EP0438381A1 - Stabilization of dyes on polyamide fibres - Google Patents

Stabilization of dyes on polyamide fibres Download PDF

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Publication number
EP0438381A1
EP0438381A1 EP91810014A EP91810014A EP0438381A1 EP 0438381 A1 EP0438381 A1 EP 0438381A1 EP 91810014 A EP91810014 A EP 91810014A EP 91810014 A EP91810014 A EP 91810014A EP 0438381 A1 EP0438381 A1 EP 0438381A1
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Prior art keywords
amino
formula
radical
hydroxy
methyl
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German (de)
French (fr)
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EP0438381B1 (en
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Gerhard Dr. Reinert
Francesco Dr. Fuso
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BASF Schweiz 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
    • 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
    • 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
    • D06M13/244—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 sulfur or phosphorus
    • D06M13/248—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 sulfur or phosphorus with compounds containing sulfur
    • D06M13/256—Sulfonated compounds esters thereof, e.g. sultones
    • 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
    • D06M13/402—Amides imides, sulfamic acids
    • D06M13/415—Amides of aromatic carboxylic acids; Acylated aromatic amines
    • 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
    • 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
    • D06P1/96—Dyeing characterised by a short bath ratio
    • 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 improving the thermal and / or photochemical stability of dyeings on polyamide fibers and the polyamide fiber material treated with it.
  • Dyes on polyamide fibers that are dyed with disperse, acid or 1: 2 metal complex dyes tend to be thermally and / or photochemically unstable. This is particularly pronounced in the case of polyamide fibers which are colored with a red dye or with a dye mixture containing at least one red component.
  • a in formula (1) means, for example, a monohydroxyphenyl radical in which at least one o-position to the hydroxyl group is substituted by an alkyl, cycloalkyl or aralkyl group and which optionally also carries further substituents.
  • Alkyl groups in the o-position to the hydroxyl group of A can be straight or branched and contain 1-12, preferably 4-8 C atoms. Preferred are a-branched alkyl groups. These are, for example, the methyl, ethyl, iso-propyl, tert-butyl, iso-amyl, octyl, tert-octyl and dodecyl group. The tert-butyl group is particularly preferred.
  • Cycloalkyl groups in the o-position to the hydroxyl group of A contain 6-10, preferably 6-8, carbon atoms. Examples include the cyclohexyl, methylcyclohexyl and cyclooctyl group.
  • Aralkyl groups in the o-position to the hydroxyl group of A contain 7-10, preferably 8-9 carbon atoms. Examples include the a-methyl and a, a-dimethylbenzyl groups.
  • the radical A can also be substituted by further alkyl, cycloalkyl or aralkyl groups as defined above, these preferably being in the o'- or p-position to the hydroxyl group, provided that these positions are not occupied by the bond to Y. Furthermore, at least one m position to the hydroxyl group is advantageously unsubstituted, while the other is substituted by lower alkyl groups, such as the methyl group can be constituted.
  • R 2 or R 3 in formulas (2) and (3) can be straight-chain or branched as an alkyl group and contain 1 to 18, preferably 1 to 8, carbon atoms. Examples include the methyl, ethyl, iso-propyl, pentyl, octyl, dodecyl and octadecyl group.
  • the substituted alkyl group R 2 or R 3 is, for example, a hydroxyalkyl, alkoxyalkyl, aminoalkyl, alkylaminoalkyl or a dialkylaminoalkyl group with a total of 2 to 10, preferably 2 to 5, carbon atoms.
  • Examples of these are the ⁇ -hydroxyethyl, ⁇ -methoxyethyl, ⁇ -aminoethyl, ⁇ , ⁇ '-diethylaminoethyl or the ⁇ -butylaminoethyl group.
  • Z can be straight-chain or branched and contain 2 to 5, preferably 2, carbon atoms. It is, for example, the ethylene, propylene, trimethylene or pentamethylene radical. This radical can optionally be substituted by carboxyl groups. An example of this is the carboxyethylene residue.
  • Z in formula (1) can be further substituted.
  • it may have straight-chain or branched C 1 -C 4 -alkyl radicals, for example substituted by the methyl, ethyl or isopropyl group; the methyl group is preferred.
  • C 1 -C 4 alkoxy groups as substituents of a benzene radical Z are, for example, the methoxy, ethoxy or butoxy group. If Z is substituted as a benzene radical by an acylamino group, its acyl radical is derived in particular from a C 2 -C 6 -aliphatic or a monocarbocyclic aromatic carboxylic acid.
  • Examples are the rest of the acetic, propionic, ⁇ -methoxypropionic, benzoic, aminobenzoic or methylbenzoic acid.
  • Examples of C 1 -C 4 alkoxycarbonylamino groups as substituents of a benzene radical Z are the methoxy, ethoxy or butoxycarbonylamino radical.
  • group Z contains phenylethyl, styryl, phenyl, phenoxy, phenylthio or phenylsulfonyl groups as substituents, these can optionally be substituted by chlorine or bromine, C 1 -C 4 -alkyl groups, such as the methyl or ethyl group, C 1 -C 4 alkoxy groups, such as the methoxy group, acylamino groups, such as the acetyl or benzoylamino group or alkoxycarbonylamino groups, such as the methoxy or ethoxycarbonylamino group.
  • the group Z can optionally be substituted by C 1 -C 4 alkyl or alkoxy groups, such as the methyl or methoxy group.
  • organic nitrogen bases which can form such ammonium salts with group W are: trimethylamine, triethylamine, triethanolamine, diethanolamine, ethanolamine, cyclohexylamine, dicyclohexylamine, hexamethyleneimine or morpholine.
  • the group W can be present in these compounds freely or in the form of the salts defined above.
  • the water-soluble compounds of the formula (1) are known, for example from US Pat. No. 3,665,031, and can be prepared by methods known per se, for example by reacting n moles of a compound of the formula (8) (8) A- (X) x -P with one mole of a compound of formula (9) ( 9 ) [W] -m Z [(X ') x -Q] n in which formulas one of P and Q is the group -NH-R 3 , the other the group
  • the compounds of the formula (1) are applied from an aqueous bath which contains the compounds in an amount of 0.01 to 10, preferably 0.25 to 3,% by weight.
  • the water-soluble phenolic antioxidant can be applied during or after dyeing, using an exhaust or continuous process. Application during dyeing is preferred.
  • the liquor ratio can be selected within a wide range, e.g. 1: 3 to 1: 100, preferably 1:10 to 1:40.
  • the purpose of the work is at a temperature of 30 to 130 ° C, preferably 50 to 95 ° C.
  • the liquor order is expediently 40-700, preferably 40-500% by weight.
  • the fiber material is then subjected to a heat treatment process in order to fix the applied dyes and the antioxidants. This fixation can also be carried out using the cold dwell method.
  • the heat treatment is preferably carried out by a steaming process with treatment in a steamer with possibly superheated steam at a temperature of 98 to 105 ° C during e.g. 1-7, preferably 1-5 minutes.
  • the dyes can be fixed in accordance with the cold residence process by storing the impregnated and preferably rolled-up goods at room temperature (15 to 30 ° C) e.g. during 3 to 24 hours, the cold residence time being known to depend on the dye.
  • the dyeings produced are washed and dried in the customary manner.
  • dyeings to be stabilized according to the invention those are suitable which are disperse, acid or metal complex dyes, in particular azo, 1,2-metal complex dyes, e.g. 1: 2 chromium, 1: 2 cobalt complex dyes or Cu complex dyes are generated.
  • azo, 1,2-metal complex dyes e.g. 1: 2 chromium, 1: 2 cobalt complex dyes or Cu complex dyes are generated.
  • colorings which are produced by red dyes or by a dye mixture having a red component.
  • Synthetic polyamide e.g. Polyamide-6, polyamide-6,6 or polyamide-12, as well as modified polyamide, e.g. understood basic dyeable polyamide.
  • fiber mixtures made of polyurethane and polyamide are also considered, e.g. Jersey material made of polyamide / polyurethane in a mixing ratio of 70:30.
  • the pure or mixed polyamide material can be in a variety of processing forms, such as as fiber, yarn, fabric, knitted fabric, fleece or molded material.
  • the method is also suitable for the thermal stabilization of so-called "molding" Processed colored polyamide material.
  • This process is a shaping process that works briefly at high temperatures (e.g. bra production).
  • Dyeing begins at 30 ° C., the mixture is held at this temperature for 10 minutes and heated at 2 / Min to 95 ° C. After a dyeing time of 20 minutes at 95 ° C, 2% acetic acid (80%) is added and dyeing is continued for 20 minutes. The mixture is then cooled to 50 ° C., rinsed, centrifuged and the samples are dried.
  • the dyeings are tested for their light fastness according to SN-ISO 105-B02 (Xenon) and DIN 75202 (Fakra) as well as in a heat test at 130 ° C for 60 hours in a circulating air dryer for color stability.
  • compound (101) imparts both photochemical and thermal protection to the stain.
  • Example 2 The procedure described in Example 1 is followed, except that 0.4% of the dye of the formula is used instead of the dye (100) a.
  • the compound (101) primarily gives the dyeing thermal protection.
  • test results show that the addition of the compound (402), in addition to hot-light stabilization, primarily results in heat stabilization of the red component (100).
  • Example 5 Five samples of 10 each of a PA-6 knitted fabric are separated, each with the following dye combination of 0.002% of the dye of the formula (300) given in Example 3 and 0.04% of the dye mixture (402) (403), and from 81 parts of the dye of the formula and 12 parts of the dye of the formula as noted in Example 1, colored.
  • Dye bath 1 contains no further additives, while baths 2-6, on the other hand, each contain 1% of the compounds of formulas (502) - (506) in dissolved form.
  • the dyeings are tested for their light fastness according to DIN 75.202 (FAKRA), for their loss of mechanical properties (test according to SN 198.461) and for their heat resistance. The following results resulted:
  • Example 6 Two samples of a PA66 jersey are colored violet as described in Example 1 with the following amounts of dye: 0.15% of the dye of the formula (100) given in Example 1 and 0.075% of the dye of the formula given in Example 4 (401 ).
  • the dye bath 1 contains no further additive, while the dye bath 2 additionally contains 1.5% of the compound of the formula (402) given in Example 4.
  • the well-rinsed and dried tricot material is then subjected to a heat treatment under so-called “molding” conditions ("molding” means a heat deformation process, such as is used in the manufacture of bras).
  • the material is heated in a controlled manner on a "System BASF" precision ironing press (manufacturer K. Schröder KG, D-Weinheim / Bergstr.).
  • the experiment gave the following result:

Abstract

A method for improving the thermal and/or photochemical stability of dyes on polyamide fibres, by absorbing onto the fibres from aqueous medium water-soluble phenolic antioxidants of the formula (A-Y-)nZ(-W)m, in which A, Y, Z, W, m and n have the meaning given in Claim 1.

