EP0030028A1 - Process for printing synthetic, hydrophobic fibrous material according to the transfer printing principle - Google Patents

Process for printing synthetic, hydrophobic fibrous material according to the transfer printing principle Download PDF

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Publication number
EP0030028A1
EP0030028A1 EP80107480A EP80107480A EP0030028A1 EP 0030028 A1 EP0030028 A1 EP 0030028A1 EP 80107480 A EP80107480 A EP 80107480A EP 80107480 A EP80107480 A EP 80107480A EP 0030028 A1 EP0030028 A1 EP 0030028A1
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Prior art keywords
straight
printing
chain
synthetic
formula
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EP80107480A
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German (de)
French (fr)
Inventor
Horst Dr. Tappe
Claus Schuster
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Sanofi Aventis Deutschland GmbH
Cassella Farbwerke Mainkur AG
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Cassella AG
Cassella Farbwerke Mainkur AG
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Publication of EP0030028A1 publication Critical patent/EP0030028A1/en
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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

  • an auxiliary carrier printed with the transfer printing ink generally paper, is pressed onto the textile material to be printed at elevated temperature on a calender or an ironing press.
  • the dye is transferred to the textile material by sublimation.
  • the textile prints obtained have excellent point and contour sharpness and do not require any of the aftertreatments usually required in textile printing, such as steaming, fixing or washing.
  • GB-PS 1,504,705 dyes of formula 1 described for transfer printing where R 4 and R 5 are H, alkyl or alkenyl having 1 to 5 C atoms and R 3 is H, CH 3 , C 2 H 5 or OCH 3 .
  • the present invention therefore relates to a process for printing synthetic, hydrophobic fiber material or mixtures of synthetic, organic fiber material with the prepared cellulose fibers, further prepared or modified cellulose fibers by the T r ansfertikkal, which is characterized in that as sublimable dyes azo dyes of the general Formula II used, wherein R is H, a straight or branched alkyl group having 1-4 carbon atoms or a straight-chain or comparable zwe IGTE alkenyl group having 3-4 carbon atoms, R 2 is a straight chain alkyl group having 1-4 carbon atoms or a straight-chain alkenyl group with 3-4 carbon atoms.
  • the dyes of the formula II are prepared by processes known per se, for example described in DE-AS 10 19 415, by diazotizing 2-amino-5-nitro-thiazole and on N-acetyl-m-phenylenediamine derivatives of the formula III
  • the coupling components are manufactured using methods known per se, e.g. easily accessible by reactions of N-acetyl-m-phenylenediamine and alkyl or alkenyl halides.
  • Suitable coupling components are, for example, are: 1 - A cetylamino-3-N, N-diethylamino-benzene, 1-acetylamino-3- (N-allyl-N-ethyl) amino-benz oil, 1-acetylamino-3-N-allylamino benzene, 1 - A cetylamino-3-isopropylamino-benzene, 1-acetylamino-3-tert-b utylamino-benzene, 1-acetylamino-3- (N-1-propenyl-N-propyl) amino-benzene; 1-acetylamino-3- (N-2-butenyl-Nn-butyl) aminobenzene, 1-acetylamino-3- (N-isopropyl-N-methyl) amino-benzene, 1-acetylamino-3-N-methallylamino-benzene, 1-acetylamino-3- (N
  • the dye of the formula V is particularly suitable for the process according to the invention
  • the transfer printing process has been described, for example, in French Patents 1,223,330 and 1,334,829.
  • the dyes are, for example, in the form of printing inks, as described, for example, in French patent specification 1,573,698, or as pastes on auxiliary supports, such as paper, other cellulose materials, such as cotton or cellophane, metal foils and the like, as described in French patent specification 1,575 .069 are known, applied by padding, splash rollers or spray guns.
  • the dyes can also be applied to the auxiliary carriers by printing processes using customary printing machines such as Rouleaux, gravure, rotary stencil, flat stencil, relief or flexographic printing machines.
  • the printing inks optionally provide synthetic resin-containing dye solutions or dispersions in suitable organic solvents, for example hydrocarbons, such as, for example, benzene, toluene, xylene, chlorinated hydrocarbons, such as, for example, chlorobenzene, chloroform, dichloroethane, trichlorethylene, perchlorethylene, alcohols, such as, for example, ethanol, isopropanol, Benzyl alcohol and esters, such as ethyl acetate and mixtures thereof.
