EP0038527A1 - Transfer printing sheets, process for their preparation and their use - Google Patents

Transfer printing sheets, process for their preparation and their use Download PDF

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Publication number
EP0038527A1
EP0038527A1 EP81102902A EP81102902A EP0038527A1 EP 0038527 A1 EP0038527 A1 EP 0038527A1 EP 81102902 A EP81102902 A EP 81102902A EP 81102902 A EP81102902 A EP 81102902A EP 0038527 A1 EP0038527 A1 EP 0038527A1
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EP
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Prior art keywords
dyes
formula
printed
printing
preparation
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EP81102902A
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German (de)
French (fr)
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EP0038527B1 (en
Inventor
Rudolf Dr. Schickfluss
Manfred Schneider
Claus Schuster
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Hoechst AG
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Hoechst AG
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
    • D06P5/003—Transfer printing
    • D06P5/004—Transfer printing using subliming dyes
    • D06P5/006—Transfer printing using subliming dyes using specified dyes

Definitions

  • the invention relates to transfer printing media, which are characterized in that they are impregnated or printed with a preparation which contains a dye of the formula I.
  • X is hydrogen, chlorine or bromine
  • R 1 is methoxy or ethoxy, or, if X is chlorine or bromine, also represents hydrogen or methyl
  • R 2 is alkyl having 1 to 4 carbon atoms
  • R 3 is hydrogen or the meaning is of R 2
  • R 4 is lenstoffatomen alkyl of 1 to 4 K OH, or mixtures of such dyes.
  • Preferred transfer printing supports according to the invention are impregnated or printed with preparations which contain dyes of the formula I in which X represents chlorine or bromine.
  • the invention furthermore relates to a process for the preparation of the supports according to the invention, which is characterized in that the support material is impregnated or printed with preparations which contain a dye of the formula I or mixtures of such dyes.
  • the invention also relates to the use of the supports according to the invention for dyeing and printing sheet-like structures by the thermal transfer printing process.
  • the sheet-like structures preferably exist from synthetic or semi-synthetic polymeric materials or from materials that have been prepared with such synthetic or semi-synthetic polymeric materials.
  • the sheet-like structures can also consist of or contain natural fiber materials, but are then treated with preparations which give these natural materials an affinity for the dyes of the formula I.
  • the dyes of the formula I are known and can be obtained by the methods customary for azo dyes. Dyes of this type and their use for dyeing polyethylene terephthalate from an aqueous dispersion with the addition of a carrier are known from US Pat. No. 4,076,498. Mixtures of dyes of the formula I are in DE-OS 28 18 653. described, where it is also mentioned that textiles containing such dye mixtures can be directly printed on textiles. These dyes are said to have good fastness properties in these documents, and it is even mentioned in US Pat. No. 4,076,498 that they have good sublimation fastness.
  • the dyes to be used according to the invention not only show extremely good transfer properties, but also provide color-deep prints with a point-sharp printed image. They are therefore also well suited in combination with other transfer printing dyes, for which it is known that it is assumed that all dyes are used under the conditions used show a largely similar transfer characteristic.
  • the dyes of the formula I have good lightfastness and have significantly higher color strengths than the blue anthraquinone dyes used in transfer printing.
  • the dyes of the formula I also have the advantage that they can be used to prepare easily pourable low-electrolyte and dispersant printing pastes with a high dye concentration, which are very sought after due to the low printing paste application on paper.
  • Sheet structures which are inert to the dyes applied and which do not hinder sublimation are suitable as carrier material for the transfer printing supports according to the invention.
  • the formulations which contain the dyes of the formula I and with which the support materials are impregnated or printed can be aqueous printing pastes, as are customary in textile printing, or organic printing inks, as are used in graphic printing.
  • Aqueous printing inks contain the usual natural or synthetic thickeners, for example polyvinyl alcohols, methyl cellulose or polymerization products containing carboxy groups, for example polyacrylates.
  • composition of the organic printing inks depends on the type of substrate, the substrate, the printing process and the equipment available.
  • such printing inks consist of one or more dyes of the formula I, a binder, a dispersant and, if appropriate, solvent agents, fillers and preservatives.
  • Natural, semi-synthetic and synthetic resins are suitable as binders, i.e. Polymerization, polycondensation and polyaddition products.
  • suitable resins are: rosin and its derivatives, maleinate resins, oil-free alkyd resins, alkyd resins made from synthetic and natural fatty acids and arylated alkyd resins.
  • terpene resins polyvinyl resins such as polyvinyl acetate and polyvinyl chloride, copolymers and graft polymers with various vinyl monomers, acrylate resins, naphthalene-formaldehyde resins, ketone resins, silicone resins and cellulose derivatives such as cellulose esters, for example nitrocellulose or cellulose acetate, and cellulose ethers, such as, for example, methyl derivative polysaccharides.
  • polyvinyl resins such as polyvinyl acetate and polyvinyl chloride
  • copolymers and graft polymers with various vinyl monomers acrylate resins, naphthalene-formaldehyde resins, ketone resins, silicone resins and cellulose derivatives such as cellulose esters, for example nitrocellulose or cellulose acetate, and cellulose ethers, such as, for example, methyl derivative polysaccharides.