Description

Die vorliegende Erfindung betrifft ein Verfahren zur Verbesserung der thermischen und/oder photochemischen Stabilität von Färbungen auf Polyamidfasern sowie das damit behandelte Polyamidfasermaterial.The present invention relates to a method for improving the thermal and / or photochemical stability of dyeings on polyamide fibers and the polyamide fiber material treated with it.

Aus US-A-3 665 031 ist bekannt, ungefärbte Polymere, wie z.B. Polyamide gegen den Einfluss von Hitze und/oder Sauerstoff (Luftoxidation) mit Hilfe von wasserlöslichen phenolischen Antioxidantien zu schützen.From US-A-3 665 031 it is known to use undyed polymers such as e.g. Protect polyamides against the influence of heat and / or oxygen (air oxidation) with the help of water-soluble phenolic antioxidants.

Färbungen auf Polyamidfasern, die mit Dispersions-, Säure- oder 1 :2 Metallkomplexfarbstoffen gefärbt sind, neigen zu einer thermischen und/oder photochemischen Instabilität. Diese ist besonders ausgeprägt bei Polyamidfasem, die eine mit einem roten Farbstoff oder mit einer mindestens eine rote Komponente enthaltenden Farbstoffmischung erzeugte Färbung aufweisen.Dyes on polyamide fibers that are dyed with disperse, acid or 1: 2 metal complex dyes tend to be thermally and / or photochemically unstable. This is particularly pronounced in the case of polyamide fibers which are colored with a red dye or with a dye mixture containing at least one red component.

Es wurde nun gefunden, dass diese Nachteile durch eine Behandlung der gefärbten Polyamidfasern mit phenolischen wasserlöslichen Antioxidantien ganz oderzumindest in grossem Masse beseitigtwerden können.It has now been found that these disadvantages can be eliminated entirely or at least to a large extent by treating the dyed polyamide fibers with phenolic water-soluble antioxidants.

Die Erfindung betrifft daher ein Verfahren zur Verbesserung der thermischen und/oder photochemischen Stabilität von Färbungen auf Polyamidfasern, welches dadurch gekennzeichnet ist, dass man eine Verbindung der Formel (1)

  • (1) (A-Y-)r7.(-W)m
  • in welcher
  • A den Rest eines sterisch gehinderten Phenols der Benzolreihe,
  • Y einen Rest der Formeln (2) oder (3)
    Figure imgb0001
    Figure imgb0002
worin
  • X und X' unabhängig voneinander Alkylen, Oxaalkylen oder Thiaalkylen,
  • R2 und R3 unabhängig voneinander Wasserstoff oder eine gegebenenfalls substituierte Alkylgruppe und
  • x, x' und y unabhängig voneinander je 0 oder 1 sind,
  • Z einen aliphatischen oder einen carbocyclischen aromatischen Rest, wobei letzterer höchstens zwei mono-oder bicyclische Kerne enthält,
  • W die Sulfogruppe und
  • m und n unabhängig voneinander 1 oder 2 bedeuten, und deren wasserlösliche Salze, aus einem wässrigen Medium auf die Polyamidfasern aufzieht.
The invention therefore relates to a process for improving the thermal and / or photochemical stability of dyeings on polyamide fibers, which is characterized in that a compound of the formula (1)
  • (1) (AY-) r7. (- W) m
  • in which
  • A is the residue of a sterically hindered phenol from the benzene series,
  • Y is a radical of the formulas (2) or (3)
    Figure imgb0001
    Figure imgb0002
wherein
  • X and X 'independently of one another alkylene, oxaalkylene or thiaalkylene,
  • R 2 and R 3 are independently hydrogen or an optionally substituted alkyl group and
  • x, x 'and y are each independently 0 or 1,
  • Z is an aliphatic or a carbocyclic aromatic radical, the latter containing at most two mono- or bicyclic nuclei,
  • W the sulfo group and
  • m and n independently of one another denote 1 or 2, and their water-soluble salts are drawn from an aqueous medium onto the polyamide fibers.

A in Formel (1) bedeutet beispielsweise einen Monohydroxyphenyl-Rest, in dem mindestens eine o-Stellung zur Hydroxylgruppe durch eine Alkyl-, Cycloalkyl- oder Aralkylgruppe substituiert ist und der gegebenenfalls noch weitere Substituenten trägt.A in formula (1) means, for example, a monohydroxyphenyl radical in which at least one o-position to the hydroxyl group is substituted by an alkyl, cycloalkyl or aralkyl group and which optionally also carries further substituents.

Alkylgruppen in o-Stellung zur Hydroxylgruppe von A können gerade oder verzweigt sein und 1-12, vorzugsweise 4-8 C-Atome enthalten. Bevorzugt sind dabei a-verzweigte Alkylgruppen. Es handelt sich dabei beispielsweise um die Methyl-, Aethyl-, iso-Propyl-, tert.Butyl-, iso-Amyl-, Octyl-, tert.Octyl- und Dodecylgruppe. Besonders bevorzugt ist dabei die tert.Butylgruppe.Alkyl groups in the o-position to the hydroxyl group of A can be straight or branched and contain 1-12, preferably 4-8 C atoms. Preferred are a-branched alkyl groups. These are, for example, the methyl, ethyl, iso-propyl, tert-butyl, iso-amyl, octyl, tert-octyl and dodecyl group. The tert-butyl group is particularly preferred.

Cycloalkylgruppen in o-Stellung zur Hydroxylgruppe von A enthalten 6-10, vorzugsweise 6-8 C-Atome. Beispiele dafür sind die Cyclohexyl-, Methylcyclohexyl- und Cyclooctylgruppe.Cycloalkyl groups in the o-position to the hydroxyl group of A contain 6-10, preferably 6-8, carbon atoms. Examples include the cyclohexyl, methylcyclohexyl and cyclooctyl group.

Aralkylgruppen in o-Stellung zur Hydroxylgruppe von A enthalten 7-10, vorzugsweise 8-9 C-Atome. Beispiele dafür sind die a-Methyl- und a,a-Dimethylbenzylgruppe.Aralkyl groups in the o-position to the hydroxyl group of A contain 7-10, preferably 8-9 carbon atoms. Examples include the a-methyl and a, a-dimethylbenzyl groups.

Der Rest A kann daneben noch durch weitere, vorstehend definierte Alkyl-, Cycloalkyl-oderAralkylgruppen substituiert sein, wobei diese bevorzugt in o'- oder p-Stellung zur Hydroxylgruppe stehen, soweit diese Stellungen nicht durch die Bindung an Y besetzt sind. Vorteilhaft ist weiterhin mindestens eine m-Stellung zur Hydroxylgruppe unsubstituiert, während die andere durch niedere Alkylgruppen, wie die Methylgruppe, substituiert sein kann.The radical A can also be substituted by further alkyl, cycloalkyl or aralkyl groups as defined above, these preferably being in the o'- or p-position to the hydroxyl group, provided that these positions are not occupied by the bond to Y. Furthermore, at least one m position to the hydroxyl group is advantageously unsubstituted, while the other is substituted by lower alkyl groups, such as the methyl group can be constituted.

Aus Gründen der leichten Zugänglichkeit und ihrer günstigen Stabilisierungswirkung sind Verbindungen der Formel (1) besonders bevorzugt, in denen A einen Rest der Formel (4)

Figure imgb0003
in der

  • R und R1 unabhängig voneinander Wasserstoff, Methyl oder tert.Butyl darstellen und die Summe der Kohlenstoffatome von R und R1 mindestens 2 beträgt, bedeutet.
  • X und X' in Formeln (2) und (3) können geradkettig oder verzweigt sein und 1 bis 8, vorzugsweise 1 bis 5 C-Atome enthalten. Beispiele dafür sind der Methylen-, Aethylen-, Trimethylen-, Propylen-, 2-Thia-trimethylen-oder der 2-Oxapentamethylenrest.
For reasons of easy accessibility and their favorable stabilizing action, compounds of the formula (1) in which A is a radical of the formula (4) are particularly preferred
Figure imgb0003
 in the
  • R and R 1 independently represent hydrogen, methyl or tert-butyl and the sum of the carbon atoms of R and R 1 is at least 2.
  • X and X 'in formulas (2) and (3) can be straight-chain or branched and contain 1 to 8, preferably 1 to 5, carbon atoms. Examples of these are the methylene, ethylene, trimethylene, propylene, 2-thia-trimethylene or the 2-oxapentamethylene radical.

Besonders bevorzugt sind Verbindungen, bei denen in den Resten X und X' nicht zwei Heteroatome an das gleiche gesättigte, d.h. tetraedrische kohlenstoffatom gebunden sind.Compounds are particularly preferred in which two heteroatoms in the radicals X and X 'do not have the same saturated, i.e. tetrahedral carbon atom are bound.

R2 oder R3 in Formeln (2) und (3) können als Alkylgruppe geradkettig oder verzweigt sein und 1 bis 18, vorzugsweise 1 bis 8 C-Atome enthalten. Beispiele dafür sind die Methyl-, Aethyl-, iso-Propyl-, Pentyl-, Octyl-, Dodecyl- und Octadecylgruppe.R 2 or R 3 in formulas (2) and (3) can be straight-chain or branched as an alkyl group and contain 1 to 18, preferably 1 to 8, carbon atoms. Examples include the methyl, ethyl, iso-propyl, pentyl, octyl, dodecyl and octadecyl group.

Als substituierte Alkylgruppe bedeuten R2 oder R3 beispielsweise eine Hydroxyalkyl-, Alkoxyalkyl-, Aminoalkyl-, Alkylaminoalkyl- oder eine Dialkylaminoalkylgruppe mit insgesamt 2 bis 10, vorzugsweise 2 bis 5 C-Atomen. Beispiele dafür sind die β-Hydroxyäthyl-, β-Methoxyäthyl-, β-Aminoäthyl-, β,β'-Diäthylaminoäthyl-oder die β-Butylaminoäthylgruppe.The substituted alkyl group R 2 or R 3 is, for example, a hydroxyalkyl, alkoxyalkyl, aminoalkyl, alkylaminoalkyl or a dialkylaminoalkyl group with a total of 2 to 10, preferably 2 to 5, carbon atoms. Examples of these are the β-hydroxyethyl, β-methoxyethyl, β-aminoethyl, β, β'-diethylaminoethyl or the β-butylaminoethyl group.

