EP0258856A2 - Dye transfer method - Google Patents

Dye transfer method Download PDF

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EP0258856A2
EP0258856A2 EP87112630A EP87112630A EP0258856A2 EP 0258856 A2 EP0258856 A2 EP 0258856A2 EP 87112630 A EP87112630 A EP 87112630A EP 87112630 A EP87112630 A EP 87112630A EP 0258856 A2 EP0258856 A2 EP 0258856A2
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Prior art keywords
alkyl
alkoxy
hydrogen
phenyl
dyes
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German (de)
French (fr)
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EP0258856B1 (en
EP0258856B2 (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 R2 are allyl, alkyl, alkoxyalkyl and XH, methyl.
  • JP-A 229786/1985 describes dyes of the formula in which R and R1 are methyl, ethyl, propyl or butyl and XH or methyl mean described for this application.
  • JP-A 239292/1985 uses dyes of the formula for the transfer described.
  • R1 is 1-8 C, alkyl
  • R2 is H or methyl
  • D is Quinone derivatives of the formula in which R and R 1 is 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.
  • R1 and R2 in addition to hydrogen, for example: C1- to C1-alkyl such as CH3, C2H5, n-propyl, isopropyl, n-butyl, isobutyl, tertiary-butyl; C1 to C4 alkoxy such as methoxy, ethoxy, propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, tertiary butyloxy; C1 to C4 alkylthio such as methylthio, ethyl and butylthio 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:
  • R and R ⁇ independently of one another for hydrogen or for C1- to C6-alkyl, optionally by C1- to C4-alkoxy, C1- to C4-alkoxycarbonyl, C1- to C4-alkoxycarbonyloxy, C2- to C5-alkanoyloxy, C1- to C4-Alkoxy-C2- or C3-alkoxycarbonyloxy, hydroxy, cyano, halogen, phenyl or C5- or C6-cycloalkyl is substituted.
  • C1 to C6 alkyl e.g. To name: methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-pentyl, i-pentyl, n-hexyl, i-hexyl.
  • halogen come as substituents on C1 to C6 alkyl, bromine, chlorine, preferably fluorine.
  • C2- to C5-alkanoyl examples include acetyl, propionyl, butanoyl and pentanoyl.
  • R ⁇ and R can also be phenyl, which is optionally substituted by methyl or methoxy, C5-C6-cycloalkyl or benzyl.
  • Suitable substituted C1 to C6 alkyl include: 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- (ethoxycarbon
  • Optionally substituted phenyl for R and R ⁇ are phenyl, 2- and 4-methylphenyl and 2- and 4-methoxyphenyl.
  • R ⁇ is preferably methyl, in particular hydrogen. can also be used for heterocyclic radicals such as stand.
  • R3 stands for hydrogen or CN.
  • R4 C1 to C4 alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertiary butyl, phenyl, benzyl or CN
  • R5 C1- to C4-alkyl such as, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertiary-butyl, C1- to C4-alkoxy such as, methoxy, ethoxy, propyloxy, isopropyloxy, n-butyloxy, isobutyloxy , tertiary-butyloxy, C1-to C Alkyl-alkylthio, benzyl, C5- or C6-cycloalkyl, C5- or C6-cycloalkylthio, C5- or C6
  • Dyes of the formula: in the R9 is hydrogen, C1- to C4alkoxy such as methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, tertiary-butyloxy, R10 and R11 independently of one another are hydrogen, C1- to C4-alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertiary-butyl C1- to C4-alkoxycarbonyl-ethyl or C2- to C5-alkanoyloxyethyl, as well as those of the formulas (IIIa), (IIIb), (IIIc) and (IIId), in which D for R represents hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertiary butyl
  • Dyes of the formula are also particularly preferred in the R, R ⁇ independently of one another hydrogen, C1- to C4-alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and tertiary-butyl, phenyl, C2- to C5-alkanoyloxyethyl, C1- to C4-alkoxy- carbonyl-ethyl, C1- to C4-alkoxycarbonyloxyethyl, benzene or cyanoethyl, R1 and R2 independently of one another hydrogen, C1- to C4-alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertiary-butyl, C1- to C4-alkoxy such as methoxy, ethoxy, n-propyloxy, isopropyl
  • the dyes (I) are synthesized by known processes or processes known per se.
  • Azo dyes of the general formula (V), in which R, R ⁇ , R1, R2 and R4 have the meaning given above, are prepared by the process described in DE-OS 32 07 290.
  • Azo dyes (I) with and R5 alkylthio were synthesized by the method described in DE-C 15 44 391.
  • 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.
  • Dyes (I) in which A for stands, were obtained by known processes by reacting corresponding p-formyl anilines with malodinitrile.
  • 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 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
  • 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. You wear it the logarithm of the absorbance A of the colored polyester films measured at different temperatures (range: 100 to 200 ° C) against the associated reciprocal absolute temperature, this gives straight lines, from the slope of which the activation energy ⁇ E T is calculated for the transfer experiment:
  • 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 AI) or AII) 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 ⁇ E T.
  • Fig. 1 the values are in the form log A against [k ⁇ 1] represented graphically.

