EP0569793B1 - Process for dyeing of polyamides in the presence of manganese (II) salts - Google Patents

Process for dyeing of polyamides in the presence of manganese (II) salts Download PDF

Info

Publication number
EP0569793B1
EP0569793B1 EP93106986A EP93106986A EP0569793B1 EP 0569793 B1 EP0569793 B1 EP 0569793B1 EP 93106986 A EP93106986 A EP 93106986A EP 93106986 A EP93106986 A EP 93106986A EP 0569793 B1 EP0569793 B1 EP 0569793B1
Authority
EP
European Patent Office
Prior art keywords
dyebath
added
process according
oder
salts
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 - Lifetime
Application number
EP93106986A
Other languages
German (de)
French (fr)
Other versions
EP0569793A1 (en
Inventor
Jürgen Dipl.-Ing. Rohr
Martin Dr. Riegels
Sylvia Lohmann
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
Original Assignee
Bayer AG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Bayer AG filed Critical Bayer AG
Publication of EP0569793A1 publication Critical patent/EP0569793A1/en
Application granted granted Critical
Publication of EP0569793B1 publication Critical patent/EP0569793B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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
    • 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
    • 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
    • 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
    • D06P1/673—Inorganic compounds
    • D06P1/67333—Salts or hydroxides
    • D06P1/67341—Salts or hydroxides of elements different from the alkaline or alkaline-earth metals or with anions containing those elements

Definitions

  • the present invention relates to a new process for dyeing polyamide microfibers with acid dyes, which provides dyeings with improved light fastness.
  • polyamide fibers For most textile uses, polyamide fibers must be matted, which is technically achieved by adding titanium dioxide pigments.
  • JP-A-57089664 describes the treatment of polyamide fibers with, inter alia, manganese compounds in neutral or alkaline solution. This should enable dyeing with acid dyes with improved light fastness.
  • the organic copper complexes known from the prior art show little or no improvement in the lightfastness of the dyeing obtained when dyeing with acid dyes.
  • the present invention relates to a process for dyeing polyamide microfibers with a fiber thickness of 0.6-1.2 dtex and a content of titanium dioxide pigments of up to 2% with acid dyes, characterized in that small amounts of manganese salts are added to the dye bath .
  • the dyeings obtained with the process according to the invention show improved light fastness.
  • the method according to the invention is suitable for dyeing ultra-deep matt microfibers with a fiber thickness of 0.6 to 1.2 dtex.
  • Ultra-deep matt polyamide fibers generally contain up to 2% titanium dioxide pigments.
  • the particle size of the pigments used is generally 0.1 to 1 »m.
  • inorganic and organic salts such as chlorides, nitrates, sulfates, acetates, phosphates, formates, oxalates or lactates of manganese are suitable for carrying out the process according to the invention.
  • Organic manganese (II) salts such as in particular manganese acetate, are preferably used.
  • the metal salts mentioned are preferably used during the dyeing process in the dye bath in amounts of 0.1 to 1 g / l, preferably 0.1 to 0.5 g / l, added.
  • the manganese salts mentioned can also be used in any mixture with one another and in a mixture with Cu (I) and Cu (II) salts.
  • Acid dyes suitable for carrying out the process according to the invention are azo, anthraquinone and metal complex dyes or combinations thereof, which have to be dyed in the acidic pH range for bath exhaustion below pH 6.
  • Examples include: Cr complex of The dyeing according to the process according to the invention is generally carried out under the conditions customary for dyeing on polyamide with acid dyes, ie at a temperature from 85 to 110 ° C. and a pH below 6, preferably between 4.0 and 6.
  • a complexing agent is added to the dyebath which is capable of forming a complex with the metal ions mentioned.
  • complexing agents are: Gluconic acid; Polyaminopolycarboxylic acids; Phosphorus compounds such as tripolyphosphates, orthophosphates, phosphonic acid, phosphonoalkane polycarboxylic acids such as 2-phosphonobutane-1,2,4-tricarboxylic acid; Polycarboxylic acids such as citric acid, ethylenediaminetetraacetic acid and polyacrylic acids and their derivatives.
  • the complexing agents, dispersants and surface-active agents mentioned can be added to the dyebath to carry out the process according to the invention both individually and in any mixture with one another.
  • the complexing agents mentioned are added to the dyebath in general amounts of 0.1 to 5 g / l, preferably 0.5 to 2 g / l.
  • the dispersants mentioned are added to the dyebath in general amounts of 0.1 to 5 g / l, preferably 0.5 to 2 g / l.
  • the surface-active agents mentioned are generally added to the dyebath in quantities of 0.5 to 4%, preferably 1 to 2%, based on the weight of the polyamide fiber to be dyed.
  • phosphonoalkane polycarboxylic acids such as 2-phosphonobutane-1,2,4-tricarboxylic acid, are preferred.
  • condensation products of naphthalenesulfonic acid and formaldehyde are preferably used.
  • alkoxylated fatty alcohols and the compounds mentioned under 1 are of particular importance.
  • the combination of the following surface-active agents is added to the dyebath: 0.05-2.5 g / l of a mixture (M) consisting of 25-35 parts by weight of a water-soluble polyalkylene glycol ether containing basic nitrogen atoms, 4-6 parts by weight of an alkoxylated fatty amine, 1-3 parts by weight of one Implementation product from alkylamines with formaldehyde, phenol and ethylene oxide and 30-56 parts by weight of water, the parts by weight being based on the total mixture (M), and 0.05-2.5 g / l of an alkoxylated fatty alcohol.
  • M a mixture consisting of 25-35 parts by weight of a water-soluble polyalkylene glycol ether containing basic nitrogen atoms, 4-6 parts by weight of an alkoxylated fatty amine, 1-3 parts by weight of one Implementation product from alkylamines with formaldehyde, phenol and ethylene oxide and 30-56 parts by weight of water, the parts by weight being
  • a polyamide microfiber (deep matt weave 1.15 dtex) that was washed, desized and fixed was mixed with a mixture of 1% C.I. Acid Yellow 242, 2% C.I. Acid Blue 264 and 1% C.I. Acid Blue 290 by the HT process (liquor ratio 1:20) at 110 ° C.

