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EP0352221A1 - Process for photochemically stabilising dyed or non dyed polypropylene fibres - Google Patents

Process for photochemically stabilising dyed or non dyed polypropylene fibres Download PDF

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Publication number
EP0352221A1
EP0352221A1 EP89810431A EP89810431A EP0352221A1 EP 0352221 A1 EP0352221 A1 EP 0352221A1 EP 89810431 A EP89810431 A EP 89810431A EP 89810431 A EP89810431 A EP 89810431A EP 0352221 A1 EP0352221 A1 EP 0352221A1
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Prior art keywords
acid
radical
hydrogen
aliphatic
cycloaliphatic
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EP89810431A
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German (de)
French (fr)
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EP0352221B1 (en
Inventor
Gerhard Dr. Reinert
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Novartis AG
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Ciba Geigy AG
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    • 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
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/61—Polyamines polyimines
    • 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
    • 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
    • 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
    • D06M13/325—Amines
    • D06M13/335—Amines having an amino group bound to a carbon atom of a six-membered aromatic ring
    • 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
    • D06M13/352—Heterocyclic compounds having five-membered heterocyclic rings
    • 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
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2933—Coated or with bond, impregnation or core
    • 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
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2933—Coated or with bond, impregnation or core
    • Y10T428/2964—Artificial fiber or filament
    • Y10T428/2967—Synthetic resin or polymer

Definitions

  • the present invention relates to a process for the photochemical stabilization of undyed and dyed polypropylene fibers.
  • the process according to the invention is characterized in that the undyed or dyed polypropylene fiber material is treated with an aqueous solution which contains a light stabilizer from the class of the sterically hindered amines.
  • a sterically hindered amine which contains at least one group of the formula I in its molecule is used as the preferred light stabilizer, where R is hydrogen or methyl.
  • Such light stabilizers can be low molecular weight (MW ⁇ 700) or higher molecular weight (oligomers, polymers). These groups preferably carry one or two polar substituents in the 4-position or a polar spiro ring system is bonded to the 4-position.
  • n is a number from 1 to 4, preferably 1 or 2
  • R is hydrogen or methyl
  • R1 is hydrogen, hydroxyl, C1-C12 alkyl, C3-C8 alkenyl, C3-C8 alkynyl, C7-C12 aralkyl, C1-C8 Alkanoyl, C3-C5 alkenoyl, glycidyl, -O-C1-C12-alkyl, -O-C1-C8-alkanoyl or a group -CH2CH (OH) -Z, where Z is hydrogen, methyl or phenyl, where R1 preferably hydrogen, C1-C4 alkyl, allyl, benzyl, acetyl or acryloyl and R2, if n is 1, is hydrogen, C1-C18 alkyl, cyanoethyl, benzyl, glycidyl optional
  • substituents are C1-C12 alkyl, they represent e.g. Methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl, 2-ethyl-hexyl, n-nonyl, n-decyl, n-undecyl or n- Dodecyl.
  • R1 or R2 can e.g. represent the groups listed above and, for example, n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl.
  • R1 is C3-C8 alkenyl, it can e.g. are 1-propenyl, allyl, methallyl, 2-butenyl, 2-pentenyl, 2-hexenyl, 2-octenyl, 4-tert-butyl-2-butenyl.
  • R1 as C3-C8 alkynyl is preferably propargyl.
  • R1 is especially phenethyll and especially benzyl.
  • R1 is as C1-C8 alkanoyl, for example formyl, propionyl, butyryl, octanoyl, but preferably acetyl and as C3-C5 alkenoyl in particular acryloyl.
  • R2 is a monovalent radical of a carboxylic acid, it is, for example, acetic, caproic, stearic, acrylic, methacrylic, benzoic or ⁇ - (3,5-di-tert-butyl-4-hydroxyphenyl) -propionic acid residue.
  • R2 is a divalent radical of a dicarboxylic acid, it represents, for example, malonic, succinic, glutaric, adipic, suberic, sebacic, maleic, phthalic, dibutylmalonic, dibenzylmalonic, butyl (3,5-di -tert.-butyl-4-hydroxybenzyl) malonic acid or bicycloheptenedicarboxylic acid residue.
  • R2 represents a trivalent carboxylic acid residue, it means, for example, a trimellitic acid or a nitrilotriacetic acid residue.
  • R2 represents a tetravalent residue of a tetracarboxylic acid, it means e.g. the tetravalent residue of butane-1,2,3,4-tetracarboxylic acid or of pyromellitic acid.
  • R2 is a divalent radical of a dicarbamic acid, it is, for example, a hexamethylene dicarbamic acid or a 2,4-tolylene dicarbamic acid radical.
  • R3 is hydrogen, C1-C12 alkyl, C2-C5 hydroxyalkyl, C5-C7 cycloalkyl, C7-C, aralkyl, C2-C18 alkanoyl, C3-C5 alkenoyl or benzoyl and R4 when n is 1, hydrogen, C1-C18 alkyl, C3-C8 alkenyl, C5-C7 cycloalkyl, C1-C4 alkyl, glycidyl substituted with a hydroxy, cyano, alkoxycarbonyl or carbamide group , a group of the formula -CH2-CH (OH) -Z or the formula -CONH-Z, wherein Z is hydrogen, methyl or phenyl; when n is 2, C2-C12 alkylene, C6-C12 arylene, xylylene, a
  • R3 is especially phenylethyl or especially benzyl.
  • R3 is in particular 2-hydroxyethyl or 2-hydroxypropyl.
  • R3 is as C2-C18 alkanoyl, for example propionyl, butyryl, octanoyl, dodecanoyl, hexadecanoyl, octadecanoyl, but preferably acetyl and as C3-C5 alkenoyl in particular acryloyl.
  • R4 C2-C8 is alkenyl, then it is e.g. allyl, methallyl, 2-butenyl, 2-pentenyl, 2-hexenyl or 2-octenyl.
  • R4 as a C1-C4-alkyl substituted with a hydroxy, cyano, alkoxycarbonyl or carbamide group can e.g. 2-Hydroxyethyl, 2-hydroxypropyl, 2-cyanoethyl, methoxycarbonylmethyl, 2-ethoxycarbonylethyl, 2-aminocarbonylpropyl or 2- (dimethylaminocarbonyl) ethyl.
  • substituents are C2-C12 alkylene, they are e.g. around ethylene, propylene, 2,2-dimethylpropylene, tetramethylene, hexamethylene, octamethylene, decamethylene or dodecamethylene.
  • substituents are C6-C15 arylene, they represent e.g. o-, m- or p-phenylene, 1,4-naphthylene or 4,4'-diphenylene.
  • D is especially cyclohexylene.
  • the dyed polypropylene fiber material to be treated according to the invention is fiber material which can be dyed with an inorganic or organic pigment or a fiber material which can be dyed from the liquor.
  • the pigment with which the material is colored can be a white, black or colored pigment. It can be a single pigment or a mixture of pigments.
  • inorganic pigments examples include titanium dioxide, zinc oxide, barium carbonate, carbon black, cadmium sulfide and selenide, chromates, chromium oxides, iron oxides or lead oxides.
  • organic pigment classes are azo pigments, anthraquinones, phthalocyanines, pyrrolopyrroles, quinacridones, isoindolines or perylene pigments.
  • the amount of pigment can vary within wide limits, in particular 0.01 to 10% by weight, based on the polypropylene, can be added.
  • the undyed polypropylene fiber material can also be stabilized photochemically and at the same time optically brightened by treating the fiber material with an aqueous light stabilizer formulation which additionally contains an optical brightener.
  • This stabilization process forms a further subject of the present invention.
  • Possible optical brighteners for the process according to the invention are those from the class of the polycyclic oxazoles, the coumarins, aryltriazoles, styrylstilbenes and naphthalimides, such as those e.g. in A.K. Sarkar "Fluorescent whitening agents", Merrow Publishing Co. Ltd., Watford England (1971), 71-72.
  • Optical brighteners of the benzooxazole type are particularly suitable.
  • the amount of the dispersed optical brightener is 0.01% - 0.5% of the fiber weight.
  • aqueous solutions which can be used according to the invention contain the compounds of the formulas (I) to (III) in an amount of 0.05 to 7.5, preferably 0.1 to 3 and in particular 0.1 to 2%, based on the fiber weight.
  • Suitable nonionic dispersants are alcohol or alkylphenolalkylene oxide reaction products, e.g. Alkylene oxide reaction products of aliphatic alcohols with 4 to 22 carbon atoms, which contain up to 80 moles of ethylene oxide and / or propylene oxide added.
  • the alcohols can preferably contain 4 to 18 carbon atoms, they can be saturated, branched or straight-chain and can be used alone or in a mixture. Branched chain alcohols are preferred.
  • Natural alcohols such as, for example, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, arachidyl alcohol or behenyl alcohol or synthetic alcohols, such as in particular butanol, 2-ethylhexanol, amyl alcohol, n-hexanol, furthermore triethylhexanol, trimethylnonyl alcohol or the Alfole (trade name - Continental Oil) (trade name - Continental Oil) be used.
  • the Alfolen are linear primary alcohols.
  • Alfol (1218) is a mixture of decyl, dodecyl, tetradecyl, hexadecyl and octadecyl alcohol.
  • Other representatives are Alfol (810), (1014), (12), (16), (18), (2022).
  • Preferred ethylene oxide-alcohol reaction products can, for example, by the formula (1) R3O (CH2CH2O) s H are shown, wherein R3 is a saturated or unsaturated hydrocarbon radical, preferably an alkyl or alkenyl radical having 8 to 18 carbon atoms and s is an integer from 1 to 80, preferably from 1 to 30.
  • R3 is a saturated or unsaturated hydrocarbon radical, preferably an alkyl or alkenyl radical having 8 to 18 carbon atoms and s is an integer from 1 to 80, preferably from 1 to 30.
  • Suitable nonionic dispersants are reaction products of ethylene oxide and / or 1,2-propylene oxide and alkylphenols having 4 to 12 carbon atoms in the alkyl part, it being possible for the phenol to contain one or more alkyl substituents.
  • R is hydrogen or at most one of the two radicals R methyl
  • p is a number from 4 to 12, preferably 8 to 9
  • t is a number from 1 to 60, in particular from 1 to 20 and preferably 1 to 6.
  • these alcohol-alkylphenol-ethylene oxide / 1,2-propylene oxide adducts may contain even smaller proportions of block polymers from the alkylene oxides mentioned.
  • reaction products which can be considered as nonionic dispersants are polyoxyethylene derivatives of the fatty acid esters of sorbitan ethers with 4 moles of polyethylene glycol, for example the laurate, palmitate, stearate, tristearate, oleate and trioleate of the ethers mentioned, such as the Tween brands of the Atlas Chemicals Division.
  • the tristearate of the ether of sorbitan with 4 mol of the polyethylene glycol of the formula is preferred (3) H (CH2CH2) 65OH.
  • Esterified alkylene oxide adducts such as e.g. addition products of alkylene oxides, especially ethylene oxide and / or propylene oxide, containing acidic ester groups of inorganic or organic acids, onto aliphatic organic hydroxyl, carboxyl or optionally also amino or amido compounds or mixtures of these compounds with a total of at least 8 carbon atoms.
  • acidic esters can be used as free acids or as salts e.g. Alkali metal, alkaline earth metal, ammonium or amine salts are present.
  • anionic dispersants are prepared by known methods by adding at least 1 mole, preferably more than 1 mole, to the organic compounds mentioned, e.g. 2 to 60 moles of ethylene oxide or alternately in any order, ethylene oxide and propylene oxide and then etherifying or esterifying the addition products and, if appropriate, converting the ethers or the esters into their salts.
  • the starting materials are e.g. higher fatty alcohols, i.e. Alkanols or alkenols with 8 to 22 carbon atoms, alicyclic alcohols, phenylphenols, alkylphenols with one or more alkyl substituents which together have at least 10 carbon atoms or fatty acids with 8 to 22 carbon atoms.
  • Particularly suitable anionic dispersants correspond to the formula wherein R1 is an aliphatic hydrocarbon radical with 8 to 22 carbon atoms or a cycloaliphatic, aromatic or aliphatic-aromatic hydrocarbon radical with 10 to 22 carbon atoms, R2 is hydrogen or methyl A -O- or - -O, X is the acid residue of an inorganic, oxygen-containing acid, the acid residue of a polybasic carboxylic acid or a carboxylalkyl residue and n is a number from 1 to 50.
  • the radical R1 -A- in the compounds of formula (4) is derived, for example, from higher alcohols such as decyl, lauryl, tridecyl, myristyl, cetyl, stearyl, oleyl, arachidyl or behenyl alcohol; alicyclic alcohols such as hydroabietyl alcohol; of fatty acids like Capryl, caprin, laurin, myristine, palmitin, stearin, arachine, behen, coconut oil (C8-C18), decene, dodecene, tetradecene, hexadecene, oil, lino, Linolenic, eicotonic, docosonic or clupanodonic acid; of alkylphenols such as butyl, hexyl, n-octy, n-nony, p-tert.
  • higher alcohols such as decyl, lauryl, tridecy
  • Residues having 10 to 18 carbon atoms are preferred, in particular those which are derived from the alkylphenols.
  • the acid residue X is usually the acid residue of a polybasic, especially low molecular weight mono- or dicarboxylic acid such as maleic acid, malonic acid, succinic acid or sulfosuccinic acid, or is a carboxyalkyl residue, especially a carboxymethyl residue (derived in particular from chloroacetic acid) and is an ether or Ester bridge with the rest R1-A- (CH2CHR2O) m - connected.
  • X is derived from inorganic polybasic acids, such as orthophosphoric acid and sulfuric acid.
  • the acid residue X is preferably in salt form, ie, for example, as an alkali metal, ammonium or amine salt.
  • alkylene oxide units ⁇ CH2CHR2O ⁇ of the formula (4) are generally ethylene oxide and 1,2-propylene oxide units, the latter preferably being in a mixture with ethylene oxide units in the compounds of the formula (4).
  • the anionic compounds of the formula are of particular interest (5) R3O (CH2CH2O) n -X, wherein R3 is a saturated or unsaturated hydrocarbon radical with 8 to 22 hydrocarbon atoms, o-phenylphenol or alkylphenyl with 4 to 12 carbon atoms in the alkyl part, and X and n have the meanings given.
  • n is an integer from 1 to 20
  • n 1 is an integer from 1 to 10
  • X 1 is a sulfuric acid or phosphoric acid residue, which is optionally in salt form and X has the meaning given, particularly preferred.
  • the application of the sterically hindered amines can be carried out separately from the application of the optical brightener or preferably at the same time as the application of the optical brightener, after an exhaust process at liquor ratios 1: 4 - 1: 200, preferably 1:10 - 1:50, using e.g. Circulation dyeing machine or reel runner. But you can also continuously using low-order systems or hot application systems e.g. with the Fluidyer® (from Whyrs), Flexnip® (from Whyndrs) etc. be applied.
  • the liquor used has a pH of 2-12, preferably 5-10 and especially 9.
  • the treatment liquors used can still contain all chemicals suitable for use in polypropylene fiber treatment, e.g. Contain electrolytes.
  • a non-ionic surfactant 0.5 g / l of a non-ionic surfactant and 1% by weight based on the weight of the compound of the formula (100) as 20% sand grinding with the sulfonated condensation product of naphthalene and formaldehyde as a dispersant, in a weight ratio of 1: 1.
  • the yarns are added to this treatment liquor (pH 10.3) at 50 ° C., heated to 90 ° C. in 15 minutes and left at this temperature for 30 minutes. Finally, it is rinsed thoroughly warm and cold and then dried at 60 ° C.
  • Table I template Tensile strength / elongation in (%) Untreated material Material stabilized - *) FAKRA 48h FAKRA 144h FAKRA 48h FAKRA 144h A 100/100 83 / 78.9 68.8 / 53.7 99.1 / 93.3 89.2 / 80.6 B 100/100 38.2 / 35.3 destroyed 79.6 / 90.1 67.6 / 68.4 C.
  • the white yarn has been significantly improved, the two dyed yarns have been significantly improved in the light / heat stability.
  • Example 2 The procedure is as described in Example 1, but the compound of the formula (200) is used instead of the compound (100) in an amount of 1% by weight, based on the weight of the yarn, as a 50% emulsion (50 parts of compound (200), 35 parts of light petroleum and 15 parts of a nonionic surfactant).
  • Pattern D is white yarn (lightened with spinning material)
  • pattern E and F are navy blue and dark blue dyeings.
  • Sample I is treated in a liquor of the following composition: 1 g / l Na2CO3 0.5 g / l of a non-ionic surfactant and 0.1% by weight, based on the weight of the fabric, of the compound of the formula (3)
  • Sample II is treated in a liquor which additionally contains 1% by weight, based on the weight of the compound (100), which is in the form of a 20% formulation.
  • Parts (a) are not further treated, while parts (b), in a liquor ratio of 1:25, are treated in a bath that is per liter 0.5 g of a nonionic surfactant, 0.5g sodium carbonate calc. and 1% by weight, based on the weight of the fabric, of the compound of the formula (100) as a 20% dispersion contains.
  • the bath is heated to 50 ° C., the temperature is raised to 75 ° C. in the course of 10 minutes and the mixture is treated at this temperature for 30 minutes.
  • the bath is then cooled and the substrates are rinsed cold and dried.
  • Example 4 The procedure is as described in Example 4, with the difference that instead of compound (100), 1% by weight, based on the fabric, as a 50% emulsion of compound (200) is used.
  • a dyeing machine e.g. ®AHIBA dyeing machine
  • the tissue is blended in at 50 ° C, the temperature is raised to 90 ° C within 30 minutes and treated at this temperature for 30 minutes.
  • the bath is then cooled to 60 ° C. and the treated fabric is rinsed warm and cold and dried.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
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Abstract

