JPS62267367A - Photochemical stabilization of dyed or undyed polyamide fiber material or mixture with other fiber material - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is characterized in that dyed or undyed polyamide fiber materials or mixtures of polyamide fiber materials and other fiber materials are treated with copper complexes, light stabilizers and antioxidants to produce photochemical Regarding the method of stabilization.

It is generally known to use copper salts, such as copper sulfate, to improve the light fastness of dyeings of polyamide fiber materials with metal complex dyes.

For example, the American Dyestuff Report (ADR)
) Volume 69 (1980), pages 3.19 and 20, see the article by I.B. Harness (1, B, HANES). However, both inorganic and organic copper salts have many drawbacks. That is, the absorption of the copper salt by the polyamide fiber material is insufficient and also irregular. Therefore, it must be used in high concentrations to achieve the desired effect. Furthermore, copper salts can only be used as post-treatments and only in discontinuous processes.

In European Patent Application No. 51188, polyamide fiber materials are treated with a mixture of a copper complex of bisazomethine and a light stabilizer before, during or after dyeing in order to improve the light fastness of polyamide dyeings. It is recommended that
It is being proposed.

However, European Patent Application No. 113856 of the same applicant
As described in the above publication, such sunfastness improvers have an undesirable inherent color and have completely insufficient hydrolytic stability as well as acid stability.

Furthermore, European Patent Application No. 162811 and “Textilveredlung” Volume 20 (1)
985),! 11, pages 346-357 describes the use of non-dyeable copper complex compounds that are stable in dye baths and have affinity for fibers in order to improve the head stability and light-thermal stability of polyamide dyeings. This is disclosed. The degree of improvement in fastness and other properties achieved thereby is currently sufficient to meet the requirements demanded by, for example, the automobile industry.

However, according to the present invention, it has now been discovered that it is possible to further improve fastness such as light fastness and tear strength and other properties by a mixture of a copper complex compound, a light stabilizer, and an antioxidant. .

The present invention therefore relates to a method for photochemical stabilization of dyed or undyed polyamide fiber materials or mixtures of polyamide fiber materials with other fiber materials, which method comprises: (A) an organocopper complex salt; B) a light stabilizer, and optionally (C) an antioxidant.

As component (A), bisazomethines, acylhydrazones, semicarbazones or thiosemicarbazones of aromatic aldehydes or ketones, or oxime non-dying copper complexes come into consideration. Such compounds have an excellent affinity for polyamide fiber materials and, if they contain water-solubilizing groups, are also very water-compatible. Therefore, even very small amounts are effective.

Bisazomethine of an aromatic aldehyde or ketone is to be understood here as a Schiff base of an aliphatic or aromatic diamine, in which case the aldehyde and ketone are H - has a group. The bonding with the metal atom takes place through these two HO- groups and the bivalent elementary atoms within the bisazomethine moiety. Therefore, these are concave ligands. The ligand may contain one or more sulfo groups;
This is present within an aldehyde or ketone moiety and/or a bisazomethine bridge.

A preferred copper complex salt for use as component (A) is one of the following formula (1).

(wherein R is hydrogen or an unsubstituted or substituted alkyl or aryl group, Q is unsubstituted or substituted alkylene,
Cycloalkylene, or aryen group, n is 0.1.
2 or 3).

Note that benzene type and B can be substituted independently of each other.

If R stands for an unsubstituted or substituted alkyl group, preference is given to a c,-C1-alkyl group, particularly preferably a C,-C,-alkyl group;
It can be linear or branched and can be unsubstituted or substituted. Substituents include halogen such as fluorine, chlorine or bromine, C+ C4-alkoxy such as methoxy or ethoxy, phenyl or carboxyl, or acetyl group;
CI C4-alkoxycarbonyl, or hydroxyl, or mono- or di-alkylated amino groups such as CI C4-alkoxycarbonyl or hydroxyl are contemplated. Furthermore, as R, a cyclohexyl group is also considered. This can also be substituted, for example, by C+ C4-alkyl or C+ C4-alkoxy.

If R denotes an unsubstituted or substituted aryl group, particular consideration is given to phenyl or naphthyl groups, which can be substituted, for example, by substituents such as:

C+ C4-alkyl such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, 5ec-butyl, ter, t-butyl, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy,
CI such as 5ec-butoxy, tert-butoxy
Halogens such as C4-alkoxy, fluorine, chlorine and bromine, C2-C5-alkanoylamino, nitro, cyano, fulvic or mono- or di-alkylated amino groups such as acetylamino, propionylamino, butyrylamino.

If Q means an alkylene group, it is preferably C
Z-, C, -fulkylene group, special number ko, -CIl□-CH
, - is a cross-linked menhar. But also C2C8-alkylene chains interrupted by oxygen or in particular by nitrogen, in particular -(CHz) x-NH-(CHz
) x-bridge members are also considered.

If Q means an arylene group, it is preferably a phenylene group, especially an O-phenylene group. This is also C
, -C4-alkyl or Cl-C4-alkoxy.

If Q means a cycloalkylene group, it is preferably a cycloaliphatic group having 5 to 7 carbon atoms, such as cyclopentylene, cyclohexylene or cyclohebutylene.

As examples of substituents which may be present on the benzene ring and B, the following may be considered: halogens, such as fluorine, chlorine or bromine, cyano or nitro groups, alkyl, alkoxy, hydroxyl, hydroxyalkyl, alkoxyalkoxy, alkoxyalkoxyalkoxy , carboxymethoxy, alkylamino, dialkylamino, -5O□NH2, -5OZ
NHRO or -3OzN (Ro) 2 .

Ro here means alkyl or alkoxyalkyl, where alkyl and alkoxy each have 1 to 4 carbon atoms. Alternatively, the groups in mutually ortho positions may form a Hensen group together with the carbon atoms to which they are attached.

The sulfo groups present in the benzene rings A and/or B and/or the bridging member Q (if this is meant as an arylene group) are preferably present as alkali metal salts, in particular as sodium salts or amine salts.

R means hydrogen, Q means ethylene or 0-phenylene bridge member, and n is O or 2;
Copper complexes of the formula filO in which two sulfo groups are present on the benzene rings A and B, in particular copper complexes in which both sulfo groups are present in the p-position relative to the oxygen, are used in the process of the invention. is particularly preferred.

Among the copper complex salts of the formula filO, the bisazomethine salt of the following formula (2) is particularly important.

In the formula, R' is hydrogen or C+ C3-alkyl, R,
, R, , R3, R, are each hydrogen, halogen, hydroxyl, hydroxyalkyl, alkyl, alkoxy,
Alkoxyalkoxy, alkoxyalkoxyalkoxy, carboxymethoxy, alkylamino, dialkylamino, -5OzNHZ, -5O2NHRO or -5
or R1 and R2 , or R2 and R1, or R3 and R4 together with the carbon atoms to which they are attached form a Hensen group.

