EP0439200A1 - Transfer process using methine dyes containing bichromophoric cyano-groups - Google Patents

Transfer process using methine dyes containing bichromophoric cyano-groups Download PDF

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Publication number
EP0439200A1
EP0439200A1 EP91101566A EP91101566A EP0439200A1 EP 0439200 A1 EP0439200 A1 EP 0439200A1 EP 91101566 A EP91101566 A EP 91101566A EP 91101566 A EP91101566 A EP 91101566A EP 0439200 A1 EP0439200 A1 EP 0439200A1
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Prior art keywords
alkyl
dyes
cyano
hydrogen
independently
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EP91101566A
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German (de)
French (fr)
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EP0439200B1 (en
Inventor
Volker Dr. Bach
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
    • B41M5/3854—Dyes containing one or more acyclic carbon-to-carbon double bonds, e.g., di- or tri-cyanovinyl, methine
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/913—Material designed to be responsive to temperature, light, moisture
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/914—Transfer or decalcomania

Definitions

  • the present invention relates to a new process for the transfer of bichromophoric cyano group-containing methine dyes, which have two individual chromophores which are connected to one another via a bridge member, from a support to a plastic-coated paper with the aid of an energy source.
  • a transfer sheet containing a thermally transferable dye in one or more binders, optionally together with suitable auxiliaries is supported on a support with an energy source, e.g. with a heating head, heated by short heating impulses (duration: fractions of a second) from the back, whereby the dye migrates from the transfer sheet and diffuses into the surface coating of a recording medium.
  • an energy source e.g. with a heating head
  • short heating impulses duration: fractions of a second
  • the object of the present invention was to provide a new process for the transfer of dyes, bichromophoric methine dyes containing cyano groups being used as the dyes and in doing so meeting the above requirements as well as possible.
  • the bridge member L which does not allow conjugation of ⁇ electrons between the residues Z and Y, generally obeys the formula -E1-D-E2- wherein D a chemical bond, oxygen, -SO2-, -O-CO-O-, 1,4-cyclohexylene, phenylene, -O-CO- (CH2) 1-CO-O-, -O- (CH2) m -O -, where l is 1 to 10 and m is 2 to 10, E1 and E2 are identical or different and each independently represent a chemical bond or C1-C15 alkylene.
  • Suitable radicals R1, R2, R3, R4, R5 and R6 are e.g. Methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, 2-methylpentyl, heptyl, octyl, 2-ethylhexyl or isooctyl.
  • R1 and R5 are, for example, nonyl, isononyl, decyl, isodecyl, 2-methoxyethyl, 2-ethoxyethyl, 2-propoxyethyl, 2-butoxyethyl, 2- or 3-methoxypropyl, 2- or 3-ethoxypropyl, 2- or 3- Propoxypropyl, 2- or 3-butoxypropyl, 4-methoxybutyl, 4-ethoxybutyl, 4-butoxybutyl, 2-cyanoethyl, 3-cyanopropyl, 4-cyanobutyl, 2-hydroxyethyl,
  • Residues R4 are still e.g. Phenyl, 2-, 3- or 4-methylphenyl, 2- or 4-isopropylphenyl, 2-butylphenyl, 2-, 3- or 4-methoxyphenyl, 2-propoxyphenyl, 4-butoxyphenyl, 2- (but-2-oxy) phenyl, benzyl, 2-, 3- or 4-methylbenzyl, 2-, 3- or 4-methoxybenzyl, fluorine, chlorine, bromine, thien-2-yl or thien-3-yl.
  • R2 and R3 are also methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, pentyloxy, isopentyloxy, neopentyloxy, hexyloxy, formylamino, acetylamino, propionylamino, butyrylamino, methylsulfonylamino, ethylsulfonylaminoamylsulfonamylamino, propylsulfonamylamyl, sulfylsulfonamyl, sulfylsulfonamyl, propylsulfonamyl,
  • Residues X are e.g. Methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, 2-methoxyethoxycarbonyl, methylcarbamoyl, ethylcarbamoyl, 2-methoxyethylcarbamoyl, cyclopentyloxycarbonyl, cyclohexyloxycarbonyl, cycloheptyloxycarbonyl, cyclopentylcarbamoylloyl cyclohexylcarbamyll cyclohexylcarbamyll cyclohexylcarbamyll cyclohexylcarbamyll cyclohexylcarbamyll cyclohexylcarbamyll cyclohexylcarbamoyl.
  • Residues E1 and E2 are e.g. Methylene, 1,2-ethylene, ethylidene, 1,2- or 1,3-propylene or 1,4-, 1,3- or 2,3-butylene.
  • Residues D are, for example
  • one or more methine dyes of the formula I are transferred, in which R1 and R5 independently of one another hydrogen, C1-C6-alkyl or cyclohexyl, R2 and R3 independently of one another hydrogen, methyl, methoxy or acetylamino, R4 Hydrogen or C1-C6-alkyl, optionally substituted by methyl or methoxy-substituted phenyl, thien-2-yl or thien-3-yl and R6 Is hydrogen or C1-C6 alkyl.
  • the bridge member L has the formula -E1-D-E2- has, wherein E1 and E2 independently of one another C1-C4 alkylene and D a chemical bond, oxygen, -SO2-, -O-CO- (CH2) 1-CO-O, where 1 is 2 to 4, or mean.
  • bichromophoric methine dyes used in the process according to the invention are generally known and are e.g. in GB-A-1 201 925, US-A-3 553 245, DE-A-1 569 678, DE-A-2 519 592, DE-A-3 020 473, WO-A-86/04904 or WO-A-87/01121 described or can be obtained by the methods mentioned there.
  • the dyes transferred in the process according to the invention are generally distinguished by improved fixation in the recording medium at room temperature, easier thermal transferability, higher lightfastness, higher stability to moisture and chemical substances, better solubility in organic solvents, higher Ribbon stability and higher color purity.
  • the dyes of the formula I used in the new process are advantageously suitable for producing a trichromatic system required for subtractive color mixing.
  • the good transferability allows a large variation of the plastics used as a receiver and thus a very good adaptation of the dyes to the overall system (donor / receiver).
  • the dyes are processed into a printing ink in a suitable organic solvent or in mixtures of solvents, with one or more binders, if appropriate with the addition of auxiliaries.
  • a printing ink in a suitable organic solvent or in mixtures of solvents, with one or more binders, if appropriate with the addition of auxiliaries.
  • the printing ink can be applied to the inert support using a doctor blade and the dyeing can be dried in air.
  • Suitable organic solvents for the dyes I are, for example, those in which the solubility of the dyes I at a temperature of 20 ° C. is greater than 1% by weight, preferably greater than 5% by weight.
  • Examples include ethanol, propanol, isobutanol, tetrahydrofuran, methylene chloride, methyl ethyl ketone, cyclopentanone, cyclohexanone, toluene, chlorobenzene or mixtures thereof.
  • binders All resins or polymer materials which are soluble in organic solvents and are capable of binding the dye to the inert support in an abrasion-resistant manner are suitable as binders. Preference is given to those binders which, after the printing ink has dried in air, absorb the dye in the form of a clear, transparent film without any visible crystallization of the dye occurring.
  • binders are cellulose derivatives, e.g. Methyl cellulose, ethyl cellulose, ethyl hydroxyethyl cellulose, hydroxypropyl cellulose, cellulose acetate or cellulose acetobutyrate, starch, alginates, alkyd resin, vinyl resin, polyvinyl alcohol, polyvinyl acetate, polyvinyl butyrate or polyvinyl pyrrolidone.
  • cellulose derivatives e.g. Methyl cellulose, ethyl cellulose, ethyl hydroxyethyl cellulose, hydroxypropyl cellulose, cellulose acetate or cellulose acetobutyrate, starch, alginates, alkyd resin, vinyl resin, polyvinyl alcohol, polyvinyl acetate, polyvinyl butyrate or polyvinyl pyrrolidone.
  • Polymers and copolymers of acrylates or their derivatives such as polyacrylic acid, polymethyl methacrylate or styrene-acrylate copolymers, polyester resins, polyamide resins, polyurethane resins or natural CH resins, such as gum arabic, are also suitable as binders.
  • Other suitable binders are e.g. in DE-A-3 524 519.
  • Preferred binders are ethyl cellulose, ethyl hydroxyethyl cellulose, polyvinyl butyrate or polyvinyl acetate.
  • the weight ratio of binder: dye is generally 1: 1 to 10: 1.
  • Inert carriers are, for example, tissue paper, blotting paper or glassine paper or plastic films with good heat resistance, for example metal-coated polyester, polyamide or polyimide.
  • the inert carrier is optionally additionally coated with a slip layer on the side facing the thermal head in order to prevent the thermal head from sticking to the carrier material.
  • Suitable lubricants are described, for example, in EP-A-216 483 or EP-A-227 095.
  • the thickness of the dye carrier is generally 3 to 30 microns, preferably 5 to 10 microns.
  • all temperature-stable plastic layers with an affinity for the dyes to be transferred can be used as the dye-receiving layer, e.g. modified polycarbonates or polyester.
  • Suitable formulations for the receiver layer composition are e.g. in EP-A-227 094, EP-A-133 012, EP-A-133 011, EP-A-111 004, JP-A-199 997/1986, JP-A-283 595/1986, JP- A-237 694/1986 or JP-A-127 392/1986 described in detail.
  • the transmission takes place by means of an energy source, e.g. by means of a laser or by means of a thermal head which must be able to be heated to a temperature of ⁇ 300 ° C. so that the dye transfer can take place in the time range t: 0 ⁇ t ⁇ 15 msec.
  • the dye migrates from the transfer sheet and diffuses into the surface coating of the recording medium.
  • the following methine dyes can be transferred in an analogous manner.

