EP0509302A1 - Process for transfer of methine dyes - Google Patents
Process for transfer of methine dyes Download PDFInfo
- Publication number
- EP0509302A1 EP0509302A1 EP92105403A EP92105403A EP0509302A1 EP 0509302 A1 EP0509302 A1 EP 0509302A1 EP 92105403 A EP92105403 A EP 92105403A EP 92105403 A EP92105403 A EP 92105403A EP 0509302 A1 EP0509302 A1 EP 0509302A1
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- EP
- European Patent Office
- Prior art keywords
- alkyl
- alkoxy
- phenyl
- dyes
- formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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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
-
- 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
- B41M5/39—Dyes containing one or more carbon-to-nitrogen double bonds, e.g. azomethine
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- 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 method for transferring methine dyes from a support to a plastic-coated paper using 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 or a laser, 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 or a laser
- short heating impulses duration: fractions of a second
- the color recording is carried out using the three subtractive primary colors yellow, magenta, cyan (and possibly black).
- JP-A-229 786/1985, JP-A-84 390/1990 and EP-A-258 856 describe aniline derivatives for this purpose which have the tricyanovinyl radical in the para position to the amino group.
- JP-A-32 164/1990 describes dyes which have 4-nitrophenylacetonitrile as a CH-acidic component.
- the object of the present invention was therefore to provide a new method for the transmission of methine dyes with absorption in the blue-green or green spectral range, the dyes used having the properties mentioned at the outset.
- Aromatic carbocyclic or heterocyclic radicals K are derived, for example, from the aniline, aminonaphthalene, indole, quinoline, benzoxazine, aminothiazole, diaminopyridine, aminothiophene, benzimidazole or benzothiazole series.
- substituted alkyl or phenyl groups occur in the formulas mentioned above, these are generally mono- to trisubstituted.
- the substituents e.g. Cyano, phenyl, tolyl, C1-C6-alkanoyloxy, C1-C4-alkoxycarbonyl or C1-C4-alkoxycarbonyloxy, in which case the alkoxy group can be substituted by phenyl, tolyl or C1-C4-alkoxy.
- Suitable radicals X2, X4, X5, R3, R4, R6 and R8 are e.g. Methyl, ethyl, propyl, isopropyl, butyl, isobutyl or sec-butyl.
- R3, R4 and R6 are also e.g. Pentyl, isopentyl, neopentyl, tert-pentyl, hexyl or 2-methylpentyl.
- R3 and R4 are further examples of heptyl, octyl, 2-ethylhexyl, 2-methoxyethyl, 2- or 3-methoxypropyl, 2-ethoxyethyl, 2- or 3-ethoxypropyl, 2-propoxyethyl, 2- or 3-propoxypropyl, 2- Butoxyethyl, 2- or 3-butoxypropyl, 3,6-dioxaheptyl, 3,6-dioxaoctyl, 2-cyanoethyl, 2- or 3-cyanopropyl, 2-acetyloxyethyl, 2- or 3-acetyloxypropyl, 2-isobutyryloxyethyl, 2- or 2-isobutyryloxypropyl, 2-methoxycarbonylethyl, 2- or 3-methoxycarbonylpropyl, 2-ethoxycarbonylethyl, 2- or 3-ethoxycarbonylpropyl 2-methoxycarbonylpropyl,
- Residues X2 and R8 are further e.g. Methoxy, ethoxy, propoxy, iospropoxy, butoxy, sec-butoxy, methylthio, ethylthio, propylthio, isopropylthio or butylthio.
- Residues R8 are still e.g. Fluorine, chlorine or bromine.
- R1 are e.g. Methylsulfonylamino, ethylsulfonylamino, propylsulfonylamino, isopropylsulfonylamino, butylsulfonylamino, mono- or dimethylaminosulfonylamino, mono- or diethylaminosulfonylamino, mono- or dipropylaminosulfonylamino, mono- or diisopropylaminosulfonylamino-nylamino or n-aminobutylamino-sulfonylamino-methyl-n-aminosulfonylamino-nyl-aminosulfonylamino-naphonamino-n-aminosulfonylamino-n-aminosulfonylamino-n-aminosulfonylamino-naphonamino-n-aminosulfony
- X1, X3 and R7 are e.g. Methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl or butoxycarbonyl.
- X1 and R7 are further e.g. Pentyloxycarbonyl, hexyloxycarbonyl, mono- or dimethylcarbamoyl, mono- or diethylcarbamoyl, mono- or dipropylcarbamoyl, mono- or diisopropylcarbamoyl, mono- or dibutylcarbamoyl or N-methyl-N-ethylcarbamoyl.
- Residues X1 are furthermore, for example, 2-methoxyethoxycarbonyl, 2-ethoxyethoxycarbonyl, 3,6-dioxaheptyloxycarbonyl, cyclopentyloxycarbonyl, cyclohexyloxycarbonyl, cycloheptyloxycarbonyl, formyl, acetyl, propionyl, butyryl, isobutyryl, benzoyl, 2-methylbenzoyloxy, 2,4-dimethylbenzoyloyl, 2,4-dimethylbenzoyloxy , 2,4-dimethoxybenzoyl, 2-chlorobenzoyl, 2,4-dichlorobenzoyl, methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, butylsulfonyl, phenylsulfonyl, 2- or 4-
- a process is particularly preferred in which there are one or more dyes of the formula I on the support, in which B represents the residue of a CH-acidic compound which is derived from a compound of the formula IIa or IIb.
- the methine dyes of the formula I can be prepared by methods known per se, as described, for example, in JP-A-32 164/1990, in the earlier application EP-A-416 434 or in the earlier German patent application P 41 05 197.1 will.
- the dyes of the formula I which are transferred in the process according to the invention are generally distinguished by improved migration properties in the recording medium at room temperature, easier thermal transferability, higher thermal and photochemical stability, easier technical accessibility, better resistance to moisture and chemical substances, higher color strength, better solubility or better suitability for the subtractive color mixture (higher color purity, less blue absorption, more favorable form of the absorption band, eg small half-width or greater edge steepness on the short-wave side). They are also particularly advantageous for dye mixtures with red or reddish-violet dyes.