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

Abstract

Verfahren zur Übertragung von Farbstoffen von einem Träger durch Sublimation/Verdampfen auf mit Kunststoff beschichtete Papiere unter Verwendung von Farbstoffen der allgemeinen Formel (I) <IMAGE> in der A für D-N=N- oder (NC)2C= ?-R³, R¹ und R² für Wasserstoff, Alkyl, Alkoxy, Alkylthio oder Halogen, wobei R¹ und R zusammen einen 5-/6-gliedrigen heterocyclischen Ring bilden können, 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 C5-Alkanoyloxy, C1- bis C4-Alkoxycarbonyloxy, C1- bis C4-Alkoxy-C2- oder C3-alkoxycarbonyloxy, Hydroxy, Cyan, Halogen, Phenyl oder C5- oder C6-Cycloalkyl substituiertes C1- bis C6-Alkyl C5/C6-Cycloalkyl, oder <IMAGE> für einen 5- oder 6-gliedrigen gesättigten heterocyclischen Ring stehen, worin D ein Rest einer Diazokomponente der Thiophen-, Thioazol-, Isothiazol oder Thiadiazol(1,2,4)-reihe und R³ Wasserstoff oder CN ist. Die Farbstoffe (I) geben bei dem Verfahren starke Färbungen, die gute Lichtechtheit aufweisen und gegenüber chemischen Stoffen beständig sind.Process for the transfer of dyes from a support by sublimation / evaporation to paper coated with plastic using dyes of the general formula (I) <IMAGE> in the A for DN = N- or (NC) 2C =? -R³, R¹ and R² for hydrogen, alkyl, alkoxy, alkylthio or halogen, where R¹ and R together can form a 5- / 6-membered heterocyclic ring, R and R 'independently of one another for hydrogen, for phenyl optionally substituted by methyl or methoxy or for optionally by C1- to C4-alkoxy, C1- to C4-alkoxycarbonyl, C2- to C5-alkanoyloxy, C1- to C4-alkoxycarbonyloxy, C1- to C4-alkoxy-C2- or C3-alkoxycarbonyloxy, hydroxy, cyan, halogen, phenyl or C5- or C6-cycloalkyl-substituted C1- to C6-alkyl C5 / C6-cycloalkyl, or <IMAGE> for a 5- or 6-membered saturated heterocyclic ring, in which D is a residue of a diazo component of the thiophene, thioazole or isothiazole or thiadiazole (1,2,4) series and R³ water is fabric or CN. In the process, the dyes (I) give strong colorations which have good lightfastness and are resistant to chemical substances.

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 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 R² 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 R¹ 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, R1 is 1-8 C, alkyl, R2 is H or methyl and D is
Figure imgb0005
 Quinone derivatives of the formula
Figure imgb0006
 in which R and R 1 is 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
    A für D-N=N- oder
Figure imgb0009
     R¹ und R² unabhängig 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 Rʹ 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 C₅-Alkanoyloxy, C₁- bis C₄-Alkoxycarbonyloxy, C₁- bis C₄-Alkoxy-C₂- oder C₃-alkoxycarbonyloxy, Hydroxy, Cyan, Halogen, Phenyl oder C₅- 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 Wasserstoff oder CN,
    R⁴ C₁- bis C₄-Alkyl, Phenyl, Benzyl oder CN,
    R⁵ C₁- bis C₄-Alkyl, C₁- bis C₄-Alkylthio, C₁- bis C₄-Alkoxy, C₅- oder C₆-Cycloalkyl, Benzyl, C₅- oder C₆-Cycloalkylthio, C₅- oder C₆-Cyclo­alkoxy, Benzyloxy oder Benzylthio,
    R⁶ CN oder -CHO,
    R⁷ C₁- bis C₄-Alkoxy, C₁- bis C₄-Alkylthio oder Chlor und
    R⁸ -CHO, CN oder Nitro bedeuten,
wobei R¹ und R² nicht Wasserstoff sein dürfen, wenn
A
Figure imgb0012
 und R⁵ Alkylthio sind oder wenn
A
Figure imgb0013
 ist.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 one uses a support on which dyes of the general formula
Figure imgb0008
 are in the
A for DN = N- or
Figure imgb0009
 R¹ and R² independently of one another are hydrogen, C₁- to C₁-alkyl, C₁-to C₄-alkoxy, C₁- to C₄-alkylthio or halogen and where R¹ together with R can form a 5- or 6-membered heterocyclic ring, and
R and Rʹ independently of one another for hydrogen, for phenyl optionally substituted by methyl or methoxy or for optionally substituted by C₁ to C₄ alkoxy, C₁ to C₄ alkoxycarbonyl, C₂ to C₅ alkanoyloxy, C₁ to C₄ alkoxycarbonyloxy, C₁- to C₄-alkoxy-C₂- or C₃-alkoxycarbonyloxy, hydroxy, cyan, halogen, phenyl or C₅- or C₆-cycloalkyl substituted C₁-to C₆-alkyl or C₅- or C₆-cycloalkyl or
Figure imgb0010
 represent a 5- or 6-membered heterocyclic ring, wherein
Figure imgb0011
 R³ is hydrogen or CN,
R⁴ C₁ to C₄ alkyl, phenyl, benzyl or CN,
R⁵ C₁ to C₄ alkyl, C₁ to C₄ alkylthio, C₁ to C₄ alkoxy, C₅ or C₆ cycloalkyl, benzyl, C₅ or C₆ cycloalkylthio, C₅ or C₆ cycloalkoxy, benzyloxy or benzylthio,
R⁶ CN or -CHO,
R⁷ C₁ to C₄ alkoxy, C₁ to C₄ alkylthio or chlorine and
R⁸ denotes -CHO, CN or nitro,
where R1 and R2 cannot be hydrogen if
A
Figure imgb0012
 and R⁵ are alkylthio or if
A
Figure imgb0013
 is.