R2 oder R3 können auch eine Arylgruppe, bevorzugt die Phenylgruppe darstellen. Besonders bevorzugt sind Verbindungen der Formel (1), in denen Y einen Rest der Formel (5)

Figure imgb0004
worin

  • R4 Wasserstoff oder C1-C4-Alkyl und
  • X" C1-C4-Alkylen bedeuten, darstellt.
  • Z in Formel (1) bedeutet beispielsweise den Rest eines unsubstituierten oder durch Carboxylgruppen substituierten niederen Alkans mit mindestens zwei C-Atomen, den Rest eines unsubstituierten oder durch Chlor oder Brom, Cl-C4-Alkyl, C1-C4-Alkoxy, C1-C4-Alkoxycarbonylamino, Hydroxy, Carboxy, Phenyläthyl, Styryl, Phenyl, Phenoxy, Phenylthio, Phenylsulfonyl oder Acylamino substituierten Benzolkerns, wobei die Gruppe W direkt an diesen Benzolkern oder an einen monocyclischen Arylrest eines seiner Substituenten gebunden sein kann, oder es bedeutet den Naphthalin- oder Tetralinrest.
R 2 or R 3 can also represent an aryl group, preferably the phenyl group. Compounds of the formula (1) in which Y is a radical of the formula (5) are particularly preferred
Figure imgb0004
 wherein
  • R 4 is hydrogen or C 1 -C 4 alkyl and
  • X "represents C 1 -C 4 alkylene.
  • Z in formula (1) means, for example, the radical of an unsubstituted or substituted by carboxyl groups lower alkane with at least two carbon atoms, the radical of an unsubstituted or by chlorine or bromine, C 1 -C 4 alkyl, C 1 -C 4 alkoxy , C 1 -C 4 alkoxycarbonylamino, hydroxy, carboxy, phenylethyl, styryl, phenyl, phenoxy, phenylthio, phenylsulfonyl or acylamino substituted benzene nucleus, where the group W can be bonded directly to this benzene nucleus or to a monocyclic aryl radical of one of its substituents, or it means the naphthalene or tetralin residue.

Als Rest eines niederen Alkans kann Z geradkettig oder verzweigt sein und 2 bis 5, vorzugsweise 2 C-Atome enthalten. Es handelt sich also beispielsweise um den Aethylen-, Propylen-, Trimethylen- oder Pentamethylenrest. Dieser Rest kann gegebenenfalls noch durch Carboxylgruppen substituiert sein. Ein Beispiel dafür ist der Carboxyäthylenrest.As the residue of a lower alkane, Z can be straight-chain or branched and contain 2 to 5, preferably 2, carbon atoms. It is, for example, the ethylene, propylene, trimethylene or pentamethylene radical. This radical can optionally be substituted by carboxyl groups. An example of this is the carboxyethylene residue.

Als Benzolrest kann Z in Formel (1) noch weiter substituiert sein. Es kann beispielsweise geradkettige oder verzweigte C1-C4-Alkylreste aufweisen, z.B. durch die Methyl-, Aethyl-oder iso-Propylgruppe substituiert sein; dabei ist die Methylgruppe bevorzugt. C1-C4-Alkoxygruppen als Substituenten eines Benzolrestes Z sind beispielsweise die Methoxy-, Aethoxy- oder Butoxygruppe. Ist Z als Benzolrest durch eine Acylaminogruppe substituiert, so leitet sich dessen Acylrest insbesondere von einer C2-C6-aliphatischen oder einer monocarbocyclischen aromatischen Carbonsäure ab. Beispiele sind der Rest der Essig-, Propion-, β-Methoxypropion-, Benzoe-, Aminobenzoe- oder Methylbenzoesäure. Beispiele für C1-C4-Alkoxycarbonylaminogruppen als Substituenten eines Benzolrestes Z sind der Methoxy-, Aethoxy- oder Butoxycarbonylaminorest.As a benzene radical, Z in formula (1) can be further substituted. For example, it may have straight-chain or branched C 1 -C 4 -alkyl radicals, for example substituted by the methyl, ethyl or isopropyl group; the methyl group is preferred. C 1 -C 4 alkoxy groups as substituents of a benzene radical Z are, for example, the methoxy, ethoxy or butoxy group. If Z is substituted as a benzene radical by an acylamino group, its acyl radical is derived in particular from a C 2 -C 6 -aliphatic or a monocarbocyclic aromatic carboxylic acid. Examples are the rest of the acetic, propionic, β-methoxypropionic, benzoic, aminobenzoic or methylbenzoic acid. Examples of C 1 -C 4 alkoxycarbonylamino groups as substituents of a benzene radical Z are the methoxy, ethoxy or butoxycarbonylamino radical.

Enthält die Gruppe Z als Substituenten Phenyläthyl-, Styryl-, Phenyl-, Phenoxy-, Phenylthio- oder Phenylsulfonylgruppen, so können diese gegebenenfalls durch Chlor oder Brom, C1-C4-Alkylgruppen, wie die Methyl-oder Ethylgruppe, C1-C4-Alkoxygruppen, wie die Methoxygruppe, Acylaminogruppen, wie die Acetyl- oder Benzoylaminogruppe oder Alkoxycarbonylaminogruppen, wie die Methoxy- oder Aethoxycarbonylaminogruppe substituiert sein.If the group Z contains phenylethyl, styryl, phenyl, phenoxy, phenylthio or phenylsulfonyl groups as substituents, these can optionally be substituted by chlorine or bromine, C 1 -C 4 -alkyl groups, such as the methyl or ethyl group, C 1 -C 4 alkoxy groups, such as the methoxy group, acylamino groups, such as the acetyl or benzoylamino group or alkoxycarbonylamino groups, such as the methoxy or ethoxycarbonylamino group.

Gegebenenfalls können auch mehrere, gleiche oder verschiedene der oben genannten Subsituenten des Benzolrestes Z oder seiner arylgruppenhaltigen Substituenten gleichzeitig vorhanden sein.Optionally, several, identical or different of the abovementioned substituents of the benzene radical Z or its aryl group-containing substituents can also be present at the same time.

Als Naphthalinrest kann die Gruppe Z gegebenenfalls noch durch C1-C4-Alkyl- oder Alkoxygruppen, wie die Methyl- oder Methoxygruppe substituiert sein.As a naphthalene radical, the group Z can optionally be substituted by C 1 -C 4 alkyl or alkoxy groups, such as the methyl or methoxy group.

Die Sulfogruppe W in Formel (1) ist vorzugsweise frei, kann aber auch in Form ihrer Alkali- oder Erdalkalisalze, des Ammoniumsalzes oder der Salze organischer Stickstoffbasen vorliegen. Wegen der Schwerlöslichkeit gewisser Calcium-, Strontium- und Bariumsalze in wasserhaltigen Medien sowie aus ökonomischen Gründen sind dabei Verbindungen der Formel (1) bevorzugt, in denen die Gruppe W in Form ihres Lithium-, Natrium-, Kalium-, Magnesium- oder Ammoniumsalzes oder als Ammoniumsalz einer organischen Stickstoffbase vorliegt, dessen Kation der Formel (6)

  • (6) NR'R"R"'R"" entspricht, worin
  • R', R", R"',R"" unabhängig voneinander Wasserstoff, einen C1-C4-Alkyl- oder β-Hydroxy-C1-C4-Alkylrest oder einen Cyclohexylrest bedeuten, wobei mindestens zwei dieser Reste miteinander ein carbo- oder heterocyclisches Ringsystem bilden können.
The sulfo group W in formula (1) is preferably free, but can also be in the form of its alkali metal or alkaline earth metal salts, the ammonium salt or the salts of organic nitrogen bases. Because of the poor solubility of certain calcium, strontium and barium salts in aqueous media and for economic reasons, preference is given to compounds of the formula (1) in which the group W is in the form of its lithium, sodium, potassium, magnesium or ammonium salt or is present as the ammonium salt of an organic nitrogen base, the cation of the formula (6)
  • (6) NR'R "R"'R"" where
  • R ', R ", R"', R "" independently of one another denote hydrogen, a C 1 -C 4 alkyl or β-hydroxy-C 1 -C 4 alkyl radical or a cyclohexyl radical, at least two of these radicals being one with the other can form carbocyclic or heterocyclic ring system.

Beispiele für organische Stickstoffbasen, die mit der Gruppe W solche Ammoniumsalze bilden können, sind : Trimethylamin, Triäthylamin, Triäthanolamin, Diäthanolamin, Aethanolamin, Cyclohexylamin, Dicyclohexylamin, Hexamethylenimin oder Morpholin.Examples of organic nitrogen bases which can form such ammonium salts with group W are: trimethylamine, triethylamine, triethanolamine, diethanolamine, ethanolamine, cyclohexylamine, dicyclohexylamine, hexamethyleneimine or morpholine.

Besonders günstig in ihrer Stabilisierungswirkung sind Verbindungen der Formel (7)

Figure imgb0005
In dieser Formel bedeuten

  • R und R1 unabhängig voneinander Methyl oder tert.Butyl,
  • R4 Wasserstoff oder C1-C4-Alkyl,
  • X" C1-C4-Alkylen,
  • Z den Aethylenrest, einen zwei- oder dreiwertigen Rest des Benzols oder Naphthalins oder einen zweiwertigen Rest des Diphenyläthers,
  • W die Sulfogruppe und
  • n 1 oder 2.
Compounds of the formula (7) are particularly favorable in their stabilizing action
Figure imgb0005
 Mean in this formula
  • R and R 1 are independently methyl or tert-butyl,
  • R 4 is hydrogen or C 1 -C 4 alkyl,
  • X "C 1 -C 4 alkylene,
  • Z is the ethylene radical, a divalent or trivalent radical of the benzene or naphthalene or a divalent radical of the diphenyl ether,
  • W the sulfo group and
  • n 1 or 2.

Die Gruppe W kann in diesen Verbindungen frei oder auch in Form ihrer vorstehend definierten Salze vorliegen.The group W can be present in these compounds freely or in the form of the salts defined above.

