EP0252386B1 - Process for improving the fastness to light of polyamide dyeings - Google Patents

Process for improving the fastness to light of polyamide dyeings

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Publication number
EP0252386B1
EP0252386B1 EP87109228A EP87109228A EP0252386B1 EP 0252386 B1 EP0252386 B1 EP 0252386B1 EP 87109228 A EP87109228 A EP 87109228A EP 87109228 A EP87109228 A EP 87109228A EP 0252386 B1 EP0252386 B1 EP 0252386B1
Authority
EP
European Patent Office
Prior art keywords
acid
process according
copper
dyeings
compounds
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP87109228A
Other languages
German (de)
French (fr)
Other versions
EP0252386A1 (en
Inventor
Thomas Dr. Scholl
Klaus-Peter Dr. Heise
Hans-Albert Dipl.-Ing. Ehlert
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer AG
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Bayer AG
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Publication of EP0252386A1 publication Critical patent/EP0252386A1/en
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Classifications

    • 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
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/653—Nitrogen-free carboxylic acids or their salts
    • D06P1/6536—Aromatic
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
    • D06M13/503—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms without bond between a carbon atom and a metal or a boron, silicon, selenium or tellurium atom
    • 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
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/62—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing low-molecular-weight organic compounds with sulfate, sulfonate, sulfenic or sulfinic groups
    • 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
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/64—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing low-molecular-weight organic compounds without sulfate or sulfonate groups
    • 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
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/64—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing low-molecular-weight organic compounds without sulfate or sulfonate groups
    • D06P1/651—Compounds without nitrogen
    • D06P1/65106—Oxygen-containing compounds
    • D06P1/65112—Compounds containing aldehyde or ketone groups
    • 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
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/64—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing low-molecular-weight organic compounds without sulfate or sulfonate groups
    • D06P1/651—Compounds without nitrogen
    • D06P1/65106—Oxygen-containing compounds
    • D06P1/65125—Compounds containing ester groups
    • 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
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/02—Material containing basic nitrogen
    • D06P3/04—Material containing basic nitrogen containing amide groups
    • D06P3/24—Polyamides; Polyurethanes
    • D06P3/241—Polyamides; Polyurethanes using acid dyes
    • 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
    • D06P5/02—After-treatment

Definitions

  • the invention relates to a method for improving the light fastness of dyeings on polyamide fiber materials, in particular textile materials for the automotive sector, using copper compounds.
  • auxiliaries have so far not been able to fully meet the high demands of automobile manufacturers, since the effects achieved were not quite sufficient.
  • Some of the auxiliaries also have an undesirable inherent color and / or are relatively expensive because of their complex production method.
  • Suitable halogen atoms are F, Br and especially Cl.
  • Suitable alkyl radicals are straight-chain or branched and optionally unsaturated.
  • the acid groups mentioned can also be in salt form.
  • Preferred compounds of the formula are symmetrical types.
  • the copper complexes according to the invention can also be obtained from mixtures of aromatic o-hydroxycarboxylic acids.
  • the amount used is 0.01 to 3, preferably 0.05 to 0.2% by weight (based on polyamide).
  • the Cu complexes according to the invention are prepared in a manner known per se by reacting alkali metal salts of aromatic o-hydroxycarboxylic acids in an aqueous medium with a copper (II) salt, such as CuCl 2 , CuSO 4 .5H 2 O, Cu (OAc) 2 -H 2 0 or CuCO 3 .Cu (OH) 2.
  • a copper (II) salt such as CuCl 2 , CuSO 4 .5H 2 O, Cu (OAc) 2 -H 2 0 or CuCO 3 .Cu (OH) 2.
  • the dyeings on polyamide fibers can be produced in a conventional manner with azo metal complex dyes and anthraquinone dyes as well as with acid dyes.
  • the metal complex dyes in particular the 1: 2 chromium or 1: 2 cobalt complexes of azo compounds, which are described in large numbers in the literature and are commercially available, are preferred. These dyes can also contain 1 to 2 sulfo groups.
  • the treatment of the polyamide materials with the copper compounds to be used according to the invention can take place before, during or after, preferably during the dyeing.
  • the copper compounds normally produced separately are used in finely divided form, as is obtained by grinding in the presence of customary dispersants.
  • this is carried out, as it were, in a "one-pot", in that the fiber materials are not treated directly with the copper compounds isolated in solid form, but - in principle in any order - are produced in situ from the corresponding starting materials on the fiber.
  • the fibers are first dyed with a dyeing liquor which, in addition to the dye and, if appropriate, customary dyeing auxiliaries, contains the metal-free compounds of the formula I and then treated with a copper (II) salt solution.
  • the compounds of the formula are preferably used without any cocatalysts.
  • the dyeings obtainable with the copper complexes to be used according to the invention are distinguished by a high resistance to hot light irradiation in accordance with DIN 75 202, and there is no discoloration of the fibers even when these auxiliaries are metered in higher amounts
  • Di-p-tert-butylsalicylate copper are made from 2 moles of 5-tert-butylsalicylic acid, 2 moles of NaOH and 1 mole of CuSO 4 .5H 2 O according to the procedure of Example 1 as green crystals with a Cu content of 14% receive.
  • Disalicylate-copper-5,5'-disulfonic acid Na salt 234 g of 2-hydroxybenzoic acid-5-sulfonic acid and 80 g of NaOH are dissolved in 620 g of water. A solution of 125 g of CUS0 4 -5H 2 0 in 350 ml of water is then added dropwise and the mixture is heated at 50 ° C. for 1 hour. A dark green, approx. 22% aqueous solution of disalicylate-copper-5,5'- is obtained. disulfonic acid Na salt, which can be used in this form to stabilize polyamide dyeings.
  • 100 parts of polyamide 6 fiber material are introduced into 2,000 parts of aqueous dye liquor, the 0.08 part of the copper complex of preparation example 1 and 0.15 part of the dye of the formula receives.
  • a pH of 8 is set by adding mono- and disodium psophate.
  • the liquor temperature is then slowly increased to 98 to 100 ° C. while the material to be dyed is kept and left at this temperature for 60 minutes.
  • the dye is then removed from the dye bath, rinsed and dried.
  • the dyeing is subjected to a hot exposure together with a comparative dyeing prepared without the copper complex mentioned in accordance with the draft DIN 75 202.
  • the dyeing thus produced shows excellent lightfastness.
  • the dye liquor is adjusted to pH 5.5 with the aid of a buffer mixture of mono-sodium phosphate and acetic acid. It is treated for one hour at 98 to 100 ° C, rinsed and dried.
  • the coloring produced in this way shows a clearly better light fastness than one produced without the copper complex mentioned.
  • the dyeing treated in this way exposed according to draft DIN 75 202, has a significantly better lightfastness than the untreated dyeing.
  • the dyeings behave as if no light stabilizer has been added to the dyeing liquor.

