EP0459950A1 - Stabilisation of dyes on polyamide fibres - Google Patents

Abstract

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, und (B) einen UV-Absorber enthält.Process for improving the thermal and / or photochemical stability of undyed and dyed polyamide fibers by treatment with an aqueous bath agent which (A) is 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)

wherein
X and X ′ independently of one another alkylene, oxaalkylene or thiaalkylene,
R₂ and R₃ 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 are independently 1 or 2, and their water-soluble salts, and (B) contains a UV absorber.

Description

The present invention relates to a method for improving the thematic and / or photochemical stability of undyed and dyed polyamide fibers and the polyamide fiber material treated therewith.

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. However, this protection does not meet today's requirements.

It has now been found that undyed and dyed polyamide fibers can be better protected by treatment with phenolic water-soluble antioxidants and UV absorbers.

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, und
(B) einen UV-Absorber enthält.The invention therefore relates to a method for improving the thermal and / or photochemical stability of undyed and dyed polyamide fibers, which is characterized in that the fibers are treated with an aqueous bath agent which
(A) a water-soluble compound of the formula (1)

(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)

wherein
X and X ′ independently of one another are alkylene, oxaalkylene or thiaalkylene,
R₂ and R₃ 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 are independently 1 or 2, and their water-soluble salts, and
(B) contains a UV absorber.

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. Alpha-branched alkyl groups are preferred. 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 α-methyl and α, α-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. are. Furthermore, at least one m position to the hydroxyl group is advantageously unsubstituted, while the other can be substituted by lower alkyl groups, such as the methyl group.

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.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

in the
R and R₁ independently represent hydrogen, methyl or tert-butyl and the sum of the carbon atoms of R and R₁ 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.

Particularly preferred are compounds in which in the radicals X and X'not two heteroatoms are saturated to the same, i.e. tetrahedral carbon atom are bound.

R₂ or R₃ 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.

As a substituted alkyl group, R₂ or R₃ 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 this are the β-hydroxyethyl, β-methoxyethyl, β-aminoethyl, β, β'-diethylaminoethyl or the β-butylaminoethyl group.

R₂ or R₃ can also represent an aryl group, preferably the phenyl group.

Compounds in which y in formulas (2) and (3) means zero generally have a substantially better stabilizing action than compounds in which y means one.

worin
R₄ Wasserstoff oder C₁-C₄-Alkyl und
X′′ C₁-C₄-Alkylen bedeuten, darstellt.Compounds of the formula (1) in which Y is a radical of the formula (5) are particularly preferred

wherein
R₄ is hydrogen or C₁-C₄ alkyl and
X '' is C₁-C₄ alkylene.

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, C₁-C₄-alkyl, C₁C₄-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 radical.

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.

As a benzene radical, Z in formula (1) can be further substituted. For example, it may have straight-chain or branched C₁-C₄ alkyl radicals, for example substituted by the methyl, ethyl or iso-propyl group; the methyl group is preferred. C₁-C₄ 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 residue by an acylamino group, its acyl residue is derived in particular from a C₂-C₄ aliphatic or a monocarbocyclic aromatic carboxylic acid. Examples are the rest of the acetic, propionic, β-methoxypropionic, benzoic, aminobenzoic or methylbenzoic acid. Examples of C₁-C₄ alkoxycarbonylamino groups as substituents of a benzene radical Z are the methoxy, ethoxy or butoxycarbonylamino radical.

If the group Z contains phenylethyl, styryl, phenyl, phenoxy, phenylthio or phenylsulfonyl groups as substituents, these can optionally be substituted by chlorine or bromine, C₁-C₄-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.

Optionally, several, identical or different of the above-mentioned substituents of the benzene radical Z or its aryl group-containing substituents can be present simultaneously.

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.

In general, compounds of the formula (1) in which the radical Z contains hydroxyl, amino, acylamino, alkoxycarbonylamino or styryl substituents show more discoloration on exposure than compounds in which Z is free of substituents or otherwise substituted.

For economic reasons, compounds in which Z is the ethylene radical, a phenylene, tolylene, chlorophenylene or naphthylene radical or a divalent radical of diphenyl ether, a methyl or a chlorodiphenyl ether, or, in certain applications, compounds in which Z is a trivalent radical are particularly preferred Rest of the benzene or naphthalene means. Compounds in which Z represents a phenyl or diphenyl ether radical show particularly good lightfastness, while compounds in which Z represents a naphthyl or phenylethylphenyl radical have excellent wash fastness properties.

