EP0310083A1 - Process for quenching or suppressing the fluorescence of optically brightened substrates - Google Patents

Process for quenching or suppressing the fluorescence of optically brightened substrates Download PDF

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Publication number
EP0310083A1
EP0310083A1 EP88116113A EP88116113A EP0310083A1 EP 0310083 A1 EP0310083 A1 EP 0310083A1 EP 88116113 A EP88116113 A EP 88116113A EP 88116113 A EP88116113 A EP 88116113A EP 0310083 A1 EP0310083 A1 EP 0310083A1
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European Patent Office
Prior art keywords
alkyl
hydrogen
sulfo
hydroxy
alkoxy
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Granted
Application number
EP88116113A
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German (de)
French (fr)
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EP0310083B1 (en
Inventor
Gerhard Dr. Reinert
Kurt Dr. Burdeska
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Novartis AG
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Ciba Geigy AG
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Classifications

    • 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
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/35—Heterocyclic compounds
    • D06M13/355—Heterocyclic compounds having six-membered heterocyclic rings
    • D06M13/358—Triazines
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
    • D06L4/60—Optical bleaching or brightening
    • D06L4/686—Fugitive optical brightening; Discharge of optical brighteners in discharge paste; Blueing; Differential optical brightening
    • 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
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/35—Heterocyclic compounds
    • D06M13/352—Heterocyclic compounds having five-membered heterocyclic rings
    • 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
    • D06P1/628—Compounds containing nitrogen
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
    • Y10S8/916—Natural fiber dyeing
    • Y10S8/917—Wool or silk
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
    • Y10S8/92—Synthetic fiber dyeing
    • Y10S8/924—Polyamide fiber

Definitions

  • the present invention relates to a method for quenching or suppressing the fluorescence of substrates made of natural or synthetic polyamides with sulfonated UV absorbers which are treated or are to be treated with optical brighteners, and the material treated therewith.
  • GB-A-2 174 731 discloses a process for the deletion or prevention of lightening effects on various substrates with UV absorbers, in which derivatives of the benzophenone series or of the non-sulfonated benzotriazole series are used as UV absorbers.
  • the present invention thus relates to a method for quenching or suppressing the fluorescence of substrates made from natural or synthetic polyamides with UV absorbers, which substrates have been treated or are to be treated with optical brighteners, which method is characterized in that a substrate is applied to these substrates before or after the optical brightening sulfonated UV absorber of the formula wherein R1 is hydrogen, halogen, C1-C12-alkyl, C5-C6-cycloalkyl, C7-C9-phenylalkyl or sulfo, R2 is hydrogen, C1-C4-alkyl, C1-C4-alkoxy, halogen, hydroxy or sulfo, R3 is hydrogen, C1-C12-alkyl, C1-C4-alkoxy, phenyl, (C1-C8-alkyl) -phenyl, C5-C6-cycloalkyl, C2-C9-alkoxycarbonyl, halogen
  • Suitable UV absorbers of the formula (1) are preferably A) 2-phenylbenzotriazoles of the formula wherein R1 is hydrogen, C1-C12-alkyl, chlorine, C5-C6-cycloalkyl, C7-C9-phenylalkyl or sulfo, R2 is hydrogen, C1-C4 alkyl, C1-C4 alkoxy, chlorine, hydroxy or sulfo R3 C1-C12-alkyl, C1-C4-alkoxy, phenyl, (C1-C8-alkyl) -phenyl, C5-C6-cycloalkyl, C2-C9-alkoxycarbonyl, chlorine, carboxyethyl or C7-C9-phenylalkyl or sulfo, R4 is hydrogen, chlorine, C1-C4-alkyl, C1-C4-alkoxy, C2-C9-alkoxycarbonyl, carboxy or sulfo and R
  • Examples of compounds of formula (2) are the sodium salt of 3- (2'H-benzotriazol-2'-yl) -5-tert-butyl-4-hydroxy-, 3- (2'H-5'-chlorobenzotriazole -2'-yl) -5-tert-butyl-4-hydroxy- and 3- (2'H-benzotriazol-2'-yl) -5-sec.-butyl-4-hydroxy-benzenesulfonic acid, and B) 2-phenyl-s-triazines of the formula wherein R1 is hydrogen, halogen, C1-C4-alkyl or sulfo, R2 is hydrogen, C1-C4-alkyl, C1-C4-alkoxy or hydroxy, R3 is hydrogen, or sulfo and R6 and R7 independently of one another are C1-C4-alkyl, C1-C4-alkoxy, C5-C6-cycloalkyl, phenyl or phenyl substituted by C
  • Examples of compounds of the formula (3) are the sodium salt of 3- (4 ′, 6′-diphenyl-s-triazin-2′-yl) -4-hydroxy-6-methoxy-, 3- (4 ′, 6 ′ -diphenyl-s-triazin-2'-yl) -4-hydroxy-6-ethoxy- and 3- (4 ', 6'-diphenyl-s-triazin-2'-yl) -4-hydroxy-6-propoxy -benzenesulfonic acid.
  • the compounds of formulas (1) to (3) given above are e.g. known from WO-A-84/02365 and WO-A-86/03528 and can be prepared by known methods.
  • UV absorbers Mixtures of UV absorbers can also be used.
  • the UV absorber is advantageously applied to the substrate from an aqueous medium.
  • the UV absorber can be impregnated and held at room or elevated temperature, for example between 20 and 90 ° C. for 30 minutes to all known methods of dyeing or printing, such as treatment in a long bath at temperatures from 20 to 140 ° C. 48 hours depending on the temperature, padding and fixing by the action of saturated steam, superheated steam, hot air, treatment with high-frequency or contact heat, are applied and fixed on the substrate.
  • the UV absorber can also be used in so-called thermal printing.
  • the UV absorber can be fixed on the substrate by mediating organic high polymers, for example in the form of aqueous or non-aqueous paints, or using the pigment printing method.
  • UV absorber The choice of application and fixing method and the amount of UV absorber depend on the substrate, the dyes used, the optical brighteners and their fastness and the properties of the UV absorbers used. In general, good extinguishing effects are obtained when the UV absorber is used in an amount of 0.1 to 5% of the weight of the goods.
  • the UV absorber can be used according to the invention after the optical brightening, or before, during or after the dyeing or printing of a substrate treated with an optical brightener.
  • the treatment with the UV absorber can also take place before, during or after dyeing or printing, before the substrate in question is treated with an optical brightener. This is the case, for example, with items of clothing that are washed after use will.
  • Commercial detergents or soaps for the household today mostly contain optical brighteners to make the laundry washed with them appear whiter. If light-colored dyed or printed textiles are now washed with such a detergent, a different color tone results after drying than before. This is particularly objectionable for light colors such as blue, rosé, beige etc.
  • optical brightening effects are deleted or suppressed locally or over the entire surface.
  • optical brightening effects are produced by commercially available optical brighteners, for example known anionic or cationic optical brighteners and dispersion brighteners as are used in detergents.
  • optical brighteners are derivatives of bis (triazinylamino) stilbene disulfonic acid, triazolyl derivatives of stilbene sulfonic acids, bis (stilbene) compounds, pyrazoline, coumarin, bis (benzimidazolyl), bis (oxazolyl), naphthalimide and cyanine -, Benzoxazolyl and Oxacyanin derivatives called.
  • Textile materials made from natural or synthetic polyamides are used as substrates and e.g. Yarns, fabrics, knitted or nonwovens understood.
  • the textile materials can also consist of mixtures of polyamides with other fibers.
  • both liquors are taken in at 50 ° C., the temperature is raised to 90 ° C. in 20 minutes and the dyeing is completed in 45 minutes. It is then rinsed cold and dried at 80 ° C.
  • Example 1 or 2 The procedure is as noted in Example 1 or 2, i.e. two dyeings are prepared with 0.01% of the dye of the formula (III) without and with 1% of the UV absorber of the formula (VII). If these dyeings are washed with the brightener-containing detergents, the conventional dyeings undergo a clear change in shade to brilliant purple, while the dyeings containing compound (VII) are practically unchanged.
  • Each 20 g piece of a bleached wool mousse line is dyed with and without UV absorber.
  • the dye liquors are charged with 2% ammonium sulfate, 2% of the sulfonated reaction product from naphthalene and formaldehyde and 0.005% of the dye of formula (X).
  • Fleet A receives no further additives, while Fleet B receives 1% of the UV absorber of the formula (X)
  • the dyeing is carried out at a liquor ratio of 1:50 by entering at 50 ° C., heating to 95 ° C. in 30 minutes and treatment for 45 minutes. Then the samples are rinsed well cold, spun and dried at 80 ° C.
  • the dye is replaced by 0.015% of the dye of the formula (V), so there are color shades which behave differently when washed in wash liquors containing brighteners: the pattern containing UV absorber remains unchanged while the conventionally colored after redder / brilliant unbeatable.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Coloring (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Paper (AREA)
  • Detergent Compositions (AREA)