  • Nonionic and anionogenic products are used as dispersants.
  • nonionic products which may be mentioned are: addition products of about 5-70 mol of alkylene oxide to higher fatty acids, fatty alcohol polyglycol ethers, phenol and alkylphenol polyglycol ethers, but also oxalkylates of fatty acids esterified with polyhydric alcohols or of resin derivatives such as hydroabietyl alcohol.
  • Suitable anionic dispersants are: naphthalenesulfonic acid-formaldehyde condensates, ligninsulfonates and sulfite waste products.
  • Suitable anionic dispersants are: naphthalenesulfonic acid-formaldehyde condensates, ligninsulfonates and sulfite waste products.
  • esters, ketones or alcohols for example butyl acetate, acetone, methyl ethyl ketone, ethanol, isopropanol or butanol, are particularly preferred.
  • the printing inks can be printed using all common printing methods, i.e. high, flat, gravure or screen printing.
  • Rotogravure and rotary film printing are particularly suitable printing processes for the production of printed paper auxiliary substrates.
  • Suitable substrates are sheet-like structures such as nonwovens, felts, furs, carpets, foils and, above all, woven and knitted fabrics made from synthetic or partially synthetic materials, in particular from aromatic polyesters such as polyethylene glycol terephthalate or cellulose acetates such as cellulose triacetate and cellulose 2 1/2 acetate or polyamides .
  • aromatic polyesters such as polyethylene glycol terephthalate or cellulose acetates such as cellulose triacetate and cellulose 2 1/2 acetate or polyamides .
  • These synthetic and semi-synthetic materials show an affinity for the dyes of formula I.
  • Corresponding methods are known for example from DE-PS 25 51
  • Thermal transfer printing is generally known and is described in detail, for example, in FR-PSS 1 223 330, 1 334 829 and 1 585 119.
  • the auxiliary carriers which are impregnated or printed with the suitable preparations, are brought into close contact with the substrate to be colored or printed, whereupon the dye is transferred from the carrier to the substrate and fixed there under the action of heat and, if appropriate, pressure or vacuum .
  • 300 parts of the dry dye of the following constitution are ground with 80 parts of a nonionic dispersant (reaction product of glycerol with castor oil fatty acid, reacted with 100 moles of ethylene oxide) and 25 parts of a lignin sulfonate and 150 parts of ethylene glycol, 200 parts of water and 5 parts of chloroacetamide as a preservative in a bead mill with silica quartz beads. After seven hours, a dispersion is obtained whose particles are more than 90% smaller than 3 ⁇ . The setting is made up to 1000 parts with water and separated from the beads.
  • a nonionic dispersant reaction product of glycerol with castor oil fatty acid, reacted with 100 moles of ethylene oxide
  • a lignin sulfonate 150 parts of ethylene glycol
  • 200 parts of water and 5 parts of chloroacetamide as a preservative in a bead mill with silica quartz beads.
  • the preparation containing 30% of dye is stable in storage at room temperature and also at 50 ° C.
  • the preparation can be stirred well into a conventional pressure thickener (alginate-based) as well as into a synthetic pressure thickener (acrylic-based) and can be printed by the usual printing methods without affecting the viscosity.
  • Transfer papers printed with the printing ink produce a greenish-blue, strong print after transfer to polyester (approx. 20 seconds at 200 ° C).
  • the setting containing 25% of the dye is stable in storage. Transfer papers printed with an aqueous printing ink produced therefrom result in a reddish-navy-blue, strong print after transfer to polyester (approx. 20 seconds at 200 ° C.).
  • 150 parts of the dry dye of the following constitution and 150 parts of the dry dye of the following constitution are ground with 85 parts of a nonionic dispersant (reaction product of glycerol with castor oil fatty acid, reacted with 100 moles of ethylene oxide) and 25 parts of a lignin sulfonate as well as 160 parts of ethylene glycol, 200 parts of water and 5 parts of chloroacetamide as preservative in a bead mill with silica quartz beads.
  • a nonionic dispersant reaction product of glycerol with castor oil fatty acid, reacted with 100 moles of ethylene oxide
  • a lignin sulfonate as well as 160 parts of ethylene glycol, 200 parts of water and 5 parts of chloroacetamide as preservative in a bead mill with silica quartz beads.
  • a dispersion is obtained whose particles are more than 90% smaller than 3 ⁇ .
  • the setting is made up to 1000 parts with water and separated from the beads.
  • the preparation containing 30% dye has a good shelf life both at room temperature and at 50 ° C.
  • Transfer papers printed with an aqueous printing paste obtained therefrom give a deep blue, strong print after transfer to polyester (approx. 20 sec. At 200 ° C.).
  • an anionic dispersant for example a lignosulfonate or a condensation product of naphthalenesulfonic acid and formaldehyde, and 130 ml of water are mixed and converted into a dispersion in a ball mill by grinding for 12 hours.
  • the approx. 33% preparation thus obtained is stable on storage.
  • the above aqueous dispersion can be processed into a printing paste as follows: 300 g are pasted with 350 g of a 10% locust bean gum ether thickener and 350 ml of water.
  • This printing paste is used to print paper using the gravure printing process. If this paper is pressed for 20 - 60 seconds at 210 ° C with a textile made of polyester fibers, you get a bright blue print.
  • the following table shows further dyestuff and the shades thus obtainable by the process given in Example 1.
  • the dyes can be mixed with one another.

Abstract

1. A transfer printing carrier sheet which has been impregnated or printed with a preparation containing a monoazo-dyestuff, wherein the preparation contains a dyestuff of the formula (I) see diagramm : EP0038527,P7,F3 in which X is hydrogen, chlorine or bromine, R**1 is methoxy or ethoxy, or, if X is chlorine or bromine, R**1 is also hydrogen or methyl, R**2 is alkyl of 1 to 4 carbon atoms, R**3 is hydrogen or alkyl of 1 to 4 carbon atoms and R**4 is alkyl of 1 to 4 carbon atoms, or a mixture of these dyestuffs.