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 imgb0014
verwendet. In der Formel steht A
für D-N=N- oder
Figure imgb0015
 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; C₁- bis C₄-Alkoxy wie Methoxy, Ethoxy, Propyloxy, Isopropyloxy, n-Butyloxy, Isobutyloxy, tertiär-Butyloxy; C₁-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 imgb0016
 den folgenden Formeln entsprechen kann:
Figure imgb0017
 In the process of the invention, dyes of the general formula
Figure imgb0014
 used. A is in the formula
for DN = N- or
Figure imgb0015
 For R¹ and R², in addition to hydrogen, for example: C₁- to C₁-alkyl such as CH₃, C₂H₅, n-propyl, isopropyl, n-butyl, isobutyl, tertiary-butyl; C₁ to C₄ alkoxy such as methoxy, ethoxy, propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, tertiary butyloxy; C₁ to C₄ alkylthio such as methylthio, ethyl and butylthio and halogen such as bromine, preferably chlorine and fluorine. R¹ can also form a heterocyclic ring together with R, so that
Figure imgb0016
 can correspond to the following formulas:
Figure imgb0017

In den Formeln (I) und (IIa) bis (IId) stehen
R und Rʹ unabhängig voneinander für Wasserstoff oder für C₁- bis C₆-Alkyl, das gegebenenfalls durch C₁- bis C₄-Alkoxy, C₁- bis C₄-Alkoxycarbonyl, C₁- bis C₄-Alkoxycarbonyloxy, C₂- bis C₅-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 (IId)
R and Rʹ independently of one another for hydrogen or for C₁- to C₆-alkyl, optionally by C₁- to C₄-alkoxy, C₁- to C₄-alkoxycarbonyl, C₁- to C₄-alkoxycarbonyloxy, C₂- to C₅-alkanoyloxy, C₁- to C₄-Alkoxy-C₂- or C₃-alkoxycarbonyloxy, hydroxy, cyano, halogen, phenyl or C₅- or C₆-cycloalkyl is substituted.

Als C₁- 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 C₁ to C₆ alkyl, e.g. To name: methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-pentyl, i-pentyl, n-hexyl, i-hexyl.

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.For C₁ to C₄ alkoxy in the alkoxy group-bearing substituents e.g. to name: methoxy, ethoxy, n- and i-propoxy and n- and i-butoxy.

Für Alkyl in den Alkyloxygruppen kommen im einzelnen die für C₁- bis C₆-Alkyl genannten Reste mit 1 bis 4 C-Atomen in Betracht.For alkyl in the alkyloxy groups, the radicals mentioned for C₁- to C Alkyl-alkyl with 1 to 4 carbon atoms are suitable.

Für Halogen kommen als Substituenten am C₁- bis C₆-Alkyl, Brom, Chlor, vorzugsweise Fluor in Betracht.For halogen come as substituents on C₁ to C₆ alkyl, bromine, chlorine, preferably fluorine.

Als C₂- bis C₅-Alkanoyl sind z.B. Acetyl, Propionyl, Butanoyl und Pentanoyl zu nennen.Examples of C₂- to C₅-alkanoyl include acetyl, propionyl, butanoyl and pentanoyl.

Außerdem können Rʹ und R auch Phenyl, das gegebenenfalls durch Methyl oder Methoxy substituiert ist, C₅-C₆-Cyxcloalkyl oder Benzyl sein.In addition, Rʹ and R can also be phenyl, which is optionally substituted by methyl or methoxy, C₅-C₆-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 suitable substituted C₁ to C₆ alkyl include:

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

Figure imgb0018
kann außerdem für heterocyclische Reste wie
Figure imgb0019
 stehen.

R³ steht für Wasserstoff oder CN.