Die wasserlöslichen Verbindungen der Formel (1) sind bekannt, z.B. aus US-A-3 665 031 und können nach an sich bekannten Methoden hergestelltwerden, z.B. durch Umsetzung von n Mol einer Verbindung der Formel (8) (8) A-(X)x-P mit einem Mol einer Verbindung der Formel (9) (9) [W]-mZ[(X')x-Q]n in welchen Formeln eines von P und Q die Gruppe -NH-R3, das andere die Gruppe

Figure imgb0006
The water-soluble compounds of the formula (1) are known, for example from US Pat. No. 3,665,031, and can be prepared by methods known per se, for example by reacting n moles of a compound of the formula (8) (8) A- (X) x -P with one mole of a compound of formula (9) ( 9 ) [W] -m Z [(X ') x -Q] n in which formulas one of P and Q is the group -NH-R 3 , the other the group
Figure imgb0006

V im Falle von y = 1 die Gruppe -OAr, im Falle von y = 0 ein Chlor oder Bromatom oder eine reaktive Aminogruppe, wobei Ar ein aromatischer Rest der Benzol- oder Naphthalinreihe ist, und A, Z, W, R2, X, X', x, m, n und y die angegebene Bedeutunghaben, unter Abspaltung von HV.V in the case of y = 1 the group -OAr, in the case of y = 0 a chlorine or bromine atom or a reactive amino group, where Ar is an aromatic radical of the benzene or naphthalene series, and A, Z, W, R 2 , X , X ', x, m, n and y have the meaning given, with elimination of HV.

Beispiele für unter Formel (8) fallende, zur Herstellung der erfindungsgemässen wasserlöslichen Verbindungen geeignete Ausgangsprodukte der Formel (10)Examples of starting materials of formula (10) falling under formula (8) and suitable for the production of the water-soluble compounds according to the invention

(10) A-(X)x-NH-R3 worin

  • A, X, x und R3 die vorstehend angegebene Bedeutung haben, sind : 4-Hydroxy-3,5-di-tert.butyl-anilin, 4-Hydroxy-3,5-di-tert.butyl-benzylamin, y-(4-Hydroxy-3,5-di-tert.butyl-phenyl)-propylamin, 4-Hydroxy-3-tert.butyl-5-methyl-anilin, 4-Hydroxy-3,5-di-cyclohexyl-anilin, 4-Hydroxy-3,5-di- tert.amyl-anilin, 4-Hydroxy-3,5-di-cyclohexyl-benzylamin, 4-Hydroxy-3-methylcyclohexyl-5-methyl-anilin, 2-Hy-droxy-3-a,a-dimethylbenzyl-5-methyl-benzylamin, 4-Hydroxy-3,5-dibenzyl-anilin, y-(4-Hydroxy-3,5-diben- zyl-phenyl)-propylamin, 2-Hydroxy-3-tertbutyl-5-dodecyl-anilin, 4-Hydroxy-3-tert.octyl-5-methyl-benzylamin, 4-Hydroxy-3,5-di-isopropyl-benzylamin, 4-Hydroxy-3-tert.butyl-6-methyl-benzylamin, 4-Hydroxy-3,5-di-tert. amyl-benzylamin, 2-Hydroxy-3,5-dimethyl-anilin und 2-Hydroxy-3-tert.butyl-5-methyl-benzylamin.
(10) A- (X) x -NH-R 3 wherein
  • A, X, x and R 3 have the meaning given above are: 4-hydroxy-3,5-di-tert-butyl-aniline, 4-hydroxy-3,5-di-tert-butyl-benzylamine, y- (4-hydroxy-3,5-di-tert-butyl-phenyl) -propylamine, 4-hydroxy-3-tert-butyl-5-methyl-aniline, 4-hydroxy-3,5-di-cyclohexyl-aniline, 4-hydroxy-3,5-di-tert-amyl-aniline, 4-hydroxy-3,5-di-cyclohexyl-benzylamine, 4-hydroxy-3-methylcyclohexyl-5-methyl-aniline, 2-hy-hydroxy 3-a, a-dimethylbenzyl-5-methyl-benzylamine, 4-hydroxy-3,5-dibenzyl-aniline, y- (4-hydroxy-3,5-dibenzyl-phenyl) propylamine, 2-hydroxy- 3-tertbutyl-5-dodecyl-aniline, 4-hydroxy-3-tert.octyl-5-methyl-benzylamine, 4-hydroxy-3,5-di-isopropyl-benzylamine, 4-hydroxy-3-tert.butyl- 6-methyl-benzylamine, 4-hydroxy-3,5-di-tert. amyl-benzylamine, 2-hydroxy-3,5-dimethyl-aniline and 2-hydroxy-3-tert-butyl-5-methyl-benzylamine.

Beispiele für unter Formel (8) fallende Ausgangsprodukte der Formel (11)

Figure imgb0007
worin

  • A, X, x, R2, y und V die vorstehend angegebene Bedeutung haben, sind :
  • β-(4-Hydroxy-3,5-di-tert-butyl-phenyl)-propionsäurechlorid, 4-Hydroxy-3,5-di-tert.butylphenyl-acetylchlorid, 4-Hydroxy-3,5-di-tert.butyl-benzoylchlorid, 4-Hydroxy-3-tert.butyl-5-methyl-phenyl-acetylchlorid, 2-Hydroxy-3,5-dimethyl-benzoylchlorid, 2-Hydroxy-3-tert.butyl-5-methyl-benzoylchlorid, S-(4-Hydroxy-3-tert.butyl-5-methylbenzyl)-thioglykolsäurechlorid, 4-Hydroxy-5-tert.butylphenyl-acetylchlorid, β-(4-Hydroxy-3,5-di-cyclohexyl- phenyl)-propionsäurebromid, (4-Hydroxy-3,5-di-cyclohexyl-phenyl)-acetylchlorid, β-(4-Hydroxy-3-benzyl-5-methyl-phenyl)-propionsäurechlorid, (4-Hydroxy-3-benzyl-5-methyl-phenyl)-acetylchlorid, 4-Hydroxy-3,5-diisopropyl-phenyl-acetylchlorid, S-(4-Hydroxy-3,5-di-isopropyl-benzyl)-thioglykolsäurechlorid, β-[ω-(4-Hydroxy-3,5-di tert.butyl-phenyl)-propyloxy]-propionsäurechlorid, [ω-(4-Hydroxy-3,5-di-tert.butyl-phenyl)-propyloxy] -acetylchlorid, β-Methyl-ß-(4-hydroxy-3,5-di-tert.butyl-phenyl)-propionsäurechlorid, 4-Hydroxy-3,5-di-tert. amyl-benzyloxy-acetylchlorid, und 4-Hydroxy-5-tert.butyl-3-äthyl-benzyloxy-acetylchlorid.
Examples of starting products of formula (11) falling under formula (8)
Figure imgb0007
 wherein
  • A, X, x, R 2 , y and V have the meaning given above are:
  • β- (4-hydroxy-3,5-di-tert-butyl-phenyl) propionic acid chloride, 4-hydroxy-3,5-di-tert-butylphenyl-acetyl chloride, 4-hydroxy-3,5-di-tert. butyl-benzoyl chloride, 4-hydroxy-3-tert-butyl-5-methyl-phenyl-acetyl chloride, 2-hydroxy-3,5-dimethyl-benzoyl chloride, 2-hydroxy-3-tert-butyl-5-methyl-benzoyl chloride, S- (4-hydroxy-3-tert-butyl-5-methylbenzyl) thioglycolic acid chloride, 4-hydroxy-5-tert-butylphenyl acetyl chloride, β- (4-hydroxy-3,5-di-cyclohexylphenyl) - propionic acid bromide, (4-hydroxy-3,5-di-cyclohexylphenyl) acetyl chloride, β- (4-hydroxy-3-benzyl-5-methylphenyl) propionic acid chloride, (4-hydroxy-3-benzyl-5 -methyl-phenyl) -acetyl chloride, 4-hydroxy-3,5-diisopropyl-phenyl-acetyl chloride, S- (4-hydroxy-3,5-di-isopropyl-benzyl) -thioglycolic acid chloride, β- [ω- (4- Hydroxy-3,5-di tert.butylphenyl) propyloxy] propionic acid chloride, [ω- (4-hydroxy-3,5-di-tert.butylphenyl) propyloxy] acetyl chloride, β-methyl-β - (4-Hydroxy-3,5-di-tert-butyl-phenyl) -propionic acid chloride, 4-hydroxy-3,5-di-tert. amyl-benzyloxy-acetyl chloride, and 4-hydroxy-5-tert-butyl-3-ethyl-benzyloxy-acetyl chloride.

Beispiele für unter Formel (9) fallende Ausgangsprodukte der Formel (12)

