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EP0258856B2 - Dye transfer method - Google Patents
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EP0258856B2 - Dye transfer method - Google Patents

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Publication number
EP0258856B2
EP0258856B2 EP87112630A EP87112630A EP0258856B2 EP 0258856 B2 EP0258856 B2 EP 0258856B2 EP 87112630 A EP87112630 A EP 87112630A EP 87112630 A EP87112630 A EP 87112630A EP 0258856 B2 EP0258856 B2 EP 0258856B2
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EP
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Prior art keywords
alkyl
alkoxy
hydrogen
butyl
benzyl
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EP87112630A
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German (de)
French (fr)
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EP0258856A3 (en
EP0258856A2 (en
EP0258856B1 (en
Inventor
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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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
    • 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 with a heating head with short (duration: fractions of a second) heating pulses from the back, 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.
  • the color recording is carried out using the three subtractive primary colors yellow, magenta and cyan (and possibly black).
  • the dyes In order to enable optimal color recording, the dyes must have the following properties:
  • 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 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 technically easily accessible.
  • 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 H 5 , n-propyl, isopropyl, n-butyl, isobutyl, tertiary-butyl; C i - to C 4 alkoxy such as methoxy, ethoxy, propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, tertiary butyloxy; C i to C 4 alkylthio such as methylthio, ethyl and butylthio and halogen such as bromine, preferably chlorine and fluorine.
  • R 1 can also form a heterocyclic ring together with R, so that can correspond to the following formulas: and
  • C i - to C 4 -alkyl which may be mentioned in detail, for example: methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl.
  • C 1 -C 4 -alkoxy in the alkoxy-bearing substituents are: methoxy, ethoxy, n- and i-propoxy and n- and i-butoxy.
  • the dyes (I) are synthesized by known or per se known methods.
  • 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 described by 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 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 support is preferably 3 to 30 ⁇ m. Further suitable carrier materials, binders and solvents for the production of the printing inks are described in DE-A
  • 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 AE 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 given 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 AE T.

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

Description

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 with a heating head with short (duration: fractions of a second) heating pulses from the back, 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:In general, the color recording is carried out using the three subtractive primary colors yellow, magenta and cyan (and possibly black). In order to enable optimal color recording, the dyes must have the following properties:

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.
i) easy sublimability or vaporizability; in general, this requirement is the most difficult to meet with cyan dyes;
  • ii) high thermal and photochemical stability as well as resistance to moisture and chemical substances;
  • 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 from the prior art for this purpose:

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 dyes of the formula
Figure imgb0002
 known in which R, R 1 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 R1 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 1 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 technically easily accessible.

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 dei
Figure imgb0009
Figure imgb0010

  • R1 und R2 inabhängig voneinander für Wasserstoff, C1- bis C4-Alkyl, C1-bis C4-Alkoxy, C1- bis C4-Alkylthio 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, C1- bis C4-Alkyl, C1- bis C4-Alkoxy-C2-alkyl, C1- bis C4-Fluoralkyl, Cs- oder C6-Cycloalkyl oder Benzyl oder
    Figure imgb0011
    für einen 5- oder 6-gliedrigen heterocyclischen Ring stehen, worin D
    Figure imgb0012
  • R3 CN,
  • R4 C1- bis C4-Alkyl, Phenyl, Benzyl oder CN,
  • R5 C1- bis C4-Alkyl, C1- bis C4-Alkylthio, C1- bis C4-Alkoxy, Cs- oder C6-Cycloalkyl, Benzyl, Cs- oder C6-Cycloalkylthio, Cs- oder C6-Cycloalkoxy, Benzyloxy oder Benzylthio,
  • R 6 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 imgb0013
  • und R5 Alkylthio sind wenn
  • A
    Figure imgb0014
    ist, oder wenn
  • A
    Figure imgb0015
  • R und R' jeweils Wasserstoff, C1- bis C4-Alkyl oder C1-bis C4-Alkoxy-C2-alkyl 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
 located in dei
Figure imgb0009
Figure imgb0010
  • R 1 and R 2 are, independently of one another, hydrogen, C 1 to C 4 alkyl, C 1 to C 4 alkoxy, C 1 to C 4 alkylthio or halogen and where R 1 together with R is a 5 or 6 -formed heterocyclic ring can form, and
  • R and R 'independently of one another for hydrogen, C 1 - to C 4 -alkyl, C 1 - to C 4 -alkoxy-C 2 -alkyl, C 1 - to C 4 -fluoroalkyl, C s - or C 6 -cycloalkyl or Benzyl or
    Figure imgb0011
     represent a 5- or 6-membered heterocyclic ring, in which D
    Figure imgb0012
  • R 3 CN,
  • R 4 is 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, C 1 to C 4 alkoxy, C s or C 6 cycloalkyl, benzyl, C s or C 6 cycloalkylthio, C s - or C 6 -cycloalkoxy, benzyloxy or benzylthio,
  • R 6 CN or -CHO,
  • R 7 is C 1 to C 4 alkoxy, C 1 to C 4 alkylthio or chlorine and
  • R 8 denotes -CHO or CN,
  • where R 1 and R 2 must not be hydrogen at the same time if
  • A
    Figure imgb0013
  • and R 5 are alkylthio if
  • A
    Figure imgb0014
     is or if
  • A
    Figure imgb0015
  • R and R 'are each hydrogen, C 1 to C 4 alkyl or C 1 to C 4 alkoxy-C 2 alkyl.

