EP0013892A2 - Process for dyeing synthetic fibre materials by the extraction method - Google Patents

Abstract

1. Process for dyeing synthetic, hydrophobic fibre materials with organophilic dyestuffs, which are free from sulphonic acid groups, by the extraction method, in which the liquor, which circulates in a closed circuit, flows through a dyestuff depot from which the dyestuff is removed by a dissolution process and is then fed to the material to be dyed, characterized in that the depot is charged with non-finished, if necessary coarsely comminuted or spray-dried dyestuffs having a minimum solubility of 20 mg/l in water at 130 degrees C and an aqueous, emulsifier-free dyeing liquor is allowed to flow through the depot at the dyeing temperature.

Description

The invention relates to a process for dyeing synthetic, hydrophobic fiber materials with organophilic dyes free of sulfonic acid groups by the extraction method.

This special variant of an exhaust process, in which the liquor, which is advantageously circulating in a circuit, flows through a dye depot, from which the dye is removed by a dissolving process and then fed to the material to be dyed, is well known (cf. DE-OS 1 918 309, 1 938 792 and 2 215 336).

The known methods are oriented almost exclusively to the use of organic solvents as the liquor medium, but they have the disadvantage that the dyes introduced therein have a distribution which is substantially lower than that of water as the coloring medium have coefficients. This fact in turn means that when organic solvents are used, complete bath exhaustion is never achieved, which necessitates complex cleaning operations on the dyeing machines.

The colorings often leave something to be desired in terms of rub fastness and levelness.

There has been no shortage of attempts to overcome these disadvantages, for example by switching on special filters (cf. DE-OS 2 047 192).

However, these methods have so far not been successful in practice.

In the patent literature cited above, the use of water as a coloring medium is sometimes also suggested, but without giving detailed information on the technical implementation of this idea.

In Example 18b of DE-OS 2 247 568 alone, a Soxhleta apparatus is described in which the colorant is deposited in a glass fiber sleeve which is de facto flowed through by the cold water condensed on the reflux condenser of the apparatus.

This variant of the method has so far not found its way into practice, since the preparation of the dyeing preparations is relatively complex and the extraction process is too slow.

It has now been found that, while overcoming the disadvantages dealt with above, the extraction process known per se can be carried out in a simple manner, i.e. can be used for dyeing hydrophobic fibers without the use of special preparations and while observing economically interesting dyeing times, if the depot is charged with a dye with a minimum solubility in water of 20 mg / l at 130 ° C and is flowed through by an aqueous dye liquor at dyeing temperature, which is free of emulsifiers and dispersants.

The flow through the fleet can take place directly or indirectly in a so-called by-pass.

The execution of this dyeing process or the dye depots is not tied to certain equipment requirements. The use of precoat filters, as recommended in DE-OS 1 918 309 for dyeing from organic solvents, is also possible, such as fine-mesh filter baskets or systems that enable liquid / liquid extraction with relatively low-melting dyes. Systems of this type are already recommended for the use of dye solutions in water-immiscible solvents (DE-OS 2 239 563).

Suitable dyes for carrying out the process are described in detail and comprehensively in the patent literature or - in the case of commercial products - are listed in the Color Index. They can belong to a wide variety of chromophoric systems. Examples include dyes from the azo, anthraquinone, quinophthalone, perinone and methine series, and organophilic optical brighteners.

Suitable dyes are, in particular, those which are more than 50 mg / l, in particular 100 mg / l, soluble in the aqueous liquor at 130 ° C.