Figure imgb0008
worin

  • W, m, Z, X', x', R3 und n die vorstehend angegebene Bedeutung haben, sind : 2-Amino-benzolsulfonsäure, 3-Amino-benzolsulfonsäure, 4-Amino-benzolsulfonsäure, 5-Chior-2-amino-benzolsulfonsäure, 5-Methyl-4-chlor-2-amino-benzolsulfonsäure, 2-Chlor-5-amino-benzolsulfonsäure, 4-Chlor-3-amino-benzolsulfonsäure. 5-Chlor-3-methyl-3-amino-benzolsulfonsäure, 2,5-Dichlor-4-amino-benzolsulfonsäure, 3-Brom-6-amino-benzolsulfonsäure, 3,4-Dichlor-6-amino-benzolsulfonsäure, 1-Amino-tetralin-4-sulfonsäure, 1-Aminobenzol-2,5-disulfonsäure, 1-Amino-benzol-2,4-disulfonsäure, 1,3-Diaminobenzol-4-sulfonsäure, 1,4-Diaminobenzol-2-sulfonsäure, 2-Amino-5-methyl- benzolsulfonsäure, 5-Amino-2,4-dimethyl-benzolsulfonsäure, 4-Amino-2-methyl-benzolsulfonsäure, 3-Amino-5-isopropyl-2-methyl-benzolsulfonsäure, 2-Amino-4,5-dimethyl-benzolsulfonsäure, 2-Amino-4,5-dimethoxy-benzolsulfonsäure, 5-Amino-2-methyl-benzolsulfonsäure, 2-Amino-S-ethyl-benzolsulfonsäure, 1-Amino-naphthalin-3-sulfonsäure, 1-Amino-naphthalin-4-sulfonsäure, 1-Amino-naphthalin-5-sulfonsäure, 1-Amino-naphthalin-6-sulfonsäure, 1-Amino-naphthalin-7-sulfonsäure, 1-Amino-naphthalin-8-sulfonsäure, 2-Amino-naphthalin-1-sulfonsäure, 2-Amino-naphthalin-5-sulfonsäure, 2-Amino-naphthalin-6-sulfonsäure, 1-Amino-naphthalin-3,6-disulfonsäure, 1-Amino-naphthalin-3,8-disulfonsäure, 2-Amino-naphthalin-4,8-disulfonsäure, 1,4-Diamino-naphthalin-6-sulfonsäure, 3-Amino-4-methoxy-benzolsulfonsäure, 1-Amino-2-methoxy-naphthalin-6-sulfonsäure, 3-Amino-4-hydroxy-benzolsulfonsäure, 3-Amino-6-hydroxybenzol- 1,5-disulfonsäure, 2-Amino-5-hydroxy-naphthalin-7-sulfonsäure, 2-Aceta- mido-5-amino-benzolsulfonsäure, 2-Amino-5-(p-amino-benzoylamino)-benzolsulfonsäure, 2-Amino-naphthalin-5,7-disulfonsäure, 2-Amino-naphthalin-6,8-disulfonsäure, 2-Amino-5-benzamido-benzolsulfonsäure, 4,4'-Diamino-thiodiphenylether-2,2'-disulfonsäure, 2-Amino-4-carboxy-5-chlor-benzolsulfonsäure, 4-Amino-3-carboxy-benzolsulfonsäure, 5-Amino-3-sulfo-salicylsäure, 2-(ß-Phenylethyl)-5-amino-benzolsulfonsäure, 1,2-Bis-[4- amino-2-sulfophenyl]-ethan, 4,4'-Diamino-stilben-2,2'-disulfonsäure, 4-Amino-stilben-2-sulfonsäure, 4,4'-Diamino-2'-methoxy-stilben-2-sulfonsäure, 4-Amino-diphenylether-3-sulfonsäure, 2-Amino-diphenylether-4-sulfonsäure, 2-Amino-2'-methyl-diphenylether-4-sulfonsäure, 2-Amino-4-chlor-4'-amyl-diphenylether-5-sulfonsäure, 2-Amino-4,4'-di-chlor-diphenylether-2'-sulfonsäure, 2-Amino-4'-methyl-diphenylsulfon-4-sulfo- säure, 2,5-Diamino-2'-methyl-diphenylether-4-sulfonsäure, Benzidin-2,2'-disu!fonsäure, 3,3'-Di-methyi-benzidin-6-sulfonsäure, Benzidin-2-sulfonsäure, 2'-Amino-diphenylsulfon-3-sulfonsäure, 5'-Amino-2'-methyl-diphenylsulfon-3-sulfonsäure, 2',5'-Diamino-4-methyldiphenylsulfon-3-sulfonsäure, 3'-Amino-4'-hydroxy-diphenylsulfon-3-sulfonsäure, 3,3'-Diamino-diphenylsulfon-4,4'-disulfonsäure, N-Ethyl-anilin-4-sulfonsäure, N-Methyl-2-naphthylamin-7-sulfonsäure, 2-Aminoethansulfonsäure, N-Methyl-, -Ethyl-, -Propyl-, -iso-Propyl-, -Amyl-, - Hexyl-, -Cyclohexyl-, -Octyl-, -Phenyl-, -Dodecyl- oder -Stearyl- 2-amino-ethansulfonsäure, 2-Methyl-2-amino- ethansulfonsäure, ω-Amino-propan-sulfonsäure, ω-Amino-butansulfonsäure, ω-Amino-pentansulfonsäure, N-Methyl-y-amino-propansulfonsäure, 1,2-Diamino-ethansulfonsäure, 2-Methylamino-propansulfonsäure und 2-Amino-2-carboxy-ethansulfonsäure.
Examples of starting products of formula (12) falling under formula (9)
Figure imgb0008
 wherein
  • W, m, Z, X ', x', R 3 and n have the meaning given above are: 2-amino-benzenesulfonic acid, 3-amino-benzenesulfonic acid, 4-amino-benzenesulfonic acid, 5-chloro-2-amino benzenesulfonic acid, 5-methyl-4-chloro-2-amino-benzenesulfonic acid, 2-chloro-5-amino-benzenesulfonic acid, 4-chloro-3-amino-benzenesulfonic acid. 5-chloro-3-methyl-3-amino-benzenesulfonic acid, 2,5-dichloro-4-amino-benzenesulfonic acid, 3-bromo-6-amino-benzenesulfonic acid, 3,4-dichloro-6-amino-benzenesulfonic acid, 1- Amino-tetralin-4-sulfonic acid, 1-aminobenzene-2,5-disulfonic acid, 1-amino-benzene-2,4-disulfonic acid, 1,3-diaminobenzene-4-sulfonic acid, 1,4-diaminobenzene-2-sulfonic acid, 2-amino-5-methyl-benzenesulfonic acid, 5-amino-2,4-dimethyl-benzenesulfonic acid, 4-amino-2-methyl-benzenesulfonic acid, 3-amino-5-isopropyl-2-methyl-benzenesulfonic acid, 2-amino- 4,5-dimethyl-benzenesulfonic acid, 2-amino-4,5-dimethoxy-benzenesulfonic acid, 5-amino-2-methyl-benzenesulfonic acid, 2-amino-S-ethyl-benzenesulfonic acid, 1-amino-naphthalene-3-sulfonic acid, 1-amino-naphthalene-4-sulfonic acid, 1-amino-naphthalene-5-sulfonic acid, 1-amino-naphthalene-6-sulfonic acid, 1-amino-naphthalene-7-sulfonic acid, 1-amino-naphthalene-8-sulfonic acid, 2-amino-naphthalene-1-sulfonic acid, 2-amino-naphthalene-5-sulfonic acid, 2-amino-naphthalene-6-sulfonic acid, 1-amino-naphthalene-3,6-disulfonic acid acid, 1-amino-naphthalene-3,8-disulfonic acid, 2-amino-naphthalene-4,8-disulfonic acid, 1,4-diamino-naphthalene-6-sulfonic acid, 3-amino-4-methoxy-benzenesulfonic acid, 1- Amino-2-methoxy-naphthalene-6-sulfonic acid, 3-amino-4-hydroxy-benzenesulfonic acid, 3-amino-6-hydroxybenzene-1,5-disulfonic acid, 2-amino-5-hydroxy-naphthalene-7-sulfonic acid, 2-acetamido-5-amino-benzenesulfonic acid, 2-amino-5- (p-amino-benzoylamino) -benzenesulfonic acid, 2-amino-naphthalene-5,7-disulfonic acid, 2-amino-naphthalene-6,8- disulfonic acid, 2-amino-5-benzamido-benzenesulfonic acid, 4,4'-diamino-thiodiphenyl ether-2,2'-disulfonic acid, 2-amino-4-carboxy-5-chlorobenzenesulfonic acid, 4-amino-3- carboxy-benzenesulfonic acid, 5-amino-3-sulfo-salicylic acid, 2- (β-phenylethyl) -5-amino-benzenesulfonic acid, 1,2-bis- [4-amino-2-sulfophenyl] ethane, 4,4 '-Diamino-stilbene-2,2'-disulfonic acid, 4-amino-stilbene-2-sulfonic acid, 4,4'-diamino-2'-methoxy-stilbene-2-sulfonic acid, 4-amino-diphenyl ether-3-sulfonic acid, 2-amino-diphenylether-4-sulfonic acid, 2-amino-2'-methyl-diphenylether-4-sulfonic acid, 2-amino-4-chloro-4'-amyl-diphenylether-5-sulfonic acid, 2-amino-4, 4'-di-chloro-diphenylether-2'-sulfonic acid, 2-amino-4'-methyl-diphenylsulfone-4-sulfonic acid, 2,5-diamino-2'-methyl-diphenylether-4-sulfonic acid, benzidine- 2,2'-disulfonic acid, 3,3'-dimethylbenzidine-6-sulfonic acid, benzidine-2-sulfonic acid, 2'-amino-diphenylsulfone-3-sulfonic acid, 5'-amino-2'-methyl -diphenylsulfone-3-sulfonic acid, 2 ', 5'-diamino-4-methyldiphenylsulfone-3-sulfonic acid, 3'-amino-4'-hydroxy-diphenylsulfone-3-sulfonic acid, 3,3'-diamino-diphenylsulfone-4, 4'-disulfonic acid, N-ethyl-aniline-4-sulfonic acid, N-methyl-2-naphthylamine-7-sulf onoic acid, 2-aminoethanesulfonic acid, N-methyl, ethyl, propyl, isopropyl, amyl, hexyl, cyclohexyl, octyl, phenyl, dodecyl or Stearyl-2-amino-ethanesulfonic acid, 2-methyl-2-amino-ethanesulfonic acid, ω-amino-propanesulfonic acid, ω-amino-butanesulfonic acid, ω-amino-pentanesulfonic acid, N-methyl-y-amino-propanesulfonic acid, 1, 2-diamino-ethanesulfonic acid, 2-methylamino-propanesulfonic acid and 2-amino-2-carboxy-ethanesulfonic acid.

Beispiele für unter Formel (9) fallende Ausgangsprodukte der Formel (13)

Figure imgb0009
worin

  • W, m, Z, X', x', R2, y, V und n die vorstehend angegebene Bedeutung haben, sind :
  • 2-Sulfo-benzoylchlorid, 3-Sulfo-benzoylchlorid, 4-Sulfo-benzoylchlorid, 3,5-Disulfo-benzoylchforid, 3-Sulfophthaloylchlorid, 3,4-Disulfo-phthaloylchlorid, 4-Sulfo-phenyl-acetylchlorid, β-(4-Sulfo-phenyl)-propionsäure- chlorid, 3-Sulfo-6-methyl-benzoylchlorid.
Examples of starting products of formula (13) falling under formula (9)
Figure imgb0009
 wherein
  • W, m, Z, X ', x', R 2 , y, V and n have the meaning given above are:
  • 2-sulfo-benzoyl chloride, 3-sulfo-benzoyl chloride, 4-sulfo-benzoyl chloride, 3,5-disulfo-benzoyl chloride, 3-sulfophthaloyl chloride, 3,4-disulfo-phthaloyl chloride, 4-sulfo-phenyl-acetyl chloride, β- (4th -Sulfo-phenyl) propionic acid chloride, 3-sulfo-6-methyl-benzoyl chloride.

Die oben genannten Ausgangsprodukte sind zum Teil bekannt und können nach an sich bekannten Methoden hergestellt werden.Some of the starting products mentioned above are known and can be prepared by methods known per se.

Die Herstellung der erfindungsgemäss verwendbaren Verbindungen der Formel (1) ist in der US-A-3 665 031 näher beschrieben.The preparation of the compounds of the formula (1) which can be used according to the invention is described in more detail in US Pat. No. 3,665,031.