A process is disclosed for the photochemical stabilization of undyed and dyed polypropylene fibre material with light stabilizers, which process comprises treating said material with an aqueous solution containing a light stabilizer from the class of the sterically hindered amines.

Description

Die vorliegende Erfindung betrifft ein Verfahren zum fotochemischen Stabilisieren von ungefärbten und gefärbten Polypropylenfasern.The present invention relates to a process for the photochemical stabilization of undyed and dyed polypropylene fibers.

Es ist bereits bekannt, dass die Verwendung von Polypropylenfasern ohne Einsatz von Stabilisatoren nicht möglich ist und dass diese Stabilisa­toren z.B. Antioxidantien und Lichtschutzmittel in die Spinnmasse eingearbeitet werden [vgl. z.B. Chemiefasern/Textilindustrie, 35, 840-847 (1985) und Melliand Textilberichte 11, 941-945 (1980)].It is already known that the use of polypropylene fibers is not possible without the use of stabilizers and that these stabilizers, for example antioxidants and light stabilizers, are incorporated into the spinning mass [cf. e.g. chemical fibers / textile industry, 35 , 840-847 (1985) and Melliand textile reports 11 , 941-945 (1980)].

Es wurde nun gefunden, dass ungefärbte und gefärbte Polypropylenfasern auch aus wässrigen Flotten stabilisiert werden können.It has now been found that undyed and dyed polypropylene fibers can also be stabilized from aqueous liquors.

Das erfindungsgemässe Verfahren ist dadurch gekennzeichnet, dass man das ungefärbte oder gefärbte Polypropylenfasermaterial mit einer wässrigen Lösung behandelt, welche ein Lichtschutzmittel aus der Klasse der sterisch gehinderten Amine enthält.The process according to the invention is characterized in that the undyed or dyed polypropylene fiber material is treated with an aqueous solution which contains a light stabilizer from the class of the sterically hindered amines.

Als bevorzugtes Lichtschutzmittel wird erfindungsgemäss ein sterisch gehindertes Amin verwendet, das in seinem Molekül mindestens eine Gruppe der Formel I enthält,

Figure imgb0001
worin R Wasserstoff oder Methyl ist.According to the invention, a sterically hindered amine which contains at least one group of the formula I in its molecule is used as the preferred light stabilizer,
Figure imgb0001
 where R is hydrogen or methyl.

Solche Lichtschutzmittel können niedermolekular (MG < 700) oder höher­molekular (Oligomere, Polymere) sein. Bevorzugt tragen diese Gruppen einen oder zwei polare Substituenten in 4-Stellung oder ein polares Spiro-Ringsystem ist an die 4-Stellung gebunden.Such light stabilizers can be low molecular weight (MW <700) or higher molecular weight (oligomers, polymers). These groups preferably carry one or two polar substituents in the 4-position or a polar spiro ring system is bonded to the 4-position.

Von besonderem Interesse sind sterisch gehinderte Amine der Formel II

Figure imgb0002
worin n eine Zahl von 1 bis 4, vorzugsweise 1 oder 2 bedeutet, R Wasser­stoff oder Methyl bedeutet, R¹ Wasserstoff, Hydroxy, C₁-C₁₂-Alkyl, C₃-C₈ Alkenyl, C₃-C₈ Alkinyl, C₇-C₁₂ Aralkyl, C₁-C₈ Alkanoyl, C₃-C₅ Alkenoyl, Glycidyl, -O-C₁-C₁₂-Alkyl, -O-C₁-C₈-Alkanoyl oder eine Gruppe -CH₂CH(OH)-Z, worin Z Wasserstoff, Methyl oder Phenyl ist, bedeutet, wobei R¹ vorzugsweise Wasserstoff, C₁-C₄ Alkyl, Allyl, Benzyl, Acetyl oder Acryloyl ist und R², wenn n 1 ist, Wasserstoff, gegebenenfalls durch ein oder mehrere Sauerstoffatome unterbrochenes C₁-C₁₈ Alkyl, Cyanethyl, Benzyl, Glycidyl, einen einwertigen Rest einer aliphatischen, cyclo­aliphatischen, araliphatischen, ungesättigten oder aromatischen Carbon­säure, Carbaminsäure oder Phosphor enthaltenden Säure oder einen ein­wertigen Silylrest, vorzugsweise einen Rest einer aliphatischen Carbon­säure mit 2 bis 18 C-Atomen, einer cycloaliphatischen Carbonsäure mit 7 bis 15 C-Atomen, einer α,ß-ungesättigten Carbonsäure mit 3 bis 5 C-Atomen oder einer aromatischen Carbonsäure mit 7 bis 15 C-Atomen bedeutet, wenn n 2 ist, C₁-C₁₂ Alkylen, C₄-C₁₂ Alkenylen, Xylylen, einen zweiwertigen Rest einer aliphatischen, cycloaliphatischen, araliphatischen oder aromatischen Dicarbonsäure, Dicarbaminsäure oder Phosphor enthaltenden Säure oder einen zweiwertigen Silylrest, vorzugsweise einen Rest einer aliphatischen Dicarbonsäure mit 2 bis 36 C-Atomen, einer cycloaliphati­schen oder aromatischen Dicarbonsäure mit 8 - 14 C-Atomen oder einer aliphatischen, cycloaliphatischen oder aromatischen Dicarbaminsäure mit 8 - 14 C-Atomen bedeutet, wenn n 3 ist, einen dreiwertigen Rest einer aliphatischen, cycloaliphatischen oder aromatischen Tricarbonsäure, einer aromatischen Tricarbaminsäure oder einer Phosphor enthaltenden Säure oder einen dreiwertigen Silylrest bedeutet und wenn n 4 ist, einen vier­wertigen Rest einer aliphatischen, cycloaliphatischen oder aromatischen Tetracarbonsäure bedeutet.Sterically hindered amines of the formula II are of particular interest
Figure imgb0002
 wherein n is a number from 1 to 4, preferably 1 or 2, R is hydrogen or methyl, R¹ is hydrogen, hydroxyl, C₁-C₁₂ alkyl, C₃-C₈ alkenyl, C₃-C₈ alkynyl, C₇-C₁₂ aralkyl, C₁-C₈ Alkanoyl, C₃-C₅ alkenoyl, glycidyl, -O-C₁-C₁₂-alkyl, -O-C₁-C₈-alkanoyl or a group -CH₂CH (OH) -Z, where Z is hydrogen, methyl or phenyl, where R¹ preferably hydrogen, C₁-C₄ alkyl, allyl, benzyl, acetyl or acryloyl and R², if n is 1, is hydrogen, C₁-C₁₈ alkyl, cyanoethyl, benzyl, glycidyl optionally interrupted by one or more oxygen atoms, a monovalent radical of an aliphatic, cycloaliphatic, araliphatic, unsaturated or aromatic carboxylic acid, carbamic acid or phosphorus-containing acid or a monovalent silyl radical, preferably a radical of an aliphatic carboxylic acid having 2 to 18 carbon atoms, a cycloaliphatic carboxylic acid having 7 to 15 carbon atoms, an α, β-u n-saturated carboxylic acid with 3 to 5 carbon atoms or an aromatic carboxylic acid with 7 to 15 carbon atoms means, if n is 2, C₁-C₁₂ alkylene, C₄-C₁₂ alkenylene, xylylene, a divalent radical of an aliphatic, cycloaliphatic, araliphatic or aromatic Dicarboxylic acid, dicarbamic acid or phosphorus-containing acid or a divalent silyl radical, preferably a radical of an aliphatic dicarboxylic acid with 2 to 36 carbon atoms, a cycloaliphatic or aromatic dicarboxylic acid with 8-14 carbon atoms or an aliphatic, cycloaliphatic or aromatic dicarbamic acid with 8-14 When n is 3, carbon atoms means a trivalent radical of an aliphatic, cycloaliphatic or aromatic tricarboxylic acid, an aromatic tricarbamic acid or a phosphorus-containing acid or means a trivalent silyl radical and, when n is 4, means a tetravalent radical of an aliphatic, cycloaliphatic or aromatic tetracarboxylic acid.