D bedeutet einen Rest der Formeln
Figure imgb0020
 worin
    R⁴ C₁- 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, C₅- oder C₆-Cycloalkyl, C₅- 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, CN oder Nitro bedeuten.Optionally substituted phenyl for R and Rʹ are phenyl, 2- and 4-methylphenyl and 2- and 4-methoxyphenyl. In the event that R is phenyl or substituted phenyl, Rʹ is preferably methyl, in particular hydrogen.
Figure imgb0018
 can also be used for heterocyclic radicals such as
Figure imgb0019
 stand.

R³ stands for hydrogen or CN.

D means a remainder of the formulas
Figure imgb0020
 wherein
R⁴ C₁ to C₄ alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertiary butyl, phenyl, benzyl or CN,
R⁵ C₁- to C₄-alkyl such as, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertiary-butyl, C₁- to C₄-alkoxy such as, methoxy, ethoxy, propyloxy, isopropyloxy, n-butyloxy, isobutyloxy , tertiary-butyloxy, C₁-to C Alkyl-alkylthio, benzyl, C₅- or C₆-cycloalkyl, C₅- or C₆-cycloalkylthio, C₅- or C₆-cycloalkoxy, benzyloxy or benzylthio,
R⁶ CN or -CHO,
R⁷ C₁- to C₄-alkoxy such as, methoxy, ethoxy, propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, tertiary-butyloxy, C₁- to C₄-alkylthio or chlorine and
R⁸ -CHO, CN or nitro mean.

Dabei sind Farbstoffe (I), in denen
    A

Figure imgb0021
und R⁵ Alkylthio sind oder
    A
Figure imgb0022
 ist, ausgenommen wenn R¹ und R² Wasserstoff sind.There are dyes (I) in which
A
Figure imgb0021
 and R⁵ are alkylthio or
A
Figure imgb0022
 except when R¹ and R² are hydrogen.

Für das vorliegende Verfahren sind bevorzugt:

  • a) Farbstoffe der Formel (I), in der
    R und Rʹ Wasserstoff, gegebenenfalls durch Hydroxy, Cyan oder Phenyl substituiertes C₁- bis C₄-Alkyl, C₁- bis C₄-Alkoxy-C₂- bis C₄-alkyl, C₁- bis C₄-Alkoxycarbonyl-C₁- bis C₄-alkyl, C₁- bis C₄-Alkoxycarbonyloxy-C₂- bis C₄-alkyl, C₁- 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 imgb0023
     bedeuten und
    worin D für
    Figure imgb0024
     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 imgb0025
     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 Rʹ are hydrogen, optionally substituted by hydroxy, cyano or phenyl, C₁ to C₄ alkyl, C₁ to C₄ alkoxy C₂ to C₄ alkyl, C₁ to C₄ alkoxycarbonyl C₁ to C₄ alkyl, C₁- to C₄-alkoxycarbonyloxy-C₂- to C₄-alkyl, C₁- to C₄-fluoroalkyl, or phenyl optionally substituted by methoxy or methyl,
    R1 and R2 are hydrogen, methyl, methoxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, tertiary-butyloxy and
    A = DN = N- or
    Figure imgb0023
     mean and
    where D for
    Figure imgb0024
     stand, and being
    R⁴ methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertiary-butyl, cyan and
    R⁵ 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 imgb0025
     R⁴ is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertiary-butyl or CN,
    R⁵ 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 imgb0026
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 C₅-Alkanoyloxyethyl bedeuten, sowie solche der Formeln (IIIa), (IIIb), (IIIc) und (IIId), worin D für
Figure imgb0027
 R für Wasserstoff, Methyl, Ethyl, n-Propyl, Isopropyl, n-Butyl, Isobutyl, tertiär-Butyl stehen.Dyes of the formula:
Figure imgb0026
 in the
R⁹ is hydrogen, C₁- to C₄alkoxy such as methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, tertiary-butyloxy,
R¹⁰ and R¹¹ independently of one another are hydrogen, C₁- to C₄-alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertiary-butyl C₁- to C₄-alkoxycarbonyl-ethyl or C₂- to C₅-alkanoyloxyethyl, as well as those of the formulas (IIIa), (IIIb), (IIIc) and (IIId), in which D for
Figure imgb0027
 R represents hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertiary butyl.