Q is Cz-c, -alkylene group, Cz Co-alkylene group interrupted with oxygen or nitrogen, phenylene group,
or bridging member -C1l-CH-Y (where X and Y each mean a C,-C,-alkyl or aromatic group, or X and Y together with the carbon atom to which they are attached) to form an alicyclic group having 5 to 7 carbon atoms).

As the cycloaliphatic group that X and Y form together with the carbon atom to which they are bonded, a cyclobenzene group, a cyclohexylene group, or a cycloalkylene group is considered.

The copper complex salt of an acylhydrazone of an aromatic aldehyde or ketone as component (A) is preferably a complex salt of the following formula (3).

(wherein R1 and R5 independently of each other mean hydrogen or an unsubstituted or substituted alkyl or aryl group).

Moreover, the semicarbazone or thiosemicarbazone as component (A) is preferably a complex salt of the following formula (3a).

(wherein R1 has the meaning defined with respect to formula (3),
and Z2 means oxygen or sulfur).

When R1 and/or R3 in (3) and (3a) denote an alkyl group, it may be linear or branched and preferably has 1 to 8 carbon atoms, particularly preferably 1 to 4 carbon atoms. It has a chain length. Substituents include halogens such as fluorine, chlorine, bromine, C,-C4-alkoxy such as methoxy, ethoxy, and also C+ Ca-alkoxycarbonyl such as phenyl or carboxyl, acetyl, or hydroxyl or also mono- or di-alkyl. Amino is considered.

If R1 and/or R1 in formulas (3) and (3a) means an unsubstituted or substituted aryl group, it is in particular a phenyl or naphthyl group, which can be methyl, ethyl, propyl, isopropyl, butyl,
C,-C,-alkyl such as isobutyl, 5ec-butyl, tert-butyl, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, 5
C,- such as ec-butoxy, tert-butoxy
C,-alkoxy groups, halogens such as fluorine, chlorine, bromine, C2C5-alkanoylamino, nitro, cyano, sulfo, or 7- or di-alkylamino such as acetylamino, propionylamino, butyrylamino are considered.

Preference is given to complex salts of the formula (3) in which R, is hydrogen and R% is hydrogen, methyl or especially phenyl, especially those in which the sulfo group is in the p-position relative to the oxygen.

The complex salts of formula (11, (3), (3a)) are preferably used in neutral form, ie in the form of alkali metal salts, especially sodium salts or amine salts.

When component (A) is a copper complex salt of oxime, the following formula (4
) is preferred.

(wherein R means H, OH, alkyl, or cycloalkyl, and ring A may be unsubstituted or further substituted). For example, copper compounds of salicylaldoxime and salicylhydroximate.

Suitable alkyl groups are those having 1 to 4 carbon atoms. Suitable cycloalkyl groups are cyclohexyl and methylcyclohexyl. Suitable substituents on the ring are methyl, methoxy or chlorine. However, it is preferred that this ring is unsubstituted.

A preferred copper complex salt of formula (2) is one represented by formula (5) below.

(In the formula, R4, R7, R8, R9 are hydrogen, hydroxyl, chlorine, bromine, methyl, tert-butyl, methoxy,
means methoxyethoxy, ethoxyethoxyethoxy, or diethylamino, and R7 can also mean sulfo, Xl means hydrogen, methyl, ethyl, or phenyl, Y means hydrogen, or R6 and R1 xI and Y2 together form a cyclohexylene group).

Particularly important is the copper complex salt of the following formula (6).

(In the formula, R1゜, R8 and R93 are hydrogen, chlorine, bromine,
means methyl or methoxy, and R11 can also mean sulfo, or RIG and R11 together form a fused benzene ring, R1□ is hydrogen or hydroxyl, ×2 is hydrogen, methyl, (means ethyl or phenyl).

Of particular interest are compounds of formula (6) in which R1°, Ro, R1□, RI3 and X2 are hydrogen.

As component (B), all compounds which are also known as UV absorbers are suitable; for example, the compounds described in the following document may be used: Kirk Osmer
-Othmer) 23. 615-627; Ni
F. Strochel (A, F, 5trobel)'s American Dyestuff Rebo-) (ADR).

50, (1961), pages 583-588; also -1'' Engineering (1962), pages 99-104; R, GΔch ter and H. Murat () 1. M CL 1ler)'s Ta5che
nbuch der Kunststoff Addit
ive', published by Garl Hansa Publishers.
ser Verlag) (Munich), 101
-198 pages (1983) and U.S. Patent No. 45115
Specification No. 96.

For example, the following compounds can be used as component (B): a) 2-hydroxyhensiphenone of the following formula (7) (
where R4 is hydrogen, hydroxyl, C+ C+ a-alkoxy, or phenoxy, R2 is hydrogen, halogen, C+ C4-alkyl, or sulfo, R3 is hydrogen, hydroxyl, or C+ C4-alkoxy, R4 is hydrogen, hydroxyl, or carboxyl), for example 4-hydroxy-14-methoxy-1
4-octyloxy-14-decyl-oquine, 4-dodecyloxy-14-methoxy-2'-carboxy-14
,2',4'-trihydroxo-14,4'-dimethoxy-2'-hydroxy-14-methoxy-5-sulfo-
12'-hydroxy-4,4'-dimethoxy-5-sulfo-14-benzyloxy-1 and 5-chloro-derivatives, etc.; b) 2-(2'-hydroxyphenyl)-hensitriazole of the following formula +81 (In the formula, R5 is hydrogen, C+ C+□-alkyl, chlorine, C3-
C,-cycloalkyl, C'r Cq -phenylalkyl, or sulfo, R2 is hydrogen, CL -C4-7/L/kyl, C, -C4
-alkoxy, chlorine, hydroxyl, or sulfo group, R3 is C, -C'+ □-7/Izkyl, CIC47)
Lt coquine, phenyl, (CI C8-alkyl)-
Phenyl, Cs Ch-cycloalkyl, C2-09
-Alkoxycarbonyl, chlorine, carboxyethyl, or C1Cq -phenylalkyl, or sulfo, R4 is hydrogen, chlorine, C, -C4-alkyl, C1-04
-alkoxy, C2Cq -alkoxycarbonyl, carboxyl, or sulfo, R2 means hydrogen or chlorine), and in this case, carboxyl and sulfo groups are salts, such as alkali metal salts, alkaline earth metal salts, ammonium It can also be present as a salt or an amine salt. Examples of compounds of formula (8) are 5'-methyl derivatives, 3',5'-di-tert-butyl derivatives, 5'-
tert-butyl derivative, 5'-(1,l,3.3,-tetramethylbutyl)-derivative, 5-chloro-3',5'-di-tert-butyl derivative, 5-chloro-3'-tert- Butyl-5'-methyl derivative, 3'-5ea-butyl-5'-tert-butyl derivative, 4' octyloxy derivative, 3',5'-di-tert-amyl derivative, 3',5'
-bis-(α,α-dimethylbenzyl)-derivatives, as well as 2-(2′-hydroxy-3′-tert-butyl-
Sodium salt of 5'-methylphenyl)-5-(2H)-benzotriazole sulfonic acid, 3-tert-butyl-4-hydroxy-5-[benzotriazole-(2)
-yl]-Hensensulfonic acid sodium salt.