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Coloring (AREA)

Description

Die vorliegende Erfindung betrifft ein neues Verfahren zum Färben von Polyamid-Mikrofasern mit Säurefarbstoffen, welches Färbungen mit verbesserter Lichtechtheit liefert.The present invention relates to a new process for dyeing polyamide microfibers with acid dyes, which provides dyeings with improved light fastness.

Für die meisten textilen Verwendungszwecke müssen Polyamidfasern mattiert sein, was technisch durch den Zusatz von Titandioxidpigmenten erreicht wird.For most textile uses, polyamide fibers must be matted, which is technically achieved by adding titanium dioxide pigments.

Es ist jedoch allgemein bekannt, daß sich die Anwesenheit von Titandioxid in der Polyamidfaser nachteilig auf deren Fotostabitität auswirkt. Je stärker eine Faser pigmentiert ist, desto weniger lichtbeständig ist sie. Aus der Literatur sind Bemühungen bekannt, die Lichtbeständigkeit von ungefärbten Polyamidfasern entweder durch den Spinnmassenzusatz von Metallionen wie z.B. Mn²⁺, Cu⁺, Cu²⁺ oder Co²⁺oder durch die Oberflächenbehandlung der Polyamidfaser zu verbessern (Textilveredelung 20, Nr. 11 (1985), 346.However, it is generally known that the presence of titanium dioxide in the polyamide fiber adversely affects its photo stability. The more pigmented a fiber is, the less lightfast it is. Efforts are known from the literature to improve the lightfastness of undyed polyamide fibers either by adding spinning material to metal ions such as Mn²⁺, Cu⁺, Cu²⁺ or Co²⁺ or by surface treatment of the polyamide fiber (Textile Finishing 20 , No. 11 (1985), 346.

In der JP-A-57089664 wird die Behandlung von Polyamidfasern mit unter anderem Manganverbindungen in neutraler bzw. alkalischer Lösung beschrieben. Dadurch sollen Färbungen mit Säurefarbstoffen mit verbesserter Lichtechtheit ermöglicht werden.JP-A-57089664 describes the treatment of polyamide fibers with, inter alia, manganese compounds in neutral or alkaline solution. This should enable dyeing with acid dyes with improved light fastness.

Weiterhin wurden Versuche unternommen, die Lichtechtheit von Färbungen mit Säurefarbstoffen auf Polyamid zu verbessern, indem man dem Färbebad Kupfer(II)-Salze zusetzte (Textilveredelung 20, loc.cit.). Wegen mangelnder Faseraffinität der Kupferionen ist hierbei ein hoher Überschuß an Kupfer(II)-Salz erforderlich. Eine bessere Faseraffinität weisen organische Kupferkomplexverbindungen auf. Es ist bekannt, solche Kupferkomplexverbindungen, insbesondere solche von Diazomethinderivaten, dem Färbebad zur Verbesserung der Lichtechtheit der Färbung zuzusetzen (Textilveredelung 20, loc.cit. und 24, Nr. 5 (1989), 182).Attempts have also been made to improve the lightfastness of dyeings with acid dyes on polyamide by adding copper (II) salts to the dyebath (textile finishing 20 , loc.cit.). Due to the lack of fiber affinity of the copper ions, a large excess of copper (II) salt is required. Organic copper complex compounds have a better fiber affinity. It is known to add such copper complex compounds, in particular those of diazomethine derivatives, to the dyebath to improve the lightfastness of the dyeing (Textile finishing 20 , loc.cit. And 24 , No. 5 (1989), 182).

Die aus dem Stand der Technik bekannten Verfahren sind jedoch nicht in allen Anforderungen zufriedenstellend. Insbesondere beim Färben von Polyamidmikrofasern, die einen hohen Mattierungsgrad aufweisen, konnten bisher mit Säurefarbstoffen, bei den für diese Farbstoffe notwendigen sauren pH-Werten nur Färbungen von unzureichender Lichtechtheit erhalten werden.However, the methods known from the prior art are not satisfactory in all requirements. In particular when dyeing polyamide microfibers that have a high degree of matting, it has hitherto been possible to obtain only dyeings of inadequate lightfastness with acid dyes at the acidic pH values required for these dyes.

Die aus dem Stand der Technik bekannten organischen Kupferkomplexe zeigen beim Färben mit Säurefarbstoffen kaum oder gar keine Verbesserung der Lichtechtheit der erhaltenen Färbung.The organic copper complexes known from the prior art show little or no improvement in the lightfastness of the dyeing obtained when dyeing with acid dyes.

Da mit Säurefarbstoffen auf Polyamid besonders tiefe Farbtöne erzielt werden können, bestand also das Bedürfnis nach einem Färbeverfahren für Säurefarbstoffe, welches Färbungen von verbesserter Lichtechtheit liefert.Since particularly deep shades can be achieved with acid dyes on polyamide, there was therefore a need for a dyeing process for acid dyes which gives dyeings of improved lightfastness.