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 free, but can also preferably be present in the form of its alkali metal salts, 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 as the ammonium salt one organic nitrogen base is present, the cation of the formula (6)

corresponds to what
R ′, R ′ ′, R ′ ′ ′, R ′ ′ ′ ′ independently of one another are hydrogen, a C₁-C₄-alkyl or β-hydroxy-C₁-C₄-alkyl radical or a cyclohexyl radical, at least two of these radicals being together can form carbocyclic or heterocyclic ring system.

Examples of organic nitrogen bases which can form such ammonium salts with group W are: trimethylamine, triethylamine, tryethanolamine, diethanolamine, ethanolamine, cyclohexylamine, dicyclohexylamine, hexamethyleneimine or morpholine.

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

Mean in this formula
R and R₁ are independently methyl or tert-butyl,
R₄ is hydrogen or C₁-C₄ 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.

The group W can be present in these compounds freely or in the form of the salts defined above.

Among the compounds of formula (7) those with R = R₁ = methyl are particularly advantageous economically, while those with R = methyl and R₁ = tert-butyl and particularly those with R = R₁ = tert-butyl have excellent alkali resistance.

As component (B), all those UV absorbers can be named, for example, which e.g. in U.S.-A-2,777,828: 2,853,521; 3,259,627; 3,293,247; 3 382183; 3 403183; 3,423,360; 4127 586; 4,230,867; 4,511,596 and 4,698,064.

However, UV absorbers made water-soluble are preferred. Such are e.g. in U.S.-A-4,141,903, 4,230,867, 4,698,064 and 4,770,667.

worin
R₁ Wasserstoff, Hydroxy, C₁-C₄-Alkoxy oder Phenoxy,
R₂ Wasserstoff, Halogen, C₁-C₄-Alkyl oder Sulfo,
R₃ Wasserstoff, Hydroxy oder C₁-C₄-Alkoxy und
R₄ Wasserstoff, Hydroxy oder Carboxy bedeuten,
b) 2-(2′-Hydroxyphenyl)-benzotriazole der Formel (9)

worin
R₁ Wasserstoff, Chlor, Sulfo, C₁-C₁₂-Alkyl, C₅-C₆-Cycloalkyl, (C₁-C₈-Alkyl)-phenyl,
C₇-C₉-Phenylalkyl oder sulfoniertes C₇-C₉-Phenylalkyl,
R₂ Wasserstoff, Chlor, C₁-C₄-Alkyl, C₁-C₄-Alkoxy, Hydroxy oder Sulfo,
R₃ C₁-C₁₂-Alkyl, Chlor, Sulfo, C₁-C₄-Alkoxy, Phenyl, (C₁-C₈-Alkyl)-phenyl,
C₅-C₆-Cycloalkyl, C₂-C₉-Akoxycarbonyl, Carboxyethyl, C₇-C₉-Phenylalkyl oder sulfoniertes C₇-C₉-Phenylalkyl,
R₄ Wasserstoff, Chlor, C₁-C₄-Alkyl, C₁-C₄-Alkoxy, C₂-C₉-Alkoxycarbonyl, Carboxy oder
Sulfo und
R₅ Wasserstoff oder Chlor bedeuten,
c) 2-(2′-Hydroxyphenyl)-s-triazine der Formel ( 10)

worin R Wasserstoff, Halogen, C₁-C₄Alkyl oder Sulfo,
R₁ Wasserstoff, C₁-C₄-Alkyl, C₁-C₄-Alkoxy oder Hydroxy,
R₂ Wasserstoff oder Sulfo und R₃ und R₄ unabhängig voneinander C₁-C₄-Akyl, C₁-C₄-Alkoxy, C₅-C₆-Cycloalkyl, Phenyl oder durch C₁-C₄-Alkyl und/oder Hydroxy substituiertes Phenyl bedeuten, und
d) s-Triazinverbindungen der Formel (11)

