
 in which R is alkyl, aralkyl, aryl or a 5- / 6-membered carbocyclic ring means described for this purpose.

Aus der JP-A 30392/1985 sind Farbstoffe der Formel

Figure imgb0002
bekannt, in der R, R1 und R2 Allyl, Alkyl, Alkoxyalkyl und X H, Methyl bedeuten.JP-A 30392/1985 are dyes of the formula
Figure imgb0002
 known in which R, R1 and R 2 are allyl, alkyl, alkoxyalkyl and XH, methyl.

In der JP-A 229786/1985 werden Farbstoffe der Formel

Figure imgb0003
in der R und Ri Methyl, Ethyl, Propyl oder Butyl und

  • X H oder Methyl bedeuten,
  • für diese Anwendung beschrieben.
JP-A 229786/1985 describes dyes of the formula
Figure imgb0003
 in which R and R i are methyl, ethyl, propyl or butyl and
  • XH or methyl mean
  • described for this application.

In der JP-A 239292/1985 werden für den Transfer Farbstoffe der Formel

Figure imgb0004
beschrieben. In der Formel stehen R1 für 1-8 C, Alkyl, R2 für H oder Methyl und D für
Figure imgb0005
Chinonderivate der Formel
Figure imgb0006
in der R und R1 Methyl, Ethyl, Propyl oder Butyl bedeutet, werden für diese Anwendung in der JP-A 229 786/1985 beschrieben.JP-A 239292/1985 uses dyes of the formula for the transfer
Figure imgb0004
 described. In the formula, R 1 is 1-8 C, alkyl, R 2 is H or methyl and D is
Figure imgb0005
 Quinone derivatives of the formula
Figure imgb0006
 in which R and R 1 denotes methyl, ethyl, propyl or butyl are described for this application in JP-A 229 786/1985.

Weiter ist die Verwendung von Indoanilinfarbstoffen der allgemeinen Formel

Figure imgb0007
in der DE-A 35 24 519 für diesen Zweck beschrieben.Next is the use of indoaniline dyes of the general formula
Figure imgb0007
 described in DE-A 35 24 519 for this purpose.

Der Erfindung lag die Aufgabe zugrunde, Farbstoffe bereitzustellen, die unter den Bedingungen eines Thermokopfes leicht sublimier- oder verdampfbar sind, die keine thermische und photochemische Zersetzung erleiden, die sich zu Druckfarben verarbeiten lassen und die den koloristischen Anforderungen genügen. Außerdem sollten die Farbstoffe technisch leicht zugänglich sein.The invention had for its object to provide dyes which are easily sublimable or evaporable under the conditions of a thermal head, which do not undergo thermal and photochemical decomposition, which can be processed into printing inks and which meet the color requirements. In addition, the dyes should be easily accessible technically.

Gegenstand der Erfindung ist ein Verfahren zur Übertragung von Farbstoffen von einem Träger durch Sublimation/Verdampfung mit Hilfe eines Thermokopfes auf ein mit Kunststoff beschichtetes Papier, das dadurch gekennzeichnet ist, daß man einen Träger verwendet, auf dem sich Farbstoffe der allgemeinen Formel

Figure imgb0008
befinden, in der
Figure imgb0009

  • R1 und R2 unabhängig voneinander für Wasserstoff, C1- bis C4-Alkyl, Ci-bis C4-Alkoxy, C1- bis C4-AI- kylthio oder Halogen und wobei R1 gemeinsam mit R einen 5- oder 6-gliedrigen heterocyclischen Ring bilden kann, und
  • R und R' unabhängig voneinander für Wasserstoff, für gegebenenfalls durch Methyl oder Methoxy substituiertes Phenyl oder für gegebenenfalls durch C1- bis C4-Alkoxy, C1- bis C4-Alkoxycarbonyl, C2-bis Cs-Alkanoyloxy, Ci- bis C4-Alkoxycarbonyloxy, C1- bis C4-Alkoxy-C2- oder C3-alkoxycarbonyl- oxy, Hydroxy, Cyan, Halogen, Phenyl oder Cs- oder C6-Cycloalkyl substituiertes C1- bis C6-Alkyl oder C5- oder C6-Cycloalkyl oder
    Figure imgb0010
für einen 5- oder 6-gliedrigen heterocyclischen Ring stehen, worin
Figure imgb0011
  • R3 CN,
  • R4 C1- bis C4-Alkyl, Phenyl, Benzyl oder CN,
  • R5 C1- bis C4-Alkyl, C1- bis C4-Alkylthio, Ci- bis C4-Alkoxy, Cs- oder C6-Cycloalkyl, Benzyl, Cs- oder C6-Cycloalkylthio, Cs- oder C6-Cycloalkoxy, Benzyloxy oder Benzylthio,
  • R6 CN oder -CHO,
  • R7 C1- bis C4-Alkoxy, C1- bis C4-Alkylthio oder Chlor und
  • R8 -CHO oder CN bedeuten,
    wobei R1 und R2 nicht gleichzeitig Wasserstoff sein dürfen, wenn A
    Figure imgb0012
    und R5 Alkylthio sind wenn A
    Figure imgb0013
    ist, oder wenn
    Figure imgb0014
    Dimethylamino, Diethylamino oder N-Ethyl-N-exthoxyethylamino sind.
The invention relates to a method for transferring dyes from a support by sublimation / evaporation with the aid of a thermal head to a plastic-coated paper, which is characterized in that a carrier is used on which dyes of the general formula
Figure imgb0008
 are in the
Figure imgb0009
  • R1 and R2 are independently hydrogen, C 1 - to C 4 -alkyl, C i -C 4 alkoxy, C 1 - to C 4 -AI- alkylthio or halogen, and wherein R 1 together with R forms a 5- or 6 -formed heterocyclic ring can form, and
  • R and R 'independently of one another for hydrogen, for phenyl optionally substituted by methyl or methoxy or for optionally substituted by C 1 - to C 4 -alkoxy, C 1 - to C 4 -alkoxycarbonyl, C 2 -bis Cs-alkanoyloxy, Ci-bis C 4 -alkoxycarbonyloxy, C 1 - to C 4 -alkoxy-C 2 - or C 3 -alkoxycarbonyl-oxy, hydroxy, cyano, halogen, phenyl or C 1 -C 6 -cycloalkyl-substituted C 1 - to C 6 -alkyl or C 5 - or C 6 -cycloalkyl or
    Figure imgb0010
represent a 5- or 6-membered heterocyclic ring, wherein
Figure imgb0011
  • R3 CN,
  • R 4 C 1 to C 4 alkyl, phenyl, benzyl or CN,
  • R 5 is C 1 - to C 4 -alkyl, C 1 - to C 4 alkylthio, Ci to C 4 alkoxy, Cs or C 6 cycloalkyl, benzyl, Cs or C 6 cycloalkylthio, Cs or C 6 Cycloalkoxy, benzyloxy or benzylthio,
  • R6 CN or -CHO,
  • R 7 is C 1 to C 4 alkoxy, C 1 to C 4 alkylthio or chlorine and
  • R8 is -CHO or CN,
    where R1 and R 2 must not simultaneously be hydrogen if A
    Figure imgb0012
     and R 5 are alkylthio when A
    Figure imgb0013
     is or if
    Figure imgb0014
     Dimethylamino, diethylamino or N-ethyl-N-exthoxyethylamino.