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

Abstract

A process for the transfer of bichromophoric methine dyes from a carrier to paper coated with plastic with the aid of an energy source, in which a carrier is used on which are situated one or more dyes of the formula <IMAGE> in which   L represents a bridging member which does not permit any conjugation of pi -electrons between the radicals Z and Y,   X denotes cyano, C1-C6-alkoxycarbonyl or C1-C6-monoalkylcarbamoyl, where the alkyl groups can be interrupted by oxygen atoms, C5-C7-cycloalkoxycarbonyl, C5-C7-monocycloalkylcarbamoyl, phenoxycarbonyl, or monophenylcarbamoyl and   Y and Z independently of one another denote an optionally benzo-fused aminophenylene radical or a heterocyclic radical.

Description

Die vorliegende Erfindung betrifft ein neues Verfahren zur Übertragung von bichromophoren Cyanogruppen enthaltenden Methinfarbstoffen, die zwei, über ein Brückenglied miteinander verbundene, Einzelchromophore aufweisen, von einem Träger auf ein mit Kunststoff beschichtetes Papier mit Hilfe einer Energiequelle.The present invention relates to a new process for the transfer of bichromophoric cyano group-containing methine dyes, which have two individual chromophores which are connected to one another via a bridge member, from a support to a plastic-coated paper with the aid of an energy source.

Beim Thermotransferdruckverfahren wird ein Transferblatt, das einen thermisch transferierbaren Farbstoff in einem oder mehreren Bindemitteln, gegebenenfalls zusammen mit geeigneten Hilfsmitteln, auf einem Träger enthält, mit einer Energiequelle, z.B. mit einem Heizkopf, durch kurze Heizimpulse (Dauer: Bruchteile einer Sekunde) von der Rückseite her erhitzt, wodurch der Farbstoff aus dem Transferblatt migriert und in die Oberflächenbeschichtung eines Aufnahmemediums hineindiffundiert. Der wesentliche Vorteil dieses Verfahrens besteht darin, daß die Steuerung der zu übertragenden Farbstoffmenge (und damit die Farbabstufung) durch Einstellung der von der Energiequelle abzugebenden Energie leicht möglich ist.In the thermal transfer printing process, a transfer sheet containing a thermally transferable dye in one or more binders, optionally together with suitable auxiliaries, is supported on a support with an energy source, e.g. with a heating head, heated by short heating impulses (duration: fractions of a second) from the back, whereby the dye migrates from the transfer sheet and diffuses into the surface coating of a recording medium. 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 released from the energy source.