Bedeuten etwaige Substituenten C₁-C₁₂ Alkyl, so stellen sie z.B. Methyl, Ethyl, n-Propyl, n-Butyl, sek.-Butyl, tert.-Butyl, n-Hexyl, n-Octyl, 2-Ethyl-hexyl, n-Nonyl, n-Decyl, n-Undecyl oder n-Dodecyl dar.If any substituents are C₁-C₁₂ alkyl, they represent e.g. Methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl, 2-ethyl-hexyl, n-nonyl, n-decyl, n-undecyl or n- Dodecyl.

In der Bedeutung von C₁-C₁₈ Alkyl kann R¹ oder R² z.B. die oben ange­führten Gruppen und dazu noch beispielsweise n-Tridecyl, n-Tetradecyl, n-Hexadecyl oder n-Octadecyl darstellen.In the meaning of C₁-C₁₈ alkyl, R¹ or R² can e.g. represent the groups listed above and, for example, n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl.

Wenn R¹ C₃-C₈ Alkenyl bedeutet, so kann es sich z.B. um 1-Propenyl, Allyl, Methallyl, 2-Butenyl, 2-Pentenyl, 2-Hexenyl, 2-Octenyl, 4-tert.-­Butyl-2-butenyl handeln.If R¹ is C₃-C₈ alkenyl, it can e.g. are 1-propenyl, allyl, methallyl, 2-butenyl, 2-pentenyl, 2-hexenyl, 2-octenyl, 4-tert-butyl-2-butenyl.

R¹ ist als C₃-C₈ Alkinyl bevorzugt Propargyl.R¹ as C₃-C₈ alkynyl is preferably propargyl.

Als C₇-C₁₂ Aralkyl ist R¹ insbesondere Phenethyll und vor allem Benzyl.As C₇-C₁₂ aralkyl, R¹ is especially phenethyll and especially benzyl.

R¹ ist als C₁-C₈ Alkanoyl beispielsweise Formyl, Propionyl, Butyryl, Octanoyl, aber bevorzugt Acetyl und als C₃-C₅ Alkenoyl insbesondere Acryloyl.R¹ is as C₁-C₈ alkanoyl, for example formyl, propionyl, butyryl, octanoyl, but preferably acetyl and as C₃-C₅ alkenoyl in particular acryloyl.

Bedeutet R² einen einwertigen Rest einer Carbonsäure, so stellt es beispielsweise einen Essigsäure-, Capronsäure-, Stearinsäure-, Acryl­säure-, Methacrylsäure-, Benzoe- oder ß-(3,5-Di-tert.-butyl-4-hydroxy phenyl)-propionsäurerest dar.If R² is a monovalent radical of a carboxylic acid, it is, for example, acetic, caproic, stearic, acrylic, methacrylic, benzoic or β- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionic acid residue.

Bedeutet R² einen zweiwertigen Rest einer Dicarbonsäure, so stellt es beispielsweise einen Malonsäure-, Bernsteinsäure-, Glutarsäure-, Adipin­säure-, Korksäure-, Sebacinsäure-, Maleinsäure-, Phthalsäure-, Dibutyl­malonsäure-, Dibenzylmalonsäure, Butyl-(3,5-di-tert.-butyl-4-hydroxy­benzyl)-malonsäure- oder Bicycloheptendicarbonsäurerest dar.If R² is a divalent radical of a dicarboxylic acid, it represents, for example, malonic, succinic, glutaric, adipic, suberic, sebacic, maleic, phthalic, dibutylmalonic, dibenzylmalonic, butyl (3,5-di -tert.-butyl-4-hydroxybenzyl) malonic acid or bicycloheptenedicarboxylic acid residue.

Stellt R² einen dreiwertigen Rest einer Tricarbonsäure dar, so bedeutet es z.B. einen Trimellitsäure- oder einen Nitrilotriessigsäurerest.If R² represents a trivalent carboxylic acid residue, it means, for example, a trimellitic acid or a nitrilotriacetic acid residue.

Stellt R² einen vierwertigen Rest einer Tetracarbonsäure dar, so bedeutet es z.B. den vierwertigen Rest von Butan-1,2,3,4-tetracarbonsäure oder von Pyromellitsäure.If R² represents a tetravalent residue of a tetracarboxylic acid, it means e.g. the tetravalent residue of butane-1,2,3,4-tetracarboxylic acid or of pyromellitic acid.

Bedeutet R² einen zweiwertigen Rest einer Dicarbaminsäure, so stellt es beispielsweise einen Hexamethylendicarbaminsäure- oder einen 2,4-Toluy­len-dicarbaminsäurerest dar.If R² is a divalent radical of a dicarbamic acid, it is, for example, a hexamethylene dicarbamic acid or a 2,4-tolylene dicarbamic acid radical.

Beispiele für Polyalkylpiperidin-Verbindungen dieser Klasse sind folgende Verbindungen:

  • 1) 4-Hydroxy-2,2,6,6-tetramethylpiperidin
  • 2) 1-Allyl-4-hydroxy-2,2,6,6-tetramethylpiperidin
  • 3) 1-Benzyl-4-hydroxy-2,2,6,6-tetramethylpiperidin
  • 4) 1-(4-tert.-Butyl-2-butenyl)-4-hydroxy-2,2,6,6-tetramethylpiperidin
  • 5) 4-Stearoyloxy-2,2,6,6-tetramethylpiperidin
  • 6) 1-Ethyl-4-salicyloyloxy-2,2,6,6-tetramethylpiperidin
  • 7) 4-methacryloyloxy-1,2,2,6,6-pentamethylpiperidin
  • 8) 1,2,2,6,6-pentamethylpiperidin-4-yl-ß-(3,5-di-tert.-butyl-4-hyd­roxyphenyl)-propionat
  • 9) Di-(1-benzyl-2,2,6,6-tetramethylpiperidin-4-yl)-maleinat
  • 10) Di-(2,2,6,6-tetramethylpiperidin-4-yl)-succinat
  • 11) Di-(2,2,6,6-tetramethylpiperidin-4-yl)-glutarat
  • 12) Di-(2,2,6,6-tetramethylpiperidin-4-yl)-adipat
  • 13) Di-(2,2,6,6-tetramethylpiperidin-4-yl)-sebacat
  • 14) Di-(1,2,2,6,6-pentamethylpiperidin-4-yl)-sebacat
  • 15) Di-(1,2,3,6-tetramethyl-2,6-diethyl-piperidin-4-yl)-sebacat
  • 16) Di-(1-allyl-2,2,6,6-tetramethylpiperidin-4-yl)-phthalat
  • 17) 1-propargyl-4-ß-cyanoethyloxy-2,2,6,6-tetramethylpiperidin
  • 18) 1-Acetyl-2,2,6,6-tetramethylpiperidin-4-yl-acetat
  • 19) Trimellithsäure-tri-(2,2,6,6-tetramethylpiperidin-4-yl)-ester
  • 20) 1-Acryloyl-4-benzyloxy-2,2,6,6-tetramethylpiperidin
  • 21) Diethylmalonsäure-di(2,2,6,6-tetramethylpiperidin-4-yl)-ester
  • 22) Dibutyl-malonsäure-di-(1,2,2,6,6-pentamethylpiperidin-4-yl)-ester
  • 23) Butyl-(3,5-di-tert.-butyl-4-hydroxybenzyl)-malonsäure-di-(1,2,2,6,6-­pentamethylpiperidin-4-yl)-ester
  • 24) Dibenzyl-malonsäure-di-(1,2,2,6,6-pentamethylpiperidin-4-yl)-ester
  • 25) Dibenzyl-malonsäure-di-(1,2,3,6-tetramethyl-2,6-diethyl-piperidin-­4-yl)-ester
  • 26) Hexan-1′,6′-bis-(4-carbamoyloxy-1-n-butyl-2,2,6,6-tetramethyl­piperidin)
  • 27) Toluol-2′,4′-bis-(4-carbamoyloxy-1-n-propyl-2,2,6,6-tetramethyl­piperidin)
  • 28) Dimethyl-bis-(2,2,6,6-tetramethylpiperidin-4-oxy)-silan
  • 29) Phenyl-tris-(2,2,6,6-tetramethylpiperidin-4-oxy)-silan
  • 30) Tris-(1-propyl-2,2,6,6-tetramethylpiperidin-4-yl)-phosphit
  • 31) Tris-(1-propyl-2,2,6,6-tetramethylpiperidin-4-yl)-phosphat
  • 32) Phenyl-[bis(1,2,2,6,6-pentamethylpiperidin-4-yl)]-phosphonat
  • 33) 4-Hydroxy-1,2,2,6,6-pentamethylpiperidin
  • 34) 4-Hydroxy-N-hydroxyethyl-2,2,6,6-tetramethylpiperidin
  • 35) 4-Hydroxy-N-(2-hydroxypropyl)-2,2,6,6-tetramethylpiperidin
  • 36) 1-Glycidyl-4-hydroxy-2,2,6,6-tetramethylpiperidin
Examples of polyalkylpiperidine compounds of this class are the following compounds:
  • 1) 4-Hydroxy-2,2,6,6-tetramethylpiperidine
  • 2) 1-Allyl-4-hydroxy-2,2,6,6-tetramethylpiperidine
  • 3) 1-Benzyl-4-hydroxy-2,2,6,6-tetramethylpiperidine
  • 4) 1- (4-tert-butyl-2-butenyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine
  • 5) 4-stearoyloxy-2,2,6,6-tetramethylpiperidine
  • 6) 1-ethyl-4-salicyloyloxy-2,2,6,6-tetramethylpiperidine
  • 7) 4-methacryloyloxy-1,2,2,6,6-pentamethylpiperidine
  • 8) 1,2,2,6,6-pentamethylpiperidin-4-yl-β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate
  • 9) Di- (1-benzyl-2,2,6,6-tetramethylpiperidin-4-yl) maleate
  • 10) Di- (2,2,6,6-tetramethylpiperidin-4-yl) succinate
  • 11) Di- (2,2,6,6-tetramethylpiperidin-4-yl) glutarate
  • 12) Di- (2,2,6,6-tetramethylpiperidin-4-yl) adipate
  • 13) Di- (2,2,6,6-tetramethylpiperidin-4-yl) sebacate
  • 14) Di- (1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate
  • 15) Di- (1,2,3,6-tetramethyl-2,6-diethyl-piperidin-4-yl) sebacate
  • 16) Di- (1-allyl-2,2,6,6-tetramethylpiperidin-4-yl) phthalate
  • 17) 1-propargyl-4-ß-cyanoethyloxy-2,2,6,6-tetramethylpiperidine
  • 18) 1-Acetyl-2,2,6,6-tetramethylpiperidin-4-yl acetate
  • 19) Trimellitic acid tri (2,2,6,6-tetramethylpiperidin-4-yl) ester
  • 20) 1-Acryloyl-4-benzyloxy-2,2,6,6-tetramethylpiperidine
  • 21) Diethylmalonic acid di (2,2,6,6-tetramethylpiperidin-4-yl) ester
  • 22) Dibutyl malonic acid di (1,2,2,6,6-pentamethylpiperidin-4-yl) ester
  • 23) Butyl- (3,5-di-tert-butyl-4-hydroxybenzyl) -malonic acid di- (1,2,2,6,6-pentamethylpiperidin-4-yl) ester
  • 24) Dibenzyl malonic acid di (1,2,2,6,6-pentamethylpiperidin-4-yl) ester
  • 25) Dibenzyl-malonic acid di- (1,2,3,6-tetramethyl-2,6-diethyl-piperidin-4-yl) ester
  • 26) hexane-1 ′, 6′-bis- (4-carbamoyloxy-1-n-butyl-2,2,6,6-tetramethylpiperidine)
  • 27) toluene-2 ′, 4′-bis- (4-carbamoyloxy-1-n-propyl-2,2,6,6-tetramethylpiperidine)
  • 28) Dimethyl bis (2,2,6,6-tetramethylpiperidine-4-oxy) silane
  • 29) Phenyl-tris (2,2,6,6-tetramethylpiperidine-4-oxy) silane
  • 30) Tris- (1-propyl-2,2,6,6-tetramethylpiperidin-4-yl) phosphite
  • 31) Tris- (1-propyl-2,2,6,6-tetramethylpiperidin-4-yl) phosphate
  • 32) Phenyl- [bis (1,2,2,6,6-pentamethylpiperidin-4-yl)] phosphonate
  • 33) 4-Hydroxy-1,2,2,6,6-pentamethylpiperidine
  • 34) 4-Hydroxy-N-hydroxyethyl-2,2,6,6-tetramethylpiperidine
  • 35) 4-Hydroxy-N- (2-hydroxypropyl) -2,2,6,6-tetramethylpiperidine
  • 36) 1-Glycidyl-4-hydroxy-2,2,6,6-tetramethylpiperidine