Die vorliegende Erfindung betrifft ein Verfahren zum Färben von Polyamid-Mikrofasern einer Faserstärke von 0,6 - 1,2 dtex und einem Gehalt an Titandioxidpigmenten von bis zu 2 % mit Säurefarbstoffen, dadurch gekennzeichnet, daß dem Färbebad geringe Mengen an Mangan-Salzen zugesetzt werden. Überraschenderweise zeigen die mit dem erfindungsgemäßen Verfahren erhaltenen Färbungen eine verbesserte Lichtechtheit.The present invention relates to a process for dyeing polyamide microfibers with a fiber thickness of 0.6-1.2 dtex and a content of titanium dioxide pigments of up to 2% with acid dyes, characterized in that small amounts of manganese salts are added to the dye bath . Surprisingly, the dyeings obtained with the process according to the invention show improved light fastness.

Das erfindungsgemäße Verfahren eignet sich zum Färben von ultratiefmatten Mikrofasern mit einer Faserstärke von 0,6 bis 1,2 dtex. Ultratiefmatte Polyamidfasern enthalten im allgemeinen bis zu 2 % Titandioxidpigmente. Die Teilchengröße der eingesetzten Pigmente beträgt im allgemeinen 0,1 bis 1 »m.The method according to the invention is suitable for dyeing ultra-deep matt microfibers with a fiber thickness of 0.6 to 1.2 dtex. Ultra-deep matt polyamide fibers generally contain up to 2% titanium dioxide pigments. The particle size of the pigments used is generally 0.1 to 1 »m.

Für die Durchführung des erfindungsgemäßen Verfahrens sind im Prinzip alle anorganischen und organischen Salze, wie z.B. Chloride, Nitrate, Sulfate, Acetate, Phosphate, Formiate, Oxalate oder Lactate von Mangan geeignet. Vorzugsweise werden organische Mangan(II)-Salze wie insbesondere Manganacetat eingesetzt. Die genannten Metallsalze werden bevorzugt während des Färbevorgangs dem Färbebad in Mengen von 0,1 bis 1 g/l, vorzugsweise 0,1 bis 0,5 g/l, zugesetzt.In principle, all inorganic and organic salts such as chlorides, nitrates, sulfates, acetates, phosphates, formates, oxalates or lactates of manganese are suitable for carrying out the process according to the invention. Organic manganese (II) salts, such as in particular manganese acetate, are preferably used. The metal salts mentioned are preferably used during the dyeing process in the dye bath in amounts of 0.1 to 1 g / l, preferably 0.1 to 0.5 g / l, added.

Die genannten Mangansalze können auch in beliebiger Mischung miteinander sowie im Gemisch mit Cu(I)- und Cu(II)-Salzen eingesetzt werden.The manganese salts mentioned can also be used in any mixture with one another and in a mixture with Cu (I) and Cu (II) salts.

Zur Durchführung des erfindungsgemäßen Verfahrens geeignete Säurefarbstoffe sind Azo-, Anthrachinon- und Metallkomplex-Farbstoffe oder deren Kombinationen, die im sauren pH-Bereich zur Baderschöpfung unter pH 6 gefärbt werden müssen.Acid dyes suitable for carrying out the process according to the invention are azo, anthraquinone and metal complex dyes or combinations thereof, which have to be dyed in the acidic pH range for bath exhaustion below pH 6.

Beispielsweise seien genannt:
Cr-Komplex von

Figure imgb0001
Figure imgb0002
Figure imgb0003
Die Färbung gemäß dem erfindungsgemäßen Verfahren erfolgt im allgemeinen unter den für Färbungen auf Polyamid mit Säurefarbstoffen üblichen Bedingungen, d.h. bei einer Temperatur von 85 bis 110°C und einem pH-Wert unterhalb von 6, vorzugsweise zwischen 4,0 und 6.Examples include:
Cr complex of
Figure imgb0001
Figure imgb0002
Figure imgb0003
The dyeing according to the process according to the invention is generally carried out under the conditions customary for dyeing on polyamide with acid dyes, ie at a temperature from 85 to 110 ° C. and a pH below 6, preferably between 4.0 and 6.

In einer bevorzugten Ausführungsform des erfindungsgemäßen Verfahrens wird dem Färbebad ein Komplexbildner zugesetzt, der befähigt ist, mit den genannten Metallionen einen Komplex zu bilden. Als Komplexbildner kommen beispielsweise infrage:
Gluconsäure; Polyaminopolycarbonsäuren; Phosphorverbindungen wie Tripolyphosphate, ortho-Phosphate, Phosphonsäure, Phosphono-alkan-polycarbonsäuren wie 2-Phosphonobutan-1,2,4-tricarbonsäure; Polycarbonsäuren wie Citronensäure, Ethylendiamintetraessigsäure sowie Polyacrylsäuren und deren Derivate.In a preferred embodiment of the process according to the invention, a complexing agent is added to the dyebath which is capable of forming a complex with the metal ions mentioned. Examples of possible complexing agents are:
Gluconic acid; Polyaminopolycarboxylic acids; Phosphorus compounds such as tripolyphosphates, orthophosphates, phosphonic acid, phosphonoalkane polycarboxylic acids such as 2-phosphonobutane-1,2,4-tricarboxylic acid; Polycarboxylic acids such as citric acid, ethylenediaminetetraacetic acid and polyacrylic acids and their derivatives.