Description

Die Erfindung betrifft Transferdruckträger, die dadurch gekennzeichnet sind, daß sie mit einer Zubereitung imprägniert oder bedruckt sind, die einen Farbstoff der Formel I

Figure imgb0001
in der X Wasserstoff, Chlor oder Brom ist, R1 für Methoxy oder Ethoxy, oder, wenn X Chlor oder Brom ist, auch für Wasserstoff oder Methyl steht, R2 Alkyl mit 1 bis 4 Kohlenstoffatomen ist, R3 Wasserstoff ist oder die Bedeutung von R2 hat und R4 Alkyl mit 1 bis 4 Koh- lenstoffatomen ist,oder Mischungen solcher Farbstoffe enthalten.The invention relates to transfer printing media, which are characterized in that they are impregnated or printed with a preparation which contains a dye of the formula I.
Figure imgb0001
 in which X is hydrogen, chlorine or bromine, R 1 is methoxy or ethoxy, or, if X is chlorine or bromine, also represents hydrogen or methyl, R 2 is alkyl having 1 to 4 carbon atoms, R 3 is hydrogen or the meaning is of R 2 and R 4 is lenstoffatomen alkyl of 1 to 4 K OH, or mixtures of such dyes.

Bevorzugte erfindungsgemäße Transferdruckträger sind mit Zubereitungen imprägniert oder bedruckt, die Farbstoffe der Formel I enthalten, in der X für Chlor oder Brom steht.Preferred transfer printing supports according to the invention are impregnated or printed with preparations which contain dyes of the formula I in which X represents chlorine or bromine.

Gegenstand der Erfindung ist weiterhin ein Verfahren zur Herstellung der erfindungsgemäßen Träger, das dadurch gekennzeichnet ist, daß das Trägermaterial mit Zubereitungen imprägniert oder bedruckt wird, die einen Farbstoff der Formel I oder Gemische solcher Farbstoffe enthalten.The invention furthermore relates to a process for the preparation of the supports according to the invention, which is characterized in that the support material is impregnated or printed with preparations which contain a dye of the formula I or mixtures of such dyes.

Gegenstand der Erfindung ist außerdem die Verwendung der erfindungsgemäßen Träger zum Färben und Bedrucken von flächenförmigen Gebilden nach dem Thermotransferdruckverfahren. Bevorzugt bestehen die flächenförmigen Gebilde aus synthetischen oder teilsynthetischen polymeren Materialien oder aus Materialien, die mit solchen synthetischen oder teilsynthetischen polymeren Materialien präpariert wurden. Die flächenförmigen Gebilde können auch aus natürlichen Fasermaterialien bestehen oder solche enthalten, sind dann aber mit Präparationen behandelt, die diesen natürlichen Materialien eine Affinität für die Farbstoffe der Formel I verleihen.The invention also relates to the use of the supports according to the invention for dyeing and printing sheet-like structures by the thermal transfer printing process. The sheet-like structures preferably exist from synthetic or semi-synthetic polymeric materials or from materials that have been prepared with such synthetic or semi-synthetic polymeric materials. The sheet-like structures can also consist of or contain natural fiber materials, but are then treated with preparations which give these natural materials an affinity for the dyes of the formula I.

Die Farbstoffe der Formel I sind bekannt und nach den für Azofarbstoffe üblichen Methoden zugänglich. Farbstoffe dieser Art und ihre Verwendung zum Färben von Polyethylenterephthalat aus wäßriger Dispersion unter Zusatz eines Carriers sind aus der US-PS 4 076 498 bekannt. Gemische von Farbstoffen der Formel I sind in der DE-OS 28 18 653 . beschrieben, wo auch erwähnt wird, daß mit solche Farbstoffgemische enthaltenden wäßrigen Druckpasten Textilien direkt bedruckt werden können. In diesen Druckschriften werden diesen Farbstoffen gute Echtheiten zugeschrieben, in der US-PS 4 076 498 wird sogar erwähnt, daß sie eine gute Sublimationsechtheit hätten. Es war somit überraschend, daß diese Farbstoffe für den Thermotransferdruck geeignet sind, bei dem es erforderlich ist, daß die Farbstoffe im Temperaturbereich von etwa 150 - 220°C innerhalb kurzer Zeit, etwa von 10 - 90 Sekunden, zum größten Teil sublimieren..Gegen die erfindungsgemäße Auswahl der Farbstoffe der Formel I sprachen auch die Ausführungen in der DE-AS 23 64 475, die Farbstoffe dieserArt als weniger gut für den Transferdruck geeignet bezeichnen.The dyes of the formula I are known and can be obtained by the methods customary for azo dyes. Dyes of this type and their use for dyeing polyethylene terephthalate from an aqueous dispersion with the addition of a carrier are known from US Pat. No. 4,076,498. Mixtures of dyes of the formula I are in DE-OS 28 18 653. described, where it is also mentioned that textiles containing such dye mixtures can be directly printed on textiles. These dyes are said to have good fastness properties in these documents, and it is even mentioned in US Pat. No. 4,076,498 that they have good sublimation fastness. It was therefore surprising that these dyes are suitable for thermal transfer printing, in which it is necessary for the dyes to sublimate for the most part in a temperature range of about 150-220 ° C. within a short time, about 10-90 seconds The selection of the dyes of the formula I according to the invention also spoke the statements in DE-AS 23 64 475, which describe dyes of this type as less suitable for transfer printing.