  • suitable organic solvents for example hydrocarbons, such as, for example, benzene, toluene, xylene, chlorinated hydrocarbons, such as, for example, chlorobenzene, chloroform, dichloroethane, trichlorethylene, perchlorethylene, alcohols, such as, for example, ethanol, isopropanol, Benzyl alcohol and esters, such as ethyl acetate and mixtures thereof.
  • the dyes are in finely dispersed form.
  • the printing inks thus produced contain thickeners, such as e.g. Kernel meal derivatives or alginates or synthetic thickeners, e.g. esterified and / or etherified cellulose derivatives, preferably in combination with ethanol.
  • Substrates suitable for transfer printing with dyes of the formula II are textile materials which consist of polyester, cellulose triacetate, cellulose 2 1/2 acetate, polyamide, polyacrylic nitrile, optionally prepared or modified cellulose fibers and mixtures of these fibers, but also non-textile objects such as foils, tapes or blocks made of commercially available polymer or polycondensate plastics.
  • the dyes are sublimed onto the material to be printed by the action of heat at 140-250 ° C., preferably at 160-220 ° C., for 15-60 seconds or longer.
  • the heat can be applied in various ways, e.g. by hot air, superheated steam, infrared radiation or contact heat, if necessary also using reduced pressure.
  • the dyes of the formula 11 used in accordance with the invention deliver prints in particular on polyester, but also on prepared polyester-cotton mixed fibers and prepared cellulose fibers, with excellent color yields, ie high color strengths, and with excellent fastness properties, such as, for example, lightfastness. Wash fastness (40 ° and 60 ° wash) and water fastness. Furthermore, the dyes of the formula I I used according to the invention have a desired navy blue shade compared to the violet hues of the dyes from GB-PS 1 504 705. In the examples below, parts are parts by weight, percentages unless stated otherwise.
  • 75 parts of the dye of the formula 50 g of an anionic dispersant, such as a lignin sulfonate or a condensation product of naphthalenesulfonic acid and formaldehyde, and 100 parts of water are converted into a finely divided form in a ball mill by grinding for eight hours.
  • 50-200 parts of the aqueous dispersion thus obtained are pasted with 400 parts of a 10% locust bean gum ether thickener and 550 to 400 parts of water. With this printing paste, paper becomes deep printing process printed. If this paper is pressed for 15 to 60 seconds at 200 ° C with a textile made of polyester fibers, you get a clear, strong, navy blue print with good fastness properties.
  • the dye was prepared in the following way: A solution of (0.2 mol) diazotized 2-amino-5-nitrothiazole in a mixture of sulfuric acid, acetic acid and propionic acid (obtained according to the procedure of Example 1 of DE-AS 1 019 415) at 0 to +5 0 C to a solution of 46 g of N, N -diallyl-N'-acetyl-m-phenylenediamine in 200 ml of a mixture of propionic acid and acetic acid (volume ratio 1: 6), which is cooled in an ice bath , added. After a short time the reaction mixture is neutralized against Congo paper by adding sodium acetate in portions and leaving the coupling mixture to itself for 2 to 3 hours. The mixture is then poured into ice water and, after brief stirring, the azo dye formed is isolated by filtration. It was washed thoroughly with water and dried. 54 g of the dye with a melting point of 162 ° C. are obtained.
  • the N, N-diallyl-N'-acetyl-m-phenylenediamine required as coupling component can be obtained by the following procedure: 1000 parts of water, 200 parts of ethanol, 150 parts of N-acetyl-m-phenylcndiamine and 383 parts of allyl chloride are refluxed for 10 hours heated, adding 200 parts of a 30% aqueous ammonia solution. Then it is distilled with steam for 2 hours, then the bottom is cooled to 20 ° C. and the product is filtered off. 195 parts of N, N-diallyl-N'-acetyl-m-phenylenediamine with a melting point of 75 ° C. are obtained.
  • 40 parts of the dye of the formula are kneaded with 60 parts of rosin at 100 to 110 ° C in a kneader until complete homogenization and, after cooling, ground on one of the usual mills.
  • a fine-grain dye powder is obtained.
  • 100 parts of the 40% dye preparation are stirred into 960 parts of varnish (for example a mixture of 20% rosin-modified maleinate resin, 10% polyvinyl butyral, 65% ethanol and 5% ethyl glycol).
  • varnish for example a mixture of 20% rosin-modified maleinate resin, 10% polyvinyl butyral, 65% ethanol and 5% ethyl glycol.
  • the printing ink obtained in this way is used for gravure printing on paper. If this paper is pressed for 15 - 60 seconds at 200 ° C with a fabric made of polyester fibers, you get a strong, navy blue print with good fastness properties.

