EP0230910B1 - Means for treating textiles - Google Patents

Means for treating textiles Download PDF

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Publication number
EP0230910B1
EP0230910B1 EP87100427A EP87100427A EP0230910B1 EP 0230910 B1 EP0230910 B1 EP 0230910B1 EP 87100427 A EP87100427 A EP 87100427A EP 87100427 A EP87100427 A EP 87100427A EP 0230910 B1 EP0230910 B1 EP 0230910B1
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Prior art keywords
treatment agents
fabric treatment
neutralization
acid
fabrics
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EP87100427A
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German (de)
French (fr)
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EP0230910A3 (en
EP0230910B2 (en
EP0230910A2 (en
Inventor
Rudolf Dr. Veitenhansl
Wolfgang Fröschke
Peter Waltenberger
Günter Uphues
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Priority to IN736/MAS/86A priority Critical patent/IN168596B/en
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Priority to AT87100427T priority patent/ATE65776T1/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/042—Acids
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
    • C11D1/528—Carboxylic amides (R1-CO-NR2R3), where at least one of the chains R1, R2 or R3 is interrupted by a functional group, e.g. a -NH-, -NR-, -CO-, or -CON- group
    • 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
    • D06M13/402—Amides imides, sulfamic acids
    • D06M13/405—Acylated polyalkylene polyamines
    • 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
    • D06M13/46—Compounds containing quaternary nitrogen atoms
    • D06M13/461—Quaternised amin-amides from polyamines or heterocyclic compounds or polyamino-acids

Definitions

  • the invention relates to non-discoloring textile treatment agents based on condensation products of carboxylic acids or carboxylic acid derivatives with polyamines, a process for their preparation and their use.
  • textile treatment agents are understood to mean products which can be used in agents for finishing fibers, yarns, knitted fabrics, fabrics or nonwovens, in detergents and in post-treatment agents for washed textiles.
  • the amide-forming derivatives of aliphatic monocarboxylic acids are understood to mean the esters derived from natural or synthetic saturated or mono- or polyunsaturated, branched or unbranched fatty acids or fatty acid mixtures with lower alkanols such as methanol or ethanol, the fatty acid glycerides and the fatty acid halides.
  • these are the derivatives derived from lauric acid, myristic acid, palmitic acid, stearic acid, coconut fatty acid, tallow fatty acid or rapeseed oil fatty acid.
  • the reaction products which can be produced from this by reaction with polyamines are referred to below as fatty acid condensation products or condensation products.
  • Suitable polyamines are, for example, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dimethylaminopropylamine, propylenediamine, di (trimethylene) triamine and in particular aminoethylethanolamine.
  • Non-oxidizing inorganic acids in the context of the present invention are hydrogen halide fe, such as hydrogen bromide or especially hydrogen chloride and oxygen acids of phosphorus such as orthophosphoric acid, hypophosphorous acid and especially phosphorous acid.
  • oxygen acids of sulfur such as sulfuric acid and sulfurous acid, as well as boric acid and phosphonic acids, with the formation of neutral or acidic salts. Particularly good results with regard to yellowing resistance, corrosion and odor are obtained if the phosphorous acid already mentioned is used in the production of the textile treatment agents according to the invention.
  • Another object of the present invention is a method for producing the textile treatment agent.
  • a) aliphatic monocarboxylic acids with 10 to 22 carbon atoms or derivatives forming their amides are heated with b) polyamines with distillate separation and the condensation product is neutralized with non-oxidizing inorganic acids.
  • the molar ratio of carboxylic acid or carboxylic acid derivative to polyamine is chosen so that there is an excess of amino groups. Depending on the polyamine used, the molar ratio of carboxylic acid to polyamine is in the range from 1: 1 to 3: 1.
  • the acid used for the neutralization with salt formation is, based on unreacted amino groups, in a stoichiometric amount or in an up to about 30% lower or excess used ie one uses 0.7 to 1.3 or 1.0 to 1.3 acid equivalents per amine equivalent.