Im Vergleich zu den bei den bekannten Verfahren verwendeten Farbstoffen zeichnen sich die bei dem erfindungsgemäßen Verfahren angewendeten Farbstoffe durch bessere Sublimierfähigkeit, zum Teil höhere Lichtechtheiten bzw. durch höhere Resistenz gegen chemische Stoffe aus.Compared to the dyes used in the known processes, the dyes used in the process according to the invention are distinguished by better sublimability, in some cases higher light fastness or by higher resistance to chemical substances.

Bei dem Verfahren der Erfindung werden Farbstoffe der allgemeinen Formel

Figure imgb0015
verwendet. In der Formel steht A
für D-N=N- oder
Figure imgb0016
 In the process of the invention, dyes of the general formula
Figure imgb0015
 used. A is in the formula
for DN = N- or
Figure imgb0016

Für R1 und R2 sind neben Wasserstoff z.B. zu nennen: C1- bis C4-Alkyl wie CH3, C2Hs, n-Propyl, Isopropyl, n-Butyl, Isobutyl, tertiär-Butyl; C1- bis C4-Alkoxy wie Methoxy, Ethoxy, Propyloxy, Isopropyloxy, n-Butyloxy, Isobutyloxy, tertiär-Butyloxy; Ci-bis C4-Alkylthio wie Methylthio, Ethyl- und Butylthio und Halogen wie Brom, vorzugsweise Chlor und Fluor. R1 kann auch gemeinsam mit R einen heterocyclischen Ring bilden, so daß

Figure imgb0017
den folgenden Formeln entsprechen kann:
Figure imgb0018
und
Figure imgb0019
 In addition to hydrogen, R 1 and R 2 include, for example: C 1 -C 4 -alkyl such as CH 3 , C 2 Hs, n-propyl, isopropyl, n-butyl, isobutyl, tertiary-butyl; C 1 - to C 4 alkoxy such as methoxy, ethoxy, propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, tertiary-butyloxy; Ci to C 4 alkylthio such as methylthio, ethyl and butyl hio and halogen such as bromine, preferably chlorine and fluorine. R1 can also form a heterocyclic ring together with R, so that
Figure imgb0017
 can correspond to the following formulas:
Figure imgb0018
 and
Figure imgb0019

In den Formeln (I) und (IIa) bis (Ild) stehen

  • R und R' unabhängig voneinander für Wasserstoff oder für Ci- bis C8-Alkyl, das gegebenenfalls durch
  • C1- bis C4-Alkoxy, Ci- bis C4-Alkoxycarbonyl, C1- bis C4-Alkoxycarbonyloxy, C2- bis Cs-Alkanoyloxy,
  • C1- bis C4-Alkoxy-C2- oder C3-alkoxycarbonyloxy, Hydroxy, Cyan, Halogen, Phenyl oder C5- oder C6-Cycloalkyl substituiert ist.
In formulas (I) and (IIa) to (Ild)
  • R and R 'independently of one another for hydrogen or for C i - to C 8 -alkyl, which may be by
  • C 1 - to C 4 -alkoxy, Ci to C 4 -alkoxycarbonyl, C 1 - to C 4 -alkoxycarbonyloxy, C 2 - to Cs-alkanoyloxy,
  • C 1 - to C 4 -alkoxy-C 2 - or C 3 -alkoxycarbonyloxy, hydroxy, cyano, halogen, phenyl or C 5 - or C 6 -cycloalkyl is substituted.

