EP0475905A1 - Process for the photochemical stabilisation of wool - Google Patents

Process for the photochemical stabilisation of wool Download PDF

Info

Publication number
EP0475905A1
EP0475905A1 EP91810709A EP91810709A EP0475905A1 EP 0475905 A1 EP0475905 A1 EP 0475905A1 EP 91810709 A EP91810709 A EP 91810709A EP 91810709 A EP91810709 A EP 91810709A EP 0475905 A1 EP0475905 A1 EP 0475905A1
Authority
EP
European Patent Office
Prior art keywords
formula
alkylamino
wool
phenyl
mono
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP91810709A
Other languages
German (de)
French (fr)
Other versions
EP0475905B1 (en
Inventor
Manfred Dr. Rembold
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF Schweiz AG
Original Assignee
Ciba Geigy AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ciba Geigy AG filed Critical Ciba Geigy AG
Publication of EP0475905A1 publication Critical patent/EP0475905A1/en
Application granted granted Critical
Publication of EP0475905B1 publication Critical patent/EP0475905B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/35—Heterocyclic compounds
    • D06M13/355—Heterocyclic compounds having six-membered heterocyclic rings
    • D06M13/358—Triazines
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/62—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing low-molecular-weight organic compounds with sulfate, sulfonate, sulfenic or sulfinic groups
    • D06P1/628—Compounds containing nitrogen
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/64—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing low-molecular-weight organic compounds without sulfate or sulfonate groups
    • D06P1/642—Compounds containing nitrogen
    • D06P1/6426—Heterocyclic compounds
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/02—Material containing basic nitrogen
    • D06P3/04—Material containing basic nitrogen containing amide groups
    • D06P3/14—Wool
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
    • Y10S8/916—Natural fiber dyeing
    • Y10S8/917—Wool or silk

Definitions

  • the present invention relates to a process for the photochemical stabilization of wool or mixed fibers containing wool, an agent and a liquor for carrying out the process, and the fiber material treated with it.
  • the method according to the invention is characterized in that the wool or the mixed fiber containing wool is treated with an aqueous liquor which has at least one UV absorber of the formula contains wherein at least one of the substituents R1, R2 and R3 are a radical of the formula is what M hydrogen; Sodium; Potassium; Calcium; Magnesium; Ammonium; Mono-, di-, tri- or tretraalkylammonium; Mono-, di- or trihydroxyalkylammonium; or mixed with hydroxyalkyl and alkyl disubstituted or trisubstituted ammonium ions; m 1; or 2; and the or the other substituents independently of one another unsubstituted or substituted C1-C12 alkyl, C1-C12 alkoxy, C1-C12 alkylthio, mono-C1-C12 alkylamino or di-C1-C12 alkylamino; unsubstituted or phenyl, phenoxy, phen
  • substituents as an individual radical e.g. alkyl
  • compound radical e.g. alkoxyl
  • C1-C12 alkyl examples include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, or dodecyl or isomers of these radicals.
  • Particularly preferred alkyl radicals contain 1 to 4 carbon atoms.
  • alkyl radicals in the mono-, di-, tri- or treaalkylammonium ions are in particular independently of one another C1-C4-alkyl radicals, such as butyl, propyl, ethyl and preferably methyl.
  • Mono-, di- or trihydroxyalkylammonium are C1-C4-hydroxyalkylammonium cations which are derived in particular from ethanolamine, diethanolamine or triethanolamine.
  • the invention also includes mixed C1-C4-hydroxyalkyl-C1-C4-alkylamines, such as the cations derived from N-methyl-N-ethanolamine or N, N-dimethyl-N-ethanolamine.
  • Suitable substituents for the phenyl radicals are alkyl or alkoxy radicals having 1 to 12 carbon atoms, such as methyl, tert. Butyl, pentyl, octyl, nonyl, decyl, dodecyl, methoxy, butoxy or pentoxy, furthermore cyclopentyl, clyclohexyl and halogen in particular chlorine, in question.
  • the radicals R1, R2 and R3 can be further substituted.
  • C1-C4 alkoxyl such as methoxy or hydroxyl, phenyl or carbalkoxy having 2 to 9 carbon atoms, are the preferred substituents on the alkyl radicals of the C1-C12 alkyl, C1-C12 alkoxy, C1-C12 alkylthio, mono -C1-C12 alkylamino or di-C1-C12 alkylamino radicals.
  • the compounds of formula (1) include the potassium salt of such compounds in which R1 phenyl and R2 and R3 each represent the rest of the formula (2) or the sodium salt of the compound of formula (1), wherein R1 p-chlorophenyl and R2 and R3 each represent the rest of the formula (2) into consideration.
  • UV absorbers those of the formula correspond to what R4 and R5 independently of one another, C1-C12 alkyl; m 1 or 2; M hydrogen; Sodium; Potassium; Calcium; Magnesium; Ammonium or tetraalkylammonium; and n1 and n2 0; 1; or 2; means.
  • R1 is phenyl, tolyl or xylyl
  • R1 and R2 means phenyl, tolyl or xylyl
  • M is hydrogen, sodium or potassium, in particular hydrogen.
  • the compounds of formula (1) can be prepared in a manner known per se, e.g. according to the processes described in EP-A-0 165 608.
  • the amount of UV absorber to be added depends on the substrate and the desired stabilization. In general, 0.1 to 5, preferably 0.3 to 3% by weight, based on the wool, is added.
  • the process according to the invention also photochemically stabilizes the dyeings applied to the wool.
  • the dyeings to be stabilized according to the invention are in particular those which are formed by acid or metal complex dyes, e.g. 1: 2 chromium, 1: 2 cobalt complex dyes or Cu complex dyes are generated.
  • the amount of dye to be added can vary within wide limits, from 0.01 to 10% by weight, based on the wool, of dye. Quantities are preferred from 0.05 to 2% by weight.
  • the compounds of the formula (1) are applied from an aqueous bath.
  • the application can take place before, during or after dyeing, the dyeing and photochemical stabilization preferably being carried out in the same bath.
  • the coloring and photochemical stabilization are expediently carried out simultaneously.
  • UV absorber, dye and the chemicals usual for the dyeing process are added to the aqueous dyeing liquor.
  • Mineral acids such as e.g. Sulfuric acid or phosphoric acid, organic acids, expediently aliphatic carboxylic acids such as formic acid, acetic acid, oxalic acid or citric acid and / or salts such as ammonium acetate, ammonium sulfate or sodium acetate.
  • the acids are used primarily to adjust the pH of the liquors used according to the invention, which can be varied within wide ranges; the pH is preferably between 3 and 8.
  • the dyeing liquors also contain commercially available dispersing and leveling agents and can furthermore contain auxiliaries customary in dyeing technology, such as electrolytes, wetting agents, defoamers, antifoams, thickeners or wool preservatives.
  • All continuous and discontinuous dyeing processes can be used with the usual dyeing machines, such as open baths, combed, strand yarn or packing machines, jiggers, paddle machines, tree dyeing machines, circulation or jet dyeing machines or reel runners for the treatment.
  • the process according to the invention expediently takes place in the exhaust process, normal pressure dyeing apparatus being used.
  • the liquor ratio can be selected within a wide range, e.g. 1: 5 to 1: 300, preferably 1:10 to 1:50. It is convenient to work at a temperature of 30 to 120 ° C, preferably 50 to 98 ° C.
  • the liquor application is expediently 30-400% by weight, preferably 75-250% by weight.
  • the fiber material is subjected to heat treatment to fix the applied dyes.
  • the fixation process 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 to 7, preferably 1 to 5 minutes.
  • the fixation of the dyes and the compounds of formula (1) according to the cold residence process can be carried out 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 type of dye applied.
  • the duration of treatment depends on the duration of dyeing, which is within the usual range and is usually 20 to 120 minutes. If the UV absorber is added before or after the dyeing stage, the treatment time is 15 to 60 minutes.
  • the dyeings produced are rinsed and dried in the customary manner.
  • Wool can be considered as the fiber material that can be dyed according to the invention.
  • the wool can be finished normally or without felt.
  • fiber blends made of wool and synthetic polyamide or wool / polyester blends can also be used, e.g. Jersey material made of wool / polyamide in a mixing ratio of 70:30.
  • the pure or mixed fiber material can be in various processing forms, such as as fiber, yarn, fabric, knitted fabric, fleece or pile material.
  • the present method is particularly advantageous for the treatment of fiber material which is exposed to light and heat and is used, for example, as a car upholstery material or carpet.
  • the UV absorbers used according to the invention can be used in a wide pH range, which means that they are also suitable for application Mixtures of wool with other fibers, such as wool and polyamide, are suitable.
  • the present invention furthermore relates to an agent for carrying out the process according to the invention, which is characterized in that it contains at least one UV absorber of the formulas (1) or (3), the meaning of which is as defined above, in addition to the customary formulation auxiliaries such as wetting and thinning agents.
  • Example 1 4 samples of 10 g each of a wool sergeant fabric are dyed at a liquor ratio of 1:25 in an open dyeing machine, for example an AHIBA®. Four fleets are prepared for this, which contain the following additives:
  • Fleet 3 (model 3): This fleet corresponds to fleet 1 with the difference that it additionally 1% of the compound of the formula contains.
  • Fleet 5 (model 5): This fleet corresponds to fleet 1 with the difference that it additionally 1% of the compound of the formula contains.
  • Fleet 6 (sample 6): This fleet corresponds to fleet 2 with the difference that no dye is used (blind dyeing with UV absorber).
  • Fleet 7 (pattern 7): This fleet corresponds to fleet 1 with the difference that no dye is used (blind dyeing without UV absorber). If necessary, the pH is adjusted to 4.5 with 10% acetic acid.
  • Table 1 shows the light fastness according to the gray scale and the colorimetric evaluations according to DIN 6174 (Cielab formula).
  • Example 2 2 samples of 10 g each of a wool sergeant fabric are dyed at a liquor ratio of 1:25 in an open dyeing machine, for example an ® AHIBA.
  • Two fleets are prepared, which contain the following additives: Fleet 1 (sample 1): 6% ammonium sulfate 5% Glauber's salt 1 g / l sodium acetate 1% of an anionic leveling agent based on an alkylaminopolyglycol ether 0.01% of the dye of the formula and 0.01% of the dye of the formula