Als erfindungsgemäss verwendbare Verbindungen der Formel (1) kommen z.B. Verbindungen der Formel

Figure imgb0010
in Betracht, worin R, R1, R4 X, Z, M, m und n die nachstehenden Bedeutungen annehmen.
Figure imgb0011
Figure imgb0012
Figure imgb0013
Figure imgb0014
Figure imgb0015
Figure imgb0016
Figure imgb0017
Figure imgb0018
 Compounds of the formula (1) which can be used according to the invention are, for example, compounds of the formula
Figure imgb0010
 into consideration, wherein R, R 1 , R 4 X, Z, M, m and n assume the meanings below.
Figure imgb0011
Figure imgb0012
Figure imgb0013
Figure imgb0014
Figure imgb0015
Figure imgb0016
Figure imgb0017
Figure imgb0018

sowie die Verbindungen der Formeln

Figure imgb0019
und
Figure imgb0020
 as well as the connections of the formulas
Figure imgb0019
 and
Figure imgb0020

Die Verbindungen der Formel (1) werden erfindungsgemäss aus wässrigem Bad appliziert, das die Verbindungen in einer Menge von 0,01 bis 10, vorzugsweise 0,25 bis 3 Gew.-% enthält.According to the invention, the compounds of the formula (1) are applied from an aqueous bath which contains the compounds in an amount of 0.01 to 10, preferably 0.25 to 3,% by weight.

Die Applikation des wasserlöslichen phenolischen Antioxidants kann während oder nach dem Färben, nach einem Auszieh- oder Kontinueverfahren erfolgen. Die Applikation während dem Färben ist bevorzugt.The water-soluble phenolic antioxidant can be applied during or after dyeing, using an exhaust or continuous process. Application during dyeing is preferred.

Beim Ausziehverfahren kann das Flottenverhältnis innerhalb eines weiten Bereiches gewählt werden, z.B. 1 :3 bis 1 :100, vorzugsweise 1:10 bis 1:40.Man arbeitetzweckmässig bei einerTemperaturvon 30 bis 130°C, vorzugsweise 50 bis 95°C.In the exhaust process, the liquor ratio can be selected within a wide range, e.g. 1: 3 to 1: 100, preferably 1:10 to 1:40. The purpose of the work is at a temperature of 30 to 130 ° C, preferably 50 to 95 ° C.

Beim Kontinueverfahren beträgt der Flottenauftrag zweckmässig 40-700, vorzugsweise 40-500 Gew.-%. Das Fasermaterial wird dann einem Hitzebehandlungsprozess unterworfen, um die applizierten Farbstoffe und die Antioxidantien zu fixieren. Dieses Fixieren kann auch nach der Kalt-Verweil-Methode erfolgen.In the continuous process, the liquor order is expediently 40-700, preferably 40-500% by weight. The fiber material is then subjected to a heat treatment process in order to fix the applied dyes and the antioxidants. This fixation can also be carried out using the cold dwell method.

Die Hitzebehandlung erfolgt vorzugsweise durch ein Dämpfverfahren unter Behandlung in einem Dämpfer mit gegebenenfalls überhitztem Dampf bei einer Temperatur von 98 bis 105°C während z.B. 1-7, vorzugsweise 1-5 Minuten. Die Fixierung der Farbstoffe gemäss dem Kaltverweilverfahren kann durch Lagerung der imprägnierten und vorzugsweise aufgerollten Ware bei Raumtemperatur (15 bis 30°C) z.B. während 3 bis 24 Stunden erfolgen, wobei die Kaltverweilzeit bekanntlich vom Farbstoff abhängig ist.The heat treatment is preferably carried out by a steaming process with treatment in a steamer with possibly superheated steam at a temperature of 98 to 105 ° C during e.g. 1-7, preferably 1-5 minutes. The dyes can be fixed in accordance with the cold residence process by storing the impregnated and preferably rolled-up goods at room temperature (15 to 30 ° C) e.g. during 3 to 24 hours, the cold residence time being known to depend on the dye.

Nach Beendigung des Färbeprozesses bzw. der Fixierung werden die hergestellten Färbungen auf übliche Weise gewaschen und getrocknet.After the dyeing process or fixation has ended, the dyeings produced are washed and dried in the customary manner.

Man erhält nach der vorliegenden Erfindung Färbungen mit guter thermischer und/oder photochemischer Stabilität.According to the present invention, dyeings with good thermal and / or photochemical stability are obtained.

Als die erfindungsgemäss zu stabilisierenden Färbungen kommen solche in Betracht, die durch Dispersions-, Säure- oder Metallkomplexfarbstoffe, besonders Azo-, 1,2-Metallkomplexfarbstoffe, z.B. 1 :2-Chrom-, 1 :2-Kobaltkomplexfarbstoffe oder Cu-komplexfarbstoffe erzeugt werden. Bevorzugt, aber ohne Beschrankung darauf, sind Färbungen, welche durch rote Farbstoffe oder durch eine rote komponente aufweisende Farbstoffmischungen erzeugt werden.As the dyeings to be stabilized according to the invention, those are suitable which are disperse, acid or metal complex dyes, in particular azo, 1,2-metal complex dyes, e.g. 1: 2 chromium, 1: 2 cobalt complex dyes or Cu complex dyes are generated. Preferred, but without limitation, are colorings which are produced by red dyes or by a dye mixture having a red component.

Beispiele für solche Farbstoffe sind in Colour Index, 3. Auflage, 1971, Band 4, beschrieben.Examples of such dyes are described in Color Index, 3rd edition, 1971, volume 4.

Unter Polyamidmaterial wird synthetisches Polyamid, wie z.B. Polyamid-6, Polyamid-6,6 oder Polyamid-12, sowie modifiziertes Polyamid, z.B. basisch anfärbbares Polyamid verstanden. Neben den reinen Polyamidfasern kommen vor allem auch Fasermischungen aus Polyurethan und Polyamid in Betracht, so z.B. Trikotmaterial aus Polyamid/Polyurethan im Mischungsverhältnis 70 :30. Grundsätzlich kann das reine oder gemischte Polyamid-material in den verschiedensten Verarbeitungsformen vorliegen, wie z.B. als Faser, Garn, Gewebe, Gewirke, Vlies oder Formaterial.Synthetic polyamide, e.g. Polyamide-6, polyamide-6,6 or polyamide-12, as well as modified polyamide, e.g. understood basic dyeable polyamide. In addition to the pure polyamide fibers, fiber mixtures made of polyurethane and polyamide are also considered, e.g. Jersey material made of polyamide / polyurethane in a mixing ratio of 70:30. Basically, the pure or mixed polyamide material can be in a variety of processing forms, such as as fiber, yarn, fabric, knitted fabric, fleece or molded material.

Vor allem Färbungen auf Polyamidmaterial, das Licht und/oder Hitze ausgesetzt wird und z.B. als Teppiche oder Autopolsterstoff vorliegt, eignet sich besonders gut dazu, nach dem vorliegenden Verfahren behandelt zu werden.Especially dyeings on polyamide material that is exposed to light and / or heat and e.g. in the form of carpets or car upholstery, is particularly well suited to being treated using the present method.

Das Verfahren eignet sich jedoch auch zur thermischen Stabilisierung von zum sogenannten "Moulding"-Prozess vorgesehenes gefärbtes Polyamid-Material. Dieses Verfahren ist ein Formungsprozess, der kurzzeitig bei hohen Temperaturen arbeitet (z.B. Büstenhalterherstellung).However, the method is also suitable for the thermal stabilization of so-called "molding" Processed colored polyamide material. This process is a shaping process that works briefly at high temperatures (e.g. bra production).

Die folgenden Beispiele veranschaulichen die Erfindung. Teile bedeuten Gewichtsteile und Prozente Gewichtsprozente.The following examples illustrate the invention. Parts mean parts by weight and percentages percent by weight.

Beispiel 1 : Es werden 2 Muster von je 10 g einer PA-6-Maschenware z.B. in einem ®AHIBA Färbeapparat bei einem Flottenverhältnis von 1 :30 gefärbt. Dazu werden 2 Flotten bereitet, die 0,5 g/l Mononatriumphosphat und 1,5 g/I Dinatriumphosphat (= pH 7) und 0,2 % des Farbstoffes der Formel

Figure imgb0021
gelöst enthalten. Die Flotte (1) erhält keinen weiteren Zusatz, die Flotte (2) dagegen 1 % der Verbindung der Formel
Figure imgb0022
 Example 1: 2 samples of 10 g each of a PA-6 knitted fabric are dyed, for example in a ®AHIBA dyeing machine at a liquor ratio of 1:30. For this purpose, 2 liquors are prepared, the 0.5 g / l monosodium phosphate and 1.5 g / I disodium phosphate (= pH 7) and 0.2% of the dye of the formula
Figure imgb0021
 solved included. The liquor (1) receives no further addition, the liquor (2), however, 1% of the compound of the formula
Figure imgb0022

Man beginnt bei 30°C mit dem Färben, verweilt 10 Minuten bei dieser Temperatur und erhitzt mit 2

Figure imgb0023
/Min auf 95°C. Nach einer Färbezeit von 20 Minuten bei 95°C gibt man 2 % Essigsäure (80 %) hinzu und färbt noch 20 Minuten. Sodann kühlt man auf 50°C ab, spült, zentrifugiert und trocknet die Muster.Dyeing begins at 30 ° C., the mixture is held at this temperature for 10 minutes and heated at 2
Figure imgb0023
 / Min to 95 ° C. After a dyeing time of 20 minutes at 95 ° C, 2% acetic acid (80%) is added and dyeing is continued for 20 minutes. The mixture is then cooled to 50 ° C., rinsed, centrifuged and the samples are dried.

Die Färbungen werden auf ihre Lichtechtheiten nach SN-ISO 105-B02 (Xenon) und DIN 75202 (Fakra) sowie in einem Hitzetest bei 130°C 60 Stunden lang in einem Umlufttrockenschrank auf Farbtonbeständigkeit geprüft.The dyeings are tested for their light fastness according to SN-ISO 105-B02 (Xenon) and DIN 75202 (Fakra) as well as in a heat test at 130 ° C for 60 hours in a circulating air dryer for color stability.

Ergebnisse:Results:

Figure imgb0024
Figure imgb0024

Aus diesen Ergebnissen ist ersichtlich, dass die Verbindung (101) der Färbung sowohl einen photochemischen als auch thermischen Schutz verleiht.From these results it can be seen that compound (101) imparts both photochemical and thermal protection to the stain.