In einer ebenfalls bevorzugten Ausführungsform des erfindungsgemäßen Verfahrens wird dem Färbebad ein Dispergiermittel, vorzugsweise ein anionisches Dispergiermittel z.B. aus der Reihe der Polykondensate aus:

  • verschiedenen Alkylarylsulfonsäuren mit Halogenarylsulfonsäuren
  • sulfonierten Phenolen, β-Naphtholen etc. mit Formaldehyd und verschiedenen Stickstoff-Verbindungen
  • reaktionsfähigen Alkylarylverbindungen mit aromatischen Sulfonsäuren, wie z.B. Benzylchlorid mit Naphthalinsulfonsäure
  • Diphenyletherderivaten u.ä mit Arylsulfonaten und Formaldehyd
  • Kresolsulfonsäuren mit Formaldehyd
  • Harnstoff-Formaldehyd mit Phenolsulfonsäure
  • Phenol und Formaldehyd, die sulfomethyliert werden,
sowie der Reihe der Ligninsulfonate, wie sie z.B. in Chwala/Anger, Handbuch der Textilhilfsmittel, 2. Auflage, Verlag Chemie, Weinheim 1977, Seite 506 ff, beschrieben sind, zugesetzt.In a likewise preferred embodiment of the process according to the invention, a dispersant, preferably an anionic dispersant, for example from the series of polycondensates, is added to the dyebath:
  • various alkylarylsulfonic acids with haloarylsulfonic acids
  • sulfonated phenols, β-naphthols etc. with formaldehyde and various nitrogen compounds
  • reactive alkylaryl compounds with aromatic sulfonic acids, such as benzyl chloride with naphthalenesulfonic acid
  • Diphenyl ether derivatives and the like with aryl sulfonates and formaldehyde
  • Cresol sulfonic acids with formaldehyde
  • Urea formaldehyde with phenol sulfonic acid
  • Phenol and formaldehyde that are sulfomethylated
as well as the series of lignin sulfonates as described, for example, in Chwala / Anger, Handbuch der Textilhilhilmittel, 2nd edition, Verlag Chemie, Weinheim 1977, page 506 ff.

In einer weiterhin bevorzugten Ausführungsform des erfindungsgemäßen Verfahrens wird dem Färbebad ein oberflächenaktives Hilfsmittel zugesetzt. Als oberflächenaktive Hilfsmittel kommen vorzugsweise infrage:

  • 1.
    • a) basische Stickstoffatome enthaltende wasserlösliche Polyalkylenglykolether, wie sie z.B. in der DE-B-1 619 652 beschrieben sind,
    • b) alkoxylierte Fettamine der allgemeinen Formel
      Figure imgb0004
          worin
      R
      für C₁₂-C₂₂-Alkyl, C₁₂-C₂₂-Alkenyl oder C₁₂-C₂₂-Cycloalkenyl steht,
      x und y
      unabhängig voneinander für eine Zahl von 5 - 70, vorzugsweise 15 - 50, stehen und
      R₁
      für Wasserstoff, Methyl, Ethyl oder Phenyl steht,
    • c) Umsetzungsprodukte von Alkylaminen mit 12 bis 22 C-Atomen mit Formaldehyd, Phenolen und 15 - 50 Äquivalenten Ethylenoxid,
      wobei die Komponenten a), b) und c) als Einzelverbindungen oder als Gemische untereinander eingesetzt werden können.
  • 2. Verbindungen der Formel (vgl. DE-B-1 940 178 und EP-A-305 858)
    Figure imgb0005
     worin
    R
    für C₁₂-C₂₂-Alkyl, C₁₂-C₂₂-Alkenyl oder C₁₂-C₂₂-Cycloalkyl steht,
    R₁
    für C₁-C₄-Alkyl oder eine Gruppe der Formel -(CH₂-CHR₂-O)y-H oder -(CH₂-CHR₂-O)y-CH₂-CH₂-A⊖M⊕ steht,
    R₂
    für H, Methyl, Ethyl oder Phenyl steht,
    M⊕
    für ein Kation, insbesondere ein Alkali-, Erdalkali- oder Ammoniumion oder ein Mono-, Di- oder Triethanolammoniumion steht,
    A⊖
    für eine anionische Gruppe, inbesondere SO₄⊖ oder SO₃⊖ steht, und
    x und y
    unabhängig voneinander für eine Zahl von 5 bis 70, vorzugsweise 15 bis 50 stehen,
    bzw. deren Quaternisierungsprodukte der Formel
    Figure imgb0006
     worin
    R, R₁, R₂, M⊕, A⊖, x und y
    die oben angegebene Bedeutung haben und
    R₃
    für gegebenenfalls durch Hydroxy, Carboxyl, niederes Carbalkoxy oder Carbonamid substituiertes C₁-C₈-Alkyl steht
    (vgl. DE-B-1 940 178; EP-A-305 858).
  • 3.
    • a) Alkoxylierte Fettalkohole (vgl. EP 312 493) der Formel



              RO(CH₂CHR₁O)x-H ,



         worin
      R
      für C₁₂-C₂₂-Alkyl, C₁₂-C₂₂-Alkenyl oder C₁₂-C₂₂-Cycloalkyl steht,
      R₁
      für H, Methyl, Ethyl oder Phenyl steht, und
      x
      für 12 - 60 steht,
      und/oder
    • b) quaternierte Ammoniumverbindungen von Polyglykolverbindungen der Formel
      Figure imgb0007
          worin
      R₁
      für Alkyl oder Alkenyl mit jeweils 12 bis 22 Kohlenstoffatomen steht,
      R₂
      für gegebenenfalls durch Hydroxy, Carboxyl, niederes Carbalkoxy oder Carbonamid substituiertes C₁-C₈-Alkyl steht,
      R₃
      für H, Methyl, Ethyl oder Phenyl steht,
      x und y
      unabhängig voneinander für eine Zahl von 5 - 70, vorzugsweise 15-50, stehen, und
      A⊖
      für ein Anion, vorzugsweise für Cl⊖ oder das Methosulfatanion, steht.
  • 4. Oberflächenaktive Schwefelsäureester- oder Sulfonsäuregruppen enthaltende Verbindungen wie (siehe auch DE-B-1 920 357)
    • a) Alkylarylsulfonsäuren,
    • b) Alkansulfonsäuren,
    • c) Amide aus höhermolekularen Fettsäuren und Aminoalkylsulfonsäuren,
    • d) sulfatierte, höhermolekulare Fettsäuren bzw. deren Ester
    • e) Alkylsulfate wie Natriumdodecylsulfat, Alkylethersulfate (z.B. wie 3a), Alkylpolyethersulfate.