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Coloring (AREA)

Abstract

The process is characterised in that the wool is treated with an aqueous solution which contains at least one UV absorber of the formula <IMAGE> in which at least one of the substituents R1, R2 and R3 is a radical of the formula <IMAGE> in which   M is hydrogen; or a cation equivalent;   m denotes 1; or 2; and   the other substituent or substituents independently of one another denote amino; C1-C12-alkyl; C1-C12-alkoxy; C1-C12-alkylthio; C1-C12-alkylamino; di-C1-C12-alkylamino; phenyl; phenoxy; phenylthio; anilino; or N-phenyl-N-C1-C4-alkylamino. <??>The UV absorbers can be used in a wide pH range and effectively reduce yellowing of the wool.

Description

Die vorliegende Erfingung betrifft ein Verfahren zum photochemischen Stablisieren von Wolle oder Wolle enthaltenden Mischfasern, ein Mittel und eine Flotte zur Ausführung des Verfahrens sowie das damit behandelte Fasermaterial.The present invention relates to a process for the photochemical stabilization of wool or mixed fibers containing wool, an agent and a liquor for carrying out the process, and the fiber material treated with it.

Das erfindunggemässe Verfahren is dadurch gekennzeichnet, dass man die Wolle oder die Wolle enthaltende Mischfaser mit einer wässrigen Flotte behandelt, welche mindestens einen UV-Absorber der Formel

Figure imgb0001

enthält,
worin mindestens einer der Substituenten
R₁, R₂ und R₃ ein Rest der Formel
Figure imgb0002
ist, worin
M Wasserstoff; Natrium; Kalium; Calcium; Magnesium; Ammonium; Mono-, Di-, Tri-oder Tretraalkylammonium; Mono-, Di- oder Trihydroxyalkylammonium; oder gemischt durch Hydroxyalkyl und Alkyl zwei- oder dreifach substituierten Ammoniumionen;
m 1; oder 2; und
der oder die übrigen Substituenten unabhängig voneinander unsubsitituiertes oder substituiertes C₁-C₁₂ Alkyl, C₁-C₁₂-Alkoxy, C₁-C₁₂-Alkylthio, mono-C₁-C₁₂-Alkylamino oder di-C₁-C₁₂-Alkylamino; unsubsituiertes oder gegebenenfalls im Phenylkern substituiertes Phenyl, Phenoxy, Phenylthio, Anilino oder N-Phenyl-N-C₁-C₄-alkylamino;
bedeutet.The method according to the invention is characterized in that the wool or the mixed fiber containing wool is treated with an aqueous liquor which has at least one UV absorber of the formula
Figure imgb0001
contains
wherein at least one of the substituents
R₁, R₂ and R₃ are a radical of the formula
Figure imgb0002
is what
M hydrogen; Sodium; Potassium; Calcium; Magnesium; Ammonium; Mono-, di-, tri- or tretraalkylammonium; Mono-, di- or trihydroxyalkylammonium; or mixed with hydroxyalkyl and alkyl disubstituted or trisubstituted ammonium ions;
m 1; or 2; and
the or the other substituents independently of one another unsubstituted or substituted C₁-C₁₂ alkyl, C₁-C₁₂ alkoxy, C₁-C₁₂ alkylthio, mono-C₁-C₁₂ alkylamino or di-C₁-C₁₂ alkylamino; unsubstituted or phenyl, phenoxy, phenylthio, anilino or N-phenyl-N-C₁-C₄-alkylamino optionally substituted in the phenyl nucleus;
means.

Die Substituenten als eizelnes Radikal (z.B. Alkyl) oder als Teil eines grösseren, zusammengesetzten Radikals (z.B. Alkoxyl) können insbesondere die nachstehenden Bedeutungen haben:The substituents as an individual radical (e.g. alkyl) or as part of a larger, compound radical (e.g. alkoxyl) can in particular have the following meanings:

Als Beispiele für C₁-C₁₂ Alkyl seien Methyl, Ethyl, Propyl, Butyl, Pentyl, Hexyl, Heptyl, Octyl, Nonyl, Decyl, Undecyl, oder Dodecyl oder Isomere dieser Reste genannt. Besonders beorzugte Alkylreste enthalten 1 bis 4 Kohlenstoffatome.Examples of C₁-C₁₂ alkyl are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, or dodecyl or isomers of these radicals. Particularly preferred alkyl radicals contain 1 to 4 carbon atoms.

Die Alkylradikale in den Mono-, Di-, Tri- oder Treaalkylammoniumionen sind insbesondere unabhängig voneinander C₁-C₄-Alkylradikale, wie Butyl, Propyl, Ethyl und vorzugsweise Methyl.The alkyl radicals in the mono-, di-, tri- or treaalkylammonium ions are in particular independently of one another C₁-C₄-alkyl radicals, such as butyl, propyl, ethyl and preferably methyl.

Mono-, Di- oder Trihydroxyalkylammonium sind C₁-C₄-Hydroxyalkylammoniumkationen, die sich insbesondere von Ethanolamin, Diethanolamin oder Triethanolamin ableiten. Weiterhin umfasst die Erfindung auch gemischte C₁-C₄-Hydroxyalkyl-C₁-C₄-alkylamine, wie etwa die von N-Methyl-N-ethanolamin oder N,N-Dimethyl-N-ethanolamin abgeleiteten Kationen.Mono-, di- or trihydroxyalkylammonium are C₁-C₄-hydroxyalkylammonium cations which are derived in particular from ethanolamine, diethanolamine or triethanolamine. Furthermore, the invention also includes mixed C₁-C₄-hydroxyalkyl-C₁-C₄-alkylamines, such as the cations derived from N-methyl-N-ethanolamine or N, N-dimethyl-N-ethanolamine.

