EP0413146A1 - Dry preparation of a better light fastness mixture - Google Patents

Dry preparation of a better light fastness mixture Download PDF

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Publication number
EP0413146A1
EP0413146A1 EP90113514A EP90113514A EP0413146A1 EP 0413146 A1 EP0413146 A1 EP 0413146A1 EP 90113514 A EP90113514 A EP 90113514A EP 90113514 A EP90113514 A EP 90113514A EP 0413146 A1 EP0413146 A1 EP 0413146A1
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EP
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Prior art keywords
parts
dry preparation
preparation according
dry
complexing agent
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EP90113514A
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German (de)
French (fr)
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EP0413146B1 (en
Inventor
Erhard D.I. Schuffenhauer
Hans-Albert D.I. Ehlert
Vincenzo Antonio Fasanella
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Bayer AG
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Bayer AG
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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • 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
    • D06P1/6423—Compounds containing azide or oxime groups
    • 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
    • D06M15/39—Aldehyde resins; Ketone resins; Polyacetals
    • D06M15/41—Phenol-aldehyde or phenol-ketone resins
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/02—Material containing basic nitrogen
    • D06P3/04—Material containing basic nitrogen containing amide groups
    • D06P3/24—Polyamides; Polyurethanes
    • D06P3/241—Polyamides; Polyurethanes using acid dyes

Definitions

  • the invention relates to dry preparations of agents for improving the light fastness of dyed textile materials, in particular polyamide fiber materials.
  • Halogen preferably stands for Cl.
  • suitable radicals Ar are especially phenyl or phenylene radicals, which can be substituted by X1-X4.
  • Preferred compounds A are those of the formulas
  • the aforementioned complexing agents can also be used in any mixture with one another.
  • Suitable copper II salts B are e.g. CuCl2, CuSO4 ⁇ 5H2O, Cu (OAc) 2 ⁇ H2O or CuCo3 ⁇ Cu (OH) 2.
  • Suitable dispersants I and II are commercially available products which are obtained by sulfite or force digestion of the wood.
  • Suitable type III dispersants are especially the alkali and ammonium salts of condensation products of aromatic sulfonic acids with formaldehyde, such as e.g. Formaldehyde condensation products from (alkyl) -naphthalenesulfonic acids, mixtures of naphthalene and benzenesulfonic acids, mixtures of cresols and naphthalenesulfonic acids, sulfated diphenyl ethers, sulfated diphenyl thioethers, sulfated diphenyl sulfones as well as mixtures of cycloalkanones and alkali bisulfite
  • formaldehyde such as e.g. Formaldehyde condensation products from (alkyl) -naphthalenesulfonic acids, mixtures of naphthalene and benzenesulfonic acids, mixtures of cresols and naphthalenesulfonic acids,
  • the ratio of A: B in the preparation is 0.8 to 2.4 moles of component A to 1 mole of component B.
  • the finished preparations generally consist of 10 - 80% by weight A + B, 78-18% by weight of C and optionally 12-2% by weight of other auxiliaries, the sum of course must be 100%.
  • Dedusting agents adjusting agents, light stabilizers, buffer substances (i.e. pH regulators) etc., as well as residual moisture.
  • the amount of the preparations according to the invention is 0.02-3, preferably 0.1-0.5% by weight, based on the fiber material.
  • Suitable fiber materials are those made of synthetic polymers, such as polyurethanes and synthetic polyamides.
  • the dyeings on these fibers can be produced in a conventional manner using both metal complex dyes and acid dyes.
  • the metal complex dyes in particular the 1: 2 chromium or 1: 2 cobalt complexes of mono- or diazo compounds, which are described in large numbers in the literature and are commercially available, are preferred. These dyes can also contain 1-2 sulfo groups.
  • Suitable acid dyes are, in particular, those types which are usually used in combination with the metal complex dyes.
  • the treatment of the polyamide materials with the copper compounds to be used according to the invention can take place before, during or after, preferably during the dyeing.
  • the dyeings are produced by conventional methods, ie. in the pull-out process on the jet dyeing machine, the jigger, the reel runner or a reel dyeing machine or on a continuous machine according to the known block or impregnation processes.
  • the main advantage of the new preparations compared to the prefabricated copper complexes is that they have no great mechanical and procedural requirements Effort can be produced.
  • the powder is then dedusted in a Lödige mixer with the addition of 7.40 parts of a dedusting agent based on mineral oil.
  • aqueous dispersion consisting of 191.00 parts of water (as template) 19.37 parts Salicylaldoxim (98%) 13.85 parts of sodium hydroxide solution (40%) 92.88 parts of lignin sulfonate (after sulfite digestion) liquid (33.6% dry) 106.38 parts Llgninsulfonat (after force application) liquid (29.4%) 4.78 parts water (for rinsing) 17.37 parts.
  • the powder obtained can be used immediately.
  • Example 3 If 20 parts of the batch mentioned in Example 3 are mixed with 80 parts of the liquid preparation in Example 5 with subsequent spray drying (E. 140 ° C./A. 70 ° C.), a preparation with a very high fine distribution in the dyebath or in the aftertreatment bath and good light fastness improving effect on colored polyamide.
  • a mix of 80 parts of powder preparation from Example 3 20 parts of powder preparation from Example 5 is placed in a Lödige mixer and mixed.
  • the powder mixture obtained can be used directly and has the same good effect as the preparation according to Example 7.
  • the dye is then removed from the dye bath, rinsed and dried.
  • the staining is carried out together with a comparative staining produced without copper preparation according to the test of Adam Opel AG Tüsselsheim / FRG GM (Engineering Standards Europe) GME No 60 202 A / B exposed for 250 h in the xenon tester.
  • the dye liquor is adjusted to pH 5.5 with the aid of a buffer mixture of monosodium phosphate and acetic acid. It is treated for one hour at 98 to 100 ° C, rinsed and dried.
  • the coloring produced in this way shows a clearly improved light fastness.