- Such dyes are for example from EP-A-216 483, EP-A-209 990, EP-A-312 211, US-A-4 698 651, EP-A-346 729 or the earlier applications EP-A-416 434, EP-A-441 208 or EP-A-460 463.
- the dyes of the formula I in combination with violet dyes, produce highly brilliant magenta stains and, in combination with cyan dyes, highly brilliant, reddish blue stains. At the same time, a deep, neutral black is achieved in combination with suitable yellow dyes.
- 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 e.g. those in which the solubility of the dyes I at room temperature 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.
- Preferred binders are ethyl cellulose, ethyl hydroxyethyl cellulose, polyvinyl butyrate, polyvinyl acetate or saturated linear polyesters.
- the weight ratio of binder: dye is generally 1: 1 to 5: 1.
- auxiliaries are release agents, such as those mentioned in the earlier application EP-A-441 282 or the corresponding patent applications cited therein. They are also particularly organic To name additives which prevent the transfer dyes from crystallizing out during storage or when the ribbon is heated, for example cholesterol or vanillin.
- Suitable inert carriers are e.g. described in the earlier application EP-A-441 282 or in the corresponding patent applications cited therein.
- the thickness of the dye carrier is generally 3 to 30 microns, preferably 5 to 10 microns.
- all temperature-stable plastic layers with affinity for the dyes to be transferred can be used as the dye-receiving layer, e.g. modified polycarbonates or polyester. Further details can e.g. from the earlier application EP-A-441 282 or the corresponding patent applications cited therein.
- 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 dyes listed in the following table were processed according to ⁇ ) and the resulting, dye-coated supports were tested for transfer behavior according to ⁇ ).
- the table shows the thermal transfer parameters T * and ⁇ E T , the absorption maxima of the dyes ⁇ max (measured in methylene chloride) and the binders used.
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- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Thermal Transfer Or Thermal Recording In General (AREA)
- Coloring (AREA)
Abstract
Description
Die vorliegende Erfindung betrifft ein neues Verfahren zur Übertragung von Methinfarbstoffen von einem Träger auf ein mit Kunststoff beschichtetes Papier mit Hilfe einer Energiequelle.The present invention relates to a new method for transferring methine dyes from a support to a plastic-coated paper using 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 oder einem Laser, 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 or a laser, 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.In general, the color recording is carried out using the three subtractive primary colors yellow, magenta, cyan (and possibly black).
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.
- 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, insbesondere solche, die die Grundfarbe Magenta aufweisen, nicht dem geforderten Anforderungsprofil.Therefore, most of the known dyes used for thermal transfer printing, in particular those which have the basic color magenta, do not meet the required profile of requirements.
So sind z.B. in der JP-A-229 786/1985, JP-A-84 390/1990 sowie in der EP-A-258 856 Anilinderivate für diesen Zweck beschrieben, die in para-Stellung zur Aminogruppe den Tricyanovinylrest aufweisen. Die JP-A-32 164/1990 beschreibt Farbstoffe, die 4-Nitrophenylacetonitril als CH-acide Komponente aufweisen.For example, JP-A-229 786/1985, JP-A-84 390/1990 and EP-A-258 856 describe aniline derivatives for this purpose which have the tricyanovinyl radical in the para position to the amino group. JP-A-32 164/1990 describes dyes which have 4-nitrophenylacetonitrile as a CH-acidic component.
Es hat sich jedoch gezeigt, daß mit diesen Farbstoffen keine ausreichenden Ergebnisse erzielt werden.However, it has been shown that these dyes do not give adequate results.
Aufgabe der vorliegenden Erfindung war es daher, ein neues Verfahren zur Übertragung von Methinfarbstoffen mit Absorption im blaugrünen oder grünen Spektralbereich bereitzustellen, wobei die zur Anwendung kommenden Farbstoffe die eingangs erwähnten Eigenschaften aufweisen sollten.The object of the present invention was therefore to provide a new method for the transmission of methine dyes with absorption in the blue-green or green spectral range, the dyes used having the properties mentioned at the outset.
Es wurde nun gefunden, daß die Übertragung von 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
K-N=B (I)
befinden, in der
- K
- für einen aromatischen carbocyclischen oder heterocyclischen Rest und
- B
- für den Rest einer CH-aciden Verbindung stehen, der sich von Nitromethan, Nitroethan, Benzimidazolen-2-ylacetamid oder einer Verbindung der Formel
ableitet, worin
- X¹
- Cyano, Nitro, C₁-C₄-Alkanoyl, gegebenenfalls durch C₁-C₄-Alkyl, C₁-C₄-Alkoxy oder Halogen substituiertes Benzoyl, C₁-C₄-Alkylsulfonyl, gegebenenfalls durch C₁-C₄-Alkyl, C₁-C₄-Alkoxy oder Halogen substituiertes Phenylsulfonyl, Carboxyl, gegebenenfalls durch 1 oder 2 Sauerstoffatome in Etherfunktion unterbrochenes C₁-C₆-Alkoxycarbonyl, C₅-C₇-Cycloalkoxycarbonyl, gegebenenfalls durch C₁-C₄-Alkyl, C₁-C₄-Alkoxy oder Halogen substituiertes Phenoxycarbonyl, Carbamoyl, gegebenenfalls durch 1 oder 2 Sauerstoffatome in Etherfunktion unterbrochenes C₁-C₆-Mono- oder Dialkylcarbamoyl, C₅-C₇-Mono- oder Dicycloalkylcarbamoyl, gegebenenfalls durch C₁-C₄-Alkyl, C₁-C₄-Alkoxy oder Halogen substituiertes Phenylcarbamoyl, gegebenenfalls durch C₁-C₄-Alkyl, Cyano, C₁-C₄-Alkoxy, Halogen oder Nitro substituiertes Phenyl, Benzthiazol-2-yl, Benzimidazol-2-yl, 5-Phenyl-1,3,4-thiadiazol-2-yl oder 2-Hydroxychinoxalin-3-yl,
- X²
- C₁-C₄-Alkyl oder C₁-C₄-Alkoxy,
- X³
- C₁-C₄-Alkoxycarbonyl, Phenylcarbamoyl oder Benzimidazol-2-yl,
- X⁴
- C₁-C₄-Alkyl und
- X⁵
- Wasserstoff, C₁-C₄-Alkyl oder Phenyl bedeuten.