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.In comparison 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 imgb0016
verwendet. In der Formel steht A

  • für D-N = N- oder
    Figure imgb0017
In the process of the invention, dyes of the general formula
Figure imgb0016
 used. A is in the formula
  • for DN = N- or
    Figure imgb0017

Für R1 und R2 sind neben Wasserstoff z.B. zu nennen: C1- bis C4-Alkyl wie CH3, C2H5, n-Propyl, Isopropyl, n-Butyl, Isobutyl, tertiär-Butyl; Ci- 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 imgb0018
den folgenden Formeln entsprechen kann:
Figure imgb0019
und
Figure imgb0020
 In addition to hydrogen, R 1 and R 2 include, for example: C 1 -C 4 -alkyl such as CH 3 , C 2 H 5 , n-propyl, isopropyl, n-butyl, isobutyl, tertiary-butyl; C i - to C 4 alkoxy such as methoxy, ethoxy, propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, tertiary butyloxy; C i to C 4 alkylthio such as methylthio, ethyl and butylthio and halogen such as bromine, preferably chlorine and fluorine. R 1 can also form a heterocyclic ring together with R, so that
Figure imgb0018
 can correspond to the following formulas:
Figure imgb0019
 and
Figure imgb0020

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

  • R und R' unabhängig voneinander für Wasserstoff, C1- bis C4-Alkyl, C1- bis C4-Alkoxy-C2-alkyl, C1- bis C4-Fluoralkyl, Cs- oder C6-Cycloalkyl oder Benzyl.
In formulas (I) and (Ila) to (Ild)
  • R and R 'independently of one another for hydrogen, C 1 - to C 4 -alkyl, C 1 - to C 4 -alkoxy-C 2 -alkyl, C 1 - to C 4 -fluoroalkyl, C s - or C 6 -cycloalkyl or Benzyl.

Als Ci- bis C4-Alkyl sind im einzelnen z.B. zu nennen: Methyl, Ethyl, Propyl, Isopropyl, n-Butyl, Isobutyl, t-Butyl.As a C i - to C 4 -alkyl which may be mentioned in detail, for example: methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl.

Für C1- 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.

C1- bis C4-Alkoxy-C2-alkyl ist z. B. Methoxyethyl, Ethoxyethyl, n- und i-Propoxyethyl oder n- und i-Butoxyethyl.

Figure imgb0021
kann außerdem für heterocyclische Reste wie
Figure imgb0022
stehen.

  • R3 steht für CN.
  • D bedeutet einen Rest der Formeln
    Figure imgb0023
    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, C1-bis C4-Alkylthio, Benzyl, Cs- oder C6-Cycloalkyl, Cs- oder C6-Cycloalkylthio, Cs- oder C6-Cycloalkoxy, Benzyloxy oder Benzylthio,
  • R 6 CN oder -CHO,
  • R7 Ci- 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.
C 1 - to C 4 alkoxy-C 2 alkyl is e.g. B. methoxyethyl, ethoxyethyl, n- and i-propoxyethyl or n- and i-butoxyethyl.
Figure imgb0021
 can also be used for heterocyclic radicals such as
Figure imgb0022
 stand.
  • R 3 stands for CN.
  • D means a remainder of the formulas
    Figure imgb0023
     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, C s - or C 6 -cycloalkyl, C s - or C 6 -cycloalkylthio, C s - or C 6 -cycloalkoxy, benzyloxy or Benzylthio,
  • R 6 CN or -CHO,
  • R 7 C i - 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, wenn R1 und R2 gleichzeitig Wasserstoff bedeuten, solche Farbstoffe (I) ausgenommen, in denen