worin mindestens einer der Substituenten R₁, R₂ und R₃ ein Rest der Formel

ist, worin A C₃-C₄-Alkylen oder 2-Hydroxytrimethylen und M Natrium, Kalium, Calcium, Magnesium, Ammonium oder Tetra-C₁-C₄-alkylammonium und m 1 oder 2 bedeuten, und der übrige Substituent bzw. die übrigen Substituenten unabhängig voneinander C₁-C₁₂-Alkyl, Phenyl, durch Sauerstoff, Schwefel, Imino oder C₁-C₁₁-Alkylimino an den Triazinylrest gebundenes C₁-C₁₂-Alkyl, Phenyl oder einen Rest der Formel (12) sind, wie z.B. das Kaliumsalz der Verbindung der Formel (11), worin
R₁ Phenyl und
R₂ und R₃ je den Rest der Formel (12) bedeuten oder das Natriumsalz der Verbindung der Formel (11), worin R₁ p-Chlorphenyl und R₂ und R₃ je den Rest der Formel (12) bedeuten.For example, the following connections can be used:
a) 2-hydroxybenzophenones of the formula (8)

wherein
R₁ is hydrogen, hydroxy, C₁-C₄ alkoxy or phenoxy,
R₂ is hydrogen, halogen, C₁-C₄ alkyl or sulfo,
R₃ is hydrogen, hydroxy or C₁-C₄ alkoxy and
R₄ is hydrogen, hydroxy or carboxy,
b) 2- (2'-hydroxyphenyl) benzotriazoles of the formula (9)

wherein
R₁ is hydrogen, chlorine, sulfo, C₁-C₁₂-alkyl, C₅-C₆-cycloalkyl, (C₁-C₈-alkyl) -phenyl,
C₇-C₉-phenylalkyl or sulfonated C₇-C₉-phenylalkyl,
R₂ is hydrogen, chlorine, C₁-C₄-alkyl, C₁-C₄-alkoxy, hydroxy or sulfo,
R₃ C₁-C₁₂-alkyl, chlorine, sulfo, C₁-C₄-alkoxy, phenyl, (C₁-C₈-alkyl) -phenyl,
C₅-C₆-cycloalkyl, C₂-C₉-acoxycarbonyl, carboxyethyl, C₇-C₉-phenylalkyl or sulfonated C₇-C₉-phenylalkyl,
R₄ is hydrogen, chlorine, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₂-C₉-alkoxycarbonyl, carboxy or
Sulfo and
R₅ is hydrogen or chlorine,
c) 2- (2′-hydroxyphenyl) -s-triazines of the formula (10)

wherein R is hydrogen, halogen, C₁-C₄alkyl or sulfo,
R₁ is hydrogen, C₁-C₄-alkyl, C₁-C₄-alkoxy or hydroxy,
R₂ is hydrogen or sulfo and R₃ and R₄ independently of one another are C₁-C₄-alkyl, C₁-C₄-alkoxy, C₅-C₆-cycloalkyl, phenyl or phenyl substituted by C₁-C₄-alkyl and / or hydroxy, and
d) s-triazine compounds of the formula (11)

wherein at least one of the substituents R₁, R₂ and R₃ is a radical of the formula

is in which A is C₃-C₄-alkylene or 2-hydroxytrimethylene and M is sodium, potassium, calcium, magnesium, ammonium or tetra-C₁-C₄-alkylammonium and m is 1 or 2, and the remaining substituent or the other substituents are independent of one another C₁-C₁₂-alkyl, phenyl, C₁-C₁₂-alkyl, phenyl or a radical of the formula (12) bonded to the triazinyl radical by oxygen, sulfur, imino or C₁-C₁₁-alkylimino, such as, for example, the potassium salt of the compound of the formula ( 11), where
R₁ phenyl and
R₂ and R₃ each represent the rest of formula (12) or the sodium salt of the compound of formula (11), wherein R₁ p-chlorophenyl and R₂ and R₃ each represent the rest of formula (12).

In the formulas (8) to (12):
C₁-C₄ alkyl, for example methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl or tert-butyl;
C₁-C₄ alkoxy eg methoxy, ethoxy, propoxy or n-butoxy;
C₁-C₁₄ alkoxy, for example methoxy, ethoxy, propoxy, n-butoxy, octyloxy, dodecyloxy or tetradecyloxy;
C₁-C₁₂-alkyl, for example ethyl, amyl, tert-octyl, n-dodecyl and preferably methyl, sec-butyl or tert-butyl;
C₂-C₉ alkoxycarbonyl, for example ethoxycarbonyl, n-octoxycarbonyl or preferably methoxycarbonyl;
C₅-C₆-cycloalkyl, for example cyclopentyl or cyclohexyl;
(C₁-C₈ alkyl) phenyl, for example methylphenyl, tert-butylphenyl, tert-amylphenyl or tert-octylphenyl;
C₇-C₉-phenylalkyl, for example benzyl, α-methylbenzyl or preferably α, α-dimethylbenzyl, and
C₁-C₁₁ alkylimino, for example methyl, ethyl, butyl, hexyl, octyl, decyl or undecylimino.