    Als sulfatierte höhermolekulare Fettsäuren bzw. deren Ester kommen in Frage:
    • Sulfatierungsprodukte der Öl- bzw. Elaidinsäure oder der Ricinolsäure und deren Alkylester, z.B. der Methyl-, Ethyl-, Propyl- oder Butylester, oder des Glycerinesters dieser Fettsäuren, z.B. des Ricinusöles.
  • 5. Sulfonierte, aromatische Kondensationsprodukte beispielsweise aus Naphthalin, Formaldehyd und Schwefelsäure.
  • 6. Verbindungen der Formel (vgl. DE-B-2 945 102)
    Figure imgb0008
        worin
    R
    für C₄-C₁₂-Alkyl, C₁-C₁₂-Alkoxy, Phenyl, Cyclohexyl oder C₂-C₈-Hydroxyalkoxy steht,
    R₁
    für H oder C₁-C₄-Alkyl steht,
    x
    für eine ganze Zahl von 1 bis 10 steht und
    y
    für Zahlen von 1 bis x+1 steht.
  • 7.
    • a) Verbindungen mit dar Formel (vgl. DE-B-1 444 267)



              R(A)xR₁,



         worin
      R
      für sulfonierte Benzol- oder Naphthalinringe,
      R₁
      für sulfonierte Benzol- oder Naphthalinringe,
      A
      für CH₂, SO₂ oder NH, und
      x
      für 0 bis 4 steht,
    • b) ein schwach kationisches komplexbildendes Mittel wie beispielsweise Polyvinylpyrrolidon oder ein Kondensationsprodukt von Ethylenoxid mit einem Fettamin mit langer Kette.
  • 8. Polyglykolether sulfogruppenhaltiger durch Kohlenwasserstoffe substituierter Phenole oder Naphthole (vgl. DE-B-1 288 066)
    Figure imgb0009
        worin
    Ar
    für einen Benzol- oder Naphthalinrest,
    R
    für einen Kohlenwasserstoffrest, insbesondere Cycloalkyl, Aralkylrest oder Alkylrest mit mindestens 7 Kohlenstoffatomen steht,
    R₁
    für H oder Methyl,
    x
    für 1 bis 8
    X
    für OH, Cl, CN, O-Alkyl oder OOC-Alkyl bzw. eine anionische Atomgruppierung wie OSO₃H, OPO₃H₂ oder OCH₂CO₂H steht; ferner die Alkali- oder Ammoniumsalze dieser Verbindungen sowie ihre Salze mit Aminen, z.B. Ethanolamin, Diethanolamin, Triethanolamin und Cyclohexylamin.
In a further preferred embodiment of the process according to the invention, a surface-active auxiliary is added to the dyebath. The following are preferably suitable as surface-active aids:
  • 1.
    • a) water-soluble polyalkylene glycol ethers containing basic nitrogen atoms, as described, for example, in DE-B-1 619 652,
    • b) alkoxylated fatty amines of the general formula
      Figure imgb0004
       wherein
      R
      represents C₁₂-C₂₂-alkyl, C₁₂-C₂₂-alkenyl or C₁₂-C₂₂-cycloalkenyl,
      x and y
      independently represent a number from 5 to 70, preferably 15 to 50, and
      R₁
      represents hydrogen, methyl, ethyl or phenyl,
    • c) reaction products of alkylamines with 12 to 22 carbon atoms with formaldehyde, phenols and 15-50 equivalents of ethylene oxide,
      where components a), b) and c) can be used as individual compounds or as mixtures with one another.
  • 2. Compounds of the formula (cf. DE-B-1 940 178 and EP-A-305 858)
    Figure imgb0005
     wherein
    R
    represents C₁₂-C₂₂-alkyl, C₁₂-C₂₂-alkenyl or C₁₂-C₂₂-cycloalkyl,
    R₁
    represents C₁-C₄-alkyl or a group of the formula - (CH₂-CHR₂-O) y -H or - (CH₂-CHR₂-O) y -CH₂-CH₂-A ⊖ M ⊕ ,
    R₂
    represents H, methyl, ethyl or phenyl,
    M ⊕
    stands for a cation, in particular an alkali, alkaline earth or ammonium ion or a mono-, di- or triethanolammonium ion,
    A ⊖
    represents an anionic group, in particular SO₄ ⊖ or SO₃ ⊖ , and
    x and y
    independently of one another represent a number from 5 to 70, preferably 15 to 50,
    or their quaternization products of the formula
    Figure imgb0006
     wherein
    R, R₁, R₂, M ⊕ , A ⊖ , x and y
    have the meaning given above and
    R₃
    represents C₁-C₈-alkyl optionally substituted by hydroxy, carboxyl, lower carbalkoxy or carbonamide
    (see DE-B-1 940 178; EP-A-305 858).
  • 3rd
    • a) Alkoxylated fatty alcohols (cf. EP 312 493) of the formula