Uberraschenderweise zeigen jedoch die erfindungsgemäß zu verwendenden Farbstoffe nicht nur ausgesprochen gute Transferiereigenschaften,sondern liefern auch farbtiefe Drucke mit punktscharfem Druckbild. Sie eignen sich deshalb auch gut in Kombination mit anderen Transferdruckfarbstoffen, wofür bekanntermaßen vorausgesetzt wird, daß alle Farbstoffe unter den angewandten Bedingungen eine weitgehend ähnliche Transfercharakteristik zeigen.Surprisingly, however, the dyes to be used according to the invention not only show extremely good transfer properties, but also provide color-deep prints with a point-sharp printed image. They are therefore also well suited in combination with other transfer printing dyes, for which it is known that it is assumed that all dyes are used under the conditions used show a largely similar transfer characteristic.

Die Farbstoffe der Formel I weisen gute Lichtechtheiten auf und haben gegenüber den im Transferdruck verwendeten blauen Anthrachinon-Farbstoffen deutliche höhere Farbstärken.The dyes of the formula I have good lightfastness and have significantly higher color strengths than the blue anthraquinone dyes used in transfer printing.

Die Farbstoffe der Formel I zeigen weiterhin den Vorzug, daß mit ihnen leicht gießbare elektrolyt- und dispergiermittelarme Druckpasten mit hoher Farbstoffkonzentration hergestellt werden können, die wegen des geringen Druckpastenauftrags auf Papier sehr gesucht sind.The dyes of the formula I also have the advantage that they can be used to prepare easily pourable low-electrolyte and dispersant printing pastes with a high dye concentration, which are very sought after due to the low printing paste application on paper.

Als Trägermaterial für die erfindungsgemäßen Transferdruckträger eignen sich bekanntermaßen alle flächenförmigen Gebilde, die inert gegenüber den aufgebrachten Farbstoffen sind und die Sublimation nicht behindern. In Betracht kommen Flächengebilde aus Metall, wie Aluminiumfolie, oder aus natürlichen oder regenerierten Cellulosematerialien, wie Folien, Gewebe, Gewirke oder vorzugsweise Papierbahnen.As is known, all sheet-like structures which are inert to the dyes applied and which do not hinder sublimation are suitable as carrier material for the transfer printing supports according to the invention. Sheet structures made of metal, such as aluminum foil, or of natural or regenerated cellulose materials, such as foils, woven fabrics, knitted fabrics or preferably paper webs, are suitable.

Die Zubereitungen, die die Farbstoffe der Formel I enthalten, und mit denen die Trägermaterialien imprägniert oder bedruckt werden, können wäßrige Druckpasten sein, wie sie im Textildruck üblich sind, oder organische Drucktinten, wie sie im graphischen Druck verwendet werden. , Wäßrige Druckfarben enthalten die üblichen natürlichen oder synthetischen Verdicker, beispielsweise Polyvinylalkohole, Methylcellulose oder Carboxygruppen enthaltende Polymerisationsprodukte, beispielsweise Polyacrylate.The formulations which contain the dyes of the formula I and with which the support materials are impregnated or printed can be aqueous printing pastes, as are customary in textile printing, or organic printing inks, as are used in graphic printing. Aqueous printing inks contain the usual natural or synthetic thickeners, for example polyvinyl alcohols, methyl cellulose or polymerization products containing carboxy groups, for example polyacrylates.

Die Zusammensetzung der organischen Drucktinten richtet sich nach der Art des Substrats, des Trägermaterials, des Druckverfahrens und der zur Verfügung stehenden Anlagen. Im allgemeinen bestehen solche Drucktinten aus einem oder mehreren Farbstoffen der Formel I, einem Bindemittel, einem Dispergiermittel und gegebenenfalls Lösemitteln, Füllstoffen und Konservierungsmitteln.The composition of the organic printing inks depends on the type of substrate, the substrate, the printing process and the equipment available. In general, such printing inks consist of one or more dyes of the formula I, a binder, a dispersant and, if appropriate, solvent agents, fillers and preservatives.

Als Bindemittel eignen sich natürliche, halbsynthetische und synthetische Harze, d.h. Polymerisations-, Polykondensations- und Polyadditionsprodukte. Als geeignete Harze seien beispielsweise genannt: Kolophonium und seine Derivate, Maleinatharze, ölfreie Alkydharze, Alkydharze aus synthetischen und natürlichen Fettsäuren und arylierte Alkydharze. Geeignet sind auch Terpenharze, Polyvinylharze wie Polyvinylacetat und Polyvinylchlorid, Copolymere und Propfpolymere mit verschiedenen Vinylmonomeren, Acrylatharze, Naphthalin-Formaldehydharze, Ketonharze, Silikonharze und Cellulosederivate wie Celluloseester, beispielsweise Nitrocellulose oder Celluloseacetat, und Celluloseether, wie beispielweise Methylcellulose, und andere Derivate anderer Polysaccharide.Natural, semi-synthetic and synthetic resins are suitable as binders, i.e. Polymerization, polycondensation and polyaddition products. Examples of suitable resins are: rosin and its derivatives, maleinate resins, oil-free alkyd resins, alkyd resins made from synthetic and natural fatty acids and arylated alkyd resins. Also suitable are terpene resins, polyvinyl resins such as polyvinyl acetate and polyvinyl chloride, copolymers and graft polymers with various vinyl monomers, acrylate resins, naphthalene-formaldehyde resins, ketone resins, silicone resins and cellulose derivatives such as cellulose esters, for example nitrocellulose or cellulose acetate, and cellulose ethers, such as, for example, methyl derivative polysaccharides.