Als Substituenten für die Phenylreste kommen Alkyl- oder Alkoxyreste mit 1 bis 12 Kohlenstoffatomen, wie Methyl, tert. Butyl, Pentyl, Octyl, Nonyl, Decyl, Dodecyl, Methoxy, Butoxy oder Pentoxy, ferner Cyclopentyl, Clyclohexyl und Halogen insbesondere Chlor, in Frage.Suitable substituents for the phenyl radicals are alkyl or alkoxy radicals having 1 to 12 carbon atoms, such as methyl, tert. Butyl, pentyl, octyl, nonyl, decyl, dodecyl, methoxy, butoxy or pentoxy, furthermore cyclopentyl, clyclohexyl and halogen in particular chlorine, in question.

Die Reste R₁, R₂ und R₃ können weiter substituiert sein. Beispeilsweise sind C₁-C₄-Alkoxyl, wie etwa Methoxy oder Hydroxyl, Phenyl oder Carbalkoxy mit 2 bis 9 Kohlenstoffatomen die bevorzugten Substituenten an den Alkylresten der C₁-C₁₂ Alkyl-, C₁-C₁₂-Alkoxy-, C₁-C₁₂-Alkylthio-, mono-C₁-C₁₂-Alkylamino- oder di-C₁-C₁₂-Alkylamino-Radikale.The radicals R₁, R₂ and R₃ can be further substituted. For example, C₁-C₄ alkoxyl, such as methoxy or hydroxyl, phenyl or carbalkoxy having 2 to 9 carbon atoms, are the preferred substituents on the alkyl radicals of the C₁-C₁₂ alkyl, C₁-C₁₂ alkoxy, C₁-C₁₂ alkylthio, mono -C₁-C₁₂ alkylamino or di-C₁-C₁₂ alkylamino radicals.

Beispielsweise kommen als Verbindungen der Formel (1) das Kaliumsalz von solchen Verbindungen worin
R₁ Phenyl und
R₂ und R₃ je den Rest der Formel (2) bedeuten oder
das Natriumsalz der Verbindung der Formel (1), worin
R₁ p-Chlorphenyl und
R₂ und R₃ je den Rest der Formel (2) bedeuten, in Betracht.For example, the compounds of formula (1) include the potassium salt of such compounds in which
R₁ phenyl and
R₂ and R₃ each represent the rest of the formula (2) or
the sodium salt of the compound of formula (1), wherein
R₁ p-chlorophenyl and
R₂ and R₃ each represent the rest of the formula (2) into consideration.

Bevorzugt sind auch Verbindungen der Formel (1), worin
M Wasserstoff und
R₂ und R₃ je den Rest der Formel (2) bedeuten und
Verbindungen der Formel (1), worin
R₃ den Rest der Formel (2) bedeutet.Compounds of the formula (1) in which
M hydrogen and
R₂ and R₃ each represent the rest of the formula (2) and
Compounds of formula (1), wherein
R₃ represents the rest of the formula (2).

Im Vordergrund des Interesses stehen UV-Absorber, die der Formel

Figure imgb0003

entsprechen, worin
R₄ und R₅ unabhängig voneinander, C₁-C₁₂-Alkyl;
m 1 oder 2;
M Wasserstoff; Natrium; Kalium; Calcium; Magnesium; Ammonium oder Tetraalkyl- ammonium; und
n₁ und n₂ 0; 1; oder 2;
bedeutet.The focus of interest is on UV absorbers, those of the formula
Figure imgb0003
correspond to what
R₄ and R₅ independently of one another, C₁-C₁₂ alkyl;
m 1 or 2;
M hydrogen; Sodium; Potassium; Calcium; Magnesium; Ammonium or tetraalkylammonium; and
n₁ and n₂ 0; 1; or 2;
means.

Besonders bevorzugt sind dabei Verbindungen der Formel (3), worin
M Wasserstoff;
R₄ und R₅ Methyl; und
n₁ und n₂ 1 oder 2 bedeuten.Compounds of the formula (3) in which
M hydrogen;
R₄ and R₅ methyl; and
n₁ and n₂ represent 1 or 2.

Hervorzuheben sind auch Verbindungen der Formel (1), worin
R₁ Phenyl, Tolyl oder Xylyl bedeutet
und
Verbindungen der Formel (1), worin
R₁ und R₂ Phenyl, Tolyl oder Xylyl bedeutet.Also to be emphasized are compounds of formula (1) in which
R₁ is phenyl, tolyl or xylyl
and
Compounds of formula (1), wherein
R₁ and R₂ means phenyl, tolyl or xylyl.

Von den hervorgehobenen Verbindungen der Formel (1) sind diejenigen bevorzugt, in denen
M Wasserstoff, Natrium oder Kalium, insbesondere Wasserstoff, bedeutet.Of the highlighted compounds of formula (1), those are preferred in which
M is hydrogen, sodium or potassium, in particular hydrogen.

Als Einzelverbindungen zu nennen sind:
2,4-Diphenyl-6-[2-hydroxy-4-(2-hydroxy-3-sulfopropoxy)-phenyl]- 1,3,5-tria zin (Verb. No. 101),
2-Phenyl-4,6-bis-[2-hydroxy-4-(2-hydroxy-3-sulfopropoxy)-phenyl]-1,3,5-triazin (Verb. No. 102),
2,4-Bis-(2,4-dimethylphenyl)-6-[2-hydroxy-4-(2-hydroxy-3-sulfopropoxy)-phenyl]-1,3,5-triazin (Verb. No. 103) und
2,4-Bis-(4-methylphenyl)-6-[2-hydroxy-4-(2-hydroxy-3-sulfopropoxy)-phenyl]-1,3,5-triazin (Verb. No. 104).The following are to be mentioned as individual connections:
2,4-diphenyl-6- [2-hydroxy-4- (2-hydroxy-3-sulfopropoxy) phenyl] -1,3,5-triazine (Verb. No. 101),
2-phenyl-4,6-bis- [2-hydroxy-4- (2-hydroxy-3-sulfopropoxy) phenyl] -1,3,5-triazine (Verb. No. 102),
2,4-bis (2,4-dimethylphenyl) -6- [2-hydroxy-4- (2-hydroxy-3-sulfopropoxy) phenyl] -1,3,5-triazine (comp.No. 103) and
2,4-bis (4-methylphenyl) -6- [2-hydroxy-4- (2-hydroxy-3-sulfopropoxy) phenyl] -1,3,5-triazine (comp. No. 104).

Die Verbindungen der Formel (1) können in an sich bekannter Weise hergestellt werden, z.B. nach den in der EP-A-0 165 608 beschriebenen Verfahren.The compounds of formula (1) can be prepared in a manner known per se, e.g. according to the processes described in EP-A-0 165 608.

Die Menge der zuzusetzenden UV-Absorber hängt vom Substrat und der gewünschten Stabilisierung ab. Im allgemeinen setzt man 0,1 bis 5, vorzugsweise 0,3 bis 3 Gew. %, bezogen auf die Wolle, zu.The amount of UV absorber to be added depends on the substrate and the desired stabilization. In general, 0.1 to 5, preferably 0.3 to 3% by weight, based on the wool, is added.

Neben der Wollfaser werden mit dem erfindungsgemässen Verfahren auch die auf die Wolle applizierten Färbungen photochemisch stabilisiert. Als die erfindungsgemäss zu stabilisierenden Färbungen kommen dabei insbesondere solche in Betracht, die durch Säure- oder Metallkomplexfarbstoffe, z.B. 1:2-Chrom, 1:2-Kobaltkomplexfarbstoffe oder Cu-Komplexfarbstoffe erzeugt werden.In addition to the wool fiber, the process according to the invention also photochemically stabilizes the dyeings applied to the wool. The dyeings to be stabilized according to the invention are in particular those which are formed by acid or metal complex dyes, e.g. 1: 2 chromium, 1: 2 cobalt complex dyes or Cu complex dyes are generated.