Description

Gegenstand der Erfindung ist ein Verfahren zur Lichtechtheitsverbesserung von Färbungen auf Polyamidfasermaterialien, insbesondere Textilmaterialien für den Automobilsektor, mit Hilfe von Kupferverbindungen.The invention relates to a method for improving the light fastness of dyeings on polyamide fiber materials, in particular textile materials for the automotive sector, using copper compounds.

An die Lichtechtheit von Sitzbezügen, Teppichen und anderen Auskleidungsstoffen für Kraftfahrzeuge werden bekanntlich allerhöchste Ansprüche gestellt, die mit zahlreichen im Handel befindlichen Farbstoffen allein nicht befriedigt werden können.As is known, the light fastness of seat covers, carpets and other lining materials for motor vehicles is subject to the highest demands, which cannot be satisfied with numerous commercially available dyes alone.

Neben der "normalen" Lichtechtheit gemäß DIN 54 003 und 54 004 wird nämlich auch eine hohe Lichtechtheit bei starker Wärmeeinwirkung verlangt, wie sie neuerdings durch Heißbelichtung gemäß DIN 75 202 (Entwurf) bestimmt wird.In addition to the "normal" light fastness according to DIN 54 003 and 54 004, a high light fastness with strong heat is also required, as has recently been determined by hot exposure according to DIN 75 202 (draft).

Zur Erfüllung dieser Norm sind daher bereits neben zahlreichen anderen Lichtechtheitsverbeserungsmitteln diverse Kupferverbindungen, so etwa Komplexverbindungen von Schiff'schen Basen, o-Hydroxybenzophenonen und Oximen (vgl. EP-A 51 188 und 113 856), vorgeschlagen werden.To meet this standard, various copper compounds, such as complex compounds of Schiff bases, o-hydroxybenzophenones and oximes (cf. EP-A 51 188 and 113 856), have already been proposed in addition to numerous other light fastness enhancers.

Dennoch konnten diese Hilfsmittel bisher nicht voll den hohen Anforderungen der Automobilhersteller gerecht werden, da die erzielten Effekte nicht ganz ausreichten. Einige der Hilfsmittel besitzen darüber hinaus eine unerwünschte Eigenfarbe und/oder sind wegen ihrer aufwendigen Herstellungsweise verhältnismäßig teuer.However, these aids have so far not been able to fully meet the high demands of automobile manufacturers, since the effects achieved were not quite sufficient. Some of the auxiliaries also have an undesirable inherent color and / or are relatively expensive because of their complex production method.