  • the neutralization can be carried out in the melt of the condensation product or preferably in acid diluted with water with simultaneous dispersion and dilution to a concentration ready for dispatch or ready for use.
  • the dispersion can be facilitated by adding a dispersion accelerator.
  • Suitable dispersion accelerators are, for example, monosaccharides of the aldose and ketose type or their hydrogenation products, water-soluble synthetic or natural polymers, alcohol alkoxylates, fatty acid partial glycerides and / or water-miscible solvents.
  • the dispersion accelerators can make up 0.5 to 70 percent by weight of the textile treatment agent.
  • the textile treatment agents according to the invention can easily be applied in aqueous dispersion, for example by the methods customary in textile technology, such as exhaust, centrifugal, padding or spraying methods.
  • the use of the textile treatment agents according to the invention for finishing fibers, yarns, knitted fabrics, card slivers, slivers, fabrics or nonwovens is a further subject of the invention.
  • the textile treatment agents according to the invention When used in detergents, they bring about an improved cleaning effect and / or a softening of the laundry washed therewith.
  • the textile treatment agents according to the invention can also be used as components of aftertreatment agents for washed textiles, as a result of which the textiles become soft and antistatic.
  • the aftertreatment of the washed textiles can usually be carried out in the last rinsing bath, but also during drying in an automatic laundry dryer, either by spraying the laundry with a dispersion of the agent during drying, or by applying the agent to a substrate, for example a flexible, textile fabric, applies.
  • the products according to the invention can have different compositions, i. H.
  • the fatty acid condensation products can contain a more or less large fatty acid component, or a fatty acid component with fatty acid residues of different lengths.
  • those products according to the invention which have a proportion of 0.7 to 1 fatty acid residue, which is preferably saturated, with essentially 16 to 22 carbon atoms on a functional group of the Have polyamines, that is, amino or hydroxyl group.
  • the aftertreatment agents according to the invention are also excellently suitable for the production of aqueous fabric softener concentrates which, instead of the usual active ingredient concentration of about 5% by weight, have an active ingredient concentration of 10 to about 50% by weight.
  • those products are preferably selected which contain condensation products from shorter fatty acid residues, i.e. H. having essentially 12 to 16 carbon atoms and a proportion of 0.3 to 1, preferably 0.3 to 0.5 fatty acid residues per functional group of the polyamine. Particularly good results are obtained with reaction products of this type which are derived from coconut fatty acid and dimethylaminopropylamine.
  • the textiles treated with the agents according to the invention also tend to yellow less than textiles treated with conventional agents when high temperatures, for example up to 200 ° C., are used for drying or fixing.
  • Comparative product 3 was prepared from 10.65 kg of hardened beef tallow, 1.3 kg of aminoethylethanolamine, 0.65 kg of glycolic acid, 70% by weight, 7.5 kg of tallow alcohol + 14 mol of ethylene oxide, 80 kg of water in a manner analogous to that of Comparative Example 2.
  • Comparative product 4 was obtained from 2275 kg of hardened beef tallow, 416 kg of aminoethylethanolamine, 440 kg of 60 percent by weight acetic acid and 9880 kg of water.
  • Products according to the invention were obtained by producing products as described above, but replacing the acetic acid or the glycolic acid with an equivalent amount of phosphorous acid.
  • the products obtained in this way are designated plasticizers I, II, III and IV.
  • swatches cotton / polyester woven fabric as a blended fabric
  • the fabric samples were then heat-treated (120 ° C or 180 ° C, 2 minutes) in a Benz laboratory stenter.
  • the color distances between the samples treated at 120 ° C and 180 ° C were calculated on the basis of colorimetric measurements. Larger numerical values mean greater discoloration.
  • the textiles treated with the textile treatment agents of the prior art change color more than the textiles treated with the textile treatment agents (I to IV) according to the invention.
  • the differences are so clear that they can be determined by visual inspection even without measuring devices.