The solubility in water is determined by methods known per se, for example by taking a measured amount of dye solution at 130 ° C. from a suitable apparatus, as described, for example, in Melliand Textile Reports 11, (1969), page 1342, using a sample with Water-miscible polar, organic solvents (eg dimethylformamide) are diluted and the dye content therein is determined photometrically.

wobei V für gegebenenfalls substituiertes Alkyl, Aralkyl oder Aryl, V₁ und V₂ für Wasserstoff oder gegebenenfalls substituiertes Alkyl, Aralkyl oder Aryl, V' für V, oder Acyl und n für Zahlen von 1 - 8 stehen.Particularly suitable are those dyes which carry a hydrophilizing substituent group R, such as

where V is optionally substituted alkyl, aralkyl or aryl, V ₁ and V _{2 is} hydrogen or optionally substituted alkyl, aralkyl or aryl, V 'is V, or acyl and n are numbers from 1-8.

wobei V und n die oben angegebene Bedeutung haben.Of particular importance from this group are those dyes which have the following substituents: - _COOH , - _COO V, -O-COOV, -O-CO-NH-V, - (CH ₂ -CH ₂ -O-) _n V

where V and n have the meaning given above.

• a) Monoazofarbstoffe der Formel
  
  in der
  • D für den Rest einer aromatischen carbocyclischen oder heterocyclischen Diazokomponente stent,
  • Ar für den Rest einer aromatischen carbocyclischen oder heterocyclischen Kupplungskomponete und
  • K₁ u. K₂ H Alkyl, Aralkyl, Aryl- oder Oxalkylgruppen bedeuten, wobei K₁, K₂ oder Ar gegebenenfalls über ein Brückenglied mindestens einmal den Substituenten R tragen.
• b) Monoazofarbstoffe der Formel
  
  in der
  • D₁ für den Rest einer carbocyclischen oder heterocvclischen Diazokomponente steht, die mindestens einmal den Substituenten R gegebenenfalls über ein Brückenglied gebunden trägt,
  • Ar die in a) angegebene Bedeutung hat und
  • K₃ u. K₄ H oder gegebenenfalls substituierte Alkyl-, Aryl-, Aralkyl-bzw. Oxalkylgruppen bedeuten.
• c) Monoazofarbstoffe der Formel
  
  in der
  • D₂ für den Rest einer carbocyclischen oder heterocyclischen Diazokomponente steht und
  • K für den Rest einer Kupplungskomponente der Phenol-, Naphthol-, Acylessigsäureamid-, Pyrazol-, Pyridin- oder Chinolin-Reihe, wobei mindestens einer der Reste D₂ oder K mindestens einmal den Substituenten R trägt, der gegebenenfalls über das phenolische bzw. enolische Sauerstoffatom gebunden ist.
• d) Disazofarbstoffe der Formel
  
  in der
  • Ar₂ einen Arylenrest bedeutet,
  • Ar₁ u. Ar₃ stehen für Aryl- oder Hetarylreste, wobei in
  • Ar₁, Ar₂ oder Ar₃ mindestens einmal ein Substituent R vorhanden sein muß.
• e) Anthrachinonfarbstoffe der allgemeinen Formel
  
  worin
  • E für Halogen, bevorzugt Brom oder Chlor steht, für Alkoxy- oder Aryloxy, für die Carboxylgruppe bzw. deren funktionelle Derivate oder gegebenenfalls su_bst. Alkyl- und Arylreste,
  • n 0, 1 oder 2 bedeutet,
  • A₁, A₂, A₃ oder A₄ jeweils Wasserstoff, eine gegebenenfalls durch Alkyl-, Aralkyl-, Cycloalkyl-, Aryl- oder Hetaryl-Reste substituierte Aminogruppe der Hydroxy-oder Nitrogruppe bedeuten, wobei mindestens einer der Rest A₁, A₂, A₃, A₄ eine gegebenenfalls subst. Aminogruppe oder Hydroxy darstellt und die Substituenten A₁-A₄ E oder der Anthrachinonkern selbst mindestens einmal den Substituenten R gegebenenfalls über ein Brückenglied gebunden trägt.
• f) Chinophthalcnfarbstoffe der Formel
  
  in der
  • E₁ u. E2 Wasserstoff, Halogen, Alkoxy, Acyloxy, Acylamino oder die Carboxylgruppe bzw. deren funktionelle Derivate bedeuten,
  • m 0, 1 oder 2 bedeuten und der Chinolin oder der Phthaloylrest mindestens einmal den Substituenten -G-R trägt.
• g) Nitro-Diarylaminofarbstoffe der Formel
  