Als Dispergiermittel kommen nichtionogene und anionogene Produkte zur Anwendung. Als nichtionogene Produkte seien beispielsweise genannt: Anlagerungsprodukte von etwa 5 - 70 Mol Alkylenoxid an höhere Fettsäuren, Fettalkoholpolyglykolether, Phenol- und Alkylphenolpolyglykolether, aber auch Oxalkylate von mit mehrwertigen Alkoholen veresterten Fettsäuren oder von Harzderivaten wie Hydroabietylalkohol. Als anionische Dispergiermittel sind geeignet: Naphthalinsulfonsäure-Formaldehydkondensate, Ligninsulfonate und Sulfitablaugeprodukte.Nonionic and anionogenic products are used as dispersants. Examples of nonionic products which may be mentioned are: addition products of about 5-70 mol of alkylene oxide to higher fatty acids, fatty alcohol polyglycol ethers, phenol and alkylphenol polyglycol ethers, but also oxalkylates of fatty acids esterified with polyhydric alcohols or of resin derivatives such as hydroabietyl alcohol. Suitable anionic dispersants are: naphthalenesulfonic acid-formaldehyde condensates, ligninsulfonates and sulfite waste products.

Als anionische Dispergiermittel sind geeignet: Naphthalinsulfonsäure-Formaldehydkondensate, Ligninsulfonate und Sulfitablaugeprodukte.Suitable anionic dispersants are: naphthalenesulfonic acid-formaldehyde condensates, ligninsulfonates and sulfite waste products.

Die Art der Lösemittel hängt von der Art des Druckverfahrens ab. Besonders bevorzugt sind Ester, Ketone oder Alkohole, beispielsweise Butylacetat, Aceton, Methylethylketon, Ethanol, Isopropanol oder Butanol.The type of solvent depends on the type of printing process. Esters, ketones or alcohols, for example butyl acetate, acetone, methyl ethyl ketone, ethanol, isopropanol or butanol, are particularly preferred.

Die Druckfarben können nach allen üblichen Druckverfahren, also Hoch-, Flach-, Tief- oder Siebdruck verdruckt werden. Besonders geeignete Druckverfahren zur Herstellung von bedruckten Papierhilfsträgern sind der Tiefdruck und der Rotationsfilmdruck.The printing inks can be printed using all common printing methods, i.e. high, flat, gravure or screen printing. Rotogravure and rotary film printing are particularly suitable printing processes for the production of printed paper auxiliary substrates.

Geeignete Substrate sind flächenförmige Gebilde wie Vliese, Filze, Pelze, Teppiche, Folien und vor allem Gewebe und Gewirke aus synthetischen oder teilsynthetischen Materialien, insbesondere aus aromatischen Polyestern wie Polyethylenglykolterephthalat oder Celluloseacetaten wie Cellulose-triacetat und Cellulose-2 1/2-acetat oder Polyamiden. Diese synthetischen und teilsynthetischen Materialien zeigen eine Affinität für die Farbstoffe der Formel I. Es ist jedoch auch möglich, andere Substrate.nach dem Thermotransferdruck zu färben und zu bedrucken, die an sich keine Affinität zu diesen Farbstoffen besitzen, indem man nämlich solche Substrate mit den genannten synthetischen oder teilsynthetischen Materialien präpariert, also beispielsweise mit einem entsprechenden Überzug an solchen Kunststoffen umhüllt. Es ist auch möglich, natürliche Fasermaterialien, die keine AfELnität für die Farbstoffe der Formel 1 aufweisen, mit geeigneten Präparationen zu behandeln und diese Stoffe so gegenüber diesen Farbstoffen affin zu machen. Entsprechende Verfahren sind beispielsweise aus der DE-PS 25 51 410, der DE-AS 24 36 783 oder der DE-OS 20 45 465 bekannt.Suitable substrates are sheet-like structures such as nonwovens, felts, furs, carpets, foils and, above all, woven and knitted fabrics made from synthetic or partially synthetic materials, in particular from aromatic polyesters such as polyethylene glycol terephthalate or cellulose acetates such as cellulose triacetate and cellulose 2 1/2 acetate or polyamides . These synthetic and semi-synthetic materials show an affinity for the dyes of formula I. However, it is also possible to dye and print other substrates prepared synthetic or semi-synthetic materials prepared, that is, for example, coated with an appropriate coating of such plastics. It is also possible to treat natural fiber materials which have no affinity for the dyes of the formula 1 with suitable preparations and thus to make these substances affine to these dyes. Corresponding methods are known for example from DE-PS 25 51 410, DE - AS 24 36 783 or DE-OS 20 45 465.

Der Thermotransferdruck ist allgemein bekannt und beispielsweise in den FR-PSS 1 223 330, 1 334 829 und 1 585 119 eingehend beschrieben. Hierbei werden die Hilfsträger, die mit den geeigneten Zubereitungen imprägniert oder bedruckt sind, in engen Kontakt mit dem zu färbenden oder bedruckenden Substrat gebracht, worauf unter Wärme-und gegebenenfalls Druck- oder Vakuumeinwirkung der Farbstoff von dem Träger auf das Substrat transferiert und dort fixiert wird.Thermal transfer printing is generally known and is described in detail, for example, in FR-PSS 1 223 330, 1 334 829 and 1 585 119. Here, the auxiliary carriers, which are impregnated or printed with the suitable preparations, are brought into close contact with the substrate to be colored or printed, whereupon the dye is transferred from the carrier to the substrate and fixed there under the action of heat and, if appropriate, pressure or vacuum .

Mit den Farbstoffen der Formel I erhält man bei deren erfindungsgemäßer Verwendung auf den Substraten rotstichigbis grünstichig-blaue, farbstarke Färbungen und Drucke mit guten Gebrauchsechtheiten.With the dyes of the formula I, when used in accordance with the invention on the substrates, reddish to greenish-blue, strong colorations and prints with good fastness properties are obtained.