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

  • leichte thermische Transferierbarkeit,
  • geringe Migration innerhalb oder aus der Oberflächenbeschichtung des Aufnahmemediums bei Raumtemperatur,
  • hohe thermische und photochemische Stabilität sowie Resistenz gegen Feuchtigkeit und chemische Stoffe,
  • für subtraktive Farbmischung die geeigneten Farbtöne aufweisen,
  • einen hohen molaren Absorptionskoeffizienten aufweisen,
  • bei Lagerung des Transferblattes nicht auskristallisieren.
In general, the color recording is carried out using the three subtractive primary colors yellow, magenta, cyan (and possibly black). To enable optimal color recording, the dyes must have the following properties:
  • easy thermal transferability,
  • low migration within or from the surface coating of the recording medium at room temperature,
  • high thermal and photochemical stability as well as resistance to moisture and chemical substances,
  • have suitable shades for subtractive color mixing,
  • have a high molar absorption coefficient,
  • do not crystallize when storing the transfer sheet.

Diese Forderungen sind erfahrungsgemäß gleichzeitig sehr schwierig zu erfüllen.Experience has shown that these requirements are very difficult to meet at the same time.

Daher entsprechen die meisten der bekannten, für den thermischen Transferdruck verwendeten Farbstoffe nicht dem geforderten Anforderungsprofil.Therefore, most of the known dyes used for thermal transfer printing do not meet the required profile.

Aufgabe der vorliegenden Erfindung war es nun, ein neues Verfahren zur Übertragung von Farbstoffen bereitzustellen, wobei als Farbstoffe bichromophore Methinfarbstoffe, die Cyanogruppen enthalten, zur Anwendung kommen und dabei die obengenannten Forderungen möglichst gut erfüllen sollten.The object of the present invention was to provide a new process for the transfer of dyes, bichromophoric methine dyes containing cyano groups being used as the dyes and in doing so meeting the above requirements as well as possible.

Es wurde nun gefunden, daß die Übertragung von bichromophoren Methinfarbstoffen von einem Träger auf ein mit Kunststoff beschichtetes Papier mit Hilfe einer Energiequelle vorteilhaft gelingt, wenn man einen Träger verwendet, auf dem sich ein oder mehrere Farbstoffe der Formel I

Figure imgb0001

befinden, in der
L
für ein Brückenglied, das keine Konjugation von π-Elektronen zwischen den Resten Z und Y zuläßt,
X
gleich oder verschieden ist und jeweils für Cyano, C₁-C₆-Alkoxycarbonyl oder C₁-C₆-Monoalkylcarbamoyl, wobei die Alkylgruppen jeweils durch 1 oder 2 Sauerstoffatome unterbrochen sein können, C₅-C₇-Cycloalkoxycarbonyl, C₅-C₇-Monocycloalkylcarbamoyl, Phenoxycarbonyl oder Monophenylcarbamoyl und
Z und Y
gleich oder verschieden sind und in Verbindung mit dem Brückenglied L unabhängig voneinander jeweils für einen Rest der Formel
Figure imgb0002
stehen, worin

n
gleich 0 oder 1,
R¹ und R⁵
gleich oder verschieden sind und unabhängig voneinander jeweils Alkyl, Alkoxyalkyl, Alkoxycarbonylalkyl oder Alkanoyloxyalkyl, wobei diese Reste jeweils bis zu 10 Kohlenstoffatome ufweisen und gegebenenfalls durch Hydroxy oder Cyano substituiert sein können, Wasserstoff, Benzyl, Cyclohexyl, Phenyl oder Tolyl,
R² und R³
gleich oder verschieden sind und unabhängig voneinander jeweils C₁-C₈-Alkyl, C₁-C₆-Alkoxy, C₁-C₆-Alkanoylamino oder C₁-C₆-Alkylsulfonylamino,
R⁴
Wasserstoff, Halogen, C₁-C₈-Alkyl, gegebenenfalls durch C₁-C₄-Alkyl oder C₁-C₄-Alkoxy substituiertes Phenyl, gegebenenfalls durch C₁-C₄-Alkyl oder C₁-C₄-Alkoxy substituiertes Benzyl, Cyclohexyl, Thienyl oder den Rest -NHR¹, wobei R¹ die obengenannte Bedeutung besitzt, und
R⁶
Wasserstoff oder C₁-C₈-Alkyl bedeuten.
It has now been found that the transfer of bichromophoric methine dyes from a support onto a plastic-coated paper with the aid of an energy source is advantageously achieved when using a support on which one or more dyes of the formula I
Figure imgb0001
are in the
L
for a bridge member that does not allow conjugation of π electrons between the residues Z and Y,
X
is identical or different and in each case for cyano, C₁-C₆-alkoxycarbonyl or C₁-C₆-monoalkylcarbamoyl, where the alkyl groups can each be interrupted by 1 or 2 oxygen atoms, C₅-C₇-cycloalkoxycarbonyl, C₅-C₇-monocycloalkylcarbamoyl, phenoxycarbonyl or monophenylcarbamoyl and
Z and Y
are identical or different and in connection with the bridge member L independently of one another each for a radical of the formula
Figure imgb0002
stand in what
n
equal to 0 or 1,
R¹ and R⁵
are identical or different and are each independently of the other alkyl, alkoxyalkyl, alkoxycarbonylalkyl or alkanoyloxyalkyl, where these radicals each have up to 10 carbon atoms and can optionally be substituted by hydroxy or cyano, hydrogen, benzyl, cyclohexyl, phenyl or tolyl,
R² and R³
are identical or different and are each independently C₁-C₈-alkyl, C₁-C₁-alkoxy, C₁-C₁-alkanoylamino or C₁-C₁-alkylsulfonylamino,
R⁴
Hydrogen, halogen, C₁-C₈-alkyl, optionally substituted by C₁-C₄-alkyl or C₁-C₄-alkoxy, phenyl optionally substituted by C₁-C₄-alkyl or C₁-C₄-alkoxy benzyl, cyclohexyl, thienyl or the radical -NHR¹ , where R¹ has the meaning given above, and
R⁶
Is hydrogen or C₁-C₈ alkyl.