  in der
  • E3 Wasserstoff, Alkoxy oder Aryloxy, substit. Amino, Halogen, Arylazo, Carboxyl oder funktionelle Derivate eines Sulfonsäure oder Carboxyl-Restes bedeuten und mindestens einer der aromatischen Ringe oder E3 mindestens einmal den Substituenten -R trägt.
• h) Methinfarbstoffe der Formel
  
  in der
  • K₁ ^u _. ^K _Z ^H oder gegebenenfalls substituierte Alkyl, Aralkyl bzw. Oxalkylgruppen bedeuten.
  • E₄ steht für Wasserstoff, Alkyl oder Alkoxy
  • V₁ u. V2 stehen für Nitril, Alkoxycarbonyl, Alkylcarbonyl oder Alkylsulfongruppen , wobei

entweder V₁, V₂, K₁, K₂, E₄ oder der aromatische Ring mindestens einmal den Substituenten R tragen.Particularly preferred dyes are derived, for example, from the following classes of compounds:

• a) Monoazo dyes of the formula
  
  in the
  • D stent for the rest of an aromatic carbocyclic or heterocyclic diazo component,
  • Ar for the rest of an aromatic carbocyclic or heterocyclic coupling component and
  • K ₁ u. K ₂ H is alkyl, aralkyl, aryl or oxalkyl groups, K ₁ , K ₂ or Ar optionally having the substituent R at least once via a bridge member.
• b) monoazo dyes of the formula
  
  in the
  • D _{1 represents} the remainder of a carbocyclic or heterocyclic diazo component which carries the substituent R at least once, optionally bonded via a bridge member,
  • Ar has the meaning given in a) and
  • K ₃ u. K ₄ H or optionally substituted alkyl, aryl, aralkyl or. Oxoxy groups mean.
• c) monoazo dyes of the formula
  
  in the
  • D _{2 represents} the rest of a carbocyclic or heterocyclic diazo component and
  • K for the rest of a coupling component of the phenol, naphthol, acylacetic acid amide, pyrazole, pyridine or quinoline series, at least one of the radicals D ₂ or K bearing at least once the substituent R, which is optionally via the phenolic or enolic Oxygen atom is bound.
• d) disazo dyes of the formula
  
  in the
  • Ar _{2 represents} an arylene radical,
  • Ar ₁ u. Ar ₃ stand for aryl or hetaryl radicals, wherein in
  • Ar ₁ , Ar ₂ or Ar ₃ must have a substituent R at least once.
• e) Anthraquinone dyes of the general formula
  
  wherein
  • E stands for halogen, preferably bromine or chlorine, for alkoxy- or aryloxy, for the carboxyl group or its functional derivatives or optionally su _bs t. Alkyl and aryl radicals,
  • n means 0, 1 or 2,
  • A ₁ , A ₂ , A ₃ or A ₄ each represent hydrogen, an amino group of the hydroxyl or nitro group which is optionally substituted by alkyl, aralkyl, cycloalkyl, aryl or hetaryl radicals, at least one of the radicals A ₁ , A ₂ , A ₃ , A ₄ an optionally subst. Represents amino group or hydroxy and the substituents A ₁ -A ₄ E or the anthraquinone nucleus itself at least once carries the substituent R optionally bonded via a bridge member.
• f) quinophthalcn dyes of the formula
  
  in the
  • E ₁ u. E2 is hydrogen, halogen, alkoxy, acyloxy, acylamino or the carboxyl group or their functional derivatives,
  • m is 0, 1 or 2 and the quinoline or the phthaloyl radical bears the substituent -GR at least once.
• g) nitro-diarylamino dyes of the formula
  
  in the
  • E3 hydrogen, alkoxy or aryloxy, substit. Amino, halogen, arylazo, carboxyl or functional derivatives of a sulfonic acid or carboxyl radical and at least one of the aromatic rings or E3 bears the substituent -R at least once.
• h) methine dyes of the formula
  
  in the
  • K ₁ ^u _. ^K _Z ^H or optionally substituted alkyl, aralkyl or oxalkyl groups.
  • E ₄ represents hydrogen, alkyl or alkoxy
  • V ₁ u. V2 stands for nitrile, alkoxycarbonyl, alkylcarbonyl or alkylsulfone groups, where

either V ₁ , V ₂ , K ₁ , K ₂ , E ₄ or the aromatic ring bear the substituent R at least once.