Description

Die Erfindung betrifft sich nicht verfärbende Textilbehandlungsmittel auf der Basis von Kondensationsprodukten aus Carbonsäuren oder Carbonsäure-Derivaten mit Polyaminen, ein Verfahren zu ihrer Herstellung und ihre Verwendung. Unter Textilbehandlungsmitteln werden im Rahmen dieser Erfindung Erzeugnisse verstanden, die in Mitteln zur Veredelung von Fasern, Garnen, Gewirken, Geweben oder Nonwovens, in Waschmitteln und in Nachbehandlungsmitteln von gewaschenen Textilien eingesetzt werden können.The invention relates to non-discoloring textile treatment agents based on condensation products of carboxylic acids or carboxylic acid derivatives with polyamines, a process for their preparation and their use. Within the scope of this invention, textile treatment agents are understood to mean products which can be used in agents for finishing fibers, yarns, knitted fabrics, fabrics or nonwovens, in detergents and in post-treatment agents for washed textiles.

Für die Behandlung von Textilfasern, -garnen oder -gewirken, geweben oder Nonwovens wird eine Vielzahl von Verbindungen oder Stoffgemischen vorgeschlagen, die den damit behandelten Textilien besonders wertvolle Eigenschaften verleihen oder die Bestandteile von Mitteln zur besonders wirksamen Textilpflege sind. Je nach Art der angewendeten Wirkstoffe können dabei die Verarbeitungseigenschaften, die Trageeigenschaften der Textilien wie auch deren Pflege verbessert werden. Die US-Patentschrift 2,340,881 beschreibt beispielsweise Kondensationsprodukte, hergestellt aus einem Hydroxyalkylpolyamin und einem Fettsäureglycerid. Diese Kondensationsprodukte verbessern die Gleitfähigkeit und die Weichheit der damit behandelten Textilien. Nach der Lehre dieser Patentschrift werden die Kondensationsprodukte in Form ihrer wäßrigen Dispersionen angewendet. Die US-Patentschrift 3,454,494 betrifft Säuresalze von Fettsäurekondensationsprodukten mit einem Zusatz an dispergierend wirkenden Polyoxyalkylenverbindungen. Die deutsche Patentschrift 19 22 046 beschreibt Waschmittel mit einem Gehalt an Fettsäurekondensationsprodukten, die von ihrer Herstellung her dispergierend wirkende Fettsäureteilglyceride enthalten und teilweise als Salze vorliegen; in der deutschen Patentschrift 19 22 047 werden diese Fettsäurekondensationsprodukte auch als Textilweichmacher für insbesondere flüssige Wäschenachbehandlungsmittel beschrieben. Diese und ähnliche Textilbehandlungsmittel werden beispielsweise auf Fasern, Garne, Gewirke, Gewebe oder Nonwovens, meist aus wäßriger Dispersion, appliziert, wobei die genannten Substrate sowohl aus natürlichen Fasern, aus synthetischen Fasern als auch aus Gemischen dieser Materialien bestehen können. Der Applikation schließt sich meist eine Hitzebehandlung an, die der Trocknung beziehungsweise der Fixierung dient. So behandelte Textilprodukte haben gegenüber unbehandelten Produkten den Vorteil einer verbesserten Verarbeitbarkeit und/oder erhöhten Pflege- oder Tragekomfort. Die Hitzebehandlung führt aber in vielen Fällen zu einer mehr oder weniger stark ausgeprägten Verfärbung der behandelten Textilprodukte. Es wurde nun gefunden, daß man die Verfärbungsneigung senken kann durch Textilbehandlungsmittel, herstellbar durch Umsetzung von

  • a) aliphatischen Monocarbonsäuren mit 10 bis 22 Kohlenstoffatomen oder deren Amide bildenden Derivaten mit
  • b) Polyaminen
    und anschließender Neutralisation nicht-umgesetzter Aminogruppen mit anorganischen Säuren, gekennzeichnet durch Neutralisation mit nichtoxidierenden anorganischen Säuren.
For the treatment of textile fibers, yarns or knits, fabrics or nonwovens, a large number of compounds or mixtures of substances are proposed which impart particularly valuable properties to the textiles treated therewith or which are components of agents for particularly effective textile care. Depending on the type of active ingredients used, the processing properties, the wearing properties of the textiles and their care can be improved. For example, U.S. Patent 2,340,881 describes condensation products made from a hydroxyalkyl polyamine and a fatty acid glyceride. These condensation products improve the lubricity and softness of the textiles treated with them. According to the teaching of this patent, the condensation products are used in the form of their aqueous dispersions. US Pat. No. 3,454,494 relates to acid salts of fatty acid condensation products with an addition of dispersing polyoxyalkylene compounds. German patent 19 22 046 describes detergents containing fatty acid condensation products which contain fatty acid partial glycerides which have a dispersing action and are partly in the form of salts; German patent specification 19 22 047 also describes these fatty acid condensation products as textile softeners for, in particular, liquid laundry aftertreatment agents. These and similar textile treatment agents are applied, for example, to fibers, yarns, knitted fabrics, fabrics or nonwovens, usually from aqueous dispersion, it being possible for the substrates mentioned to consist of both natural fibers, synthetic fibers and mixtures of these materials. The application is usually followed by heat treatment, which is used for drying or fixing. Textile products treated in this way have the advantage over untreated products of improved processability and / or increased care or wearing comfort. In many cases, however, the heat treatment leads to a more or less pronounced discoloration of the treated textile products. It has now been found that the tendency to discoloration can be reduced by means of textile treatment agents, which can be prepared by reacting
  • a) with aliphatic monocarboxylic acids having 10 to 22 carbon atoms or their amide-forming derivatives
  • b) polyamines
    and subsequent neutralization of unreacted amino groups with inorganic acids, characterized by neutralization with non-oxidizing inorganic acids.

Unter den Amide bildenden Derivaten von aliphatischen Monocarbonsäuren sind die sich von natürlichen oder synthetischen gesättigten bzw. einfach- oder mehrfach-ungesättigten, verzweigten oder unverzweigten Fettsäuren oder Fettsäuregemischen ableitenden Ester mit niederen Alkanolen wie beispielsweise Methanol oder Ethanol, die Fettsäureglyceride und die Fettsäurehalogenide zu verstehen. Beispielsweise sind dies die von Laurinsäure, Myristinsäure, Palmitinsäure, Stearinsäure, Kokosfettsäure, Talgfettsäure oder Rübölfettsäure abgeleiteten Derivate. Die hieraus durch Umsetzung mit Polyaminen herstellbaren Reaktionsprodukte werden im folgenden Fettsäurekondensationsprodukte oder Kondensationsprodukte genannt.The amide-forming derivatives of aliphatic monocarboxylic acids are understood to mean the esters derived from natural or synthetic saturated or mono- or polyunsaturated, branched or unbranched fatty acids or fatty acid mixtures with lower alkanols such as methanol or ethanol, the fatty acid glycerides and the fatty acid halides. For example, these are the derivatives derived from lauric acid, myristic acid, palmitic acid, stearic acid, coconut fatty acid, tallow fatty acid or rapeseed oil fatty acid. The reaction products which can be produced from this by reaction with polyamines are referred to below as fatty acid condensation products or condensation products.