Abstract

Process for printing synthetic, hydrophobic fibre material or blends of synthetic, hydrophobic fibre material with prepared cellulose materials or prepared cellulose materials by the transfer printing method with sublimable azo dyes of the formula II <IMAGE> where R<1> is H, straight-chain or branched alkyl of 1 to 4 carbon atoms or straight-chain or branched alkenyl of 3 to 4 carbon atoms, R<2> is straight-chain alkyl of 1 to 4 carbon atoms or straight-chain alkenyl of 3 to 4 carbon atoms.

Description

Beim Transferdruck wird ein mit der Transferdruckfarbe bedruckter Hilfsträger, im allgemeinen Papier, auf einem Kalander oder einer Bügelpresse auf das zu bedruckende Textilmaterial bei erhöhter Temperatur aufgedrückt. Dabei wird der Farbstoff durch Sublimation auf das Textilmaterial übertragen. Die erhaltenen Textildrucke besitzen eine hervorragende Punkt-und Konturschärfe und benötigen keine der üblicherweise im Textildruck erforderlichen Nachbehandlungen, wie Dämpfen, Fixieren oder Waschen.In transfer printing, an auxiliary carrier printed with the transfer printing ink, generally paper, is pressed onto the textile material to be printed at elevated temperature on a calender or an ironing press. The dye is transferred to the textile material by sublimation. The textile prints obtained have excellent point and contour sharpness and do not require any of the aftertreatments usually required in textile printing, such as steaming, fixing or washing.

In der GB-PS 1.504.705 werden Farbstoffe der Formel 1

Figure imgb0001
für den Transferdruck beschrieben, wobei R4 und R5 H, Alkyl oder Alkenyl mit 1 bis 5 C-Atomen und R3 H, CH3, C2H5 oder OCH3 bedeuten. Überraschenderweise wurde nun gefunden, daß die Farbstoffe der nachstehenden Formel 11 für das Transferdruckverfahren besonders gut geeignet sind. Die vorliegende Erfindung betrifft daher ein Verfahren zum Bedrucken von synthetischem, hydrophobem Fasermaterial oder von Mischungen von synthetischem, organischem Fasermaterial mit präparierten Cellulosefasern, ferner präparierten oder modifizierten Cellulosefasern nach dem Transferdruckprinzip, das dadurch gekennzeichnet ist, daß man als sublimierbare Farbstoffe Azofarbstoffe der allgemeinen Formel II
Figure imgb0002
 verwendet, worin R H, eine geradkettige oder verzweigte Alkylgruppe mit 1-4 C-Atomen oder eine geradkettige oder ver- zweigte Alkenylgruppe mit 3-4 C-Atomen, R2 eine geradkettige Alkylgruppe mit 1-4 C-Atomen oder eine geradkettige Alkenylgruppe mit 3-4 C-Atomen-hedeuten. Die Farbstoffe der Formel II werden nach an sich bekannten, z.B. in der DE-AS 10 19 415 beschriebenen Verfahren hergestellt, indem man 2-Amino-5-nitro-thiazol diazotiert und auf N-Acetyl-m-phenylendiaminderivate der Formel IIIGB-PS 1,504,705 dyes of formula 1
Figure imgb0001
 described for transfer printing, where R 4 and R 5 are H, alkyl or alkenyl having 1 to 5 C atoms and R 3 is H, CH 3 , C 2 H 5 or OCH 3 . Surprisingly, it has now been found that the dyes of formula 11 below are particularly suitable for the transfer printing process. The present invention therefore relates to a process for printing synthetic, hydrophobic fiber material or mixtures of synthetic, organic fiber material with the prepared cellulose fibers, further prepared or modified cellulose fibers by the T r ansferdruckprinzip, which is characterized in that as sublimable dyes azo dyes of the general Formula II
Figure imgb0002
 used, wherein R is H, a straight or branched alkyl group having 1-4 carbon atoms or a straight-chain or comparable zwe IGTE alkenyl group having 3-4 carbon atoms, R 2 is a straight chain alkyl group having 1-4 carbon atoms or a straight-chain alkenyl group with 3-4 carbon atoms. The dyes of the formula II are prepared by processes known per se, for example described in DE-AS 10 19 415, by diazotizing 2-amino-5-nitro-thiazole and on N-acetyl-m-phenylenediamine derivatives of the formula III