Besonders nachteilig ist schließlich die Tatsache, daß die Wirkung der vorstehend genannten Substanzklassen bei höheren Konzentrationen abnimmt, so daß deren Anwendungsmöglichkeiten limitiert sind.Finally, the fact that the effect of the abovementioned classes of substances decreases at higher concentrations is particularly disadvantageous, so that their possible uses are limited.

Es wurde nun überraschenderweise gefunden, daß man weitgehend ohne diese Nachteile zu sehr lichtechten Färbungen gelangt, wenn man als Hilfsmittel 1:2-Kupferkomplexe der Formel

Figure imgb0001
verwendet, worin

  • R1 und R2 unabhängig voneinander H, OH oder OW und
  • X1-X8 unabhängig voneinander H, W, OH, Halogen, CN, NH2, NVW, SOaH, COOH, COOW, CONVW oder CONH2 bedeuten und zwei benachbarte Reste
  • X1-X8 auch gemeinsam die restlichen Glieder eines ankondensierten Benzolringes bilden können,
  • wobei
  • W für C1-C18-Alkyl und
  • V für W oder H stehen,
It has now surprisingly been found that very lightfast dyeings can be achieved largely without these disadvantages if 1: 2 copper complexes of the formula are used as auxiliaries
Figure imgb0001
 used where
  • R 1 and R 2 independently of one another H, OH or OW and
  • X 1 -X 8 independently of one another denote H, W, OH, halogen, CN, NH 2 , NVW, SOaH, COOH, COOW, CONVW or CONH 2 and two adjacent radicals
  • X 1 -X 8 can also together form the remaining members of a fused-on benzene ring,
  • in which
  • W for C 1 -C 18 alkyl and
  • V stands for W or H,

mit der Maßgabe, daß die vorstehend für X1-X8 genannten Substituenten 2. Ordnung maximal 2fach in einem Benzolrest auftreten.with the proviso that the second-order substituents mentioned above for X 1 -X 8 occur at most twice in a benzene radical.

Geeignete Halogenatome sind F, Br und vor allem Cl. Geeignete Alkylreste sind geradkettig oder verzweigt und gegebenenfalls ungesättigt. Die genannten Säuregruppen können auch in Salzform vorliegen.Suitable halogen atoms are F, Br and especially Cl. Suitable alkyl radicals are straight-chain or branched and optionally unsaturated. The acid groups mentioned can also be in salt form.

Bevorzugte Verbindungen der Formel sind symmetrische Typen.Preferred compounds of the formula are symmetrical types.

Besonders bevorzugt sind solche der Formel I, worin X3 und X6 für C1-C10-Alkyl oder Chlor stehenThose of the formula I in which X 3 and X 6 are C 1 -C 10 -alkyl or chlorine are particularly preferred

sowie solche dieser Formel, worin X2 und X7 für OH stehen, wobei die übrigen X-Reste Wasserstoff bedeuten.as well as those of this formula in which X 2 and X 7 are OH, the remaining X radicals being hydrogen.

Ganz besonders bevorzugt sind Verbindungen der Formel mit den vorstehend genannten allgemeinen und bevorzugten Bedeutungen worin R1 und R2 = OH bedeuten.Very particular preference is given to compounds of the formula having the general and preferred meanings mentioned above in which R 1 and R 2 are OH.

Beispiele der erfindungsgemäß zu verwendenden Verbindungen sind 1:2-Komplexe des Kupfers mit

  • a) Salicylsäure
  • b) 5-Methylsalicylsäure (p-Kresotinsäure)
  • c) 5-tert.-Butylsalicylsäure
  • d) 5-Chlorsalicylsäure
  • e) 5-tert.-Octylsalicylsäure
  • f) 2,4-Dihydroxybenzoesäure (ß-Resourcylsaüre)
  • g) 2-Hydroxynaphtalin-1-carbonsäure (2-Hydroxy-1-naphthoesäure)
  • h) 4-Hydroxy-1,3-benzoldicarbonsäure (4-Hydroxy-isophthalsäure)
  • i) Salicylaldehyd
  • j) 5-Chlorsalicylaldehyd
  • k) 3-Methoxysalicylaldehyd.
Examples of the compounds to be used according to the invention are 1: 2 complexes of copper with
  • a) Salicylic acid
  • b) 5-methylsalicylic acid (p-cresotinic acid)
  • c) 5-tert-butylsalicylic acid
  • d) 5-chlorosalicylic acid
  • e) 5-tert-octylsalicylic acid
  • f) 2,4-dihydroxybenzoic acid ( ß -resourcyl acid)
  • g) 2-hydroxy-naphthalene-1-carboxylic acid (2-hydroxy-1-naphthoic acid)
  • h) 4-hydroxy-1,3-benzenedicarboxylic acid (4-hydroxy-isophthalic acid)
  • i) salicylaldehyde
  • j) 5-chlorosalicylaldehyde
  • k) 3-methoxysalicylaldehyde.

