[go: up one dir, main page]
More Web Proxy on the site http://driver.im/

EP0438381B1 - Stabilization of dyes on polyamide fibres - Google Patents

Stabilization of dyes on polyamide fibres Download PDF

Info

Publication number
EP0438381B1
EP0438381B1 EP91810014A EP91810014A EP0438381B1 EP 0438381 B1 EP0438381 B1 EP 0438381B1 EP 91810014 A EP91810014 A EP 91810014A EP 91810014 A EP91810014 A EP 91810014A EP 0438381 B1 EP0438381 B1 EP 0438381B1
Authority
EP
European Patent Office
Prior art keywords
amino
formula
radical
use according
methyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP91810014A
Other languages
German (de)
French (fr)
Other versions
EP0438381A1 (en
Inventor
Gerhard Dr. Reinert
Francesco Dr. Fuso
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF Schweiz AG
Original Assignee
Ciba Geigy AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ciba Geigy AG filed Critical Ciba Geigy AG
Publication of EP0438381A1 publication Critical patent/EP0438381A1/en
Application granted granted Critical
Publication of EP0438381B1 publication Critical patent/EP0438381B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/02—Material containing basic nitrogen
    • D06P3/04—Material containing basic nitrogen containing amide groups
    • D06P3/24—Polyamides; Polyurethanes
    • 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

  • Dyes on polyamide fibers which 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. At least one m- Position on the hydroxyl group is unsubstituted, while the other may be substituted by lower alkyl groups, such as the methyl group.
  • 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-thiatrimethylene or the 2-oxapentamethylene radical.
  • 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 include the ß-hydroxyethyl, ß-methoxyethyl, ß-aminoethyl, ⁇ , ⁇ '-diethylamino-ethyl or the ⁇ -butylaminoethyl group.
  • Z in formula (1) means, for example, the residue of an unsubstituted or substituted by carboxyl groups lower alkane having at least two carbon atoms, the residue of an unsubstituted or by chlorine or bromine, C 1 -C 4 alkyl, C 1 -C 4 alkoxy , C1-C4-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.
  • 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 residue 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 alkox ycarbonylamino 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, C1-C4 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.
  • C 1 -C 4 -alkyl groups such as the methyl or ethyl group
  • C1-C4 Alkoxy groups such as the methoxy group
  • acylamino groups such as the acetyl or benzoylamino group
  • alkoxycarbonylamino groups such as the methoxy or ethoxycarbonylamino
  • the group Z can optionally be substituted by C1-C4-alkyl or alkoxy groups, such as the methyl or methoxy group.
  • the sulfo group W in formula (1) is preferably free, but can also be present 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)
  • 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.
  • Examples of starting products of formula (11) falling under formula (8) wherein A, X, x, R 2 , y and V have the meaning given above are: ⁇ - (4-hydroxy-3,5-di-tert-butyl-phenyl) propionic acid chloride, 4-hydroxy-3,5 -di-tert-butyl-phenyl-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-methyl-benzyl) thioglycolic acid chloride, 4-hydroxy-5 -tert.butylphenyl-acetyl chloride, ⁇ - (4-hydroxy-3,5-di-cyclohex
  • the compounds of 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, for example 1: 3 to 1: 100, preferably 1:10 to 1:40. It is convenient to work 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 done 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.
  • colorations which are produced by red dyes or by dye mixtures 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 wide variety of processing forms, e.g. as fiber, yarn, fabric, knitted fabric, fleece or pile material.
  • the use according to the invention is particularly suitable for dyeings on polyamide material which is exposed to light and / or heat and e.g. is available as carpets or upholstery.
  • the use is also suitable for the thermal stabilization of colored polyamide material provided for the so-called "molding" process.
  • This process is a shaping process that works briefly at high temperatures (e.g. bra production).
  • Example 1 2 samples of 10 g each of a PA-6 knitted fabric are dyed, for example in an @AHIBA dyeing machine at a liquor ratio of 1:30.
  • the liquor (1) receives no further addition, the liquor (2), however, 1% of the compound of the formula 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 lightfastness 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 convection oven for color stability.
  • compound (101) imparts both photochemical and thermal protection to the stain.
  • EXAMPLE 2 The procedure is as described in Example 1, but 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.
  • Example 4 2 samples of 10 g each of a PA-6 knitwear are dyed beige, for example in an @AHIBA dyeing machine at a liquor ratio of 1:30.
  • the liquor (1) receives no further addition, the liquor (2), however, 1% of the compound of the formula
  • the examination of the colors gave the following result:
  • Example 5 Five samples of 10 g 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 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).
  • 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.).
  • System BASF precision ironing press

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Coloring (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Anti-Oxidant Or Stabilizer Compositions (AREA)
  • Artificial Filaments (AREA)

Description

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 Polyamidfasern, die eine mit einem roten Farbstoff oder mit einer mindestens eine rote Komponente enthaltenden Farbstoffmischung erzeugte Färbung aufweisen.Dyes on polyamide fibers which 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 oder zumindest in grossem Masse beseitigt werden können.It has now been found that these disadvantages can be completely or at least largely eliminated by treating the dyed polyamide fibers with phenolic water-soluble antioxidants.