Abstract

A process for quenching or suppressing the fluorescence of substrates treated, or to be treated, with optical brighteners and consisting of natural or synthetic polyamides with UV absorbers is described, which is characterised in that a sulphonated UV absorber of the formula <IMAGE> in which X, R1, R2 and R3 have the meaning stated in Patent Claim 1, is applied to and fixed on these substrates before or after the optical brightening process.

Description

Die vorliegende Erfindung betrifft ein Verfahren zum Löschen oder Unterdrücken der Fluoreszenz von mit optischen Aufhellern behandelten oder zu behandelnden Substraten aus natürlichen oder synthetischen Polyamiden mit sulfonierten UV-Absorbern sowie das damit behandelte Material.The present invention relates to a method for quenching or suppressing the fluorescence of substrates made of natural or synthetic polyamides with sulfonated UV absorbers which are treated or are to be treated with optical brighteners, and the material treated therewith.

Verfahren zum Löschen der Fluoreszenz von mit optischen Aufhellern behandelten Substraten sind bereits bekannt. So ist z.B. aus der GB-A-2 174 731 ein Verfahren zur Löschung oder Verhinderung von Aufhell­effekten auf verschiedenen Substraten mit UV-Absorbern bekannt, bei welchem als UV-Absorber Derivate der Benzophenonreihe oder der nicht sulfonierten Benzotriazolreihe verwendet werden.Methods for quenching the fluorescence from substrates treated with optical brighteners are already known. For example, GB-A-2 174 731 discloses a process for the deletion or prevention of lightening effects on various substrates with UV absorbers, in which derivatives of the benzophenone series or of the non-sulfonated benzotriazole series are used as UV absorbers.

Es wurde nun gefunden, dass sulfonierte 2-Hydroxyphenyl-benzotriazole und 2-Hydroxyphenyl-s-triazine sich sehr gut eignen, um Fluoreszenzef­fekte optisch aufgehellter Substrate zu löschen oder zu unterdrücken.It has now been found that sulfonated 2-hydroxyphenyl-benzotriazoles and 2-hydroxyphenyl-s-triazines are very suitable for quenching or suppressing fluorescence effects of optically brightened substrates.