Die erfindungsgemäßen Kupfer-Komplexe können auch aus Mischungen aromatischer o-Hydroxycarbonsäuren erhalten werden. Die Einsatzmenge beträgt 0,01 bis 3, vorzugsweise 0,05 bis 0,2 Gew.-% (bezogen auf Polyamid).The copper complexes according to the invention can also be obtained from mixtures of aromatic o-hydroxycarboxylic acids. The amount used is 0.01 to 3, preferably 0.05 to 0.2% by weight (based on polyamide).

Die Herstellung der erfindungsgemäßen Cu-Komplexe erfolgt in an sich bekannter Weise durch Umsetzung von Alkalisalzen von aromatischen o-Hydroxycarbonsäuren in wäßrigem Medium, mit einem Kupfer-II-Salz, wie z.B. CuCI2, CuSO4·5H2O, Cu(OAc)2-H20 oder CuCO3·Cu(OH)2. The Cu complexes according to the invention are prepared in a manner known per se by reacting alkali metal salts of aromatic o-hydroxycarboxylic acids in an aqueous medium with a copper (II) salt, such as CuCl 2 , CuSO 4 .5H 2 O, Cu (OAc) 2 -H 2 0 or CuCO 3 .Cu (OH) 2.

1:2 Cu-Komplexe der Salicylsäure sind z.B. in Gmelins Handbuch der anorganischen Chemie 8. Auflage, Verlag Chemie Weinheim 1961, System-Nr. 60, Seite 800-804 beschrieben.1: 2 Cu complexes of salicylic acid are e.g. in Gmelin's Handbook of Inorganic Chemistry 8th edition, Verlag Chemie Weinheim 1961, system no. 60, page 800-804.

Die Färbungen auf Polyamidfasern können in herkömmlicher Weise sowohl mit Azo-Metallkomplexfarbstoffen und Anthrachinon-Farbstoffen als auch mit Säurefarbstoffen erzeugt werden. Bevorzugt sind die Metallkomplexfarbstoffe, insbesondere die 1:2-Chrom-oder 1:2-Kobalt-Komplexe von Azoverbindungen, die in der Literatur in großer Zahl beschrieben und im Handel erhältlich sind. Diese Farbstoffe können auch 1 bis 2 Sulfogruppen enthalten.The dyeings on polyamide fibers can be produced in a conventional manner with azo metal complex dyes and anthraquinone dyes as well as with acid dyes. The metal complex dyes, in particular the 1: 2 chromium or 1: 2 cobalt complexes of azo compounds, which are described in large numbers in the literature and are commercially available, are preferred. These dyes can also contain 1 to 2 sulfo groups.

Die Behandlung der Polyamidmaterialien mit den erfindungsgemäß zu verwendenden Kupferverbindungen kann vor, während oder nach, bevorzugt während der Färbung, erfolgen.The treatment of the polyamide materials with the copper compounds to be used according to the invention can take place before, during or after, preferably during the dyeing.

Die im Normalfall separat hergestellten Kupferverbindungen kommen, sofern sie nicht wasserlöslich sind, in fein verteilter Form, wie sie durch Mahlung in Gegenwart üblicher Dispergiermittel erhalten wird, zum Einsatz.Provided that they are not water-soluble, the copper compounds normally produced separately are used in finely divided form, as is obtained by grinding in the presence of customary dispersants.

Gemäß einer speziellen Ausführungsform des erfindungsgemäßen Verfahrens wird dieses gewissermaßen im "Eintopf" durchgeführt, indem man die Fasermaterialien nicht direkt mit den in fester Form isolierten Kupferverbindungen behandelt, sondern - prinzipiell in beliebiger Reihenfolge - in situ aus den entsprechenden Ausgangsmaterialien auf der Faser erzeugt.According to a special embodiment of the method according to the invention, this is carried out, as it were, in a "one-pot", in that the fiber materials are not treated directly with the copper compounds isolated in solid form, but - in principle in any order - are produced in situ from the corresponding starting materials on the fiber.