Die Menge an zuzusetzendem Farbstoffkann in weiten Grenzen schwanken, man kann 0,01 bis 10 Gew.%, bezogen auf die Wolle, Farbstoff zusetzen. Bevorzugt sind Mengen von 0,05 bis 2 Gew.%.The amount of dye to be added can vary within wide limits, from 0.01 to 10% by weight, based on the wool, of dye. Quantities are preferred from 0.05 to 2% by weight.

Die Verbindungen der Formel (1) werden erfindungsgemäss aus wässrigem Bad appliziert. Die Applikation kann dabei vor, während oder nach dem Färben erfolgen, wobei Färbung und photochemische Stabilisierung vorzugsweise im gleichen Bad vorgenommen werden. Zweckmässigerweise wird die Färbung und photochemische Stabilisierung gleichzeitig vorgenommen. Dabei werden UV-Absorber, Farbstoff und die für den Färbeprozess üblichen Chemikalien zusammen der wässrigen Färbeflotte zugefügt.According to the invention, the compounds of the formula (1) are applied from an aqueous bath. The application can take place before, during or after dyeing, the dyeing and photochemical stabilization preferably being carried out in the same bath. The coloring and photochemical stabilization are expediently carried out simultaneously. UV absorber, dye and the chemicals usual for the dyeing process are added to the aqueous dyeing liquor.

Als übliche Chemikalien können Mineralsäuren, wie z.B. Schwefelsäure oder Phosphorsäure, organische Säuren, zweckmässig aliphatische Carbonssäuren wie Ameisensäure, Essigsäure, Oxalsäure oder Zitronensäure und/oder Salze wie Ammoniumacetat, Ammoniumsulfat oder Natriumacetat in Betracht kommen. Die Säuren dienen vor allem der Einstellung des pH-Wertes der erfindungsgemäss verwendeten Flotten, der in weiten Bereichen variiert werden kann, vorzugsweise liegt der pH-Wert zwischen 3 und 8.Mineral acids, such as e.g. Sulfuric acid or phosphoric acid, organic acids, expediently aliphatic carboxylic acids such as formic acid, acetic acid, oxalic acid or citric acid and / or salts such as ammonium acetate, ammonium sulfate or sodium acetate. The acids are used primarily to adjust the pH of the liquors used according to the invention, which can be varied within wide ranges; the pH is preferably between 3 and 8.

Die Färbeflotten enthalten ausserdem handelsübliche Dispergier- und Egalisiermittel und können weiterhin in der Färbetechnik übliche Hilfsmittel wie Elektrolyte, Netzmittel, Entschäumer, Schaumverhütungsmittel, Verdicker oder Wollschutzmittel enthalten.The dyeing liquors also contain commercially available dispersing and leveling agents and can furthermore contain auxiliaries customary in dyeing technology, such as electrolytes, wetting agents, defoamers, antifoams, thickeners or wool preservatives.

Besondere Vorrichtungen sind für die Durchführung des erfindungsgemässen Verfahrens nicht erforderlich. Es können für die Behandlung alle kontinuierlichen und diskontinuierlichen Färbeverfahren mit den dafür üblichen Färbeapparaturen, wie beispielsweise offene Bäder, Kammzug-, Stranggarn- oder Packapparate, Jigger-, Paddelapparate, Baumfärbeapparate, Zirkulations- oder Düsenfärbeapparate oder Haspelkufen verwendet werden. Zweckmässigerweise erfolgt das erfindungsgemässe Verfahren im Ausziehverfahren, wobei Normaldruckfärbeapparate verwendet werden.Special devices are not required to carry out the method according to the invention. All continuous and discontinuous dyeing processes can be used with the usual dyeing machines, such as open baths, combed, strand yarn or packing machines, jiggers, paddle machines, tree dyeing machines, circulation or jet dyeing machines or reel runners for the treatment. The process according to the invention expediently takes place in the exhaust process, normal pressure dyeing apparatus being used.

Beim Ausziehverfahren kann das Flottenverhältnis innerhalb eines weiten Bereiches gewählt werden, z.B. 1:5 bis 1:300, vorzugsweise 1:10 bis 1:50. Man arbeitet zweckmässig bei einer Temperatur von 30 bis 120°C, vorzugsweise 50 bis 98°C.In the exhaust process, the liquor ratio can be selected within a wide range, e.g. 1: 5 to 1: 300, preferably 1:10 to 1:50. It is convenient to work at a temperature of 30 to 120 ° C, preferably 50 to 98 ° C.

Beim Kontinue-Verfahren beträgt der Flottenauftrag zweckmässig 30-400 Gew. %, vorzugsweise 75-250 Gew.%. Zur Fixierung der applizierten Farbstoffe wird das Fasermaterial einer Hitzebehanldung unterworfen. Der Fixieprozess kann auch nach der Kaltverweilmethode erfolgen.In the continuous process, the liquor application is expediently 30-400% by weight, preferably 75-250% by weight. The fiber material is subjected to heat treatment to fix the applied dyes. The fixation process can also be carried out using the cold dwell method.

Die Hitzebehandlung erfolgt vorzugsweise durch ein Dämpfverfahren unter Behandlung in einem Dämpfer mit gegebenenfalls überhitztem Dampf bei einer Temperatur von 98 bis 105°C während z.B. 1 bis 7, voorzugsweise 1 bis 5 Minuten. Die Fixierung der Farbstoffe und der Verbindungen der Formel ( 1) gemäss dem Kaltverweilverfahren kann durch Lagerung der imprägnierten und vorzugsweise aufgeerollten Ware bei Raumtemperatur (15 bis 30°C), z.B. wärhend 3 bis 24 Stunden erfolgen, wobei die Kaltverweilzeit bekanntlich von der Art des applizierten Farbstoffes abhängig ist.The heat treatment is preferably carried out by a steaming process with treatment in a steamer with possibly superheated steam at a temperature of 98 to 105 ° C during e.g. 1 to 7, preferably 1 to 5 minutes. The fixation of the dyes and the compounds of formula (1) according to the cold residence process can be carried out 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 type of dye applied.

Die Behandlungsdauer richtet sich bei gleichzeitiger Applikation mit dem Farbstoff nach der Färbedauer, die sich im üblichen Rahmen hält und in der Regel 20 bis 120 Minuten beträgt. Wird der UV-Absorber vor oder nach der Färstufe zugefügt, beträgt die Behandlungsdauer 15 bis 60 Minuten.The duration of treatment depends on the duration of dyeing, which is within the usual range and is usually 20 to 120 minutes. If the UV absorber is added before or after the dyeing stage, the treatment time is 15 to 60 minutes.

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

Man erhält mit dem erfindungsgemässen Verfarhen Woll-Färbungen und -fasern mit guter thermischer und photochemischer Stabilität. Ausserdem wird die Abrieb- und Reissfestigkeit der Fasern gegenüber photochemischen Einwirkungen verbesssert.With the process according to the invention, wool dyeings and fibers with good thermal and photochemical stability are obtained. In addition, the abrasion and tear resistance of the fibers against photochemical effects is improved.

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

Als Fasermaterial, das erfindungsgemäss gefärbt werden kann, kommt Wolle in Betracht. Die Wolle kann normal oder filzfrei ausgerüstet sein. Neben den reinen Wollfasern kommen auch Fasermischungen aus Wolle und synthetischem Polyamid oder Wolle/Polyestergemische in Betracht, so z.B. Trikotmaterial aus Wolle/Polyamid im Mischungsverhältnis 70:30. Grundsätzlich kann das reine oder gemischte Fasermateral in den verschiedensten Verarbeitungsformen vorliegen, wie z.B. als Faser, Garn, Gewebe, Gewirke, Vlies oder Flormaterial.Wool can be considered as the fiber material that can be dyed according to the invention. The wool can be finished normally or without felt. In addition to pure wool fibers, fiber blends made of wool and synthetic polyamide or wool / polyester blends can also be used, e.g. Jersey material made of wool / polyamide in a mixing ratio of 70:30. Basically, the pure or mixed fiber material can be in various processing forms, such as as fiber, yarn, fabric, knitted fabric, fleece or pile material.