Abstract

Pulverulent preparations comprising A) a phenolic complexing agent, B) a complexible copper(II) salt and C) a dispersant are highly suitable for the photochemical stabilisation of dyed polyamide fibres.

Description

Gegenstand der Erfindung sind Trockenpräparationen von Mitteln zur Verbesserung der Lichtechtheit von gefärb­ten Textilmaterialien, insbesondere Polyamidfasermate­rialien.The invention relates to dry preparations of agents for improving the light fastness of dyed textile materials, in particular polyamide fiber materials.

Die Präparationen sind dadurch gekennzeichnet, daß sie

  • A) einen phenolischen Komplexbildner,
  • B) ein komplexierbares Kupfer-II-Salz und
  • C) ein Dispergiermittel enthalten.
The preparations are characterized in that they
  • A) a phenolic complexing agent,
  • B) a complexable copper (II) salt and
  • C) contain a dispersant.

Geeignete Komplexbildner A sind solche der Formel (I)

Figure imgb0001
worin - unabhängig voneinander -
Y =N-W, =N-Ar, =N-N-CH-Ar, =N-OH, =N-Ar-N=CH-Ar, -N-AK-N=CH-Ar oder Sauerstoff,
R H, OH, W oder OW und
X₁-X₄ H, W, OH, Halogen, CN, NH₂, NVW, SO₃H, COOH, COOW, CONVW oder CONH₂ bedeuten und zwei be­nachbarte Reste
X₁-X₄ auch gemeinsam die restlichen Glieder eines ankondensierten Benzolringes bilden können,
wobei
AK für C₂-C₄-Alkylen,
Ar für Aryl bzw Arylen,
W für C₁-C₁₈-Alkyl oder Cyclohexyl und
V für W oder H stehen,
wobei auch die entsprechenden Alkali- oder Ammoniumsalze verwendet werden können.Suitable complexing agents A are those of the formula (I)
Figure imgb0001
 in which - independently of one another -
Y = NW, = N-Ar, = NN-CH-Ar, = N-OH, = N-Ar-N = CH-Ar, -N-AK-N = CH-Ar or oxygen,
RH, OH, W or OW and
X₁-X₄ H, W, OH, halogen, CN, NH₂, NVW, SO₃H, COOH, COOW, CONVW or CONH₂ mean and two adjacent radicals
X₁-X₄ can also together form the remaining members of a condensed benzene ring,
in which
AK for C₂-C₄ alkylene,
Ar for aryl or arylene,
W for C₁-C₁₈ alkyl or cyclohexyl and
V stands for W or H,
the corresponding alkali or ammonium salts can also be used.

"Halogen" steht vorzugsweise für Cl. Beispiele für ge­eignete Reste Ar sind vor allem Phenyl- bzw. Phenylen­reste, die durch X₁-X₄ substituiert sein können."Halogen" preferably stands for Cl. Examples of suitable radicals Ar are especially phenyl or phenylene radicals, which can be substituted by X₁-X₄.

Bevorzugte Verbindungen A sind solche der Formeln

Figure imgb0002
Figure imgb0003
 Preferred compounds A are those of the formulas
Figure imgb0002
Figure imgb0003

Vorzugsweise stehen X₁-X₄ für Cl, C₁-C₄-Alkyl, Methoxy und insbesondere für Wasserstoff. Beispiele der erfindungsgemäß zu verwendenden Verbindungen (VIII) sind

  • a) Salicylsäure
  • b) 5-Methylsalicylsäure (p-Kresotinsäure)
  • c) 5-tert.-Butylsalicylsäure
  • d) 5-Chlorsalicylsäure
  • e) 5-tert.-Octylsalicylsäure
  • f) 2,4-Dihydroxybenzoesäure (β-Resourcylsäure)
  • g) 2-Hydroxynaphthalin-1-carbonsäure (2-Hydroxy-1-­naphthoesäure)
  • h) 4-Hydroxy-1,3-benzoldicarbonsaure (4-Hydroxy­isophthalsäure
  • i) Salicylaldehyd
  • j) 5-Chlorsalicylaldehyd
  • k) 3-Methoxysalicylaldehyd.
X₁-X₄ are preferably Cl, C₁-C₄-alkyl, methoxy and in particular hydrogen. Examples of the compounds (VIII) to be used according to the invention are
  • a) Salicylic acid
  • b) 5-methylsalicylic acid (p-cresotinic acid)
  • c) 5-tert-butylsalicylic acid
  • d) 5-chlorosalicylic acid
  • e) 5-tert-octylsalicylic acid
  • f) 2,4-dihydroxybenzoic acid (β-resourcylic acid)
  • g) 2-hydroxy-naphthalene-1-carboxylic acid (2-hydroxy-1-naphthoic acid)
  • h) 4-Hydroxy-1,3-benzenedicarboxylic acid (4-hydroxyisophthalic acid
  • i) salicylaldehyde
  • j) 5-chlorosalicylaldehyde
  • k) 3-methoxysalicylaldehyde.