Als Ci- bis C6-Alkyl sind im einzelnen z.B. zu nennen: Methyl, Ethyl, Propyl, Isopropyl, n-Butyl, Isobutyl, t-Butyl, n-Pentyl, i-Pentyl, n-Hexyl, i-Hexyl.As a C i - to C 6 alkyl which may be mentioned in detail, for example: methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-pentyl, i-pentyl, n-hexyl, i-hexyl.

Für Ci- bis C4-Alkoxy sind in den Alkoxygruppen tragenden Substituenten z.B. zu nennen: Methoxy, Ethoxy, n- und i-Propoxy und n- und i-Butoxy.Examples of C 1 -C 4 -alkoxy in the alkoxy-bearing substituents are: methoxy, ethoxy, n- and i-propoxy and n- and i-butoxy.

Für Alkyl in den Alkyloxygruppen kommen im einzelnen die für Ci- bis C6-Alkyl genannten Reste mit 1 bis 4 C-Atomen in Betracht.Radicals mentioned to C 6 alkyl having 1 to 4 C-atoms are suitable - for alkyl in the alkyloxy groups for the C i come in detail.

Für Halogen kommen als Substituenten am C1- bis C6-Alkyl, Brom, Chlor, vorzugsweise Fluor in Betracht.Halogen is suitable as a substituent on C 1 -C 6 -alkyl, bromine, chlorine, preferably fluorine.

Als C2- bis Cs-Alkanoyl sind z.B. Acetyl, Propionyl, Butanoyl und Pentanoyl zu nennen.Examples of C 2 - to Cs-alkanoyl include acetyl, propionyl, butanoyl and pentanoyl.

Außerdem können R' und R auch Phenyl, das gegebenenfalls durch Methyl oder Methoxy substituiert ist, C5-C6-Cyxcloalkyl oder Benzyl sein.In addition, R 'and R can also be phenyl which is optionally substituted by methyl or methoxy, C 5 -C 6 -cycloalkyl or benzyl.

Als substituiertes C1- bis C6-Alkyl sind z.B. im einzelnen zu nennen:

  • 2-Hydroxyethyl, 2- und 3-Hydroxypropyl, 3- und 4-Hydroxybutyl; 2-Cyanethyl, 3-Cyanpropyl und 4-Cyanbutyl; Benzyl, 2-Phenylethyl, 2- und 3-Phenylpropyl; Methoxyethyl, 2- und 3-Methoxypropyl, Ethoxyethyl, n- und i-Propoxyethyl, n- und i-Butoxyethyl; 2-Acetoxyethyl, 2-Propanoyloxyethyl, 2-Butanoyloxyethyl und 2-Pentanoyloxyethyl, 2- und 3-Acetoxypropyl, 2- und 3-Propanoyloxypropyl, 2- und 3-Butanoyloxypropyl und 2- und 3-Pentanoyloxypropyl; 2-(Methoxycarbonyl)-ethyl, 2-(Ethoxycarbonyl)-ethyl, 2-Propoxycarbonyl)-ethyl, 2-Butoxycarbonyl)ethyl und die entsprechenden 3-Propylderivate; 2-(Methoxycarbonyloxy)ethyl, 2-(Ethoxycarbonyloxy)-ethyl, 2-(n-und i-Propoxycarbonyloxy)-ethyl, 2-(n-und i-Butoxycarbonyloxy)-ethyl sowie die entsprechenden 3-(Alkoxycarbonyloxy)-propylderivate; 2-(Methoxy-ethoxy-carbonyloxy)ethyl, 2-(Ethoxy-ethoxy-carbonyloxy)ethyl, 2-(n- und i-Propoxy-ethoxy- carbonyloxy)ethyl und 2-(n- und i-Butoxy- ethoxy-carbonyloxy)ethyl sowie die entsprechenden 3-(Alkoxy-alkoxy- carbonyloxy)-propylderivate; Cyclopentylmethyl und Cyclohexylmethyl.
Examples of substituted C 1 -C 6 -alkyl which may be mentioned are:
  • 2-hydroxyethyl, 2- and 3-hydroxypropyl, 3- and 4-hydroxybutyl; 2-cyanoethyl, 3-cyanopropyl and 4-cyanobutyl; Benzyl, 2-phenylethyl, 2- and 3-phenylpropyl; Methoxyethyl, 2- and 3-methoxypropyl, ethoxyethyl, n- and i-propoxyethyl, n- and i-butoxyethyl; 2-acetoxyethyl, 2-propanoyloxyethyl, 2-butanoyloxyethyl and 2-pentanoyloxyethyl, 2- and 3-acetoxypropyl, 2- and 3-propanoyloxypropyl, 2- and 3-butanoyloxypropyl and 2- and 3-pentanoyloxypropyl; 2- (methoxycarbonyl) ethyl, 2- (ethoxycarbonyl) ethyl, 2-propoxycarbonyl) ethyl, 2-butoxycarbonyl) ethyl and the corresponding 3-propyl derivatives; 2- (methoxycarbonyloxy) ethyl, 2- (ethoxycarbonyloxy) ethyl, 2- (n- and i-propoxycarbonyloxy) ethyl, 2- (n- and i-butoxycarbonyloxy) ethyl and the corresponding 3- (alkoxycarbonyloxy) propyl derivatives ; 2- (methoxy-ethoxy-carbonyloxy) ethyl, 2- (ethoxy-ethoxy-carbonyloxy) ethyl, 2- (n- and i-propoxy-ethoxy-carbonyloxy) ethyl and 2- (n- and i-butoxy-ethoxy- carbonyloxy) ethyl and the corresponding 3- (alkoxy-alkoxy-carbonyloxy) propyl derivatives; Cyclopentylmethyl and cyclohexylmethyl.