Figure imgb0003
kuppelt, worin R1 und R2 die oben angegebene Bedeutung be-sitzen.
Figure imgb0003
 couples, wherein R 1 and R 2 have the meaning given above.

Die Kupplungskomponenten sind nach an sich bekannten Verfahren z.B. durch Umsetzungen von N-Acetyl-m-phenylendiamin und Alkyl- bzw. Alkenylhalogeniden leicht zugänglich.The coupling components are manufactured using methods known per se, e.g. easily accessible by reactions of N-acetyl-m-phenylenediamine and alkyl or alkenyl halides.

Als Kupplungskomponenten kommen beispielsweise in Betracht: 1-Acetylamino-3-N,N-diethylamino-benzol, 1-Acetylamino-3-(N-allyl-N-ethyl)amino-benzöl, 1-Acetylamino-3-N-allylamino-benzol, 1-Acetylamino-3-isopropylamino-benzol, 1-Acetylamino-3-tert.-butylamino-benzol, 1-Acetylamino-3-(N-1-propenyl-N-propyl)-amino-benzol, 1-Acetylamino-3-(N-2-butenyl-N-n-butyl)aminobenzol, 1-Acetylamino-3-(N-isopropyl-N-methyl)amino-benzol, 1-Acetylamino-3-N-methallylamino-benzol, 1-Acetylamino-3-(N-methallyl-N-allyl)amino-benzol, 1-Acetylamino-3-(N-isopropyl-N-allyl)amino-benzol.Suitable coupling components are, for example, are: 1 - A cetylamino-3-N, N-diethylamino-benzene, 1-acetylamino-3- (N-allyl-N-ethyl) amino-benz oil, 1-acetylamino-3-N-allylamino benzene, 1 - A cetylamino-3-isopropylamino-benzene, 1-acetylamino-3-tert-b utylamino-benzene, 1-acetylamino-3- (N-1-propenyl-N-propyl) amino-benzene; 1-acetylamino-3- (N-2-butenyl-Nn-butyl) aminobenzene, 1-acetylamino-3- (N-isopropyl-N-methyl) amino-benzene, 1-acetylamino-3-N-methallylamino-benzene, 1-acetylamino-3- (N-methallyl-N-allyl) amino-benzene, 1-acetylamino-3- (N-isopropyl-N-allyl) amino-benzene.