Das vorliegende Verfahren eignet sich besonders vorteilhaft zur Behandlung von Fasermateral, das Licht und Hitze ausgesetzt wird und z.B. als Autopolsterstoff oder Teppich Verwendung findet. Die erfinindungsgemäss verwendeten UV-Absorber können dabei in einem weiten pH-Bereich eingesetzt werden, wodurch sie auch für die Applikation bei Mischungen von Wolle mit anderen Fasern, z.B. Wolle und Polyamid, geeignet sind.The present method is particularly advantageous for the treatment of fiber material which is exposed to light and heat and is used, for example, as a car upholstery material or carpet. The UV absorbers used according to the invention can be used in a wide pH range, which means that they are also suitable for application Mixtures of wool with other fibers, such as wool and polyamide, are suitable.

Ein weiterer Gegenstand der vorliegenden Erfindung ist ein Mittel zur Ausführung des erfindungsgemässen Verfahrens, das dadurch gekennzeichnet ist, dass es mindestens einen UV-Absorber der Formeln (1) oder (3), dessen Bedeutung wie zuvor definiert ist, enthält, neben den üblichen Formulierungshilfsstoffen, wie etwa Netz- und Verdünnungsmittel.The present invention furthermore relates to an agent for carrying out the process according to the invention, which is characterized in that it contains at least one UV absorber of the formulas (1) or (3), the meaning of which is as defined above, in addition to the customary formulation auxiliaries such as wetting and thinning agents.

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

Beispiel 1: 4 Muster von je 10 g eines Woll-Sèrge-Gewebes werden bei einem Flottenverhältnis von 1:25 in einem offenen Färbeapparat, z.B. einem® AHIBA gefärbt. Es werden dazu 4 Flotten bereitet, die folgende Zusätze enthalten: Example 1: 4 samples of 10 g each of a wool sergeant fabric are dyed at a liquor ratio of 1:25 in an open dyeing machine, for example an AHIBA®. Four fleets are prepared for this, which contain the following additives:

Flotte 1 (Muster 1):
   0,4 ml/l eines nichtionogenen Dispergators 0,5 %ig, z.B.
   das Amagerungsprodukt aus 1 Mol 4-Isooctylphenol und
   8 Mol Ethylenoxid
   5 % Glaubersalz
   1 g/l Natriumacetat
   1 % eines anionischen Egalisiermittels
   0,01 % des Färbstoffes der Formel

Figure imgb0004
   0,01 % des Färbstoffes der Formel
Figure imgb0005
 Fleet 1 (sample 1):
0.4 ml / l of a non-ionic dispersant 0.5%, e.g.
the amager product from 1 mol of 4-isooctylphenol and
8 moles of ethylene oxide
5% Glauber's salt
1 g / l sodium acetate
1% of an anionic leveling agent
0.01% of the dye of the formula
Figure imgb0004
 0.01% of the dye of the formula
Figure imgb0005

Flotte 2 (Muster 2): Diese Flotte enthält zusätzlich 1 % der Verbindung der Formel

Figure imgb0006
Fleet 2 (model 2): This fleet additionally contains 1% of the compound of the formula
Figure imgb0006

Flotte 3 (Muster 3): Diese Flotte entspricht Flotte 1 mit dem Unterschied, dass sie zusätzlich 1 % der Verbindung der Formel

Figure imgb0007

enthält. Fleet 3 (model 3): This fleet corresponds to fleet 1 with the difference that it additionally 1% of the compound of the formula
Figure imgb0007
contains.

Flotte 4 (Muster 4): Diese Flotte entspricht Flotte 1 mit dem Unterschied, dass sie zusätzlich 1 % der Verbindung der Formel

Figure imgb0008

enthält. Fleet 4 (Model 4): This fleet corresponds to Fleet 1 with the difference that it additionally 1% of the compound of the formula
Figure imgb0008
contains.

Flotte 5 (Muster 5): Diese Flotte entspricht Flotte 1 mit dem Unterschied, dass sie zusätzlich 1 % der Verbindung der Formel

Figure imgb0009

enthält. Fleet 5 (model 5): This fleet corresponds to fleet 1 with the difference that it additionally 1% of the compound of the formula
Figure imgb0009
contains.

Flotte 6 (Muster 6): Diese Flotte entspricht Flotte 2 mit dem Unterschied, dass kein Färbstoff eingesetzt wird (Blindfärbung mit UV-Absorber). Fleet 6 (sample 6): This fleet corresponds to fleet 2 with the difference that no dye is used (blind dyeing with UV absorber).

Flotte 7 (Muster 7): Diese Flotte entspricht Flotte 1 mit dem Unterschied, dass kein Färbstoff eingesetzt wird (Blindfärbung ohne UV-Absorber). Bei Bedarf wird der pH-Wert mit 10%iger Essigsäure auf den Wert 4,5 eingestellt. Fleet 7 (pattern 7): This fleet corresponds to fleet 1 with the difference that no dye is used (blind dyeing without UV absorber). If necessary, the pH is adjusted to 4.5 with 10% acetic acid.

Man geht bei 50° ein, erhitzt das Färbebad innerhalb von 30 Minuten auf 98° und färbt bei dieser Temperatur. Danach wird auf 60° abgekült und mit kaltem Wasser gespült. Die Muster werden sodann bei Raumtemperatur getrocknet.One enters at 50 °, heats the dyebath to 98 ° within 30 minutes and dyes at this temperature. Then it is cooled to 60 ° and rinsed with cold water. The samples are then dried at room temperature.

Die Muster werden gemäss DIN 75202 (FAKRA) auf ihre Lichtechtheit geprüft. In Tabelle 1 sind die Lichtechtheiten nach Graumassstab und die farbmetrischen Bewertungen nach DIN 6174 angegeben (Cielab-Formel).

Figure imgb0010
The samples are tested for light fastness in accordance with DIN 75202 (FAKRA). Table 1 shows the light fastness according to the gray scale and the colorimetric evaluations according to DIN 6174 (Cielab formula).
Figure imgb0010

Beispiel 2: 2 Muster von je 10 g eines Woll-Sèrge-Gewebes werden bei einem Flottenverhältnis von 1:25 in einem offenen Färbeapparat, z.B. einem ® AHIBA, gefärbt. Es werden 2 Flotten bereitet, die folgende Zusätze enthalten:
Flotte 1 (Muster 1 ):
   6 % Ammoniumsulfat
   5 % Glaubersalz
   1 g/l Natriumacetat
   1 % eines anionischen Egalisiemittel auf der Basis eines Alkylaminopolyglykolethers
   0,01 % des Farbstoffes der Formel

Figure imgb0011

und
   0,01 % des Farbstoffes der Formel
Figure imgb0012
 Example 2: 2 samples of 10 g each of a wool sergeant fabric are dyed at a liquor ratio of 1:25 in an open dyeing machine, for example an ® AHIBA. Two fleets are prepared, which contain the following additives:
Fleet 1 (sample 1):
6% ammonium sulfate
5% Glauber's salt
1 g / l sodium acetate
1% of an anionic leveling agent based on an alkylaminopolyglycol ether
0.01% of the dye of the formula
Figure imgb0011
and
0.01% of the dye of the formula
Figure imgb0012

Flotte 2 (Muster 2): Diese Flotte enthält zusätzlich 1 % der Verbindung der Formel (101). Fleet 2 (sample 2): This liquor additionally contains 1% of the compound of the formula (101).