Unless otherwise defined, the alkyl and alkoxy radicals mentioned above in any context preferably have 1 to 4 carbon atoms and can be substituted by substituents customary in dye or auxiliary chemistry (for example OH, CN, Cl, N0 ₂ , F, Br, alkoxycarbonyl or alkoxy), with the exception of ionic radicals (except COOH) for the dye radicals.

Suitable aryl or aryloxy radicals are naphthalene and especially benzene radicals, which may be substituted by, for example, alkyl, alkoxy, Cl, F, Br, N0 ₂ , alkoxycarbonyl, CF ₃ , CN or COOH. are.

Suitable hetaryl radicals are pyridyl, thienyl, furyl, quinolinyl, thiazolyl, thiadiazolyl and pyrazolyl.

Suitable alkylene radicals preferably have 2-10 carbon atoms in the chain, which can optionally be substituted by alkyl, aryl, aralkyl or COOH. -C ₂ H ₄ - is preferred.

Suitable arylene residues are naphthylene - and especially phenyl residues, which e.g. by alkyl or aryl subst. could be.

Suitable bridge members are 0, S, CO, alkylene, phenylene and others.

Suitable derivatives of the carboxyl group are nitriles, carboxamides, alkyl esters, acid anhydrides and imides.

On the one hand, very particular preference is given to those dyes of the formulas given above which have at least one radical R = - (CH ₂ CH ₂ 0) _n -V and where n = 2-5, preferably = 3-4, and on the other hand those of these formulas, which have at least one radical R = COOV, OCOOV, OCONHV, C2H4oH or C ₂ H ₄ CN.

• Farbstoffe der Azobenzolreihe,
  die in der Kupplungskomponente die vorstehend genannten Reste und in der Diazokomponente in ortho- und/oder paraStellung zur Azolreihe stark elektronenziehende Substituenten, wie CN, N0₂, S0₂-Alkyl, aufweisen, sowie der Hetarylazobenzolreihe.

Within the latter type are preferred:

• Azobenzene series dyes,
  which in the coupling component have the abovementioned radicals and in the diazo component in the ortho and / or para position to the azole series strongly electron-withdrawing substituents, such as CN, N0 ₂ , S0 ₂ alkyl, and the hetarylazobenzene series.

worin

• R₁ für C₂H₄OH, C₂H₄OCOCH₃, C₂H₄OCOOCH₃, C₂H₄OCOOC₂H₅, C₂H₄COOCH₃, C₂H₄COOC₂H₅, C₂H₄OC₂H₄OCH₃, C₂H₄OCONHX
• R₂ für R₁ oder H, C₂H₅, C₂H₄CN, C₂H₄OCH₃,
• R₃ für H, CH₃ oder NHCOCH₃,
• R₄ für _H, _Cl oder OCH₃,
• R₅ für _Cl, _Br, CN, ^N0 ₂,
• R₆ für NO₂, CN.
• R₇ für H, Cl, Br oder CN und
• X für C₁-C₄-Alkyl oder Phenyl stehen.