Bevorzugt werden Farbstoffe der Formel IVDyes of the formula IV are preferred

Figure imgb0004
worin R1 die oben angegebene Bedeutung besitzt. Besonders geeignet für das erfindungsgemäße Verfahren ist der Farbstoff der Formel V
Figure imgb0005
Das Transferdruckverfahren ist z.B. in den französichen Patentschriften 1.223.330 und 1.334.829 beschrieben worden. Die Farbstoffe werden z.B. in Form von Drucktinten, wie sie z.B. in der französischen Patentschrift 1.573.698 beschrieben sind, oder als Pasten auf Hilfsträger, wie Papier, andere Cellulosematerialien, wie Baumwolle oder Cellophan, Metallfolien und dergleichen, wie sie aus der französischen Patentschrift 1.575.069 bekannt sind, durch Foulardieren, Pflatsch-Walzen oder Spritzpistolen aufgebracht. Die Farbstoffe können auf die Hilfsträger auch nach Druckverfahren mit üblichen Druckmaschinen wie z.B. Rouleaux-, Tief-, Rotationsschablonen-, Flachschablonen-, Relief- oder Flexo-Druckmaschinen aufgebracht werden. Die Drucktinten stellen gegebenenfalls kunstharzhaltige Farbstofflösungen oder -dispersionen in geeigneten, organischen Lösungsmitteln, beispielsweise Kohlenwasserstoffen, wie z.B. Benzol, Toluol, Xylol, Chlorkohlenwasserstoffen, wie z.B. Chlorbenzol, Chloroform, Dichloräthan, Trichloräthylen, Perchloräthylen, Alkoholen, wie z.B. Ethanol, iso-Propanol, Benzylalkohol und Estern, wie z.B. Essigester und deren Mischungen dar.
Figure imgb0004
 wherein R 1 has the meaning given above. The dye of the formula V is particularly suitable for the process according to the invention
Figure imgb0005
 The transfer printing process has been described, for example, in French Patents 1,223,330 and 1,334,829. The dyes are, for example, in the form of printing inks, as described, for example, in French patent specification 1,573,698, or as pastes on auxiliary supports, such as paper, other cellulose materials, such as cotton or cellophane, metal foils and the like, as described in French patent specification 1,575 .069 are known, applied by padding, splash rollers or spray guns. The dyes can also be applied to the auxiliary carriers by printing processes using customary printing machines such as Rouleaux, gravure, rotary stencil, flat stencil, relief or flexographic printing machines. The printing inks optionally provide synthetic resin-containing dye solutions or dispersions in suitable organic solvents, for example hydrocarbons, such as, for example, benzene, toluene, xylene, chlorinated hydrocarbons, such as, for example, chlorobenzene, chloroform, dichloroethane, trichlorethylene, perchlorethylene, alcohols, such as, for example, ethanol, isopropanol, Benzyl alcohol and esters, such as ethyl acetate and mixtures thereof.

Bei wäßrigen Systemen liegen die Farbstoffe in fein dispergierter Form vor. Die damit hergestellten Druckfarben enthalten Verdickungsmittel, wie z.B. Kernmehlderivate oder Alginate oder synthetische Verdicker, wie z.B. veresterte und/oder verätherte Cellulosederivate, bevorzugt in Kombination mit Ethanol.In aqueous systems, the dyes are in finely dispersed form. The printing inks thus produced contain thickeners, such as e.g. Kernel meal derivatives or alginates or synthetic thickeners, e.g. esterified and / or etherified cellulose derivatives, preferably in combination with ethanol.

Für den Transferdruck mit Farbstoffen der Formel II geeignete Substrate sind textile Materialien, die aus Polyester, Cellulosetriacetat, Cellulose 2 1/2-acetat, Polyamid, Polyacrylnitril, gegebenenfalls präparierte oder modifizierte Cellulosefasern und Mischungen dieser Fasern, aber auch nichttextile Gegenstände wie Folien, Bänder oder Blöcke aus handelsüblichen Polymerisat- oder Polykondensatkunststoffen.Substrates suitable for transfer printing with dyes of the formula II are textile materials which consist of polyester, cellulose triacetate, cellulose 2 1/2 acetate, polyamide, polyacrylic nitrile, optionally prepared or modified cellulose fibers and mixtures of these fibers, but also non-textile objects such as foils, tapes or blocks made of commercially available polymer or polycondensate plastics.

Vom Hilfsträger werden die Farbstoffe auf das zu bedruckende Material durch Hitzeeinwirkung bei 140 - 250°C, vorzugsweise bei 160 - 220°C, während 15 - 60 Sekunden oder länger übersublimiert. Die Hitzeeinwirkung kann auf verschiedene Weise, z.B. durch Heißluft, Heißdampf, Infrarotstrahlung oder Kontakthitze, gegebenenfalls auch unter Anwendung von vermindertem Druck, erfolgen.The dyes are sublimed onto the material to be printed by the action of heat at 140-250 ° C., preferably at 160-220 ° C., for 15-60 seconds or longer. The heat can be applied in various ways, e.g. by hot air, superheated steam, infrared radiation or contact heat, if necessary also using reduced pressure.