KN = B (I)
are in the
- K
- for an aromatic carbocyclic or heterocyclic radical and
- B
- represent the remainder of a CH-acidic compound which is derived from nitromethane, nitroethane, benzimidazolen-2-ylacetamide or a compound of the formula
derives what
- X¹
- Cyano, nitro, C₁-C₄-alkanoyl, optionally substituted by C₁-C Alkyl-alkyl, C₁-C₄-alkoxy or halogen-substituted benzoyl, C₁-C₄-alkylsulfonyl, optionally substituted by C₁-C₄-alkyl, C₁-C₄-alkoxy or halogen Phenylsulfonyl, carboxyl, optionally interrupted by 1 or 2 oxygen atoms in ether function C₁-C₆-alkoxycarbonyl, C₅-C₇-cycloalkoxycarbonyl, optionally substituted by C₁-C₄-alkyl, C₁-C₄-alkoxy or halogen, phenoxycarbonyl, carbamoyl, optionally by 1 or 2 Oxygen atoms in ether function interrupted C₁-C₆-mono- or dialkylcarbamoyl, C₅-C Mon-mono- or dicycloalkylcarbamoyl, optionally substituted by C₁-C₄-alkyl, C₁-C₄-alkoxy or halogen, phenylcarbamoyl, optionally by C₁-C₄-alkyl, cyano, C₁-C₄ alkoxy, halogen or nitro substituted phenyl, benzthiazol-2-yl, benzimidazol-2-yl, 5-phenyl-1,3,4-thiadiazol-2-yl or 2-hydroxyquinoxalin-3-yl,
- X²
- C₁-C₄-alkyl or C₁-C₄-alkoxy,
- X³
- C₁-C₄ alkoxycarbonyl, phenylcarbamoyl or benzimidazol-2-yl,
- X⁴
- C₁-C₄ alkyl and
- X⁵
- Is hydrogen, C₁-C₄ alkyl or phenyl.
Aromatische carbocyclische oder heterocyclische Reste K leiten sich beispielsweise aus der Anilin-, Aminonaphthalin-, Indol-, Chinolin-, Benzoxazin-, Aminothiazol-, Diaminopyridin-, Aminothiophen-, Benzimidazol- oder Benzthiazolreihe ab.Aromatic carbocyclic or heterocyclic radicals K are derived, for example, from the aniline, aminonaphthalene, indole, quinoline, benzoxazine, aminothiazole, diaminopyridine, aminothiophene, benzimidazole or benzothiazole series.
Bevorzugt ist eine Verfahrensweise , bei der sich auf dem Träger ein oder mehrere Farbstoffe der Formel I befinden, worin
- K
- für einen Rest der Formel
steht, worin
- n
- 0 oder 1,
- R¹
- Wasserstoff, Methyl, Methoxy, C₁-C₄-Mono- oder Dialkylaminosulfonylamino, C₁-C₄-Alkylsulfonylamino oder den Rest -NHCOR⁹ oder -NHCO₂R⁹, wobei R⁹ die Bedeutung von Phenyl, Benzyl, Tolyl oder C₁-C₈-Alkyl, das gegebenenfalls durch ein oder zwei Sauerstoffatome in Etherfunktion unterbrochen ist, besitzt,
- R²
- Wasserstoff, Methyl, Methoxy oder Ethoxy,
- R³ und R⁴
- gleich oder verschieden sind und unabhängig voneinander jeweils Wasserstoff, C₁-C₈-Alkyl, das gegebenenfalls substituiert ist und durch ein oder zwei Sauerstoffatome in Etherfunktion unterbrochen sein kann, oder C₅-C₇-Cycloalkyl,
- R⁵
- C₁-C₈-Alkyl, das gegebenenfalls substituiert ist und durch ein oder zwei Sauerstoffatome in Etherfunktion unterbrochen sein kann, C₅-C₇-Cycloalkyl, Phenyl oder Tolyl,
- R⁶
- Wasserstoff, Halogen, C₁-C₆-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, Hydroxy oder C₁-C₈-Monoalkylamino,
- R⁷
- Cyano, Carbamoyl, C₁-C₆-Mono- oder Dialkylcarbamoyl oder C₁-C₆-Alkoxycarbonyl und
- R⁸
- Halogen, Wasserstoff, C₁-C₄-Alkyl, C₁-C₄-Alkoxy, C₁-C₄-Alkylthio oder gegebenenfalls durch C₁-C₄-Alkyl substituiertes Phenyl bedeuten.
- K
- for a remainder of the formula
stands in what
- n
- 0 or 1,
- R¹
- Hydrogen, methyl, methoxy, C₁-C₄ mono- or dialkylaminosulfonylamino, C₁-C₄-alkylsulfonylamino or the radical -NHCOR⁹ or -NHCO₂R⁹, where R⁹ is phenyl, benzyl, tolyl or C₁-C₈-alkyl, which may be replaced by a or has two oxygen atoms interrupted in ether function,
- R²
- Hydrogen, methyl, methoxy or ethoxy,
- R³ and R⁴
- are identical or different and are each independently hydrogen, C₁-C₈-alkyl, which is optionally substituted and can be interrupted by one or two oxygen atoms in ether function, or C₅-C₇-cycloalkyl,
- R⁵
- C₁-C₈-alkyl, which is optionally substituted and can be interrupted by one or two oxygen atoms in ether function, C₅-C₇-cycloalkyl, phenyl or tolyl,
- R⁶
- Hydrogen, halogen, C₁-C₆-alkyl, phenyl optionally substituted by C₁-C₄-alkyl or C₁-C₄-alkoxy, optionally benzyl, cyclohexyl, thienyl, hydroxy or C₁- substituted by C₁-C₄-alkyl or C₁-C₄-alkoxy C₈-monoalkylamino,
- R⁷
- Cyano, carbamoyl, C₁-C₆ mono- or dialkylcarbamoyl or C₁-C₆ alkoxycarbonyl and
- R⁸
- Halogen, hydrogen, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-alkylthio or optionally substituted by C₁-C₄-alkyl phenyl.