Besonders bevorzugt sind außerdem Farbstoffe der Formel

Figure imgb0028
in der
    R, Rʹ unabhängig voneinander Wasserstoff, C₁- bis C₄-Alkyl wie Methyl, Ethyl, n-Propyl, Isopropyl, n-Butyl, Isobutyl und tertiär-Butyl, Phenyl, C₂- bis C₅-Alkanoyloxyethyl, C₁- bis C₄-Alkoxy-carbonyl-ethyl, C₁- bis C₄-Alkoxycarbonyloxyethyl, Benzol oder Cyanethyl,
    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 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 imgb0028
 in the
R, Rʹ independently of one another hydrogen, C₁- to C₄-alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and tertiary-butyl, phenyl, C₂- to C₅-alkanoyloxyethyl, C₁- to C₄-alkoxy- carbonyl-ethyl, C₁- to C₄-alkoxycarbonyloxyethyl, benzene or cyanoethyl,
R¹ and R² independently of one another hydrogen, C₁- to C₄-alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertiary-butyl, C₁- to C₄-alkoxy such as methoxy, ethoxy, n-propyloxy, isopropyloxy , n-butyloxy, isobutyloxy and tertiary-butyloxy or C₁- to C₄-thioalkyl and
R⁴ C₁ to C₄ 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, Rʹ, 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 imgb0029
ist aus der DE-A 34 02 024 bekannt.
Azofarbstoffe (I) mit
Figure imgb0030
 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, Rʹ, R¹, 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 imgb0029
 is known from DE-A 34 02 024.
Azo dyes (I) with
Figure imgb0030
 and R⁵ alkylthio
were synthesized by the method described in DE-C 15 44 391. Diazo components with R⁵ = alkyl were according to the in Chem. Ber. 87 , p. 57 (1954).

Azofarbstoffe (I) mit

Figure imgb0031
wurden nach dem in der DE-A 31 08 077 bzw. 35 29 831 beschriebenen Ver­fahren synthetisiert.Azo dyes (I) with
Figure imgb0031
 were synthesized by the method described in DE-A 31 08 077 and 35 29 831.

Farbstoffe des Typs

Figure imgb0032
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 imgb0032
 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.

Farbstoffe (I), in denen
    A für

Figure imgb0033
steht,
wurden nach bekannten Verfahren durch Umsatz entsprechender p-Formyl-Ani­line mit Malodinitril erhalten.Dyes (I) in which
A for
Figure imgb0033
 stands,
were obtained by known processes by reacting corresponding p-formyl anilines with malodinitrile.

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 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-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:
    • AI) 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 ⌀)
      in Gefäße gefüllt und nach dem Verschließen auf einem Schüttelgerät (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.
    • AII) 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 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 a binder is dispensed with in the production of the dye carrier to be tested.
  • A) General recipes for coating the carrier with dye:
    • AI) 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 ⌀)
      filled into vessels and shaken on a shaker (Red Devil®) until the average particle size of the dye is µm 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.
    • AII) The dye is spin-coated onto the backing paper once or several times in the form of a solution which is approximately 90% saturated 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 ΔET für das Transferexperiment berechnet wird:

Figure imgb0034
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. You wear it the logarithm of the absorbance A of the colored polyester films measured at different temperatures (range: 100 to 200 ° C) against the associated reciprocal absolute temperature, this gives straight lines, from the slope of which the activation energy ΔE T is calculated for the transfer experiment:
Figure imgb0034

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 AI) oder AII) 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 imgb0035
Figure imgb0036
Figure imgb0037
Figure imgb0038
Figure imgb0039
Figure imgb0040
Figure imgb0041
Figure imgb0042
 The dyes specified in Tables 1 to 6 were processed according to AI) or AII) 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 ΔE T.
Figure imgb0035
Figure imgb0036
Figure imgb0037
Figure imgb0038
Figure imgb0039
Figure imgb0040
Figure imgb0041
Figure imgb0042

Im Falle des Farbstoffs Beispiel 23 wurden Proben nach B) jeweils 30 sec. lang auf die in der Tabelle 6 angegebenen Temperaturen erhitzt und anschließend die Extinktion der Färbung auf PES bestimmt. Die Extinktionen und Temperaturen für 6 Meßpunkte sind in der Tabelle 6 angegeben.

Figure imgb0043
In the case of the dye of Example 23, samples according to B) were each heated for 30 seconds to the temperatures given in Table 6 and then the extinction of the color on PES was determined. The extinctions and temperatures for 6 measuring points are given in Table 6.
Figure imgb0043

In der Fig. 1 sind die Werte in der Form log A gegen
    

Figure imgb0044
[k⁻₁]
graphisch dargestellt.In Fig. 1 the values are in the form log A against
Figure imgb0044
[k⁻₁]
represented graphically.

In der Darstellung kann
    Δ log A = 1,14 mit Δ

Figure imgb0045
= 0,209 · 10⁻³k⁻¹
entnommen und somit ΔET berechnet werden:
Figure imgb0046
 In the illustration can
Δ log A = 1.14 with Δ
Figure imgb0045
= 0.209 · 10⁻³k⁻¹
taken and thus calculated ΔE T :
Figure imgb0046

Aus der Darstellung ergibt sich außerdem
    

Figure imgb0047
= 2,282 · 10⁻³ · k⁻¹ und damit T = 438°k
    ≙165°CThe illustration also shows
Figure imgb0047
= 2.282 · 10⁻³ · k⁻¹ and thus T = 438 ° k
≙165 ° C

Claims (9)