Als gegebenenfalls substituiertes Phenyl sind für R und R' neben Phenyl, 2- und 4-Methylphenyl und 2- und 4-Methoxyphenyl zu nennen. Im Falle, daß R Phenyl oder substituiertes Phenyl ist, steht R' vorzugsweise für Methyl, insbesondere für Wasserstoff.

Figure imgb0020
kann außerdem für heterocyclische Reste wie
Figure imgb0021
stehen.

  • R3 steht für CN.
  • D bedeutet einen Rest der Formeln
    Figure imgb0022
    worin
  • R4 Ci- bis C4-Alkyl wie, Methyl, Ethyl, n-Propyl, Isopropyl, n-Butyl, Isobutyl, tertiär-Butyl, Phenyl, Benzyl oder CN,
  • R5 C1- bis C4-Alkyl wie, Methyl, Ethyl, n-Propyl, Isopropyl, n-Butyl, Isobutyl, tertiär-Butyl, C1- bis C4-Alkoxy wie, Methoxy, Ethoxy, Propyloxy, Isopropyloxy, n-Butyloxy, Isobutyloxy, tertiär-Butyloxy, Ci-bis C4-Alkylthio, Benzyl, Cs- oder C6-Cycloalkyl, Cs- oder C6-Cycloalkylthio, C5- oder C6-Cycloalkoxy, Benzyloxy oder Benzylthio,
  • R6 CN oder -CHO,
  • R7 C1- bis C4-Alkoxy wie, Methoxy, Ethoxy, Propyloxy, Isopropyloxy, n-Butyloxy, Isobutyloxy, tertiär-Butyloxy, C1- bis C4-Alkylthio oder Chlor und
  • R8 -CHO oder CN bedeuten.
Optionally substituted phenyl for R and R 'are phenyl, 2- and 4-methylphenyl and 2- and 4-methoxyphenyl. In the event that R is phenyl or substituted phenyl, R 'is preferably methyl, in particular hydrogen.
Figure imgb0020
 can also be used for heterocyclic radicals such as
Figure imgb0021
 stand.
  • R3 stands for CN.
  • D means a remainder of the formulas
    Figure imgb0022
     wherein
  • R 4 C i - to C 4 -alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertiary-butyl, phenyl, benzyl or CN,
  • R 5 C 1 - to C 4 -alkyl such as, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertiary-butyl, C 1 - to C 4 -alkoxy such as, methoxy, ethoxy, propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, tertiary butyloxy, C 1 -C 4 -alkylthio, benzyl, Cs- or C 6 -cycloalkyl, Cs- or C 6 -cycloalkylthio, C 5 - or C 6 -cycloalkoxy, benzyloxy or benzylthio,
  • R 6 CN or -CHO,
  • R7 C 1 - to C 4 -alkoxy such as, methoxy, ethoxy, propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, tertiary-butyloxy, C 1 - to C 4 -alkylthio or chlorine and
  • R 8 is -CHO or CN.

Dabei sind Farbstoffe (I), in denen A

Figure imgb0023
und R5 Alkylthio sind, A
Figure imgb0024
ist, oder A, ausgenommen wenn R1 1 und R2 1 Wasserstoff sind.
Figure imgb0025
Dimethylamino, Diethylamino oder N-Ethyl-N-exthoxyethylamino sind, ausgenommen wenn R1 und R2 Wasserstoff sind.Dyes (I) in which A
Figure imgb0023
 and R5 are alkylthio, A
Figure imgb0024
 or A, except when R 1 1 and R 2 1 are hydrogen.
Figure imgb0025
 Dimethylamino, diethylamino or N-ethyl-N-exthoxyethylamino are, except when R 1 and R 2 are hydrogen.

Für das vorliegende Verfahren sind bevorzugt:

  • a) Farbstoffe der Formel (I), in der
    • R und R' Wasserstoff, gegebenenfalls durch Hydroxy, Cyan oder Phenyl substituiertes Ci- bis C4-AI- kyl, C1- bis C4-Alkoxy-C2- bis C4-alkyl, C1- bis C4-Alkoxycarbonyl-C1- bis C4-alkyl, C1- bis C4-Alk- oxycarbonyloxy-C2- bis C4-alkyl, Ci- bis C4-Fluoralkyl, oder gegebenenfalls durch Methoxy oder Methyl substituiertes Phenyl,
    • R1 und R2 Wasserstoff, Methyl, Methoxy, n-Propyloxy, Isopropyloxy, n-Butyloxy, Isobutyloxy, tertiär-Butyloxy und
    • A = D-N=N- oder
      Figure imgb0026
      bedeuten und
    • worin D für
      Figure imgb0027
      stehen, und wobei
    • R4 Methyl, Ethyl, n-Propyl, Isopropyl, n-Butyl, Isobutyl, tertiär- Butyl, Cyan und
    • R5 Methyl, Ethyl, n-Propyl, Isopropyl, n-Butyl, Isobutyl, tertiär- Butyl, Methylthio, Ethylthio, n-Propylthio, Isopropylthio, n-Butylthio, Isobutylthio, tertiär-Butylthio sind.
  • b) Farbstoffe der Formeln
    Figure imgb0028
    und
    Figure imgb0029
    worin D für
    Figure imgb0030
    • R4 für Methyl, Ethyl, n-Propyl, Isopropyl, n-Butyl, Isobutyl, tertiär-Butyl oder CN,
    • R5 für Methyl, Ethyl, n-Propyl, Isopropyl, n-Butyl, Isobutyl, tertiär-Butyl, Methylthio, Ethylthio, n-Propylthio, Isopropylthio, n-Butyl-thio, Isobutylthio oder tertiär-Butylthio und
    • R für Wasserstoff, Methyl, Ethyl, n- oder i-Propyl, n- oder i-Butyl oder tert.-Butyl stehen.
The following are preferred for the present method:
  • a) dyes of the formula (I) in which
    • R and R 'are hydrogen, optionally substituted by hydroxy, cyano or phenyl, C 1 -C 4 -alkyl, C 1 - to C 4 -alkoxy-C 2 - to C 4 -alkyl, C 1 - to C 4 -alkoxycarbonyl -C 1 - to C 4 -alkyl, C 1 - to C 4 -alkoxycarbonyloxy-C 2 - to C 4 -alkyl, Ci- to C 4 -fluoroalkyl, or phenyl optionally substituted by methoxy or methyl,
    • R 1 and R 2 are hydrogen, methyl, methoxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, tertiary-butyloxy and
    • A = DN = N- or
      Figure imgb0026
       mean and
    • where D for
      Figure imgb0027
       stand, and being
    • R 4 is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertiary-butyl, cyano and
    • R 5 are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertiary butyl, methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, tertiary butylthio.
  • b) dyes of the formulas
    Figure imgb0028
     and
    Figure imgb0029
     where D for
    Figure imgb0030
    • R 4 is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertiary-butyl or CN,
    • R 5 is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertiary butyl, methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio or tertiary butylthio and
    • R represents hydrogen, methyl, ethyl, n- or i-propyl, n- or i-butyl or tert-butyl.

Besonders bevorzugt sind Farbstoffe der Formel:

Figure imgb0031
in der

  • R9 Wasserstoff, C1- bis C4-Alkoxy wie Methoxy, Ethoxy, n-Propyloxy, Isopropyloxy, n-Butyloxy, Isobutyloxy, tertiär-Butyloxy,
  • R10 und R11 unabhängig voneinander Wasserstoff, C1- bis C4-Alkyl wie Methyl, Ethyl, n-Propyl, Isopropyl, n-Butyl, Isobutyl, tertiär-Butyl C1- bis C4-Alkoxycarbonyl-ethyl oder C2- bis Cs-Alkanoyloxyethyl bedeuten, sowie solche der Formeln (Illa), (IIIb), (lllc) und (IIId), worin D für
    Figure imgb0032
    und R für Wasserstoff, Methyl, Ethyl, n-Propyl, Isopropyl, n-Butyl, Isobutyl, tertiär-Butyl stehen.
Dyes of the formula:
Figure imgb0031
 in the
  • R 9 is hydrogen, C 1 -C 4 -alkoxy such as methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, tertiary-butyloxy,
  • R 10 and R 11 independently of one another are hydrogen, C 1 - to C 4 -alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertiary-butyl C 1 - to C 4 -alkoxycarbonyl-ethyl or C 2 - to C s -alkanoyloxyethyl, as well as those of the formulas (Illa), (IIIb), (IIIc) and (IIId), in which D is for
    Figure imgb0032
     and R represents hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertiary butyl.

Besonders bevorzugt sind außerdem Farbstoffe der Formel

Figure imgb0033
in der

  • R, R' unabhängig voneinander Wasserstoff, C1- bis C4-Alkyl wie Methyl, Ethyl, n-Propyl, Isopropyl, n-Butyl, Isobutyl und tertiär-Butyl, Phenyl, C2- bis Cs-Alkanoyloxyethyl, C1- bis C4-Alkoxy-carbonyl- ethyl, Ci- bis C4-Alkoxycarbonyloxyethyl, Benzyl oder Cyanethyl,
  • R1 und R2 unabhängig voneinander Wasserstoff, Ci- bis C4-Alkyl wie Methyl, Ethyl, n-Propyl, lsopropyl, n-Butyl, Isobutyl, tertiär-Butyl, Ci- bis C4-Alkoxy wie Methoxy, Ethoxy, n-Propyloxy, Isopropyloxy, n-Butyloxy, Isobutyloxy und tertiär-Butyloxy oder C1- bis C4-Thioalkyl und
  • R4 C1- bis C4-Alkyl wie Methyl, Ethyl, n-Propyl, Isopropyl, n-Butyl, Isobutyl oder tertiär-Butyl oder Phenyl bedeuten.
Dyes of the formula are also particularly preferred
Figure imgb0033
 in the
  • R, R 'independently of one another are hydrogen, C 1 - to C 4 -alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and tertiary-butyl, phenyl, C 2 - to C s -alkanoyloxyethyl, C 1 - to C 4 -alkoxy-carbonyl-ethyl, C i - to C 4 -alkoxycarbonyloxyethyl, benzyl or cyanoethyl,
  • R 1 and R2 independently of one another are hydrogen, C i - to C 4 -alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertiary-butyl, C i - to C 4 -alkoxy such as methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy and tertiary-butyloxy or C 1 - to C 4 -thioalkyl and
  • R 4 is C 1 - to C 4 -alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tertiary-butyl or phenyl.