Das Brückenglied L, das keine Konjugation von π-Elektronen zwischen den Resten Z und Y zuläßt, gehorcht im allgemeinen der Formel



        -E¹-D-E²-



worin
D
eine chemische Bindung, Sauerstoff, -SO₂-, -O-CO-O-, 1,4-Cyclohexylen, Phenylen, -O-CO-(CH₂)₁-CO-O-, -O-(CH₂)m-O-,

Figure imgb0003

wobei l für 1 bis 10 und m für 2 bis 10 stehen,
Figure imgb0004
E¹ und E²
gleich oder verschieden sind und unabhängig voneinander jeweils eine chemische Bindung oder C₁-C₁₅-Alkylen bedeuten.The bridge member L, which does not allow conjugation of π electrons between the residues Z and Y, generally obeys the formula



-E¹-D-E²-



wherein
D
a chemical bond, oxygen, -SO₂-, -O-CO-O-, 1,4-cyclohexylene, phenylene, -O-CO- (CH₂) ₁-CO-O-, -O- (CH₂) m -O -,
Figure imgb0003
where l is 1 to 10 and m is 2 to 10,
Figure imgb0004
E¹ and E²
are identical or different and each independently represent a chemical bond or C₁-C₁₅ alkylene.

Alle in den obengenannten Formeln auftretenden Alkyl- und Alkylenreste können sowohl geradkettig als auch verzweigt sein.All alkyl and alkylene radicals occurring in the above formulas can be both straight-chain and branched.

Geeignete Reste R¹, R², R³, R⁴, R⁵ und R⁶ sind z.B. Methyl, Ethyl, Propyl, Isopropyl, Butyl, Isobutyl, sec-Butyl, tert-Butyl, Pentyl, Isopentyl, Neopentyl, tert-Pentyl, Hexyl, 2-Methylpentyl, Heptyl, Octyl, 2-Ethylhexyl oder Isooctyl.Suitable radicals R¹, R², R³, R⁴, R⁵ and R⁶ are e.g. Methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, 2-methylpentyl, heptyl, octyl, 2-ethylhexyl or isooctyl.

Reste R¹ und R⁵ sind weiterhin z.B. Nonyl, Isononyl, Decyl, Isodecyl, 2-Methoxyethyl, 2-Ethoxyethyl, 2-Propoxyethyl, 2-Butoxyethyl, 2-oder 3-Methoxypropyl, 2-oder 3-Ethoxypropyl, 2- oder 3-Propoxypropyl, 2-oder 3-Butoxypropyl, 4-Methoxybutyl, 4-Ethoxybutyl, 4-Butoxybutyl, 2-Cyanoethyl, 3-Cyanopropyl, 4-Cyanobutyl, 2-Hydroxyethyl,

Figure imgb0005
R¹ and R⁵ are, for example, nonyl, isononyl, decyl, isodecyl, 2-methoxyethyl, 2-ethoxyethyl, 2-propoxyethyl, 2-butoxyethyl, 2- or 3-methoxypropyl, 2- or 3-ethoxypropyl, 2- or 3- Propoxypropyl, 2- or 3-butoxypropyl, 4-methoxybutyl, 4-ethoxybutyl, 4-butoxybutyl, 2-cyanoethyl, 3-cyanopropyl, 4-cyanobutyl, 2-hydroxyethyl,
Figure imgb0005

Reste R⁴ sind weiterhin z.B. Phenyl, 2-, 3- oder 4-Methylphenyl, 2- oder 4-Isopropylphenyl, 2-Butylphenyl, 2-, 3- oder 4-Methoxyphenyl, 2-Propoxyphenyl, 4-Butoxyphenyl, 2-(But-2-oxy)phenyl, Benzyl, 2-, 3- oder 4-Methylbenzyl, 2-, 3- oder 4-Methoxybenzyl, Fluor, Chlor, Brom, Thien-2-yl oder Thien-3-yl.Residues R⁴ are still e.g. Phenyl, 2-, 3- or 4-methylphenyl, 2- or 4-isopropylphenyl, 2-butylphenyl, 2-, 3- or 4-methoxyphenyl, 2-propoxyphenyl, 4-butoxyphenyl, 2- (but-2-oxy) phenyl, benzyl, 2-, 3- or 4-methylbenzyl, 2-, 3- or 4-methoxybenzyl, fluorine, chlorine, bromine, thien-2-yl or thien-3-yl.

R² und R³ sind weiterhin Methoxy, Ethoxy, Propoxy, Isopropoxy, Butoxy, Isobutoxy, sec-Butoxy, Pentyloxy, Isopentyloxy, Neopentyloxy, Hexyloxy, Formylamino, Acetylamino, Propionylamino, Butyrylamino, Methylsulfonylamino, Ethylsulfonylamino, Propylsulfonylamino, Isopropylsulfonylamino oder Butylsulfonylamino.R² and R³ are also methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, pentyloxy, isopentyloxy, neopentyloxy, hexyloxy, formylamino, acetylamino, propionylamino, butyrylamino, methylsulfonylamino, ethylsulfonylaminoamylsulfonamylamino, propylsulfonamylamyl, sulfylsulfonamyl, sulfylsulfonamyl, propylsulfonamyl,

Reste X sind z.B. Methoxycarbonyl, Ethoxycarbonyl, Propoxycarbonyl, Isopropoxycarbonyl, Butoxycarbonyl, 2-Methoxyethoxycarbonyl, Methylcarbamoyl, Ethylcarbamoyl, 2-Methoxyethylcarbamoyl, Cyclopentyloxycarbonyl, Cyclohexyloxycarbonyl, Cycloheptyloxycarbonyl, Cyclopentylcarbamoyl, Cyclohexylcarbamoyl oder Cycloheptylcarbamoyl.Residues X are e.g. Methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, 2-methoxyethoxycarbonyl, methylcarbamoyl, ethylcarbamoyl, 2-methoxyethylcarbamoyl, cyclopentyloxycarbonyl, cyclohexyloxycarbonyl, cycloheptyloxycarbonyl, cyclopentylcarbamoylloyl cyclohexylcarbamyll cyclohexylcarbamyll cyclohexylcarbamyll cyclohexylcarbamyll cyclohexylcarbamyll cyclohexylcarbamoyl.

Reste E¹ und E² sind z.B. Methylen, 1,2-Ethylen, Ethyliden, 1,2- oder 1,3-Propylen oder 1,4-, 1,3- oder 2,3-Butylen.Residues E¹ and E² are e.g. Methylene, 1,2-ethylene, ethylidene, 1,2- or 1,3-propylene or 1,4-, 1,3- or 2,3-butylene.