In den folgenden Beispielen wird die Erfindung näher erläutert. Angaben über Teile und Prozente beziehen sich hierbei, sofern nichts anderes vermerkt ist, auf das Gewicht.The invention is illustrated in the following examples purifies. Unless otherwise stated, details of parts and percentages relate to the weight.

Beispiel 1example 1

300 Teile des trockenen Farbstoffes der folgenden Konstitution

Figure imgb0002
werden mit 80 Teilen eines nichtionogenen Dispergiermittels (Reaktionsprodukt von Glycerin mit Rizinusölfettsäure, umgesetzt mit 100 Mol Ethylenoxid) und 25. Teilen eines Ligninsulfonates sowie 150 Teilen Ethylenglykol, 200 Teilen Wasser und 5 Teilen Chloracetamid als Konservierungsmittel in einer Perlmühle mit Siliquarzitperlen gemahlen. Nach sieben Stunden erhält man eine Dispersion, deren Teilchen zu über 90 % kleiner als 3 µ sind. Die Einstellung wird mit Wasser auf 1000 Teile aufgefüllt und von den Perlen abgetrennt.300 parts of the dry dye of the following constitution
Figure imgb0002
 are ground with 80 parts of a nonionic dispersant (reaction product of glycerol with castor oil fatty acid, reacted with 100 moles of ethylene oxide) and 25 parts of a lignin sulfonate and 150 parts of ethylene glycol, 200 parts of water and 5 parts of chloroacetamide as a preservative in a bead mill with silica quartz beads. After seven hours, a dispersion is obtained whose particles are more than 90% smaller than 3 µ. The setting is made up to 1000 parts with water and separated from the beads.

Die 30 % Farbstoff enthaltende Präparation ist bei Raumtemperatur und auch bei 50°C gut lagerstabil. Die Präparation läßt sich gut sowohl in eine konventionelle Druckverdickung (Alginat-Basis) als auch in eine synthetische Druckverdickung (Acryl-Basis) einrühren und ist ohne Beeinträchtigung der Viskosität nach den üblichen Druckverfahren druckbar. Mit der Druckfarbe bedruckte Transferpapiere ergeben nach dem Transfer auf Polyester (ca. 20 sec. bei 200°C) einen grünstichig-blauen, kräftigen Druck.The preparation containing 30% of dye is stable in storage at room temperature and also at 50 ° C. The preparation can be stirred well into a conventional pressure thickener (alginate-based) as well as into a synthetic pressure thickener (acrylic-based) and can be printed by the usual printing methods without affecting the viscosity. Transfer papers printed with the printing ink produce a greenish-blue, strong print after transfer to polyester (approx. 20 seconds at 200 ° C).

Beispiel 2Example 2

538 Teile eines feuchten Preßkuchens des Farbstoffes der folgenden Konstitution

Figure imgb0003
mit einem Feststoffgehalt von 46,4 % werden mit 100 Teilen eines nichtionogenen Dispergiermittels (Blockpolymerisat aus Propylen- und Ethylenoxid) und 30 Teilen eines Kondensationsproduktes aus Methylnaphthalinsulfonsäure und Formaldehyd (wie es in Beispiel D der DE-PS 2 442 514 beschrieben ist), 180 Teilen Ethylenglykol und 5 Teilen Chloracetamid als Konservierungsmittel in einer Perlmühle mit Siliquarzitperlen gemahlen. Nach 5 Stunden erhält man eine Dispersion, deren Teilchen zu über 90 % kleiner als 3 µ sind. Die Präparation wird mit Wasser auf 1000 Teile aufgefüllt und von den Perlen abgetrennt.538 parts of a moist press cake of the dye of the following constitution
Figure imgb0003
 with a solids content of 46.4% with 180 parts of a nonionic dispersant (block polymer made of propylene and ethylene oxide) and 30 parts of a condensation product of methylnaphthalenesulfonic acid and formaldehyde (as described in Example D of DE-PS 2 442 514), 180 Parts of ethylene glycol and 5 parts of chloroacetamide as a preservative are ground in a bead mill with silica quartz beads. After 5 hours, a dispersion is obtained, the particles of which are more than 90% smaller than 3 μ. The preparation is made up to 1000 parts with water and separated from the beads.

Die 25 % Farbstoff enthaltende Einstellung ist gut lagerstabil. Mit einer daraus hergestellten wäßrigen Druckfarbe bedruckte Transferpapiere ergeben nach dem Transfer auf Polyester (ca. 20 sec..bei 200°C) einen rotstichig-marineblauen, kräftigen Druck.The setting containing 25% of the dye is stable in storage. Transfer papers printed with an aqueous printing ink produced therefrom result in a reddish-navy-blue, strong print after transfer to polyester (approx. 20 seconds at 200 ° C.).

Beispiel 3Example 3

150 Teile des trockenen Farbstoffs der folgenden Konstitution

Figure imgb0004
und 150 Teile des trockenen Farbstoffs der folgenden Konstitution
Figure imgb0005
werden mit 85 Teilen eines nichtionogenen Dispergiermittels (Reaktionsprodukt von Glycerin mit Rizinusölfettsäure, umgesetzt mit 100 Mol Ethylenoxid) und 25 Teilens eines Ligninsulfonates sowie 160 Teilen Ethylenglykol, 200 Teilen Wasser und 5 Teilen Chloracetamid als Konservierungsmittel in einer Perlmühle mit Siliquarzitperlen gemahlen.150 parts of the dry dye of the following constitution
Figure imgb0004
 and 150 parts of the dry dye of the following constitution
Figure imgb0005
 are ground with 85 parts of a nonionic dispersant (reaction product of glycerol with castor oil fatty acid, reacted with 100 moles of ethylene oxide) and 25 parts of a lignin sulfonate as well as 160 parts of ethylene glycol, 200 parts of water and 5 parts of chloroacetamide as preservative in a bead mill with silica quartz beads.

