EP0185611B1 - Procédé de stabilisation photochimique de matières fibreuses synthétiques contenant des fibres en polyamide - Google Patents

Procédé de stabilisation photochimique de matières fibreuses synthétiques contenant des fibres en polyamide Download PDF

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Publication number
EP0185611B1
EP0185611B1 EP85810513A EP85810513A EP0185611B1 EP 0185611 B1 EP0185611 B1 EP 0185611B1 EP 85810513 A EP85810513 A EP 85810513A EP 85810513 A EP85810513 A EP 85810513A EP 0185611 B1 EP0185611 B1 EP 0185611B1
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Prior art keywords
copper
amino
process according
dye
radical
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EP85810513A
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German (de)
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EP0185611A1 (fr
Inventor
Gerhard Dr. Reinert
Hans Ulrich Schütz
Gerhard Dr. Back
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Novartis AG
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Ciba Geigy AG
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • 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
    • D06P1/642—Compounds containing nitrogen
    • D06P1/6423—Compounds containing azide or oxime groups
    • 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 the photochemical stabilization of synthetic polyamide fiber materials with water-soluble copper complex dyes.
  • Dyed synthetic polyamide fiber material is damaged when exposed to light, especially when exposed to heat; therefore synthetic polyamide fibers are used in some areas of application, such as. B. viewed as car upholstery or sail fabrics, as problem fibers.
  • the aim is to improve the photochemical stability of synthetic polyamide fiber materials.
  • inorganic or organic copper salts often have the disadvantage that they are insufficiently and unevenly applied to the polyamide fiber and are therefore used in high concentrations and are often used only in an aftertreatment process can be.
  • the object underlying the present invention was to find a process for the photochemical stabilization of synthetic polyamide fiber materials which does not have the disadvantages described above and which meets today's requirements.
  • the present invention thus relates to a process for the photochemical stabilization of fiber materials made of synthetic polyamides, which is characterized in that the fiber material is mixed with a mixture of a water-soluble copper complex dye and a fiber-affine, water-soluble, non-chromophoric copper complex of bisazomethines, acylhydrazone, semicarbazones or Treated thiosemicarbazones of aromatic aldehydes or ketones.
  • photochemical stabilization here refers to both the light fastness and the maintenance of the mechanical properties of the undyed or dyed polyamide fiber, i.e. Photochemical stabilization against visible and UV light.
  • Preferred embodiments of the process according to the invention are characterized in that water-soluble copper complex dyes, in particular water-soluble copper complex azo or azomethine dyes, are used.
  • the mixtures mentioned are expediently used in an amount such that 2 to 1000 ⁇ g of copper, in particular 5 to 200 ⁇ g of copper, are added to 1 g of polyamide fiber material.
  • a particularly preferred embodiment of the process according to the invention is characterized in that copper complexes of azo or azomethine dyes of the formula which contain water-solubilizing groups where D is a residue of the benzene or naphthalene series, X is a nitrogen atom or the CH group, Y is the HO, CH 3 0 or HOOC group and Y 'is the HO or an amino group, and wherein K is for the Where X is a nitrogen atom, the residue of a coupling component of the benzene, naphthalene or heterocyclic series or the residue of a ketomethylene compound, or, if X is the CH group, K is the residue of an o-hydroxyaldehyde .
  • the copper complex dyes come as water-solubilizing groups such.
  • Suitable sulfone groups are alkyl sulfone and in particular Cl-4 alkyl sulfone groups.
  • N-mono- or N, N-dialkylsulfonamide group is one having one or two C 1-4 -alkyl radicals.
  • copper complex dyes with one to two water-solubilizing groups are used in the process according to the invention.
  • An interesting embodiment of the method according to the invention is characterized in that a copper complex dye of the formula used, in which A is an optionally substituted carboxyphenyl or sulfophenyl radical, R, hydrogen or C 1-4 alkyl, X is a nitrogen atom or the CH group and K, in the event that X is a nitrogen atom, the residue of a coupling component of the benzene, Naphthalene, pyrazolone, aminopyrazole, acetoacetanilide, 2,4-dioxyquinoline, pyridone or pyridine series, or, if X is the CH group, is the remainder of an o-hydroxybenzaldehyde, and the ring B optionally z.
  • B. may be further substituted by chlorine or nitro.