Reste D sind z.B.

Figure imgb0006
Residues D are, for example
Figure imgb0006

Vorteilhafte Ergebnisse erhält man bei der Übertragung ein oder mehrerer Methinfarbstoffe der Formel I, worin die Reste Z und Y den Formeln IIa bis IIg gehorchen.Advantageous results are obtained when one or more methine dyes of the formula I are transferred, in which the radicals Z and Y obey the formulas IIa to IIg.

Weiterhin gute Ergebnisse erzielt man, wenn man ein oder mehrere Methinfarbstoffe der Formel I überträgt, worin
R¹ und R⁵
unabhängig voneinander Wasserstoff, C₁-C₆-Alkyl oder Cyclohexyl,
R² und R³
unabhängig voneinander Wasserstoff, Methyl, Methoxy oder Acetylamino,
R⁴
Wasserstoff oder C₁-C₆-Alkyl, gegebenenfalls durch Methyl oder Methoxy substituiertes Phenyl, Thien-2-yl oder Thien-3-yl und
R⁶
Wasserstoff oder C₁-C₆-Alkyl bedeuten.Further good results are obtained if one or more methine dyes of the formula I are transferred, in which
R¹ and R⁵
independently of one another hydrogen, C₁-C₆-alkyl or cyclohexyl,
R² and R³
independently of one another hydrogen, methyl, methoxy or acetylamino,
R⁴
Hydrogen or C₁-C₆-alkyl, optionally substituted by methyl or methoxy-substituted phenyl, thien-2-yl or thien-3-yl and
R⁶
Is hydrogen or C₁-C₆ alkyl.

Besonders gute Ergebnisse werden erzielt, wenn man einen oder mehrere Methinfarbstoffe der Formel I überträgt, worin das Brückenglied L die Formel



        -E¹-D-E²-



aufweist, wobei
E¹ und E²
unabhängig voneinander C₁-C₄-Alkylen und
D
eine chemische Bindung, Sauerstoff, -SO₂-, -O-CO-(CH₂)₁-CO-O, wobei 1 für 2 bis 4 steht,

Figure imgb0007

oder
Figure imgb0008
 bedeuten.Particularly good results are achieved if one or more methine dyes of the formula I are transferred, in which the bridge member L has the formula



-E¹-D-E²-



has, wherein
E¹ and E²
independently of one another C₁-C₄ alkylene and
D
a chemical bond, oxygen, -SO₂-, -O-CO- (CH₂) ₁-CO-O, where 1 is 2 to 4,
Figure imgb0007
or
Figure imgb0008
 mean.

Besonders gute Ergebnisse werden weiterhin erzielt, wenn man einen oder mehrere Methinfarbstoffe der Formel I überträgt, worin X Cyano bedeutet.Particularly good results are also achieved if one or more methine dyes of the formula I are transferred, in which X is cyano.

Die im erfindungsgemäßen Verfahren zur Anwendung kommenden bichromophoren Methinfarbstoffe sind in der Regel bekannt und z.B. in der GB-A-1 201 925, US-A-3 553 245, DE-A-1 569 678, DE-A-2 519 592, DE-A-3 020 473, WO-A-86/04904 oder WO-A-87/01121 beschrieben oder können nach den dort genannten Methoden erhalten werden.The bichromophoric methine dyes used in the process according to the invention are generally known and are e.g. in GB-A-1 201 925, US-A-3 553 245, DE-A-1 569 678, DE-A-2 519 592, DE-A-3 020 473, WO-A-86/04904 or WO-A-87/01121 described or can be obtained by the methods mentioned there.

Im Vergleich zu den bei den bekannten Verfahren verwendeten Farbstoffen zeichnen sich die beim erfindungsgemäßen Verfahren übertragenen Farbstoffe im allgemeinen durch verbesserte Fixierung im Aufnahmemedium bei Raumtemperatur, leichtere thermische Transferierbarkeit, höhere Lichtechtheit, höhere Stabilität gegenüber Feuchtigkeit und chemischen Stoffen, bessere Löslichkeit in organischen Lösungsmitteln, höhere Farbbandstabilität und höhere Farbtonreinheit aus.Compared to the dyes used in the known processes, the dyes transferred in the process according to the invention are generally distinguished by improved fixation in the recording medium at room temperature, easier thermal transferability, higher lightfastness, higher stability to moisture and chemical substances, better solubility in organic solvents, higher Ribbon stability and higher color purity.

Weiterhin ist überraschend, daß die Farbstoffe der Formel I gut transferierbar sind und hohe Farbbandstabilität aufweisen, obwohl sie ein sehr hohes Molekulargewicht aufweisen.It is also surprising that the dyes of the formula I are readily transferable and have high ribbon stability, even though they have a very high molecular weight.

Aufgrund ihrer hohen molaren Extinktionskoeffizienten und ihrer hohen Brillanz sind die im neuen Verfaren angewandten Farbstoffe der Formel I für die Herstellung eines, für die subtraktive Farbmischung erforderlichen, Trichromiesystems vorteilhaft geeignet.Because of their high molar extinction coefficients and their high brilliance, the dyes of the formula I used in the new process are advantageously suitable for producing a trichromatic system required for subtractive color mixing.

Zusätzlich erlaubt die gute Transferierbarkeit eine große Variation der als Nehmer verwendeten Kunststoffe und somit eine sehr gute Anpassung der Farbstoffe in das Gesamtsystem (Geber/Nehmer).In addition, the good transferability allows a large variation of the plastics used as a receiver and thus a very good adaptation of the dyes to the overall system (donor / receiver).

Zur Herstellung der für das erfindungsgemäße Verfahren benötigten Farbstoffträger werden die Farbstoffe in einem geeigneten organischen Lösungsmittel oder in Mischungen von Lösungsmitteln, mit einem oder mehreren Bindemitteln, gegebenenfalls unter Zugabe von Hilfsmitteln, zu einer Druckfarbe verarbeitet. Diese enthält den Farbstoff vorzugsweise in molekular-dispers gelöster Form. Die Druckfarbe kann mittels einer Rakel auf den inerten Träger aufgetragen und die Färbung an der Luft getrocknet werden.To produce the dye carriers required for the process according to the invention, the dyes are processed into a printing ink in a suitable organic solvent or in mixtures of solvents, with one or more binders, if appropriate with the addition of auxiliaries. This contains the dye preferably in a molecularly dispersed, dissolved form. The printing ink can be applied to the inert support using a doctor blade and the dyeing can be dried in air.