Geeignete Polyamine entsprechen der Formel

Figure imgb0001
in dieser Formel bedeuten R = Wasserstoff, Methyl, Ethyl oder Hydroxyethyl, R = Wasserstoff, Methyl, Ethyl, Hydroxyethyl oder -(CH2)o-NHR, n bedeutet eine ganze Zahl zwischen 2 und 4, m bedeutet eine ganze Zahl zwischen 1 und 4. Geeignete Polyamine sind beispielsweise Diethylentriamin, Triethylentetramin, Tetraethylenpentamin, Dimethylaminopropylamin, Propylendiamin, Di(trimethylen)triamin und insbesondere Aminoethylethanolamin.Suitable polyamines correspond to the formula
Figure imgb0001
 in this formula, R = hydrogen, methyl, ethyl or hydroxyethyl, R = hydrogen, methyl, ethyl, hydroxyethyl or - (CH 2 ) o -NHR, n means an integer between 2 and 4, m means an integer between 1 and 4. Suitable polyamines are, for example, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dimethylaminopropylamine, propylenediamine, di (trimethylene) triamine and in particular aminoethylethanolamine.

Nichtoxidierende anorganische Säuren im Rahmen der vorliegenden Erfindung sind Halogenwasserstoffe, wie beispielsweise Bromwasserstoff oder insbesondere Chlorwasserstoff und Sauerstoffsäuren des Phosphors wie beispielsweise Orthophosphorsäure, unterphosphorige Säure und insbesondere phosphorige Säure. Ebenfalls sind die Sauerstoffsäuren des Schwefels wie Schwefelsäure und schweflige Säure sowie Borsäure und Phosphonsäuren unter Bildung von neutralen oder sauren Salzen geeignet. Hinsichtlich Vergilbungsbeständigkeit, Korrosion und Geruch besonders gute Resultate erhält man aber, wenn man die bereits genannte phosphorige Säure bei der Herstellung der erfindungsgemäßen Textilbehandlungsmittel verwendet.Non-oxidizing inorganic acids in the context of the present invention are hydrogen halide fe, such as hydrogen bromide or especially hydrogen chloride and oxygen acids of phosphorus such as orthophosphoric acid, hypophosphorous acid and especially phosphorous acid. Also suitable are the oxygen acids of sulfur, such as sulfuric acid and sulfurous acid, as well as boric acid and phosphonic acids, with the formation of neutral or acidic salts. Particularly good results with regard to yellowing resistance, corrosion and odor are obtained if the phosphorous acid already mentioned is used in the production of the textile treatment agents according to the invention.

Ein weiterer Gegenstand der vorliegenden Erfindung ist ein Verfahren zur Herstellung der Textilbehandlungsmittel. Bei diesem Verfahren erhitzt man a) aliphatische Monocarbonsäuren mit 10 bis 22 Kohlenstoffatomen oder deren Amide bildende Derivate mit b) Polyaminen unter Destillatabscheidung und neutralisiert das Kondensationsprodukt mit nichtoxidierenden anorganischen Säuren. Das molare Verhältnis von Carbonsäure beziehungsweise Carbonsäurederivat zu Polyamin wird so gewählt, daß ein Überschuß an Aminogruppen vorliegt. Je nach verwendetem Polyamin liegt das Molverhältnis von Carbonsäure zu Polyamin im Bereich von 1 : 1 bis 3 : 1. Die zur Neutralisation unter Salzbildung verwendete Säure wird, bezogen auf nichtumgesetzte Aminogruppen, in stöchiometrischer Menge oder in einem bis zu etwa 30 %igen Unter-oder Überschuß eingesetzt d.h. man setzt pro Amin-Aquivalent 0,7 bis 1,3 beziehungsweise 1,0 bis 1,3 Säureaquivalente ein. Die Neutralisation kann man in der Schmelze des Kondensationsproduktes oder vorzugsweise in mit Wasser verdünnter Säure unter gleichzeitiger Dispergierung und Verdünnung auf versandfertige oder gebrauchsfertige Konzentration vornehmen.Another object of the present invention is a method for producing the textile treatment agent. In this process, a) aliphatic monocarboxylic acids with 10 to 22 carbon atoms or derivatives forming their amides are heated with b) polyamines with distillate separation and the condensation product is neutralized with non-oxidizing inorganic acids. The molar ratio of carboxylic acid or carboxylic acid derivative to polyamine is chosen so that there is an excess of amino groups. Depending on the polyamine used, the molar ratio of carboxylic acid to polyamine is in the range from 1: 1 to 3: 1. The acid used for the neutralization with salt formation is, based on unreacted amino groups, in a stoichiometric amount or in an up to about 30% lower or excess used ie one uses 0.7 to 1.3 or 1.0 to 1.3 acid equivalents per amine equivalent. The neutralization can be carried out in the melt of the condensation product or preferably in acid diluted with water with simultaneous dispersion and dilution to a concentration ready for dispatch or ready for use.