Alle in den obengenannten Formeln auftretenden Alkylgruppen können sowohl geradkettig als auch verzweigt sein.All alkyl groups occurring in the above formulas can be straight-chain or branched.
Wenn in den obengenannten Formeln substituierte Alkyl- oder Phenylgruppen auftreten, so sind diese in der Regel ein- bis dreifach substituiert.If substituted alkyl or phenyl groups occur in the formulas mentioned above, these are generally mono- to trisubstituted.
Wenn in den obengenannten Formeln substituierte Alkylgruppen auftreten, so können als Substituenten z.B. Cyano, Phenyl, Tolyl, C₁-C₆-Alkanoyloxy, C₁-C₄-Alkoxycarbonyl oder C₁-C₄-Alkoxycarbonyloxy, wobei im letzten Fall die Alkoxygruppe durch Phenyl, Tolyl oder C₁-C₄-Alkoxy substituiert sein kann, in Betracht kommen.When substituted alkyl groups occur in the above formulas, the substituents e.g. Cyano, phenyl, tolyl, C₁-C₆-alkanoyloxy, C₁-C₄-alkoxycarbonyl or C₁-C₄-alkoxycarbonyloxy, in which case the alkoxy group can be substituted by phenyl, tolyl or C₁-C₄-alkoxy.
Geeignete Reste X², X⁴, X⁵, R³, R⁴, R⁶ und R⁸ sind z.B. Methyl, Ethyl, Propyl, Isopropyl, Butyl, Isobutyl oder sec-Butyl.Suitable radicals X², X⁴, X⁵, R³, R⁴, R⁶ and R⁸ are e.g. Methyl, ethyl, propyl, isopropyl, butyl, isobutyl or sec-butyl.
Reste R³, R⁴ und R⁶ sind weiterhin z.B. Pentyl, Isopentyl, Neopentyl, tert-Pentyl, Hexyl oder 2-Methylpentyl.R³, R⁴ and R⁶ are also e.g. Pentyl, isopentyl, neopentyl, tert-pentyl, hexyl or 2-methylpentyl.
Reste R³ und R⁴ sind weiterhin z.B. Heptyl, Octyl, 2-Ethylhexyl, 2-Methoxyethyl, 2- oder 3-Methoxypropyl, 2-Ethoxyethyl, 2- oder 3-Ethoxypropyl, 2-Propoxyethyl, 2- oder 3-Propoxypropyl, 2-Butoxyethyl, 2- oder 3-Butoxypropyl, 3,6-Dioxaheptyl, 3,6-Dioxaoctyl, 2-Cyanoethyl, 2- oder 3-Cyanopropyl, 2-Acetyloxyethyl, 2- oder 3-Acetyloxypropyl, 2-Isobutyryloxyethyl, 2- oder 2-Isobutyryloxypropyl, 2-Methoxycarbonylethyl, 2- oder 3-Methoxycarbonylpropyl, 2-Ethoxycarbonylethyl, 2- oder 3-Ethoxycarbonylpropyl 2-Methoxycarbonyloxyethyl, 2- oder 3-Methoxycarbonyloxypropyl, 2-Ethoxycarbonyloxyethyl, 2- oder 3-Ethoxycarbonyloxypropyl, 2-Butoxycarbonyloxyethyl, 2- oder 3-Butoxycarbonyloxypropyl, 2-(2-Phenylethoxycarbonyloxy)ethyl, 2- oder 3-(2-Phenylethoxycarbonyloxy)propyl, 2-(2-Ethoxyethoxycarbonyloxy)ethyl, 2- oder 3-(2-Ethoxyethoxycarbonyloxy)propyl, Benzyl, 2-Methylbenzyl, 1- oder 2-Phenylethyl, Cyclopentyl, Cyclohexyl oder Cycloheptyl.R³ and R⁴ are further examples of heptyl, octyl, 2-ethylhexyl, 2-methoxyethyl, 2- or 3-methoxypropyl, 2-ethoxyethyl, 2- or 3-ethoxypropyl, 2-propoxyethyl, 2- or 3-propoxypropyl, 2- Butoxyethyl, 2- or 3-butoxypropyl, 3,6-dioxaheptyl, 3,6-dioxaoctyl, 2-cyanoethyl, 2- or 3-cyanopropyl, 2-acetyloxyethyl, 2- or 3-acetyloxypropyl, 2-isobutyryloxyethyl, 2- or 2-isobutyryloxypropyl, 2-methoxycarbonylethyl, 2- or 3-methoxycarbonylpropyl, 2-ethoxycarbonylethyl, 2- or 3-ethoxycarbonylpropyl 2-methoxycarbonyloxyethyl, 2- or 3-methoxycarbonyloxypropyl, 2-ethoxycarbonyloxyethyl, 2- or 3-ethoxycarbonyloxypropyl, 2-butoxycarbonyloxyethyl, 2- or 3-butoxycarbonyloxypropyl, 2- (2-phenylethoxycarbonyloxy) ethyl, 2- or 3- (2-phenylethoxycarbonyloxy) propyl, 2- ( 2-ethoxyethoxycarbonyloxy) ethyl, 2- or 3- (2-ethoxyethoxycarbonyloxy) propyl, benzyl, 2-methylbenzyl, 1- or 2-phenylethyl, cyclopentyl, cyclohexyl or cycloheptyl.