Bei dieser Variante werden die Fasern zunächst mit einer Färbeflotte, die außer dem Farbstoff und gegebenenfalls üblichen Färbereihilfsmitteln die metallfreien Verbindungen der Formel I enthält, gefärbt und anschließend mit einer Kupfer-II-Salz-Lösung nachbehandelt. Vorzugsweise werden die Verbindungen der Formel ohne irgendwelche Co-Katalysatoren eingesetzt. Die mit den erfindungsgemäß zu verwendenden Kupferkomplexen erhältlichen Färbungen zeichnen sich durch eine hohe Beständigkeit gegen Heißlichtbestrahlung gemäß DIN 75 202 aus, wobei auch bei höherer Dosierung dieser Hilfsmittel keine Verfärbung der Faser eintrittIn this variant, the fibers are first dyed with a dyeing liquor which, in addition to the dye and, if appropriate, customary dyeing auxiliaries, contains the metal-free compounds of the formula I and then treated with a copper (II) salt solution. The compounds of the formula are preferably used without any cocatalysts. The dyeings obtainable with the copper complexes to be used according to the invention are distinguished by a high resistance to hot light irradiation in accordance with DIN 75 202, and there is no discoloration of the fibers even when these auxiliaries are metered in higher amounts

Aus der DE-A-2 000 688 sind zwar auch bereits Salicylsäurederivate als Färbereihilfsmittel bekannt. Jedoch werden diese Verbindungen dort für einen völlig anderen Zweck, nämlich zur Vermeidung des sogenannten Catalytic-Fading-Effekten, eingesetzt.From DE-A-2 000 688 salicylic acid derivatives are already known as dyeing aids. However, these connections are used there for a completely different purpose, namely to avoid the so-called catalytic fading effects.

Auch wurde nich erkannt, daß gerade die Cu-Komplexe eine herausragende lichtechtheitsverbessernde Wirkung besitzen und von diesen im besonderen die 1:2-Komplexe. 1:1-Komplexe erreichen überraschenderweise nicht den Stand der Technik. Andere Metallsalze aromatischer Hydroxycarbonsäuren wirken noch viel schwächer.It was also not recognized that the Cu complexes in particular have an outstanding lightfastness-improving effect, and in particular the 1: 2 complexes. Surprisingly, 1: 1 complexes do not reach the state of the art. Other metal salts of aromatic hydroxycarboxylic acids have a much weaker effect.

In den nachfolgenden Beispielen bedeuten "Teile" Gewichtsteile.In the examples below, "parts" mean parts by weight.

Beispiel 1example 1

Herstellung von Disalicylat-Kupfer 138 g Salicylsäure werden in 500 ml Wasser unter Zugabe von 100 g 40 %iger NaOH gelöst. Anschließend tropft man bei 50°C eine Lösung von 125 g CuSO4·5H2O in 350 ml H20 hinzu und rührt 1 Stunde bei 50°C nach. Nach dem Abfiltrieren erhält man 160 g Kupferkomplex als grüne Kristalle mit einem Cu-Gehalt von 18 %.Preparation of disalicylate copper 138 g of salicylic acid are dissolved in 500 ml of water with the addition of 100 g of 40% NaOH. A solution of 125 g of CuSO 4 .5H 2 O in 350 ml of H 2 O is then added dropwise at 50 ° C. and the mixture is stirred at 50 ° C. for 1 hour. After filtering off, 160 g of copper complex are obtained as green crystals with a Cu content of 18%.

Beispiel 2Example 2

Di-p-tert.-butylsalicylat-Kupfer werden aus 2 Mol 5-tert.-Butylsalicylsäure, 2 Mol NaOH und 1 Mol CuSO4·5H2O nach dem Verfahren von Beispiel 1 als grüne Kristalle mit einem Cu-Gehalt von 14 % erhalten.Di-p-tert-butylsalicylate copper are made from 2 moles of 5-tert-butylsalicylic acid, 2 moles of NaOH and 1 mole of CuSO 4 .5H 2 O according to the procedure of Example 1 as green crystals with a Cu content of 14% receive.

Beispiel 3Example 3

Disalicylat-Kupfer-5,5'-disulfonsäüre-Na-Salz 234 g 2-Hydroxybenzoesäure-5-sulfonsäure und 80 g NaOH werden in 620 g Wasser aufgelöst. Dann tropft man eine Lösung von 125 g CUS04-5H20 in 350 ml Wasser hinzu und erhitzt 1 Stunde auf 50°C. Man erhält eine dunkelgrüne, ca. 22 %ige wäßrige Lösung von Disalicylat-Kupfer-5,5'-disulfonsäure-Na-Salz, die in dieser Form zur Stabilisierung von Polyamid-Färbungen eingesetzt werden kann.Disalicylate-copper-5,5'-disulfonic acid Na salt 234 g of 2-hydroxybenzoic acid-5-sulfonic acid and 80 g of NaOH are dissolved in 620 g of water. A solution of 125 g of CUS0 4 -5H 2 0 in 350 ml of water is then added dropwise and the mixture is heated at 50 ° C. for 1 hour. A dark green, approx. 22% aqueous solution of disalicylate-copper-5,5'- is obtained. disulfonic acid Na salt, which can be used in this form to stabilize polyamide dyeings.