Verbindungen der Formel (III)

Figure imgb0003
worin n die Zahl 1 oder 2 bedeutet, R und R¹ die unter Formel (II) angegebene Bedeutung haben, R³ Wasserstoff, C₁-C₁₂ Alkyl, C₂-C₅ Hydroxy­alkyl, C₅-C₇ Cycloalkyl, C₇-C₈ Aralkyl, C₂-C₁₈ Alkanoyl, C₃-C₅ Alkenoyl oder Benzoyl ist und R⁴ wenn n 1 ist, Wasserstoff, C₁-C₁₈ Alkyl, C₃-C₈ Alkenyl, C₅-C₇ Cycloalkyl, mit einer Hydroxy-, Cyano-, Alkoxycarbonyl- oder Carbamidgruppe substituiertes C₁-C₄ Alkyl, Glycidyl, eine Gruppe der Formel -CH₂-CH(OH)-Z oder der Formel -CONH-Z ist, worin Z Wasserstoff, Methyl oder Phenyl bedeutet; wenn n 2 ist, C₂-C₁₂ Alkylen, C₆-C₁₂ Arylen, Xylylen, eine -CH₂-CH(OH)-CH₂-Gruppe oder eine Gruppe -CH₂-CH(OH)-CH₂-O-D-O- bedeutet, worin D C₂-C₁₀ Alkylen, C₆-C₁₅ Arylen, C₆-C₁₂ Cycloalkylen ist, oder vorausgesetzt, dass R³ nicht Alkanoyl, Alkenoyl oder Benzoyl bedeutet, R⁴ auch einen zweiwertigen Rest einer aliphatischen, cycloaliphatischen oder aromatischen Dicarbonsäure oder Dicarbaminsäure oder auch die Gruppe -CO- bedeuten kann, oder R³ und R⁴ zusammen, wenn n 1 ist, den zweiwertigen Rest einer aliphatischen, cycloaliphatischen oder aromatischen 1,2- oder 1,3-Dicarbonsäure bedeuten können.Compounds of formula (III)
Figure imgb0003
 in which n is the number 1 or 2, R and R¹ have the meaning given under formula (II), R³ is hydrogen, C₁-C₁₂ alkyl, C₂-C₅ hydroxyalkyl, C₅-C₇ cycloalkyl, C₇-C, aralkyl, C₂-C₁₈ alkanoyl, C₃-C₅ alkenoyl or benzoyl and R⁴ when n is 1, hydrogen, C₁-C₁₈ alkyl, C₃-C₈ alkenyl, C₅-C₇ cycloalkyl, C₁-C₄ alkyl, glycidyl substituted with a hydroxy, cyano, alkoxycarbonyl or carbamide group , a group of the formula -CH₂-CH (OH) -Z or the formula -CONH-Z, wherein Z is hydrogen, methyl or phenyl; when n is 2, C₂-C₁₂ alkylene, C₆-C₁₂ arylene, xylylene, a -CH₂-CH (OH) -CH₂ group or a group -CH₂-CH (OH) -CH₂-ODO-, where D is C₂- C₁₀ alkylene, C₆-C₁₅ arylene, C₆-C₁₂ cycloalkylene, or provided that R³ is not alkanoyl, alkenoyl or benzoyl, R⁴ also a divalent radical of an aliphatic, cycloaliphatic or aromatic dicarboxylic acid or Dicarbamic acid or the group -CO- can mean, or R³ and R⁴ together, if n is 1, can mean the divalent radical of an aliphatic, cycloaliphatic or aromatic 1,2- or 1,3-dicarboxylic acid.

Stellen etwaige Substituenten C₁-C₁₂- oder C₁-C₁₈-Alkyl dar, so haben sie die bereits unter Formel (II) angegebene Bedeutung.If any substituents are C₁-C₁₂- or C₁-C₁₈-alkyl, they have the meaning already given under formula (II).

Bedeuten etwaige Substituenten C₅-C₇ Cycloalkyl, so stellen sie insbeson­dere Cyclohexyl dar.Any substituents C₅-C₇ cycloalkyl, they represent in particular cyclohexyl.

Als C₇-C₈ Aralkyl ist R³ insbesondere Phenylethyl oder vor allem Benzyl. Als C₂-C₅Hydroxyalkyl ist R³ insbesondere 2-Hydroxyethyl oder 2-Hydroxy­propyl.As C₇-C₈ aralkyl, R³ is especially phenylethyl or especially benzyl. As C₂-C₅Hydroxyalkyl R³ is in particular 2-hydroxyethyl or 2-hydroxypropyl.

R³ ist als C₂-C₁₈ Alkanoyl beispielsweise Propionyl, Butyryl, Octanoyl, Dodecanoyl, Hexadecanoyl, Octadecanoyl, aber bevorzugt Acetyl und als C₃-C₅ Alkenoyl insbesondere Acryloyl.R³ is as C₂-C₁₈ alkanoyl, for example propionyl, butyryl, octanoyl, dodecanoyl, hexadecanoyl, octadecanoyl, but preferably acetyl and as C₃-C₅ alkenoyl in particular acryloyl.

Bedeutet R⁴ C₂-C₈ Alkenyl, dann handelt es sich z.B. um Allyl, Methallyl, 2-Butenyl, 2-Pentenyl, 2-Hexenyl oder 2-Octenyl.If R⁴ C₂-C₈ is alkenyl, then it is e.g. allyl, methallyl, 2-butenyl, 2-pentenyl, 2-hexenyl or 2-octenyl.

R⁴ als mit einer Hydroxy-, Cyano-, Alkoxycarbonyl- oder Carbamidgruppe substituiertes C₁-C₄-Alkyl kann z.B. 2-Hydroxyethyl, 2-Hydroxypropyl, 2-Cyanethyl, Methoxycarbonylmethyl, 2-Ethoxycarbonylethyl, 2-Amino­carbonylpropyl oder 2-(Dimethylaminocarbonyl)-ethyl sein.R⁴ as a C₁-C₄-alkyl substituted with a hydroxy, cyano, alkoxycarbonyl or carbamide group can e.g. 2-Hydroxyethyl, 2-hydroxypropyl, 2-cyanoethyl, methoxycarbonylmethyl, 2-ethoxycarbonylethyl, 2-aminocarbonylpropyl or 2- (dimethylaminocarbonyl) ethyl.

Stellen etwaige Substituenten C₂-C₁₂ Alkylen dar, so handelt es sich z.B. um Ethylen, Propylen, 2,2-Dimethylpropylen, Tetramethylen, Hexamethylen, Octamethylen, Decamethylen oder Dodecamethylen.If any substituents are C₂-C₁₂ alkylene, they are e.g. around ethylene, propylene, 2,2-dimethylpropylene, tetramethylene, hexamethylene, octamethylene, decamethylene or dodecamethylene.

Bedeuten etwaige Substituenten C₆-C₁₅-Arylen, so stellen sie z.B. o-, m- oder p-Phenylen, 1,4-Naphthylen oder 4,4′-Diphenylen dar.If any substituents are C₆-C₁₅ arylene, they represent e.g. o-, m- or p-phenylene, 1,4-naphthylene or 4,4'-diphenylene.

Als C₆-C₁₂ Cycloalkylen ist D insbesondere Cyclohexylen.As C₆-C₁₂ cycloalkylene, D is especially cyclohexylene.

Beispiele für Polyalkylpiperidin-Verbindungen dieser Klasse sind folgende Verbindungen:

  • 37) N,N′-Bis-(2,2,6,6-tetramethylpiperidin-4-yl)-hexamethylen-1,6-diamin
  • 38) N,N′-Bis-(2,2,6,6-tetramethylpiperidin-4-yl)-hexamethylen-1,6-diacet­amid
  • 39) 1-Acetyl-4-(N-cyclohexylacetamido)-2,2,6,6-tetramethylpiperidin
  • 40) 4-Benzoylamino-2,2,6,6-tetramethylpiperidin
  • 41) N,N′-Bis-(2,2,6,6-tetramethylpiperidin-4-yl)-N,N′-dibutyl-adipamid
  • 42)N,′-Bis-(2,2,6,6-tetramethylpiperidin-4-yl)-N,N′-dicyclohexyl-2-­hydroxypropylen-1,3-diamin
  • 43) N,N′-Bis-(2,2,6,6-tetramethylpiperidin-4-yl)-p-xylylen-diamin
  • 44) N,N′-Bis-(2,2,6,6-tetramethylpiperidin-4-yl)-succindiamid
  • 45) N-(2,2,6,6-Tetramethylpiperidin-4-yl)-ß-aminodipropionsäure-di-­(2,2,6,6-tetramethylpiperidin-4-yl)-ester
  • 46) Die Verbindung der Formel
    Figure imgb0004
  • 47) 4-(Bis-2-hydroxyethylamino)-1,2,2,6,6-pentamethylpiperidin
  • 48) 4-(3-Methyl-4-hydroxy-5-tert.-butyl-benzoesäureamido)-2,2,6,6-tetra­methylpiperidin
  • 49) 4-Methacrylamido-1,2,2,6,6-pentamethylpiperidin
Examples of polyalkylpiperidine compounds of this class are the following compounds:
  • 37) N, N'-bis (2,2,6,6-tetramethylpiperidin-4-yl) hexamethylene-1,6-diamine
  • 38) N, N'-bis (2,2,6,6-tetramethylpiperidin-4-yl) hexamethylene-1,6-diacetamide
  • 39) 1-Acetyl-4- (N-cyclohexylacetamido) -2,2,6,6-tetramethylpiperidine
  • 40) 4-Benzoylamino-2,2,6,6-tetramethylpiperidine
  • 41) N, N'-bis (2,2,6,6-tetramethylpiperidin-4-yl) -N, N'-dibutyl adipamide
  • 42) N, '- bis (2,2,6,6-tetramethylpiperidin-4-yl) -N, N'-dicyclohexyl-2-hydroxypropylene-1,3-diamine
  • 43) N, N'-bis (2,2,6,6-tetramethylpiperidin-4-yl) -p-xylylene diamine
  • 44) N, N'-bis (2,2,6,6-tetramethylpiperidin-4-yl) succinic diamide
  • 45) N- (2,2,6,6-Tetramethylpiperidin-4-yl) -ß-aminodipropionic acid di- (2,2,6,6-tetramethylpiperidin-4-yl) ester
  • 46) The compound of the formula
    Figure imgb0004
  • 47) 4- (bis-2-hydroxyethylamino) -1,2,2,6,6-pentamethylpiperidine
  • 48) 4- (3-Methyl-4-hydroxy-5-tert-butyl-benzoic acid amido) -2,2,6,6-tetramethylpiperidine
  • 49) 4-methacrylamido-1,2,2,6,6-pentamethylpiperidine

Verbindungen mit mindestens einer Gruppe der Formel (I) sind bekannt z.B. aus US-A-3,840,494 und können nach den dort beschriebenen Verfahren hergestellt werden.Compounds with at least one group of the formula (I) are known, for example from US Pat. No. 3,840,494, and can be prepared by the processes described there.

Beim erfindungsgemäss zu behandelnden gefärben Polypropylenfasermaterial handelt es sich um Fasermaterial, das mit einem anorganischen oder organischen Pigment gefärbt sein kann oder um ein aus der Flotte anfärb­bares Fasermaterial. Das Pigment mit welchem das Material gefärbt ist kann ein weisses, schwarzes oder farbiges Pigment sein. Es kann ein einzelnes Pigment oder eine Mischung von Pigmenten sein.The dyed polypropylene fiber material to be treated according to the invention is fiber material which can be dyed with an inorganic or organic pigment or a fiber material which can be dyed from the liquor. The pigment with which the material is colored can be a white, black or colored pigment. It can be a single pigment or a mixture of pigments.

Beispiele für anorganische Pigmente sind Titandioxid, Zinkoxid, Barium­carbonat, Russ, Cadmiumsulfid und -selenid, Chromate, Chromoxide, Eisenoxide oder Bleioxide.Examples of inorganic pigments are titanium dioxide, zinc oxide, barium carbonate, carbon black, cadmium sulfide and selenide, chromates, chromium oxides, iron oxides or lead oxides.

Beispiele für organische Pigmentklassen sind Azopigmente, Anthrachinone, Phthalocyanine, Pyrrolopyrrole, Chinacridone, Isoindoline oder Perylen-­Pigmente.Examples of organic pigment classes are azo pigments, anthraquinones, phthalocyanines, pyrrolopyrroles, quinacridones, isoindolines or perylene pigments.

Die Menge an Pigment kann in weiten Grenzen schwanken, man kann insbeson­dere 0,01 bis 10 Gew.-%, bezogen auf das Polypropylen zusetzen.The amount of pigment can vary within wide limits, in particular 0.01 to 10% by weight, based on the polypropylene, can be added.