Reste X² und R⁸ sind weiterhin z.B. Methoxy, Ethoxy, Propoxy, Iospropoxy, Butoxy, sec-Butoxy, Methylthio, Ethylthio,, Propylthio, Isopropylthio oder Butylthio.Residues X² and R⁸ are further e.g. Methoxy, ethoxy, propoxy, iospropoxy, butoxy, sec-butoxy, methylthio, ethylthio, propylthio, isopropylthio or butylthio.
Reste R⁸ sind weiterhin z.B. Fluor, Chlor oder Brom.Residues R⁸ are still e.g. Fluorine, chlorine or bromine.
Reste R¹ sind z.B. Methylsulfonylamino, Ethylsulfonylamino, Propylsulfonylamino, Isopropylsulfonylamino, Butylsulfonylamino, Mono- oder Dimethylaminosulfonylamino, Mono- oder Diethylaminosulfonylamino, Mono- oder Dipropylaminosulfonylamino, Mono- oder Diisopropylaminosulfonylamino, Mono- oder Dibutylaminosulfonylamino oder (N-Methyl-N-ethylaminosulfonyl)amino.R¹ are e.g. Methylsulfonylamino, ethylsulfonylamino, propylsulfonylamino, isopropylsulfonylamino, butylsulfonylamino, mono- or dimethylaminosulfonylamino, mono- or diethylaminosulfonylamino, mono- or dipropylaminosulfonylamino, mono- or diisopropylaminosulfonylamino-nylamino or n-aminobutylamino-sulfonylamino-methyl-n-aminosulfonylamino-nyl-aminosulfonylamino-naphonamino-naphonamino-n-aminosulfonylamino-n-aminosulfonylamino-n-aminosulfonylamino-naphonamino-n-aminosulfonylamino-n-aminosulfonylamino-nyl-aminosulfonylamino-n-aminosulfonylamino-n-aminosulfonylamino-n-aminosulfonyl-aminosulfonylamino-
Reste X¹, X³ und R⁷ sind z.B. Methoxycarbonyl, Ethoxycarbonyl, Propoxycarbonyl, Isopropoxycarbonyl oder Butoxycarbonyl.X¹, X³ and R⁷ are e.g. Methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl or butoxycarbonyl.
Reste X¹ und R⁷ sind weiterhin z.B. Pentyloxycarbonyl, Hexyloxycarbonyl, Mono- oder Dimethylcarbamoyl, Mono- oder Diethylcarbamoyl, Mono- oder Dipropylcarbamoyl, Mono- oder Diisopropylcarbamoyl, Mono- oder Dibutylcarbamoyl oder N-Methyl-N-ethylcarbamoyl.X¹ and R⁷ are further e.g. Pentyloxycarbonyl, hexyloxycarbonyl, mono- or dimethylcarbamoyl, mono- or diethylcarbamoyl, mono- or dipropylcarbamoyl, mono- or diisopropylcarbamoyl, mono- or dibutylcarbamoyl or N-methyl-N-ethylcarbamoyl.
Reste X¹ sind weiterhin z.B. 2-Methoxyethoxycarbonyl, 2-Ethoxyethoxycarbonyl, 3,6-Dioxaheptyloxycarbonyl, Cyclopentyloxycarbonyl, Cyclohexyloxycarbonyl, Cycloheptyloxycarbonyl, Formyl, Acetyl, Propionyl, Butyryl, Isobutyryl, Benzoyl, 2-Methylbenzoyl, 2,4-Dimethylbenzoyl, 2-Methoxybenzoyl, 2,4-Dimethoxybenzoyl, 2-Chlorbenzoyl, 2,4-Dichlorbenzoyl, Methylsulfonyl, Ethylsulfonyl, Propylsulfonyl, Isopropylsulfonyl, Butylsulfonyl, Phenylsulfonyl, 2- oder 4-Methylphenylsulfonyl, Mono- oder Dipentylcarbamoyl, Mono- oder Dihexylcarbamoyl, Mono- oder Bis(2-methoxyethyl)carbamoyl, Mono- oder Bis(2-ethoxyethyl)carbamoyl, Mono- oder Bis(3,6-dioxaheptyl)carbamoyl, Mono- oder Dicyclopentylcarbamoyl, Mono- oder Dicyclohexylcarbamoyl, Mono-oder Dicycloheptylcarbamoyl, Phenylcarbamoyl, 2-Methylphenylcarbamoyl, 2,4-Dimethylphenylcarbamoyl, 2-Methoxyphenylcarbamoyl, 2,4-Dimethoxyphenylcarbamoyl, 2-Chlorphenylcarbamoyl, 2,4-Dichlorphenylcarbamoyl, Phenyl, 2-, 3- oder 4-Chlorphenyl, 2-, 3- oder 4-Methylphenyl, 2,4-Dimethylphenyl, 2-, 3- oder 4-Cyanophenyl, 2-, 3- oder 4-Methoxyphenyl, 2,4-Dimethoxyphenyl oder 2-, 3- oder 4-Nitrophenyl.Residues X¹ are furthermore, for example, 2-methoxyethoxycarbonyl, 2-ethoxyethoxycarbonyl, 3,6-dioxaheptyloxycarbonyl, cyclopentyloxycarbonyl, cyclohexyloxycarbonyl, cycloheptyloxycarbonyl, formyl, acetyl, propionyl, butyryl, isobutyryl, benzoyl, 2-methylbenzoyloxy, 2,4-dimethylbenzoyloyl, 2,4-dimethylbenzoyloxy , 2,4-dimethoxybenzoyl, 2-chlorobenzoyl, 2,4-dichlorobenzoyl, methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, butylsulfonyl, phenylsulfonyl, 2- or 4-methylphenylsulfonyl, mono- or dipentylcarbamoyl, mono- or di- or mono- or di- (2-methoxyethyl) carbamoyl, mono- or bis (2-ethoxyethyl) carbamoyl, mono- or bis (3,6-dioxaheptyl) carbamoyl, mono- or dicyclopentylcarbamoyl, mono- or dicyclohexylcarbamoyl, mono- or dicycloheptylcarbamoyl, Phenylcarbamoyl, 2-methylphenylcarbamoyl, 2,4-dimethylphenylcarbamoyl, 2-methoxyphenylcarbamoyl, 2,4-dimethoxyphenylcarbamoyl, 2-chlorophenylcarbamoyl, 2,4-dichlorophenylcarbamoyl, phenyl, 2-, 3- or 4-chlorophenyl, 2-, 3- or 4-methylphenyl, 2,4-dimethylphenyl, 2-, 3- or 4-cyanophenyl, 2-, 3- or 4-methoxyphenyl, 2,4-dimethoxyphenyl or 2-, 3- or 4-nitrophenyl.