Beispiel 4Example 4

61 g Salicylaldehyd und 20 g NaOH werden zu 350 ml Wasser gelöst und bei Raumtemperatur mit einer Lösung von 62,5 g CuSO4·5H2O in 175 ml Wasser versetzt. Nach Absaugen und Trocknen erhält man ca. 70 g grüne Kristalle mit einem Cu-Gehalt von 18,4 %.61 g of salicylaldehyde and 20 g of NaOH are dissolved in 350 ml of water and a solution of 62.5 g of CuSO 4 .5H 2 O in 175 ml of water is added at room temperature. After suction and drying, about 70 g of green crystals with a Cu content of 18.4% are obtained.

Beispiel 5Example 5

100 Teile Polyamid-6-Fasermaterial werden in 2.000 Teile wäßrige Färbeflotte eingetragen die 0,08 Teile des Kupfer-Komplexes des Herstellungsbeispiels 1 und 0,15 Teile des Farbstoffes der Formel

Figure imgb0002
erthält. Durch Zugabe von Mono- und Dinatriumpsophat wird ein pH-Wert von 8 eingestellt. Dann wird die Flottentemperatur unter Bewegung des Färbegutes langsam auf 98 bis 100°C erhöht und 60 Minuten bei dieser Temperatur belassen. Anschließend wird die Färbung dem Färbebad entnommen, gespült und getrocknet.100 parts of polyamide 6 fiber material are introduced into 2,000 parts of aqueous dye liquor, the 0.08 part of the copper complex of preparation example 1 and 0.15 part of the dye of the formula
Figure imgb0002
 receives. A pH of 8 is set by adding mono- and disodium psophate. The liquor temperature is then slowly increased to 98 to 100 ° C. while the material to be dyed is kept and left at this temperature for 60 minutes. The dye is then removed from the dye bath, rinsed and dried.

Die Färbung wird zusammen mit einer ohne den genannten Kupferkomplex hergestellten Vergleichsfärbung gemäß dem Entwurf DIN 75 202 einer Heißbelichtung ausgesetzt. Die so hergestellte Färbung zeigt eine ausgezeichnete Lichtechtheit.The dyeing is subjected to a hot exposure together with a comparative dyeing prepared without the copper complex mentioned in accordance with the draft DIN 75 202. The dyeing thus produced shows excellent lightfastness.

Beispiel 6Example 6

Eine gleichgute Verbesserung der Beständigkeit gegenüber Heißbelichtung erhält man, wenn die Flotte nicht auf pH 8, sondern mit Mononatriumphosphat und Essigsäure auf pH 5,5 eingestellt wird.An equally good improvement in the resistance to hot exposure is obtained if the liquor is adjusted to pH 5.5 instead of pH 8 but with monosodium phosphate and acetic acid.

Beispiel 7Example 7

100 Teile Polyamid-6-Material werden in 2.000 Teile wäßriger Färbeflotte eingetragen, die 0,15 Teile des in Beispiel 1 beschriebenen Kupferkomplexes und 0,15 Teile des Farbstoffes der Formel

Figure imgb0003
enthalten.100 parts of polyamide 6 material are introduced into 2,000 parts of aqueous dye liquor, the 0.15 part of the copper complex described in Example 1 and 0.15 part of the dye of the formula
Figure imgb0003
 contain.

Die Farbeflotte wird auf pH 5,5 unter Zuhilfenahme eines Puffergemisches aus Monoatriumphosphat und Essigsäure eingestellt. Man behandelt eine Stunde bei 98 biz 100°C, spült und trocknet.The dye liquor is adjusted to pH 5.5 with the aid of a buffer mixture of mono-sodium phosphate and acetic acid. It is treated for one hour at 98 to 100 ° C, rinsed and dried.

Die so hergestellte Färbung zeigt eine deutlich bessere Lichtechtheit als eine ohne den genannten Kupferkomplex hergestellt.The coloring produced in this way shows a clearly better light fastness than one produced without the copper complex mentioned.

Beispiel 8Example 8

Werden die nach den Beispielen 5 bis 7 hergestellten Färbungen anschließend bei 180°C während 30 sec. thermofixiert, so bleibt die Lichtechtheitsverbesserung voll erhalten.If the dyeings prepared according to Examples 5 to 7 are subsequently heat-set at 180 ° C. for 30 seconds, the improvement in light fastness is fully retained.