In vielen Fällen läßt sich die Dispergierung durch Zusatz eines Dispersionsbeschleunigers erleichtern. Geeignete Dispersionsbeschleuniger sind beispielsweise Monosaccharide vom Typ der Aldosen und Ketosen beziehungsweise deren Hydrierungsprodukte, wasserlösliche synthetische oder natürliche Polymere, Alkoholalkoxylate, Fettsäurepartialglyceride und/oder mit Wasser mischbare Lösungsmittel. Die Dispersionsbeschleuniger können 0,5 bis 70 Gewichtsprozent des Textilbehandlungsmittels ausmachen.In many cases, the dispersion can be facilitated by adding a dispersion accelerator. Suitable dispersion accelerators are, for example, monosaccharides of the aldose and ketose type or their hydrogenation products, water-soluble synthetic or natural polymers, alcohol alkoxylates, fatty acid partial glycerides and / or water-miscible solvents. The dispersion accelerators can make up 0.5 to 70 percent by weight of the textile treatment agent.

Bei der Herstellung des Kondensationsproduktes ist das Arbeiten unter Inertgasatmosphäre und/oder der Zusatz eines Reduktionsmittels zweckmäßig, wenn Wert auf hellfarbige Kondensationsprodukte gelegt wird. Als Reduktionsmittel hat sich unterphosphorige Säure in geringen Mengen bewährt.When producing the condensation product, it is advisable to work under an inert gas atmosphere and / or to add a reducing agent if importance is attached to light-colored condensation products. Hypophosphorous acid has proven itself as a reducing agent in small amounts.

Die erfindungsgemäßen Textilbehandlungsmittel lassen sich in wäßriger Dispersion leicht, beispielsweise durch die textiltechnisch üblichen Methoden, wie Auszieh-, Tauchschleuder-, Foulard- oder Sprühverfahren applizieren. Die Verwendung der erfindungsgemäßen Textilbehandlungsmittel zur Veredlung von Fasern, Garnen, Gewirken, Kardenbändern, Kammzügen, Geweben oder Nonwovens ist ein weiterer Gegenstand der Erfindung.The textile treatment agents according to the invention can easily be applied in aqueous dispersion, for example by the methods customary in textile technology, such as exhaust, centrifugal, padding or spraying methods. The use of the textile treatment agents according to the invention for finishing fibers, yarns, knitted fabrics, card slivers, slivers, fabrics or nonwovens is a further subject of the invention.

Bei der Verwendung der erfindungsgemäßen Textilbehandlungsmittel in Waschmitteln bewirken diese eine verbesserte Reinigungswirkung und/oder eine Weichmachung der damit gewaschenen Wäsche. Die erfindungsgemäßen Textilbehandlungsmittel können schließlich auch als Bestandteile von Nachbehandlungsmitteln für gewaschene Textilien verwendet werden, wodurch die Textilien weich und antistatisch werden. Die Nachbehandlung der gewaschenen Textilien kann üblicherweise im letzten Spülbad aber auch während des Trocknens in einem automatischen Wäschetrockner erfolgen, wobei man entweder die Wäsche während des Trocknens mit einer Dispersion des Mittels besprüht oder indem man das Mittel, aufgetragen auf ein Substrat, beispielsweise ein flexibles, textiles Flächengebilde, anwendet. Je nach der Art der Textilbehandlung können die erfindungsgemäßen Erzeugnisse unterschiedlich zusammengesetzt sein, d. h. die Fettsäurekondensationsprodukte können einen mehr oder weniger großen Fettsäureanteil, bzw. einen Fettsäureanteil mit unterschiedlich langen Fettsäureresten enthalten. Für die Behandlung von Fasern und Garnen sowie für die Nachbehandlung von gewaschenen Textilien haben sich besonders diejenigen erfindungsgemäßen Erzeugnisse bewährt, die einen Anteil von 0,7 bis 1 Fettsäurerest, der vorzugsweise gesättigt ist, mit im wesentlichen 16 bis 22 Kohlenstoffatomen auf eine funktionale Gruppe des Polyamins, also Amino- oder Hydroxylgruppe, aufweisen. Die erfindungsgemäßen Nachbehandlungsmittel eignen sich auch ausgezeichnet zur Herstellung von wäßrigen Textilweichmacher-Konzentraten, die statt der üblichen Wirkstoffkonzentration von ca. 5 Gew.-% eine Wirkstoffkonzentration von 10 bis etwa 50 Gew.-% aufweisen. Für die Verwendung in Waschmitteln werden vorzugsweise solche Erzeugnisse ausgewählt, die Kondensationsprodukte aus kürzeren Fettsäureresten, d. h. mit im wesentlichen 12 bis 16 Kohlenstoffatomen und einem Anteil von 0,3 bis 1, vorzugsweise 0,3 bis 0,5 Fettsäurereste pro funktionale Gruppe des Polyamins aufweisen. Besonders gute Ergebnisse erhält man mit Umsetzungsprodukten dieser Art, die sich von Kokosfettsäure und Dimethylaminopropylamin ableiten.When the textile treatment agents according to the invention are used in detergents, they bring about an improved cleaning effect and / or a softening of the laundry washed therewith. Finally, the textile treatment agents according to the invention can also be used as components of aftertreatment agents for washed textiles, as a result of which the textiles become soft and antistatic. The aftertreatment of the washed textiles can usually be carried out in the last rinsing bath, but also during drying in an automatic laundry dryer, either by spraying the laundry with a dispersion of the agent during drying, or by applying the agent to a substrate, for example a flexible, textile fabric, applies. Depending on the type of textile treatment, the products according to the invention can have different compositions, i. H. the fatty acid condensation products can contain a more or less large fatty acid component, or a fatty acid component with fatty acid residues of different lengths. For the treatment of fibers and yarns and for the aftertreatment of washed textiles, those products according to the invention which have a proportion of 0.7 to 1 fatty acid residue, which is preferably saturated, with essentially 16 to 22 carbon atoms on a functional group of the Have polyamines, that is, amino or hydroxyl group. The aftertreatment agents according to the invention are also excellently suitable for the production of aqueous fabric softener concentrates which, instead of the usual active ingredient concentration of about 5% by weight, have an active ingredient concentration of 10 to about 50% by weight. For use in detergents, those products are preferably selected which contain condensation products from shorter fatty acid residues, i.e. H. having essentially 12 to 16 carbon atoms and a proportion of 0.3 to 1, preferably 0.3 to 0.5 fatty acid residues per functional group of the polyamine. Particularly good results are obtained with reaction products of this type which are derived from coconut fatty acid and dimethylaminopropylamine.