  • A
    Figure imgb0024
    und R5 Alkylthio sind,
  • A
    Figure imgb0025
    ist, oder A
    Figure imgb0026
  • R und R1 jeweils Wasserstoff, C1- bis C4-Alkyl oder C1- bis C4-Alkoxy-C2-alkyl sind.
If R 1 and R 2 are both hydrogen, dyes (I) are excluded in which
  • A
    Figure imgb0024
     and R 5 are alkylthio,
  • A
    Figure imgb0025
     is, or A
    Figure imgb0026
  • R and R 1 are each hydrogen, C 1 - to C 4 -alkyl or C 1 - to C 4 -alkoxy-C 2 -alkyl.

Für das vorliegende Verfahren sind bevorzugt:

  • a) Farbstoffe der Formel (I), in der
    • R und R' Wasserstoff, C1- bis C4-Alkyl, C1- bis C4-Alkoxy-C2- bis C4-alkyl oder C1- bis C4-Fluoralkyl,
    • R1 und R2 Wasserstoff, Methyl, Methoxy, n-Propyloxy, Isopropyloxy, n-Butyloxy, Isobutyloxy, tertiär-Butyloxy und
    • A = D-N = N- oder
      Figure imgb0027
      bedeuten und
    • worin D für
      Figure imgb0028
      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 imgb0029
    und
    Figure imgb0030
    worin
    • D für
      Figure imgb0031
    • 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, C 1 - to C 4 -alkyl, C 1 - to C 4 -alkoxy-C 2 - to C 4 -alkyl or C 1 - to C 4 -fluoroalkyl,
    • R 1 and R 2 are hydrogen, methyl, methoxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, tertiary-butyloxy and
    • A = DN = N- or
      Figure imgb0027
       mean and
    • where D for
      Figure imgb0028
       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 imgb0029
     and
    Figure imgb0030
     wherein
    • D for
      Figure imgb0031
    • R 4 represents methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertiary-butyl or CN,
    • R 5 for 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 imgb0032
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 oder Ci- bis C4-Alkyl, wie Methyl, Ethyl, n-Propyl, Isopropyl, n-Butyl, Isobutyl oder tertiär-Butyl bedeuten, sowie solche der Formeln (Illa), (lllb), (lllc) und (llld), worin D für
    Figure imgb0033
    und R für Wasserstoff, Methyl, Ethyl, n-Propyl, Isopropyl, n-Butyl, Isobutyl, tertiär-Butyl stehen.
Dyes of the formula are particularly preferred:
Figure imgb0032
 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 or C i - to C 4 -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tertiary-butyl, and also those of the formulas (IIla), (IIIb ), (lllc) and (llld), where D is for
    Figure imgb0033
     and R represents hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertiary-butyl.

Besonders bevorzugt sind außerdem Farbstoffe der Formel

Figure imgb0034
in der

  • R, R' unabhängig voneinander Wasserstoff, C1- bis C4-Alkyl wie Methyl, Ethyl, n-Propyl, Isopropyl, n-Butyl, Isobutyl und tertiär-Butyl oder Benzyl,
  • R1 und R2 unabhängig voneinander Wasserstoff, C1- bis C4-Alkyl wie Methyl, Ethyl, n-Propyl, Isopropyl, n-Butyl, Isobutyl, tertiär-Butyl, C1- bis C4-Alkoxy wie Methoxy, Ethoxy, n-Propyloxy, Isopropyloxy, n-Butyloxy, Isobutyloxy und tertiär-Butyloxy oder C1- bis C4-Thioalkyl und
  • R4 Ci- 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 imgb0034
 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 or benzyl,
  • R 1 and R 2 independently of one another hydrogen, 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 , n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy and tertiary-butyloxy or C 1 - to C 4 -thioalkyl and
  • R 4 is C i - 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 or per se known methods.

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 imgb0035
ist aus der DE-A 34 02 024 bekannt.

  • Azofarbstoffe (I) mit
    Figure imgb0036
  • 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 , R 2 and R 4 have the meaning given above are prepared by the process described in DE-OS 32 07 290. The diazo component (R 4 = CN)
Figure imgb0035
 is known from DE-A 34 02 024.
  • Azo dyes (I) with
    Figure imgb0036
  • and R 5 alkylthio
  • were synthesized by the method described in DE-C 15 44 391. Diazo components with R 5 = alkyl were prepared according to the synthesis described in Chem Ber 87, p. 57 (1954).