Die Erfindung betrifft daher die Verwendung einer Verbindung der Formel (1)

Figure imgb0001
in welcher

  • A den Rest eines sterisch gehinderten Phenols der Benzolreihe,
  • Y einen Rest der Formeln (2) oder (3)
    Figure imgb0002
    Figure imgb0003
    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 zur Verbesserung der thermischen und/oder photochemischen Stabilität von Farbungen auf Polyamidfasern.
The invention therefore relates to the use of a compound of the formula (1)
Figure imgb0001
 in which
  • A the residue of a sterically hindered phenol from the benzene series,
  • Y is a radical of the formulas (2) or (3)
    Figure imgb0002
    Figure imgb0003
     wherein
  • X and X 'independently of one another are 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 to improve the thermal and / or photochemical stability of dyeings on polyamide fibers.

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 der Formel (1) zu schützen. Ein Einfluß auf Farbungen von Polyamidfasern ist nicht genannt.From US-A-3 665 031 it is known to use undyed polymers such as e.g. To protect polyamides against the influence of heat and / or oxygen (air oxidation) with the help of water-soluble phenolic antioxidants of the formula (1). An influence on the coloring of polyamide fibers is not mentioned.

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- oder Aralkylgruppen 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. At least one m- Position on the hydroxyl group is unsubstituted, while the other may be substituted by lower alkyl groups, such as the methyl group.

Aus Gründen der leichten Zugänglichkeit und ihrer günstigen Stabilisierungswirkung sind Verbindungen der Formel (1) besonders bevorzugt, in denen A einen Rest der Formel (4)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 imgb0004
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.
Figure imgb0004
 in which 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 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-Thiatrimethylen- oder der 2-Oxapentamethylenrest.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-thiatrimethylene 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 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 ß-Hydroxyäthyl-, ß-Methoxyäthyl-, ß-Aminoäthyl-, β,β'-Diäthylamino- äthyl- 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 include the ß-hydroxyethyl, ß-methoxyethyl, ß-aminoethyl, β, β'-diethylamino-ethyl 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 imgb0005
worin

  • R4 Wasserstoff oder C1-C4-Alkyl und
  • X" C1-C4-Alkylen bedeuten, darstellt.
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 imgb0005
 wherein
  • R 4 is hydrogen or C 1 -C 4 alkyl and
  • X "represents C 1 -C 4 alkylene.

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, C1-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.Z in formula (1) means, for example, the residue of an unsubstituted or substituted by carboxyl groups lower alkane having at least two carbon atoms, the residue of an unsubstituted or by chlorine or bromine, C 1 -C 4 alkyl, C 1 -C 4 alkoxy , C1-C4-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 residue 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 alkox ycarbonylamino 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, C1-C4 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 Substituenten des Benzolrestes Z oder seiner arylgruppenhaltigen Substituenten gleichzeitig vorhanden sein.Optionally, several, identical or different of the above-mentioned 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 C1-C4-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)The sulfo group W in formula (1) is preferably free, but can also be present 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)

Figure imgb0006
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.
Figure imgb0006
 corresponds to what
  • R ', R ", R"', R "" independently of one another are hydrogen, a C1-C4-alkyl or β-hydroxy-C 1 -C 4 -alkyl radical or a cyclohexyl radical, at least two of these radicals being together a carbo- or heterocyclic ring system can form.