Die Synthese der Farbstoffe (I) erfolgt nach bekannten oder an sich bekannten Verfahren.The dyes (I) are synthesized by known processes or processes known per se.

Azo-Farbstoffe der allgemeinen Formel (V), in der R, R', R1, R2 und R4 die oben angegebene Bedeutung haben, werden nach dem in der DE-OS 32 07 290 beschriebenen Verfahren hergestellt. Die Diazokomponente (R4 = CN)

Figure imgb0034
ist aus der DE-A 34 02 024 bekannt.

  • Azofarbstoffe (1) mit
    Figure imgb0035
    und R5 Alkylthio
    wurden nach dem in der DE-C 15 44 391 beschriebenen Verfahren synthetisiert. Diazokomponenten mit R5 = Alkyl wurden nach der in Chem. Ber. 87, S. 57 (1954) beschriebenen Synthese hergestellt.
Azo dyes of the general formula (V), in which R, R ', R 1 , R2 and R4 have the meaning given above, are prepared by the process described in DE-OS 32 07 290. The diazo component (R4 = CN)
Figure imgb0034
 is known from DE-A 34 02 024.
  • Azo dyes (1) with
    Figure imgb0035
     and R5 alkylthio
    were synthesized by the method described in DE-C 15 44 391. Diazo components with R 5 = alkyl were according to the in Chem. Ber. 87, p. 57 (1954).

Azofarbstoffe (I) mit

Figure imgb0036
wurden nach dem in der DE-A 31 08 077 bzw. 35 29 831 beschriebenen Verfahren synthetisiert.Azo dyes (I) with
Figure imgb0036
 were synthesized by the method described in DE-A 31 08 077 and 35 29 831.

Farbstoffe des Typs

Figure imgb0037
wurden nach dem von Mc Kusick et al., J. Am. Chem. Soc. (1958), 80, 2806 beschriebenen Verfahren durch Umsetzen der entsprechenden Anilinderivate mit Tetracyanoethylen hergestellt.Dyes of the type
Figure imgb0037
 were developed according to the method of Mc Kusick et al., J. Am. Chem. Soc. (1958), 80, 2806 described process by reacting the corresponding aniline derivatives with tetracyanoethylene.

Zur Herstellung der für das Verfahren benötigten Farbstoffträger werden die Farbstoffe in einem geeigneten Lösungsmittel, z.B. Chlorbenzol oder Isobutanol mit einem Bindemittel zu einer Druckfarbe verarbeitet. Diese enthält den Farbstoff in gelöster oder dispergierter Form. Die Druckfarbe wird mittels einer Rakel auf den inerten Träger aufgetragen und die Färbung an der Luft getrocknet. Als Bindemittel kommen z.B. Ethylcellulose, Polysulfone oder Polyethersulfone in Betracht. Inerte Träger sind z.B. Seidenpapier, Löschpapier oder Pergaminpapier sowie Kunststoffolien mit guter Wärmebeständigkeit, z.B. gegebenenfalls metallbeschichteter Polyester, Polyamid oder Polyimid. Die Dicke des Trägers beträgt vorzugsweise 3 bis 30 µm. Weitere für das erfindungsgemäße Verfahren geeignete Trägermaterialien, Bindemittel sowie Lösungsmittel zur Herstellung der Druckfarben sind in der DE-A 35 24 519 beschrieben.To prepare the dye carriers required for the process, the dyes are in a suitable solvent, e.g. Chlorobenzene or isobutanol processed with a binder to form a printing ink. This contains the dye in dissolved or dispersed form. The printing ink is applied to the inert carrier using a doctor blade and the dyeing is air-dried. As binders come e.g. Ethyl cellulose, polysulfones or polyethersulfones into consideration. Inert carriers are e.g. Tissue paper, blotting paper or glassine paper as well as plastic films with good heat resistance, e.g. optionally metal-coated polyester, polyamide or polyimide. The thickness of the carrier is preferably 3 to 30 microns. Further suitable carrier materials, binders and solvents for the production of the printing inks are described in DE-A 35 24 519.

Als Farbstoffnehmerschicht kommen prinzipiell alle temperaturstabilen Kunststoffschichten mit Affinität zu den zu transferierenden Farbstoffen wie Polyester in Betracht.In principle, all temperature-stable plastic layers with an affinity for the dyes to be transferred, such as polyester, come into consideration as the dye receiver layer.

Die Übertragung erfolgt mittels Thermokopf, welcher genügend Heizleistung abgeben muß, damit innerhalb weniger Millisekunden der Farbstoff übertragen wird.The transfer takes place by means of a thermal head, which must deliver sufficient heating power so that the dye is transferred within a few milliseconds.

Die Erfindung soll durch die folgenden Ausführungsbeispiele zusätzlich erläutert werden:The invention is further illustrated by the following examples:

Um das Transferverhalten der Farbstoffe quantitativ und in einfacher Weise prüfen zu können, wird der Thermotransfer mit großflächigen Heizbacken statt eines Thermokopfes durchgeführt und bei der Herstellung der zu prüfenden Farbstoffträger auf ein Bindemittel verzichtet.