Flotte 3 (Muster 3): Diese Flotte enthält gegenüber der Flotte 11 % der Verbindung der Formel (102). Fleet 3 (sample 3): This fleet contains 11% of the compound of the formula (102) compared to the fleet.

Flotte 4 (Muster 4): Diese Flotte enthält gegenüber der Flotte 11 % der Verbindung der Formel (103). Fleet 4 (sample 4): This fleet contains 11% of the compound of the formula (103) compared to the fleet.

Flotte 5 (Muster 5): Diese Flotte enthält gegenüber der Flotte 11 % der Verbindung der Formel ( 104). Fleet 5 (sample 5): This fleet contains 11% of the compound of the formula (104) compared to the fleet.

Der pH-Wert der Flotte stellt sich auf den Wert 6,2 ein. Man behandelt weiter und wertet aus wie in Beispiel 1 beschrieben.The pH of the liquor adjusts to 6.2. You continue to treat and evaluate from as described in Example 1.

Die Ergebnisse der Lichtechtheitsbewertung sind in Tabelle 2 aufgeführt:

Figure imgb0013
The results of the light fastness assessment are listed in Table 2:
Figure imgb0013

Claims (11)

Verfahren zum photochemischen Stabilisieren von Wolle oder Wolle enthaltenden Mischfasern, dadurch gekennzeichnet, dass man die Fasern mit einer wässrigen Lösung behandelt, welche mindestens einen UV-Absorber der Formel
Figure imgb0014
 enthält,
worin mindestens einer der Substituenten
R₁, R₂ und R₃ ein Rest der Formel
Figure imgb0015
 ist, worin
M Wasserstoff; Natrium; Kalium; Calcium; Magnesium; Ammonium; Mono-, Di-, Tri-oder Tetraalkylammonium; Mono-, Di- oder Trihydroxyalkylammonium; oder gemischt durch Hydroxyalkyl und Alkyl zwei- oder dreifach subsituierten Ammoniumionen;
m 1; oder 2; und
der oder die übrigen Substituenten unabhängig voneinander unsubstituiertes oder substituiertes C₁-C₁₂Alkyl, C₁-C₁₂-Alkoxy, C₁-C₁₂-Alkylthio, mono-C₁-C₁₂-Alkylamino oder di-C₁-C₁₂-Alkylamino; unsubstituiertes oder gegebenenfalls im Phenylkern substituiertes Phenyl, Phenoxy, Phenylthio, Anilino oder N-Phenyl-N-C₁-C₄-Alkylamino;
bedeutet. Process for the photochemical stabilization of wool or wool-containing mixed fibers, characterized in that the fibers are treated with an aqueous solution which has at least one UV absorber of the formula
Figure imgb0014
 contains
wherein at least one of the substituents
R₁, R₂ and R₃ are a radical of the formula
Figure imgb0015
 is what
M hydrogen; Sodium; Potassium; Calcium; Magnesium; Ammonium; Mono-, di-, tri- or tetraalkylammonium; Mono-, di- or trihydroxyalkylammonium; or mixed with hydroxyalkyl and alkyl, two or three times substituted ammonium ions;
m 1; or 2; and
the other substituent (s) independently of one another unsubstituted or substituted C₁-C₁₂alkyl, C₁-C₁₂-alkoxy, C₁-C₁₂-alkylthio, mono-C₁-C₁₂-alkylamino or di-C₁-C₁₂-alkylamino; unsubstituted or optionally substituted in the phenyl nucleus phenyl, phenoxy, phenylthio, anilino or N-phenyl-N-C₁-C₄-alkylamino;
means. Verfahren gemäss Anspruch 1, dadurch gekennzeichnet, dass ein UV-Absorber der Formel
Figure imgb0016
 entsprechen, worin
R₄ und R₅, unabhängig voneinander, C₁-C₁₂-Alkyl;
m 1 oder 2;
M Wasserstoff; Natrium; Kalium; Calcium; Magnesium; Ammonium oder Tetraalkylammonium; und
n₁ und n₂ 0; 1 oder 2;
bedeutet verwendet werden.A method according to claim 1, characterized in that a UV absorber of the formula
Figure imgb0016
 correspond to what
R₄ and R₅, independently of one another, C₁-C₁₂ alkyl;
m 1 or 2;
M hydrogen; Sodium; Potassium; Calcium; Magnesium; Ammonium or tetraalkylammonium; and
n₁ and n₂ 0; 1 or 2;
means to be used. Verfahren gemäss Anspruch 2, dadurch gekennzeichnet, dass UV-Absorber der Formel (3),
worin
M Wasserstoff;
R₄ und R₅ Methyl; und
n₁ und n₂ 1 oder 2 bedeuten,
verwendet werden.A method according to claim 2, characterized in that UV absorbers of the formula (3),
wherein
M hydrogen;
R₄ and R₅ methyl; and
n₁ and n₂ represent 1 or 2,
be used. Verfahren gemäss einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass die photochemische Stabilisierung vor, während oder nach dem Färben durchgefürht wird.Method according to one of claims 1 to 3, characterized in that the photochemical stabilization is carried out before, during or after dyeing. Verfahren gemäss einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass der UV-Absorber dem Färbebad zugefügt wird.Method according to one of claims 1 to 4, characterized in that the UV absorber is added to the dyebath. Verfahren gemäss einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass die Färbeflotte einen pH-Wert von 3 bis 8 aufweist.Method according to one of claims 1 to 5, characterized in that the dyeing liquor has a pH of 3 to 8. Mittel zum photochemischen Stabilisieren von Wolle oder wollhaltigen Mischfasern, enthaltend einen UV-Absorber der Formel
Figure imgb0017
 enthält,worin mindestens einer der Substituenten
R₁, R₂ und R₃ ein Rest der Formel
Figure imgb0018
 ist, worin
M Wasserstoff; Natrium; Kalium; Calcium; Magnesium; Ammonium; Mono-, Di-, Tri-oder Tetraalkylammonium; Mono-, Di- oder Trihydroxyalkylammonium; oder gemischt durch Hydroxyalkyl und Alkyl zwei- oder dreifach subsituierten Ammoniumionen;
m 1; oder 2; und
der oder die übrigen Substituenten unabhängig voneinander unsubstituiertes oder substituiertes C₁-C₁₂Alkyl, C₁-C₁₂-Alkoxy, C₁-C₁₂ -Alkylthio, mono-C₁-C₁₂-Alkylamino oder di-C₁-C₁₂-Alkylamino; unsubstituiertes oder gegebenenfalls im Phenylkern substituiertes Phenyl, Phenoxy, Phenylthio, Anilino oder N-Phenyl-N-C₁-C₄-alkylamino;
bedeutet, und ein Netzmittel.Agent for the photochemical stabilization of wool or wool-containing mixed fibers, containing a UV absorber of the formula
Figure imgb0017
 contains, wherein at least one of the substituents
R₁, R₂ and R₃ are a radical of the formula
Figure imgb0018
 is what
M hydrogen; Sodium; Potassium; Calcium; Magnesium; Ammonium; Mono-, di-, tri- or tetraalkylammonium; Mono-, di- or trihydroxyalkylammonium; or mixed with hydroxyalkyl and alkyl, two or three times substituted ammonium ions;
m 1; or 2; and
the other substituent (s) independently of one another unsubstituted or substituted C₁-C₁₂alkyl, C₁-C₁₂-alkoxy, C₁-C₁₂-alkylthio, mono-C₁-C₁₂-alkylamino or di-C₁-C₁₂-alkylamino; unsubstituted or optionally substituted in the phenyl nucleus phenyl, phenoxy, phenylthio, anilino or N-phenyl-N-C₁-C₄-alkylamino;
means, and a wetting agent. Mittel gemäss Anspruch 7, dadurch gekennzeichnet, dass es einen UV-Absorber der Formel
Figure imgb0019
 entsprechen, worin
R₄ und R₅, unabhängig voneinander, C₁-C₁₂-Alkyl;
m 1 oder 2;
M Wasserstoff; Natrium; Kalium; Calcium; Magnesium; Ammonium oder Tetraalkylammonium; und
n₁ und n₂ 0; 1 oder 2;
bedeutet.Agent according to claim 7, characterized in that it is a UV absorber of the formula
Figure imgb0019
 correspond to what
R₄ and R₅, independently of one another, C₁-C₁₂ alkyl;
m 1 or 2;
M hydrogen; Sodium; Potassium; Calcium; Magnesium; Ammonium or tetraalkylammonium; and
n₁ and n₂ 0; 1 or 2;
means. Flotte zur Ausführung des Verfahrens gemäss Anspruch 1, dadurch gekennzeichnet, dass sie den UV-Absorber der Formel (1) in einer Menge von 0,1 bis 5 Gew.% enthält.Fleet for carrying out the method according to claim 1, characterized in that it contains the UV absorber of the formula (1) in an amount of 0.1 to 5% by weight. Das gemäss einem der Ansprüche 1 bis 6 behandelte Fasermaterial.The fiber material treated according to one of claims 1 to 6. Die Verwendung einer Verbindung der Formel
Figure imgb0020
 worin mindestens einer der Substituenten
R₁, R₂ und R₃ ein Rest der Formel
Figure imgb0021
 ist, worin
M Wasserstoff; Natrium; Kalium; Calcium; Magnesium; Ammonium; Mono-, Di-, Tri-oder Tetraalkylammonium; Mono-, Di- oder Trihydroxyalkylammonium; oder gemischt durch Hydroxyalkyl und Alkyl zwei- oder dreifach subsituierten Ammoniumionen;
m 1; oder 2; und
der oder die übrigen Substituenten unabhängig voneinander unsubstituiertes oder substituiertes C₁-C₁₂Alkyl, C₁-C₁₂-Alkoxy, C₁-C₁₂-Alkythio, mono-C₁-C₁₂-Alkylamino oder di-C₁-C₁₂-Alkylamino; unsubstituiertes oder gegebenenfalls im Phenylkern substituiertes Phenyl, Phenoxy, Phenylthio, Anilino oder N-Phenyl-N-C₁-C₄-alkylamino;
bedeutet, zum photochemischen Stabilisieren von Wolle oder Wolle enthaltenden Mischfasern.The use of a compound of the formula
Figure imgb0020
 wherein at least one of the substituents
R₁, R₂ and R₃ are a radical of the formula
Figure imgb0021
 is what
M hydrogen; Sodium; Potassium; Calcium; Magnesium; Ammonium; Mono-, di-, tri- or tetraalkylammonium; Mono-, di- or trihydroxyalkylammonium; or mixed with hydroxyalkyl and alkyl, two or three times substituted ammonium ions;
m 1; or 2; and
the other substituent (s) independently of one another unsubstituted or substituted C₁-C₁₂alkyl, C₁-C₁₂-alkoxy, C₁-C₁₂-alkythio, mono-C₁-C₁₂-alkylamino or di-C₁-C₁₂-alkylamino; unsubstituted or optionally substituted in the phenyl nucleus phenyl, phenoxy, phenylthio, anilino or N-phenyl-N-C₁-C₄-alkylamino;
means for the photochemical stabilization of wool or mixed fibers containing wool.
EP91810709A 1990-09-13 1991-09-04 Photochemical stabilisation of wool Expired - Lifetime EP0475905B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH2973/90 1990-09-13
CH297390 1990-09-13