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 imgb0007

  • 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 imgb0007
  • Mean in this formula
  • R and R 1 independently of one another are methyl or tert-butyl,
  • R 4 is hydrogen or C 1 -C 4 alkyl,
  • X "C1-C4 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 hergestellt werden, z.B. durch Umsetzung von n Mol einer Verbindung der Formel (8)

Figure imgb0008

  • mit einem Mol einer Verbindung der Formel (9)
    Figure imgb0009
    in welchen Formeln eines von P und Q die Gruppe -NH-R3, das andere die Gruppe
    Figure imgb0010
    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 Bedeutung haben, unter Abspaltung von HV. Beispiele für unter Formel (8) fallende, zur Herstellung der erfindungsgemässen wasserlöslichen Verbindungen geeignete Ausgangsprodukte der Formel (10)
    Figure imgb0011
    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-Hydroxy-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-tert.butyl-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.
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)
Figure imgb0008
  • with one mole of a compound of formula (9)
    Figure imgb0009
     in which formulas one of P and Q the group -NH-R 3 , the other the group
    Figure imgb0010
     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 the elimination of HV. 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
    Figure imgb0011
     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-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- tert-butyl-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 imgb0012
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.butyl-phenyl-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-methyl-benzyl)-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-di-isopropyl-phenyl-acetylchlorid, S-(4-Hydroxy-3,5-di-isopropyl-benzyl)-thioglykolsäurechlorid, β-[ω-(4-Hydroxy-3,5-di-tert.butyl-phenyl)-propyloxy]-propionsäurechlorid, [w-(4-Hydroxy-3,5-di-tert.butyl-phenyl)-propy- loxy]-acetylchlorid, β-Methyl-β-(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 imgb0012
 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-butyl-phenyl-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-methyl-benzyl) thioglycolic acid chloride, 4-hydroxy-5 -tert.butylphenyl-acetyl chloride, β- (4-hydroxy-3,5-di-cyclohexyl-phenyl) -propionic acid bromide, (4-hydroxy-3,5-di-cyclohexyl-phenyl) -acetyl chloride, β- (4- Hydroxy-3-benzyl-5-methylphenyl) propionic acid chloride, (4-hydroxy-3-benzyl-5-methylphenyl) acetyl chloride, 4-hydroxy-3,5-di-isopropylphenyl acetyl chloride, p - (4-Hydroxy-3,5-di-isopropyl-benzyl) thioglycolic acid chloride, β- [ω- (4-hydroxy-3,5-di-tert-butylphenyl) propyloxy] propionic acid chloride, [w- (4-hydroxy-3,5-di-tert-butylphenyl) propyloxy] acetyl chloride, β-methyl-β- (4-hydroxy-3,5-d i-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 imgb0013
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-Chlor-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-5-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-sulfonsäure, 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-hydroxy-benzol-1,5-disulfonsäure, 2-Amino-5-hydroxy-naphthalin-7-sulfonsäure, 2-Acetamido-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'-dichlor-diphenylether-2'-sulfonsäure, 2-Amino-4'-methyl-diphenylsulfon-4-sulfosäure, 2,5-Diamino-2'-methyl-diphenylether-4-sulfonsäure, Benzidin-2,2'-disulfonsäure, 3,3'-Dimethyl-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, w-Amino-propan-sulfonsäure, m-Amino-butansulfonsäure, m-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 imgb0013
 where 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-5-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-sulfonic 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-hydroxy-benzene-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-chloro-benzenesulfonic acid, 4-amino-3-carboxy-benzenesulfonic acid, 5-amino-3-sulfo-salicylic acid, 2- (ß-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-diphenyl ether-4-sulfonic acid, 2-amino-2'-methyl-diphenyl ether-4-sulfonic acid, 2-amino-4-chloro 4'-amyl-diphenylether-5-sulfonic acid, 2-amino-4,4'-dichloro-diphenylether-2'-sulfonic acid, 2-amino-4'-methyl-diphenylsulfone-4-sulfonic acid, 2,5-diamino- 2'-methyl-diphenyl ether-4-sulfonic acid, benzidine-2,2'-disulfonic acid, 3,3'-dimethyl-benzidine-6-sulfonic acid, benzidine-2-sulfonic acid, 2'-amino-diphenyl sulfone-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-sulfonic acid, 2-aminoethanesulfonic acid, N-methyl-, -ethyl-, - Propyl, iso propyl, amyl, hexyl,
  • -Cyclohexyl-, -Octyl-, -Phenyl-, -Dodecyl- or -Stearyl-2-amino-ethanesulfonic acid, 2-methyl-2-amino-ethanesulfonic acid, w-amino-propane-sulfonic acid, m-amino-butanesulfonic acid, m -Amino-pentanesulfonic acid, N-methyl-y-aminopropanesulfonic 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 imgb0014
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-benzoylchlorid, 3-Sulfophthaloylchlorid, 3,4-Disulfo-phthaloylchlorid, 4-Sulfo-phenylacetylchlorid, β-(4-Sulfo-phenyl)-propionsäure- chlorid, 3-Sulfo-6-methyl-benzoylchlorid.
Examples of starting products of formula (13) falling under formula (9)
Figure imgb0014
 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-phenylacetyl chloride, β- (4-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 imgb0015
in Betracht, worin R, R1, R4 X, Z, M, m und n die nachstehenden Bedeutungen annehmen.
Figure imgb0016
Figure imgb0017
Figure imgb0018
Figure imgb0019
Figure imgb0020
Figure imgb0021
Figure imgb0022
Figure imgb0023
 Compounds of the formula (1) which can be used according to the invention are, for example, compounds of the formula
Figure imgb0015
 into consideration, wherein R, R 1 , R 4 X, Z, M, m and n assume the meanings below.
Figure imgb0016
Figure imgb0017
Figure imgb0018
Figure imgb0019
Figure imgb0020
Figure imgb0021
Figure imgb0022
Figure imgb0023