  • A) Allgemeine Rezepte für die Beschichtung der Träger mit Farbstoff:
    • Al) 1 g Ethylenglykol
      • 1 g Dispergiermittel auf der Basis eines Kondensationsproduktes aus Phenol + Formaldehyd + Na-hydrogensulfit
      • 7,5 g Wasser und
      • 0,5 g Farbstoff werden zusammen mit
      • 10 g Glaskugeln (2 mm 0)
      • in Gefäße gefüllt und nach dem Verschließen auf einem Schütteigerät (Red Devil@) geschüttelt, bis die mittlere Teilchengröße des Farbstoffs ≤ 1 µm ist (Dauer: je nach Farbstoff 8 bis 12 Stdn.). Die Glaskugeln werden abgesiebt, die so erhaltene Farbstoffdispersion, die gegebenenfalls mit Wasser auf das doppelte Volumen verdünnt wird, mit einer 6 µm-Rakel auf Papier abgezogen und an der Luft getrocknet.
    • All) Der Farbstoff wird in Form einer zu ca. 90 % gesättigten Lösung in einem Lösungsmittel (z.B. Chlorbenzol, Tetrahydrofuran, Methylethylketon, Isobutanol oder Gemischen davon) nach dem Spin coating-Verfahren auf das Trägerpapier einmal oder mehrerer Male aufgeschleudert. Die Menge an aufgeschleudertem Farbstoff wird so eingestellt, daß beim vollständigen Transfer auf eine 80 µm dicke Polyesterfolie (Nehmer) eine Extinktion von mindestens 2 erzielt wird.
  • B) Prüfung auf SublimationsNerdampfungs-Verhalten Die verwendeten Farbstoffe wurden in der folgenden Weise geprüft:
In order to be able to check the transfer behavior of the dyes quantitatively and in a simple manner, the thermal transfer is carried out with large-area heating jaws instead of a thermal head and a binder is dispensed with in the production of the dye carrier to be tested.
  • A) General recipes for coating the carrier with dye:
    • Al) 1 g of ethylene glycol
      • 1 g of dispersant based on a condensation product of phenol + formaldehyde + Na hydrogensulfite
      • 7.5 g of water and
      • 0.5 g of dye are mixed with
      • 10 g glass balls (2 mm 0)
      • filled into containers and shaken after closing on a red devil @ until the average particle size of the dye is ≤ 1 µm (duration: 8 to 12 hours depending on the dye). The glass balls are screened off, the dye dispersion thus obtained, which is optionally diluted to twice the volume with water, is drawn off on paper using a 6 μm doctor blade and dried in air.
    • All) The dye is spin-coated onto the backing paper once or several times in the form of an approximately 90% saturated solution in a solvent (for example chlorobenzene, tetrahydrofuran, methyl ethyl ketone, isobutanol or mixtures thereof). The amount of spin-on dye is adjusted so that an absorbance of at least 2 is achieved on complete transfer to an 80 μm thick polyester film (receiver).
  • B) Testing for Sublimation Evaporation Behavior The dyes used were tested in the following way:

Die mit dem zu prüfenden Farbstoff beschichtete Papierschicht (Geber) wird mit der Farbstoffschicht auf eine 80 µm dicke Polyesterfolie (Nehmer) gelegt und angedrückt. Geber/Nehmer werden dann mit Alu-Folie umwickelt und zwischen zwei beheizten Platten 30 sec. lang erhitzt. Die in die PES- Folie überwanderte Farbstoffmenge wird photometrisch bestimmt. Trägt man den Logarithmus der bei verschiedenen Temperaturen (Bereich: 100 bis 200°C) gemessenen Extinktion A der angefärbten Polyesterfolien gegen die zugehörige reziproke absolute Temperatur auf, so erhält man Geraden, aus deren Steigung die Aktivierungsenergie AET für das Transferexperiment berechnet wird:

Figure imgb0038
The paper layer (donor) coated with the dye to be tested is placed with the dye layer on an 80 μm thick polyester film (receiver) and pressed on. The encoder / receiver is then wrapped with aluminum foil and heated between two heated plates for 30 seconds. The amount of dye migrated into the PES film is determined photometrically. If the logarithm of the absorbance A of the colored polyester films measured at different temperatures (range: 100 to 200 ° C) is plotted against the associated reciprocal absolute temperature, straight lines are obtained, from the slope of which the activation energy A E T for the transfer experiment is calculated:
Figure imgb0038

Zur vollständigen Charakterisierung wird aus den Auftragungen zusätzlich die Temperatur T* [°C] entnommen, bei der die Extinktion A der angefärbten Polyesterfolie den Wert 1 erreicht.For complete characterization, the temperature T * [ ° C] is additionally taken from the plots at which the extinction A of the colored polyester film reaches the value 1.

Beispiele 1 bis 27Examples 1 to 27

Die in den Tabellen 1 bis 6 angegebenen Farbstoffe wurden nach Al) oder All) verarbeitet und die erhaltenen, mit Farbstoff beschichteten Träger nach B) auf das Sublimationsverhalten geprüft. In der Tabelle sind der Farbton auf Polyester sowie die Thermotransferparameter T* und ΔET aufgeführt.