Gegenstand der vorliegenden Erfindung ist somit ein Verfahren zum Löschen oder Unterdrücken der Fluoreszenz von mit optischen Aufhellern behandel­ten oder zu behandelnden Substraten aus natürlichen oder synthetischen Polyamiden mit UV-Absorbern, das dadurch gekennzeichnet ist, dass man auf diese Substrate vor oder nach dem optischen Aufhellen einer sulfo­nierten UV-Absorber der Formel

Figure imgb0001
worin
R₁ Wasserstoff, Halogen, C₁-C₁₂-Alkyl, C₅-C₆-Cycloalkyl, C₇-C₉-Phenyl­alkyl oder Sulfo,
R₂ Wasserstoff, C₁-C₄-Alkyl, C₁-C₄-Alkoxy, Halogen, Hydroxy oder Sulfo,
R₃ Wasserstoff, C₁-C₁₂-Alkyl, C₁-C₄-Alkoxy, Phenyl, (C₁-C₈-Alkyl)-phenyl, C₅-C₆-Cycloalkyl, C₂-C₉-Alkoxycarbonyl, Halogen, Carboxy-C₁-C₄-alkyl, C₂-C₉-Phenylalkyl oder Sulfo und
X einen Rest der Formel
Figure imgb0002
 bedeuten, worin
R₄ für Wasserstoff, Halogen, C₁-C₄-Alkyl, C₁-C₄-Alkoxy, C₂-C₉-Alkoxy­carbonyl, Carboxy oder Sulfo,
R₅ für Wasserstoff oder Halogen und
R₆ und R₇ unabhängig voneinander für C₁-C₄-Alkyl, C₁-C₄-Alkoxy, C₅-C₆-­Cycloalkyl, Phenyl oder durch C₁-C₄-Alkyl und Hydroxy substituiertes Phenyl
stehen,
aufbringt und fixiert.The present invention thus relates to a method for quenching or suppressing the fluorescence of substrates made from natural or synthetic polyamides with UV absorbers, which substrates have been treated or are to be treated with optical brighteners, which method is characterized in that a substrate is applied to these substrates before or after the optical brightening sulfonated UV absorber of the formula
Figure imgb0001
 wherein
R₁ is hydrogen, halogen, C₁-C₁₂-alkyl, C₅-C₆-cycloalkyl, C₇-C₉-phenylalkyl or sulfo,
R₂ is hydrogen, C₁-C₄-alkyl, C₁-C₄-alkoxy, halogen, hydroxy or sulfo,
R₃ is hydrogen, C₁-C₁₂-alkyl, C₁-C₄-alkoxy, phenyl, (C₁-C₈-alkyl) -phenyl, C₅-C₆-cycloalkyl, C₂-C₉-alkoxycarbonyl, halogen, carboxy-C₁-C₄-alkyl, C₂ -C₉-phenylalkyl or sulfo and
X is a radical of the formula
Figure imgb0002
 mean what
R₄ represents hydrogen, halogen, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₂-C₉-alkoxycarbonyl, carboxy or sulfo,
R₅ for hydrogen or halogen and
R₆ and R₇ independently of one another for C₁-C₄-alkyl, C₁-C₄-alkoxy, C₅-C₆-cycloalkyl, phenyl or phenyl substituted by C₁-C₄-alkyl and hydroxy
stand,
applies and fixes.

Als UV-Absorber der Formel (1) kommen bevorzugt in Betracht A) 2-Phenylbenzotriazole der Formel