sowie die Verbindungen der Formeln

Figure imgb0024
und
Figure imgb0025
Die Verbindungen der Formel (1) werden aus wässrigem Bad appliziert, das die Verbindungen in einer Menge von 0,01 bis 10, vorzugsweise 0,25 bis 3 Gew.-% enthält.as well as the connections of the formulas
Figure imgb0024
 and
Figure imgb0025
 The compounds of 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 arbeitet zweckmässig bei einer Temperatur von 30 bis 130 ° C, vorzugsweise 50 bis 95 ° C.In the exhaust process, the liquor ratio can be selected within a wide range, for example 1: 3 to 1: 100, preferably 1:10 to 1:40. It is convenient to work 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 done 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 Beschränkung 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 not limited to, are colorations which are produced by red dyes or by dye mixtures 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 Polyamidmaterial in den verschiedensten Verarbeitungsformen vorliegen, wie z.B. als Faser, Garn, Gewebe, Gewirke, Vlies oder Flormaterial.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. In principle, the pure or mixed polyamide material can be in a wide variety of processing forms, e.g. as fiber, yarn, fabric, knitted fabric, fleece or pile material.

Die erfindungsgemäße Verwendung eignet sich vor allem Färbungen auf Polyamidmaterial, das Licht und/oder Hitze ausgesetzt wird und z.B. als Teppiche oder Autopolsterstoff vorliegt.The use according to the invention is particularly suitable for dyeings on polyamide material which is exposed to light and / or heat and e.g. is available as carpets or upholstery.

Die Verwendung 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 use is also suitable for the thermal stabilization of colored polyamide material provided for the so-called "molding" process. 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 percentages 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/I Mononatriumphosphat und 1,5 g/I Dinatriumphosphat (= pH 7) und 0,2 % des Farbstoffes der Formel

Figure imgb0026
gelöst enthalten. Die Flotte (1) erhält keinen weiteren Zusatz, die Flotte (2) dagegen 1 % der Verbindung der Formel
Figure imgb0027
Man beginnt bei 30 ° C mit dem Färben, verweilt 10 Minuten bei dieser Temperatur und erhitzt mit 2
Figure imgb0028
 ° /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.Example 1: 2 samples of 10 g each of a PA-6 knitted fabric are dyed, for example in an @AHIBA dyeing machine at a liquor ratio of 1:30. For this purpose, 2 liquors are prepared, the 0.5 g / I monosodium phosphate and 1.5 g / I disodium phosphate (= pH 7) and 0.2% of the dye of the formula
Figure imgb0026
 solved included. The liquor (1) receives no further addition, the liquor (2), however, 1% of the compound of the formula
Figure imgb0027
 Dyeing begins at 30 ° C., the mixture is held at this temperature for 10 minutes and heated at 2
Figure imgb0028
 ° / 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 lightfastness 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 convection oven for color stability.

Ergebnisse:Results:

Figure imgb0029
Figure imgb0029

Aus diesen Ergebnissen ist ersichtlich, dass die Verbindung (101) der Färbung sowohl einen photochemischen als auch thermischen Schutz verleiht.It can be seen from these results 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 imgb0030
ein.EXAMPLE 2 The procedure is as described in Example 1, but 0.4% of the dye of the formula is used instead of the dye (100)
Figure imgb0030
 a.