Vorgenannte Komplexbildner können auch in beliebiger Mischung untereinander verwendet werden.The aforementioned complexing agents can also be used in any mixture with one another.

Geeignete Kupfer-II-Salze B sind z.B. CuCl₂, CuSO₄·5H₂O, Cu(OAc)₂·H₂O oder CuCo₃·Cu(OH)₂.Suitable copper II salts B are e.g. CuCl₂, CuSO₄ · 5H₂O, Cu (OAc) ₂ · H₂O or CuCo₃ · Cu (OH) ₂.

Geeignete Dispergiermittel C sind:

  • a) Ligninsulfonate mit einem Schwefelgehalt von 4 - 6 Gew.-% und einer mittleren Molmasse von 1,500 g mol⁻¹ (Typ I),
  • b) Ligninsulfonate mit einem Schwefelgehalt von min­destens 6 Gew.-% und einer mittleren Molmasse von 6.500 g mol⁻¹ (Typ II) und
  • c) salzarme Kondensationsprodukte von cycloaliphati­schen oder aromatischen Sulfonsäuren und Formal­dehyd (Typ III),
wobei die Molmassen mit Hilfe eines wäßrigen Gelpermea­tionsverfahrens bestimmt werden, in welchem die Molmas­senverteilungen über ein Trenngel SEPHACRYL S 300 re­fraktometrisch aufgenommen und mit Hilfe einer Eichung in 0,9 %iger NaCl-Lösung bekannten Dextranmolmassen zu­geordnet werden.Suitable dispersants C are:
  • a) lignin sulfonates with a sulfur content of 4-6% by weight and an average molecular weight of 1,500 g mol⁻¹ (type I),
  • b) Ligninsulfonate with a sulfur content of at least 6 wt .-% and an average molecular weight of 6,500 g mol⁻¹ (type II) and
  • c) low-salt condensation products of cycloaliphatic or aromatic sulfonic acids and formaldehyde (type III),
wherein the molar masses are determined with the aid of an aqueous gel permeation method in which the molar mass distributions are refractometrically recorded using a separating gel SEPHACRYL S 300 and assigned to known dextran molar masses with the aid of a calibration in 0.9% NaCl solution.

Geeignete Dispergiermittel I und II sind handelsübliche Produkte, die durch Sulfit- oder Kraftaufschluß des Holzes gewonnen werden.Suitable dispersants I and II are commercially available products which are obtained by sulfite or force digestion of the wood.

Geeignete Dispergiermittel vom Typ III sind vor allem die Alkali- und Ammoniumsalze von Kondensationsprodukten aromatischer Sulfonsäuren mit Formaldehyd, wie z.B. Formaldehyd-Kondensationsprodukte aus (Alkyl)-Naphtha­linsulfonsäuren, Mischungen von Naphthalin- und Benzol­sulfonsäuren, Mischungen von Kresolen und Naphthalinsul­fonsäuren, sulfierten Diphenylethern, sulfierten Di­phenylthioethern, sulfierten Diphenylsulfonen sowie von Mischungen von Cycloalkanonen und AlkalibisulfitSuitable type III dispersants are especially the alkali and ammonium salts of condensation products of aromatic sulfonic acids with formaldehyde, such as e.g. Formaldehyde condensation products from (alkyl) -naphthalenesulfonic acids, mixtures of naphthalene and benzenesulfonic acids, mixtures of cresols and naphthalenesulfonic acids, sulfated diphenyl ethers, sulfated diphenyl thioethers, sulfated diphenyl sulfones as well as mixtures of cycloalkanones and alkali bisulfite

Solche Produkte, die vorzugsweise in elektrolytarmer Form eingesetzt werden, sind vielfach in der Literatur beschrieben, vergl. z.B. US-A 2 315 951, GB-A 715 919, DE-A 24 42 514, DE-A 25 42 090, DE-A 28 56 222.Such products, which are preferably used in low-electrolyte form, have been described many times in the literature, cf. e.g. US-A 2 315 951, GB-A 715 919, DE-A 24 42 514, DE-A 25 42 090, DE-A 28 56 222.