Die mit den erfindungsgemäßen Mitteln behandelten Textilien neigen auch dann deutlich weniger zum Vergilben als mit konventionellen Mitteln behandelte Textilien, wenn zum Trocknen oder Fixieren hohe Temperaturen, beispielsweise bis zu 200 ° C angewendet werden.The textiles treated with the agents according to the invention also tend to yellow less than textiles treated with conventional agents when high temperatures, for example up to 200 ° C., are used for drying or fixing.

Vergleichsbeispiel 1Comparative Example 1

Aus 839 kg Stearin (Jodzahl 1) und 217 kg Aminoethylethanolamin wurde unter Zusatz von 1 kg 50 gewichtsprozentiger unterphosphoriger Säure als Oxydationsschutzmittel unter Stickstoffatmosphäre bei Temperaturen bis 200 ° C unter Wasserabspaltung ein Kondensationsprodukt (Säurezahl unter 2, Schmelzbereich 62 -65 °C) hergestellt und nach Abkühlen in ein Gemisch aus 2856 kg Wasser und 144 kg 60 gewichtsprozentige Essigsäure bei 50 °C eingerührt. Man erhielt eine gelblich-weiße Dispersion (Vergleichsprodukt 1).From 839 kg of stearin (iodine number 1) and 217 kg of aminoethylethanolamine with the addition of 1 kg of 50 percent by weight hypophosphorous acid as an antioxidant under nitrogen atmosphere at temperatures up to 200 ° C with elimination of water a condensation product (acid number below 2, melting range 62 -65 ° C) was prepared and after cooling, stirred into a mixture of 2856 kg of water and 144 kg of 60 percent by weight acetic acid at 50 ° C. A yellowish-white dispersion was obtained (comparative product 1).

Vergleichsbeispiel 2Comparative Example 2

1950 kg gehärteter Rindertalg wurden bei 95 C aufgeschmolzen; man ließ hierzu langsam 240 kg Aminoethylethanolamin zulaufen, rührte 4 Stunden lang bei 105 °C nach, fügte dann 200 kg Polyethylenglykoldistearatzu, pumpte 550 kg 60-gewichtsprozentige Essigsäure, vermischt mit 8600 kg Wasser, in den Reaktionsbehälter und fügte nach Abkühlen auf 65 °C 10 kg Duftstoff zu (Vergleichsprodukt 2).1950 kg of hardened beef tallow was melted at 95 C; 240 kg of aminoethylethanolamine were slowly run in, the mixture was stirred at 105 ° C. for 4 hours, then 200 kg of polyethylene glycol distearate were added, 550 kg of 60% strength by weight acetic acid, mixed with 8600 kg of water, were pumped into the reaction vessel and, after cooling to 65 ° C., was added 10 kg of fragrance (comparison product 2).

Vergleichsbeispiel 3Comparative Example 3

Aus 10,65 kg gehärtetem Rindertalg, 1,3 kg Aminoethylethanolamin, 0,65 kg Glykolsäure, 70 gewichtsprozentig, 7,5 kg Talgalkohol + 14 Mol Ethylenoxid, 80 kg Wasser wurde Vergleichsprodukt 3 in analoger Weise wie in Vergleichsbeispiel 2 hergestellt.Comparative product 3 was prepared from 10.65 kg of hardened beef tallow, 1.3 kg of aminoethylethanolamine, 0.65 kg of glycolic acid, 70% by weight, 7.5 kg of tallow alcohol + 14 mol of ethylene oxide, 80 kg of water in a manner analogous to that of Comparative Example 2.