Die Prüfung erbrachte folgendes Ergebnis:

Figure imgb0031
The test gave the following result:
Figure imgb0031

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 Formel

Figure imgb0032
EXAMPLE 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 imgb0032

Die Prüfung der Lichtechtheiten und der Hitzebeständigkeit erbrachte folgende Ergebnisse:

Figure imgb0033
The test of light fastness and heat resistance gave the following results:
Figure imgb0033

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 Flotten bereitet, die 0,5 g/I Mononatriumphosphat und 1,5 g/I 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 Formel

Figure imgb0034
0,08 % des Farbstoffes der Formel
Figure imgb0035
gelöst enthalten. Die Flotte (1) erhält keinen weiteren Zusatz, die Flotte (2) dagegen 1 % der Verbindung der Formel
Figure imgb0036
Die Prüfung der Färbungen erbrachte folgendes Resultat:
Figure imgb0037
 Example 4: 2 samples of 10 g each of a PA-6 knitwear are dyed beige, for example in an @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 / 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 imgb0034
 0.08% of the dye of the formula
Figure imgb0035
 solved included. The liquor (1) receives no further addition, the liquor (2), however, 1% of the compound of the formula
Figure imgb0036
 The examination of the colors gave the following result:
Figure imgb0037

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, above all brings about a heat stabilization of the red component (100).

Beispiel 5: Fünf Muster von je 10 g einer PA-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 imgb0038
und 12 Teilen des Farbstoffes der Formel
Figure imgb0039
wie in Beispiel 1 vermerkt, gefärbt.Example 5: Five samples of 10 g 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 imgb0038
 and 12 parts of the dye of the formula
Figure imgb0039
 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 imgb0040
Figure imgb0041
Figure imgb0042
Figure imgb0043
Figure imgb0044
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 imgb0045
 Dye bath 1 contains no further additives, while baths 2-6 each contain 1% of the compounds of formulas (502) - (506) in dissolved form.
Figure imgb0040
Figure imgb0041
Figure imgb0042
Figure imgb0043
Figure imgb0044
 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 imgb0045

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.It can be seen from the results given that the gray colorings are significantly improved in terms of their photochemical and thermal stability by the compounds (502-506) used in the coloring.

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.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.

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 Büstenhälterherstellung 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 imgb0046
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 imgb0046

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 (13)

1. The use of a compound of formula
Figure imgb0057
wherein
A is the radical of a sterically hindered phenol of the benzene series
Y is a radical of formula (2) or (3)
Figure imgb0058
Figure imgb0059
wherein
X and X' are each independently of the other alkylene, oxaalkylene or thiaalkylene,
R2 and R3 are each independently of the other hydrogen or an unsubstituted or substituted alkyl group, and
x, x' and y are each independently of the other 0 or 1,
Z is an aliphatic or a carbocyclic aromatic radical, which last-mentioned radical contains not more than
two mono- or bicyclic nuclei,
W is the sulfo group, and
m and n are each independently of the other 1 or 2, and the water-soluble salts thereof, for improving the thermal and/or photochemical stability of dyeings on polyamide fibres.