Die Herstellung der neuen Trockenpräparationen kann auf verschiedene Weise erfolgen:

  • 1. Durch Trockenmahlung einer Mischung der Komponenten A, B, C und gegebenenfalls weiterer Formierhilfs­mittel bis zu einer Teilchengröße von < 50 µm, vor­ zugsweise < 20 µm. Für die Trockenmahlung geeignete Mühlen sind neben der Kugelmühle oder dem Desinte­grator, vorzugsweise aber solche Rotor-Stator-Sieb­mühlen, die eine ⌀ Korngröße kleiner 20 µm, bevor­zugt unter 5 µm erzielen oder sogenannte Strahl­mühlen, bzw Prallkammermühlen. Bevorzugt wird un­ter Zugabe eines Kältemittels gemahlen, beispiels­weise Trockeneis oder flüssigem Stickstoff.
  • 2. Die erfindungsgemäßen Präparationen können aber auch in besonderer Weise unter Verzicht auf ein Mahlaggregat so hergestellt werden, daß die er­findungsgemäßen Komponenten A, B und C in Form ihrer wäßrigen Lösungen, Suspensionen oder An­schlämmungen in einem Rührwerkskessel zusammen­gegeben werden und nach guter Durchmischung einem Trockenprozeß unterworfen werden, z.B. in einem Schaufeltrockner, Band- oder Siebtrockner, vorzugs­weise aber einen Zerstäubertrockner, wenn die Prä­parationen nicht in flüssiger Form in den Handel gebracht werden sollen.
The new dry preparations can be manufactured in different ways:
  • 1. By dry grinding a mixture of components A, B, C and optionally other forming aids up to a particle size of <50 microns before preferably <20 µm. Mills suitable for dry grinding are, in addition to the ball mill or the disintegrator, but preferably those rotor-stator sieve mills which achieve a ⌀ grain size of less than 20 μm, preferably less than 5 μm, or so-called jet mills or impact chamber mills. It is preferred to add a refrigerant, for example dry ice or liquid nitrogen.
  • 2. However, the preparations according to the invention can also be produced in a special way, without a grinding unit, in such a way that components A, B and C according to the invention are combined in the form of their aqueous solutions, suspensions or slurries in a stirred tank and, after thorough mixing, are subjected to a drying process are, for example in a paddle dryer, belt or screen dryer, but preferably an atomizer dryer, if the preparations are not to be marketed in liquid form.

Das Verhältnis von A:B in der Präparation beträgt 0,8 bis 2,4 Mol Komponente A zu 1 Mol Komponente B.The ratio of A: B in the preparation is 0.8 to 2.4 moles of component A to 1 mole of component B.

Die fertigen Präparationen bestehen im allgemeinen aus
10 - 80 Gew.-% A + B,
78 - 18 Gew.-% C und gegebenenfalls
12 - 2 Gew.-% übrige Hilfsmittel,
wobei die Summe selbstverständlich 100 % ergeben muß.The finished preparations generally consist of
10 - 80% by weight A + B,
78-18% by weight of C and optionally
12-2% by weight of other auxiliaries,
the sum of course must be 100%.

Beispiele für die gegebenenfalls anwesenden übrigen Hilfsmittel sind:Examples of the other aids that may be present are:

Entstaubungsmittel, Stellmittel, Lichtschutzmittel, Puffersubstanzen (d. h pH-Regulatoren) etc, sowie Restfeuchte.Dedusting agents, adjusting agents, light stabilizers, buffer substances (i.e. pH regulators) etc., as well as residual moisture.

Die Einsatzmenge der erfindungsgemäßen Präparationen beträgt 0,02 - 3, vorzugsweise 0,1 - 0,5 Gew.-%, be­zogen auf Fasermaterial.The amount of the preparations according to the invention is 0.02-3, preferably 0.1-0.5% by weight, based on the fiber material.

Geeignete Fasermaterialien sind solche aus synthe­tischen Polymeren, wie Polyurethanen und synthetischen Polyamiden.Suitable fiber materials are those made of synthetic polymers, such as polyurethanes and synthetic polyamides.

Die Färbungen auf diesen Fasern können in herkömmlicher Weise sowohl mit Metallkomplexfarbstoffen als auch mit Säurefarbstoffen erzeugt werden. Bevorzugt sind die Me­tallkomplexfarbstoffe, insbesondere die 1:2 Chrom- oder 1:2 Kobalt-Komplexe von Mono- oder Diazoverbindungen, die in der Literatur in großer Zahl beschrieben und im Handel erhältlich sind. Diese Farbstoffe können auch 1 - 2 Sulfogruppen enthalten.The dyeings on these fibers can be produced in a conventional manner using both metal complex dyes and acid dyes. The metal complex dyes, in particular the 1: 2 chromium or 1: 2 cobalt complexes of mono- or diazo compounds, which are described in large numbers in the literature and are commercially available, are preferred. These dyes can also contain 1-2 sulfo groups.

Geeignete Säurefarbstoffe sind insbesondere solche Ty­pen, die üblicherweise in Kombination mit den Metall­komplexfarbstoffen eingesetzt werden.Suitable acid dyes are, in particular, those types which are usually used in combination with the metal complex dyes.

Die Behandlung der Polyamidmaterialien mit den erfin­dungsgemäß zu verwendenden Kupferverbindungen kann vor, während oder nach, bevorzugt während der Färbung, er­folgen.The treatment of the polyamide materials with the copper compounds to be used according to the invention can take place before, during or after, preferably during the dyeing.

Die Färbungen werden nach üblichen Verfahren herge­stellt, dh. im Ausziehverfahren auf dem Jet-Färbe­apparat, dem Jigger, der Haspelkufe oder einem Spul­färbeapparat oder aufeiner Kontinue-Anlage nach den be­kannten Klotz- oder Imprägierverfahren.The dyeings are produced by conventional methods, ie. in the pull-out process on the jet dyeing machine, the jigger, the reel runner or a reel dyeing machine or on a continuous machine according to the known block or impregnation processes.