The carboxy and sulfo groups can be in free form or in salt form, for example as alkali metal, alkaline earth metal, ammonium or amine salts.

in welchen Formeln eines von
P und Q die Gruppe -NH-R₃, das andere die Gruppe

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 (13)

(13) A- (X) _x -P

with one mole of a compound of formula (14)

in what formulas one of
P and Q the group -NH-R₃, the other the group

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, with elimination of HV.

Examples of starting materials of the formula (15) which come under formula (13) and are suitable for the preparation of the water-soluble compounds according to the invention

(15) A- (X) _x -NH-R₃

wherein
A, X, x and R₃ have the meaning given above are:
4-hydroxy-3,5-di-tert-butyl-aniline, 4-hydroxy-3,5-di-tert-butyl-benzylamine, γ- (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-α, α-dimethylbenzyl-5-methyl-benzylamine, 4-hydroxy- 3,5-dibenzyl-aniline, γ- (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.

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, [ω(4-Hydroxy-3,5-di-tert.butyl-phenyl)-propyloxy]-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 the formula (16) falling under formula (13)

wherein
A, X, x, R₂, 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-methyl-phenyl) -propionic acid chloride, (4-hydroxy-3 -benzyl-5-methyl-phenyl) -acetyl chloride, 4-hydroxy-3,5-di-isopropyl-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-a cetyl chloride, and 4-hydroxy-5-tert-butyl-3-ethyl-benzyloxy-acetyl chloride.

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-benzol-sulfonsäure, 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-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-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-(β-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-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, ω-Amino-propan-sulfonsäure, ω-Amino-butansulfonsäure, ω-Amino-pentansulfonsäure, N-Methyl-γ-amino-propansulfonsäure, 1,2-Diamino-ethansulfonsäure, 2-Methylamino-propansulfonsäure und 2-Amino-2-carboxy-ethansulfonsäure.Examples of starting products of the formula (17) falling under formula (14)

wherein
W, m, Z, X ′, x ′, R₃ 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-disulfonic 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- (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-diphenyl ether-4-sulfonic acid, 2-amino-2'-methyl-diphenyl ether-4-sulfonic acid, 2-amino-4-chlorine -4'-amyl-diphenyl ether-5-sulfonic acid, 2-amino-4,4'-di-chloro-diphenyl ether-2'-sulfonic acid, 2-amino-4'-methyl-diphenyl sulfone-4-sulfonic acid, 2.5 -Diamino-2'-methyl-diphenylether-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, ω-amino-propanesulfonic acid , ω-amino-butanesulfonic acid, ω-amino-pentanesulfonic acid, N-methyl-γ-amino-propanesulfonic acid, 1,2-diamino-ethanesulfonic acid, 2-methylamino-propanesulfonic acid and 2-amino-2-carboxy-ethanesulfonic acid.

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-Disulfobenzoylchlorid, 3-Sulfo-phthaloylchlorid, 3,4-Disulfo-phthaloylchlorid, 4-Sulfo-phenyl-acetylchlorid, β-(4-Sulfo-phenyl)-propionsäurechlorid, 3-Sulfo-6-methyl-benzoylchlorid.Examples of starting products of the formula (18) falling under formula (14)

wherein
W, m, Z, X ′, x ′, R₂, y, V and n have the meaning given above are:
2-sulfo-benzoyl chloride, 3-sulfo-benzoyl chloride, 4-sulfo-benzoyl chloride, 3,5-disulfobenzoyl chloride, 3-sulfo-phthaloyl chloride, 3,4-disulfo-phthaloyl chloride, 4-sulfo-phenyl-acetyl chloride, β- (4th -Sulfo-phenyl) -propionic acid chloride, 3-sulfo-6-methyl-benzoyl chloride.

Some of the starting products mentioned above are known and can be prepared by methods known per se.

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.

in Betracht, worin R, R₁, R₄, X und Z-S0₃M die nachstehenden Bedeutungen annehmen.