Nach acht Stunden erhält man eine Dispersion, deren Teilchen zu über 90 % kleiner als 3 µ sind. Die Einstellung wird mit Wasser auf 1000 Teile aufgefüllt und von den Perlen abgetrennt.After eight hours, a dispersion is obtained whose particles are more than 90% smaller than 3 µ. The setting is made up to 1000 parts with water and separated from the beads.

Die 30 % Farbstoff enthaltende Präparation ist sowohl bei Raumtemperatur als auch bei 50°C gut lagerstabil. Mit einer daraus erhaltenen wäßrigen Druckpaste bedruckte Transferpapiere ergeben nach dem Transfer auf Polyester (ca. 20 sec. bei 200°C) einen tiefblauen, kräftigen Druck.The preparation containing 30% dye has a good shelf life both at room temperature and at 50 ° C. Transfer papers printed with an aqueous printing paste obtained therefrom give a deep blue, strong print after transfer to polyester (approx. 20 sec. At 200 ° C.).

Beispiel 4Example 4

75 Teile des trockenen Farbstoffs der folgenden Konstitution

Figure imgb0006
und 25 Teile des trockenen Farbstoffs der folgenden Konstitution .
Figure imgb0007
70 g eines anionischen Dispergiermittels, z.B. eines Ligninsulfonates oder eines Kondensationsproduktes aus Naphthalinsulfonsäure und Formaldehyd, und 130 ml Wasser werden gemischt und in einer Kugelmühle durch 12-stündiges Mahlen in eine Dispersion übergeführt.75 parts of the dry dye of the following constitution
Figure imgb0006
 and 25 parts of the dry dye of the following constitution.
Figure imgb0007
 70 g of an anionic dispersant, for example a lignosulfonate or a condensation product of naphthalenesulfonic acid and formaldehyde, and 130 ml of water are mixed and converted into a dispersion in a ball mill by grinding for 12 hours.

Die so erhaltene, ca. 33 %ige Präparation ist lagerstabil. Die obige wäßrige Dispersion kann wie folgt zu einer Druckpaste verarbeitet werden: 300 g werden mit 350 g einer 10 %igen Johannisbrotkernmehletherverdickung und 350 ml Wasser angeteigt.The approx. 33% preparation thus obtained is stable on storage. The above aqueous dispersion can be processed into a printing paste as follows: 300 g are pasted with 350 g of a 10% locust bean gum ether thickener and 350 ml of water.

Mit dieser Druckpaste wird ein Papier im Tiefdruckverfahren bedruckt. Verpreßt man dieses Papier während 20 - 60 sec. bei 210°C mit einem Textil aus Polyesterfasern, so erhält man einen farbkräftigen blauen Druck.This printing paste is used to print paper using the gravure printing process. If this paper is pressed for 20 - 60 seconds at 210 ° C with a textile made of polyester fibers, you get a bright blue print.

In der folgenden Tabelle sind weitere Farbstoff angegeben sowie die damit erhältlichen Nuancen nach dem in Beispiel 1 angegebenen Verfahren. Die Farbstoffe sind untereinander mischbar.

Figure imgb0008
Figure imgb0009
Figure imgb0010
Figure imgb0011
Figure imgb0012
Figure imgb0013
Figure imgb0014
Figure imgb0015
Figure imgb0016
Figure imgb0017
Figure imgb0018
Figure imgb0019
Figure imgb0020
Figure imgb0021
 The following table shows further dyestuff and the shades thus obtainable by the process given in Example 1. The dyes can be mixed with one another.
Figure imgb0008
Figure imgb0009
Figure imgb0010
Figure imgb0011
Figure imgb0012
Figure imgb0013
Figure imgb0014
Figure imgb0015
Figure imgb0016
Figure imgb0017
Figure imgb0018
Figure imgb0019
Figure imgb0020
Figure imgb0021

Claims (6)