Der wesentliche Vorteil der neuen Präparationen im Ver­gleich zu den vorgefertigten Kupfer-Komplexen (vergl. z.B. EP-A 51 188, 245 204, 252 386, 255 481 und DE-A 32 47 051) besteht darin, daß sie ohne großen mechani­schen und verfahrenstechnischen Aufwand herstellbar sind.The main advantage of the new preparations compared to the prefabricated copper complexes (cf., for example, EP-A 51 188, 245 204, 252 386, 255 481 and DE-A 32 47 051) is that they have no great mechanical and procedural requirements Effort can be produced.

Dabei ist es als überraschend anzusehen, daß die neuen Präparationen praktisch die gleiche Wirksamkeit wie die separat hergestellten Kupfer-Komplexe aufweisen.It is surprising that the new preparations have practically the same effectiveness as the separately prepared copper complexes.

In den nachfolgenden Beispielen bedeuten "Teile" Ge­wichtsteile.In the examples below, "parts" mean parts by weight.

BeispieleExamples Beispiel 1example 1

Eine Mischung aus
192.40 Tle. Salicylaldoxim (techn. Ware)
171.50 Tle. CuSO₄·5H₂O
231.70 Tle. Ligninsulfonat (Sulfitaufschluß)
231.70 Tle. Naphthalinsulfonsäure-Formaldehydharz
163.30 Tle. Trinatriumphosphat calc.
wird in einem Reibschnitzler vorzerkleinert. Danach fol­gen zwei Mahlgänge in einer Siebmühle (Typ Baumeister), und zwar
a) einmal mit 5 mm Sieb + Trockeneis (1 0,25)
b) einmal mit 2 mm Sieb + Trockeneis (1 : 0,5).A mix of
192.40 parts Salicylaldoxim (technical goods)
171.50 parts CuSO₄.5H₂O
231.70 parts lignin sulfonate (sulfite digestion)
231.70 parts of naphthalenesulfonic acid-formaldehyde resin
163.30 parts of trisodium phosphate calc.
is shredded in a shredder. This is followed by two grinding cycles in a sieve mill (Baumeister type)
a) once with 5 mm sieve + dry ice (1 0.25)
b) once with 2 mm sieve + dry ice (1: 0.5).

Anschließend wird das Pulver entstaubt in einem Lödige-­Mischer unter Zusatz von 7.40 Tln. eines Entstaubungs­mittels auf Mlneralöl-Basis gegeben.The powder is then dedusted in a Lödige mixer with the addition of 7.40 parts of a dedusting agent based on mineral oil.

Man erhält 1.000 g einsatzfähiges Lichtechtheitsverbes­serungsmittel, das in seiner Wirkung dem vorgefertigten Kupfer-Komplex gemäß DE-A 32 47 051 in keiner Weise nachsteht.This gives 1,000 g of ready-to-use light fastness improver, the effect of which is in no way inferior to the prefabricated copper complex according to DE-A 32 47 051.

Beispiel 2Example 2

Eine wäßrige Dispersion, bestehend aus
191.00 Tle. Wasser (als Vorlage)
19.37 Tle. Salicylaldoxim (98 %ig)
13.85 Tle. Natronlauge (40 %ig)
92.88 Tle. Ligninsulfonat (nach Sulfitaufschluß) flüssig (33,6 % trocken)
106.38 Tle. Llgninsulfonat (nach Kraftaufschluß) flüssig (29,4 %)
4.78 Tle. Wasser (zum Spülen)
17.37 Tle. CuSO₄·5H₂O
55.76 Tle. Wasser (zum Lösen des Cu-Salzes)
0.47 Tle. Entstaubungsmittel auf Mineralöl-Basis
4.70 Tle. Wasser (zum Emulgieren des Öls)
wird einer Sprühtrocknung (Eingangstemperatur: 170°C Ausgangstempertur 90°C; Einstoffdüse) unterworfen.An aqueous dispersion consisting of
191.00 parts of water (as template)
19.37 parts Salicylaldoxim (98%)
13.85 parts of sodium hydroxide solution (40%)
92.88 parts of lignin sulfonate (after sulfite digestion) liquid (33.6% dry)
106.38 parts Llgninsulfonat (after force application) liquid (29.4%)
4.78 parts water (for rinsing)
17.37 parts. CuSO₄.5H₂O
55.76 parts water (for dissolving the copper salt)
0.47 parts mineral oil-based dedusting agent
4.70 parts water (for emulsifying the oil)
is subjected to spray drying (inlet temperature: 170 ° C outlet temperature 90 ° C; single-component nozzle).

Das erhaltene Pulver ist direkt einsatzfähig.The powder obtained can be used immediately.