      RO (CH₂CHR₁O) x -H,



      wherein
      R
      represents C₁₂-C₂₂-alkyl, C₁₂-C₂₂-alkenyl or C₁₂-C₂₂-cycloalkyl,
      R₁
      represents H, methyl, ethyl or phenyl, and
      x
      stands for 12 - 60,
      and or
    • b) quaternized ammonium compounds of polyglycol compounds of the formula
      Figure imgb0007
       wherein
      R₁
      represents alkyl or alkenyl each having 12 to 22 carbon atoms,
      R₂
      represents C₁-C₈-alkyl optionally substituted by hydroxy, carboxyl, lower carbalkoxy or carbonamide,
      R₃
      represents H, methyl, ethyl or phenyl,
      x and y
      independently represent a number from 5 to 70, preferably 15 to 50, and
      A ⊖
      stands for an anion, preferably for Cl ⊖ or the methosulfate anion.
  • 4. Compounds containing surface-active sulfuric acid ester or sulfonic acid groups such as (see also DE-B-1 920 357)
    • a) alkylarylsulfonic acids,
    • b) alkanesulfonic acids,
    • c) amides from higher molecular weight fatty acids and aminoalkylsulfonic acids,
    • d) sulfated, higher molecular weight fatty acids or their esters
    • e) alkyl sulfates such as sodium dodecyl sulfate, alkyl ether sulfates (eg as 3a), alkyl polyether sulfates.

    Possible sulfated higher molecular fatty acids or their esters are:
    • Sulfation products of oleic or elaidic acid or of ricinoleic acid and their alkyl esters, for example the methyl, ethyl, propyl or butyl ester, or of the glycerol ester of these fatty acids, for example of castor oil.
  • 5. Sulfonated, aromatic condensation products, for example from naphthalene, formaldehyde and sulfuric acid.
  • 6. Compounds of the formula (cf. DE-B-2 945 102)
    Figure imgb0008
     wherein
    R
    represents C₄-C₁₂-alkyl, C₁-C₁₂-alkoxy, phenyl, cyclohexyl or C₂-C₈-hydroxyalkoxy,
    R₁
    represents H or C₁-C₄-alkyl,
    x
    represents an integer from 1 to 10 and
    y
    stands for numbers from 1 to x + 1.
  • 7.
    • a) Compounds with the formula (cf. DE-B-1 444 267)



      R (A) x R₁,



      wherein
      R
      for sulfonated benzene or naphthalene rings,
      R₁
      for sulfonated benzene or naphthalene rings,
      A
      for CH₂, SO₂ or NH, and
      x
      represents 0 to 4,
    • b) a weakly cationic complexing agent such as polyvinyl pyrrolidone or a condensation product of ethylene oxide with a long chain fatty amine.
  • 8. Polyglycol ethers of sulfo-containing phenols or naphthols substituted by hydrocarbons (cf. DE-B-1 288 066)
    Figure imgb0009
     wherein
    Ar
    for a benzene or naphthalene residue,
    R
    represents a hydrocarbon radical, in particular cycloalkyl, aralkyl radical or alkyl radical with at least 7 carbon atoms,
    R₁
    for H or methyl,
    x
    for 1 to 8
    X
    represents OH, Cl, CN, O-alkyl or OOC-alkyl or an anionic atomic grouping such as OSO₃H, OPO₃H₂ or OCH₂CO₂H; furthermore the alkali or ammonium salts of these compounds as well their salts with amines, for example ethanolamine, diethanolamine, triethanolamine and cyclohexylamine.

Im Prinzip können zur Durchführung des erfindungsgemäßen Verfahrens dem Färbebad die genannten Komplexbildner, Dispergiermittel und oberflächenaktiven Mittel sowohl einzeln als auch in beliebigem Gemisch untereinander zugesetzt werden.In principle, the complexing agents, dispersants and surface-active agents mentioned can be added to the dyebath to carry out the process according to the invention both individually and in any mixture with one another.

Die genannten Komplexbildner werden dem Färbebad in allgemeinen Mengen von 0,1 bis 5 g/l, vorzugsweise von 0,5 bis 2 g/l, zugesetzt.The complexing agents mentioned are added to the dyebath in general amounts of 0.1 to 5 g / l, preferably 0.5 to 2 g / l.

Die genannten Dispergiermittel werden dem Färbebad in allgemeinen Mengen von 0,1 bis 5 g/l, vorzugsweise von 0,5 bis 2 g/l, zugesetzt.The dispersants mentioned are added to the dyebath in general amounts of 0.1 to 5 g / l, preferably 0.5 to 2 g / l.

Die genannten oberflächenaktiven Mittel werden dem Färbebad im allgemeinen in Mengen von 0,5 bis 4 %, vorzugsweise von 1 bis 2 %, bezogen auf das Warengewicht der zu färbenden Polyamidfaser, zugesetzt.The surface-active agents mentioned are generally added to the dyebath in quantities of 0.5 to 4%, preferably 1 to 2%, based on the weight of the polyamide fiber to be dyed.

Von den genannten Komplexbildnern sind Phosphonoalkanpolycarbonsäuren, wie 2-Phosphonobutan-1,2,4-tricarbonsäure, bevorzugt.Of the complexing agents mentioned, phosphonoalkane polycarboxylic acids, such as 2-phosphonobutane-1,2,4-tricarboxylic acid, are preferred.

Von den genanten Dispergiermittel werden vorzugsweise Kondensationsprodukte aus Naphthalinsulfonsäure und Formaldehyd eingesetzt.Of the dispersants mentioned, condensation products of naphthalenesulfonic acid and formaldehyde are preferably used.