Figure imgb0003
worin
R₁ Wasserstoff, C₁-C₁₂-Alkyl, Chlor, C₅-C₆-Cycloalkyl, C₇-C₉-Phenylalkyl oder Sulfo,
R₂ Wasserstoff, C₁-C₄-Alkyl, C₁-C₄-Alkoxy, Chlor, Hydroxy oder Sulfo
R₃ C₁-C₁₂-Alkyl, C₁-C₄-Alkoxy, Phenyl, (C₁-C₈-Alkyl)-phenyl, C₅-C₆-­Cycloalkyl, C₂-C₉-Alkoxycarbonyl, Chlor, Carboxyethyl oder C₇-C₉-Phe­nylalkyl oder Sulfo,
R₄ Wasserstoff, Chlor, C₁-C₄-Alkyl, C₁-C₄-Alkoxy, C₂-C₉-Alkoxycarbonyl, Carboxy oder Sulfo und
R₅ Wasserstoff oder Chlor
bedeuten, wobei Carboxy- oder Sulfongruppen auch als Salze, z.B. Alkali­metall- Erdalkalimetall-, Ammonium- oder Aminsalze vorliegen können. Beispiele von Verbindungen der Formel (2) sind das Natriumsalz der 3-(2′H-benzotriazol-2′-yl)-5-tert.-butyl-4-hydroxy-, 3-(2′H-5′-chlor­benzotriazol-2′-yl)-5-tert.-butyl-4-hydroxy- und 3-(2′H-benzotriazol-­2′-yl)-5-sec.-butyl-4-hydroxy-benzolsulfonsäure, und B) 2-Phenyl-s-triazine der Formel
Figure imgb0004
 worin
R₁ Wasserstoff, Halogen, C₁-C₄-Alkyl oder Sulfo,
R₂ Wasserstoff, C₁-C₄-Alkyl, C₁-C₄-Alkoxy oder Hydroxy,
R₃ Wasserstoff, oder Sulfo und
R₆ und R₇ unabhängig voneinander C₁-C₄-Alkyl, C₁-C₄-Alkoxy, C₅-C₆-Cyclo­alkyl, Phenyl oder durch C₁-C₄-Alkyl und Hydroxy substituiertes Phenyl bedeuten, wobei die Sulfongruppen in freier Form oder in Salzform, z.B. als Alkalimetall-, Erdalkalimetall-, Ammonium- oder Aminsalz vorliegen können. Beispiele von Verbindungen der Formel (3) sind das Natriumsalz der 3-(4′,6′-diphenyl-s-triazin-2′-yl)-4-hydroxy-6-methoxy-, 3-(4′,6′-­diphenyl-s-triazin-2′-yl)-4-hydroxy-6-ethoxy- und 3-(4′,6′-diphenyl-s-­triazin-2′-yl)-4-hydroxy-6-propoxy-benzolsulfonsäure.Suitable UV absorbers of the formula (1) are preferably A) 2-phenylbenzotriazoles of the formula
Figure imgb0003
 wherein
R₁ is hydrogen, C₁-C₁₂-alkyl, chlorine, C₅-C₆-cycloalkyl, C₇-C₉-phenylalkyl or sulfo,
R₂ is hydrogen, C₁-C₄ alkyl, C₁-C₄ alkoxy, chlorine, hydroxy or sulfo
R₃ C₁-C₁₂-alkyl, C₁-C₄-alkoxy, phenyl, (C₁-C₈-alkyl) -phenyl, C₅-C₆-cycloalkyl, C₂-C₉-alkoxycarbonyl, chlorine, carboxyethyl or C₇-C₉-phenylalkyl or sulfo,
R₄ is hydrogen, chlorine, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₂-C₉-alkoxycarbonyl, carboxy or sulfo and
R₅ is hydrogen or chlorine
mean, where carboxy or sulfone groups can also be present as salts, for example alkali metal, alkaline earth metal, ammonium or amine salts. Examples of compounds of formula (2) are the sodium salt of 3- (2'H-benzotriazol-2'-yl) -5-tert-butyl-4-hydroxy-, 3- (2'H-5'-chlorobenzotriazole -2'-yl) -5-tert-butyl-4-hydroxy- and 3- (2'H-benzotriazol-2'-yl) -5-sec.-butyl-4-hydroxy-benzenesulfonic acid, and B) 2-phenyl-s-triazines of the formula
Figure imgb0004
 wherein
R₁ is hydrogen, halogen, C₁-C₄-alkyl or sulfo,
R₂ is hydrogen, C₁-C₄-alkyl, C₁-C₄-alkoxy or hydroxy,
R₃ is hydrogen, or sulfo and
R₆ and R₇ independently of one another are C₁-C₄-alkyl, C₁-C₄-alkoxy, C₅-C₆-cycloalkyl, phenyl or phenyl substituted by C₁-C₄-alkyl and hydroxy, the sulfone groups in free form or in salt form, for example as alkali metal -, Alkaline earth metal, ammonium or amine salt may be present. Examples of compounds of the formula (3) are the sodium salt of 3- (4 ′, 6′-diphenyl-s-triazin-2′-yl) -4-hydroxy-6-methoxy-, 3- (4 ′, 6 ′ -diphenyl-s-triazin-2'-yl) -4-hydroxy-6-ethoxy- and 3- (4 ', 6'-diphenyl-s-triazin-2'-yl) -4-hydroxy-6-propoxy -benzenesulfonic acid.

Die oben angegebenen Verbindungen der Formeln (1) bis (3) sind z.B. aus dem WO-A-84/02365 und WO-A-86/03528 bekannt und können nach bekannten Verfahren hergestellt werden.The compounds of formulas (1) to (3) given above are e.g. known from WO-A-84/02365 and WO-A-86/03528 and can be prepared by known methods.

Es können auch Mischungen von UV-Absorbern eingesetzt werden.Mixtures of UV absorbers can also be used.

Der UV-Absorber wird vorteilhaft aus einem wässrigen Medium auf das Substrat aufgebracht.The UV absorber is advantageously applied to the substrate from an aqueous medium.

Erfindungsgemäss kann der UV-Absorber nach allen bekannten Methoden des Färbens oder Bedruckens, wie Behandlung im langen Bad bei Temperaturen von 20 bis 140°C, Imprägnieren und Verweilen bei Raum- oder erhöhter Temperatur, beispielsweise zwischen 20 und 90°C während 30 Minuten bis 48 Stunden je nach Temperatur, Foulardieren und Fixieren durch Einwirkung von Sattdampf, überhitztem Dampf, Heissluft, Behandlung mit Hochfrequenz- oder Kontakthitze, auf dem Substrat aufgebracht und fixiert werden. Auch kann der UV-Absorber in sogenannten Thermodruck eingesetzt werden. Weiterhin kann der UV-Absorber durch Vermittlung von organischen Hochpolymeren, beispielsweise in Form von wässrigen oder nicht wässrigen Anstrichfarben oder nach der Methode des Pigmentdruckes auf dem Substrat fixiert werden.According to the invention, the UV absorber can be impregnated and held at room or elevated temperature, for example between 20 and 90 ° C. for 30 minutes to all known methods of dyeing or printing, such as treatment in a long bath at temperatures from 20 to 140 ° C. 48 hours depending on the temperature, padding and fixing by the action of saturated steam, superheated steam, hot air, treatment with high-frequency or contact heat, are applied and fixed on the substrate. The UV absorber can also be used in so-called thermal printing. Furthermore, the UV absorber can be fixed on the substrate by mediating organic high polymers, for example in the form of aqueous or non-aqueous paints, or using the pigment printing method.