Die erfindungsgemäß benutzten Farbstoffe der Formel 11 liefern insbesondere auf Polyester, aber auch auf präparierten Polyester-Baumwoll-Mischfasern und präparierten Cellulosefasern Drucke mit vorzüglichen Farbausbeuten, d.h. hohen Farbstärken, und mit exzellenten Echtheiten wie z.B. Lichtechtheit. Waschechtheit (Wäsche 40° und 60°) und Wasserechtheit. Ferner besitzen die erfindungsgemäß verwendeten Farbstoffe der Formel II eine gewünschte marineblaue Nuance gegenüber den violetten Farbtönen der Farbstoffe aus der GB-PS 1 504 705. In den nachfolgenden Beispielen sind Teile Gewichtsteile, Prozente, sofern nichts anderes angegeben, Gewichtsprozente.The dyes of the formula 11 used in accordance with the invention deliver prints in particular on polyester, but also on prepared polyester-cotton mixed fibers and prepared cellulose fibers, with excellent color yields, ie high color strengths, and with excellent fastness properties, such as, for example, lightfastness. Wash fastness (40 ° and 60 ° wash) and water fastness. Furthermore, the dyes of the formula I I used according to the invention have a desired navy blue shade compared to the violet hues of the dyes from GB-PS 1 504 705. In the examples below, parts are parts by weight, percentages unless stated otherwise.

Beispiel 1example 1

75 Teile des Farbstoffs der Formel

Figure imgb0006
50 g eines anionischen Dispergiermittels, wie z.B. eines Ligninsulfonates oder eines Kondensationsproduktes aus Naphthalinsulfonsäure und Formaldehyd, und 100 Teile Wasser werden in einer Kugelmühle durch achtstündiges Mahlen in eine feinverteilte Form übergeführt. 50 - 200 Teile der so erhaltenen, wäßrigen Dispersion werden mit 400 Teilen einer 10%igen Johannisbrotkernmehlätherverdickung und 550 bis 400 Teilen Wasser angeteigt. Mit dieser Druckpaste wird ein Papier im Tiefdruckverfahren bedruckt. Verpreßt man dieses Papier während 15 bis 60 Sekunden bei 200°C mit einem Textil aus Polyesterfasern, so erhält man einen klaren, farbstarken, marineblauen Druck mit guten Echtheiten.75 parts of the dye of the formula
Figure imgb0006
 50 g of an anionic dispersant, such as a lignin sulfonate or a condensation product of naphthalenesulfonic acid and formaldehyde, and 100 parts of water are converted into a finely divided form in a ball mill by grinding for eight hours. 50-200 parts of the aqueous dispersion thus obtained are pasted with 400 parts of a 10% locust bean gum ether thickener and 550 to 400 parts of water. With this printing paste, paper becomes deep printing process printed. If this paper is pressed for 15 to 60 seconds at 200 ° C with a textile made of polyester fibers, you get a clear, strong, navy blue print with good fastness properties.

Der Farbstoff wurde auf folgendem Wege hergestellt: Eine Lösung von (0,2 Mol) diazotiertem 2-Amino-5-nitrothiazol in einem Gemisch aus Schwefelsäure, Essigsäure und Propionsäure (erhalten nach der Vorschrift des Beispiels 1 von DE-AS 1 019 415) wird bei 0 bis +50C zu einer Lösung von 46 g N,N-Diallyl-N'-acetyl-m-phenylendiamin in 200 ml einer Mischung von Propionsäure und Essigsäure (Volumenverhältnis 1:6), die in einem Eisbad gekühlt wird, zugesetzt. Nach einer kurzen Zeit wird die Reaktionsmischung gegen Kongopapier neutralisiert, indem man Natriumacetat portionsweise zusetzt und das Kupplungsgemisch 2 bis 3 Stunden lang sich selbst überläßt. Die Mischung wird dann in Eiswasser gegossen und nach kurzem Rühren der entstandene Azofarbstoff durch Filtrieren isoliert. Es wurde gründlich mit Wasser gewaschen und getrocknet. Man erhält 54 g des Farbstoffs vom Schmelzpunkt 162°C.The dye was prepared in the following way: A solution of (0.2 mol) diazotized 2-amino-5-nitrothiazole in a mixture of sulfuric acid, acetic acid and propionic acid (obtained according to the procedure of Example 1 of DE-AS 1 019 415) at 0 to +5 0 C to a solution of 46 g of N, N -diallyl-N'-acetyl-m-phenylenediamine in 200 ml of a mixture of propionic acid and acetic acid (volume ratio 1: 6), which is cooled in an ice bath , added. After a short time the reaction mixture is neutralized against Congo paper by adding sodium acetate in portions and leaving the coupling mixture to itself for 2 to 3 hours. The mixture is then poured into ice water and, after brief stirring, the azo dye formed is isolated by filtration. It was washed thoroughly with water and dried. 54 g of the dye with a melting point of 162 ° C. are obtained.