Beispiel 3Example 3

1475 kg einer wäßrigen Lösung von Ditolylethersulfon­säure/Formaldehyd-Kondensat mit einem Trockensubstanz­gehalt von 508,6 kg werden in einem Rührkessel vermischt mit 144,78 kg Natronlauge (40 %) sowie 199,8 kg Salicylsäure und 181 kg Kupfer-II-sulfat. Nach Zugabe von 299 kg Wasser, vermischt mit 4,7 kg eines Entstau­bungsmittels wird im Zerstäubertrockner abgesprüht, d.h. getrocknet. Man erhält eine Präparation mit sehr hoher Feinverteilung im Färbebad bzw. im Nachbehandlungsbad und guter lichtechtheitsverbessernder Wirkung auf ge­färbtem Polyamid.1475 kg of an aqueous solution of ditolyl ether sulfonic acid / formaldehyde condensate with a dry matter content of 508.6 kg are mixed in a stirred kettle with 144.78 kg sodium hydroxide solution (40%) as well as 199.8 kg salicylic acid and 181 kg copper (II) sulfate. After adding 299 kg of water, mixed with 4.7 kg of a dedusting agent, it is sprayed off in the atomizer dryer, ie dried. A preparation with a very high fine distribution in the dyebath or in the aftertreatment bath and a good lightfastness-improving effect on dyed polyamide is obtained.

Beispiel 4Example 4

Eine Trockenmischung aus
20 Tle. Salicylaldoxim
30 Tle. Ditolylethersulfonsäure/Formaldehyd-Kondensat
15 Tle. Ligninsulfonat (Sulfitaufschluß)
10 Tle. Kupfer-22-chlorid
19 Tle. Trinatriumphopshat
Rest auf 100 : Wasser
zeigt eine ähnlich gute Wirkung wie das Präparat gemäß Beispiel 1.A dry mix
20 parts Salicylaldoxim
30 parts of ditolyl ether sulfonic acid / formaldehyde condensate
15 parts of lignin sulfonate (sulfite digestion)
10 parts of copper-22-chloride
19 parts of trisodium phosphate
Rest on 100: water
shows a similarly good effect as the preparation according to Example 1.

Beispiel 5Example 5


*(Eingangstemperatur: 140°C, Ausgangstemperatur: 70°C)
* (Inlet temperature: 140 ° C, outlet temperature: 70 ° C)

2239,0 kg einer wäßrigen Lösung von Ligninsulfonat (Sul­fitaufschluß) mit einem Trockensubstanzgehalt von 312 kg und
1065,0 kg flüssiges Naphthalinsulfonsäure-Formaldehyd­harz mit einem Trockensubstanzgehalt von 312 kg werden in einem Rührkessel vermischt mit
138,5 kg Natronlauge 40 %ig sowie
193,7 kg Salicylaldoxim 98 %ig und
172,8 kg Kupfer-22-sulfat · 5H₂O. Nach Zugabe von
649,5 kg Wasser, vermischt mit
4,7 kg eines Entstaubungsmittel auf Mineralöl-Basis, wird im Zerstäubertrockner* abgesprüht, d.h. ge­trocknet. Man erhält eine Präparation mit sehr hoher Feinverteilung im Färbebad bzw. im Nachbe­ handlungsbad und guter Lichtechtheitsverbessern­der Wirkung auf gefärbtem Polyamid.2239.0 kg of an aqueous solution of lignin sulfonate (sulfite digestion) with a dry substance content of 312 kg and
1,065.0 kg of liquid naphthalenesulfonic acid-formaldehyde resin with a dry substance content of 312 kg are mixed in a stirred kettle
138.5 kg sodium hydroxide solution 40% as well
193.7 kg of 98% salicylaldoxime and
172.8 kg copper 22 sulfate · 5H₂O. After adding
649.5 kg of water mixed with
4.7 kg of a mineral oil-based dedusting agent is sprayed in an atomizer dryer *, ie dried. A preparation with a very high fine distribution is obtained in the dye bath or in the afterbeing treatment bath and good lightfastness-improving effect on colored polyamide.

Beispiel 6Example 6

77,05 Tle. getrocknete Mischkomponente (wäßrige Zube­reitung aus 20,38 g Salicyxlaldoxim-Roh­produkt, vorher bei 50°C/60°C geschmolzen, 75,42 g flüssiges Naphthalinsulfonsäure-­Formaldehydharz, 82,28 g wäßrige Lösung von Ligninsulfonat (Sulfitaufschluß), 14,86 g Natronlauge 40 %ig (Sprühtrock­nung: 160°C/80°C (Einstoffdüse) = 77,05 Tle.)
18,08 Tle. CuSO₄ · 5H₂O (vorher trocken gemahlen bzw. vorzerkleinert)
2,07 Tle. Naphthalinsulfonsäure-Formaldehydharz 92,7 %ig
2,06 Tle. Ligninsulfonat (Sulfitaufschluß) 92,7 %ig
Anschließend wird das Pulver entstaubt in einem Lödige-Mischer unter Zusatz von 0,74 Tln. eines Entstaubungsmittels auf Mineralöl-Basis gegeben.
Man erhält 100 g einsatzfähiges Licht­echtheitsverbesserungsmittel mit gleichen guten Eigenschaften wie Beispiel 5.77.05 parts of dried mixed component (aqueous preparation from 20.38 g of crude salicyxlaldoxime, previously melted at 50 ° C./60 ° C., 75.42 g of liquid naphthalenesulfonic acid / formaldehyde resin, 82.28 g of aqueous solution of lignin sulfonate (sulfite digestion) , 14.86 g sodium hydroxide solution 40% (spray drying: 160 ° C / 80 ° C (single component nozzle) = 77.05 parts)
18.08 parts CuSO₄5H₂O (previously dry ground or pre-crushed)
2.07 parts of naphthalenesulfonic acid-formaldehyde resin 92.7%
2.06 parts of lignin sulfonate (sulfite digestion) 92.7%
The powder is then dedusted in a Lödige mixer with the addition of 0.74 parts of a dedusting agent based on mineral oil.
100 g of usable light fastness improver with the same good properties as Example 5 are obtained.