Besonders bevorzugt ist ein Verfahren, bei dem sich auf dem Träger ein oder mehrere Farbstoffe der Formel I befinden, in der B für den Rest einer CH-aciden Verbindung, der sich von einer Verbindung der Formel IIa oder IIb ableitet, steht.A process is particularly preferred in which there are one or more dyes of the formula I on the support, in which B represents the residue of a CH-acidic compound which is derived from a compound of the formula IIa or IIb.
Besonders bevorzugt ist weiterhin ein Verfahren, bei dem sich auf dem Träger ein oder mehrere Farbstoffe der Formel I befinden, in der K für einen Rest der Formel IIIa, IIIc, IIIj, IIIk, IIIl oder IIIm steht.Furthermore, a method is particularly preferred in which there are one or more dyes of the formula I on the support in which K represents a radical of the formula IIIa, IIIc, IIIj, IIIk, IIIl or IIIm.
Insbesondere hervorzuheben ist ein Verfahren, bei dem sich auf dem Träger ein oder mehrere Farbstoffe der Formel I befinden, in der B für den Rest der Formel
steht.Particularly noteworthy is a process in which one or more dyes of the formula I are on the support, in the B for the rest of the formula
stands.
Die Methinfarbstoffe der Formel I können nach an sich bekannten Methoden, wie sie beispielsweise in der JP-A-32 164/1990, in der älteren Anmeldung EP-A-416 434 oder in der älteren deutschen Patentanmeldung P 41 05 197.1 beschrieben sind, hergestellt werden.The methine dyes of the formula I can be prepared by methods known per se, as described, for example, in JP-A-32 164/1990, in the earlier application EP-A-416 434 or in the earlier German patent application P 41 05 197.1 will.
Im Vergleich zu den bei den bekannten Verfahren verwendeten Farbstoffen zeichnen sich die im erfindungsgemäßen Verfahren übertragenen Farbstoffe der Formel I im allgemeinen durch verbesserte Migrationseigenschaften im Aufnahmemedium bei Raumtemperatur, leichtere thermische Transferierbarkeit, höhere thermische und photochemische Stabilität, leichtere technische Zugänglichkeit, bessere Resistenz gegen Feuchtigkeit und chemische Stoffe, höhere Farbstärke, bessere Löslichkeit oder bessere Eignung für die subtraktive Farbmischung (höhere Farbtonreinheit, geringere Blauabsorption, günstigere Form der Absorptionsbande, z.B. geringe Halbwertsbreite oder größere Flankensteilheit auf der kurzwelligen Seite) aus. Außerdem eignen sie sich besonders vorteilhaft für Farbstoffmischungen mit roten oder rötlich-violetten Farbstoffen. Solche Farbstoffe sind beispielsweise aus der EP-A-216 483, EP-A-209 990, EP-A-312 211, US-A-4 698 651, EP-A-346 729 oder den älteren Anmeldungen EP-A-416 434, EP-A-441 208 oder EP-A-460 463 bekannt.In comparison to the dyes used in the known processes, the dyes of the formula I which are transferred in the process according to the invention are generally distinguished by improved migration properties in the recording medium at room temperature, easier thermal transferability, higher thermal and photochemical stability, easier technical accessibility, better resistance to moisture and chemical substances, higher color strength, better solubility or better suitability for the subtractive color mixture (higher color purity, less blue absorption, more favorable form of the absorption band, eg small half-width or greater edge steepness on the short-wave side). They are also particularly advantageous for dye mixtures with red or reddish-violet dyes. Such dyes are for example from EP-A-216 483, EP-A-209 990, EP-A-312 211, US-A-4 698 651, EP-A-346 729 or the earlier applications EP-A-416 434, EP-A-441 208 or EP-A-460 463.
Die Farbstoffe der Formel I ergeben in Kombination mit violetten Farbstoffen hochbrillante Magentafärbungen sowie in Kombination mit Cyanfarbstoffen hochbrillante, rotstichige Blaufärbungen. Gleichzeitig wird in Kombination mit geeigneten Gelbfarbstoffen ein tiefes, neutrales Schwarz erzielt.The dyes of the formula I, in combination with violet dyes, produce highly brilliant magenta stains and, in combination with cyan dyes, highly brilliant, reddish blue stains. At the same time, a deep, neutral black is achieved in combination with suitable yellow dyes.
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 Raumtemperatur größer als 1 Gew.%, vorzugsweise größer als 5 Gew.% ist.Suitable organic solvents for the dyes I are e.g. those in which the solubility of the dyes I at room temperature 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.
Solche Bindemittel sind beispielsweise in der älteren Anmeldung EP-A-441 282 oder in den entsprechenden dort zitierten Patentanmeldungen genannt.Such binders are mentioned, for example, in the earlier application EP-A-441 282 or in the corresponding patent applications cited therein.
Bevorzugte Bindemittel sind Ethylcellulose, Ethylhydroxyethylcellulose, Polyvinylbutyrat, Polyvinylacetat oder gesättigte lineare Polyester.Preferred binders are ethyl cellulose, ethyl hydroxyethyl cellulose, polyvinyl butyrate, polyvinyl acetate or saturated linear polyesters.