C) Containing at least one group of the following formula (9)% (wherein R means hydrogen or methyl) in the molecule, for example, 2.2.6.6-tetraalkylbi Compounds from sterically hindered amines such as peridine derivatives.

The light stabilizer may contain one or more groups of formula (9). For example, mono-, bis-, tris-
, tetra-5 or oligo-piperidine derivatives. Preferred is a group of formula (9) in which R means hydrogen, or a group of formula (9) in which the ring nitrogen has no hydrogen atoms.
If it contains one or more groups, it is a veridine derivative.

Most piperidine light stabilizers have a polar substituent at the 4 position of the piperidine ring.

Particularly important piperidine compounds are shown below. C111-alkyl, C
3-cs-alkenyl, C3Co-alkynyl, Cq
C+□-aralkyl, C,-C,l-furkayl, Cs Cs-alkenoyl, glycidyl or group -c) IzCH(OH)-Z, where Z means hydrogen, methyl or phenyl , and preferably R1 means C,-C,□-alkyl, allyl, benzyl, acetyl or acryloyl, RZ is hydrogen, optionally one or more, when n is 1 C, -C,S interrupted by oxygen of
- monovalent radicals of alkyl, cyanoethyl, benzyl, glycidyl, aliphatic, cycloaliphatic, araliphatic, unsaturated or aromatic carboxylic acids, carbamic acids or phosphorus-containing acids, -valent silyl groups, preferably Residues of aliphatic carboxylic acids with 2 to 18 carbon atoms, residues of cycloaliphatic carboxylic acids with 7 to 15 carbon atoms, α, β-union with 3 to 5 carbon atoms, residues of saturated carboxylic acids,
or a residue of an aromatic carboxylic acid having 7 to 15 carbon atoms, and when n is 2, C, -C, □-
alkylene, C,-C,□-alkenylene, xylylene, aliphatic, cycloaliphatic, araliphatic or aromatic dicarboxylic acids, dicarboxylic acids, or divalent groups of phosphorus-containing acids;
Divalent silyl groups, preferably residues of aliphatic dicarboxylic acids having 2 to 36 carbon atoms, residues of cycloaliphatic or aromatic dicarboxylic acids having 8 to 14 carbon atoms, 8 to 14 means the residue of an aliphatic, cycloaliphatic or aromatic dicarboxylic acid having 3 carbon atoms; if n is 3, an aliphatic, cycloaliphatic or aromatic tricarboxylic acid, or a phosphorus-containing acid; or a trivalent silyl group, and when n is 4, it means a tetravalent group of an aliphatic, cycloaliphatic or aromatic tetracarboxylic acid.

When the substituent is C+C+□-alkyl, it is, for example, methyl, ethyl, n-propyl, n-
butyl, 5ec-butyl, tert-butyl, n-hexyl, n-octyl, 2-ethyl-hexyl, n-nonyl, n-decyl, n-undecyl, or n-dodecyl.

When R1 or R2 means CIC+ a-alkyl, for example, in addition to those exemplified above, n-
) lysosyl, n-tetradecyl, n-hexadecyl, or n-octadecyl.

When R1 means C,-C11-alkenyl, examples are 1-propenyl, allyl, methallyl, 2-butenyl, 2-pentenyl, 2-hexenyl, 2-octenyl, 4 tert-butyl-2-butenyl. It is.

When R1 means C3-C,-alkynyl, it is preferably proparginyl.

When R1 means C,-C,□-aralkyl, phenethyl is preferred, particularly benzyl.

When R' is c,'-c11-alkanoyl,
For example, formyl, propionyl, butyryl, octanoyl, preferably acetyl, and C, -C,
-In the case of alkenoyl, acryloyl is particularly preferred.

If R2 denotes a monovalent group of carboxylic acid, it is for example acetic acid, caproic acid, stearic acid, acrylic acid, methacrylic acid, benzoic acid or β-(3,5-di-tert-butyl-4-hydroquine). -phenyl)-propionic acid group.

If R2 denotes a divalent radical of a dicarboxylic acid, it is, for example, malonic acid, adipic acid, corkic acid, sebacic acid, maleic acid, phthalic acid, dibutylmalonic acid, dihenzylmalonic acid, phthyl (3,5-di ter t-
(butyl-4-hydroxybenzyl)-malonic acid, or the residue of bicyclohebutenedicarboxylic acid.

When R2 means a trivalent group of tricarboxylic acid,
It is, for example, the residue of trimellidic acid or nitrilotriacetic acid.

If R2 denotes a tetravalent radical of tetracarboxylic acid, it is, for example, a tetravalent radical of butane=1.2.3.4-tetraacetic acid or pyromellitic acid.

If R2 denotes a divalent group of dicarboxylic acid, it is for example a hexamethylenedicarbamate group or a dicarboxylic acid group.
．． 4-Tolutolene dirubamate group.

Specific examples of the above-mentioned classes of tetraalkylpiperidine compounds are shown below: 1) 4-hydroxy-2,2,6,6-titramethylpiperidine, 2) 1-hydroxy-4-hydroxy-2,2,6 , 6-titramethylpiperidine, 3) 1-benzyl-4-hydroxy-2,2,6,6-
Titramethylpiperidine, 4) 1 (4-tert-butyl-2-butenyl)-4-hydroxy-2,2,6,6-tetramethylbiperidine, 5) 4-stearoyloxy-2,2,6, 6-titramethylpiperidine, 6) 1-ethyl-4-salicyloyloxy-2,2,6
, 6-tetramethylbiperidine, 7) 4-methacryloyloxy-1,2,2,6,6-pentamethylpiperidine, 8) 1.2.2.6.6-bentamethylpiperidole 4-
yl-β-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionate, 9) di(l-
Hensyl-2,2,6,6-tetramethylpiperid-4
-yl)-maleate, 10) di(2,2,6,6-
Tetramethylbiperido-4-yl)-adipate, 11) Di(2,2,6,6-tetramethylpiperido-
4-yl)-sebacate, 12) di(1,2,3,6-titramethyl-2,6-
diethyl-piperid-4-yl)-sebacate, 13) di(1-allyl-2,2,6,6-tetramethylpiperid-4-yl)-phthalate, 14) ■-propargyl-4-β-cyanoethyl Oxy-2,2,6,6
-Titramethylpiperidine.