Vergleichsbeispiel 4Comparative Example 4

Vergleichsprodukt 4 erhielt man aus 2275 kg gehärtetem Rindertalg, 416 kg Aminoethylethanolamin, 440 kg 60 gewichtsprozentige Essigsäure und 9880 kg Wasser.Comparative product 4 was obtained from 2275 kg of hardened beef tallow, 416 kg of aminoethylethanolamine, 440 kg of 60 percent by weight acetic acid and 9880 kg of water.

Beispiele 1 bis IVExamples 1 to IV

Erfindungsgemäße Produkte erhielt man, indem man Produkte herstellte, wie zuvor beschrieben, wobei aber die Essigsäure beziehungsweise die Glykolsäure durch eine äquivalente Menge phosphorige Säure ersetzt wurde. Die so erhaltenen Produkte werden mit Weichmacher I, II, III und IV bezeichnet.Products according to the invention were obtained by producing products as described above, but replacing the acetic acid or the glycolic acid with an equivalent amount of phosphorous acid. The products obtained in this way are designated plasticizers I, II, III and IV.

Mit den erfindungsgemäßen Produkten I bis IV und den Vergleichsprodukten 1 bis 4 wurden Stoffmuster (Baumwolle/Polyester-Webware als Mischgewebe) im Foulard-Verfahren in Form einer Dispersion, die 10 g Produkt pro Liter Dispersion enthielt, behandelt. Anschließend erfolgte eine Hitzebehandlung (120 °C beziehungsweise 180 °C, 2 Minuten) der Stoffmuster in einem Benz-Laborspannrahmen. Auf der Basis von farbmetrischen Messungen erfolgte eine Berechnung der Farbabstände zwischen den bei 120 °C und bei 180 °C behandelten Muster. Größere Zahlenwerte bedeuten stärkere Verfärbung.With the products I to IV according to the invention and the comparative products 1 to 4, swatches (cotton / polyester woven fabric as a blended fabric) were treated in the padding process in the form of a dispersion which contained 10 g of product per liter of dispersion. The fabric samples were then heat-treated (120 ° C or 180 ° C, 2 minutes) in a Benz laboratory stenter. The color distances between the samples treated at 120 ° C and 180 ° C were calculated on the basis of colorimetric measurements. Larger numerical values mean greater discoloration.

Beispiel VExample V

Verfährt man wie in Vergleichsbeispiel 2 beschrieben und führt die Neutralisation statt mit Essigsäure mit 66,4 kg phosphoriger Säure durch, erhält man eine Schmelze, die nach dem Versprühen aus der Schmelze in einem Sprühturm in einem hellfarbigen Pulver resultierte. Auch die damit behandelten Gewebe zeigten keinerlei Vergilbung; die in gleicher Weise versprühte Schmelze nach Vergleichsbeispiel 2 resultierte dagegen in stark gebräunten Pulvern und war somit ungeeignet zur Behandlung von Textilien.

Figure imgb0002
If the procedure is as described in Comparative Example 2 and the neutralization is carried out using 66.4 kg of phosphorous acid instead of acetic acid, a melt is obtained which, after spraying, resulted from the melt in a spray tower in a light-colored powder. The tissues treated with it also showed no yellowing; the melt sprayed in the same way according to Comparative Example 2, on the other hand, resulted in heavily browned powders and was therefore unsuitable for treating textiles.
Figure imgb0002

Wie Tabelle 1 zu entnehmen ist, verfärben sich die mit den Textilbehandlungsmitteln des Standes der Technik (1 bis 4) behandelten Textilien stärker als die mit den erfindungsgemäßen Textilbehandlungsmitteln (I bis IV) behandelten Textilien. Die Unterschiede sind so deutlich, daß sie auch ohne Meßgeräte durch visuelle Betrachtung feststellbar sind.As can be seen in Table 1, the textiles treated with the textile treatment agents of the prior art (1 to 4) change color more than the textiles treated with the textile treatment agents (I to IV) according to the invention. The differences are so clear that they can be determined by visual inspection even without measuring devices.

Verwendet man in diesen oder ähnlich aufgebauten Textilbehandlungsmitteln zur Neutralisation nicht-umgesetzter Aminogruppen andere nichtoxidierende anorganische Säuren und vergleicht die damit erzielbaren Ergebnisse mit denen, die man mit konventionellen Textilbehandlungsmitteln erhält, stellt man ähnliche Unterschiede zugunsten der erfindungsgemäßen Produkte fest.If other non-oxidizing inorganic acids are used in these or similarly structured textile treatment agents for neutralizing unreacted amino groups and if the results obtained are compared with those obtained with conventional textile treatment agents, similar differences are found in favor of the products according to the invention.