Das als Kupplungskomponente benötigte N,N-Diallyl-N'-acetyl-m-phenylendiamin ist nach folgendem Verfahren zugänglich: 1000 Teile Wasser, 200 Teile Ethanol, 150 Teile N-Acetyl-m-phenylcndiamin und 383 Teile Allylchlorid werden 10 Stunden am Rückfluß erhitzt, wobei man 200 Teile einer 30 %igen, wäßrigen Ammoniaklösung zusetzt. Anschließend wird 2 Stunden mit Wasserdampf destilliert, dann der Sumpf auf 20°C abgekühlt und das Produkt abfiltriert. Man erhält 195 Teile N,N-Diallyl-N'- acetyl-m-phenylendiamin vom Schmelzpunkt 75°C.The N, N-diallyl-N'-acetyl-m-phenylenediamine required as coupling component can be obtained by the following procedure: 1000 parts of water, 200 parts of ethanol, 150 parts of N-acetyl-m-phenylcndiamine and 383 parts of allyl chloride are refluxed for 10 hours heated, adding 200 parts of a 30% aqueous ammonia solution. Then it is distilled with steam for 2 hours, then the bottom is cooled to 20 ° C. and the product is filtered off. 195 parts of N, N-diallyl-N'-acetyl-m-phenylenediamine with a melting point of 75 ° C. are obtained.

Beispiel 2Example 2

40 Teile des Farbstoffs der Formel

Figure imgb0007
werden mit 60 Teilen Kolophonium bei 100 bis 110°C in einem Kneter bis zur vollständigen Homogenisierung geknetet und nach dem Abkühlen auf einer der üblichen Mühlen gemahlen. Man erhält ein feinkörniges Farbstoffpulver. 100 Teile der 40 %igen Farbstoffpräparation werden in 960 Teilen Firnis (beispielsweise ein Gemisch aus 20 % kolophoniummodifiziertem Maleinat-Harz, 10 % Polyvinylbutyral, 65% Ethanol und 5 % Ethylglykol) eingerührt. Mit der so erhaltenen Drucktinte wird im Tiefdruck Papier bedruckt. Verpreßt man dieses Papier während 15 - 60 Sekunden bei 200°C mit einem Gewebe aus Polyesterfasern, so erhält man einen farbstarken, marineblauen Druck mit guten Echtheiten.40 parts of the dye of the formula
Figure imgb0007
 are kneaded with 60 parts of rosin at 100 to 110 ° C in a kneader until complete homogenization and, after cooling, ground on one of the usual mills. A fine-grain dye powder is obtained. 100 parts of the 40% dye preparation are stirred into 960 parts of varnish (for example a mixture of 20% rosin-modified maleinate resin, 10% polyvinyl butyral, 65% ethanol and 5% ethyl glycol). The printing ink obtained in this way is used for gravure printing on paper. If this paper is pressed for 15 - 60 seconds at 200 ° C with a fabric made of polyester fibers, you get a strong, navy blue print with good fastness properties.

Claims (3)

1. Verfahren zum Bedrucken von synthetischem, hydrophobem Fasermaterial oder von Mischungen von synthetischem, hydrophobem Fasermaterial mit präparierten Cellulosematerialien oder präparierten Cellulosematerialien nach dem Transferdruckprinzip, dadurch gekennzeichnet, daß man als sublimierbaren Farbstoff einen Azofarbstoff der allgemeinen Formel II
Figure imgb0008
verwendet, worin R1 H, eine geradkettige oder verzweigte Alkylgruppe mit 1-4 C-Atomen oder eine geradkettige oder verzweigte Alkenylgruppe mit 3-4 C-Atomen, R2 eine geradkettige Alkylgruppe mit 1-4 C-Atomen oder eine geradkettige Alkenylgruppe mit 3-4 C-Atomen bedeuten.1. Process for printing synthetic, hydrophobic fiber material or of mixtures of synthetic, hydrophobic fiber material with prepared cellulose materials or prepared cellulose materials according to the transfer printing principle, characterized in that an azo dye of the general formula II is used as the sublimable dye
Figure imgb0008
 used, wherein R 1 H, a straight-chain or branched alkyl group with 1-4 C-atoms or a straight-chain or branched alkenyl group with 3-4 C-atoms, R 2 a straight-chain alkyl group with 1-4 C-atoms or a straight-chain alkenyl group 3-4 C atoms mean. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man Farbstoffe der Formel IV
Figure imgb0009
verwendet, worin R1 die im Anspruch 1 angegebene Bedeutung besitzt.2. The method according to claim 1, characterized in that dyes of the formula IV
Figure imgb0009
 used, wherein R 1 has the meaning given in claim 1. 3. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man den Farbstoff der Formel V
Figure imgb0010
verwendet.3. The method according to claim 1, characterized in that the dye of the formula V
Figure imgb0010
 used.
EP80107480A 1979-12-04 1980-11-29 Process for printing synthetic, hydrophobic fibrous material according to the transfer printing principle Withdrawn EP0030028A1 (en)