Geeignete organische Lösungsmittel für die Farbstoffe I sind z.B. solche, in denen die Löslichkeit der Farbstoffe I bei einer Temperatur von 20°C größer als 1 Gew.-%, vorzugsweise größer als 5 Gew.-% ist.Suitable organic solvents for the dyes I are, for example, those in which the solubility of the dyes I at a temperature of 20 ° C. is greater than 1% by weight, preferably greater than 5% by weight.

Beispielhaft seien Ethanol, Propanol, Isobutanol, Tetrahydrofuran, Methylenchlorid, Methylethylketon, Cyclopentanon, Cyclohexanon, Toluol, Chlorbenzol oder deren Mischungen genannt.Examples include ethanol, propanol, isobutanol, tetrahydrofuran, methylene chloride, methyl ethyl ketone, cyclopentanone, cyclohexanone, toluene, chlorobenzene or mixtures thereof.

Als Bindemittel kommen alle Resins oder Polymermaterialien in Betracht, welche in organischen Lösungsmitteln löslich sind und den Farbstoff an den inerten Träger abriebfest zu binden vermögen. Dabei werden solche Bindemittel bevorzugt, welche den Farbstoff nach Trocknung der Druckfarbe an der Luft in Form eines klaren, transparenten Films aufnehmen, ohne daß dabei eine sichtbare Auskristallisation des Farbstoffes auftritt.All resins or polymer materials which are soluble in organic solvents and are capable of binding the dye to the inert support in an abrasion-resistant manner are suitable as binders. Preference is given to those binders which, after the printing ink has dried in air, absorb the dye in the form of a clear, transparent film without any visible crystallization of the dye occurring.

Beispiele für solche Bindemittel sind Cellulosederivate, z.B. Methylcellulose, Ethylcellulose, Ethylhydroxyethylcellulose, Hydroxypropylcellulose, Celluloseacetat oder Celluloseacetobutyrat, Stärke, Alginate, Alkydresins, Vinylresins, Polyvinylalkohol, Polyvinylacetat, Polyvinylbutyrat oder Polyvinylpyrrolidone. Weiterhin kommen Polymere und Copolymere von Acrylaten oder deren Derivate, wie Polyacrylsäure, Polymethylmethacrylat oder Styrolacrylatcopolymere, Polyesterresins, Polyamidresins, Polyurethanresins oder natürliche CH-Resins, wie Gummi Arabicum, als Bindemittel in Betracht. Weitere geeignete Bindemittel sind z.B. in der DE-A-3 524 519 beschrieben.Examples of such binders are cellulose derivatives, e.g. Methyl cellulose, ethyl cellulose, ethyl hydroxyethyl cellulose, hydroxypropyl cellulose, cellulose acetate or cellulose acetobutyrate, starch, alginates, alkyd resin, vinyl resin, polyvinyl alcohol, polyvinyl acetate, polyvinyl butyrate or polyvinyl pyrrolidone. Polymers and copolymers of acrylates or their derivatives, such as polyacrylic acid, polymethyl methacrylate or styrene-acrylate copolymers, polyester resins, polyamide resins, polyurethane resins or natural CH resins, such as gum arabic, are also suitable as binders. Other suitable binders are e.g. in DE-A-3 524 519.

Bevorzugte Bindemittel sind Ethylcellulose, Ethylhydroxyethylcellulose, Polyvinylbutyrat oder Polyvinylacetat.Preferred binders are ethyl cellulose, ethyl hydroxyethyl cellulose, polyvinyl butyrate or polyvinyl acetate.

Das Gewichtsverhältnis Bindemittel:Farbstoff beträgt im allgemeinen 1:1 bis 10:1.The weight ratio of binder: dye is generally 1: 1 to 10: 1.

Als Hilfsmittel kommen z.B. Trennmittel in Betracht, wie sie in der EP-A-227 092, EP-A-192 435 oder den dort zitierten Patentanmeldungen genannt sind. Darüber hinaus sind besonders organische Additive zu nennen, welche das Auskristallisieren der Transferfarbstoffe bei Lagerung und beim Erhitzen des Farbbandes verhindern, z.B. Cholesterin oder Vanillin.As aids come e.g. Release agents into consideration, as they are mentioned in EP-A-227 092, EP-A-192 435 or the patent applications cited therein. Organic additives which prevent the transfer dyes from crystallizing out during storage and when the ribbon is heated, e.g. Cholesterol or vanillin.

Inerte Träger sind z.B. Seiden-, Lösch- oder Pergaminpapier oder Kunststoffolien mit guter Wärmebeständigkeit, z.B. gegebenenfalls metallbeschichteter Polyester, Polyamid oder Polyimid. Der inerte Träger wird auf der dem Thermokopf zugewandten Seite gegebenenfalls zusätzlich mit einer Gleitmittelschicht (Slipping layer) beschichtet, um ein Verkleben des Thermokopfes mit dem Trägermaterial zu verhindern. Geeignete Gleitmittel werden z.B. in der EP-A-216 483 oder EP-A-227 095 beschrieben. Die Dicke des Farbstoff-Trägers beträgt im allgemeinen 3 bis 30 µm, vorzugsweise 5 bis 10 µm.Inert carriers are, for example, tissue paper, blotting paper or glassine paper or plastic films with good heat resistance, for example metal-coated polyester, polyamide or polyimide. The inert carrier is optionally additionally coated with a slip layer on the side facing the thermal head in order to prevent the thermal head from sticking to the carrier material. Suitable lubricants are described, for example, in EP-A-216 483 or EP-A-227 095. The thickness of the dye carrier is generally 3 to 30 microns, preferably 5 to 10 microns.