1. Verfahren zur Übertragung von Farbstoffen von einem Träger durch Sublimation/Verdampfung mit Hilfe eines Thermokopfes auf ein mit Kunststoff beschichtetes Papier, dadurch gekennzeichnet, daß man einen Träger verwendet, auf dem sich Farbstoffe der allgemeinen Formel
Figure imgb0048
 befinden, in der
      A für D-N=N- oder
Figure imgb0049
       R¹ und R² unabhängig 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 Rʹ 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 C₅-Alkanoyloxy, C₁- bis C₄-Alkoxycarbonyloxy, C₁- bis C₄-Alkoxy-C₂- oder C₃-alkoxycarbonyloxy, Hydroxy, Cyan, Halogen, Phenyl oder C₅- oder C₆-Cycloalkyl substituiertes C₁- bis C₆-Alkyl oder C₅-­oder C₆-Cycloalkyl oder
Figure imgb0050
 für einen 5- oder 6-gliedrigen heterocyclischen Ring stehen, worin
Figure imgb0051
       R³ Wasserstoff oder CN,
      R⁴ C₁- bis C₄-Alkyl, Phenyl, Benzyl oder CN,
      R⁵ C₁- bis C₄-Alkyl, C₁- bis C₄-Alkylthio, C₁- bis C₄-Alkoxy, C₅-oder C₆-Cycloalkyl, Benzyl, C₅- oder C₆-Cycloalkylthio, C₅-­oder C₆-Cycloalkoxy, Benzyloxy oder Benzylthio,
      R⁶ CN oder -CHO,
      R⁷ C₁- bis C₄-Alkoxy, C₁- bis C₄-Alkylthio oder Chlor und
      R⁸ -CHO, CN oder Nitro bedeuten,
wobei R¹ und R² nicht Wasserstoff sein dürfen, wenn
A
Figure imgb0052
 und R⁵ Alkylthio sind oder wenn
A
Figure imgb0053
 ist.1. A method for transferring dyes from a support by sublimation / evaporation using a thermal head on a plastic-coated paper, characterized in that a carrier is used on which dyes of the general formula
Figure imgb0048
 are in the
A for DN = N- or
Figure imgb0049
 R¹ and R² independently of one another are hydrogen, C₁- to C₁-alkyl, C₁-to C₄-alkoxy, C₁- to C₄-alkylthio or halogen and where R¹ together with R can form a 5- or 6-membered heterocyclic ring, and
R and Rʹ independently of one another for hydrogen, for phenyl optionally substituted by methyl or methoxy or for optionally substituted by C₁ to C₄ alkoxy, C₁ to C₄ alkoxycarbonyl, C₂ to C₅ alkanoyloxy, C₁ to C₄ alkoxycarbonyloxy, C₁- to C₄-alkoxy-C₂- or C₃-alkoxycarbonyloxy, hydroxy, cyano, halogen, phenyl or C₅- or C₆-cycloalkyl substituted C₁- to C₆-alkyl or C₅- or C₆-cycloalkyl or
Figure imgb0050
 represent a 5- or 6-membered heterocyclic ring, wherein
Figure imgb0051
 R³ is hydrogen or CN,
R⁴ C₁ to C₄ alkyl, phenyl, benzyl or CN,
R⁵ C₁ to C₄ alkyl, C₁ to C₄ alkylthio, C₁ to C₄ alkoxy, C₅ or C₆ cycloalkyl, benzyl, C₅ or C₆ cycloalkylthio, C₅ or C₆ cycloalkoxy, benzyloxy or benzylthio,
R⁶ CN or -CHO,
R⁷ C₁ to C₄ alkoxy, C₁ to C₄ alkylthio or chlorine and
R⁸ denotes -CHO, CN or nitro,
where R1 and R2 cannot be hydrogen if
A
Figure imgb0052
 and R⁵ are alkylthio or if
A
Figure imgb0053
 is. 2. Verfahren gemäß Anspruch 1, dadurch gekennzeichnet, daß
      R und Rʹ unabhängig voneinander für Wasserstoff, für gegebenenfalls durch Hydroxy, Cyan oder Phenyl substituiertes C₁- bis C₄-Alkyl, C₁- bis C₄-Alkoxy-C₂-bis C₄-alkyl, C₁- bis C₄-Alkoxycarbonyl-C₁- bis C₄-alkyl, C₁- bis C₄-Alkoxycarbonyloxy-C₂- bis C₄-alkyl oder C₁-bis C₄-Fluoralkyl,
      R¹ und R² unabhängig voneinander für Wasserstoff, C₁- bis C₄-Alkyl oder C₁- bis C₄-Alkoxy und
      A für D-N=N- oder
Figure imgb0054
 stehen.2. The method according to claim 1, characterized in that
R and Rʹ independently of one another for hydrogen, for C₁- to C₄-alkyl optionally substituted by hydroxy, cyano or phenyl, C₁- to C--alkoxy-C₂-to C₄-alkyl, C₁- to C₄-alkoxycarbonyl-C₁- to C₄- alkyl, C₁ to C₄ alkoxycarbonyloxy C₂ to C₄ alkyl or C₁ to C₄ fluoroalkyl,