Das ungefärbte Polypropylenfasermaterial kann aber auch fotochemisch stabilisiert und gleichzeitig optisch aufgehellt werden, indem man das Fasermaterial mit einer wässrigen Lichtschutzmittelformulierung behan­delt, welche zusätzlich einen optischen Aufheller enthält.The undyed polypropylene fiber material can also be stabilized photochemically and at the same time optically brightened by treating the fiber material with an aqueous light stabilizer formulation which additionally contains an optical brightener.

Dieses Stabilisierungsverfahren bildet einen weiteren Gegenstand der vorliegenden Erfindung.This stabilization process forms a further subject of the present invention.

Als optische Aufheller für das erfindungsgemässe Verfahren kommen solche aus der Klasse der polycyclischen Oxazole, der Cumarine, Aryltriazole, Styrylstilbene und Naphthalimide in Betracht wie sie z.B. in A.K. Sarkar "Fluorescent whitening agents", Merrow Publishing Co. Ltd., Watford England (1971), 71 - 72 angegeben sind.Possible optical brighteners for the process according to the invention are those from the class of the polycyclic oxazoles, the coumarins, aryltriazoles, styrylstilbenes and naphthalimides, such as those e.g. in A.K. Sarkar "Fluorescent whitening agents", Merrow Publishing Co. Ltd., Watford England (1971), 71-72.

Besonders geeignet sind optische Aufheller vom Benzooxazoltyps.Optical brighteners of the benzooxazole type are particularly suitable.

Die Menge des dispergierten optischen Aufhellers beträgt 0,01 % - 0,5 % vom Fasergewicht.The amount of the dispersed optical brightener is 0.01% - 0.5% of the fiber weight.

Die erfindungsgemäss verwendbaren wässrigen Lösungen enthalten die Verbindungen der Formeln (I) bis (III) in einer Menge von 0,05 bis 7,5, vorzugsweise 0,1 bis 3 und besonderes 0,1 bis 2 % bezogen auf das Fasergewicht.The aqueous solutions which can be used according to the invention contain the compounds of the formulas (I) to (III) in an amount of 0.05 to 7.5, preferably 0.1 to 3 and in particular 0.1 to 2%, based on the fiber weight.

Das erfindungsgemässe Verfahren kann mit Mitteln ausgeführt werden, die im allgemeinen

  • a) 5 bis 75 Gew.% eines Lichtschutzmittels aus der Klasse der sterisch gehinderten Amine,
  • b) 0 bis 25 Gew.% eines Aufhellers aus der Klasse der polycyclischen Oxazole, der Cumarine, Aryltriazole, Styrylstilbene und Naphthalimide,
  • c) 3 bis 25 Gew.% eines nichtionogenen oder anionischen Dispergators und
  • d) ad 100 Gew.% Wasser
enthalten.The process according to the invention can be carried out using agents which are generally
  • a) 5 to 75% by weight of a light stabilizer from the class of the sterically hindered amines,
  • b) 0 to 25% by weight of a brightener from the class of the polycyclic oxazoles, the coumarins, aryltriazoles, styrylstilbenes and naphthalimides,
  • c) 3 to 25% by weight of a nonionic or anionic dispersant and
  • d) ad 100% by weight of water
contain.

Als nichtionogene Dispergatoren kommen Alkohol- oder Alkylphenolalkylen­oxidumsetzungsprodukte, z.B. Alkylenoxidumsetzungsprodukte von aliphati­schen Alkoholen mit 4 bis 22 Kohlenstoffatomen, die bis zu 80 Mol Ethylenoxid und/oder Propylenoxid angelagert enthalten, in Betracht. Die Alkohole können vorzugsweise 4 bis 18 Kohlenstoffatome enthalten, sie können gesättigt, verzweigt oder geradkettig sein und können allein oder im Gemisch eingesetzt werden. Alkohole mit verzweigten Ketten sind bevorzugt.Suitable nonionic dispersants are alcohol or alkylphenolalkylene oxide reaction products, e.g. Alkylene oxide reaction products of aliphatic alcohols with 4 to 22 carbon atoms, which contain up to 80 moles of ethylene oxide and / or propylene oxide added. The alcohols can preferably contain 4 to 18 carbon atoms, they can be saturated, branched or straight-chain and can be used alone or in a mixture. Branched chain alcohols are preferred.

Es können natürliche Alkohole, wie z.B. Myristylalkohol, Cetylalkohol, Stearylalkohol, Oleylalkohol, Arachidylalkohol oder Behenylalkohol oder synthetische Alkohole, wie insbesondere Butanol, 2-Aethylhexanol, Amylalkohol, n-Hexanol, ferner Triäthylhexanol, Trimethylnonylalkohol oder die Alfole (Handelsname - Continental Oil Company) verwendet werden. Bei den Alfolen handelt es sich um lineare primäre Alkohole. Die Nummer hinter dem Namen gibt die durchschnittliche Kohlenstoffzahl des Alkohols an; so ist z.B. Alfol (1218) ein Gemisch aus Decyl-, Dodecyl-, Tetra­decyl-, Hexadecyl- und Octadecylalkohol. Weitere Vertreter sind Alfol (810), (1014), (12), (16), (18), (2022).Natural alcohols, such as, for example, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, arachidyl alcohol or behenyl alcohol or synthetic alcohols, such as in particular butanol, 2-ethylhexanol, amyl alcohol, n-hexanol, furthermore triethylhexanol, trimethylnonyl alcohol or the Alfole (trade name - Continental Oil) (trade name - Continental Oil) be used. The Alfolen are linear primary alcohols. The number after the name indicates the average carbon number of the alcohol; for example, Alfol (1218) is a mixture of decyl, dodecyl, tetradecyl, hexadecyl and octadecyl alcohol. Other representatives are Alfol (810), (1014), (12), (16), (18), (2022).

Bevorzugte Aethylenoxid-Alkohol-Umsetzungsprodukte können z.B. durch die Formel
(1)       R₃O(CH₂CH₂O)sH
dargestellt werden, worin R₃ ein gesättigter oder ungesättigter Kohlen­wasserstoffrest, vorzugsweise ein Alkyl- oder Alkenylrest mit 8 bis 18 Kohlenstoffatomen und s eine ganze Zahl von 1 bis 80, vorzugsweise von 1 bis 30 ist.Preferred ethylene oxide-alcohol reaction products can, for example, by the formula
(1) R₃O (CH₂CH₂O) s H
are shown, wherein R₃ is a saturated or unsaturated hydrocarbon radical, preferably an alkyl or alkenyl radical having 8 to 18 carbon atoms and s is an integer from 1 to 80, preferably from 1 to 30.

Als nichtionogene Dispergatoren kommen ferner Umsetzungsprodukte aus Aethylenoxid und/oder 1,2-Propylenoxid und Alkylphenolen mit 4 bis 12 Kohlenstoffatomen im Alkylteil, wobei das Phenol ein oder mehrere Alkylsubstituenten enthalten kann, in Betracht. Vorzugsweise entsprechen diese Verbindungen der Formel

Figure imgb0005
worin R Wasserstoff oder höchstens einer der beiden Reste R Methyl, p eine Zahl von 4 bis 12, vorzugsweise 8 bis 9, und t eine Zahl von 1 bis 60, insbesondere von 1 bis 20 und vorzugsweise 1 bis 6 ist.Other suitable nonionic dispersants are reaction products of ethylene oxide and / or 1,2-propylene oxide and alkylphenols having 4 to 12 carbon atoms in the alkyl part, it being possible for the phenol to contain one or more alkyl substituents. These compounds preferably correspond to the formula
Figure imgb0005
 wherein R is hydrogen or at most one of the two radicals R methyl, p is a number from 4 to 12, preferably 8 to 9, and t is a number from 1 to 60, in particular from 1 to 20 and preferably 1 to 6.

Gegebenenfalls können diese Alkohol-Alkylphenol-Aethylenoxid/1,2-Pro­pylenoxid-Addukte noch kleinere Anteile von Blockpolymeren aus den genannten Alkylenoxiden enthalten.Optionally, these alcohol-alkylphenol-ethylene oxide / 1,2-propylene oxide adducts may contain even smaller proportions of block polymers from the alkylene oxides mentioned.

Weitere Umsetzungsprodukte, die als nichtionogene Dispergatoren in Betracht kommen, sind Polyoxyethylenderivate der Fettsäureester der Ether des Sorbitans mit 4 Mol Polyethylenglykol, z.B. das Laurat, Palmitat, Stearat, Tristearat, Oleat und Trioleat der genannten Ether wie die Tween-Marken der Atlas Chemicals Division. Bevorzugt ist das Tristearat des Ethers des Sorbitans mit 4 Mol des Polyethylenglykols der Formel
(3)       H(CH₂CH₂)₆₅OH.Other reaction products which can be considered as nonionic dispersants are polyoxyethylene derivatives of the fatty acid esters of sorbitan ethers with 4 moles of polyethylene glycol, for example the laurate, palmitate, stearate, tristearate, oleate and trioleate of the ethers mentioned, such as the Tween brands of the Atlas Chemicals Division. The tristearate of the ether of sorbitan with 4 mol of the polyethylene glycol of the formula is preferred
(3) H (CH₂CH₂) ₆₅OH.

Als anionische Dispergatoren sind veresterte Alkylenoxidaddukte, wie z.B. saure Estergruppen von anorganischen oder organischen Säuren enthaltende Anlagerungsprodukte von Alkylenoxiden, besonders Aethylenoxid und/oder Propylenoxid, an aliphatische, insgesamt mindestens 8 Kohlen­stoffatome aufweisende organische Hydroxyl-, Carboxyl- gegebenenfalls auch Amino- oder Amidoverbindungen bzw. Mischungen dieser Verbindungen. Diese sauren Ester können als freie Säuren oder als Salze z.B. Alkali­metall-, Erdalkalimetall-, Ammonium- oder Aminsalze vorliegen.Esterified alkylene oxide adducts such as e.g. addition products of alkylene oxides, especially ethylene oxide and / or propylene oxide, containing acidic ester groups of inorganic or organic acids, onto aliphatic organic hydroxyl, carboxyl or optionally also amino or amido compounds or mixtures of these compounds with a total of at least 8 carbon atoms. These acidic esters can be used as free acids or as salts e.g. Alkali metal, alkaline earth metal, ammonium or amine salts are present.

Die Herstellung dieser anionischen Dispergatoren erfolgt nach bekannten Methoden, indem man an die genannten organischen Verbindungen mindestens 1 Mol vorzugsweise mehr als 1 Mol z.B. 2 bis 60 Mol Aethylenoxid oder alternierend in beliebiger Reihenfolge Aethylenoxid und Propylenoxid anlagert und anschliessend die Anlagerungsprodukte veräthert bzw. ver­estert und gegebenenfalls die Aether bzw. die Ester in ihre Salze überführt. Als Ausgangsstoffe kommen z.B. höhere Fettalkohole, d.h. Alka­nole oder Alkenole mit 8 bis 22 Kohlenstoffatomen, alicyclische Alkohole, Phenylphenole, Alkylphenole mit einem oder mehreren Alkylsubstituenten, der bzw. die zusammen mindestens 10 Kohlenstoffatome aufweisen oder Fettsäuren mit 8 bis 22 Kohlenstoffatomen in Betracht.These anionic dispersants are prepared by known methods by adding at least 1 mole, preferably more than 1 mole, to the organic compounds mentioned, e.g. 2 to 60 moles of ethylene oxide or alternately in any order, ethylene oxide and propylene oxide and then etherifying or esterifying the addition products and, if appropriate, converting the ethers or the esters into their salts. The starting materials are e.g. higher fatty alcohols, i.e. Alkanols or alkenols with 8 to 22 carbon atoms, alicyclic alcohols, phenylphenols, alkylphenols with one or more alkyl substituents which together have at least 10 carbon atoms or fatty acids with 8 to 22 carbon atoms.

Besonders geeignete anionische Dispergatoren entsprechen der Formel

Figure imgb0006
worin R₁ ein aliphatischer Kohlenwasserstoffrest mit 8 bis 22 Kohlen­stoffatomen oder ein cycloaliphatischer, aromatischer oder aliphatisch­aromatischer Kohlenwasserstoffrest mit 10 bis 22 Kohlenstoffatomen, R₂ Wasserstoff oder Methyl A -O- oder -
Figure imgb0007
-O,

X der Säurerest einer anorganischen, Sauerstoff enthaltenden Säure, der Säurerest einer mehrbasischen Carbonsäure oder ein Carboxylalkylrest und n eine Zahl von 1 bis 50 ist.Particularly suitable anionic dispersants correspond to the formula
Figure imgb0006
 wherein R₁ is an aliphatic hydrocarbon radical with 8 to 22 carbon atoms or a cycloaliphatic, aromatic or aliphatic-aromatic hydrocarbon radical with 10 to 22 carbon atoms, R₂ is hydrogen or methyl A -O- or -
Figure imgb0007
-O,

X is the acid residue of an inorganic, oxygen-containing acid, the acid residue of a polybasic carboxylic acid or a carboxylalkyl residue and n is a number from 1 to 50.