Die Wahl der Applikations- und Fixiermethode und die Menge des UV-Absor­bers richten sich nach dem Substrat, den verwendeten Farbstoffen, den optischen Aufhellern und deren Echtheiten und den Eigenschaften der verwendeten UV-Absorber. Im allgemeinen werden gute Löscheffekte erhalten wenn der UV-Absorber in einer Menge von 0,1 bis 5 % von Warengewicht eingesetzt wird.The choice of application and fixing method and the amount of UV absorber depend on the substrate, the dyes used, the optical brighteners and their fastness and the properties of the UV absorbers used. In general, good extinguishing effects are obtained when the UV absorber is used in an amount of 0.1 to 5% of the weight of the goods.

Wie schon erwähnt, kann der UV-Absorber erfindungsgemäss nach dem optischen Aufhellen, bzw. vor, während oder nach dem Färben oder Be­drucken eines mit einem optischen Aufheller behandelten Substrates eingesetzt werden. Die Behandlung mit dem UV-Absorber kann auch vor, während oder nach dem Färben oder Bedrucken erfolgen, bevor das be­treffende Substrat mit einem optischen Aufheller behandelt wird. Dies ist z.B. der Fall bei Bekleidungsstücken, die nach dem Gebrauch gewaschen werden. Handelsübliche Waschmittel oder Seifen für den Haushalt enthalten heute meistens optische Aufheller, um die damit gewaschene Wäsche weisser erschienen zu lassen. Werden nun mit einem solchen Waschmittel hellfarbig gefärbte bzw. bedruckte Textilien gewaschen, so ergibt sich nach dem Trocknen ein anderer Farbton als vorher. Dies wird besonders bei hellen Farbtönen wie bleu, rosé, beige usw. beanstandet.As already mentioned, the UV absorber can be used according to the invention after the optical brightening, or before, during or after the dyeing or printing of a substrate treated with an optical brightener. The treatment with the UV absorber can also take place before, during or after dyeing or printing, before the substrate in question is treated with an optical brightener. This is the case, for example, with items of clothing that are washed after use will. Commercial detergents or soaps for the household today mostly contain optical brighteners to make the laundry washed with them appear whiter. If light-colored dyed or printed textiles are now washed with such a detergent, a different color tone results after drying than before. This is particularly objectionable for light colors such as bleu, rosé, beige etc.

Je nach angewandten Verfahren werden die optischen Aufhellungseffekte örtlich oder auf der ganzen Fläche gelöscht oder unterdrückt. Diese optischen Aufhellungseffekte sind durch handelsübliche optische Aufheller erzeugt, beispielsweise bekannte anionische oder kationisch optische Aufheller sowie Disperisonsaufheller wie sie in Waschmitteln, eingesetzt werden. Als Beispiele von solche Aufhellern seien Derivate der Bis­(triazinylamino)-stilbendisulfonsäure, Triazolyl-Derivate von Stilben­sulfonsäuren, Bis(stilben)-Verbindungen, Pyrazolin-, Cumarin-, Bis(benz­imidazolyl)-, Bis(oxazolyl)-, Naphthalimid-, Cyanin-, Benzoxazolyl- und Oxacyanin-Derivate genannt.Depending on the process used, the optical brightening effects are deleted or suppressed locally or over the entire surface. These optical brightening effects are produced by commercially available optical brighteners, for example known anionic or cationic optical brighteners and dispersion brighteners as are used in detergents. Examples of such brighteners are derivatives of bis (triazinylamino) stilbene disulfonic acid, triazolyl derivatives of stilbene sulfonic acids, bis (stilbene) compounds, pyrazoline, coumarin, bis (benzimidazolyl), bis (oxazolyl), naphthalimide and cyanine -, Benzoxazolyl and Oxacyanin derivatives called.

Unter Substraten werden aus natürlichen oder synthetischen Polyamiden bestehenden textilen Materialien und unter letzteren z.B. Garnen, Geweben, Gewirken oder Vliessen verstanden. Die textilen Materialien können auch aus Mischungen von Polyamiden mit anderen Fasern bestehen.Textile materials made from natural or synthetic polyamides are used as substrates and e.g. Yarns, fabrics, knitted or nonwovens understood. The textile materials can also consist of mixtures of polyamides with other fibers.

Die nachfolgenden Beispiele erläutern die Erfindung ohne sie zu be­grenzen.The following examples illustrate the invention without limiting it.

Beispiel 1example 1

2 Stücke eines Nylon-Tricots von je 20 g werden bei einem Flottenver­hältnis von 1 : 30, unter Zusatz von 1 % Essigsäure (80 %) und unter Zuhilfenahme von 0,5 g/l des Adduktes von 10,5 Mol Ethylenoxid an 1 Mol Nonylphenol, mit 0,0075 % des Farbstoffes der Formel I ohne (= Muster A) und mit (= Muster B) 1 % der Verbindung der Formel II gefärbt,

Figure imgb0005
2 pieces of a nylon tricot of 20 g each with a liquor ratio of 1:30, with the addition of 1% acetic acid (80%) and with the help of 0.5 g / l of the adduct of 10.5 moles of ethylene oxide with 1 mole Nonylphenol, colored with 0.0075% of the dye of the formula I without (= sample A ) and with (= sample B ) 1% of the compound of the formula II,
Figure imgb0005

Zur Färben wird in beiden Flotten bei 50°C eingegangen, die Temperatur in 20 Minuten auf 90°C erhöht und während 45 Minuten fertig gefärbt. Anschliessend wird kalt gespült und bei 80°C getrocknet.For dyeing, both liquors are taken in at 50 ° C., the temperature is raised to 90 ° C. in 20 minutes and the dyeing is completed in 45 minutes. It is then rinsed cold and dried at 80 ° C.