  • azo dyes of the formula (1) have been described in the literature.
  • the azo dyes of the formula (1) are prepared in a manner known per se by using an amine of the formula diazotized and on a coupling component of the formula couples.
  • the diazotization of the diazo component of the formula (3) is generally carried out by the action of nitrous acid in aqueous mineral acid solution at low temperature, the coupling to the coupling component of the formula (4) at acidic, neutral to alkaline pH values.
  • a process variant for the preparation of the copper complex of an azomethine dye of the formula (1) is characterized in that the copper complex can also be prepared with a mixture of the amine of the formula (3) and an o-hydroxyaldehyde instead of with the azomethine of the formula (1).
  • the metal complexes are prepared by methods known per se in an aqueous or organic medium.
  • copper salts such as. B. copper sulfate and copper nitrate.
  • the freshly precipitated hydroxides can also be used.
  • the reaction is carried out in the weakly acidic to alkaline range.
  • reaction is carried out with heating, e.g. B. slightly below the boiling point of the solvent used.
  • Preferred copper complexes of bisazomethines, acylhydrazones, semicarbazones and thiosemicarbazones of aromatic aldehydes or ketones are those which contain sulfonic acid groups. They are readily water-soluble and also have an excellent affinity for polyamide fibers. Such complexes are therefore effective even in small amounts. In addition, it has been shown that they not only increase the lightfastness of the dyed polyamide material, but also generally protect the polyamide fiber against photochemical degradation and thus largely maintain its mechanical properties, such as tear resistance and elasticity.
  • Bisazomethines of aromatic aldehydes and ketones are understood to mean Schiff bases of aliphatic, cycloaliphatic or aromatic diamines, the aldehydes and ketones having an OH group in the o-position to the formyl or acyl radical.
  • the bond with the copper atom takes place via these two OH groups and the two nitrogen atoms in the bisazomethine part. Accordingly, these are tidentate ligands.
  • the ligands contain one or more sulfo groups which are located in the aldehyde or ketone part and / or in the bisazomethine bridge.
  • R 2 , R 3 or R 5 denotes an optionally substituted alkyl radical
  • the cyclohexyl radical can also be used, which can also be substituted, for example by C 1 to C 4 alkyl or C 1 to C 4 alkoxy.
  • R 2 , R 3 or R 5 is an optionally substituted aryl radical
  • a phenyl or naphthyl radical which can be substituted by C 1 -C 4 alkyl, such as methyl, ethyl, propyl, iso-isopropyl, butyl, is particularly suitable.
  • C 2 -C 5 alkanoylamino such as acetylamino, propionylamino and butyrylamino, nitro, cyano, sulfo or a mono- or dialkylated amino group.
  • Z is an alkylene radical, it is primarily a C 2 to C 4 alkylene radical, in particular a —CH 2 —CH 2 bridge.
  • a C 2 to C 8 alkylene chain which is interrupted by oxygen or, in particular, nitrogen is also suitable, in particular the - (CH 2 ) 3 -NH- (CH 2 ) 3 bridge.
  • Z is a cycloalkylene radical, this is preferably cyclohexylene and can have one or two methyl groups.
  • Z is an arylene radical, it is primarily a phenylene radical, in particular an o-phenylene radical. This can also be substituted by C 1 to C 4 alkyl or C 1 to C 4 alkoxy.
  • Suitable substituents for the benzene rings M and N are: C 1 to C 4 alkyl, C 1 to C 4 alkoxy, halogen, such as. As fluorine, chlorine or bromine, furthermore the cyano or nitro groups.
  • the sulfo groups which are located in the benzene rings M and / or N and / or in the bridge member Z, if this denotes an arylene radical, are preferably in the form of the alkali metal salt, in particular the sodium salt or also the amine salt.
  • the Z is preferably -CH 2 -CH 2 -.
  • R 4 is an alkyl radical, this can be branched or unbranched and has a chain length of preferably 1 to 8, in particular 1 to 4, carbon atoms.
  • Suitable substituents are halogen, such as fluorine, chlorine or bromine, C 1 to C 4 alkoxy, such as methoxy or ethoxy, further phenyl or carboxyl, C 1 to C 4 alkylcarbonyl, such as. B. acetyl or hydroxy, mono- or dialkylamino.