Applications Claiming Priority (2)

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DE2948678 1979-12-04
DE19792948678 DE2948678A1 (en) 1979-12-04 1979-12-04 METHOD FOR PRINTING SYNTHETIC, HYDROPHOBIC FIBER MATERIAL ACCORDING TO THE TRANSFER PRINTING PRINCIPLE

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EP0030028A1 true EP0030028A1 (en) 1981-06-10

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0216483A1 (en) * 1985-08-27 1987-04-01 Zeneca Limited Thermal transfer printing
EP0227095A2 (en) * 1985-12-24 1987-07-01 EASTMAN KODAK COMPANY (a New Jersey corporation) Magenta dye-donor element used in thermal dye transfer
USRE33819E (en) * 1985-12-24 1992-02-11 Eastman Kodak Company Magenta dye-donor element used in thermal dye transfer
US5358536A (en) * 1991-07-31 1994-10-25 Mitsui Toatsu Chemicals, Incorporated Dyestuff for heat-sensitive transfer record and transfer sheet containing same

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57209057A (en) * 1981-06-16 1982-12-22 Tsuneo Kumaki Neck part tracting machine

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1019415B (en) * 1951-06-23 1957-11-14 Eastman Kodak Co Process for the preparation of monoazo dyes
JPS54156882A (en) * 1978-05-26 1979-12-11 Mitsubishi Chem Ind Transfer printing method

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1019415B (en) * 1951-06-23 1957-11-14 Eastman Kodak Co Process for the preparation of monoazo dyes
JPS54156882A (en) * 1978-05-26 1979-12-11 Mitsubishi Chem Ind Transfer printing method

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, Band 92, Nr. 18, 5. Mai 1980, Seite 89, Zusammenfassung Nr. 148442r, Columbus, Ohio, US, & JP - A - 79 156 882 (MITSUBISHI CHEMICAL INDUSTRIES) (11.12.1979). *

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0216483A1 (en) * 1985-08-27 1987-04-01 Zeneca Limited Thermal transfer printing
US4764178A (en) * 1985-08-27 1988-08-16 Imperial Chemical Industries Plc Thermal transfer printing: hetero-aromatic azo dye
USRE36357E (en) * 1985-08-27 1999-10-26 Imperial Chemical Industries Plc Thermal transfer printing: hetero-aromatic azo dye
EP0227095A2 (en) * 1985-12-24 1987-07-01 EASTMAN KODAK COMPANY (a New Jersey corporation) Magenta dye-donor element used in thermal dye transfer
US4698651A (en) * 1985-12-24 1987-10-06 Eastman Kodak Company Magenta dye-donor element used in thermal dye transfer
EP0227095A3 (en) * 1985-12-24 1988-07-27 Eastman Kodak Company Magenta dye-donor element used in thermal dye transfer
USRE33819E (en) * 1985-12-24 1992-02-11 Eastman Kodak Company Magenta dye-donor element used in thermal dye transfer
US5358536A (en) * 1991-07-31 1994-10-25 Mitsui Toatsu Chemicals, Incorporated Dyestuff for heat-sensitive transfer record and transfer sheet containing same
US5567470A (en) * 1991-07-31 1996-10-22 Mitsui Toatsu Chemicals, Incorporated Heat-sensitive transfer sheet containing blue dyestuff

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JPS5691087A (en) 1981-07-23

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