15) 1-7 cetyl-2.2.6.6-tetramethyl-
piperid-4-yl-acetate, 16) tri(2
, 2,6,6-tetramethylbiperido-4-yl)-trimelitate, 17) l-acryloyl-4-benzyloxy-2,2,6,6-titramethylpiperidine 18
) di(122,2,6,6-bentamethylbiperido-4-yl)-diptyl malonic acid ester, 19) di(1,2,2,6,6-bentamethylpiperido-4-yl)-butyl -(3,5-Gt6rt-7
"Tyl-4-hydroxybenzyl)-malonic acid ester, 20) Di(1,2,2,6,6-bentamethylpiperido-4-yl)-dibenzyl-malonic acid ester, 21) Di(l,2 .3.6-thitramethyl-2.6-
diethyl-piperid-4-yl)-dibenzyl-malonic acid-ester, 22) hexane-1',6'-bis-(4-carbamoyloxy-1-n-butyl-2,2,6,6-tetramethyl 23) Toluene-2',4'-bis=(4-carbamoyloxy-1-n-propyl-2,2,6,6-tetramethylpiveridine), 24) Dimethyl-bis- (2,2,6,6-Tetramethylbiveridol-4-yloxy)-silane, 25) Phenyl-tris-(2,2,6,6-tetramethylbiveridol-4-yloxy)-silane, 26) Tris-(1-propyl-2,2,6,6-tetramethylpiperid-4-
yl)-phosphite, 27) Tris-(l-propyl-2,2,6,6-tetramethylpiperid-4-yl)phosphonate, 28) Bis-(l,2.2.6.6-penc) methylpiperido-4-yl)-phenyl-phosphonate, 29) di(l,2.2.6.6-bentamethylpiperido-4-yl)-sebacate, 30) 4-hydroxy-1,2,2, 6,6-pentamethylpiperidine, 31) 4-hydroxy-N-hydroxyethyl-2,2
, 6,6-tetramethylbiperidine, 32) 4-hydroxy-N-(2-hydroxypropyl)-2,2,6,
6-titramethylpiperidine, 33) l-glycidyl-4-hydroxy-2,2,6,
6-tetramethylpiveridine.

b b) In the compound formula of the following formula 〇υ, n is the number 1 or 2, R and R1 have the meanings described in aa) above, and R3 is hydrogen, C, -C, □-alkyl, Cz Cs-hydroxyalkyl, C6-C1-cycloalkyl, C, -C
,-aralkyl, Cz Cle-alkanoyl, C
al means Cs-alkenoyl or benzyl, and when n is 1, R4 is hydrogen, CI CIl+-
Alkyl, C, -C, -alkenyl, C5-c.

- C substituted by cycloalkyl, hydroxyl, cyano, alkoxycarbonyl or carboxamido groups
, -C,-alkyl, glycidyl, or the group -CH! −
C:H(0)1)-Z or group -CONH-Z (,:
(Z means hydrogen, methyl, or phenyl); When n is 2, Cz C+□-alkylene, C6-01□-arylene, xylylene, group -C
H2-CI(OH)-CH2- or group -CHZ-C
I (OH) -CI+□-0-D-0- (where D means C2-C, .-alkylene, 06CI S-arylene, C6-Cl□-cycloalkylene), or R4 may further be an aliphatic, cycloaliphatic, or aromatic dicarboxylic or dicarboxylic acid group, or also a group -c, with the proviso that R does not mean alkanoyl, alkenoyl, or benzoyl.

-, or alternatively, when n is 1, R3 and R' are both aliphatic, cycloaliphatic, or aromatic 1.2- or 1. It can mean a divalent group of 3-dicarboxylic acid.

When the substituent is C, -C, □- or CI-C+@-alkyl, it is an alkyl group as exemplified under aa).

An example of a substituent for Cs C'r -cycloalkyl is especially cyclohexyl.

When R3 means C, -c, -aralkyl,
Preference is given to phenylethyl or especially benzyl. If R3 means CtCs-hydroxyalkyl, 2-hydroxyethyl or 2-hydroxypropyl is preferred.

Examples of R3 as C2C11-alkanoyl are propionyl, butyryl, octanoyl, dodecanoyl, hexadecanoyl, octadecanoyl, preferably acetyl and, in the case of C3Cs-alkenoyl, especially acroyl.

Examples when R4 is C,-C,-alkenyl are allyl, methallyl, 2-butenyl, 2-pentenyl, 2-hexenyl, 2-octenyl.

C, -C, - in which R4 is substituted with hydroxyl, cyano, alkoxycarbonyl, or carbamide group
When alkyl, examples include 2-hydroxyethyl, 2-hydroxypropyl, 2-cyanoethyl,
Examples include methoxycarbonylmethyl, 2-ethoxycarbonylethyl, 2-aminocarbonylpropyl, and 2-(dimethylaminocarbonyl)-ethyl.

Examples of substituted M c z c +□-alkylene are ethylene, propylene, 2,2-dimethylpropylene, tetramethylene, hexamethylene, octamethylene, decamethylene, dodecamethylene and the like.

Examples of substituents for C6Cls-arylene are o −+m−
or p-phenylene, 1,4-naphthylene, 4.4'
- Diphenylene, etc.

Cb CIz-cycloalkylene denoted by D includes in particular cyclohexylene.

Specific examples of this class of tetraalkylpiperidine compounds are shown below: 34) N,N'-bis-(2,2,6,6-tetramethylpiperid-4-yl)-hexamethylene-1,
6-diamine, 35) N,N'-bis-(2,2,6,6-tetramethylpiperid-4-yl)-hexamethylene-1,6-diacedeamide, 36) ■-acetyl-4-(N -cyclohexylacetamide)-2,2,6,6-tetramethylpiperidine, 37) 4-benzoylamino-2,2,6,6-tetramethylpiperidine, 3B) N,N'-bis-(2, 2,6,6-tetramethylpiperid-4-yl)-N,N'dibutyl-adipamide, 39)N,N'-bis=(2,2,6,6-tetramethylpiperid-4-yl) )-N,N'dicyclohexyl-
2-hydroxypropylene-1,3-diamine, 40) N, N'-bis-(2,2,6,6-tetramethylpiperid-4-yl>-p-xylylene-diamine, 41) of the following formula Compound 42) 4-(bis-2-hydroxyethylamine)-1
,2,2,6,6-pentamethylpiperidine, 43)4
-(3-methyl-4-hydroxy-5-tert-butyl-benzamide)-2,2,6,6-tetramethylpiperidine, 44) 4-methacrylic 7mido L-2,2,6,6-penta Methylpiperidine; d) 2-(2'-hydroxyphenyl)-3-triazine of the following formula (12) (wherein R is hydrogen, halogen, C1-C4-alkyl, or sulfo, R1 is hydrogen, C+ C4- Alkyl, C, -C.