Particularly preferred dyes correspond to the formula

wherein

• R ₁ for C ₂ H ₄ OH, C ₂ H ₄ OCOCH ₃ , C ₂ H ₄ OCOOCH ₃ , C ₂ H ₄ OCOOC ₂ H ₅ , C ₂ H ₄ COOCH ₃ , C ₂ H ₄ COOC ₂ H ₅ , C ₂ H ₄ OC ₂ H ₄ OCH ₃ , C ₂ H ₄ OCONHX
• R ₂ for R ₁ or H, C ₂ H ₅ , C ₂ H ₄ CN, C ₂ H ₄ OCH ₃ ,
• R ₃ for H, CH ₃ or NHCOCH ₃ ,
• R ₄ for _H , _Cl or OCH ₃ ,
• R ₅ for _Cl , _B r, CN, ^N0 ₂ ,
• R ₆ for NO ₂ , CN.
• R ₇ for H, Cl, Br or CN and
• X represents C ₁ -C ₄ alkyl or phenyl.

Suitable diazo components of these particularly preferred types are also

Very particularly preferred polyether dyes are those of the formula IX, in which at least one of the radicals R ₁ -R _{7 represents} the radical - (C ₂ H ₄ O) _m X, which is present directly or via a bridge, for example 0 or CO to which the azobenzene molecule is bound and m is 2-5.

The dyes are used in the form of powder or granules or - according to a preferred process variant - as tablets. If appropriate, these formation forms can contain customary auxiliaries such as dispersants, mold release agents, blending agents, etc. An intensive grinding process, however, is not necessary when producing these preparations.

The dyeings can be carried out at the boiling point of the aqueous dye liquor or - preferably - in closed dyeing systems at temperatures of approx. 130 ° C.

The fiber material is dyed in a weakly acidic to weakly alkaline bath, advantageously at a pH of 3.5-6; the liquor ratio can vary between 1: 3 - 1:40, preferably in the range 1: 8 to 1:20.

Auxiliaries with a known effect can be added to the dye liquor - for example phenol derivatives such as o-phenylphenol, methyl salicylic acid, chlorinated aromatic hydrocarbons such as o-dichlorobenzene or methylnaphthalenes or 2,2'-dinaphthylsulfonic acid sodium. Depending on the color depth and liquor ratio, the amounts of auxiliary agents that are added vary between 0.1 g / 1 and 4 g / l.

The aqueous moths, which apart from the indicated auxiliaries can only contain the substances necessary for pH regulation, are generally free of organic solvents.

For dyeing according to the claimed process, structures made of polyesters, cellulose acetates or polyamides are suitable as textile materials, these fibers being able to be used in a mixture with one another or together with natural fibers such as wool or cotton.

In the case of fiber mixtures, the present process for dyeing the synthetic fibers can be combined with dyeing operations for dyeing the native fiber components. Of course, dye mixtures are also used for dyeing a type of fiber according to the dyeing process claimed.

The following examples illustrate the invention without being limited thereto. The percentages given are percentages by weight based on the material to be colored; the temperatures are given in degrees Celsius.

example 1

beschickt, die Anlage mit Wasser ohne jeden weiteren Zusatz gefüllt und die wäßrige Flotte rasch auf 130°C aufgeheizt. Die Zirkulation durch den Wickelkörper erfolgt im Wechsel von 3 Min. bzw. 5 _Min. von innen nach außen und umgekehrt. Der Wasserstrom kann dabei sofort, d.h. mit Beginn der Aufheizphase oder auch erst nach Erreichen von 100 bzw. 130°C durch das Depot geleitet werden. Nach einer Färbezeit von 45 Min. bei 130°C ist der Farbstoff vollständig aus dem Depot gelöst und auf die Polyester-Kreuzspule aufgezogen. Das Färbebad wird nach Abkühlen auf ca. 80°C abgelassen. Nach einer kurzen Spülpassage erhält man eine Gelbfärbung in 1/1 Richttyptiefe von ausgezeichneter Egalität, die sich in keiner Weise in Farbtiefe und Farbton von einer wie üblich reduktive nachbehandelten 6 %igen Färbung unterscheidet, die mit formiertem Handelsfarbstoff hergestellt wurde.500 parts of polyester yarn are dyed in the form of a bobbin in a bobbin dyeing machine with a dye depot; for this purpose, the depot with 9 parts of a coarsely comminuted, unformed dye of the formula