Beispiel 7Example 7

Vermischt man 20 Tle. des unter Beispiel 3 genannten Ansatzes mit 80 Tln. der flüssigen Präparation im Bei­spiel 5 mit anschließender Sprühtrocknung (E. 140°C/A. 70°C), so erhält man eine Präparation mit sehr hoher Feinverteilung im Färbebad bzw im Nachbehandlungsbad und guter Lichtechtheitsverbessernder Wirkung auf ge­färbtem Polyamid.If 20 parts of the batch mentioned in Example 3 are mixed with 80 parts of the liquid preparation in Example 5 with subsequent spray drying (E. 140 ° C./A. 70 ° C.), a preparation with a very high fine distribution in the dyebath or in the aftertreatment bath and good light fastness improving effect on colored polyamide.

Beispiel 8Example 8

Eine Mischung aus
80 Tle. Pulver-Präparation von Beispiel 3
20 Tle. Pulver-Präparation von Beispiel 5
wird in einem Lödige-Mischer gegeben und vermischt.A mix of
80 parts of powder preparation from Example 3
20 parts of powder preparation from Example 5
is placed in a Lödige mixer and mixed.

Die erhaltene Pulver-Mischung ist direkt einsatzfähig und zeigt gleiche gute Wirkung wie das Präparat gemäß Beispiel 7.The powder mixture obtained can be used directly and has the same good effect as the preparation according to Example 7.

Applikationsbeispiel AApplication example A

100 Teile Polyamid-6-Fasermaterial werden in 2.000 Teile wäßrige Färbeflotte eingetragen, die 0,15 Teile des Prä­parats gemäß Beispiel 1 und 0,15 Teile des Metallkom­plex-Farbstoffes der Formel

Figure imgb0004
enthält. Durch Zugabe von Dinatriumphosphat und Mono­natriumphosphat wird ein pH-Wert von 8 eingestellt. Dann wird die Flottentemperatur unter Bewegung des Färbegutes langsam auf 98 - 100°C erhöht und für 60 min bei dieser Temperatur belassen.100 parts of polyamide 6 fiber material are introduced into 2,000 parts of aqueous dyeing liquor, the 0.15 part of the preparation according to Example 1 and 0.15 part of the metal complex dye of the formula
Figure imgb0004
 contains. A pH of 8 is set by adding disodium phosphate and monosodium phosphate. The liquor temperature is then slowly increased to 98-100 ° C. while the material to be dyed is kept and left at this temperature for 60 min.

Anschließend wird die Färbung dem Färbebad entnommen, gespült und getrocknet.The dye is then removed from the dye bath, rinsed and dried.

Die Färbung wird zusammen mit einer ohne Kupfer-Präpara­tion hergestellten Vergleichsfärbung gemäß Test der
Adam Opel AG
Tüsselsheim / BRD
GM (Engineering Standards Europe)
GME No 60 202 A/B
während 250 h im Xenontestgerät belichtet.The staining is carried out together with a comparative staining produced without copper preparation according to the test of
Adam Opel AG
Tüsselsheim / FRG
GM (Engineering Standards Europe)
GME No 60 202 A / B
exposed for 250 h in the xenon tester.

Ergebnis: Die mit der Präparation behandelte Färbung zeigt eine erheblich bessere Lichtechtheit als der Ver­gleich.Result: The coloration treated with the preparation shows a considerably better light fastness than the comparison.

Applikationsbeispiel BApplication example B

100 Teile Polyamid-6-Material werden in 2.000 Teile wäß­riger Färbeflotte eingetragen, die 0,45 Teile der in Beispiel 3 beschriebenen Präparation und 0,15 Teile des Farbstoffes der Formel

Figure imgb0005
enthalten.100 parts of polyamide 6 material are introduced into 2,000 parts of aqueous dye liquor, the 0.45 parts of the preparation described in Example 3 and 0.15 parts of the dye of the formula
Figure imgb0005
 contain.

Die Farbeflotte wird auf pH 5,5 unter Zuhilfenahme eines Puffergemisches aus Mononatriumphosphat und Essigsäure eingestellt. Man behandelt eine Stunde bei 98 bis 100°C, spült und trocknet.The dye liquor is adjusted to pH 5.5 with the aid of a buffer mixture of monosodium phosphate and acetic acid. It is treated for one hour at 98 to 100 ° C, rinsed and dried.

Die so hergestellte Färbung zeigt eine deutlich ver­besserte Lichtechtheit.The coloring produced in this way shows a clearly improved light fastness.