-alkoxy, or hydroxyl, R2 is hydrogen or sulfo, R3 and R4 are substituted independently of each other by C+ Ca-alkyl, CIC--alkoxy, C5-Cb-cycloalkyl, phenyl, or C+ Ca-alkyl and hydroxyl; phenyl). Note that the sulfo group can exist in the form of a salt, such as an alkali metal salt, an alkaline earth metal salt, an ammonium salt, or an amine salt, even in a free form. Formula (12)
Specific examples of compounds are as follows: 2-(2',4'-dihydroxyphenyl)-4゜6-
diphenyl-3-triazine, 2-(2'-hydroxy-4'-methoxyphenyl-4
,6-diphenyl-5-)su7dine, 2-(2'hydroxy-5'-methylphenyl)-4,6-diphenyl-
5-) riazine, 2,4-bis-(2'-hydroxy-
3'-methylphenyl)-6-ethyl-5-1-riazine, 2,4-bis-(2'-hydroxyphenyl)-6
-Medoxys-) riazine, 2,4-bis-cyclohexyl-6-(2'hydroxy-4'-methoxyphenyl)-S=nitriazine and 2-(2'-hydroxy-4'-methoxyphenyl-5
'-sulfophenyl)-4,6-diphenyJLt-3-
Triazines; (e.g. WO-A-8610352
8).

e) The following formula 〇s-triazine compound (12a) 〒゛■'') RguV''''R3 [In the formula, at least one of the substituents R+, R2, R3 is of the formula (In the formula, M is sodium, (potassium, calcium, magnesium, ammonium, or tetra-C1Ca-alkylammonium, and m is 1 or 2), and the remaining substituents are independently of each other c+ Cl2-alkyl, phenyl , or C, -C,□-alkyl or phenyl bonded to the triazinyl group by oxygen, sulfur, imino, or C+ Ca-alkylimino]. For example, R, is phenyl and R2 and R1 are of the formula ( 12b), or R1 is p-chlorphenyl and R2 and Rff are the residues of formula (12b);
) and the like. Other compounds are described in European Patent Application No. 165,608.

As component (C), it is possible to use, for example, the compounds described in the following literature: Kirk-Othmer (3,)
, pp. 3.132-135; or R, Gachter and H, Müller.
u 1ler) to the Tanoschenbuch der Kunststof Adity ("Ta5chenbuch
der Kunststoff-＾dditive″)
, Karl Hanser Publishers (Cart 1)
Verlag (Munich), pp. 4-78 (
(1983) Component (C) is typically a sterically hindered phenol such as hydroxyphenylpropionate of the following formula (13).

(In the formula, n is an integer from 1 to 4, A is Ca C24-alkoxy, -0 of the crosslinking member
(CIlz)ho-, -0(CHz)zO(C1lz)
zO-, -0(C)IzhO(CHz)zO(CHz)
zO-, -11N-(CHz)z-6-NH-, or -0(CHz)z-5-(CH2)zO-, or the group →CH20)4-C).

For example, 3-(3',5'-di-tert-butyl-4-hydroxyphenyl)-propionic acid with methanol, octadecasole, 1,6-hexanediol, diethylene glycol, triethylene glycol, or pentaerydrift. ester, or 3-(3'
, 5'-tert-butyl-4-hydroxyphenyl)-propionic acid with ethylene diamine, trimethylene diamine, or hexamethylene diamine.

Furthermore, the use of phenylalkylphosphonates of the following formula (14) as component (C) is also considered.

(In the formula, R is hydroxyl, phenyl, phenoxy, C1Cps
-alkylphenoxy, C, -C2, -alkylthio,
or C+ C2a-alcoquine, R1 is phenoxy, CI Cps-alkylphenoxy, CI C
za-alkylthio, or C,-CI4-alkoxy, R2 and R1 independently of each other C+ C+ s-1, preferably CICb-alkyl, particularly preferably tert-butyl in the 3- and 5-positions, R4 represents hydrogen or CIC4-alkyl, and n is 0.1
．． 2. or 3, preferably 0 or 1).

Examples are as follows.

Di-n-octadecyl 3-tert-butyl-4-hydroxy-5-methylbenzyl-phosphonate, di-n-
Octadecyl 1-(3',5'-di-tert-butyl-4'-hydroxyphenyl)-ethane-phosphonate, Di-n-octadecyl 3,5-di-tert-butyl-2-hydroxybenzyl-phosphonate, Di-n-dodecyl 2-(3',5'-di-tert-butyl-4
'-Hydroxyphenyl)-echun-phosphonate, diethyl 3,5-di-tert-butyl-4-hydroxybenzyl-phosphonate, dimethyl 3,5-di-tert-butyl-4-hydroxybenzyl-phosphonate, di-p-tert- octylphenyl 3,5-te
rt-Butyl-4-hydroxybenzyl-phosphonate, 0-n-butyl 3.5-di-tert-butyl-4-hydroxybenzyl-phosphonate, di-n-butyl 3.5-di-tert-butyl-4-
Hydroxybenzyl-phosphonate, 0-ethyl 3,5-di-tert-butyl-4-hydroxybenzyl-phosphonic acid.

The said compounds which can be used as components (A), (B), (C) are known and can be prepared by methods known per se.

For example, compounds of formulas (1) to (6) are
P) No. 51188, No. 113856 and No. 1
62811 and can be produced by known methods.

Moreover, the compounds of formulas (7) and (8) can be produced by methods known per se, such as those described in US Pat. No. 3,403,183 and US Pat. No. 4,127,586. Compounds of formula (8) in which R, , R2, R3 and/or R4 mean sulfo can be prepared by the method described in EP 112120.

Formula (8) in which R1 means CI C+□-1 preferably C,-C4-alkyl and R1 means sulfo
The compounds in which the corresponding R3 is CI-CIZ-1, preferably C,-C,-alkyl, are also sulfonated using fuming sulfuric acid, preferably 25% oleum, at a temperature of 10 to 30°C; And the obtained product is p
It is also produced by neutralizing H7.

Methods for producing compounds of the sterically hindered amine class of formulas (9) to (11) are described, for example, in U.S. Pat. No. 3,640,928.
No. 3840494 and No. 3993655.

Compound 2 (12) can be prepared by a method known per se, for example,
Helvetei force (Helv,) 55. 1566-15
95 (1972) and WO86103528
It can be manufactured by the method described in .

The preparation of compounds of formula (13) can be carried out by methods known per se, for example the method described in GB 1103144.

The compound of formula (14) can be prepared by a method known per se, for example,
It can be manufactured by the method described in US Pat. No. 3,268,630.

The agents according to the invention are suitably applied using an aqueous bath. In this case, 5 to 20% of copper metal is used per 1g of polyamide.
It is advantageous to use amounts such that 0 pg, especially 10 to 1100 a, are provided. The aqueous bath used therefore contains: a) from 0,000 s to 0.2% by weight of an organic copper complex salt;
b) 0.05 to 3% by weight of light stabilizer, preferably 0
．． 1 to 1% by weight, and if desired C) 0.05 to 3% by weight of an antioxidant, preferably
Contains 0.1 to 1% by weight.