2. The use according to claim 1, which comprises the use of a compound of formula (1) wherein A is a monohydroxyphenyl radical which is substituted in at least one ortho-position to the hydroxyl group by alkyl of 1 to 12 carbon atoms, cycloalkyl of 6 to 10 carbon atoms or aralkyl of 7 to 10 carbon atoms, and which may carry additional substituents.
3. The use according to one of claims 1 and 2, which comprises the use of a compound of formula (1) wherein A is a radical of formula (4)
Figure imgb0060
 wherein
R and R1 are each independently of the other hydrogen, methyl or tert-butyl, and the sum of the carbon atoms of R and R1 is not less than 2.
4. The use according to any one of claims 1 to 3, wherein X and X' in the compounds of formulae (2) and (3) are straight-chain or branched alkylene of 1 to 8 carbon atoms.
5. The use according to any one of claims 1 to 4, wherein R2 and R3 in the compounds of formulae (2) and (3) are straight-chain or branched C1-C8alkyl.
6. The use according to any one of claims 1 to 4, wherein R2 and R3 in the compounds of formulae (2) and (3) are hydroxyalkyl, alkoxyalkyl, aminoalkyl, alkylaminoalkyl or dialkylaminoalkyl, each containing a total of 2 to 10 carbon atoms, or are phenyl.
7. The use according to claim 1, wherein Y in formula (1) is a radical of formula (5)
Figure imgb0061
wherein
R4 is hydrogen or C1-C4alkyl and
X" is C1-C4alkylene.
8. The use according to any one of claims 1 to 7, wherein Z in formula (1) is the radical of an unsubstituted or carboxy-substituted alkane of at least 2 carbon atoms, the radical of an unsubstituted benzene nucleus or of a benzene nucleus which is substituted by chlorine or bromine, Ci-C4.alkyl, Ci-C4alkoxy, C1-C4alkoxycarbonylamino, hydroxy, carboxy, phenylethyl, styryl, phenyl, phenoxy, phenylthio, phenylsulfonyl or acylamino, and the group W may be attached direct to said benzene nucleus or to a monocyclic aryl radical of one of the substituents thereof, or is a naphthalene or tetralin radical.
9. The use according to claim 1, which comprises the use of a compound of formula (7)
Figure imgb0062
wherein
R and R1 are each independently of the other methyl or tert-butyl,
R4 is hydrogen or C,-C4alkyl,
X" is C1-C4alkylene,
Z is ethylene, a divalent or trivalent radical of benzene or naphthalene or is a divalent radical of diphenyl ether,
W is the sulfo group, and n is 1 or 2.
10. The use according to claim 9, which comprises the use of compounds of formula (7) wherein R and R1 are tert-butyl, X" is methylene or ethylene, R4 is hydrogen, methyl or ethyl, and Z is ethylene, o-, m- or p-phenylene, 1,4-naphthylene, 1,8-naphthylene, 2-methoxy-1,6-naphthylene, 1,5-naphthylene, 2,5-naphthylene, 2,6-naphthylene, 1,4,6-naphthalenetriyl or the radicals
Figure imgb0063
Figure imgb0064
Figure imgb0065
Figure imgb0066
and wherein the sulfo group W may also be in the form of its alkali metal salts or ammonium salts.
11. The use according to any one of claims 1 to 10, wherein the compound of formula (1) goes on to the fibres by an exhaust or continuous process.
12. The use according to any one of claims 1 to 11 for improving the thermal and/or photochemical stability of polyamide fibres dyed with acid or metal complex dyes.
13. The use according to claim 12 for improving the thermal and/or photochemical stability of polyamide fibres dyed with red acid or 1:2 metal complex dyes or with a mixture of dyes comprising a red component.
EP91810014A 1990-01-19 1991-01-10 Stabilization of dyes on polyamide fibres Expired - Lifetime EP0438381B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH17390 1990-01-19
CH173/90 1990-01-19