Compounds of the formula (1) which can be used according to the invention are, for example, compounds of the formula

into consideration, wherein R, R₁, R₄, X and Z-S0₃M assume the meanings below.

as well as the connections of the formulas

The compounds of the formulas (8) and (9) can be prepared by methods known per se, e.g. in US-A-3 403 183 and US-A-4127 586, respectively.

The compounds of formula (10) can be prepared in a manner known per se, e.g. following the procedures described in US-A-3,259,627, 3,293,247, 3,423,360 and 4,698,064.

The compounds of formula (11) can be prepared by methods known per se, e.g. in US-A-3 444 164 or EP-A-165 608.

The agents used in the process according to the invention contain components (A) and (B) in an amount of 0.01 to 10, preferably 0.2 to 2% by weight in a weight ratio (A) :( B) of 95 : 5 to 5:95, preferably 60:40 to 40:60, always calculated on the material to be dyed.

The application can take place before, during or after dyeing, using an exhausting or continuous process. Application during dyeing is preferred.

In the pull-out process, the liquor ratio can be within a wide range can be selected, for example 1: 3 to 1: 200, preferably 1:10 to 1:40. It is convenient to work at a temperature of 20 to 120 ° C, preferably 40 to 100 ° C.

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.

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.

After the dyeing process or fixation has ended, the dyeings produced are washed and dried in the customary manner.

According to the present invention, undyed and dyed fiber materials with good thermal and / or photochemical stability are obtained.

The dyeings to be stabilized according to the invention are those which are obtained by 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.

Examples of such dyes are described in Color Index, 3rd edition, 1971, volume 4

Polyamide material is understood to mean synthetic polyamide, such as, for example, polyamide-6, polyamide-6,6 or polyamide-12, as well as modified polyamide, for example polyamide which can be dyed with base. In addition to the pure polyamide fibers, fiber mixtures made of polyurethane and polyamide are also considered, for example tricot 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, such as fiber, yarn, woven, knitted, nonwoven or pile material.

Especially dyeings on polyamide material that is exposed to light and / or jokes and e.g. in the form of carpets or car upholstery, is particularly well suited to being treated using the present method.

The following examples illustrate the invention. Parts mean parts by weight and percentages percent by weight.

gelöst enthalten. Die Flotte (1) erhält keinen weiteren Zusatz, die Flotte (2) dagegen 1 % der Verbindung der Formel

und die Flotte (3) 1 % der Verbindung (101) und zusätzlich 1% der Verbindung der Formel ( 102), stets auf das zu färbende Material berechnet.

Example 1: 3 samples of 10 g each of a PA-6 knitted fabric are dyed, for example in a ®Zeltex-Vistracolor dyeing machine at a liquor ratio of 1:30. For this, 3 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 of the formula

solved included. The liquor (1) receives no further addition, the liquor (2), however, 1% of the compound of the formula

and the liquor (3) 1% of the compound (101) and additionally 1% of the compound of the formula (102), always calculated on the material to be colored.

Dyeing is started at 40 ° C., the mixture is held at this temperature for 10 minutes and heated to 95 ° C. in 30 minutes. After a dyeing time of 20 minutes at 95 ° C, 2% acetic acid (80%) is added to each liquor and dyeing is continued for 30 minutes. The mixture is then cooled to 70 ° C., rinsed, centrifuged and the samples are dried at 80 ° C.

The dyeings are tested for their light fastness according to SN-ISO 105-BO2 (Xenon) and DIN 75202 (Fakra). To investigate the photochemical stability of the fiber material, samples are exposed for 216 hours in accordance with DIN 75202 and tested for their tear strength and elongation in accordance with SN 198.461.

It can be seen from these results that compounds (101) and (102) impart both photochemical and thermal protection to the staining.

verwendet wird.

Example 2: Three dyeings (4), (5) and (6) are prepared as described in Example 1, with the difference that the following 1: 2 metal complex dye of the formula (200)

is used.

It can be seen that the use of the compounds (101) and (102) brings about an improvement in the photochemical stability.

Example 3: 2 samples of 10 g each of a PA knitted fabric are dyed, for example in a ®Zeltex-Vistracolor dyeing machine at a liquor ratio of 1:30. For this purpose, 2 dye liquors, 0.5 g / l monosodium phosphate and 1.5 g / l disodium phosphate (= pH 7) and 0.04% of the dye are used

enthalten, verwendet.1: 2 co-complex and
7% surfactant substances,
0.002% of the dye of formula (200)
and 1% of the connection

included, used.