Von den genannten oberflächenaktiven Mitteln sind alkoxylierte Fettalkohole sowie die unter 1. genannten Verbindungen von besonderer Bedeutung.Of the surface-active agents mentioned, alkoxylated fatty alcohols and the compounds mentioned under 1 are of particular importance.

In einer ganz besonders bevorzugten Ausführungsform des erfindungsgemäßen Verfahrens wird dem Färbebad die Kombination folgender oberflächenaktiver Mittel zugesetzt:
0,05-2,5 g/l einer Mischung (M) bestehend aus 25-35 Gew.-Teilen eines basische Stickstoffatome enthaltenden wasserlöslichen Polyalkylenglykolethers, 4-6 Gew.-Teilen eines alkoxylierten Fettamins, 1-3 Gew.-Teilen eines Umsetzungsproduktes aus Alkylaminen mit Formaldehyd, Phenol und Ethylenoxid und 30-56 Gew.-Teilen Wasser, wobei die Gewichtsteile jeweils auf die gesamte Mischung (M) bezogen sind, sowie 0,05-2,5 g/l eines alkoxylierten Fettalkohols.In a very particularly preferred embodiment of the process according to the invention, the combination of the following surface-active agents is added to the dyebath:
0.05-2.5 g / l of a mixture (M) consisting of 25-35 parts by weight of a water-soluble polyalkylene glycol ether containing basic nitrogen atoms, 4-6 parts by weight of an alkoxylated fatty amine, 1-3 parts by weight of one Implementation product from alkylamines with formaldehyde, phenol and ethylene oxide and 30-56 parts by weight of water, the parts by weight being based on the total mixture (M), and 0.05-2.5 g / l of an alkoxylated fatty alcohol.

Beispiel 1example 1

Eine Polyamidmikrofaser (Tiefmatt-Webware 1,15 dtex) die gewaschen, entschlichtet und fixiert wurde, wurde mit einer Mischung aus 1 % C.I. Acid Yellow 242, 2 % C.I.Acid Blue 264 und 1 % C.I. Acid Blue 290 nach dem HT-Verfahren (Flottenverhältnis 1:20) bei 110°C und einem pH-Wert von 5 in Gegenwart von 0,1 g/l Mangan(II)-Acetat, 1,0 g/l eines handelsüblichen oberflächenaktiven Mittels, bestehend aus Polyalkylenglykolether (LEVEGAL LPA®) sowie 1,0 g/l eines oberflächenaktiven Mittels, bestehend aus dem Umsetzungsprodukt von Oleylalkohol mit 50 Äquivalenten Ethylenoxid für 60 Minuten gefärbt.A polyamide microfiber (deep matt weave 1.15 dtex) that was washed, desized and fixed was mixed with a mixture of 1% C.I. Acid Yellow 242, 2% C.I. Acid Blue 264 and 1% C.I. Acid Blue 290 by the HT process (liquor ratio 1:20) at 110 ° C. and a pH of 5 in the presence of 0.1 g / l manganese (II) acetate, 1.0 g / l of a commercially available surface-active agent Agent consisting of polyalkylene glycol ether (LEVEGAL LPA®) and 1.0 g / l of a surface-active agent consisting of the reaction product of oleyl alcohol colored with 50 equivalents of ethylene oxide for 60 minutes.

Claims (7)

  1. Process for dyeing polyamide microfibres of a fibre thickness of 0.6 to 1.2 dtex and a content of titanium dioxide pigments of up to 2% with acid dye-stuffs, characterised in that small amounts of salts of manganese are added to the dyebath.
  2. Process according to Claim 1, characterised in that small amounts of manganese(II) salts in the form of the chlorides, nitrates, sulphates, acetates, phosphates, formates, oxalates or lactates are added to the dyebath.
  3. Process according to Claim 1, characterised in that the salts are added to the dyebath in amounts of 0.1 to 1 g/l, preferably 0.1 to 0.5 g/l.
  4. Process according to Claim 1, characterised in that the acid dyestuffs are azo dyestuffs, anthraquinone dyestuffs and metal complex dyestuffs or mixtures thereof.
  5. Process according to Claim 1, characterised in that a complexing agent and/or an anionic dispersing agent and/or a surface-active agent is added to the dyebath.
  6. Process according to Claim 1, characterised in that one or more surface-active agents are added to the dyebath.
  7. Process according to Claim 1, characterised in that a combination of a water-soluble polyalkylene glycol ether containing basic nitrogen atoms, an alkoxylated fatty amine and a reaction product of alkylamines with formaldehyde, phenols and ethylene oxide is added to the dyebath as a surface-active agent.
EP93106986A 1992-05-12 1993-04-29 Process for dyeing of polyamides in the presence of manganese (II) salts Expired - Lifetime EP0569793B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4215589 1992-05-12
DE4215589A DE4215589A1 (en) 1992-05-12 1992-05-12 Dyeing process

Publications (2)

Publication Number Publication Date
EP0569793A1 EP0569793A1 (en) 1993-11-18
EP0569793B1 true EP0569793B1 (en) 1995-11-29

Family

ID=6458656

Family Applications (1)

Application Number Title Priority Date Filing Date
EP93106986A Expired - Lifetime EP0569793B1 (en) 1992-05-12 1993-04-29 Process for dyeing of polyamides in the presence of manganese (II) salts

Country Status (5)