The agents that are the object of the invention are used for the stabilization of the material to be dyed before, after or during dyeing. The basic rule is that it is appropriate to add it directly to the dyebath. Staining can be carried out continuously or discontinuously.

If the agent according to the invention is not water-soluble, it is used as a fine dispersion obtained by grinding in the presence of customary dispersants.

Polyamide materials as used herein include, for example, polyamide-6, polyamide-6,6, or polyamide-1
2 is to be understood as a synthetic polyamide such as No. 2. Not only pure polyamide fiber materials are included, but also mixed fiber materials, such as fiber mixtures of polyurethane and polyamide. For example, polyamide/polyurethane mixing ratio 70
:30 mixed fiber materials etc. are considered. In principle, both pure polyamide fiber materials and mixed polyamide fiber materials can be in various processing forms. For example, it can be a fibre, thread, woven or knitted fabric.

Polyamide materials that are exposed to light and heat, such as automobile seat cushions and tongues, are particularly suitable fiber materials to be treated by the method of the present invention.

Dyeing is carried out by customary methods, for example using metal complex dyes, anthraquinone dyes or azo dyes. Metal complex dyes are of the known type, many of which are described in the literature, in particular 1:2-chromium complex dyes of monoazo- or disazo- or azomethine dyes;
:2-Cobalt complex salt dyes may be used. Of course, other classes of dyes may also be used, such as disperse dyes and vat dyes.

Hereinafter, the present invention will be further explained by examples.

In the examples, parts are parts by weight, and percentages are percentages by weight. The percentage values for additives in each treatment bath or dye bath are based on the fiber material to be treated, unless otherwise specified.

Example 1 Improvement of the photostability and light fastness of olive dyeings Four skeins of staple yarn of polyamide-66, each 10 g, were dyed in a dyeing machine, each in a dye bath (bath) as described below. The ratio was 1:20).

The dye bath used commonly contains 1g/I of ammonium sulfate! (
pH 6.5) and the following dyes (amounts calculated based on yarn weight):

These compounds were dissolved and added to the dyebath.

The dyebath used additionally contained the following additives:

Dye bath 1: no other additives.

Dye bath 2: 0.04% copper complex salt of the following formula This is in the form of a fine dispersion (particle size <2 μ), and is a condensation product of naphthalene sulfonic acid and formaldehyde as a dispersant (weight ratio 1: l) It is a ground aqueous dispersion.

Dye bath 3: Light stabilizer of the following formula 1% This is in the form of a fine dispersion (particle size 2-), and is a condensation product of naphthalene sulfonic acid and formaldehyde as a dispersant (weight ratio 1:1) It was crushed together.

□ Dye bath 4: combination of additives from dye baths 2 and 3.

Put the material to be dyed into the bath prepared as above, and
C for 5 minutes and heated to 95 C at a rate of 1.5 C per minute. This temperature was maintained for 60 minutes, after which the dyebath was cooled to 70° C., the dyeing was washed with cold water, centrifugally dehydrated and dried at 80° C. in a circulating air oven.

The dyed yarns were then tested according to the following test: (a + M"lf:, " Exposure to xenon light according to Swiss Standard Industrial Standard 5N-ISO105-BO2 - Sunlight according to German Standard Industrial Standard DIN 75.202
Exposure (Thermal Exposure) (b) by Tomomata The polyamide staple yarn treated as described above was wound onto cardboard and exposed to xenon light for 750 hours or sunlight for 120 hours.

After that, the exposed thread is SNV (Σchweze
rische Normen-Vereinigun
Tensile strength and elongation measurement tests were carried out according to the method of Standard 197.461 of the Swiss Standards Association.

The test results are shown in the table below. Note that tensile strength and elongation are for unexposed, untreated polyamide-66 staple.
The values are shown with yarn as 100%.

Table 1 The results show that: a) the Iil complex improves the light fastness and photostability under thermal exposure; b) the light stabilizer improves the light fastness and photostability under xenon exposure. C) The combination of both compounds improves the light fastness and the light stability both in the case of thermal exposure and in the case of xenon exposure.

Example 2 Improvement of photostability and light fastness of beige dyeings Staining was performed as described in Example 1.

However, this time the following dye combinations were used.

Dye 4 Dye 5 Dye 3 described in Example 1 (black) 0,003
% Tests on the dyed products were carried out as in Example 1. The dye baths used are as follows: Dye bath 5: Only dyes 3, 4, and 5; Dye bath 6: Furthermore, a copper complex salt of formula (100) is added; Dye bath 7:
Furthermore, a light stabilizer of formula (101) is added; dyebath 8: further a combination of compounds of formula (100) and (lot) is added.

The results are summarized in the table below.

Table 2. Treatment and testing were performed as described in Example 1 with the following modifications.

(al Dye baths 9 to 12 were prepared using the following dyes: Dye 1 Same as Example 1 (yellow) 0
．． 05χ Dye 7 Dye 3 of Example 1 81 parts of 0.14χ (black) + Dye bath 9 contains no further additives. Dye baths 10 and 12 further contain 0.075% of a copper complex salt of the following formula.

Dye baths 11 and 12 further contain 1% of the light stabilizer of the formula (101).
Contains.

(b) All dyebaths 9 to 1 after dye exhaustion at 95°C.
2 further added 2% acetic acid (80%).

The results are summarized in Table 3 below.

Table 3 Improvement of photostability and light fastness of Sm-branch gray dyeings Three bundles of 10 g each of polyamide-66 staple yarn were dyed gray in the manner described in Examples 1 and 3. After washing the dyed product, the yarn bundle was post-treated in one of the following baths at a temperature of 60° C. with addition of 2% acetic acid (80%) in a bath ratio of 1:20 for 45 minutes.

Bath 1: No other additives.

Bath 2: Added 0.05% of the compound of formula (200) (the amount added is based on the weight of the material to be treated) Bath 3: Added 0.05% of the compound of formula (200), based on the weight of the material to be treated; 0.25% of the compound of the following formula was added; 0.25% of the compound of the following formula was added.

The compounds of formulas (400) and (401) have a particle size of <2+a
It was crushed to.

The lightfastness of the dyeings treated with baths 2 and 3 was comparable, but 0.5 points (xenon light) and 2 points (internal light) superior to dyeing 1. Regarding the photochemical stability after 1000 hours of exposure to xenon light, the yarn treated with bath 3 showed approximately 20% improved tensile strength compared to the yarn treated with bath 2, and the initial
An intensity of 50% of the u1 intensity was still maintained.

In contrast, the yarn treated in Bath 1 had only 2 of its initial strength.
It had only 0%.

Thread 1 coarse i polyamide 66 staple yarn each log bundle 1
Two bundles were dyed beige using the following dye mixture.

Dye 4 as described in Example 2 0.0422 Dye 6 as described in Example 3 0.016χ Dye 7 as described in Example 3 0.
The dye bath used in 008χ further contained the following additives.