Das Gewichtsverhältnis Bindemittel:Farbstoff beträgt im allgemeinen 1:1 bis 5:1.The weight ratio of binder: dye is generally 1: 1 to 5: 1.
Als Hilfsmittel kommen z.B. Trennmittel in Betracht, wie sie in der älteren Anmeldung EP-A-441 282 oder den entsprechenden dort zitierten Patentanmeldungen genannt sind. Darüber hinaus sind besonders organische Additive zu nennen, welche das Auskristallisieren der Transferfarbstoffe bei Lagerung oder beim Erhitzen des Farbbandes verhindern, z.B. Cholesterin oder Vanillin.Examples of suitable auxiliaries are release agents, such as those mentioned in the earlier application EP-A-441 282 or the corresponding patent applications cited therein. They are also particularly organic To name additives which prevent the transfer dyes from crystallizing out during storage or when the ribbon is heated, for example cholesterol or vanillin.
Geeignete inerte Träger sind z.B. in der älteren Anmeldung EP-A-441 282 oder in den entsprechenden dort zitierten Patentanmeldungen beschrieben. Die Dicke des Farbstoff-Trägers beträgt im allgemeinen 3 bis 30 µm, vorzugsweise 5 bis 10 µm.Suitable inert carriers are e.g. described in the earlier application EP-A-441 282 or in the corresponding patent applications cited therein. The thickness of the dye carrier is generally 3 to 30 microns, preferably 5 to 10 microns.
Als Farbstoffnehmerschicht kommen prinzipiell alle temperaturstabilen Kunststoffschichten mit Affinität zu den zu transferierenden Farbstoffen in Betracht, z.B. modifizierte Polycarbonate oder Polyester. Weitere Einzelheiten dazu können z.B. aus der älteren Anmeldung EP-A-441 282 oder den entsprechenden dort zitierten Patentanmeldungen entnommen werden.In principle, all temperature-stable plastic layers with affinity for the dyes to be transferred can be used as the dye-receiving layer, e.g. modified polycarbonates or polyester. Further details can e.g. from the earlier application EP-A-441 282 or the corresponding patent applications cited therein.
Die Übertragung erfolgt mittels einer Energiequelle, z.B. mittels eines Lasers oder mittels eines Thermokopfes, wobei dieser 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 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 wurden 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 30 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 Hitachi Color Video Print Paper (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 40 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:
- α) General recipe for coating the carrier 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 30 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 dye to be tested in the coating composition (front) containing polyester film (donor) was placed with the front side on commercially available Hitachi Color Video Print Paper (slave) and pressed. 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. If one plots the logarithm of the extinction A of the stained receiving paper measured in the temperature interval between 40 and 110 ° C against the associated reciprocal absolute temperature, straight lines are obtained, from the slope of which the activation energy ΔE T for the transfer experiment is calculated:
Die in der folgenden Tabelle aufgeführten Farbstoffe wurden nach α) verarbeitet und die erhaltenen, mit Farbstoff beschichteten Träger nach β) auf das Transferverhalten geprüft. In der Tabelle sind jeweils die Thermotransferparameter T* und ΔET, die Absorptionsmaxima der Farbstoffe λmax (gemessen in Methylenchlorid) sowie die verwendeten Bindemittel aufgeführt.The dyes listed in the following table were processed according to α) and the resulting, dye-coated supports were tested for transfer behavior according to β). The table shows the thermal transfer parameters T * and ΔE T , the absorption maxima of the dyes λ max (measured in methylene chloride) and the binders used.
Dabei gelten folgende Abkürzungen:
- B
- = Bindemittel
- V
- = Vylon® 290 der Fa. Toyobo
- B
- = Binder
- V
- = Vylon® 290 from Toyobo
Claims (4)
K-N=B (I)
befinden, in der
KN = B (I)
are in the
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4112654 | 1991-04-18 | ||
DE4112654A DE4112654A1 (en) | 1991-04-18 | 1991-04-18 | METHOD FOR TRANSMITTING METHINE DYES |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0509302A1 true EP0509302A1 (en) | 1992-10-21 |
EP0509302B1 EP0509302B1 (en) | 1997-01-29 |
Family
ID=6429850
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP92105403A Expired - Lifetime EP0509302B1 (en) | 1991-04-18 | 1992-03-28 | Process for transfer of methine dyes |
Country Status (6)
Country | Link |
---|---|
US (1) | US5256624A (en) |
EP (1) | EP0509302B1 (en) |
JP (1) | JP3272393B2 (en) |
KR (1) | KR920019548A (en) |
CA (1) | CA2064340A1 (en) |
DE (2) | DE4112654A1 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0792757A1 (en) * | 1996-02-27 | 1997-09-03 | Agfa-Gevaert N.V. | Dye donor element for use in thermal transfer printing |
US6302924B1 (en) | 1996-03-22 | 2001-10-16 | Basf Aktiengesellschaft | Dye mixtures containing thienyl and/or thiazolazo dyes |