Beispiel 9Example 9

Werden die nach den Beispielen 5 bis 7 hergestellten Färbungen bei pH 8 bzw. bei pH 5,5 eingestellt mit den entsprechenden Puffermischungen, während 30 Minuten bei 98 bis 100°C in wäßrigem Medium behandelt, bleibt die Lichtechtheitsverbesserung voll erhalten.If the dyeings prepared according to Examples 5 to 7 are adjusted to pH 8 or pH 5.5 with the appropriate buffer mixtures and treated in an aqueous medium at 98 to 100 ° C. for 30 minutes, the improvement in light fastness is fully retained.

Beispiel 10Example 10

Bei den nach den Beispielen 5 bis 7 hergestellten Färbung ist der Farbton gegenüber den ohne den genannten Kupferkomplex hergestellten Färbungen praktisch nicht beeinflußt, im Gegensatz zu den in EP-A-51 188, Applikationsbeispiel 2a und EP-A-113 856, Applikationsbeispielen 1a und 2 aufgeführten Färbungen.In the dyeing prepared according to Examples 5 to 7, the hue is practically unaffected by the dyeings produced without the copper complex mentioned, in contrast to those in EP-A-51 188, application example 2a and EP-A-113 856, application examples 1a and 2 listed colors.

Wird wie in den Beispielen 5 bis 7 beschrieben verfahren, jedoch die in Herstellungsbeispiel 2 beschriebene Kupferverbindung verwendet, erhält man sowohl bei pH 8 als auch bei pH 5,5 eine deutliche Verbesserung der Heißlichtechtheit.If the procedure is as described in Examples 5 to 7, but the copper compound described in Preparation Example 2 is used, a clear improvement in the hot light fastness is obtained both at pH 8 and at pH 5.5.

Beispiel 11 (Vergleichsbeispiel)Example 11 (comparative example)

Wird wie in den Beispielen 5 bis 7 beschrieben verfahren, jedoch der literaturbekannte 1:1-Kupersalicylat-Komplex verwendet wird sowohl bei pH 8 als auch bei pH 5,5 der Färbeflotte nur eine geringe Verbesserung der Heißlichtechtheit erzielt.If the procedure is as described in Examples 5 to 7, but the 1: 1 copper salicylate complex known from the literature is used, only a slight improvement in the fastness to hot light is achieved both at pH 8 and at pH 5.5 of the dyeing liquor.

Beispiel 12Example 12

Eine in bekannter Weise aus langer Flotte hergestellte Polyamid-6-Färbung mit dem Farbstoff "Acid Yellow 151" (C.I. 14906) wird nach Fertigstellung und Trocknen wie folgt behandelt:

  • Die Färbung wird mit 0,7 g/I einer 20 %igen wäßrigen Dispersion des in Beispiel 1 beschriebenen Kupferkomplexes auf dem Foulard imprägniert. Die Naßgewichtszunahme beträgt 70 %.
A polyamide 6 dyeing prepared in a known manner from a long liquor with the dye "Acid Yellow 151" (CI 14906) is treated as follows after completion and drying:
  • The dyeing is impregnated on the pad with 0.7 g / l of a 20% aqueous dispersion of the copper complex described in Example 1. The wet weight gain is 70%.

Nach dem Imprägnieren wird bei 120°C getrocknet und anschließend während 30 sec. bei 180°C thermofixiert.After impregnation, it is dried at 120 ° C. and then heat-set at 180 ° C. for 30 seconds.

Die so behandelte Färbung hat, nach Entwurf DIN 75 202 belichtet, eine deutlich bessere Lichtechtheit gegenüber der unbehandelten Färbung.The dyeing treated in this way, exposed according to draft DIN 75 202, has a significantly better lightfastness than the untreated dyeing.

Beispiel 13Example 13

Setzt man dem Färbebad gemäß Beispielen 5 bis 7 bzw. dem Imprägnierbad aus dem Beispiel 12 anstelle des Kupferkomplexes, aus dem Herstellungsbeispiel 1 Kupfersulfat und Natriumsalicylat im Molverhältnis 1:1,8 bis 1:3 ein, so wird auch dann eine Verbesserung der Lichtechtheit erzielt.If the dyebath according to Examples 5 to 7 or the impregnation bath from Example 12 is used instead of the copper complex from Preparation Example 1, copper sulfate and sodium salicylate in a molar ratio of 1: 1.8 to 1: 3, then an improvement in the lightfastness is achieved .

Beisoiel14 (Vergleichsbeispiel)Beisoiel14 (comparative example)

Wird wie in den Beispielen 5 bis 7 beschrieben gefärbt, jedoch anstelle des Kupfer-Komplexes aus Beispiel 1 der entsprechende Nickel- oder Zink-Komplex mit 0,1 % bezogen auf das Fasergewicht verwendet, so erhält man weder bei pH 5,5 noch bei pH 8 der Färbeflotte eine Lichtechtheitsverbesserung.If dyeing is carried out as described in Examples 5 to 7, but instead of the copper complex from Example 1 the corresponding nickel or zinc complex is used at 0.1% based on the fiber weight, neither at pH 5.5 nor at pH 8 of the dye liquor an improvement in light fastness.