Claims (9)

1. Fabric treatment agents obtainable by reaction of
a) aliphatic Cio-22 monocarboxylic acids or amide-forming derivatives thereof with
b) polyamines
and subsequent neutralization of unreacted amino groups with inorganic acids, characterized by neutralization with non-oxidizing inorganic acids.
2. Fabric treatment agents as claimed in claim 1, characterized by neutralization with hydrogen halide.
3. Fabric treatment agents as claimed in claim 1, characterized by neutralization with oxyacids of phosphorus.
4. Fabric treatment agents as claimed in claim 1 or 3, characterized by neutralization with phosphorous acid.
5. A process for producing the fabric treatment agents claimed in any of claims 1 to 4, characterized in that the neutralization is carried out with a 1.0 to 1.3-fold quantity of acid, based on the equivalents of unreacted amino groups.
6. A process for producing fabric treatment agents as claimed in claim 5, characterized by an addition of dispersion accelerators.
7. The use of fabric treatment agents according to any of claims 1 to 6 for finishing fibres, yarns, knitted fabrics, woven fabrics or nonwovens.
8. The use of fabric treatment agents according to any of claims 1 to 6 in the washing of fabrics.
9. The use of fabric treatment agents according to any of claims 1 to 6 for the aftertreatment of washed fabrics.
EP87100427A 1986-01-23 1987-01-15 Means for treating textiles Expired - Lifetime EP0230910B2 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
IN736/MAS/86A IN168596B (en) 1986-01-23 1986-09-17
AT87100427T ATE65776T1 (en) 1986-01-23 1987-01-15 TEXTILE TREATMENT AGENTS.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3601856 1986-01-23
DE19863601856 DE3601856A1 (en) 1986-01-23 1986-01-23 TEXTILE TREATMENT AGENTS

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EP0230910A3 EP0230910A3 (en) 1988-06-08
EP0230910B1 true EP0230910B1 (en) 1991-07-31
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ES (1) ES2023124T5 (en)
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Publication number Priority date Publication date Assignee Title
DE3842057A1 (en) * 1988-12-14 1990-06-28 Henkel Kgaa TEXTILE SOFTENER FOR FLEETS WITH HIGH CONTENTS OF ELECTROLYTE AND / OR OPTICAL BRIGHTENER
DE3901820A1 (en) * 1989-01-23 1990-08-09 Henkel Kgaa TEXTILE TREATMENT AGENT
DE4020271A1 (en) * 1990-06-26 1992-01-02 Henkel Kgaa SALTS OF FATTY ACID AMIDES AND FATTY ACID IMIDAZOLINES
FR2717181B1 (en) * 1994-03-08 1996-07-26 Hoechst France Softening wax for textiles, process for its preparation, aqueous compositions containing it and its applications for the treatment of textiles.
PT1021608E (en) * 1997-10-03 2002-02-28 Clariant Finance Bvi Ltd FINISHING PRODUCT FOR MATERIAL INTENDED FOR "JEANS" ¬GANGAS |
US6140413A (en) * 1999-03-29 2000-10-31 Henkel Corporation Silicone softener viscosity reducer
WO2008023493A1 (en) * 2006-08-22 2008-02-28 Nicca Chemical Co., Ltd. In-bath quality enhancing agent for fiber processing and method of processing

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US2340881A (en) * 1939-08-22 1944-02-08 Nat Oil Prod Co Composition for lubricating and softening textile fibers
CH325736A (en) * 1952-12-12 1957-11-15 Ciba Geigy Process for the production of nitrogen-containing condensation products
US3454494A (en) * 1965-08-03 1969-07-08 Standard Chem Products Inc Textile softener compositions
DE1922047C3 (en) * 1969-04-30 1978-03-30 Henkel Kgaa, 4000 Duesseldorf Rinse aid for washed laundry
NL7609628A (en) * 1975-09-04 1977-03-08 Hoechst Ag TEXTILE TREATMENT AGENT.
DE2966608D1 (en) * 1979-08-03 1984-03-08 Albright & Wilson Compositions containing amido amine salts, and their use as fabric softeners
DE3137044A1 (en) * 1981-09-17 1983-03-24 Bayer Ag, 5090 Leverkusen IMIDAZOLINDERVATE
DE3137043A1 (en) * 1981-09-17 1983-03-24 Bayer Ag, 5090 Leverkusen AMMONIUM COMPOUNDS
DE3501521A1 (en) * 1985-01-18 1986-07-24 Henkel KGaA, 4000 Düsseldorf AQUEOUS CONCENTRATED TEXTILE SOFTENER

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JPS62184180A (en) 1987-08-12
JP2548714B2 (en) 1996-10-30
ES2023124B3 (en) 1992-01-01
TR23179A (en) 1989-06-06
EP0230910A3 (en) 1988-06-08
BR8700281A (en) 1987-12-08
US4865768A (en) 1989-09-12
ES2023124T5 (en) 1997-03-01
EP0230910B2 (en) 1997-01-15
EP0230910A2 (en) 1987-08-05
ZA87481B (en) 1987-08-26
DE3771734D1 (en) 1991-09-05

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