Publications (2)

Publication Number Publication Date
EP0475905A1 true EP0475905A1 (en) 1992-03-18
EP0475905B1 EP0475905B1 (en) 1998-01-14

Family

ID=4245798

Family Applications (1)

Application Number Title Priority Date Filing Date
EP91810709A Expired - Lifetime EP0475905B1 (en) 1990-09-13 1991-09-04 Photochemical stabilisation of wool

Country Status (6)

Country Link
US (1) US5197991A (en)
EP (1) EP0475905B1 (en)
JP (1) JP3184259B2 (en)
AU (1) AU8387591A (en)
DE (1) DE59108923D1 (en)
NZ (1) NZ239755A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2175059A1 (en) * 2008-10-07 2010-04-14 Fabryka Dywanow Agnella S.A. Wool yam

Families Citing this family (39)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5298030A (en) * 1992-02-21 1994-03-29 Ciba-Geigy Corporation Process for the photochemical and thermal stabilization of undyed and dyed or printed polyester fiber materials
US5700850A (en) 1993-08-05 1997-12-23 Kimberly-Clark Worldwide Colorant compositions and colorant stabilizers
US6017661A (en) 1994-11-09 2000-01-25 Kimberly-Clark Corporation Temporary marking using photoerasable colorants
US5645964A (en) 1993-08-05 1997-07-08 Kimberly-Clark Corporation Digital information recording media and method of using same
US5865471A (en) 1993-08-05 1999-02-02 Kimberly-Clark Worldwide, Inc. Photo-erasable data processing forms
US5721287A (en) 1993-08-05 1998-02-24 Kimberly-Clark Worldwide, Inc. Method of mutating a colorant by irradiation
US5681380A (en) 1995-06-05 1997-10-28 Kimberly-Clark Worldwide, Inc. Ink for ink jet printers
US5773182A (en) 1993-08-05 1998-06-30 Kimberly-Clark Worldwide, Inc. Method of light stabilizing a colorant
US6017471A (en) 1993-08-05 2000-01-25 Kimberly-Clark Worldwide, Inc. Colorants and colorant modifiers
US5733693A (en) 1993-08-05 1998-03-31 Kimberly-Clark Worldwide, Inc. Method for improving the readability of data processing forms
US6211383B1 (en) 1993-08-05 2001-04-03 Kimberly-Clark Worldwide, Inc. Nohr-McDonald elimination reaction
US6033465A (en) 1995-06-28 2000-03-07 Kimberly-Clark Worldwide, Inc. Colorants and colorant modifiers
GB9326358D0 (en) 1993-12-23 1994-02-23 Ciba Geigy Ag Compositions for the treatment of textiles
US6242057B1 (en) 1994-06-30 2001-06-05 Kimberly-Clark Worldwide, Inc. Photoreactor composition and applications therefor
US6071979A (en) 1994-06-30 2000-06-06 Kimberly-Clark Worldwide, Inc. Photoreactor composition method of generating a reactive species and applications therefor
US5685754A (en) 1994-06-30 1997-11-11 Kimberly-Clark Corporation Method of generating a reactive species and polymer coating applications therefor
GB2291658B (en) * 1994-07-23 1998-08-12 Ciba Geigy Ag Aqueous textile treatment compositions containing an ultra-violet absorbing agent
US6008268A (en) 1994-10-21 1999-12-28 Kimberly-Clark Worldwide, Inc. Photoreactor composition, method of generating a reactive species, and applications therefor
TW290606B (en) * 1995-03-17 1996-11-11 Ciba Geigy Ag
US5786132A (en) 1995-06-05 1998-07-28 Kimberly-Clark Corporation Pre-dyes, mutable dye compositions, and methods of developing a color
ATE195815T1 (en) 1995-06-05 2000-09-15 Kimberly Clark Co DYE PRECURSORS AND COMPOSITIONS CONTAINING SAME
JPH10513502A (en) 1995-11-28 1998-12-22 キンバリー クラーク ワールドワイド インコーポレイテッド Improved colorant stabilizer
US6099628A (en) 1996-03-29 2000-08-08 Kimberly-Clark Worldwide, Inc. Colorant stabilizers
US5855655A (en) 1996-03-29 1999-01-05 Kimberly-Clark Worldwide, Inc. Colorant stabilizers
US5782963A (en) 1996-03-29 1998-07-21 Kimberly-Clark Worldwide, Inc. Colorant stabilizers
US5891229A (en) 1996-03-29 1999-04-06 Kimberly-Clark Worldwide, Inc. Colorant stabilizers
GB9611614D0 (en) * 1996-06-04 1996-08-07 Ciba Geigy Ag Process for inhibiting the effect of flourescent whitening agents
GB2313850A (en) * 1996-06-04 1997-12-10 Ciba Geigy Ag Triazine based UVA compounds as quenchers in paper making processes
US6524379B2 (en) 1997-08-15 2003-02-25 Kimberly-Clark Worldwide, Inc. Colorants, colorant stabilizers, ink compositions, and improved methods of making the same
CA2298615C (en) 1998-06-03 2009-03-31 Kimberly-Clark Worldwide, Inc. Neonanoplasts produced by microemulsion technology and inks for ink jet printing
CA2298468A1 (en) 1998-06-03 1999-12-09 John Gavin Macdonald Novel photoinitiators and applications therefor
WO2000004104A1 (en) 1998-07-20 2000-01-27 Kimberly-Clark Worldwide, Inc. Improved ink jet ink compositions
JP2003533548A (en) 1998-09-28 2003-11-11 キンバリー クラーク ワールドワイド インコーポレイテッド Chelates containing quinoid groups as photopolymerization initiators
ES2195869T3 (en) 1999-01-19 2003-12-16 Kimberly Clark Co NEW COLORS, COLOR STABILIZERS, INK COMPOUNDS AND IMPROVED METHODS FOR MANUFACTURING.
US6331056B1 (en) 1999-02-25 2001-12-18 Kimberly-Clark Worldwide, Inc. Printing apparatus and applications therefor
US6294698B1 (en) 1999-04-16 2001-09-25 Kimberly-Clark Worldwide, Inc. Photoinitiators and applications therefor
US6368395B1 (en) 1999-05-24 2002-04-09 Kimberly-Clark Worldwide, Inc. Subphthalocyanine colorants, ink compositions, and method of making the same
CA2530759C (en) * 2003-07-08 2012-02-21 Karl J. Scheidler Methods and compositions for improving light-fade resistance and soil repellency of textiles and leathers
US7824566B2 (en) * 2003-07-08 2010-11-02 Scheidler Karl J Methods and compositions for improving light-fade resistance and soil repellency of textiles and leathers