Claims (7)

1. Trockenpräparationen von Mitteln zur Verbesserung der Lichtechtheit von gefärbten Textilmaterialien, dadurch gekennzeichnet, daß sie
A) einen phenolischen Komplexbildner,
B) ein komplexierbares Kupfer-22-Salz und
C) ein Dispergiermittel
enthalten.1. Dry preparations of agents for improving the light fastness of dyed textile materials, characterized in that they
A) a phenolic complexing agent,
B) a complexable copper 22 salt and
C) a dispersant
contain. 2. Trockenpraparation gemäß Anspruch 1, dadurch ge­kennzeichnet, daß der Komplexbildner eine Verbin­dung der Formel
Figure imgb0006
 worin - unabhängig voneinander
Y =N-W, =N-Ar, =N-N-CH-Ar, =N-OH, =N-Ar-­N=CH-Ar, -N-AK-N=CH-Ar oder Sauerstoff,
R H, OH, U oder OW und
X₁-X₄ H, W, OH, Halogen, CN, NH₂, NVW, SO₃H, COOH, COOW, CONVW oder CONH₂ bedeuten und zwei benachbarte Reste
X₁-X₄ auch gemeinsam die restlichen Glieder eines ankondensierten Benzolringes bilden können,
wobei
AK für C₂-C₄-Alkylen,
Ar für Aryl oder Arylen,
W für C₁-C₁₈-Alkyl oder Cyclohexyl und
V für W oder H stehen.2. Dry preparation according to claim 1, characterized in that the complexing agent is a compound of the formula
Figure imgb0006
 in which - independently of each other
Y = NW, = N-Ar, = NN-CH-Ar, = N-OH, = N-Ar-N = CH-Ar, -N-AK-N = CH-Ar or oxygen,
RH, OH, U or OW and
X₁-X₄ H, W, OH, halogen, CN, NH₂, NVW, SO₃H, COOH, COOW, CONVW or CONH₂ mean and two adjacent radicals
X₁-X₄ can also together form the remaining members of a condensed benzene ring,
in which
AK for C₂-C₄ alkylene,
Ar for aryl or arylene,
W for C₁-C₁₈ alkyl or cyclohexyl and
V stands for W or H. 3. Trockenpräparation gemäß Anspruch 1, dadurch ge­kennzeichnet, daß die Teilchengröße der Präparation < 50 µm ist.3. Dry preparation according to claim 1, characterized in that the particle size of the preparation is <50 microns. 4. Trockenpräparation gemäß Anspruch 1, dadurch ge­kennzeichnet, daß der Komplexblldner Salicylaldoxim ist.4. Dry preparation according to claim 1, characterized in that the complex agent is salicylaldoxime. 5. Trockenpräparation gemäß Anspruch 1, dadurch ge­kennzeichnet, daß der Komplexbildner Salicylsäure ist.5. Dry preparation according to claim 1, characterized in that the complexing agent is salicylic acid. 6. Trockenpräparation gemäß Anspruch 2, dadurch ge­kennzeichnet, daß zwei oder mehr Komplexbildner verwendet werden.6. Dry preparation according to claim 2, characterized in that two or more complexing agents are used. 7. Trockenpräparation gemäß Anspruch 6, dadurch gekennzeichnet, daß die Mischung aus den Komplex­bildner gemäß Anspruch 4 und 5 im Verhältnis 1:1, vorzugsweise 80:20 beträgt.7. Dry preparation according to claim 6, characterized in that the mixture of the complexing agent according to claim 4 and 5 in a ratio of 1: 1, preferably 80:20.
EP90113514A 1989-07-29 1990-07-14 Dry preparation of a better light fastness mixture Expired - Lifetime EP0413146B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3925259A DE3925259A1 (en) 1989-07-29 1989-07-29 DRY PREPARATION OF LIGHT fastness improvers
DE3925259 1989-07-29

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EP0413146A1 true EP0413146A1 (en) 1991-02-20
EP0413146B1 EP0413146B1 (en) 1994-06-08

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995006095A2 (en) * 1993-08-26 1995-03-02 Basf Aktiengesellschaft Phenolic complexing agents
WO2008101833A1 (en) * 2007-02-20 2008-08-28 Huntsman Advanced Materials (Switzerland) Gmbh Uva formulation

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0113856A1 (en) * 1982-12-20 1984-07-25 Bayer Ag Process for improving the fastness to light of polyamide dyeings
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
EP0252386A1 (en) * 1986-07-08 1988-01-13 Bayer Ag Process for improving the fastness to light of polyamide dyeings

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0113856A1 (en) * 1982-12-20 1984-07-25 Bayer Ag Process for improving the fastness to light of polyamide dyeings
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
EP0252386A1 (en) * 1986-07-08 1988-01-13 Bayer Ag Process for improving the fastness to light of polyamide dyeings

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995006095A2 (en) * 1993-08-26 1995-03-02 Basf Aktiengesellschaft Phenolic complexing agents
WO1995006095A3 (en) * 1993-08-26 1995-08-03 Basf Ag Phenolic complexing agents
EP0785250A1 (en) * 1993-08-26 1997-07-23 Basf Aktiengesellschaft Phenolic complexing agents
WO2008101833A1 (en) * 2007-02-20 2008-08-28 Huntsman Advanced Materials (Switzerland) Gmbh Uva formulation

Also Published As

Publication number Publication date
EP0413146B1 (en) 1994-06-08
DE3925259A1 (en) 1991-01-31
JPH0364584A (en) 1991-03-19
ATE106960T1 (en) 1994-06-15
DE59006007D1 (en) 1994-07-14

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