Beispiel 2 : Man verfährt wie in Beispiel 1 beschrieben, setzt jedoch anstelle des Farbstoffes (100) 0,4 % des Farbstoffes der Formel

Figure imgb0025
ein.Example 2: The procedure described in Example 1 is followed, except that 0.4% of the dye of the formula is used instead of the dye (100)
Figure imgb0025
 a.

Die Prüfung erbrachte folgendes Ergebnis:

Figure imgb0026
The test gave the following result:
Figure imgb0026

Es ist ersichtlich, dass die Verbindung (101) der Färbung vor allem einen thermischen Schutz gibt.It can be seen that the compound (101) primarily gives the dyeing thermal protection.

Beispiel 3 : Man verfährt wie in Beispiel 1 beschrieben, setzt jedoch anstelle des Farbstoffes (100) 0,15 % des Farbstoffes der FormelEXAMPLE 3 The procedure is as described in Example 1, but 0.15% of the dye of the formula is used instead of the dye (100)

Figure imgb0027
Die Prüfung der Lichtechtheiten und der Hitzebeständigkeit erbrachte folgende Ergebnisse:
Figure imgb0028
Figure imgb0027
 The test of light fastness and heat resistance gave the following results:
Figure imgb0028

Auch hier kann sowohl eine Licht-, als auch Wärmestabilisierung des Farbstoffes festgestellt werden.Here, too, both light and heat stabilization of the dye can be determined.

Beispiel 4 : Es werden 2 Muster von je 10 g einer PA-6-Maschenware z.B. in einem ®AHIBA Färbeapparat bei einem Flottenverhältnis von 1 :30 beige gefärbt. Dazu werden 2 Motten bereitet, die 0,5 g/1 Mononatriumphosphat und 1,5 g/l Dinatriumphosphat (= pH 7) und 0,2 % der Farbstoffmischung aus 0,04 % des Farbstoffes der in Beispiel 1 angegebenen Formel (100), 0,08 % des Farbstoffes der FormelExample 4: 2 samples of 10 g each of a PA-6 knitwear are e.g. dyed beige in a ®AHIBA dyeing machine at a liquor ratio of 1:30. For this, 2 moths are prepared, the 0.5 g / 1 monosodium phosphate and 1.5 g / l disodium phosphate (= pH 7) and 0.2% of the dye mixture from 0.04% of the dye of the formula (100) given in Example 1 , 0.08% of the dye of the formula

Figure imgb0029
0,08 % des Farbstoffes der Formel
Figure imgb0030
gelöst enthalten. Die Flotte (1) erhält keinen weiteren Zusatz, die Motte (2) dagegen 1 % der Verbindung der Formel
Figure imgb0031
Figure imgb0029
 0.08% of the dye of the formula
Figure imgb0030
 solved included. The liquor (1) receives no further addition, the moth (2), however, 1% of the compound of the formula
Figure imgb0031

Die Prüfung der Färbungen erbrachte folgendes Resultat:

Figure imgb0032
The examination of the colors gave the following result:
Figure imgb0032

Die Prüfergebnisse zeigen, dass durch den Zusatz der Verbindung (402) neben einer Heisslichtstabilisierung vor allem eine Hitzestabilisierung der Rotkomponente (100) bewirkt wird.The test results show that the addition of the compound (402), in addition to hot-light stabilization, primarily results in heat stabilization of the red component (100).

Beispiel 5 : Fünf Muster von je 10 einerPA-6-Maschenware werden,jeweils getrennt, mit folgender Farbstoffkombination von 0,002 % des Farbstoffes der in Beispiel 3 angegebenen Formel (300) und 0,04% des Farbstoffgemisches (402) (403), und aus 81 Teilen des Farbstoffes der Formel

Figure imgb0033
und 12 Teilen des Farbstoffes der Formel
Figure imgb0034
wie in Beispiel 1 vermerkt, gefärbt.Example 5: Five samples of 10 each of a PA-6 knitted fabric are separated, each with the following dye combination of 0.002% of the dye of the formula (300) given in Example 3 and 0.04% of the dye mixture (402) (403), and from 81 parts of the dye of the formula
Figure imgb0033
 and 12 parts of the dye of the formula
Figure imgb0034
 as noted in Example 1, colored.

Das Färbebad 1 enthält keinen weiteren Zusatz, während die Bäder 2-6 dagegen jeweils 1 % der Verbindungen der Formeln (502)-(506) in gelöster Form enthalten.

Figure imgb0035
Figure imgb0036
Figure imgb0037
Figure imgb0038
Figure imgb0039
 Dye bath 1 contains no further additives, while baths 2-6, on the other hand, each contain 1% of the compounds of formulas (502) - (506) in dissolved form.
Figure imgb0035
Figure imgb0036
Figure imgb0037
Figure imgb0038
Figure imgb0039

Die Färbungen werden auf ihre Lichtechtheiten nach DIN 75.202 (FAKRA), auf ihren Verlust an mechanischen Eigenschaften (Prüfung nach SN 198.461) und auf ihre Hitzebeständigkeit geprüft. Folgende Ergebnisse resultierten :

Figure imgb0040
The dyeings are tested for their light fastness according to DIN 75.202 (FAKRA), for their loss of mechanical properties (test according to SN 198.461) and for their heat resistance. The following results resulted:
Figure imgb0040

Aus den aufgeführten Resultaten ist ersichtlich, dass die Graufärbungen hinsichtlich ihrer photochemischen und thermischen Stabilität durch die beim Färben eingesetzten Verbindungen (502-506) deutlich verbessert werden.From the results listed it can be seen that the gray colorations are significantly improved with regard to their photochemical and thermal stability by the compounds used in the coloring (502-506).

Beispiel 6 : Zwei Muster eines PA66-Trikots werden wie in Beispiel 1 beschrieben mit folgenden Mengen Farbstoff violett gefärbt : 0,15% des Farbstoffes der in Beispiel 1 angegebenen Formel (100) und 0,075 % des Farbstoffes der in Beispiel 4 angegebenen Formel (401). Das Färbebad 1 enthält keinen weiteren Zusatz, während das Färbebad 2 zusätzlich 1,5 % der Verbindung der in Beispiel 4 angegebenen Formel (402) enthält. Das gut gespülte und getrocknete Trikotmaterial wird anschliessend einer Hitzebehandlung unter sogenannten "Moulding"-Bedingungen (unter "Moulding" versteht man einen Hitzeverformungsprozess, wie er z.B. bei der Büstenhalterherstellung verwendet wird) unterworfen. Dazu wird das Material auf einer Präzisionsbügelpresse "System BASF" (Hersteller K. Schröder KG, D-Weinheim / Bergstr.) kontrolliert erhitzt. Der Versuch erbrachte folgendes Ergebnis :

Figure imgb0041
Example 6: Two samples of a PA66 jersey are colored violet as described in Example 1 with the following amounts of dye: 0.15% of the dye of the formula (100) given in Example 1 and 0.075% of the dye of the formula given in Example 4 (401 ). The dye bath 1 contains no further additive, while the dye bath 2 additionally contains 1.5% of the compound of the formula (402) given in Example 4. The well-rinsed and dried tricot material is then subjected to a heat treatment under so-called "molding" conditions ("molding" means a heat deformation process, such as is used in the manufacture of bras). For this purpose, the material is heated in a controlled manner on a "System BASF" precision ironing press (manufacturer K. Schröder KG, D-Weinheim / Bergstr.). The experiment gave the following result:
Figure imgb0041

Die Resultate der kurzzeitkontakthitzebehandlungen zeigen, dass die die Verbindung (402) enthaltende Färbung zu keinen oder geringeren Farbtonumschlägen (=Farbstoffzerstörung) neigt.The results of the short-term contact heat treatments show that the coloring containing the compound (402) tends to no or less color changes (= dye destruction).

Claims (14)