  • R 4 is an optionally substituted aryl radical
  • a phenyl or naphthyl radical is particularly suitable, which can be substituted by C 1-4 alkyl, such as. B. methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl and tert-butyl, C 1-4 alkoxy, such as. B. methoxy, ethoxy, propoxy, isopropoxy, butoxy, tsobutoxy, sec-butoxy and tert-butoxy, halogen, such as. B.
  • C 2-5 alkanoylamino such as acetylamino, propionylamino and butyrylamino, nitro, cyano, sulfo or a mono- or dialkylated amino group.
  • the complexes of the formula (6) are also preferred in neutral form, ie as the alkali salt, in particular Sodium salt or amine salt used.
  • Complexes of the formula (6) are preferably used in which R 3 is hydrogen and R 4 is hydrogen, methyl or in particular the phenyl radical, especially the complexes in which the sulfo group is in turn in the p-position to the oxygen.
  • the ligands of which are derived from sulfosalicylaldehyde or the corresponding phenyl ketones z. B. also those in which instead of mononuclear, multinuclear aromatic aldehydes and ketones, such as. B. the 2-hydroxy-1-naphthaldehyde sulfonic acid can be used to build up the ligand. It is also pointed out that the fourth coordination point of the metal atom in the complexes of formulas (6) and (7) is occupied by water as the neutral ligand.
  • the copper complexes of the formulas (5) and (6) are preferably used in the present process for photochemical stabilization.
  • the ratio of copper complex dye: fiber-affine, water-soluble, non-chromophoric copper complex is preferably 99: 1 to 10:90.
  • the mixing ratio depends on the number of copper complex dyes used and the desired color depth of the dyeings.
  • the copper complexes of the formulas (5), (6) and (7) given and their alkali metal salts, such as potassium and lithium salts, and in particular their sodium salts, are obtained by known methods.
  • the metal complexes of the formula (5) are accessible, for example, in two different ways. So you can first metallize the aldehyde or the ketone and then react with the corresponding diamine to the finished complex of formula (5). However, one can also first synthesize the ligand from aldehyde or ketone and diamine and then carry out the metallization.
  • the acylhydrazones, the ligands of the complexes (6) are obtained, for example, by reacting the aldehyde or ketone with the corresponding monoacylhydrazine and subsequent metallization.
  • the complexes of the formula (7) can also be prepared quite analogously. At least one of the starting products for the preparation of the compounds of the formula (5), (6) and (7) must contain a sulfonic acid group.
  • the copper complexes of the formulas (5) to (7) are preferably used, in particular the copper complexes of the formulas (5) and (6).
  • the copper complexes of the formulas are very particularly preferred within the group of metal complexes with bisazomethine ligand and within the group of metal complexes with acylhydrazone ligand, the copper complexes of the formulas
  • the fourth coordination point of the copper in the complexes of formulas (10), (11) and (12) is occupied by water without this being explicitly stated in the structural formulas.
  • Another preferred embodiment of the method according to the invention is characterized in that the mixture of the copper complex compounds is used together with acid dyes, in particular in the same dye bath.
  • acid dyes come e.g. B. metal-free mono- or polyazo dyes, 1: 2-chromium or 1: 2-cobalt complex azo dyes, anthraquinone, dioxazine, phthalocyanine, nitroaryl or stilbene dyes into consideration, which have at least one acid group, such as. B. carboxyl or preferably have a sulfonic acid group.
  • An interesting embodiment of the method according to the invention is characterized in that a mixture of at least one red-dyeing dye, at least one yellow- or orange-dyeing dye and at least one blue-dyeing dye is used for trichromatic dyeing, the mixture containing at least one copper complex dye.
  • polyamide fiber material such synthetic polyamides, such as. B. polyamide-6, polyamide-66 or polyamide-12 used.
  • the polyamide fiber material can be in a wide variety of processing forms, such as. B. fiber, yarn, woven or knitted fabric, in particular textile fiber material.
  • the dyes containing sulfo groups used in the process according to the invention are present either in the form of their free sulfonic acid or preferably as their salts.
  • suitable salts are the alkali metal, alkaline earth metal or ammonium salts or the salts of an organic amine.
  • suitable salts include the sodium, lithium, potassium or ammonium salts or the salt of triethanolamine.
  • the dyes used in the inventive method usually contain other additives such as. B. table salt or dextrin.