Beide Muster werden nun dreigeteilt und davon werden 2 gewaschen. Das dritte Muster dient als Vergleich. Die Wäsche wird bei 40°C, während 30 Minuten, bei einem Flottenverhältnis von 1 : 20 mit je 4 g/l TOTAL® - Waschmittel (Aufhellergehalt 0,22 %) bzw. WOOLITE® -Waschmittel (Auf­hellergehalt 0,07 %) vorgenommen. Die Ergebnisse sind in Tabelle I zusammengefasst: Tabelle I UNGEWASCHEN mit TOTAL® mit WOOLITE® MUSTER A1-3 grünliches Türkis rötliches Türkis starke Fluoreszenz rötliches Türkis starke Fluoreszenz MUSTER B1-3 grünliches Türkis grünliches Türkis grünliches Türkis Im Gegensatz zu den Mustern A bleiben die Muster B beim Waschen unverändert.Both patterns are now divided into three and two of them are washed. The third pattern serves as a comparison. The laundry is carried out at 40 ° C, for 30 minutes, with a liquor ratio of 1:20 with 4 g / l TOTAL® detergent (brightener content 0.22%) or WOOLITE® detergent (brightener content 0.07%) . The results are summarized in Table I: Table I UNWASHED with TOTAL® with WOOLITE® PATTERN A 1-3 greenish turquoise reddish turquoise strong fluorescence reddish turquoise strong fluorescence PATTERN B 1-3 greenish turquoise greenish turquoise greenish turquoise In contrast to the patterns A, the patterns B remain unchanged during washing.

Beispiele 2 - 4Examples 2-4

Verfährt man wie im Beispiel 1 angegebenen, setzt jedoch die Farbstoffe der Formeln (III), (IV) und (V) ein, so erhält man ein ähnliches Ergebnis, d.h. die Muster, die die Verbindung (II) enthalten, bleiben in ihrer Nuance beim Waschen praktisch unverändert, während die herkömmlichen Färbungen Nuancenumschläge erleiden.

Figure imgb0006
If the procedure described in Example 1 is followed, but the dyes of the formulas (III), (IV) and (V) are used, a similar result is obtained, ie the patterns which contain the compound (II) remain in their shade practically unchanged when washing, while the traditional dyeings experience nuances.
Figure imgb0006

Beispiele 5 - 7Examples 5-7

Wie im Beispiel 1 beschrieben, werden 0,0075%ige Färbungen mit dem Farbstoff der Formeln (I) mit und ohne UV-Absorber hergestellt. Als UV-Absorber wurden Verbindungen der Formel

Figure imgb0007
As described in Example 1, 0.0075% dyeings with the dye of the formulas (I) are produced with and without UV absorber. Compounds of the formula were used as UV absorbers
Figure imgb0007

Die wie in Beispiel 1 beschrieben gefärbten Muster A (= ohne UV-Ab­sorber) und B (= jeweils mit 1 % der Verbindungen (VII), (VIII), (IX) gefärbt) werden geteilt und mit den Waschmitteln TOTAL® und WOOLITE® gewaschen. Die Ergebnisse sind in Tabelle II zusammengefasst:

Figure imgb0008
The patterns A (= without UV absorber) and B (= each colored with 1% of the compounds (VII), (VIII), (IX) colored as described in Example 1) are divided and with the detergents TOTAL® and WOOLITE® washed. The results are summarized in Table II:
Figure imgb0008

Alle UV-Absorber enthaltende Muster zeigen nach dem Waschen keine Farbverschiebungen.All samples containing UV absorbers show no color shifts after washing.

Beispiel 9Example 9

Man verfährt wie im Beispiel 1 bzw. 2 vermerkt, d.h. man bereitet zwei Färbungen mit 0,01 % des Farbstoffes der Formel (III) ohne und mit 1 % des UV-Absorbers der Formel (VII). Wäscht man diese Färbungen mit den aufhellerhaltigen Waschmitteln, so erleiden die herkömmlichen Fär­bungen einen deutlichen Nuancenumschlag ins brillanter-violett, während die Verbindung (VII) enthaltenden Färbungen praktisch unver­ändert sind.The procedure is as noted in Example 1 or 2, i.e. two dyeings are prepared with 0.01% of the dye of the formula (III) without and with 1% of the UV absorber of the formula (VII). If these dyeings are washed with the brightener-containing detergents, the conventional dyeings undergo a clear change in shade to brilliant purple, while the dyeings containing compound (VII) are practically unchanged.

Beispiel 10Example 10

Es werden je Stück à 20 g eines gebleichten Woll-Mousseline mit und ohne UV-Absorber gefärbt. Dazu beschickt man die Färbeflotten mit 2 % Ammoniumsulfat, 2 % des sulfonierten Umsetzungsprodukts aus Naphthalin und Formaldehyd sowie 0,005 % des Farbstoffes der Formel (X). Die Flotte A erhält keine weiteren Zusätze, die Flotte B dagegen noch 1 % des UV-Absorbers der Formel ( X)

Figure imgb0009
Each 20 g piece of a bleached wool mousse line is dyed with and without UV absorber. For this purpose, the dye liquors are charged with 2% ammonium sulfate, 2% of the sulfonated reaction product from naphthalene and formaldehyde and 0.005% of the dye of formula (X). Fleet A receives no further additives, while Fleet B receives 1% of the UV absorber of the formula (X)
Figure imgb0009

Man färbt bei einem Flottenverhältnis von 1 : 50 indem man bei 50°C eingeht, in 30 Minuten auf 95°C aufheizt und während 45 Minuten behandelt. Danach werden die Muster gut kalt gespült, geschleudert und bei 80°C getrocknet.The dyeing is carried out at a liquor ratio of 1:50 by entering at 50 ° C., heating to 95 ° C. in 30 minutes and treatment for 45 minutes. Then the samples are rinsed well cold, spun and dried at 80 ° C.