Country Link
US (1) US5462565A (en)
EP (1) EP0569793B1 (en)
JP (1) JPH07268783A (en)
CA (1) CA2095798A1 (en)
DE (2) DE4215589A1 (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0735181A3 (en) * 1995-03-27 1998-04-15 Ciba SC Holding AG Multicolor dyeing with manganese compounds of fibrous materials containing polyamide fibres
JP2011084645A (en) 2009-10-15 2011-04-28 Seiko Epson Corp Ink composition and process for producing the same
CN103132349B (en) * 2013-03-13 2015-04-29 盛虹集团有限公司 Dyeing and finishing method of superfine denier nylon fabric
CN110284340A (en) * 2019-07-10 2019-09-27 浙江俏尔婷婷服饰有限公司 A kind of seamless swimsuit fabric colouring method of fine-denier full-dull nylon contaminating special dark color

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1050110A (en) * 1952-02-01 1954-01-05 Rhodiaceta Process for fixing manganese salts on cellulosic fibers and in cellulosic derivatives
US3479313A (en) * 1964-05-06 1969-11-18 Gen Tire & Rubber Co Oil extension of latices
CH425713A (en) * 1964-07-07 1967-06-15 Sandoz Ag Process for dyeing polyamide fibers with water-soluble, non-metallizable dyes
DE1619542B1 (en) * 1967-08-08 1971-02-04 Bayer Ag Process for dyeing nitrogen-containing fiber materials
US3606693A (en) * 1969-03-10 1971-09-21 Richards Corp The Film viewing means
DE2857196C3 (en) * 1977-04-19 1981-04-16 CIBA-GEIGY AG, CH 4002 Basel Block dyeing method
FR2398834A1 (en) * 1977-07-28 1979-02-23 Ugine Kuhlmann PROCESS FOR DYING OR PRINTING MATERIALS BASED ON SYNTHETIC FIBERS BY MEANS OF DISPERSION DYES AND TINCTORIAL COMPOSITIONS USED FOR THIS PURPOSE
DE3872824D1 (en) * 1987-10-14 1992-08-20 Ciba Geigy Ag METHOD FOR COLORING NATURAL POLYAMIDE FIBERS WITH REACTIVE DYES.
US5142000A (en) * 1991-08-28 1992-08-25 E. I. Du Pont De Nemours And Company Process for increasing polyamide molecular weight with organophosphonic acid or ester catalysts in the presence of alumina-containing titanium dioxide

Also Published As

Publication number Publication date
DE4215589A1 (en) 1993-11-18
US5462565A (en) 1995-10-31
EP0569793A1 (en) 1993-11-18
DE59301039D1 (en) 1996-01-11
JPH07268783A (en) 1995-10-17
CA2095798A1 (en) 1993-11-13

Similar Documents

Publication Publication Date Title
EP0089004B1 (en) Process for dyeing fibrous material from natural polyamides
EP0074923B1 (en) Dyeing auxiliary and its use in dyeing or printing synthetic polyamide fibrous materials
DE4209261B4 (en) Anionic disazo compounds
EP0468921B2 (en) Aqueous dispersions of slightly soluble UV absorbing agents
EP0102926A1 (en) Dyeing auxiliary and its use in dyeing or printing synthetic polyamide fibres
EP0225281B1 (en) Auxiliary agent combination and its use as a textile-finishing agent
DE2633615C3 (en) Process for dyeing synthetic polyamide fiber materials
EP0135198B1 (en) Process for dyeing synthetic polyamide fibrous material
DE1940178B2 (en) Process for coloring nitrogen-containing fiber materials
EP0569793B1 (en) Process for dyeing of polyamides in the presence of manganese (II) salts
EP0163608B1 (en) Process for dyeing natural or synthetic polyamide fibrous material with 1:1 metallic complex dyes
DE2744316C2 (en)
DE3103815A1 (en) METHOD FOR TREATING DYED FELT-FREE FIBER MATERIALS
EP0593392B1 (en) Process for dyeing of natural and synthetic polyamide fibers with dye mixtures
EP0828023B1 (en) Agent for printing or dyeing textile materials
EP0414631A1 (en) Auxiliary agent mixture and its use in dyeing polyester fibre materials
EP0203890B1 (en) Process for dyeing natural fibrous polyamide material with dye mixtures
DE2802304A1 (en) METHOD OF COLORING WOOL FIBER MATERIAL
DE1794190B2 (en) Process for coloring synthetic fibers with disperse dyes
DE1288066B (en)
EP0474594B1 (en) Process for dyeing of wool and mixtures thereof with other fibres with reactive dyestuffs
EP0305858B1 (en) Process for dyeing polyamide fibres
DE1953069C3 (en) Oxalkylation products of bis (2 hydroxy 3 alkoxy propylamines and their use
DE3333457A1 (en) PERFLUORALKYL-ANTHRANIL ACID ESTER, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS A DIRT-REPELLENT AGENT
CH366661A (en) Construction for rapid construction buildings

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): CH DE FR GB IT LI

17P Request for examination filed

Effective date: 19940413

17Q First examination report despatched

Effective date: 19941208

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): CH DE FR GB IT LI

REF Corresponds to:

Ref document number: 59301039

Country of ref document: DE

Date of ref document: 19960111

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

Effective date: 19951222

ITF It: translation for a ep patent filed

Owner name: SOCIETA' ITALIANA BREVETTI S.P.A.

REG Reference to a national code

Ref country code: CH

Ref legal event code: NV

Representative=s name: E. BLUM & CO. PATENTANWAELTE

ET Fr: translation filed
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19980316

Year of fee payment: 6

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 19980415

Year of fee payment: 6

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19980416

Year of fee payment: 6

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19980420

Year of fee payment: 6

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19990429

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19990430

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19990430

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19990429

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19991231

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20000201

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20050429