The dye liquor 2 additionally contains 1% of the compound of the formula

It is dyed and tested as described in Example 1. The results can be found in the following table.

Example 4: Three 20 g samples of a PA66 car carpet (approx. 850 g / m2; pile / total thickness = 5.5 / 7 mm) are in a bomb dyeing machine, for example a Labomat® (Mathis company), with a liquor ratio of 1:20 (as described in Example 3) colored.

während zu Flotte 31 % der Verbindung (400) und 0,75 % der Verbindung (102) gegeben werden. Alle Verbindungen werden auf das Gewicht des Teppichmusters berechnet und in gelöster Form der Färbeflotte zugegeben.The fleet 1 contains no further additive. Fleet 2 contains 1% of the compound of the formula

while 31% of compound (400) and 0.75% of compound (102) are added to liquor. All compounds are calculated based on the weight of the carpet sample and added to the dyeing liquor in dissolved form.

The dyeing process is carried out as described in Example 1.

The finished dyeings are exposed on the one hand to determine their light fastness according to DIN 75.202 (= Fakra), on the other hand exposed in Mustem of 4.5x12 cm 360 h according to DM 75.202 for the abrasion test according to Martindale (SN 198.529).

The results obtained are summarized in the table below:

The results show that the carpet dyeing is significantly stabilized with the compound (400), but can be further improved by combining it with the UV absorber.

Example 5: Three 10 g samples of a polyamide 66 / Lycra® jersey (80:20) are dyed with 0.2% dye (100) as noted in Example 1. Fleet 1 is given no further addition. The liquor 2 is mixed with 1% of the compound (300) in dissolved form, the liquor 3 with 1% of the compound (300) and 0.75% of the compound (102).

The lightfastness and photochemical stability of the dyeings are also determined as described in Example 1. The following results were obtained:

It can be seen from these results that the use of the compounds (300) brings about an improvement in the photochemical stability which is further improved by combination with the compound (102).

Examples 6-10: 6 samples of 10 g of a PA 6 jersey are dyed according to Example 3 and dyed according to the methods noted in Example 1, but with the addition of subsequent UV absorbers, finished and according to SN-ISO 105-BO2 (xenon ) and DIN 75.202 (Fakra) examined for light fastness.

The following compounds are used in the amounts given in the table:

The results of the light fastness assessments can be found in the following table.

It can be seen that the additional use of the compounds of the formulas (600) to (604) leads to an improvement in the hot light fastness.

Examples 11-15: 12 samples of 10 g each of a PA06 jersey are noted, dyed and tested as in Examples 6-10, but the compounds specified in the table are used in the amounts mentioned.

From these results it can be seen that the combination of the phenolic antioxidants with UV absorbers, e.g. of the formula (600) always leads to an improvement in hot light fastness.

Claims (17)

Process for improving the thermal and / or photochemical stability of undyed and dyed polyamide fibers, characterized in that the fibers are treated with an aqueous bath agent which
(A) 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)

wherein
X and X ′ independently of one another are alkylene, oxaalkylene or thiaalkylene,
R₂ and R₃ 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 are independently 1 or 2, and their water-soluble salts, and
(B) contains a UV absorber. Process according to Claim 1, characterized in that a component of the formula (1) is used as component (A), in which A denotes a monohydroxyphenyl radical, in which at least one o-position to the hydroxyl group is substituted by alkyl with 1-12 C atoms, cycloalkyl with 6-10 C atoms or aralkyl with 7-10 C atoms and which optionally also carries further substituents. Process according to one of claims 1 and 2, characterized in that a component of formula (1) is used as component (A), in which A is a radical of formula (4)

in the
R and R₁ independently represent hydrogen, methyl or tert-butyl and the sum of the carbon atoms of R and R₁ is at least 2. Process according to one of claims 1 to 3, wherein in the compounds of the formulas (2) and (3) X and X′ are straight-chain or branched alkylene having 1-8 C atoms. Process according to one of claims 1 to 4, wherein in the compounds of the formulas (2) and (3) R₂ and R₃ represent straight-chain or branched C₁-C₈-alkyl. Process according to one of claims 1 and 4, wherein in the compounds of the formulas (2) and (3) R₂ and R₃ are hydroxyalkyl, alkoxyalkyl, aminoalkyl, alkylaminoalkyl or dialkylaminoalkyl each with a total of 2-10 C atoms or phenyl. A process according to claim 1, wherein in formula (1) Y is a radical of formula (5)