  • the process according to the invention for dyeing synthetic polyamide fiber materials can be applied to the customary dyeing processes.
  • the dyeing liquors can contain further additives, for example wetting agents, anti-foaming agents, leveling agents, salts, acids or buffer substances.
  • synthetic polyamide fiber materials are stabilized photochemically, i.e. protected against exposure, especially hot exposure, with visible and UV light.
  • a particularly noteworthy advantage of the method according to the invention is that, compared to previously known methods for the photochemical stabilization of synthetic polyamide fiber materials, no pre- or post-treatment of the fiber material is required.
  • the mixtures of copper complex dyes with the non-chromophoric copper complex compounds used in accordance with the process according to the invention have the advantage that, regardless of the desired depth of color of the dyeings contained with the copper complex dyes, a constant copper content of the fiber can be set, i.e. the protective effect is not subject to nuance-related fluctuations.
  • parts represent parts by weight.
  • the temperatures are degrees Celsius.
  • the relationship between parts by weight and parts by volume is the same as that between grams and cubic centimeters.
  • the tensile strength and elongation values of untreated and unexposed polyamide fiber material are set equal to 100%.
  • a portion of the yarn of the individual treatments is wound up on cardboard and exposed in a fade-ometer (manufacturer: Atlas Electric Devices Co., Chicago) for 250 hours and a "black panel temperature" of 83 ° C.
  • the yarn of both exposure tests is then tested for its tensile strength and elongation values in accordance with SNV (Swiss Standards Association) standard 97 461.
  • SNV Standard 97 461.
  • the tensile strength and elongation values of unexposed and untreated polyamide 66 fiber material are set equal to 100%:
  • treatment bath 1A the colorations obtained with the addition of the compound of the formula (103) being referred to as treatment bath 1A, 2A, 3A and 4A.
  • Table 1 shows that the photochemical stability of light dyeings with copper complex dyes on synthetic polyamide materials [treatment baths (2) (3) and (4)] can be further improved by adding colorless fiber-affine copper complex compounds [treatment baths (2A), (3A) and (4A)].
  • Dyeing on nylon filament yarn is carried out with 0.05% dyestuff of the formula (100), as described in Example 1, but at 95 ° C. and in each case with the use of 0.05% of each of the copper complex compounds of the formulas (103), (104) and (105) and with the addition of 2% acetic acid 80%.
  • the material is exposed according to DIN 75 202 (Fakra) and xenon (SN-ISO 105 B02) and tested for its tensile strength and elongation. The following results are obtained, the tensile strength values and elongation values of unexposed and untreated polyamide fiber material being set equal to 100%.

Claims (14)

1. Procédé pour la stabilisation photochimique de matériau en fibres de polyamides de synthèse, caractérisé en ce que l'on traite le matériau en fibres avec un mélange constitué d'un colorant complexe de cuivre soluble dans l'eau et d'un complexe de cuivre non chromophore, soluble dans l'eau et ayant une affinité pour les fibres, de bisazométhines, acylhydrazones, semicarbazones ou thiosemicarbazones d'aldéhydes ou cétones aromatiques.
2. Procédé selon la revendication 1, caractérisé en ce que, comme colorant complexe de cuivre, on utilise un complexe de cuivre de colorant azo ou azométhine, soluble dans l'eau.
3. Procédé selon la revendication 2, caractérisé en ce qu'on utilise des complexes de cuivre de colorants azo ou azométhine contenant des groupes hydrosolubilisants, de formule
Figure imgb0031
dans laquelle D représente un reste de la série du benzène ou du naphtalène, X représente un atome d'azote ou un groupe CH-, Y représente un groupe OH-, CH30- ou HOOC- et Y' représente un groupe OH ou amino, et dans la quelle K, dans le cas où X est un atome d'azote, représente un reste d'un composant de copulation de la série du benzène, du naphtalène ou d'une série hétérocyclique, ou un reste d'un composé cétométhylènique, ou bien, dans le cas où X est un groupe CH-, K représente un reste d'un o-hydroxyaldehyde.