Publications (2)

Publication Number Publication Date
EP0438381A1 EP0438381A1 (en) 1991-07-24
EP0438381B1 true EP0438381B1 (en) 1995-04-05

Family

ID=4180929

Family Applications (1)

Application Number Title Priority Date Filing Date
EP91810014A Expired - Lifetime EP0438381B1 (en) 1990-01-19 1991-01-10 Stabilization of dyes on polyamide fibres

Country Status (5)

Country Link
US (1) US5096456A (en)
EP (1) EP0438381B1 (en)
JP (1) JP3051461B2 (en)
CA (1) CA2034393C (en)
DE (1) DE59105066D1 (en)

Families Citing this family (39)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0459950B1 (en) * 1990-05-31 1997-03-12 Ciba SC Holding AG Stabilisation of dyes on polyamide fibres
ATE130882T1 (en) * 1990-07-12 1995-12-15 Ciba Geigy Ag METHOD FOR THE PHOTOCHEMICAL AND THERMAL STABILIZATION OF POLYAMIDE FIBER MATERIALS.
CH688013B5 (en) * 1992-09-08 1997-10-31 Ciba Geigy Ag 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
US6017471A (en) 1993-08-05 2000-01-25 Kimberly-Clark Worldwide, Inc. Colorants and colorant modifiers
US6017661A (en) 1994-11-09 2000-01-25 Kimberly-Clark Corporation Temporary marking using photoerasable colorants
US5733693A (en) 1993-08-05 1998-03-31 Kimberly-Clark Worldwide, Inc. Method for improving the readability of data processing forms
US5645964A (en) 1993-08-05 1997-07-08 Kimberly-Clark Corporation Digital information recording media and method of using same
US5681380A (en) 1995-06-05 1997-10-28 Kimberly-Clark Worldwide, Inc. Ink for ink jet printers
US5721287A (en) 1993-08-05 1998-02-24 Kimberly-Clark Worldwide, Inc. Method of mutating a colorant by irradiation
US5865471A (en) 1993-08-05 1999-02-02 Kimberly-Clark Worldwide, Inc. Photo-erasable data processing forms
US6211383B1 (en) 1993-08-05 2001-04-03 Kimberly-Clark Worldwide, Inc. Nohr-McDonald elimination reaction
US5773182A (en) 1993-08-05 1998-06-30 Kimberly-Clark Worldwide, Inc. Method of light stabilizing a colorant
US5700850A (en) 1993-08-05 1997-12-23 Kimberly-Clark Worldwide Colorant compositions and colorant stabilizers
US6071979A (en) 1994-06-30 2000-06-06 Kimberly-Clark Worldwide, Inc. Photoreactor composition method of generating a reactive species and applications therefor
US6242057B1 (en) 1994-06-30 2001-06-05 Kimberly-Clark Worldwide, Inc. Photoreactor composition and applications therefor
US5685754A (en) 1994-06-30 1997-11-11 Kimberly-Clark Corporation Method of generating a reactive species and polymer coating applications therefor
US6008268A (en) 1994-10-21 1999-12-28 Kimberly-Clark Worldwide, Inc. Photoreactor composition, method of generating a reactive species, and applications therefor
US5786132A (en) 1995-06-05 1998-07-28 Kimberly-Clark Corporation Pre-dyes, mutable dye compositions, and methods of developing a color
EP0830638B1 (en) 1995-06-05 2000-08-23 Kimberly-Clark Worldwide, Inc. Pre-dyes and compositions comprising them
CA2221565A1 (en) 1995-06-28 1997-01-16 Kimberly-Clark Worldwide, Inc. Novel colorants and colorant modifiers
US5782963A (en) 1996-03-29 1998-07-21 Kimberly-Clark Worldwide, Inc. Colorant stabilizers
US6099628A (en) 1996-03-29 2000-08-08 Kimberly-Clark Worldwide, Inc. Colorant stabilizers
SK102397A3 (en) 1995-11-28 1998-02-04 Kimberly Clark Co Colorant stabilizers
US5855655A (en) 1996-03-29 1999-01-05 Kimberly-Clark Worldwide, Inc. Colorant stabilizers
US5891229A (en) 1996-03-29 1999-04-06 Kimberly-Clark Worldwide, Inc. Colorant stabilizers
US6524379B2 (en) 1997-08-15 2003-02-25 Kimberly-Clark Worldwide, Inc. Colorants, colorant stabilizers, ink compositions, and improved methods of making the same
US5834544A (en) * 1997-10-20 1998-11-10 Uniroyal Chemical Company, Inc. Organic materials stabilized by compounds containing both amine and hindered phenol functional functionalities
JP2002517523A (en) 1998-06-03 2002-06-18 キンバリー クラーク ワールドワイド インコーポレイテッド Novel photoinitiator and its use
BR9906580A (en) 1998-06-03 2000-09-26 Kimberly Clark Co Neonanoplast and microemulsion technology for inks and inkjet printing
US6228157B1 (en) 1998-07-20 2001-05-08 Ronald S. Nohr Ink jet ink compositions
CA2353685A1 (en) 1998-09-28 2000-04-06 Kimberly-Clark Worldwide, Inc. Chelates comprising chinoid groups as photoinitiators
ATE238393T1 (en) 1999-01-19 2003-05-15 Kimberly Clark Co DYES, DYE STABILIZERS, INK COMPOSITIONS AND METHOD FOR THE PRODUCTION THEREOF
US6331056B1 (en) 1999-02-25 2001-12-18 Kimberly-Clark Worldwide, Inc. Printing apparatus and applications therefor
US6294698B1 (en) 1999-04-16 2001-09-25 Kimberly-Clark Worldwide, Inc. Photoinitiators and applications therefor
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
JP2006144148A (en) * 2004-11-17 2006-06-08 Fukoku Kogyo Kk Method for accelerating separation of impurity in waste paper pulp
JP6421132B2 (en) * 2016-01-12 2018-11-07 大日精化工業株式会社 Pigment dispersant, pigment composition, and pigment colorant

Family Cites Families (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

Also Published As

Publication number Publication date
CA2034393C (en) 2002-01-08
JPH04214483A (en) 1992-08-05
CA2034393A1 (en) 1991-07-20
EP0438381A1 (en) 1991-07-24
US5096456A (en) 1992-03-17
JP3051461B2 (en) 2000-06-12
DE59105066D1 (en) 1995-05-11