Der Rest R₁ -A- in den Verbindungen der Formel (4) leitet sich z.B. von höheren Alkoholen wie Decyl-, Lauryl-, Tridecyl-, Myristyl-, Cetyl-, Stearyl-, Oleyl-, Arachidyl- oder Behenylalkohol ab; ferner von ali­cyclischen Alkoholen, wie Hydroabietylalkohol; von Fettsäuren, wie Capryl-, Caprin-, Laurin-, Myristin-, Palmitin-, Stearin-, Arachin-, Behen-, Kokosfett- (C₈-C₁₈), Decen-, Dodecen-, Tetradecen-, Hexadecen-, Oel-, Lino-, Linolen-, Eikosen-, Dokosen- oder Clupanodonsäure; von Alkylphenolen, wie Butyl-, Hexyl-, n-Octy-, n-Nony-, p-tert. Octyl-, p-tert. Nonyl-, Decyl-, Dodecy-, Tetradecyl- oder Hexadecylphenol oder von Arylphenolen, wie den o- oder p-Phenylphenolen. Bevorzugt sind Reste mit 10 bis 18 Kohlenstoffatomen, insbesondere solche, die sich von den Alkylphenolen ableiten.The radical R₁ -A- in the compounds of formula (4) is derived, for example, from higher alcohols such as decyl, lauryl, tridecyl, myristyl, cetyl, stearyl, oleyl, arachidyl or behenyl alcohol; alicyclic alcohols such as hydroabietyl alcohol; of fatty acids like Capryl, caprin, laurin, myristine, palmitin, stearin, arachine, behen, coconut oil (C₈-C₁₈), decene, dodecene, tetradecene, hexadecene, oil, lino, Linolenic, eicotonic, docosonic or clupanodonic acid; of alkylphenols such as butyl, hexyl, n-octy, n-nony, p-tert. Octyl, p-tert. Nonyl, decyl, dodecy, tetradecyl or hexadecylphenol or of arylphenols, such as the o- or p-phenylphenols. Residues having 10 to 18 carbon atoms are preferred, in particular those which are derived from the alkylphenols.

Der Säurerest X ist in der Regel der Säurerest einer mehrbasischen, insbesondere niedermolekularen Mono- oder Dicarbonsäure wie z.B. von Maleinsäure, Malonsäure, Bernsteinsäure oder Sulfobernsteinsäure, oder ist ein Carboxyalkylrest, insbesondere ein Carboxymethylrest (abgeleitet insbesondere von Chloressigsäure) und ist über eine Aether- oder Ester­brücke mit dem Rest R₁-A-(CH₂CHR₂O)m- verbunden. Insbesondere leitet sich X jedoch von anorganischen mehrbasischen Säuren ab, wie Orthophosphor­säure und Schwefelsäure. Der Säurerest X liegt vorzugsweise in Salzform, d.h. z.B. als Alkalimetall-, Ammonium- oder Aminsalz, vor.The acid residue X is usually the acid residue of a polybasic, especially low molecular weight mono- or dicarboxylic acid such as maleic acid, malonic acid, succinic acid or sulfosuccinic acid, or is a carboxyalkyl residue, especially a carboxymethyl residue (derived in particular from chloroacetic acid) and is an ether or Ester bridge with the rest R₁-A- (CH₂CHR₂O) m - connected. In particular, however, X is derived from inorganic polybasic acids, such as orthophosphoric acid and sulfuric acid. The acid residue X is preferably in salt form, ie, for example, as an alkali metal, ammonium or amine salt.

Beispiele für solche Salze sind Natrium-, Kalzium-, Ammonium-, Tri­methylamin-, Aethanolamin-, Diäthanolamin- oder Triäthanolaminsalze. Bei den Alkylenoxideinheiten CH₂CHR₂O der Formel (4) handelt es sich in der Regel um Aethylenoxid und 1,2-Propylenoxideinheiten, letztere befinden sich vorzugsweise im Gemisch mit Aethylenoxideinheiten in den Verbindungen der Formel (4).Examples of such salts are sodium, calcium, ammonium, trimethylamine, ethanolamine, diethanolamine or triethanolamine salts. The alkylene oxide units CH₂CHR₂O of the formula (4) are generally ethylene oxide and 1,2-propylene oxide units, the latter preferably being in a mixture with ethylene oxide units in the compounds of the formula (4).

Von besonderem Interesse sind nun die anionischen Verbindungen der Formel
(5)       R₃O(CH₂CH₂O)n -X,
worin R₃ ein gesattigter oder ungesättigter Kohlenwasserstoffrest mit 8 bis 22 Kohlenwasserstoffatomen, o-Phenylphenol oder Alkylphenyl mit 4 bis 12 Kohlenstoffatomen im Alkylteil ist, und X und n die angegebenen Bedeutungen haben.The anionic compounds of the formula are of particular interest
(5) R₃O (CH₂CH₂O) n -X,
wherein R₃ is a saturated or unsaturated hydrocarbon radical with 8 to 22 hydrocarbon atoms, o-phenylphenol or alkylphenyl with 4 to 12 carbon atoms in the alkyl part, and X and n have the meanings given.

Von den Verbindungen, die sich von Alkylphenyl-Aethylenoxidaddukten ableiten, sind ferner solche der Formeln

Figure imgb0008
worin p eine Zahl von 4 bis 12, n eine ganze Zahl von 1 bis 20, n₁ eine ganze Zahl von 1 bis 10, X₁ ein Schwefelsäure oder Phosphorsäurerest, der gegebenenfalls in Salzform vorliegt und X die angegebene Bedeutung hat, besonders bevorzugt.Of the compounds derived from alkylphenyl ethylene oxide adducts, those of the formulas are also
Figure imgb0008
 wherein p is a number from 4 to 12, n is an integer from 1 to 20, n 1 is an integer from 1 to 10, X 1 is a sulfuric acid or phosphoric acid residue, which is optionally in salt form and X has the meaning given, particularly preferred.

Die Applikation der sterisch gehinderten Amine kann getrennt von der Applikation des optischen Aufhellers oder vorzugsweise gleichzeitig mit der Applikation des optischen Aufhellers, nach einem Ausziehverfahren bei Flottenverhältnissen 1:4 - 1:200 vorzugsweise 1:10 - 1:50 mittels z.B. Zirkulationsfärbeapparat oder Haspelkufe, erfolgen. Sie können aber auch kontinuierlich mittels Niedrigauftragsysteme oder Heissapplikations­systeme z.B. mit dem Fluidyer® (Fa. Küsters), Flexnip® (Fa. Küsters) u.ä. appliziert werden.The application of the sterically hindered amines can be carried out separately from the application of the optical brightener or preferably at the same time as the application of the optical brightener, after an exhaust process at liquor ratios 1: 4 - 1: 200, preferably 1:10 - 1:50, using e.g. Circulation dyeing machine or reel runner. But you can also continuously using low-order systems or hot application systems e.g. with the Fluidyer® (from Küsters), Flexnip® (from Küsters) etc. be applied.

Die zur Anwendung gelangende Flotte weist einen pH von 2 - 12, vorzugs­weise 5 - 10 und besonders 9 auf.The liquor used has a pH of 2-12, preferably 5-10 and especially 9.

Die zur Anwendung gelangenden Behandlungsflotten können noch alle für den Einsatz in der Polypropylenfaser-Behandlung geeigneten Chemikalien, z.B. Elektrolyten enthalten.The treatment liquors used can still contain all chemicals suitable for use in polypropylene fiber treatment, e.g. Contain electrolytes.

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:Example 1:

Drei Stränge aus Polypropylengarn der Feinheit Nm 60/1 z.B. Polycolon® von je 5 g in den Farben weiss (Muster A, spinnmassenauf­gehellt), marineblau (Muster B, spinnmassengefärbt) und dunkelblau (Muster C, spinnmassengefärbt) werden bei einem Flottenverhältnis von 1:30 in drei Flotten behandelt, die folgende Zusätze enthalten:
1 g/l Na₂CO₃ kalz.
0,5 g/l eines nicht-ionischen Tensides und
1 Gew.% bezogen auf das Garngewicht der Verbindung der Formel (100)

Figure imgb0009
als 20 %ige Sandmahlung mit dem sulfonierten Kondensationsprodukt aus Naphthalin und Formaldehyd als Dispergator, im Gewichtsverhältnis 1:1.Three skeins of polypropylene yarn with a fineness of Nm 60/1, e.g. Polycolon® of 5 g each, in the colors white (pattern A, lightened by the spinning mass), navy blue (pattern B, colored by spinning mass) and dark blue (pattern C, colored by the spinning mass) at a liquor ratio of 1: 30 treated in three fleets, which contain the following additives:
1 g / l Na₂CO₃ calc.
0.5 g / l of a non-ionic surfactant and
1% by weight based on the weight of the compound of the formula (100)
Figure imgb0009
 as 20% sand grinding with the sulfonated condensation product of naphthalene and formaldehyde as a dispersant, in a weight ratio of 1: 1.

Man geht mit den Garnen bei 50°C in diese Behandlungsflotte (pH-Wert 10,3) ein, erwärmt in 15 Min. auf 90°C und belässt 30 Min. bei dieser Temperatur. Schliesslich wird gründlich warm und kalt gespült und anschliessend bei 60°C getrocknet.The yarns are added to this treatment liquor (pH 10.3) at 50 ° C., heated to 90 ° C. in 15 minutes and left at this temperature for 30 minutes. Finally, it is rinsed thoroughly warm and cold and then dried at 60 ° C.

Zur Bestimmung der photochemischen Stabilität der Garne A - C werden je ca. 25 Lagen auf einen Belichtungskarton von 13 x4,3 cm gewickelt und nach DIN 75.202 (Entwurf 1/88) bzw. nach SN-ISO 105-BO2 (Xenontest) heissbelichtet. Nach dem Belichten wird nach SNV 197.461 die Reissfestig­keit und die Dehnung der einzelnen Garne ermittelt, wobei die Ausgangs­materialien als Standard und die belichteten, unbehandelten Garne als Bezugsgrössen gelten.To determine the photochemical stability of the yarns A - C, approx. 25 layers are wound onto an exposure cardboard of 13 x 4.3 cm and hot-exposed according to DIN 75.202 (draft 1/88) or according to SN-ISO 105-BO2 (xenon test). After exposure, the tensile strength and the elongation of the individual yarns are determined in accordance with SNV 197.461, the starting materials being the standard and the exposed, untreated yarns being the reference values.

Die Resultate sind in der nachfolgenden Tabelle I zusammengefasst. Tabelle I Muster Reissfestigkeit/Dehnung in (%) Material unbehandelt Material nachstabilisiert -*) FAKRA 48h FAKRA 144h FAKRA 48h FAKRA 144h A 100/100 83 /78,9 68,8/53,7 99,1/93,3 89,2/80,6 B 100/100 38,2/35,3 zerstört 79,6/90,1 67,6/68,4 C 100/100 37,4/40,2 zerstört 100 /89,0 75,2/64,0 *) Standard Muster Reissfestigkeit/Dehnung in (%) Material unbehandelt Material nachstabilisiert -*) Xenon 500h Xenon 1000h Xenon 500h Xenon 1000h A 100/100 100/82 77/76 100/91 93/91 B 100/100 69/68 zerstört 89/100 88/93 C 100/100 62/66 17/23 84/87 87/86 *) Standard The results are summarized in Table I below. Table I template Tensile strength / elongation in (%) Untreated material Material stabilized - *) FAKRA 48h FAKRA 144h FAKRA 48h FAKRA 144h A 100/100 83 / 78.9 68.8 / 53.7 99.1 / 93.3 89.2 / 80.6 B 100/100 38.2 / 35.3 destroyed 79.6 / 90.1 67.6 / 68.4 C. 100/100 37.4 / 40.2 destroyed 100 / 89.0 75.2 / 64.0 *) Default template Tensile strength / elongation in (%) Untreated material Material stabilized - *) Xenon 500h Xenon 1000h Xenon 500h Xenon 1000h A 100/100 100/82 77/76 100/91 93/91 B 100/100 69/68 destroyed 89/100 88/93 C. 100/100 62/66 17/23 84/87 87/86 *) Default

Es ist ersichtlich, dass das weisse Garn deutlich, die beiden gefärbten Garne massgeblich in der Licht-/Wärmestabilität verbessert wurden.It can be seen that the white yarn has been significantly improved, the two dyed yarns have been significantly improved in the light / heat stability.