4. Procédé selon la revendication 3, caractérisé en ce qu'on utilise un colorant complexe de cuivre de formule
Figure imgb0032
dans laquelle A représente un reste carboxyphényle ou sulfophényle, éventuellement substitué, R, représente un hydrogène ou un groupe alkyle en Cl-4, X représente un atome d'azote ou un groupe CH- et K représente, dans le cas où X est un atome d'azote, un reste d'un composant de copulation de la serie du benzène, du naphtalène, de la pyrazolone, de l'aminopyrazole, de l'acétoacétanilide, de la 2,4-dioxyquinoléine, de la pyridone ou de la pyridine, ou bien dans le cas où X est un groupe CH-, un reste d'un hydroxybenzaldéhyde, et le cycle B peut éventuellement accepter d'autres substituants.
5. Procédé selon la revendication 1, caractérisé en ce que, comme complexe de cuivre soluble dans l'eau, ayant une affinité pour les fibres, on utilise un composé de formule
Figure imgb0033
dans laquelle Me représente le cuivre, R2 représente l'hydrogène ou un groupe alkyle ou aryle éventuellement substitué, et Z représente un goupe alkylène, cycloalkylène ou arylène éventuellement substitué et n vaut 1,2 ou 3.
6. Procédé selon la revendication 1, caractéerisé en ce que, comme complexe de cuivre soluble dans l'eau, ayant une affinité pour les fibres, on utilise un composé de formule
Figure imgb0034
dans laquelle Me représente le cuivre, R3 et R4 répondent, indépendamment l'un de l'autre, à la même definition que dans la revendication 5.
7. Procédé selon la revendication 1, caractérisé en ce que, comme complexe de cuivre soluble dans l'eau, ayant une affinite pour les fibres, on utilise un composé de formule
Figure imgb0035
dans laquelle Me représente le cuivre, R5 représente l'hydrogène ou un groupe alkyle ou aryle éventuellement subsitué et V représente un atome d'oxygène ou de soufre.
8. Procédé selon la revendication 1, caractérisé en ce qu'on utilise un mélange dans lequelle rapport du colorant complexe de cuivre au composé complexe de cuivre soluble dans l'eau, ayant une affinité pour les fibre, est de 99 : 1 à 10 : 90.
9. Procédé selon la revendicaion 1, caractérisé en ce qu'on met en oeuvre des mélanges de composés complexes de cuivre dans une proportion telle que pour 1 g de matériau polyamide, on compte 2 à 1000 µg de cuivre, et en particulier, que pour 1 g de matériau polyamide, on compte 5 à 200 gg de cuivre.
10. Procédé selon la revendication 1, caractérisé en ce qu'on utilise le mélange des composés complexes de cuivre en commun avec des colorants acides.
11. Procédé selon la revendication 10, caractérisé en ce qu'on utilise le mélange des composés complexe de cuivre en commun avec des colorants acides, dans le même bain de teinture.
12. Procédé selon la revendication 10 ou 11, caractérisé en ce que, comme colorants acides, on utilise des colorants monoazoîques ou polyazoiques non-métallés, des colorants complexe de chrome 1 : 2 ou de cobalt 1: 2, des colorants anthraquinone, dioxazine, phtalocyanine, nitroaryle ou stilbèniques, qui présentent au moins un groupe acide, en particulier un groupe acide sulfonique.
13. Procédé selon la revendication 10, caractérisé en ce que pour la teinture en trichromie, on utilise un mélange d'au moins un colorant qui teinte en rouge au moins un colorant qui teinte en jaune ou orange, et au moins un colorant qui teinte en bleu, les mélanges contenant au moins un colorant complexe de cuivre.
14. Bain de teinture aqueux, caractérisé en ce qu'il contient un mélange d'un colorant complexe de cuivre soluble dans l'eau et d'un complexe de cuivre non chromophore, soluble dans l'eau, et ayant une affinité pour les fibres, de bisazométhines, acylhydrazones, semicarbazones ou thiosemicarbazones d'aldéhydes ou cétones aromatiques.
EP85810513A 1984-12-21 1985-11-04 Procédé de stabilisation photochimique de matières fibreuses synthétiques contenant des fibres en polyamide Expired EP0185611B1 (fr)

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JP (1) JPS61152881A (fr)
BR (1) BR8505622A (fr)
DE (1) DE3565136D1 (fr)

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DE3565136D1 (en) 1988-10-27
JPS61152881A (ja) 1986-07-11
BR8505622A (pt) 1986-08-12
EP0185611A1 (fr) 1986-06-25
US4704133A (en) 1987-11-03

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