Als Farbstoffnehmerschicht kommen prinzipiell alle temperaturstabilen Kunststoffschichten min Affinität zu den zu transferierenden Farbstoffen in Betracht, z.B. modifizierte Polycarbonate oder Polyester. Geeignete Rezepturen für die Nehmerschichtzusammensetzung werden z.B. in der EP-A-227 094, EP-A-133 012, EP-A-133 011, EP-A-111 004, JP-A-199 997/1986, JP-A-283 595/1986, JP-A-237 694/1986 oder JP-A-127 392/1986 ausführlich beschrieben.In principle, all temperature-stable plastic layers with an affinity for the dyes to be transferred can be used as the dye-receiving layer, e.g. modified polycarbonates or polyester. Suitable formulations for the receiver layer composition are e.g. in EP-A-227 094, EP-A-133 012, EP-A-133 011, EP-A-111 004, JP-A-199 997/1986, JP-A-283 595/1986, JP- A-237 694/1986 or JP-A-127 392/1986 described in detail.

Die Übertragung erfolgt mittels einer Energiequelle, z.B. mittels eines Lasers oder mittels eines Thermokopfes, der auf eine Temperatur von ≧ 300°C aufheizbar sein muß, damit der Farbstofftransfer im Zeitbereich t: 0 < t < 15 msec erfolgen kann. Dabei migriert der Farbstoff aus dem Transferblatt und diffundiert in die Oberflächenbeschichtung des Aufnahmemediums.The transmission takes place by means of an energy source, e.g. by means of a laser or by means of a thermal head which must be able to be heated to a temperature of ≧ 300 ° C. so that the dye transfer can take place in the time range t: 0 <t <15 msec. The dye migrates from the transfer sheet and diffuses into the surface coating of the recording medium.

Die folgenden Beispiele sollen die Erfindung näher erläutern. Angaben über Prozente beziehen sich, sofern nicht anders vermerkt, auf das Gewicht.The following examples are intended to explain the invention in more detail. Unless otherwise stated, percentages relate to weight.

Um das Transferverhalten der Farbstoffe quantitativ und in einfacher Weise prüfen zu können, wurde der Thermotransfer mit großflächigen Heizbacken statt eines Thermokopfes durchgeführt, wobei die Transfertemperatur im Bereich 70 °C < T < 120 °C variiert und die Transferzeit auf 2 Minuten festgelegt wurde.

  • α) Allgemeines Rezept für die Beschichtung der Träger mit Farbstoff: 1 g Bindemittel wurde in 8 ml Toluol/Ethanol (8:2 v/v) bei 40 bis 50 °C gelöst. Dazu wurde eine Lösung aus 0,25 g Farbstoff in 5 ml Tetrahydrofuran eingerührt und gegebenenfalls von unlöslichem Rückstand abfiltriert. Die so erhaltene Druckpaste wurde mit einer 80 µm Rakel auf eine Polyesterfolie (Dicke: 6 bis 10 µm) abgezogen und mit einem Fön getrocknet.
  • β) Prüfung auf thermische Transferierbarkeit
    Die verwendeten Farbstoffe wurden in der folgenden Weise geprüft:
    Die den zu prüfenden Farbstoff in der Beschichtungsmasse (Vorderseite) enthaltende Polyesterfolie (Geber) wurde mit der Vorderseite auf kommerziell erhältliches (unten näher bezeichnetes) Papier (Nehmer) gelegt und aufgedrückt. Geber/Nehmer wurden dann mit Aluminiumfolie umwickelt und zwischen zwei beheizten Platten bei verschiedener Temperatur T (im Temperaturintervall 70°C < T < 120°C) erhitzt. Die in die glänzende Kunststoffschicht des Nehmers diffundierte Farbstoffmenge ist proportional der optischen Dichte (= Extinktion A). Letztere wurde photometrisch bestimmt. Trägt man den Logarithmus der im Temperaturintervall zwischen 80 und 110°C gemessenen Extinktion A der angefärbten Nehmerpapiere gegen die zugehörige reziproke absolute Temperatur auf, so erhält man Geraden, aus deren Steigung die Aktivierungsenergie ΔET für das Transferexperiment berechnet wird:
    Figure imgb0009
    Zur vollständigen Charakterisierung wurde aus den Auftragungen zusätzlich die Temperatur T* [°C] entnommen, bei der die Extinktion A der angefärbten Nehmerpapiere den Wert 1 erreicht.
    Die in den folgenden Tabellen aufgeführten Farbstoffe wurden nach α) verarbeitet und die erhaltenen, mit Farbstoff beschichteten Träger nach β) auf das Transferverhalten geprüft. In den Tabellen sind jeweils die Thermotransferparameter T* und ΔET, die Absorptionsmaxima der Farbstoffe λmax (gemessen in Methylenchlorid), die verwendeten Bindemittel sowie das Gewichtsverhältnis Farbstoff:Bindemittel:Hilfsmittel aufgeführt.
    Dabei gelten folgende Abkürzungen:
    F
    = Farbstoff
    B
    = Bindemittel
    EC
    = Ethylcellulose
    PVB
    = Polyvinylbutyrat
    Cellit
    = Celluloseacetobutyrat
    HCVPP
    = Hitachi Color Video Print Paper (Nehmer)
    PBTP
    = Polybutylenterephthalat-Folie (Nehmer)
    SV 100
    = Color Video Print Paper/Kodak AG (Nehmer)
Figure imgb0010
Figure imgb0011
Figure imgb0012
Figure imgb0013
Figure imgb0014
Figure imgb0015
 In order to be able to check the transfer behavior of the dyes quantitatively and easily, the thermal transfer was carried out with large-area heating jaws instead of a thermal head, the transfer temperature varying in the range from 70 ° C <T <120 ° C and the transfer time being set at 2 minutes.
  • α) General recipe for coating the support with dye: 1 g of binder was dissolved in 8 ml of toluene / ethanol (8: 2 v / v) at 40 to 50 ° C. For this purpose, a solution of 0.25 g of dye was stirred into 5 ml of tetrahydrofuran and any insoluble residue was filtered off. The printing paste thus obtained was drawn off onto a polyester film (thickness: 6 to 10 μm) using an 80 μm doctor blade and dried using a hairdryer.
  • β) Testing for thermal transferability
    The dyes used were tested in the following way:
    The polyester film (donor) containing the dye to be tested in the coating composition (front side) was placed with the front side on commercially available (recipient) and pressed on. The encoder / receiver was then wrapped with aluminum foil and heated between two heated plates at different temperatures T (in the temperature interval 70 ° C <T <120 ° C). The amount of dye diffused into the glossy plastic layer of the receiver is proportional to the optical density (= extinction A). The latter was determined photometrically. One carries the logarithm in the temperature interval between 80 and 110 ° C measured extinction A of the stained paper against the associated reciprocal absolute temperature, then straight lines are obtained, from whose slope the activation energy ΔE T is calculated for the transfer experiment:
    Figure imgb0009
    For complete characterization, the temperature T * [° C] was additionally taken from the plots at which the extinction A of the colored receiving papers reached the value 1.
    The dyes listed in the following tables were processed according to α) and the resulting, dye-coated supports were tested for transfer behavior according to β). The tables show the thermal transfer parameters T * and ΔE T , the absorption maxima of the dyes λ max (measured in methylene chloride), the binders used and the weight ratio of dye: binder: auxiliaries.
    The following abbreviations apply:
    F
    = Dye
    B
    = Binder
    EC
    = Ethyl cellulose
    PVB
    = Polyvinyl butyrate
    Cellite
    = Cellulose acetobutyrate
    HCVPP
    = Hitachi Color Video Print Paper (taker)
    PBTP
    = Polybutylene terephthalate film (taker)
    SV 100
    = Color Video Print Paper / Kodak AG (recipient)
Figure imgb0010
Figure imgb0011
Figure imgb0012
Figure imgb0013
Figure imgb0014
Figure imgb0015