Beispiel 2:Example 2:

Man verfährt wie in Beispiel 1 beschrieben, verwendet jedoch anstelle der Verbindung (100) die Verbindung der Formel (200)

Figure imgb0010
in einer Menge von 1 Gew. % bezogen auf das Garngewicht, als 50 %-ige Emulsion (50 Teile Verbindung (200), 35 Teile Leichtbenzin und 15 Teile eines nicht-ionischen Tensides). Bei Muster D handelt es sich um weisses Garn (spinnmassenaufgehellt), bei Muster E und F um marineblaue und dunkelblaue Spinnmassenfärbungen.The procedure is as described in Example 1, but the compound of the formula (200) is used instead of the compound (100)
Figure imgb0010
 in an amount of 1% by weight, based on the weight of the yarn, as a 50% emulsion (50 parts of compound (200), 35 parts of light petroleum and 15 parts of a nonionic surfactant). Pattern D is white yarn (lightened with spinning material), pattern E and F are navy blue and dark blue dyeings.

Die Resultate sind in der nachfolgenden Tabelle II zusammengefasst. Tabelle II Muster Reissfestigkeit/Dehnung in (%) Material unbehandelt Material nachstabilisiert -*) FAKRA 48h FAKRA 144h FAKRA 48h FAKRA 144h D 100/100 83 /78,9 68,8/53,7 96,6/97,6 96,2/87,9 E 100/100 38,2/35,3 zerstört 79,2/85,5 72,7/70,1 F 100/100 37,4/40,2 zerstört 100/100 71,4/61,6 *) Standard Muster Reissfestigkeit/Dehnung in (%) Material unbehandelt Material nachstabilisiert -*) Xenon 500h Xenon 1000h Xenon 500h Xenon 1000h D 100/100 100/82 77/76 88/94 89/95 E 100/100 69/68 zerstört 100/93 95/85 F 100/100 62/66 17/23 92/100 84/96 *) Standard The results are summarized in Table II below. Table II template Tensile strength / elongation in (%) Untreated material Material stabilized - *) FAKRA 48h FAKRA 144h FAKRA 48h FAKRA 144h D 100/100 83 / 78.9 68.8 / 53.7 96.6 / 97.6 96.2 / 87.9 E 100/100 38.2 / 35.3 destroyed 79.2 / 85.5 72.7 / 70.1 F 100/100 37.4 / 40.2 destroyed 100/100 71.4 / 61.6 *) Default template Tensile strength / elongation in (%) Untreated material Material stabilized - *) Xenon 500h Xenon 1000h Xenon 500h Xenon 1000h D 100/100 100/82 77/76 88/94 89/95 E 100/100 69/68 destroyed 100/93 95/85 F 100/100 62/66 17/23 92/100 84/96 *) Default

Auch bei Verwendung der Verbindung (200) wurde bei allen 3 Mustern eine gute bis sehr gute Nachstabilisierung gegen einen Licht-/Hitzeabbau der Faser erhalten.Even when compound (200) was used, good to very good post-stabilization against light / heat degradation of the fiber was obtained in all 3 samples.

Beispiel 3:Example 3:

Je 2 Muster von 10 g eines ®Maraklon-Stapelgewebes (unstabi­lisiertes Polypropylen) werden wie folgt aufgehellt bzw. aufgehellt und stabilisiert: Muster I wird in einer Flotte folgender Zusammensetzung, behandelt:
1 g/l Na₂CO₃
0,5 g/l eines nicht-ionischen Tensides und
0,1 Gew.% bezogen auf das Gewebegewicht, der Verbindung der Formel (3)

Figure imgb0011
2 samples each of 10 g of a ®Maraklon staple fabric (unstabilized polypropylene) are lightened or lightened and stabilized as follows: Sample I is treated in a liquor of the following composition:
1 g / l Na₂CO₃
0.5 g / l of a non-ionic surfactant and
0.1% by weight, based on the weight of the fabric, of the compound of the formula (3)
Figure imgb0011

Als 20 %-ige Sandmahlung mit dem sulfonierten Kondensationsprodukt aus Naphthalin und Formaldehyd als Dispergator, im Gewichtsverhältnis 2:1.As 20% sand grinding with the sulfonated condensation product of naphthalene and formaldehyde as a dispersant, in a weight ratio of 2: 1.

Muster II wird in einer Flotte behandelt, die zusätzlich noch 1 Gew.% bezogen auf das Gewebegewicht der Verbindung (100) enthält, die als 20 %ige Formulierung vorliegt.Sample II is treated in a liquor which additionally contains 1% by weight, based on the weight of the compound (100), which is in the form of a 20% formulation.

Die Behandlung erfolgt wie in Beispiel 1 vermerkt.­The treatment is carried out as noted in Example 1.

In beiden Fällen resultieren Aufhellungen mit einem guten Weissgrad. Unterwirft man die Muster I und II einer Belichtung, z.B. einer Belich­tung nach DIN 75 202 (Entwurf 1/88), so genügen bei Muster I bereits 20 Stunden Belichtungszeit, um zu einem völlig zerstörten Textilmaterial zu gelangen. Das stabilisierte Muster II ist dagegen nach einer (Heiss-)Belichtungszeit von 144 Stunden noch intakt und hoch reissfest.In both cases brightening results with a good degree of whiteness. Submitting patterns I and II to exposure, e.g. exposure to DIN 75 202 (draft 1/88), 20 hours of exposure are sufficient for pattern I to achieve a completely destroyed textile material. In contrast, the stabilized pattern II is still intact and highly tear-resistant after a (hot) exposure time of 144 hours.

Beispiel 4:Example 4:

Je 2 Muster von 10 g eines ®Maraklon-Stapelgewebes (unstabi­lisiertes Polypropylen) werden gebleicht bzw. aufgehellt und stabili­siert, in dem man sie
bei 50°C, bei einem Flottenverhältnis von 1:25, in zwei Bleichbädern einbringt, die jeweils pro Liter
2 g Natriumchlorit (80 %),
2 g Natriumnitrat,
1,5 ml Ameisensäure (85 %) und
0,5 g eines nichtionischen Tensides
und das Bad Nr. 2 zusätzlich noch 0,1 Gew.%, bezogen auf das Gewebegewicht, des Aufhellers der Formel (300)
(als 20%ige Dispersion eigesetzt) enthalten. Man erhitzt die Bleichbäder innerhalb von 30 Minuten auf 85°C und behandelt 60 Minuten bei dieser Temperatur. Alsdann werden die Bäder abgekühlt und die Substrate zweimal kalt gespült, zentrifugiert und getrocknet.2 samples of 10 g each of a ®Maraklon staple fabric (unstabilized polypropylene) are bleached or lightened and stabilized by pressing them
at 50 ° C, with a liquor ratio of 1:25, in two bleaching baths, each per liter
2 g sodium chlorite (80%),
2 g sodium nitrate,
1.5 ml of formic acid (85%) and
0.5 g of a nonionic surfactant
and bath no. 2 additionally 0.1% by weight, based on the weight of the fabric, of the brightener of the formula (300)
(used as a 20% dispersion). The bleaching baths are heated to 85 ° C. within 30 minutes and treated at this temperature for 60 minutes. The baths are then cooled and the substrates are rinsed cold twice, centrifuged and dried.

Die beiden Muster werden nun halbiert. Die Teile (a) werden nicht weiterbehandelt, die Teile (b) dagegen, bei einem Flottenverhältnis 1:25, in einem Bad behandelt, das pro Liter
0,5 g eines nichtionischen Tensides,
0,5g Natriumkarbonat calc. und
1 Gew.% bezogen auf das Gewebegewicht, der Verbindung der Formel (100) als 20%ige Dispersion
enthält. Man erhitzt das Bad auf 50°C, erhöht die Temperatur innerhalb von 10 Minuten auf 75°C und behandelt 30 Minuten bei dieser Temperatur. Alsdann wird das Bad abgekühlt und die Substrate kalt gespült und getrocknet.The two patterns are now halved. Parts (a) are not further treated, while parts (b), in a liquor ratio of 1:25, are treated in a bath that is per liter
0.5 g of a nonionic surfactant,
0.5g sodium carbonate calc. and
1% by weight, based on the weight of the fabric, of the compound of the formula (100) as a 20% dispersion
contains. The bath is heated to 50 ° C., the temperature is raised to 75 ° C. in the course of 10 minutes and the mixture is treated at this temperature for 30 minutes. The bath is then cooled and the substrates are rinsed cold and dried.

In beiden Fällen resultieren Aufhellungen mit einem sehr guten Weissgrad. Unterwirft man die Muster 1a, 1b, 2a und 2b einer Belichtung von 350 Stunden nach SN-ISO 105-BO2 (Xenontest) und von 72 Stunden nach DIN 75 202 (Entwurf 1/88; Fakratest), so weisen die Muster 1a und 2a eine geringe bzw. keine, die Muster 1b und 2b dagegen eine gute mechanische Festigkeit auf.In both cases, brightening results with a very good degree of whiteness. If the samples 1a, 1b, 2a and 2b are subjected to an exposure of 350 hours according to SN-ISO 105-BO2 (xenon test) and of 72 hours according to DIN 75 202 (draft 1/88; fakratest), the samples 1a and 2a show little or no, the samples 1b and 2b, however, good mechanical strength.

Beispiel 5:Example 5:

Man verfährt wie in Beispiel 4 angegeben mit dem Unter­schied, dass statt Verbindung (100) 1 Gew.% bezogen auf das Gewebe, als 50%ige Emulsion, der Verbindung (200) eingesetzt wird.The procedure is as described in Example 4, with the difference that instead of compound (100), 1% by weight, based on the fabric, as a 50% emulsion of compound (200) is used.

Es resultieren auch hier 4 Aufhellungen mit hohem Weissgrad. Das aufge­hellte Fasermaterial der Muster 1a und 2a sind ebenfalls nur mangelhaft licht- und wärmestabil, während das Fasermaterial der Muster 1b und 2b eine 72stündige Heissbelichtung nach DIN 75.202 (Entwurf 1/88) unzerstört überstehen.This also results in 4 brightenings with a high degree of whiteness. The lightened fiber material of samples 1a and 2a are also poorly stable to light and heat, while the fiber material of samples 1b and 2b survive a 72-hour hot exposure according to DIN 75.202 (draft 1/88) without being destroyed.

Beispiele 6-8:Examples 6-8:

Man geht wie in Beispiel 4 beschrieben vor, verwendet jedoch als Aufheller die Verbindung der Formel

Figure imgb0012
The procedure is as described in Example 4, but using the compound of the formula as brightener
Figure imgb0012

Es werden Aufhellungen mit einem ähnlichen Weissgrad, wie in Beispiel 4 beschrieben, erhalten. Das aufgehellte Gewebe ist jedoch erst nach der Stabilisierung mit der Verbindung der Formel (200) lichtstabil, d.h. nach dem Belichten noch mechanisch belastbar.Brightenings with a similar degree of whiteness as described in Example 4 are obtained. However, the lightened tissue is only light-stable after stabilization with the compound of formula (200), i.e. still mechanically loadable after exposure.

Beispiele 9-11:Examples 9-11:

Drei Muster à 10 g eines ®Maraklon-Gewebes werden bei einem Flottenverhältnis von 1:20 in einem Bad behandelt, das pro Liter 0,5 g eines nichtionogenen Tensides,
1,0 g Ammoniumsulfat
sowie 1 % folgender Verbindungen in formulierter Form enthält:

Figure imgb0013
(Die Verbindungen (403) und (404) liegen in 20%iger gemahlener Form, die Verbindung (405) dagegen als emulgierbare Flüssigformulierung vor wie sie bei Verbindung (200) beschrieben ist).Three samples of 10 g each of a ®Maraklon fabric are treated with a liquor ratio of 1:20 in a bath containing 0.5 g of a non-ionic surfactant,
1.0 g ammonium sulfate
and 1% of the following compounds in formulated form:
Figure imgb0013
 (Compounds (403) and (404) are in 20% ground form, while compound (405) is in the form of an emulsifiable liquid formulation as described for compound (200).

In einem Färbeapparat (z.B. ®AHIBA-Färbegerät) geht man bei 50°C mit dem Gewebe ein, erhöht die Temperatur innerhalb 30 Minuten auf 90°C und behandelt 30 Minuten bei dieser Temperatur. Danach wird das Bad auf 60°C abgekühlt und das behandelte Gewebe warm und kalt gespühlt und getrock­net.In a dyeing machine (e.g. ®AHIBA dyeing machine), the tissue is blended in at 50 ° C, the temperature is raised to 90 ° C within 30 minutes and treated at this temperature for 30 minutes. The bath is then cooled to 60 ° C. and the treated fabric is rinsed warm and cold and dried.

Unterwirft man das Ausgangsmaterial und die so behandelten Muster 144 Stunden lang dem Heissbelichtungstest nach DIN 75.202 (Fakratest), so ist das behandelte Gewebe noch völlig intakt, während das unbehandelte beim Berühren zerfällt.If the starting material and the samples treated in this way are subjected to the hot exposure test according to DIN 75.202 (fakratest) for 144 hours, the treated fabric is still completely intact, while the untreated one disintegrates when touched.