represents what
R₄ is hydrogen or C₁-C₄ alkyl and
X '' mean C₁-C₄ alkylene. Method according to 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, C₁-C₄-alkyl , C₁-C₄-alkoxy, C₁-C₄-alkoxycarbonylamino, hydroxy, carboxy, phenylethyl, styryl, phenyl, phenoxy, phenylthio, phenylsulfonyl or acylamino substituted benzene nucleus, the group W being bonded directly to this benzene nucleus or to a monocyclic aryl radical of one of its substituents can be, or it means the naphthalene or tetralin residue. A method according to claim 1, characterized in that as component (A) a compound of formula (7)

used where
R and R₁ are independently methyl or tert-butyl,
R₄ is hydrogen or C₁-C₄ 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 is 1 or 2. A method according to claim 9, characterized in that a component of formula (7) is used as component (A), wherein R and R₁ tert-butyl, X '' methylene or ethylene, R₄hydrogen, methyl or ethyl and Z 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-Naphthalintriyl or the residues

wherein the sulfo group W is in the form of its alkali or ammonium salts. Method according to one of claims 1 to 10, characterized in that a 2-hydroxybenzophenone of the formula is used as component (B)

used where
R₁ is hydrogen, hydroxy, C₁-C₁₄ alkoxy or phenoxy,
R₂ is hydrogen, halogen, C₁-C₄ alkyl or sulfo,
R₃ is hydrogen, hydroxy or C₁-C₄ alkoxy and
R₄ is hydrogen, hydroxy or carboxy. Process according to one of claims 1 to 10, characterized in that a 2- (2'-hydroxyphenyl) benzotriazole of the formula is used as component (B)

used where
R₁ is hydrogen, chlorine, sulfo, C₁-C₁₂-alkyl, C₅-C₆-cycloalkyl, (C₁-C₈-alkyl) -phenyl, C₇-C₉-phenylalkyl or sulfonated C₇-C₉-phenylalkyl,
R₂ is hydrogen, chlorine, C₁-C₄-alkyl, C₁-C₄-alkoxy, hydroxy or sulfo,
R₃ C₁-C₁₂-alkyl, chloro, sulfo, C₁-C₄-alkoxy, phenyl, (C₁-C₈-alkyl) -phenyl, C₅-C₆-cycloalkyl, C₂-C₉-alkoxycarbonyl, carboxyethyl, C₇-C₉-phenylalkyl or sulfonated C₇-C₉-phenylalkyl,
R₄ is hydrogen, chlorine, C₁-C₄-alkyl, C₂-C₉-alkoxy, C₂-C₉-alkoxycarbonyl, carboxy or sulfo and
R₅ is hydrogen or chlorine. Method according to one of claims 1 to 10, characterized in that as component (B) a 2- (2'-hydroxyphenyl) -s-triazine of the formula

used, wherein R is hydrogen, halogen, C₁-C₄-alkyl or sulfo,
R₁ is hydrogen, C₁-C₄-alkyl, C₁-C₄-alkoxy or hydroxy,
R₂ is hydrogen or sulfo and R₃ and R₄ independently of one another are C₁-C₄-alkyl, C₁-C₄-alkoxy, C₅-C₆-cycloalkyl, phenyl or phenyl substituted by C₁-C₄-alkyl and / or hydroxy. Process according to one of Claims 1 to 10, characterized in that an s-triazine compound of the formula is used as component (B)

used, wherein at least one of the substituents R₁, R₂ and R₃ is a radical of the formula

is in which A is C₃-C₄alkylene or 2-hydroxytrimethylene and M is sodium, potassium, calcium, magnesium, ammonium or tetra-C₁-C₄-alkylammonium and m is 1 or 2, and the remaining substituent or the other substituents are independent of one another C₁-C₁₂-alkyl, phenyl, C₁-C₁₂-alkyl, phenyl or a radical of the formula (12) bonded to the triazinyl radical by oxygen, sulfur, imino or C₁-C₁₁-alkylimino. Method according to one of claims 1 to 14, characterized in that the agent is drawn onto the fibers by an exhaust or continuous process. Method according to one of claims 1 to 15, for improving the thermal and / or photochemical stability of polyamide fibers dyed with dispersion, acid or metal complex dyes. The undyed and dyed polyamide fibers treated according to the method of claim 1.