In analoger Weise können die folgenden Methinfarbstoffe übertragen werden.

Figure imgb0016
The following methine dyes can be transferred in an analogous manner.
Figure imgb0016

Claims (2)

Verfahren zur Übertragung von bichromophoren Methinfarbstoffen von einem Träger auf ein mit Kunststoff beschichtetes Papier mit Hilfe einer Energiequelle, dadurch gekennzeichnet, daß man einen Träger verwendet, auf dem sich ein oder mehrere Farbstoffe der Formel I
Figure imgb0017
 befinden, in der
L
für ein Brückenglied, das keine Konjugation von π-Elektronen zwischen den Resten Z und Y zuläßt,
X
gleich oder verschieden ist und jeweils für Cyano, C₁-C₆-Alkoxycarbonyl oder C₁-C₆-Monoalkylcarbamoyl, wobei die Alkylgruppen jeweils durch 1 oder 2 Sauerstoffatome unterbrochen sein können, C₅-C₇-Cycloalkoxycarbonyl, C₅-C₇-Monocycloalkylcarbamoyl, Phenoxycarbonyl oder Monophenylcarbamoyl und
Z und Y
gleich oder verschieden sind und in Verbindung mit dem Brückenglied L unabhängig voneinander jeweils für einen Rest der Formel
Figure imgb0018
 stehen, worin n   gleich 0 oder 1, R¹ und R⁵   gleich oder verschieden sind und unabhängig voneinander jeweils Alkyl, Alkoxyalkyl, Alkoxycarbonylalkyl oder Alkanoyloxyalkyl, wobei diese Reste jeweils bis zu 10 Kohlenstoffatome aufweisen und gegebenenfalls durch Hydroxy oder Cyano substituiert sein können, Wasserstoff, Benzyl, Cyclohexyl, Phenyl oder Tolyl, R² und R³   gleich oder verschieden sind und unabhängig voneinander jeweils Wasserstoff, C₁-C₈-Alkyl, C₁-C₆-Alkoxy, C₁-C₆-Alkanoylamino oder C₁-C₆-Alkylsulfonylamino, R⁴   Wasserstoff, Halogen, C₁-C₈-Alkyl, gegebenenfalls durch C₁-C₄-Alkyl oder C₁-C₄-Alkoxy substituiertes Phenyl, gegebenenfalls durch C₁-C₄-Alkyl oder C₁-C₄-Alkoxy substituiertes Benzyl, Cyclohexyl, Thienyl oder den Rest -NHR¹, wobei R¹ die obengenannte Bedeutung besitzt, und R⁶   Wasserstoff oder C₁-C₈-Alkyl bedeuten, Process for the transfer of bichromophoric methine dyes from a support to a plastic-coated paper with the aid of an energy source, characterized in that a support is used on which one or more dyes of the formula I
Figure imgb0017
 are in the
L
for a bridge member that does not allow conjugation of π electrons between the residues Z and Y,
X
is identical or different and in each case for cyano, C₁-C₆-alkoxycarbonyl or C₁-C₆-monoalkylcarbamoyl, where the alkyl groups can each be interrupted by 1 or 2 oxygen atoms, C₅-C₇-cycloalkoxycarbonyl, C₅-C₇-monocycloalkylcarbamoyl, phenoxycarbonyl or monophenylcarbamoyl and
Z and Y
are identical or different and in connection with the bridge member L independently of one another each for a radical of the formula
Figure imgb0018
 stand in what n is 0 or 1, R¹ and R⁵ are the same or different and are each independently of the other alkyl, alkoxyalkyl, alkoxycarbonylalkyl or alkanoyloxyalkyl, where these radicals each have up to 10 carbon atoms and can optionally be substituted by hydroxy or cyano, hydrogen, benzyl, cyclohexyl, phenyl or tolyl, R² and R³ are the same or different and are each independently hydrogen, C₁-C₈-alkyl, C₁-C₆-alkoxy, C₁-C₆-alkanoylamino or C₁-C₆-alkylsulfonylamino, R⁴ is hydrogen, halogen, C₁-C₈-alkyl, optionally substituted by C₁-C₄-alkyl or C₁-C₄-alkoxy, phenyl optionally substituted by C₁-C₄-alkyl or C₁-C₄-alkoxy benzyl, cyclohexyl, thienyl or the rest - NHR¹, where R¹ is as defined above, and R⁶ is hydrogen or C₁-C₈-alkyl, Verfahren gemäß Anspruch 1, dadurch gekennzeichnet, daß X Cyano bedeutet.A method according to claim 1, characterized in that X is cyano.
EP91101566A 1990-02-15 1991-02-06 Transfer process using methine dyes containing bichromophoric cyano-groups Expired - Lifetime EP0439200B1 (en)

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