charged, the system filled with water without any further additives and the aqueous liquor heated to 130 ° C quickly. The circulation through the wound body is performed in the change of 3 min. And 5 _M in. From the inside out and vice versa. The water flow can be directed through the depot immediately, ie at the beginning of the heating phase or only after reaching 100 or 130 ° C. After a dyeing time of 45 minutes at 130 ° C, the dye is completely detached from the depot and applied to the polyester cheese. The dyebath is drained after cooling to approx. 80 ° C. After a short rinsing passage, a yellow color in 1/1 standard depth of excellent levelness is obtained, which in no way differs in color depth and color tone from a reductive aftertreated 6% coloration, which was produced with formed commercial dye.

For example, 1 g / 1 sodium acetate and 1 ml / 1 acetic acid 30% strength is added to the aqueous liquors for pH regulation. in this way dyeings with the same depth of color, brilliance and fastness are achieved.

Example 2

und 5 % Binde- bzw. Trennmittel (hergestellt auf einem Rundlauf oder Exzenter-Tabletten-Presse mit Druck von 900 - 1000 Atmosphären) beschickt und die Anlage mit Wasser gefüllt. Die Flotte wird so schnell wie möglich auf 130°C gebracht und 50 Minuten bei dieser Temperatur gefärbt. Nach dem Abkühlen und Ablassen der Flotte und Spülen erhält man eine rotviolette Färbung in 1/1 RTT, die sich nicht von einer red. nachbehandelten Färbung unterscheidet, die mit gefinishtem Farbstoff erhalten wird, wenn die eingesetzten Reinfarbstoffmengen beider Färbungen gleich sind.200 parts of polyester piece goods are wound onto a material carrier and inserted into the cross-winder dyeing machine described above. The depot is filled with 1.1 parts of a tabletted dye, consisting of 95% of the dye of the formula

and 5% binder or release agent (produced on a rotary machine or eccentric tablet press with a pressure of 900-1000 atmospheres) and the system is filled with water. The liquor is brought to 130 ° C. as quickly as possible and dyed at this temperature for 50 minutes. After cooling and draining the liquor and rinsing, a red-violet color in 1/1 RTT is obtained, which does not differ from a red. post-treated coloring, which is obtained with finished dye if the amounts of pure dye used are the same for both dyeings.

Example 3

in Form eines Sprühgranulates und verfährt im übrigen wie in den Beispielen 1 - 2 angegeben, so erhält man eine brillante Rotfärbung, die in Farbtiefe, Farbton und Echtheiten einer Färbung nach konventioneller Färbemethode entspricht.Instead of the dye mentioned in Example 1, 0.22% of the dye of the formula is used

in the form of a spray granulate and otherwise operates as described in Examples 1-2, a brilliant red color is obtained which corresponds in color depth, color tone and fastness to a dyeing according to the conventional dyeing method.

If, instead of the dyes used in Examples 1-3, which are listed in the following table, the same procedure is used to obtain level dyeings with the same or even slightly higher color depths than those obtained with conventionally finished disperse dyes according to the usual dyeing method.

Claims (4)

1) Process for dyeing synthetic, hydrophobic fiber materials with organophilic dyes free from sulfonic acid groups, using the extraction method, the circulating liquor flowing through a dye depot from which the dye is removed by a dissolution process and then fed to the material to be dyed, characterized in that that the depot is charged with dyes with a minimum solubility in hot water of 130 ° C. of 20 mg / l and is flowed through by an aqueous, emulsifier-free dye liquor at dyeing temperature. 2) Method according to claim 1, characterized in that the dyes have a minimum solubility in water of 50 mg / l at 130 ° C. 3) Method according to claim 1, characterized in that the dyes have a minimum solubility in water of 100 mg / l at 130 ° C. 4) Process according to claim 1, characterized in that the dyes used are those which include a hydrophilizing substituent group from the series

where V is optionally substituted alkyl, aralkyl or aryl, V ₁ and V _{2 are} hydrogen or optionally substituted alkyl, aralkyl or aryl, V 'is V ₁ or acyl and n are numbers from 1-8.