Similar Documents

Publication Publication Date Title
EP0438381B1 (en) Stabilization of dyes on polyamide fibres
EP0459950B1 (en) Stabilisation of dyes on polyamide fibres
EP0280653B1 (en) Process for improving the photochemical stability of dyeings on fibrous polyester materials
EP0200843B1 (en) Process for the photochemical stabilisation of undyed and dyed polyamide fibrous material and its mixtures
EP0255481A1 (en) Process for the photochemical stabilisation of a fibrous polyamide material and its mixtures with other fibres
EP0475905A1 (en) Process for the photochemical stabilisation of wool
DE4209261B4 (en) Anionic disazo compounds
EP0245204A1 (en) Process for the photochemical stabilization of undyed and dyed fibrous polyamide material and its mixture with other fibres
EP0511166A1 (en) Process for photochemical and thermic stabilization of polyamide fibre material with a fiberaffinitive copper complex and an oxalicacid diarylamide
EP0613976A1 (en) Agent for textile wet finishing processes
DE4330283B4 (en) Stabilization of dyeings on polyamide fibers
CH480402A (en) Process for stabilizing heat- and / or oxidation-sensitive non-textile materials
EP0527704A2 (en) Dyestuffs, process for their preparation and the use thereof
EP0621266A1 (en) Sterically hindered phenols and their use for the stabilisation of polyamide fibres
EP0475907B1 (en) Process for the production of good quality moulded articles
EP0651028A1 (en) Process of trichromic dyeing or printing
EP0618205A1 (en) Water soluble triazine derivatives for the photochemical and thermal stabilisation of polyamide fiber materials
DE1244314B (en) Process for the preparation of water-insoluble disazo dyes
DE2056009C (en) Process for uniform and streak-free dyeing of synthetic polyamide fiber material
US3495929A (en) Method for improving the fastness to gas fading of dyed material
AT233685B (en) Process for the production of new metal-containing, water-insoluble azo dyes
AT167095B (en) Process for the production of colorations of acidic dyeable complex chromium compounds and preparations for the implementation thereof.
DE2429524C2 (en) Chromium-containing azo dyes, their production and use
CH271896A (en) Dye preparation.
CH591544A5 (en) Red azo dyes contg sulphonic acid gps - for wet-fast dyeing of polyamides, paper, leather, cellulosics etc

Legal Events

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

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19910114

AK Designated contracting states

Kind code of ref document: A1

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

17Q First examination report despatched

Effective date: 19930928

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

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

ET Fr: translation filed
REF Corresponds to:

Ref document number: 59105066

Country of ref document: DE

Date of ref document: 19950511

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

Effective date: 19950615

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

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

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

26N No opposition filed
REG Reference to a national code

Ref country code: CH

Ref legal event code: PUE

Owner name: CIBA-GEIGY AG TRANSFER- CIBA SC HOLDING AG

BECN Be: change of holder's name

Effective date: 19961129

NLS Nl: assignments of ep-patents

Owner name: CIBA SC HOLDING AG

REG Reference to a national code

Ref country code: FR

Ref legal event code: TP

REG Reference to a national code

Ref country code: CH

Ref legal event code: PFA

Free format text: CIBA SC HOLDING AG TRANSFER- CIBA SPECIALTY CHEMICALS HOLDING INC.

REG Reference to a national code

Ref country code: GB

Ref legal event code: 732E

NLT1 Nl: modifications of names registered in virtue of documents presented to the patent office pursuant to art. 16 a, paragraph 1

Owner name: CIBA SPECIALTY CHEMICALS HOLDING INC.

REG Reference to a national code

Ref country code: FR

Ref legal event code: CD

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

Ref country code: CH

Payment date: 19991129

Year of fee payment: 10

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

Ref country code: NL

Payment date: 19991213

Year of fee payment: 10

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

Ref country code: SE

Payment date: 19991215

Year of fee payment: 10

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

Ref country code: SE

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

Effective date: 20010111

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

Ref country code: LI

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

Effective date: 20010131

Ref country code: CH

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

Effective date: 20010131

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

Ref country code: NL

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

Effective date: 20010801

EUG Se: european patent has lapsed

Ref document number: 91810014.0

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 20010801

REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

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

Ref country code: GB

Payment date: 20030108

Year of fee payment: 13

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

Ref country code: BE

Payment date: 20030402

Year of fee payment: 13

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

Ref country code: GB

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

Effective date: 20040110

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

Ref country code: BE

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

Effective date: 20040131

BERE Be: lapsed

Owner name: *CIBA SPECIALTY CHEMICALS HOLDING INC.

Effective date: 20040131

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

Effective date: 20040110

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

Ref country code: DE

Payment date: 20050106

Year of fee payment: 15

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

Ref country code: IT

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

Effective date: 20050110

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

Ref country code: DE

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

Effective date: 20060801

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

Ref country code: FR

Payment date: 20070111

Year of fee payment: 17

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20081029

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

Ref country code: FR

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

Effective date: 20080131