1. Transferdruckträger, dadurch gekennzeichnet, daß er mit einer Zubereitung imprägniert oder bedruckt ist, die einen Farbstoff der Formel I
Figure imgb0022
in der X Wasserstoff, Chlor oder Brom ist, R 1 für Methoxy oder Ethoxy, oder, wenn X Chlor oder Brom ist, auch für Wasserstoff oder Methyl steht, R 2 Alkyl mit 1 bis 4 Kohlenstoffatomen ist, R3 Wasserstoff ist oder die Bedeutung von R hat und R4 Alkyl mit 1 bis 4 Kohlenstoffatomen ist, oder Mischungen solcher Farbstoffe enthält.1. Transfer print carrier, characterized in that it is impregnated or printed with a preparation which contains a dye of the formula I.
Figure imgb0022
 in which X is hydrogen, chlorine or bromine, R 1 is methoxy or ethoxy, or, if X is chlorine or bromine, also represents hydrogen or methyl, R 2 is alkyl having 1 to 4 carbon atoms, R 3 is hydrogen or the meaning of R and R 4 is alkyl of 1 to 4 carbon atoms, or contains mixtures of such dyes. 2. Träger nach Anspruch 1, dadurch gekennzeichnet, daß sie mit Zubereitungen imprägniert oder bedruckt sind, die Farbstoffe der Formel I enthalten, in der X für Chlor oder Brom steht.2. Carrier according to claim 1, characterized in that they are impregnated or printed with preparations which contain dyes of the formula I in which X is chlorine or bromine. 3. Verfahren zur Herstellung der Träger nach Anspruch 1 und 2, dadurch gekennzeichnet, daß das Trägermaterial mit Zubereitungen imprägniert oder bedruckt wird, die einen Farbstoff der Formel I oder Gemische solcher Farbstoffe enthalten.3. A process for the preparation of the carrier according to claim 1 and 2, characterized in that the carrier material is impregnated or printed with preparations which contain a dye of the formula I or mixtures of such dyes. 4. Verwendung der Träger nach Anspruch 1 und 2 zum Färben und Bedrucken von flächenförmigen Gebilden nach dem Thermotransferdruckverfahren.4. Use of the carrier according to claim 1 and 2 for dyeing and printing sheet-like structures by the thermal transfer printing process. 5. Verwendung der Träger nach Anspruch 1 und 2 zum Färben und Bedrucken von flächenförmigen Gebilden, die aus synthetischen oder teilsynthetischen polymeren Materialien bestehen oder damit präpariert wurden, nach dem Thermotransferdruckverfahren.5. Use of the carrier according to claim 1 and 2 for dyeing and printing sheet-like structures, the consist of synthetic or partially synthetic polymeric materials or were prepared with them, according to the thermal transfer printing process. 6. Verwendung der Träger nach Anspruch 1 und 2 zum Färben und Bedrucken von flächenförmigen Gebilden, die aus natürlichen Fasermaterialien bestehen oder solche enthalten und die mit Präparationen behandelt wurden, die diesen Materialien eine Affinität für die Farbstoffe der Formel I verleihen, nach dem Thermotransferdruckverfahren.6. Use of the carrier according to claim 1 and 2 for dyeing and printing sheet-like structures which consist of or contain natural fiber materials and which have been treated with preparations which give these materials an affinity for the dyes of the formula I, by the thermal transfer printing process.
EP81102902A 1980-04-23 1981-04-15 Transfer printing sheets, process for their preparation and their use Expired EP0038527B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19803015571 DE3015571A1 (en) 1980-04-23 1980-04-23 TRANSFER PRINT CARRIER, METHOD FOR THE PRODUCTION AND USE THEREOF
DE3015571 1980-04-23

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Cited By (2)

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EP0072019A1 (en) * 1981-08-12 1983-02-16 Hoechst Aktiengesellschaft Transfer printing sheet, process for its preparation and its use
EP0126406A2 (en) * 1983-05-20 1984-11-28 BASF Aktiengesellschaft Dye mixtures

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19740325C5 (en) * 1997-09-13 2010-01-21 Siempelkamp Maschinen- Und Anlagenbau Gmbh & Co. Kg Continuous press for pressing pressed material mats to press plates

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DE2300237A1 (en) * 1972-01-05 1973-07-12 Sandoz Ag PRINTING PROCEDURE
DE2364475A1 (en) * 1973-12-24 1975-07-10 Bayer Ag TRANSFER PRINTING PROCEDURE
DE2557002B1 (en) * 1975-12-18 1976-11-04 Hoechst Ag Transfer printing of synthetic fibres using aq. dye dispersions - and polymeric thickeners contg. carboxyl gps.
DE2655882A1 (en) * 1975-12-11 1977-06-23 Toms River Chemical Corp TRANSFER RAILWAYS FOR TRANSFER PRINTING AND PROCEDURES FOR THEIR USE
GB1489016A (en) * 1976-04-02 1977-10-19 Yorkshire Chemicals Ltd Monoazo disperse dyes
DE2832179A1 (en) * 1977-07-25 1979-02-01 Ciba Geigy Ag TRANSFER PRINTING INKS

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JPS5845509B2 (en) * 1976-05-12 1983-10-11 日本化薬株式会社 Transfer printing method for polyester moldings
US4076498A (en) * 1976-09-20 1978-02-28 Martin Marietta Corporation Dyed polyethylene terephthalate textile fibers with greenish blue shade
JPS5358083A (en) * 1976-11-01 1978-05-25 Mitsubishi Chem Ind Process of transfer printing

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2300237A1 (en) * 1972-01-05 1973-07-12 Sandoz Ag PRINTING PROCEDURE
DE2364475A1 (en) * 1973-12-24 1975-07-10 Bayer Ag TRANSFER PRINTING PROCEDURE
DE2655882A1 (en) * 1975-12-11 1977-06-23 Toms River Chemical Corp TRANSFER RAILWAYS FOR TRANSFER PRINTING AND PROCEDURES FOR THEIR USE
DE2557002B1 (en) * 1975-12-18 1976-11-04 Hoechst Ag Transfer printing of synthetic fibres using aq. dye dispersions - and polymeric thickeners contg. carboxyl gps.
GB1489016A (en) * 1976-04-02 1977-10-19 Yorkshire Chemicals Ltd Monoazo disperse dyes
DE2832179A1 (en) * 1977-07-25 1979-02-01 Ciba Geigy Ag TRANSFER PRINTING INKS

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0072019A1 (en) * 1981-08-12 1983-02-16 Hoechst Aktiengesellschaft Transfer printing sheet, process for its preparation and its use
EP0126406A2 (en) * 1983-05-20 1984-11-28 BASF Aktiengesellschaft Dye mixtures
EP0126406A3 (en) * 1983-05-20 1986-07-30 BASF Aktiengesellschaft Dye mixtures

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EP0038527B1 (en) 1984-12-05
DE3015571A1 (en) 1981-10-29
JPS56165078A (en) 1981-12-18
DE3167551D1 (en) 1985-01-17

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