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3444164A (en) * 1965-09-24 1969-05-13 Ciba Ltd Hydroxyphenyl-1,3,5-triazines containing sulfonic acid groups and their preparation
EP0165608A2 (en) * 1984-06-22 1985-12-27 Ilford Ag Hydroxyphenyltriazines, process for their preparation and their use as UV absorbers
EP0245204A1 (en) * 1986-05-05 1987-11-11 Ciba-Geigy Ag Process for the photochemical stabilization of undyed and dyed fibrous polyamide material and its mixture with other fibres
EP0310083A1 (en) * 1987-10-02 1989-04-05 Ciba-Geigy Ag Process for quenching or suppressing the fluorescence of optically brightened substrates

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3444164A (en) * 1965-09-24 1969-05-13 Ciba Ltd Hydroxyphenyl-1,3,5-triazines containing sulfonic acid groups and their preparation
EP0165608A2 (en) * 1984-06-22 1985-12-27 Ilford Ag Hydroxyphenyltriazines, process for their preparation and their use as UV absorbers
EP0245204A1 (en) * 1986-05-05 1987-11-11 Ciba-Geigy Ag Process for the photochemical stabilization of undyed and dyed fibrous polyamide material and its mixture with other fibres
EP0310083A1 (en) * 1987-10-02 1989-04-05 Ciba-Geigy Ag Process for quenching or suppressing the fluorescence of optically brightened substrates

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2175059A1 (en) * 2008-10-07 2010-04-14 Fabryka Dywanow Agnella S.A. Wool yam

Also Published As

Publication number Publication date
JPH04281070A (en) 1992-10-06
AU8387591A (en) 1992-03-19
JP3184259B2 (en) 2001-07-09
EP0475905B1 (en) 1998-01-14
NZ239755A (en) 1993-05-26
DE59108923D1 (en) 1998-02-19
US5197991A (en) 1993-03-30

Similar Documents

Publication Publication Date Title
EP0475905A1 (en) Process for the photochemical stabilisation of wool
EP0200843B1 (en) Process for the photochemical stabilisation of undyed and dyed polyamide fibrous material and its mixtures
EP0459950B1 (en) Stabilisation of dyes on polyamide fibres
EP0345212A1 (en) Process to prevent yellowing of polyamide fibres finished with stain-proofing agents
EP0417040A1 (en) Dyeing process for wool
EP0255481A1 (en) Process for the photochemical stabilisation of a fibrous polyamide material and its mixtures with other fibres
DE2726433A1 (en) PROCESS FOR IMPROVING THE COLOR YIELD AND THE FASTENNESSES OF COLORS, CATIONIC FIBER-REACTIVE COMPOUNDS AND THEIR PRODUCTION
DE2834997B1 (en) Process for dyeing synthetic polyamide fibers with reactive dyes using the pull-out method
CH689479B5 (en) Compounds of the s-triazine.
EP0584044A1 (en) Process for photochemical and thermal stabilization of undyert and dyert polyester fibrous materials
EP0657577A1 (en) Process for photochemical and thermal stabilization of dyed and undyed or printed polyester fibrous materials
DE1099494B (en) Process for finishing dyeings which have been produced in an acid bath on nitrogen-containing fibers with dyes which are soluble in the bath and which contain at least one mobile halogen atom that is reactive with the fibers
EP0302013A1 (en) Process for dyeing polyamide textile fabrics
DE2653284B2 (en) Process for the uniform color of synthetic fiber materials
EP0950751B1 (en) Process for the treatment of cellulose fibers
EP0474594B1 (en) Process for dyeing of wool and mixtures thereof with other fibres with reactive dyestuffs
EP0735181A2 (en) Multicolor dyeing with manganese compounds of fibrous materials containing polyamide fibres
DE2148867C3 (en) Process for the continuous fixation of disperse dyes on polyester, cellulose triacetate, cellulose-2 l / 2-acetate and mixtures thereof
EP0890671A2 (en) Use of modified fatty amines for preventing deposition of low molecular weight by-products on textile materials
EP0621266A1 (en) Sterically hindered phenols and their use for the stabilisation of polyamide fibres
DE1909518C3 (en) Process for the single bath dyeing of mixtures of polyester and cellulose fibers
EP0950750B1 (en) Process for the treatment of cellulose fibers
AT210382B (en) Method of finishing staining
AT226190B (en) Process for dyeing nitrogen-containing fibers with copper phthalocyanines containing sulfonic acid groups and means for carrying out the process
DE2521106C3 (en) Process for dyeing materials containing synthetic fibers

Legal Events

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

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19910906

AK Designated contracting states

Kind code of ref document: A1

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

17Q First examination report despatched

Effective date: 19940203

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: CIBA SC HOLDING AG

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

RAP3 Party data changed (applicant data changed or rights of an application transferred)

Owner name: CIBA SPECIALTY CHEMICALS HOLDING INC.

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

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

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

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRE;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.SCRIBED TIME-LIMIT

Effective date: 19980114

Ref country code: FR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19980114

Ref country code: GB

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19980114

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REF Corresponds to:

Ref document number: 59108923

Country of ref document: DE

Date of ref document: 19980219

EN Fr: translation not filed
GBV Gb: ep patent (uk) treated as always having been void in accordance with gb section 77(7)/1977 [no translation filed]

Effective date: 19980114

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

Ref country code: BE

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

Effective date: 19980930

Ref country code: LI

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

Effective date: 19980930

Ref country code: CH

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

Effective date: 19980930

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

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

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

26N No opposition filed
BERE Be: lapsed

Owner name: CIBA SPECIALTY CHEMICALS HOLDING INC.

Effective date: 19980930

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

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

Ref country code: DE

Payment date: 20000811

Year of fee payment: 10

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

Ref country code: DE

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

Effective date: 20020501