1. Verfahren zur Verbesserung der thermischen und/oder photochemischen Stabilität von Färbungen auf Polyamidfasern, dadurch gekennzeichnet, dass man eine Verbindung der Formel (1) (A-Y-)nZ(-W)m in welcher A den Rest eines sterisch gehinderten Phenols der Benzolreihe, Y einen Rest der Formeln (2) oder (3)
Figure imgb0042
Figure imgb0043
 worin X und X' unabhängig voneinander Alkylen, Oxaalkylen oder Thiaalkylen, R2 und R3 unabhängig voneinander Wasserstoff oder eine gegebenenfalls substituierte Alkylgruppe und x, x' und y unabhängig voneinander je 0 oder 1 sind, Z einen aliphatischen oder einen carbocyclischen aromatischen Rest, wobei letzterer höchstens zwei mono- oder bicyclische Kerne enthält, W die Sulfogruppe und m und n unabhängig voneinander 1 oder 2 bedeuten, und deren wasserlösliche Salze, aus einem wässrigen Medium auf die Polyamidfasem aufzieht. 1. A method for improving the thermal and / or photochemical stability of dyeings on polyamide fibers, characterized in that a compound of the formula (1) (AY-) n Z (-W) m in which A is the residue of a sterically hindered phenol from the benzene series, Y is a radical of the formulas (2) or (3)
Figure imgb0042
Figure imgb0043
 wherein X and X 'independently of one another alkylene, oxaalkylene or thiaalkylene, R 2 and R 3 are independently hydrogen or an optionally substituted alkyl group and x, x 'and y are each independently 0 or 1, Z is an aliphatic or a carbocyclic aromatic radical, the latter containing at most two mono- or bicyclic nuclei, W the sulfo group and m and n independently of one another denote 1 or 2, and their water-soluble salts are drawn onto the polyamide fibers from an aqueous medium. 2. Verfahren gemäss Anspruch 1, dadurch gekennzeichnet, dass man eine Verbindung der Formel (1) verwendet, worin A einen Monohydroxyphenyl-Rest bedeutet, in dem mindestens eine o-Stellung zur Hydroxylgruppe durch Alkyl mit 1-12 C-Atomen, Cycloalkyl mit 6-10 C-Atomen oder Aralkyl mit 7-10 C-Atomen substituiert ist und der gegebenenfalls noch weitere Substituenten trägt.2. The method according to claim 1, characterized in that one uses a compound of formula (1), wherein A is a monohydroxyphenyl radical in which at least one o-position to the hydroxyl group by alkyl having 1-12 C atoms, cycloalkyl 6-10 C-atoms or aralkyl is substituted with 7-10 C-atoms and which optionally carries further substituents. 3. Verfahren gemäss einem der Ansprüche 1 und 2, dadurch gekennzeichnet, dass man eine Verbindung der Formel (1) verwendet, worin A einen Rest der Formel (4)
Figure imgb0044
in der R und R1 unabhängig voneinander Wasserstoff, Methyl oder tert.Butyl darstellen und die Summe der Kohlenstoffatome von R und R1 mindestens 2 beträgt, bedeutet. 3. The method according to any one of claims 1 and 2, characterized in that one uses a compound of formula (1), wherein A is a radical of formula (4)
Figure imgb0044
 in the R and R 1 independently represent hydrogen, methyl or tert-butyl and the sum of the carbon atoms of R and R 1 is at least 2. 4. Verfahren gemäss einem der Ansprüche 1 bis 3, worin in den Verbindungen der Formeln (2) und (3) X und X' geradkettiges oder verzweigtes Alkylen mit 1-8 C-Atomen bedeuten.4. The method according to any one of claims 1 to 3, wherein in the compounds of formulas (2) and (3) X and X 'are straight-chain or branched alkylene having 1-8 C atoms. 5. Verfahren gemäss einem der Ansprüche 1 bis 4, worin in den Verbindungen der Formeln (2) und (3) R2 und R3 geradkettiges oder verzweigtes C1-C8-Alkyl bedeuten.5. The method according to any one of claims 1 to 4, wherein in the compounds of formulas (2) and (3) R 2 and R 3 are straight-chain or branched C 1 -C 8 alkyl. 6. Verfahren gemäss einem der Ansprüche 1 und 4, worin in den Verbindungen der Formeln (2) und (3) R2 und R3 Hydroxyalkyl, Alkoxyalkyl, Aminoalkyl, Alkylaminoalkyl oder Dialkylaminoalkyl je mit insgesamt 2-10 C-Atomen oder Phenyl bedeuten.6. The method according to any one of claims 1 and 4, wherein in the compounds of formulas (2) and (3) R 2 and R 3 are hydroxyalkyl, alkoxyalkyl, aminoalkyl, alkylaminoalkyl or dialkylaminoalkyl each with a total of 2-10 C atoms or phenyl . 7. Verfahren gemäss Anspruch 1, worin in Formel (1) Y einen Rest der Formel (5)
Figure imgb0045
darstellt, worin R4 Wasserstoff oder C1-C4-Alkyl und X" C1-C4-Alkylen bedeuten.7. The method according to claim 1, wherein in formula (1) Y is a radical of formula (5)
Figure imgb0045
 represents, wherein R 4 is hydrogen or C 1 -C 4 alkyl and X "C 1 -C 4 alkylene. 8. Verfahren gemäss einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass Z in Formel (1) den Rest eines unsubstituierten oder durch Carboxylgruppen substituierten Alkans mit mindestens 2 C-Atomen, den Rest eines unsubstituierten oder durch Chlor oder Brom, CI-C4-Alkyl, C1-C4-Alkoxy, C1-C4-Alkoxycarbo- nylarnino, Hydroxy, Carboxy, Phenylethyl, Styryl, Phenyl, Phenoxy, Phenylthio, Phenylsulfonyl oderAcylamino substituierten Benzolkernes, wobei die Gruppe W direkt an diesen Benzolkem oder an einen monocyclischen Arylrest eines seiner Substituenten gebunden sein kann, oder es den Naphthalin- oder Tetralinrest bedeutet.8. The method according to any one of claims 1 to 7, characterized in that Z in formula (1) the residue of an unsubstituted or substituted by carboxyl groups alkane having at least 2 carbon atoms, the residue of an unsubstituted or by chlorine or bromine, C I - C 4 -alkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -alkoxycarbonylarnino, hydroxy, carboxy, phenylethyl, styryl, phenyl, phenoxy, phenylthio, phenylsulfonyl or acylamino substituted benzene nucleus, the group W directly on these benzene cores or can be bound to a monocyclic aryl radical of one of its substituents, or it means the naphthalene or tetralin radical. 9. Verfahren gemäss Anspruch 1, dadurch gekennzeichnet, dass man eine Verbindung der Formel (7)
Figure imgb0046
verwendet, worin R und R1 unabhängig voneinander Methyl oder tert.Butyl, R4 Wasserstoff oder C1-C4-Alkyl, X" Cl-C4-Alkylen, Z den Aethylenrest, einen zwei- oder dreiwertigen Rest des Benzols oder Naphthalins oder einen zwei- wertigen Rest des Diphenyläthers, W die Sulfogruppe und n 1 oder 2 bedeuten. 9. The method according to claim 1, characterized in that a compound of formula (7)
Figure imgb0046
 used where R and R 1 are independently methyl or tert-butyl, R 4 is hydrogen or C 1 -C 4 alkyl, X "C 1 -C 4 alkylene, Z is the ethylene radical, a divalent or trivalent radical of benzene or naphthalene or a divalent valuable rest of the diphenyl ether, W the sulfo group and n is 1 or 2. 10. Verfahren gemäss Anspruch 9, dadurch gekennzeichnet, dass man Verbindungen der Formel (7) verwendet, worin R und R1 tert.-Butyl, X" Methylen oder Ethylen, R4 Wasserstoff, Methyl oder Ethyl und Z Ethylen, o-, m- oder p-Phenylen, 1,4-Naphthyien, 1,8-Naphthylen, 2-Methoxy-1,6-Naphthyien, 1,5-Naphthy)en, 2,5-Naphthylen, 2,6-Naphthylen, 1,4,6-Naphthalintriyl oder die Reste
Figure imgb0047
Figure imgb0048
Figure imgb0049
Figure imgb0050
worin die Sulfogruppe W auch in Form ihrer Alkali- oder Ammoniumsalze vorliegen kann.10. The method according to claim 9, characterized in that compounds of the formula (7) are used in which R and R 1 are tert-butyl, X "methylene or ethylene, R 4 is hydrogen, methyl or ethyl and Z is ethylene, o-, m- or p-phenylene, 1,4-naphthyiene, 1,8-naphthylene, 2-methoxy-1,6-naphthyiene, 1,5-naphthy) en, 2,5-naphthylene, 2,6-naphthylene, 1 , 4,6-Naphthalintriyl or the residues
Figure imgb0047
Figure imgb0048
Figure imgb0049
Figure imgb0050
 wherein the sulfo group W can also be in the form of its alkali or ammonium salts. 11. Verfahren nach einem der Ansprüche 1 bis 10, dadurch gekennzeichnet, dass man die Verbindung der Formel (1) nach einem Auszieh- oder Kontinueverfahren auf die Fasern aufzieht.11. The method according to any one of claims 1 to 10, characterized in that the compound of formula (1) is drawn onto the fibers by an exhaust or continuous process. 12. Verfahren nach einem der Ansprüche 1 bis 11, zur Verbesserung der thermischen und/oder photochemischen Stabilität von mit Säure- oder Metallkomplexfarbstoffen gefärbten Polyamidfasern.12. The method according to any one of claims 1 to 11, for improving the thermal and / or photochemical stability of polyamide fibers dyed with acid or metal complex dyes. 13. Verfahren nach Anspruch 12, zur Verbesserung der thermischen und/oder photochemischen Stabilität von mit Säure- oder 1 :2 Metallkomplexfarbstoffen oder einer eine rote Komponente enthaltenden Farbstoffmischung gefärbten Polyamidfasern.13. The method according to claim 12, for improving the thermal and / or photochemical stability of with acid or 1: 2 metal complex dyes or a dye mixture containing a red component dyed polyamide fibers. 14. Die gemäss dem Verfahren nach Anspruch 1 behandelten Färbungen auf Polyamidfasern.14. The dyeings treated according to the method of claim 1 on polyamide fibers.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2695416A1 (en) * 1992-09-08 1994-03-11 Ciba Geigy Ag A method of stabilizing dyes on polyamide fibers and dyes on polyamide fibers treated according to this process.
EP0621266A1 (en) * 1993-04-22 1994-10-26 Ciba-Geigy Ag Sterically hindered phenols and their use for the stabilisation of polyamide fibres
WO1999020686A2 (en) * 1997-10-20 1999-04-29 Uniroyal Chemical Company, Inc. Organic materials stabilized by compounds containing both amine and hindered phenol functionalities

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US6228157B1 (en) 1998-07-20 2001-05-08 Ronald S. Nohr Ink jet ink compositions
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US6297296B1 (en) 1999-05-19 2001-10-02 Kodak Polychrome Graphics Llc Latex complexes as stabilized colorant
US6368395B1 (en) 1999-05-24 2002-04-09 Kimberly-Clark Worldwide, Inc. Subphthalocyanine colorants, ink compositions, and method of making the same
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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH480402A (en) * 1967-09-20 1969-10-31 Geigy Ag J R Process for stabilizing heat- and / or oxidation-sensitive non-textile materials

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH480402A (en) * 1967-09-20 1969-10-31 Geigy Ag J R Process for stabilizing heat- and / or oxidation-sensitive non-textile materials
CH478947A (en) * 1967-09-20 1969-11-14 Geigy Ag J R Process for stabilizing heat- and / or oxidation-sensitive textile material
CH534136A (en) * 1967-09-20 1973-02-28 Ciba Geigy Ag Phenolic antioxidants for organic polymers containing

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2695416A1 (en) * 1992-09-08 1994-03-11 Ciba Geigy Ag A method of stabilizing dyes on polyamide fibers and dyes on polyamide fibers treated according to this process.
BE1006499A5 (en) * 1992-09-08 1994-09-13 Ciba Geigy Ag Stabilization process of dyes on polyamide and fiber dyes on fibre polyamide treated as the method.
CH688013GA3 (en) * 1992-09-08 1997-04-30 Ciba Geigy Ag Stabilization of dyes on polyamide fibers.
DE4330283B4 (en) * 1992-09-08 2004-08-19 Ciba Speciality Chemicals Holding Inc. Stabilization of dyeings on polyamide fibers
EP0621266A1 (en) * 1993-04-22 1994-10-26 Ciba-Geigy Ag Sterically hindered phenols and their use for the stabilisation of polyamide fibres
US5650509A (en) * 1993-04-22 1997-07-22 Ciba-Geigy Corporation Sterically hindered phenols
WO1999020686A2 (en) * 1997-10-20 1999-04-29 Uniroyal Chemical Company, Inc. Organic materials stabilized by compounds containing both amine and hindered phenol functionalities
WO1999020686A3 (en) * 1997-10-20 1999-09-30 Uniroyal Chem Co Inc Organic materials stabilized by compounds containing both amine and hindered phenol functionalities

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US5096456A (en) 1992-03-17

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