Figure imgb0039
Figure imgb0040
Figure imgb0041
Figure imgb0042
Figure imgb0043
Figure imgb0044
Figure imgb0045
 The dyes specified in Tables 1 to 6 were processed according to Al) or All) and the dye-coated supports obtained according to B) were tested for the sublimation behavior. The table shows the color shade on polyester as well as the thermal transfer parameters T * and ΔET.
Figure imgb0039
Figure imgb0040
Figure imgb0041
Figure imgb0042
Figure imgb0043
Figure imgb0044
Figure imgb0045

Claims (9)

1. A process for transferring a dye from a carrier by sublimation/vaporization with the aid of a thermal printing head to a plastic-coated paper, wherein a carrier is used on which dyes of the formula where
Figure imgb0061
Figure imgb0062
R1 and R2 independently of one another are each hydrogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio or halogen and R1 together with R may form a 5-membered or 6-membered heterocyclic ring, and R and R' independently of one another are each hydrogen, phenyl which is unsubstituted or substituted by methyl or methoxy, or Cs- or C6-cycloalkyl or C1-C6-alkyl which is unsubstituted or substituted by C1-C6- alkoxy, C1-C4-alkoxycarbonyl, C2-C5-alkanoyloxy, C1-C4-alkoxycarbonyloxy, C1-C4-alkoxy C2- or C3-alkoxycarbonyloxy, hydroxyl, cyano, halogen, phenyl or Cs- or C6-cycloalkyl, or
Figure imgb0063
is a 5-membered or 6-membered heterocyclic ring, D is
Figure imgb0064
 R3 is CN, R4 is C1-C4-alkyl, phenyl, benzyl or CN, R5 is C1-C4-alkyl, Ci-C4-alkylthio, C1-C4-alkoxy, C5- or C6-cycloalkyl, benzyl, C5- or C6-cycloalkylthio, C5- or C6-cycloalkoxy, benzyloxy or benzylthio, R6 is CN or -CHO, R7 is C1-C4-alkoxy, Ci-C4-alkylthio or chlorine and R8 is CHO or CN, and R1 and R2 must not be hydrogen when A is
Figure imgb0065
and R5 is alkylthio when
Figure imgb0066
or when
Figure imgb0067
dimethylamino, diethylamino or N-ethyl-N-ethoxyethylamino are present.
2. A process as claimed in claim 1, wherein R and R' independently of one another are each hydrogen or C1-C4-alkyl which is unsubstituted or substituted by hydroxyl, cyano or phenyl, or are each C1-C4- alkoxy-C2-C4-alkyl, C1-C4-alkoxycarbonyl-C1-C4-alkyl, C1-C4-alkoxy-carbonyloxy-C2-C4-alkyl or C1-C4-fluoroalkyl, R1 and R2 independently of one another are each hydrogen, C1-C4-alkyl or C1-C4- alkoxy and A is D-N=N- or
Figure imgb0068
3. A process as claimed in 1 or 2, wherein A is D-N=N-, where D is
Figure imgb0069
R4 is C1-C4-alkyl, phenyl, benzyl or CN and R5 is C1-C4-alkyl, C1-C4-alkylthio, benzyl, Cs- or C6-cycloalkyl, benzylthio or Cs- or C6-cycloalkylthio.
4. A process as claimed in claim 1, wherein a dye of the formula
Figure imgb0070
or
Figure imgb0071
is used, where D is
Figure imgb0072
R is hydrogen, C1-C4-alkyl, C1-C4-alkoxy-C2-alkyl, C1-C4-fluoroalkyl, Cs- or C6-cycloalkyl or benzyl, R4 is C1-C4-alkyl, phenyl, benzyl or CN and R5 is C1-C4-alkyl, C1-C4-alkylthio, benzyl, C5- or C6-cycloalkyl, benzylthio or C5- or C6-cycloalkylthio.
5. A process as claimed in claim 2, wherein a dye of the formula
Figure imgb0073
is used, where R9 is hydrogen or C1-C4-alkoxy and R10 and R11 independently of one another are each hydrogen, C1-C4-alkyl, C1-C4-alkoxycarbonylethyl or Cs-Cs-alkanoyloxyethyl.
6. A process as claimed in claim 4, wherein a dye is used in which D is
Figure imgb0074
7. A process as claimed in claim 2, wherein a dye of the formula
Figure imgb0075
is used, where R, R', R1, R2 and R4 have the meanings stated in claim 1.
8. A process as claimed in claim 7, wherein R and R', independently of one another are each hydrogen or Ci-C4-alkyl which is unsubstituted or substituted by hydroxyl, cyano or phenyl, or are each C1-C4- alkoxy-C2-C4-alkyl, C1-C4-alkoxycarbonyl-C1-C4-alkyl, C1-C4-alkoxycarbonyloxy-C1-C4-alkyl, C1-C4-fluoroalkyl, phenyl, methylphenyl or methoxyphenyl, R1 and R2 independently of one another are each hydrogen, Cl-C4-alkyl, C1-C4-alkoxy or C1-C4-alkylthio and R4 is C1-C4-alkyl, phenyl, benzyl or cyano.
9. A process as claimed in claim 7, wherein R and R' independently of one another are each hydrogen, C1-C4-alkyl, phenyl, C2-Cs-alkanoyloxyethyl, C1-C4-alkoxycarbonylethyl, C1-C4-alkoxycarbonylxoye- thyl, benzyl or cyanoethyl, R1 and R2 independently of one another are each hydrogen, C1-C4-alkyl, C1-C4-alkoxy or C1-C4-thioalkyl and R4 is C1-C4-alkyl or phenyl.
EP87112630A 1986-09-05 1987-08-29 Dye transfer method Expired - Lifetime EP0258856B2 (en)

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Also Published As

Publication number Publication date
DE3766194D1 (en) 1990-12-20
EP0258856B2 (en) 1994-12-07
JP2677564B2 (en) 1997-11-17
US4999026A (en) 1991-03-12
DE3630279A1 (en) 1988-03-17
EP0258856A2 (en) 1988-03-09
EP0258856A3 (en) 1988-08-24
JPS6369693A (en) 1988-03-29

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