R¹ and R² independently of one another for hydrogen, C₁- to C₄-alkyl or C₁- to C₄-alkoxy and
A for DN = N- or
Figure imgb0054
 stand. 3. Verfahren gemäß Anspruch 1 oder 2, dadurch gekennzeichnet, daß A für D-N=N- steht, worin
Figure imgb0055
       R⁴ C₁- bis C₄-Alkyl, Phenyl, Benzyl oder CN und
      R⁵ C₁- bis C₄-Alkyl, C₁- bis C₄-Alkylthio, Benzyl, C₅- oder C₆-Cycloalkyl, Benzylthio oder C₅- oder C₆-Cycloalkylthio bedeuten.3. The method according to claim 1 or 2, characterized in that A is DN = N-, wherein
Figure imgb0055
 R⁴ C₁ to C₄ alkyl, phenyl, benzyl or CN and
R⁵ is C₁ to C₄ alkyl, C₁ to C₄ alkylthio, benzyl, C₅ or C₆ cycloalkyl, benzylthio or C₅ or C₆ cycloalkylthio. 4. Verfahren gemäß Anspruch 1, dadurch gekennzeichnet, daß man Farbstoffe der allgemeinen Formeln
Figure imgb0056
       R für Wasserstoff C₁- bis C₄-Alkyl, C₁- bis C₄-Alkoxy-C₂-alkyl, , C₁- bis C₄-Fluoralkyl, C₅-oder C₆-Cycloalkyl oder Benzyl,
      R⁴ für C₁- bis C₄-Alkyl, Phenyl, Benzyl oder CN und
      R⁵ für C₁- bis C₄-Alkyl, C₁- bis C₄-Alkylthio, Benzyl, C₅- oder C₆-Cycloalkyl, Benzylthio oder C₅- oder C₆-Cycloalkylthio stehen.4. The method according to claim 1, characterized in that dyes of the general formulas
Figure imgb0056
 R represents hydrogen C₁- to C₄-alkyl, C₁- to C₄-alkoxy-C₂-alkyl,, C₁- to C₄-fluoroalkyl, C₅- or C₆-cycloalkyl or benzyl,
R⁴ for C₁ to C₄ alkyl, phenyl, benzyl or CN and
R⁵ is C₁ to C₄ alkyl, C₁ to C₄ alkylthio, benzyl, C₅ or C₆ cycloalkyl, benzylthio or C₅ or Cio cycloalkylthio. 5. Verfahren gemäß Anspruch 2, dadurch gekennzeichnet, daß man Farbstoffe der allgemeinen Formel
Figure imgb0057
 verwendet, in der
      R⁹ Wasserstoff oder C₁- bis C₄-Alkoxy,
      R¹⁰ und R¹¹, unabhängig voneinander, Wasserstoff, C₁- bis C₄-Alkyl, C₁- bis C₄-Alkoxycarbonylethyl oder C₂- bis C₅-Alkanoyloxyethyl bedeuten.5. The method according to claim 2, characterized in that dyes of the general formula
Figure imgb0057
 used in the
R⁹ is hydrogen or C₁- to C₄-alkoxy,
R¹⁰ and R¹¹, independently of one another, are hydrogen, C₁- to C₄-alkyl, C₁- to C₄-alkoxycarbonylethyl or C₂- to C₅-alkanoyloxyethyl. 6. Verfahren gemäß Anspruch 4, dadurch gekennzeichnet, daß man Farbstoffe verwendet, in denen
Figure imgb0058
 steht.6. The method according to claim 4, characterized in that dyes are used in which
Figure imgb0058
 stands. 7. Verfahren gemäß Anspruch 2, dadurch gekennzeichnet, daß man Farbstoffe der allgemeinen Formel
Figure imgb0059
 verwendet, worin R, Rʹ, R¹, R² und R⁴ die in Anspruch 1 angegebene Be­deutung haben.7. The method according to claim 2, characterized in that dyes of the general formula
Figure imgb0059
 used, wherein R, Rʹ, R¹, R² and R⁴ have the meaning given in claim 1. 8. Verfahren gemäß Anspruch 7, dadurch gekennzeichnet, daß
      R und Rʹ unabhängig voneinander für Wasserstoff, für gegebenenfalls durch Hydroxy, Cyan oder Phenyl substituiertes C₁- bis C₄-Alkyl, für C₁- bis C₄-Alkoxy-C₂- bis C₄-alkyl, C₁- bis C₄-Alkoxycarbonyl-C₁- bis C₄-alkyl, C₁- bis C₄-Alkoxycarbonyloxy-C₁- bis C₄-alkyl, C₁- bis C₄-Fluoralkyl, Phenyl, Methylphenyl oder Methoxyphenyl,
      R¹ und R² unabhängig voneinander für Wasserstoff, C₁- bis C₄-Alkyl, C₁- bis C₄-Alkoxy oder C₁- bis C₄-Alkylthio und
      R⁴ für C₁- bis C₄-Alkyl, Phenyl, Benzyl oder Cyan stehen.8. The method according to claim 7, characterized in that