Die Waschversuche werden wie unter Beispiel 1 geschildert, vorgenom­men.The washing tests are carried out as described in Example 1.

Auch bei den Woll-Mustern verändert sich das herkömmlich (in Flotte A) gefärbte deutlich in der Farbnuance, wenn es mit aufhellerhaltigen Waschmittel gewaschen wird: Die Färbung wird röter und brillanter. Das in der Flotte B gefärbte Muster bleibt dagegen unverändert; im Gegen­satz zu ersteren zeigt es auch im UV-Licht keine Fluoreszenz.Even with the wool samples, the color traditionally (in fleet A) changes significantly when washed with brightening detergent: the color becomes redder and more brilliant. In contrast, the pattern colored in fleet B remains unchanged; in contrast to the former, it shows no fluorescence even in UV light.

Beispiel 11Example 11

Verfährt man wie in Beispiel 10 beschrieben sind, wechselt den Farb­stoff gegen 0,015 % des Farbstoffes der Formel (V) aus, so erhält man Farbnuancen, die sich beim Waschen in aufhellerhaltigen Waschflotten unterschiedlich verhalten: das UV-Absorber enthaltende Muster bleibt unverändert, während das herkömmlich gefärbte nach röter/brillanter unschlägt.If the procedure is as described in Example 10, the dye is replaced by 0.015% of the dye of the formula (V), so there are color shades which behave differently when washed in wash liquors containing brighteners: the pattern containing UV absorber remains unchanged while the conventionally colored after redder / brilliant unbeatable.

Claims (8)