Bath 1: No additive Bath 2: Addition of the compound of formula (100) at 0.04% based on the weight of the object to be dyed Bath 3: Addition of the compound of the following formula at 1% based on the weight of the object to be dyed・/°ゝOH Bath 4: Added 1% of the compound of the following formula to the weight of the object to be dyed Bath 5: Added 1% of the compound of the following formula to the weight of the object to be dyed Bath 6: Added the compound of the following formula to 1% of the weight of the object to be dyed Addition of 1% compound to the weight of the object to be dyed Bath 7: Addition of the compound of the following formula at 1% to the weight of the object to be dyed? H*Amount of active substance relative to the material to be treated The dyeing of 12 bundles of yarn was carried out as described in Example 1. However, 2% of acetic acid (80%) was further added to the 95°C dye bath after 20 minutes of dyeing time.

The dyeing was then done according to the Swiss standard 5N-ISo 105.
-BO2 (=xenon light), German standard DIN75
．． 202 provisional (inner light), and Fort standard FORD
A light fastness measurement test was carried out using EU-BO5O-2 (=Ford Light), and the light stability was also tested. The photostability test was carried out by exposing the yarn to incandescent light (Fakra) for 150 hours and then measuring the tensile strength and elongation according to the provisions of 5VN 197.461.

The test results are summarized in the table below.

Table 4 From the table it can be seen that the Cu complex particularly improves the fiber stability and also the incandescent light fastness. It is also found that the ultraviolet absorber contributes to improving the light fastness after exposure to xenon light, and especially after exposure to Ford light (light containing a large amount of ultraviolet light).

Preparation of compound of formula (502) 2-(2'-hydroxy-3',5'-tert
80.9 g of -butylphenyl)-benzotriazole
15 (1/2) over 1 hour at a temperature of 15 to 20℃
Place in 5% oleum. The solution is stirred for a further 16 hours at room temperature. Next, mix this solution with 600g of ice and 40031/ml of water.
Add to the mixture with vigorous stirring.

The precipitated product is heated to 80"C and filtered off after cooling to room temperature. The acid obtained is well squeezed and then suspended in 11" of water. It is then heated to 30"C for 1.5 hours with stirring. Neutralize by adding % sodium hydroxide (pH 7)
Then, the precipitated thick mud crystals are heated again to 80°C. This results in a conveniently filterable crystalline form. After cooling to room temperature, filter and separate. This is vacuum dried at 100°C.

Yield: 83.5g.

This product can be recrystallized from an 8:2 mixture of ethanol/water.

Example 6 Ten pieces of highly matte polyamide 6-tricot fiber samples of 10 g each were dyed in the manner described in Example 1 using the olive dye mixture described in Example 1. The dye bath contained the following additives and 2% acetic acid (80%) was added after dyeing at 95° C. for 20 minutes.

Bath 1: No additives, Bath 2: Added 1% of the compound of formula (500) to the weight of the object to be dyed, Bath 3: Added the compound of the following formula at 0.0% to the weight of the object to be dyed.
Added 3% (as a fine dispersion, similar to compound (100)) Bath 4: Added 0.06% of the compound of the following formula to the weight of the object to be dyed, (as a dispersion, similar to compound (100)) Bath 5: 0.06% of the compound of the following formula was added to the weight of the object to be dyed. Bath 6: 0.06% of the compound of the following formula was added to the weight of the object to be dyed.
06% addition, the light fastness of dyed products meets the German standard D [N75.20
2.Measurement was made provisionally (tip of the mouth).

The test results are summarized in the table below.

Table 5 Five bundles of polyamide 6-carpet yarn, each weighing 10 g, were dyed in a dyeing machine at a bath ratio of 1:30, using 1% acetic acid (80%) and dye 8 of the following formula at 1% of the object to be dyed. and stained.

Dyeing started at 50°C, treated at this temperature for 5 minutes, then increased the temperature to 85°C for 20 minutes, added 1% acetic acid (80%) and dyed for 30 minutes, and after cooling, the dyeing Rinse the item with cold water and dry.

The dyebath used further contained the following additives:

Bath 1: Additive-free Bath 2: Finely dispersed compound of formula (600) added at 0.04% based on the weight of the object to be dyed Bath 3: Addition of the dissolved compound of the following formula (700) to the object to be dyed Addition bath 4: 1.5% by weight of the finely dispersed compound of formula (700) based on the weight of the object to be dyed.

The light fastness (xenon light, incandescent light) of the dyed yarn was measured by adding a finely dispersed compound of 2 (600) at 0.04% based on the weight of the dyed material, and after 100 hours of exposure to incandescent light. And the tensile strength and elongation after exposure to xenon light for 1000 hours were measured.

The following table summarizes the results.

The following is confirmed from the results in the table: a) Cu complex salts very significantly suppress photochemical fiber decomposition, especially in thermal exposure.

(Note) Antioxidants have the effect of preventing the decomposition of dyes.

This is particularly evident from the improvement in light fastness to incandescent light.

c) By using a combination of two stabilizers, the effect of protecting the dye and fiber from photochemical degradation is significantly improved.

Claims (1)