Azofarbstoffe (I) mit

Figure imgb0037
wurden nach dem in der DE-A 31 08 077 bzw. 35 29 831 beschriebenen Verfahren synthetisiert.Azo dyes (I) with
Figure imgb0037
 were synthesized by the method described in DE-A 31 08 077 and 35 29 831.

Farbstoffe des Typs

Figure imgb0038
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 imgb0038
 were developed according to the method described by 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 um. 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 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 support is preferably 3 to 30 µm. 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-receiving 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 + Nahydrogensulfit
      • 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 Schüttelgerät (Red Devil®) geschüttelt, bis die mittlere Teilchengröße des Farbstoffs 1 um 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 um-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 um dicke Polyesterfolie (Nehmer) eine Extinktion von mindestens 2 erzielt wird.
  • B) Prüfung auf Sublimations/Verdampfungs-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 no binder is used 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 dispersant based on a condensation product of phenol + formaldehyde + near hydrogensulfite
      • 7.5 g of water and
      • 0.5 g of dye are mixed with
      • 10 g glass balls (2 mm 0)
      • filled into vessels and shaken on a shaker (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 when completely transferred to an 80 μm thick polyester film (taker).
  • 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 um dicke Polyestenfolie (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 imgb0039
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 AE T for the transfer experiment is calculated:
Figure imgb0039

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 AET aufgeführt.

Figure imgb0040
Figure imgb0041
Figure imgb0042
Figure imgb0043
Figure imgb0044
Figure imgb0045
Figure imgb0046
 The dyes given 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 AE T.
Figure imgb0040
Figure imgb0041
Figure imgb0042
Figure imgb0043
Figure imgb0044
Figure imgb0045
Figure imgb0046

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
Figure imgb0062
where A is D-N = N- or
Figure imgb0063
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, C1-C4-alkyl, C1-C4-alkoxy-C2-alkyl, C1-C4- fluoroalkyl, C5- or C6-cycloalkyl or benzyl,
Figure imgb0064
is a 5-membered or 6-membered heterocyclic ring, D is
D
Figure imgb0065
R3 is CN, R4 is C1-C4-alkyl, phenyl, benzyl or CN, R5 is C1-C4-alkyl, C1-C4-alkylthio, C1-C4-alkoxy, Cs-or C6-cycloalkyl, benzyl, Cs- or C6-cycloalkylthio, Cs- or C6-cycloalkoxy, benzyloxy or benzylthio, R6 is CN or -CHO, R7 is C1-C4-alkoxy, C1-C4-alkylthio or chlorine and R8 is -CHO or CN, and R1 and R2 must not simultaneously be hydrogen when A is
Figure imgb0066
and R5 is alkylthio when
A is
Figure imgb0067
or when
A is
Figure imgb0068
R and R' are each hydrogen, C1-C4-alkyl or C1-C4-alkoxy-C2-alkyl, are present.
2. A process as claimed in claim 1, wherein R and R' independently of one another are each hydrogen, C1-C4-alkyl, C1-C4-alkoxy-C2-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 imgb0069
3. A process as claimed in claim 1 or 2, wherein A is D-N = N-, where D is D
Figure imgb0070
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 C5- or C6-cycloalkylthio.
4. A process as claimed in claim 1, wherein a dye of the formula
Figure imgb0071
or
Figure imgb0072
is used where D is
Figure imgb0073
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, Cs- or C6-cycloalkyl, benzylthio or C5- or C6-cycloalkylthio.
5. A process as claimed in claim 2, wherein a dye of the formula
Figure imgb0074
is used, where R9 is hydrogen or C1-C4-alkoxy and R10 and R11 independently of one another are each hydrogen or C1-C4-alkyl.
6. A process as claimed in claim 4, wherein a dye is used in which D is
Figure imgb0075
7. A process as claimed in claim 2, wherein a dye of the formula
Figure imgb0076
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, C1-C4-alkyl, C1-C4-alkoxy-C2-alkyl or C1-C4-fluoroalkyl, R1 and R2 independently of one another are each hydrogen, C1-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, or benzyl, 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.
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EP0258856A3 (en) 1988-08-24
JP2677564B2 (en) 1997-11-17
DE3630279A1 (en) 1988-03-17
EP0258856A2 (en) 1988-03-09
EP0258856B1 (en) 1990-11-14
JPS6369693A (en) 1988-03-29
DE3766194D1 (en) 1990-12-20
US4999026A (en) 1991-03-12

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