1. Verfahren zum Löschen oder Unterdrücken der Fluoreszenz von mit optischen Aufhellern behandelten oder zu behandelnden Substraten aus natürlichen oder synthetischen Polyamiden mit UV-Absorbern, dadurch gekennzeichnet, dass man auf diese Substrate vor oder nach dem opti­schen Aufhellen einen sulfonierten UV-Absorber der Formel
Figure imgb0010
 worin
R₁ Wasserstoff, Halogen, C₁-C₁₂-Alkyl, C₅-C₆-Cycloalkyl, C₇-C₉-Phenyl­alkyl oder Sulfo,
R₂ Wasserstoff, C₁-C₄-Alkyl, C₁-C₄-Alkoxy, Halogen, Hydroxy oder Sulfo,
R₃ Wasserstoff, C₁-C₁₂-Alkyl, C₁-C₄-Alkoxy, Phenyl, (C₁-C₈-Alkyl)­phenyl, C₅-C₆-Cycloalkyl, C₂-C₉-Alkoxycarbonyl, Halogen, Carboxy-­C₁-C₄-alkyl, C₂-C₉-Phenylalkyl oder Sulfo und
X einen Rest der Formel
Figure imgb0011
 bedeuten, worin
R₄ für Wasserstoff, Halogen, C₁-C₄-Alkyl, C₁-C₄-Alkoxy, C₂-C₉-Alkoxy­carbonyl, Carboxy oder Sulfo,
R₅ für Wasserstoff oder Halogen und
R₆ und R₇ unabhängig voneinander für C₁-C₄-Alkyl, C₁-C₄-Alkoxy, C₅-C₆-Cycloalkyl, Phenyl oder durch C₁-C₄-Alkyl und Hydroxy sub­stituiertes Phenyl
stehen,
aufbringt und fixiert.1. A method for quenching or suppressing the fluorescence of substrates treated with optical brighteners or to be treated from natural or synthetic polyamides with UV absorbers, characterized in that a sulfonated UV absorber of the formula is used on these substrates before or after the optical brightening
Figure imgb0010
 wherein
R₁ is hydrogen, halogen, C₁-C₁₂-alkyl, C₅-C₆-cycloalkyl, C₇-C₉-phenylalkyl or sulfo,
R₂ is hydrogen, C₁-C₄-alkyl, C₁-C₄-alkoxy, halogen, hydroxy or sulfo,
R₃ is hydrogen, C₁-C₁₂-alkyl, C₁-C₄-alkoxy, phenyl, (C₁-C₈-alkyl) phenyl, C₅-C₆-cycloalkyl, C₂-C₉-alkoxycarbonyl, halogen, carboxy-C₁-C₄-alkyl, C₂- C₉-phenylalkyl or sulfo and
X is a radical of the formula
Figure imgb0011
 mean what
R₄ represents hydrogen, halogen, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₂-C₉-alkoxycarbonyl, carboxy or sulfo,
R₅ for hydrogen or halogen and
R₆ and R₇ independently of one another for C₁-C₄-alkyl, C₁-C₄-alkoxy, C₅-C₆-cycloalkyl, phenyl or phenyl substituted by C₁-C₄-alkyl and hydroxy
stand,
applies and fixes. 2. Verfahren gemäss Anspruch 1, dadurch gekennzeichnet, dass man als UV-Absorber ein 2-Phenylbenzoltriazol oder ein Salz davon der Formel
Figure imgb0012
 aufbringt, worin
R₁ Wasserstoff, C₁-C₁₂-Alkyl, Chlor, C₅-C₆-Cycloalkyl, C₇-C₉-Phenyl­alkyl oder Sulfo,
R₂ Wasserstoff, C₁-C₄-Alkyl, C₁-C₄-Alkoxy, Chlor, Hydroxy oder Sulfo,
R₃ C₁-C₁₂-Alkyl, C₁-C₄-Alkoxy, Phenyl, (C₁-C₈-Alkyl)-phenyl, C₅-C₆-­Cycloalkyl, C₂-C₉-Alkoxycarbonyl, Chlor, Carboxyethyl oder C₇-C₉-­Phenylalkyl oder Sulfo,
R₄ Wasserstoff, Chlor, C₁-C₄-Alkyl, C₁-C₄-Alkoxy, C₂-C₉-Alkoxycar­bonyl, Carboxy oder Sulfo und
R₅ Wasserstoff oder Chlor
bedeuten.2. The method according to claim 1, characterized in that the UV absorber is a 2-phenylbenzenetriazole or a salt thereof of the formula
Figure imgb0012
 brings up what
R₁ is hydrogen, C₁-C₁₂-alkyl, chlorine, C₅-C₆-cycloalkyl, C₇-C₉-phenylalkyl or sulfo,
R₂ is hydrogen, C₁-C₄-alkyl, C₁-C₄-alkoxy, chlorine, hydroxy or sulfo,
R₃ C₁-C₁₂-alkyl, C₁-C₄-alkoxy, phenyl, (C₁-C₈-alkyl) -phenyl, C₅-C₆-cycloalkyl, C₂-C₉-alkoxycarbonyl, chlorine, carboxyethyl or C₇-C₉-phenylalkyl or sulfo,
R₄ is hydrogen, chlorine, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₂-C₉-alkoxycarbonyl, carboxy or sulfo and
R₅ is hydrogen or chlorine
mean. 3. Verfahren gemäss Anspruch 2, dadurch gekennzeichnet, dass man das Natriumsalz der 3-(2′H-benzotriazol-2′-yl)-5-tert.-butyl-4-hydroxy-, 3-(2′H-5′-chlor-benzotriazol-2′-yl)-5-tert.-butyl-4-hydroxy- oder 3-(2′H-benzotriazol-2′-yl)-5-sec.-butyl-4-hydroxy-benzolsulfonsäure aufbringt.3. The method according to claim 2, characterized in that the sodium salt of 3- (2'H-benzotriazol-2'-yl) -5-tert-butyl-4-hydroxy-, 3- (2'H-5 '-Chloro-benzotriazol-2'-yl) -5-tert-butyl-4-hydroxy- or 3- (2'H-benzotriazol-2'-yl) -5-sec-butyl-4-hydroxy- applies benzenesulfonic acid. 4. Verfahren gemäss Anspruch 1, dadurch gekennzeichnet, dass man als UV-Absorber ein 2-Phenyl-s-triazin oder ein Salz davon der Formel
Figure imgb0013
 aufbringt, worin
R₁ Wasserstoff, Halogen, C₁-C₄-Alkyl oder Sulfo,
R₂ Wasserstoff, C₁-C₄-Alkyl, C₁-C₄-Alkoxy oder Hydroxy,
R₃ Wasserstoff, oder Sulfo und
R₆ und R₇ unabhängig voneinander C₁-C₄-Alkyl, C₁-C₄-Alkoxy, C₅-C₆-­Cycloalkyl, Phenyl oder durch C₁-C₄-Alkyl und Hydroxy substituiertes Phenyl bedeuten.4. The method according to claim 1, characterized in that the UV absorber is a 2-phenyl-s-triazine or a salt thereof of the formula
Figure imgb0013
 brings up what
R₁ is hydrogen, halogen, C₁-C₄-alkyl or sulfo,
R₂ is hydrogen, C₁-C₄-alkyl, C₁-C₄-alkoxy or hydroxy,
R₃ is hydrogen, or sulfo and
R₆ and R₇ independently of one another are C₁-C₄-alkyl, C₁-C₄-alkoxy, C₅-C₆-cycloalkyl, phenyl or phenyl substituted by C₁-C₄-alkyl and hydroxy. 5. Verfahren gemäss Anspruch 4, dadurch gekennzeichnet, dass man das Natriumsalz der 3-(4′,6′-diphenyl-s-triazin-2′-yl)-4-hydroxy-6-meth­oxy-, 6-ethoxy-oder -6-propoxy-benzolsulfonsäure aufbringt.5. The method according to claim 4, characterized in that the sodium salt of 3- (4 ', 6'-diphenyl-s-triazin-2'-yl) -4-hydroxy-6-methoxy, 6-ethoxy or -6-propoxy-benzenesulfonic acid. 6. Verfahren gemäss Anspruch 1, daduch gekennzeichnet, dass der UV-Absorber vor dem optischen Aufhellen auf das Substrat aufgebracht und fixiert wird.6. The method according to claim 1, characterized in that the UV absorber is applied to the substrate and fixed before the optical brightening. 7. Verfahren gemäss Anspruch 1, daduch gekennzeichnet, dass der UV-Absorber vor, während oder nach dem Färben oder Bedrucken des Substrates aufgebracht wird.7. The method according to claim 1, characterized in that the UV absorber is applied before, during or after the dyeing or printing of the substrate. 8. Das nach dem Verfahren gemäss Anspruch 1 behandelte Material.8. The material treated by the method according to claim 1.
EP88116113A 1987-10-02 1988-09-29 Process for quenching or suppressing the fluorescence of optically brightened substrates Expired - Lifetime EP0310083B1 (en)

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EP0310083B1 (en) 1993-01-13

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