Die Färbungen verhalten sich so, als sei kein Lichtschutzmittel der Färbeflotte zugesetzt worden.The dyeings behave as if no light stabilizer has been added to the dyeing liquor.

Claims (8)

1. Process for improving the light fastness of dyeings on polyamide fibre materials by using copper compounds, characterized in that the copper compounds used are the 1:2 complexes of aromatic hydroxycarbonyl compounds of the formula (I)
Figure imgb0006
wherein
Ri and R2 independently of each other denote H, OH or OW and
X1-X8 independently of one another denote H, W, OH, halogen, CN, NHz, NVW, S03H, COOH, COOW, CONVW or CONHz and two adjacent radicals
X1-X8 can also together form the remaining members of a fused-on benzene ring, where
W represents C1-C18 alkyl and
V represents W or H,
subject to the proviso that the 2nd order substituents mentioned above for X1-X8 appear at most twice in a benzene radical.
2. Process according to Claim 1, characterized in that 0.01 to 3% (on weight of fibre) of the copper compound is used.
3. Process according to Claim 1, characterized in that the 1:2 copper compounds of salicylic acid, 5-methylsalicylic acid, 5-tert.-butylsalicylic acid, 5-chlorosalicylic acid or naphthoic acid are used.
4. Process according to Claim 1, characterized in that the 1:2 copper compound of salicylaldehyde or 5-chlorosalicylaldehyde is used.
5. Process according to Claim 1, characterized in that the 1:2 copper compound of salicylic acid is used.
6. Process according to Claim 1, characterized in that the copper compounds are added to the dyebath.
7. Process according to Claim 1, characterized in that polyamide dyeings of metal complex dyestuffs are improved.
8. Process according to Claim 1, characterized in that dyeings of synthetic polyamides are improved.
EP87109228A 1986-07-08 1987-06-26 Process for improving the fastness to light of polyamide dyeings Expired EP0252386B1 (en)

Applications Claiming Priority (2)

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DE3622864 1986-07-08
DE19863622864 DE3622864A1 (en) 1986-07-08 1986-07-08 METHOD FOR IMPROVING THE LIGHT FASTNESS OF POLYAMIDE COLORS

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EP0252386B1 true EP0252386B1 (en) 1989-12-13

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US4775386A (en) * 1986-05-05 1988-10-04 Ciba-Geigy Corporation Process for photochemical stabilization of undyed and dyed polyamide fibre material and blends thereof with other fibres: copper complex and light stabilizer treatment
FR2643395A1 (en) * 1989-02-22 1990-08-24 Sandoz Sa NOVEL METHOD FOR DYING POLYAMIDE FIBERS
DE3925259A1 (en) * 1989-07-29 1991-01-31 Bayer Ag DRY PREPARATION OF LIGHT fastness improvers
DE3941295A1 (en) * 1989-12-14 1991-06-20 Basf Ag METHOD FOR COLORING POLYAMIDE SUBSTRATES
KR101495050B1 (en) * 2014-10-21 2015-02-25 아이씨이아이우방(주) Ionic-light fastness enhancer and dying auxiliary having that
WO2024057867A1 (en) * 2022-09-16 2024-03-21 東レ株式会社 Color conversion composition, color conversion sheet, light source unit, display device and lighting device

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GB689629A (en) * 1950-01-20 1953-04-01 Ici Ltd Compositions comprising nylon
DE1264388B (en) * 1962-10-10 1968-03-28 Basf Ag Process for improving the thermal stability of colorings on structures made of linear polyesters or their mixtures with cellulose or animal fibers
US3226178A (en) * 1962-10-31 1965-12-28 Du Pont Process for dyeing and aftertreating polyethylene oxide modified nylon fibers
JPS5756590A (en) * 1980-09-16 1982-04-05 Toray Industries Treatment for enhancing light fastness of dyed polyamide fiber
DE3041153A1 (en) * 1980-10-31 1982-06-16 Bayer Ag, 5090 Leverkusen METHOD FOR IMPROVING THE LIGHT FASTNESS OF POLYAMIDE COLORS
EP0162811B1 (en) * 1984-05-22 1989-10-11 Ciba-Geigy Ag Process for the photochemical stabilisation of materials containing polyamide fibres
EP0181836B1 (en) * 1984-11-09 1988-12-21 Ciba-Geigy Ag Process for improving the light fastness of dyed leathers

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Title
Lehrbuch der organischen Chemie von Prof.Dr.Hans Beyer, Seiten 400+401 (1967). *

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