[Claims] 1. A method for photochemical stabilization of a dyed or undyed polyamide fiber material or a mixture of a polyamide fiber material and another fiber material, wherein the fiber material is treated with (A) an organic copper complex salt, ( B) A process characterized in that it is treated with a mixture of light stabilizers and optionally (C) antioxidants. 2. Aromatic aldehyde or ketone bisazomethine, acylhydrazone, semicarbazone as component (A),
or thiosemicarbazone, or a non-staining copper complex salt of oxime.
The method described in section. 3. Component (A) is the following formula (1) (1) ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R is hydrogen, or an unsubstituted or substituted alkyl or aryl group, Q is unsubstituted or substituted alkylene,
characterized by using a copper complex salt of a cycloalkylene or arylene group, n means 0, 1, 2 or 3, and benzene rings A and B can be substituted independently of each other. A method according to any one of claims 1 and 2. 4. Component (A) is the following formula (2) (2) ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, R' is hydrogen or C_1-C_3-alkyl, R_1,
R_2, R_3, R_4 are hydrogen, halogen,
Hydroxyl, hydroxyalkyl, alkyl, alkoxy, alkoxyalkoxy, alkoxyalkoxyalkoxy, carboxymethoxy, alkylamino, dialkylamino, -SO_2NN_2-, -SO_2NH
Ro or -SO_2N(Ro)_2 (wherein Ro means alkyl or alkoxy and each alkyl or alkoxy has 1 to 4 carbon atoms), or R_1 and R_2, or R_2 and R_3, or R_3
and R_4 together with the carbon atoms to which they are attached form a benzene group, Q_1 is a C_2-C_4 alkylene group, a C_2-C_8-alkylene group interrupted with oxygen or nitrogen, a phenylene group, or a bridging member ▲ , chemical formulas, tables, etc. ▼ (where X and Y each mean C_1-C_4-alkyl or aromatic group, or 4. A process according to claim 1, characterized in that a bisazomethine complex salt is used which forms an alicyclic group having 7 carbon atoms. 5. Component (A) is the following formula (3) (3) ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R_1 and R_5 are independently hydrogen, unsubstituted or substituted 3. Process according to claim 1, characterized in that an acylhydrazone of an aromatic aldehyde or ketone (meaning an alkyl or aryl group) is used. 6. Component (A) is the following formula (3a) (3a) ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R_1 means hydrogen, or an unsubstituted or substituted alkyl or aryl group. , Z_
3. The method according to claim 1, characterized in that a semicarbazone or a thiosemicarbazone (2 stands for oxygen or sulfur) is used. 7. Component (A) is the following formula (4) (4) ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R means H, OH, alkyl, or cycloalkyl, and ring A is 3. Process according to claim 1, characterized in that a copper compound of a phenol (which can be further substituted) is used. 8. Component (A) is the following formula (5) (5) ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R_6, R_7, R_8, R_9 are hydrogen, hydroxyl, chlorine, bromine, methyl, tert- means butyl, methoxy, methoxyethoxy, ethoxyethoxyethoxy, or diethylamino, and R_7 can also mean sulfo, X_1 means hydrogen, methyl, ethyl, or phenyl, Y_1 means hydrogen, or R_6 Together with R_7, they form a benzene ring, and X
The method according to claim 4, characterized in that a bisazomethine complex salt of _1 and Y_2 together forming a cyclohexylene group is used. 9. Component (A) is the following formula (6) (6) ▲ Numerical formula, chemical formula, table, etc. , and R_1_1 can also mean sulfo, or R_1_0 together with R_1_1 form a benzene ring, R_1_2 means hydrogen or hydroxyl, and X_2 means hydrogen, methyl, ethyl, or phenyl). 9. A method according to claim 8, characterized in that a complex salt is used. 10. Component (B) is the following formula (7) (7) ▲ Numerical formula, chemical formula, table, etc. ▼, (In the formula, R_1 is hydrogen, hydroxyl, or C_1-C_1_
4-alkoxy, R_2 is hydrogen, C_1-C_4-alkyl, or sulfo, R_3 is hydrogen, hydroxyl, or C_1-C_4-
10. Process according to any one of claims 1 to 9, characterized in that a 2-hydroxybenzophenone of alkoxy, R_4 means hydrogen, hydroxyl or carboxyl is used. 11. Component (B) is the following formula (8) (8) ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R_1 is hydrogen, C_1-C_1_2-alkyl, chlorine,
C_5-C_6-cycloalkyl, C_7-C_9-phenylalkyl, or sulfo, R_2 is hydrogen, C_1-C_4-alkyl, C_1-C
_4-alkoxy, chlorine, hydroxyl, or sulfo, R_3 is C_1-C_1_2-alkyl, C_1-C_
4-Alkoxy, phenyl, (C_1-C_6-alkyl)-phenyl, C_3-C_6-cycloalkyl, C
_2-C_9-alkoxycarbonyl, chlorine, carboxyethyl, C_7-C_9-phenylalkyl, or sulfo, R_4 is hydrogen, chlorine, C_1-C_4-alkyl, C_
1-C_4-alkoxy, C_2-C_9 alkoxycarbonyl, carboxyl, or sulfo, R_5 means hydrogen or chlorine) 2-(2'-hydroxyphenyl)-benzotriazole or a salt thereof is used. A method according to any one of claims 1 to 9. 12. The method according to any one of claims 1 to 9, characterized in that as component (B) a compound selected from the class of sterically hindered amines is used. 13. At least one sterically hindered amine in the molecule
2,2,6,6-tetraalkylpiperidine containing the following formula (9) (9) ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R means hydrogen or methyl) Claim 12, characterized in that a derivative is used.
The method described in section. 14. Component (B) is the following formula (12) (12) ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R is hydrogen, halogen, C_1-C_4-alkyl, or sulfo, R_1 is hydrogen, C_1- C_4-alkyl, C_1-C
_4-alkoxy or hydroxyl, R_2 is hydrogen or sulfo, R_3 and R_4 are independently C_1-C_4-alkyl, C_1-C_4-alkoxy, C_5-C_6
-cycloalkyl, phenyl, or C_1-C_4-
2-(2'-hydroxyphenyl)-, meaning phenyl substituted by alkyl and hydroxyl
The method according to any one of claims 1 to 9, characterized in that s-triazine or a salt thereof is used. 15. Component (B) is formula (12a) ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, at least one of the substituents R_1, R_2, R_3 is formula (12b) ▲ Numerical formula, chemical formula, etc.▼ (where M is sodium, potassium, calcium, magnesium, ammonium, or tetra-C_1-C_
4-alkylammonium and m is 1 or 2), and the remaining substituents are independently of each other C_1-C_1_2-alkyl, phenyl,
or C_ attached to the triazinyl group by oxygen, sulfur, imino, or C_1-C_4-alkylimino
1-C_1_2-means alkyl or phenyl]
10. The method according to claim 1, wherein the s-triazine compound is used. 16. Component (C) is the following formula (13) (13) ▲ Numerical formula, chemical formula, table, etc. -O(CH_2)_6O-, -O(CH_2)_2O(
CH_2)_2O-, -O(CH_2)_2O(CH_
2)_2O(CH_2)_2O-, HN-(CH_2)
_2_6-NH-, or -O(CH_2)_2-S-
(CH_2)_2O- or group -(CH_2O)_4-
Claims 1 to 1 are characterized in that hydroxyphenylpropionate (C) is used.
The method described in any of Section 5. 17. Component (C) is the following formula (14) (14) ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R is hydroxyl, phenyl, phenoxy, C_1-C
_1_8-alkylphenoxy, C_1-C_2_4-
Alkylthio, or C_1-C_2_4-alkoxy, R_1 is phenoxy, C_1-C_1_8-alkylphenoxy, C_1-C_2_4-alkylthio, or C_1-C_2_4-alkoxy, R_2 and R_3 are independently C_1-C_1_8
-alkyl, R_4 means hydrogen or C_1-C_4-alkyl and n is 0, 1, 2 or 3). 16. The method according to any one of Item 15. 18, (a) 0.005 to 0.20% by weight of an organic copper complex salt, (b) 0.05 to 3% by weight of a light stabilizer, preferably 0
．． dyed or undyed, characterized in that it contains 1 to 1% by weight, and optionally (c) 0.05 to 3% by weight, preferably 0.1 to 1% by weight of an antioxidant. photochemical stabilizers of polyamide fiber materials or mixtures of polyamide fiber materials with other fiber materials. 19. Polyamide fiber materials and mixtures of polyamide fiber materials and other fiber materials treated by the method according to any one of claims 1 to 16.