R and Rʹ independently of one another for hydrogen, for C₁- to C Alkyl-alkyl optionally substituted by hydroxy, cyano or phenyl, for C₁- to C₄-alkoxy-C₂- to C₄-alkyl, C₁- to C₄-alkoxycarbonyl-C₁- to C₄ -alkyl, C₁- to C₄-alkoxycarbonyloxy-C₁- to C₄-alkyl, C₁- to C₄-fluoroalkyl, phenyl, methylphenyl or methoxyphenyl,
R¹ and R² independently of one another for hydrogen, C₁- to C₄-alkyl, C₁- to C₄-alkoxy or C₁- to C₄-alkylthio and
R⁴ are C₁ to C₄ alkyl, phenyl, benzyl or cyan. 9. Verfahren gemäß Anspruch 7, dadurch gekennzeichnet, daß
      R und Rʹ unabhängig voneinander für Wasserstoff, C₁- bis C₄-Alkyl, Phenyl, C₂- bis C₅-Alkanoyloxyethyl, C₁- bis C₄-Alkoxycarbonylethyl, C₁- bis C₄-Alkoxycarbonyloxyethyl, Benzyl oder Cyanethyl,
      R¹ und R² unabhängig voneinander für Wasserstoff, C₁- bis C₄-Alkyl, C₁- bis C₄-Alkoxy oder C₁- bis C₄-Thioalkyl und
      R⁴ für C₁- bis C₄-Alkyl oder Phenyl stehen.9. The method according to claim 7, characterized in that
R and Rʹ independently of one another are hydrogen, C₁- to C₄-alkyl, phenyl, C₂- to C₅-alkanoyloxyethyl, C₁- to C₄-alkoxycarbonylethyl, C₁- to C₄-alkoxycarbonyloxyethyl, benzyl or cyanoethyl,
R¹ and R² independently of one another for hydrogen, C₁- to C₄-alkyl, C₁- to C₄-alkoxy or C₁- to C₄-thioalkyl and
R⁴ are C₁ to C₄ alkyl or phenyl.
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EP0490338A1 (en) * 1990-12-14 1992-06-17 Eastman Kodak Company Yellow dye mixture for thermal color proofing
US5256624A (en) * 1991-04-18 1993-10-26 Basf Aktiengesellschaft Transfer of methine dyes
EP0550817A2 (en) * 1991-11-14 1993-07-14 Dai Nippon Printing Co., Ltd. Thermal transfer sheet
EP0550817A3 (en) * 1991-11-14 1993-07-28 Dai Nippon Printing Co., Ltd. Thermal transfer sheet
US5369078A (en) * 1991-11-14 1994-11-29 Dai Nippon Printing Co., Ltd. Thermal transfer sheet
US5607895A (en) * 1991-11-14 1997-03-04 Dai Nippon Printing Co., Ltd. Thermal transfer sheet
US5550098A (en) * 1991-11-14 1996-08-27 Dai Nippon Printing Co., Ltd. Thermal transfer sheet
EP0594239A1 (en) * 1992-10-20 1994-04-27 Agfa-Gevaert N.V. Dye-donor element comprising magenta tricyanovinylaniline dyes
EP0593817A1 (en) * 1992-10-20 1994-04-27 Agfa-Gevaert N.V. Dye-donor element comprising tricyanovinylaniline dyes
US5518983A (en) * 1992-10-21 1996-05-21 Imperial Chemical Industries Plc Dye diffusion thermal transfer printing
WO1994008797A1 (en) * 1992-10-21 1994-04-28 Imperial Chemical Industries Plc Dye diffusion thermal transfer printing
US5635442A (en) * 1992-10-21 1997-06-03 Imperial Chemical Industries Plc Dye diffusion thermal transfer printing
EP0701907A1 (en) 1994-09-13 1996-03-20 Agfa-Gevaert N.V. A dye donor element for use in a thermal dye transfer process
EP0733487A2 (en) 1995-01-30 1996-09-25 Agfa-Gevaert N.V. Method for making a lithographic printing plate requiring no wet processing
US6951841B2 (en) 1995-11-29 2005-10-04 Novartis Ag Pharmaceutical compositions of macrolides or cyclosporine with a polyethoxylated saturated hydroxy-fatty acid
EP0792757A1 (en) 1996-02-27 1997-09-03 Agfa-Gevaert N.V. Dye donor element for use in thermal transfer printing

Also Published As

Publication number Publication date
US4999026A (en) 1991-03-12
DE3766194D1 (en) 1990-12-20
EP0258856B1 (en) 1990-11-14
JP2677564B2 (en) 1997-11-17
EP0258856B2 (en) 1994-12-07
DE3630279A1 (en) 1988-03-17
EP0258856A3 (en) 1988-08-24
JPS6369693A (en) 1988-03-29

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