Claims (9)

1. Verfahren zum fotochemischen Stabilisieren von ungefärbten und gefärbten Polypropylenfasern mit Lichtschutzmitteln, dadurch gekenn­zeichnet, dass man das Polypropylenfasermaterial mit einer wässrigen Lösung enthaltend ein Lichtschutzmittel aus der Klasse der sterisch gehinderten Amine behandelt.1. A process for the photochemical stabilization of undyed and dyed polypropylene fibers with light stabilizers, characterized in that the polypropylene fiber material is treated with an aqueous solution containing a light stabilizer from the class of sterically hindered amines. 2. Verfahren gemäss Anspruch 1, worin als Lichtschutzmittel ein sterisch gehindertes Amin verwendet wird, das in seinem Molekül mindestens eine Gruppe der Formel I enthält,
Figure imgb0014
 worin R Wasserstoff oder Methyl ist.2. The method according to claim 1, wherein a sterically hindered amine is used as the light stabilizer which contains at least one group of the formula I in its molecule,
Figure imgb0014
 where R is hydrogen or methyl. 3. Verfahren gemäss einem der Ansprüche 1 und 2, worin als Lichtschutz­mittel ein sterisch gehindertes Amin der Formel II
Figure imgb0015
 verwendet wird, worin n eine Zahl von 1 bis 4, vorzugsweise 1 oder 2 bedeutet, R Wasserstoff oder Methyl bedeutet, R¹ Wasserstoff, Hydroxy, C₁-C₁₂-Alkyl, C₃-C₈ Alkenyl, C₃-C₆ Alkinyl, C₇-C₁₂ Aralkyl, C₁-C₈ Alkanoyl, C₃-C₅ Alkenoyl, Glycidyl, -O-C₁-C₁₂-Alkyl, -O-C₁-C₈-Alkanoyl oder eine Gruppe -CH₂CH(OH)-Z, worin Z Wasserstoff, Methyl oder Phenyl ist, bedeutet, wobei R¹ vorzugsweise Wasserstoff, C₁-C₄ Alkyl, Allyl, Benzyl, Acetyl oder Acryloyl ist und R², wenn n 1 ist, Wasserstoff, gegebenenfalls durch ein oder mehrere Sauerstoffatome unterbrochenes C₁-C₁₈ Alkyl, Cyanethyl, Benzyl, Glycidyl, einen einwertigen Rest einer aliphatischen, cycloaliphatischen, araliphatischen, ungesättigten oder aromatischen Carbonsäure, Carbaminsäure oder Phosphor enthaltenden Säure oder einen einwertigen Silylrest, vorzugsweise einen Rest einer alipha­tischen Carbonsäure mit 2 bis 18 C-Atomen, einer cycloaliphatischen Car­bonsäure mit 7 bis 15 C-Atomen, einer α,β-ungesättigten Carbonsäure mit 3 bis 5 C-Atomen oder einer aromatischen Carbonsäure mit 7 bis 15 C-Atomen bedeutet, wenn n 2 ist, C₁-C₁₂ Alkylen, C₄-C₁₂ Alkenylen, Xylylen, einen zweiwertigen Rest einer aliphatischen, cycloaliphatischen, araliphati­schen oder aromatischen Dicarbonsäure, Dicarbaminsäure oder Phosphor enthaltenden Säure oder einen zweiwertigen Silylrest, vorzugsweise einen Rest einer aliphatischen Dicarbonsäure mit 2 bis 36 C-Atomen, einer cycloaliphatischen oder aromatischen Dicarbonsäure mit 8 - 14 C-Atomen oder einer aliphatischen, cycloaliphatischen oder aromatischen Dicar­baminsäure mit 8 - 14 C-Atomen bedeutet, wenn n 3 ist, einen dreiwertigen Rest einer aliphatischen, cycloaliphatischen oder aromatischen Tricar­bonsäure, einer aromatischen Tricarbaminsäure oder einer Phosphor enthaltenden Säure oder einen dreiwertigen Silylrest bedeutet und wenn n 4 ist, einen vierwertigen Rest einer aliphatischen, cycloaliphatischen oder aromatischen Tetracarbonsäure bedeutet.3. The method according to any one of claims 1 and 2, wherein a sterically hindered amine of formula II as light stabilizer
Figure imgb0015
 is used, in which n is a number from 1 to 4, preferably 1 or 2, R is hydrogen or methyl, R¹ is hydrogen, hydroxy, C₁-C₁₂-alkyl, C₃-C₈ alkenyl, C₃-C₆ alkynyl, C₇-C₁₂ aralkyl, C₁-C₈ alkanoyl, C₃-C₅ alkenoyl, glycidyl, -O-C₁-C₁₂-alkyl, -O-C₁-C₈-alkanoyl or a group -CH₂CH (OH) -Z, where Z is hydrogen, methyl or phenyl , wherein R¹ is preferably hydrogen, C₁-C₄ alkyl, allyl, benzyl, acetyl or acryloyl and R², if n is 1, hydrogen, optionally interrupted by one or more oxygen atoms C₁-C₁₈ alkyl, cyanoethyl, benzyl, glycidyl, a monovalent radical an acid containing aliphatic, cycloaliphatic, araliphatic, unsaturated or aromatic carboxylic acid, carbamic acid or phosphorus or a monovalent silyl radical, preferably a radical of an aliphatic carboxylic acid with 2 to 18 C atoms, a cycloaliphatic carboxylic acid with 7 to 15 C atoms, an α, β-unsaturated carboxylic acid with 3 to 5 C atoms or an aromatic carboxylic acid with 7 to 15 carbon atoms, when n is 2, C₁-C₁₂ alkylene, C₄-C₁₂ alkenylene, xylylene, a divalent radical of an aliphatic, cycloaliphatic, araliphatic or aromatic dicarboxylic acid, dicarbamic acid or phosphorus-containing acid or a divalent silyl radical, preferably a radical an aliphatic dicarboxylic acid with 2 to 36 C atoms, a cycloaliphatic or aromatic dicarboxylic acid with 8 - 14 C atoms or an aliphatic, cycloaliphatic or aromatic dicarbamic acid with 8 - 14 C atoms, when n is 3, means a trivalent radical of an aliphatic , cycloaliphatic or aromatic tricarboxylic acid, an aromatic tricarbamic acid or means a phosphorus-containing acid or a trivalent silyl radical and, when n is 4, means a tetravalent radical of an aliphatic, cycloaliphatic or aromatic tetracarboxylic acid. 4. Verfahren gemäss einem der Ansprüche 1 und 2, worin als Lichtschutz­mittel ein sterisch gehindertes Amin der Formel III
Figure imgb0016
 verwendet wird, worin n die Zahl 1 oder 2 bedeutet, R und R¹ die unter a) angegebene Bedeutung haben, R³ Wasserstoff, C₁-C₁₂ Alkyl, C₂-C₅ Hydroxy­alkyl, C₅-C₇ Cycloalkyl,C₇-C₈ Aralkyl, C₂-C₁₈ Alkanoyl, C₃-C₅ Alkenoyl oder Benzoyl ist und R⁴ wenn n 1 ist, Wasserstoff, C₁-C₁₈ Alkyl, C₃-C₈ Alkenyl, C₅-C₇ Cycloalkyl, mit einer Hydroxy-, Cyano-, Alkoxycarbonyl-­oder Carbamidgruppe substituiertes C₁-C₄ Alkyl, Glycidyl, eine Gruppe der Formel -CH₂-CH(OH)-Z oder der Formel -CONH-Z ist, worin Z Wasser­stoff, Methyl oder Phenyl bedeutet; wenn n 2 ist, C₂-C₁₂ Alkylen, C₆-C₁₂ Arylen, Xylylen, eine -CH₂-CH(OH)-CH₂-Gruppe oder eine Gruppe -CH₂-CH(OH)-CH₂-O-D-O- bedeutet, worin D C₂-C₁₀ Alkylen, C₆-C₁₅ Arylen, C₆-C₁₂ Cycloalkylen ist, oder vorausgesetzt, dass R³ nicht Alkanoyl, Alkenoyl oder Benzoyl bedeutet, R⁴ auch einen zweiwertigen Rest einer aliphatischen, cycloaliphatischen oder aromatischen Dicarbonsäure oder Dicarbaminsäure oder auch die Gruppe -CO- bedeuten kann, oder R³ und R⁴ zusammen, wenn n 1 ist, den zweiwertigen Rest einer aliphatischen, cycloaliphatischen oder aromatischen 1,2- oder 1,3-Dicarbonsäure bedeuten können.4. The method according to any one of claims 1 and 2, wherein a sterically hindered amine of formula III as light stabilizer
Figure imgb0016
 is used, wherein n is the number 1 or 2, R and R¹ have the meaning given under a), R³ is hydrogen, C₁-C₁₂ alkyl, C₂-C₅ hydroxyalkyl, C₅-C₇ cycloalkyl, C₇-C₈ aralkyl, C₂-C₁₈ alkanoyl , C₃-C₅ is alkenoyl or benzoyl and R⁴ when n is 1, hydrogen, C₁-C₁₈ alkyl, C₃-C₈ alkenyl, C₅-C₇ cycloalkyl, C₁-C₄ alkyl substituted with a hydroxy, cyano, alkoxycarbonyl or carbamide group, Glycidyl, a group of the formula -CH₂-CH (OH) -Z or the formula -CONH-Z, wherein Z is hydrogen, methyl or phenyl; when n is 2, C₂-C₁₂ alkylene, C₆-C₁₂ arylene, xylylene, a -CH₂-CH (OH) -CH₂ group or a group -CH₂-CH (OH) -CH₂-ODO-, where D is C₂- C₁₀ alkylene, C₆-C₁₅ arylene, C₆-C₁₂ is cycloalkylene, or provided that R³ is not alkanoyl, Alkenoyl or benzoyl means R⁴ can also mean a divalent radical of an aliphatic, cycloaliphatic or aromatic dicarboxylic acid or dicarbamic acid or also the group -CO-, or R³ and R⁴ together, when n is 1, the divalent radical of an aliphatic, cycloaliphatic or aromatic 1 , 2- or 1,3-dicarboxylic acid can mean. 5. Verfahren gemäss Anspruch 3, worin als sterisch gehinderte Amine Verbindungen der in Anspruch 3 definierten Formel verwendet werden, worin n die Zahl 1 oder 2, R Wasserstoff, R¹ Wasserstoff oder C₁-C₄-Alkyl und R², wenn n 1 ist einen einwertigen Rest einer aliphatischen Carbonsäure mit 8 bis 10 C-Atomen und wenn n 2 ist einen zweiwertigen Rest mit einer aliphatischen Dicarbonsäure mit 6 bis 10 C-Atomen, bedeuten.5. The method according to claim 3, wherein as sterically hindered amines compounds of the formula defined in claim 3 are used, wherein n is 1 or 2, R is hydrogen, R¹ is hydrogen or C₁-C₄-alkyl and R², if n is a monovalent Radical of an aliphatic carboxylic acid with 8 to 10 C atoms and if n 2 is a divalent radical with an aliphatic dicarboxylic acid with 6 to 10 C atoms. 6. Verfahren gemäss Anspruch 3, worin ein Gemisch von Verbindungen der in Anspruch 3 definierten Formel mit n gleich 1 und 2 verwendet wird.6. The method according to claim 3, wherein a mixture of compounds of the formula defined in claim 3 with n equal to 1 and 2 is used. 7. Verfahren gemäss Anspruch 1, dadurch gekennzeichnet, dass man das ungefärbte Polypropylenfasermaterial mit einer wässrigen Lichtschutz­mittelzusammensetzung behandelt, welche zusätzlich einen Aufheller enthält.7. The method according to claim 1, characterized in that the undyed polypropylene fiber material is treated with an aqueous light stabilizer composition which additionally contains a brightener. 8. Verfahren gemäss einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass die Behandlung diskontinuierlich nach einem Ausziehverfahren vorgenommen wird.8. The method according to any one of claims 1 to 7, characterized in that the treatment is carried out discontinuously according to an exhaust process. 9. Das gemäss dem Verfahren nach einem der Ansprüche 1 bis 8 behandelte Polypropylenfasermaterial.9. The polypropylene fiber material treated according to the method according to one of claims 1 to 8.
EP89810431A 1988-06-14 1989-06-07 Process for photochemically stabilising dyed or non dyed polypropylene fibres Expired - Lifetime EP0352221B1 (en)

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JPH0284557A (en) 1990-03-26
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DE58907159D1 (en) 1994-04-14
KR910001157A (en) 1991-01-30
ES2050274T3 (en) 1994-05-16
EP0352221B1 (en) 1994-03-09
JPH0823108B2 (en) 1996-03-06

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