WO2011045253A1 (en) | 2009-10-13 | 2011-04-21 | Basf Se | Mixtures for producing photoactive layers for organic solar cells and organic photodetectors |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0279467A2 (en) * | 1987-02-20 | 1988-08-24 | Dai Nippon Insatsu Kabushiki Kaisha | Heat transfer sheet |
EP0416434A2 (en) * | 1989-09-07 | 1991-03-13 | BASF Aktiengesellschaft | Triazole pyridine dyes and a thermal transfer process of methine dyes |
EP0444327A1 (en) * | 1990-03-01 | 1991-09-04 | Agfa-Gevaert N.V. | Dyes for use in thermal dye transfer |
Family Cites Families (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS60229786A (en) * | 1984-04-27 | 1985-11-15 | Matsushita Electric Ind Co Ltd | Heat transfer thermal recording |
DE3676245D1 (en) * | 1985-07-23 | 1991-01-31 | Ici Plc | THERMAL TRANSFER PRINT. |
GB8521327D0 (en) * | 1985-08-27 | 1985-10-02 | Ici Plc | Thermal transfer printing |
JPH0749535B2 (en) * | 1985-09-12 | 1995-05-31 | 三井東圧化学株式会社 | Novel plastid generation method |
US4698651A (en) * | 1985-12-24 | 1987-10-06 | Eastman Kodak Company | Magenta dye-donor element used in thermal dye transfer |
DE3630279A1 (en) * | 1986-09-05 | 1988-03-17 | Basf Ag | METHOD FOR TRANSMITTING DYES |
GB8724028D0 (en) * | 1987-10-13 | 1987-11-18 | Ici Plc | Thermal transfer printing |
DE3820313A1 (en) * | 1988-06-15 | 1989-12-21 | Basf Ag | METHOD FOR TRANSMITTING AZO DYES WITH A PYRIDINE CLUTCH COMPONENT |
JPH0232164A (en) * | 1988-07-20 | 1990-02-01 | Sumitomo Chem Co Ltd | Alpha-cyanoazomethine-based compound, production thereof and optical information recording medium using said compound |
JPH0284390A (en) * | 1988-09-21 | 1990-03-26 | Hitachi Ltd | Thermal transfer sheet |
JP2844345B2 (en) * | 1989-05-02 | 1999-01-06 | 大日本印刷株式会社 | Thermal transfer sheet |
US5223476A (en) * | 1989-05-02 | 1993-06-29 | Dai Nippon Insatsu Kabushiki Kaisha | Heat transfer sheet |
JPH02292371A (en) * | 1989-05-02 | 1990-12-03 | Sankyo Kagaku Kk | Coloring matter for thermal transfer recording |
DE4003780A1 (en) * | 1990-02-08 | 1991-08-14 | Basf Ag | USE OF AZO DYES FOR THERMAL TRANSFER PRINTING |
DE4004612A1 (en) * | 1990-02-15 | 1991-08-22 | Basf Ag | New bi:chromophoric methine and aza-methine dyestuff cpds. and use |
DE4018067A1 (en) * | 1990-06-06 | 1991-12-12 | Basf Ag | USE OF AZO DYES FOR THERMAL TRANSFER PRINTING |
DE4105197A1 (en) * | 1991-02-20 | 1992-08-27 | Basf Ag | BICHROMOPHORE METHINE DYES |
-
1991
- 1991-04-18 DE DE4112654A patent/DE4112654A1/en not_active Withdrawn
-
1992
- 1992-03-23 CA CA002064340A patent/CA2064340A1/en not_active Abandoned
- 1992-03-28 DE DE59207973T patent/DE59207973D1/en not_active Expired - Lifetime
- 1992-03-28 EP EP92105403A patent/EP0509302B1/en not_active Expired - Lifetime
- 1992-03-30 US US07/860,156 patent/US5256624A/en not_active Expired - Fee Related
- 1992-04-10 KR KR1019920005961A patent/KR920019548A/en active IP Right Grant
- 1992-04-16 JP JP09620292A patent/JP3272393B2/en not_active Expired - Fee Related
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0279467A2 (en) * | 1987-02-20 | 1988-08-24 | Dai Nippon Insatsu Kabushiki Kaisha | Heat transfer sheet |
EP0416434A2 (en) * | 1989-09-07 | 1991-03-13 | BASF Aktiengesellschaft | Triazole pyridine dyes and a thermal transfer process of methine dyes |
EP0444327A1 (en) * | 1990-03-01 | 1991-09-04 | Agfa-Gevaert N.V. | Dyes for use in thermal dye transfer |
Non-Patent Citations (5)
Title |
---|
CHEMICAL ABSTRACTS, vol. 112, no. 1, 1. Januar 1990, Columbus, Ohio, US; abstract no. 6938Q, H.MUSTROPH ET AL: 'Different substituent effects on the absorption maxima of azomethines and hydrazones.' Seite 682 ;Spalte RECHT ; * |
PATENT ABSTRACTS OF JAPAN vol. 11, no. 262 (C-442)(2709) 25. August 1987 & JP-A-62 062 866 ( MITSUI TOATSU CHEM INC ) 19. März 1987 * |
PATENT ABSTRACTS OF JAPAN vol. 15, no. 65 (M-1082)15. Februar 1991 & JP-A-2 292 090 ( DAI NIPPON PRINTING CO LTD ) 3. Dezember 1990 * |
WORLD PATENTS INDEX LATEST Week 9011, Derwent Publications Ltd., London, GB; AN 90-079267 * |
WORLD PATENTS INDEX LATEST Week 9103, Derwent Publications Ltd., London, GB; AN 91-019242 & JP-A-2 292 371 (SANKYO KAGAKU KK) 3. Dezember 1990 * |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0792757A1 (en) * | 1996-02-27 | 1997-09-03 | Agfa-Gevaert N.V. | Dye donor element for use in thermal transfer printing |
US6302924B1 (en) | 1996-03-22 | 2001-10-16 | Basf Aktiengesellschaft | Dye mixtures containing thienyl and/or thiazolazo dyes |
WO2011045253A1 (en) | 2009-10-13 | 2011-04-21 | Basf Se | Mixtures for producing photoactive layers for organic solar cells and organic photodetectors |
US9368729B2 (en) | 2009-10-13 | 2016-06-14 | Basf Se | Mixtures for producing photoactive layers for organic solar cells and organic photodetectors |
Also Published As
Publication number | Publication date |
---|---|
EP0509302B1 (en) | 1997-01-29 |
DE59207973D1 (en) | 1997-03-13 |
CA2064340A1 (en) | 1992-10-19 |
DE4112654A1 (en) | 1992-10-22 |
KR920019548A (en) | 1992-11-19 |
US5256624A (en) | 1993-10-26 |
JP3272393B2 (en) | 2002-04-08 |
JPH05104863A (en) | 1993-04-27 |
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