EP0017120A1 - Textile detergent acting as a finishing agent - Google Patents

Textile detergent acting as a finishing agent Download PDF

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Publication number
EP0017120A1
EP0017120A1 EP80101534A EP80101534A EP0017120A1 EP 0017120 A1 EP0017120 A1 EP 0017120A1 EP 80101534 A EP80101534 A EP 80101534A EP 80101534 A EP80101534 A EP 80101534A EP 0017120 A1 EP0017120 A1 EP 0017120A1
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Prior art keywords
ethers
content
percent
weight
composition according
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EP80101534A
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German (de)
French (fr)
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EP0017120B2 (en
EP0017120B1 (en
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Rudolf Weber
Hans Dr. Andree
Gertrud Geb. Lamers Wetzel
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/22Carbohydrates or derivatives thereof
    • C11D3/222Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C11D3/227Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin with nitrogen-containing groups
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/22Carbohydrates or derivatives thereof
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/01Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
    • D06M15/03Polysaccharides or derivatives thereof

Definitions

  • the invention relates to a textile detergent which exerts a finishing or stiffening effect on the washed textiles during the washing process, so that a separate aftertreatment process, usually after the last rinse cycle, is unnecessary.
  • appretierend acting, nonionic and / or zwitterionic surfactants containing laundry detergent is characterized by a content of 0.5 to 10 percent by weight of water-soluble, quaternary ammonium group-containing amino-ethers of P oly- saccharides.
  • Suitable quaternary group ethers of polysaccharides are in particular ethers of polygalactomannan and starch.
  • polygalactomannan is the main component of guar flour and is made up of trisaccharide units with the following structure:
  • the ether groups can form on the -CH 2 0H groups, the degree of substitution being in the range from 0.05 to 0.2, preferably from 0.07 to 0.15, ether groups per anhydrogalactomannan unit shown above.
  • the degree of substitution for starch ethers is 0.05 to 0.12, preferably 0.07 to 0.1 ether groups per anhydroglucose unit.
  • the ether group can be introduced in a manner known per se, for example by reacting the polygalactomannan or starch with ethyleneimine (compare US Pat. No. 3,303,184) and then partially or completely quaternizing the amino group.
  • ethyleneimine compare US Pat. No. 3,303,184
  • Such reaction products are described for example in GB-PS 1 136 842 and are known as additives in paper manufacture or as flocculants.
  • the quaternary salts can be present as halides, in particular chlorides, sulfates, alkyl sulfates, nitrates, phosphates and as salts of organic acids, for example as acetates, citrates or lactates.
  • the detergent content of the aforementioned quaternary ammonium ether is preferably 1 to 5 percent by weight.
  • the detergents contain at least one nonionic or zwitterionic surfactant and calcium ion-binding skeleton salts as further constituents. They can also contain conventional detergent components, such as washing alkalis, neutral salts, graying inhibitors, bleaching agents and stabilizers or activators for bleaching agents, enzymes, dyes and fragrances. Con - compounds with anionic character, can react with the quaternary sparingly polysaccharide to form esters or insoluble electroneutral salts are not to be included in the media.
  • Useful zwitterionic compounds are those with a betaine structure, such as carboxylate betaines, sulfate betaines and sulfobetaines, containing a straight-chain hydrocarbon radical having 12 to 18 carbon atoms, such as, for example, by reacting tertiary amines with halocarboxylic acids (for example monochloroacetic acid), haloalkylsulfonic acid esters, haloalkylsulfonic acids or sultones (for example propane sultone) are available.
  • halocarboxylic acids for example monochloroacetic acid
  • haloalkylsulfonic acid esters for example haloalkylsulfonic acids or sultones
  • propane sultone propane sultone
  • the surfactant component preferably consists of nonionic compounds.
  • the content of nonionic surfactants in the laundry detergent is generally 1 to 30 percent by weight.
  • the maximum content is slightly lower in powdery to granular detergents, i.e. it generally does not exceed 25 percent by weight and is preferably 3-15 percent by weight.
  • Suitable nonionic surfactants are, in particular, ethoxylation products of saturated or monounsaturated aliphatic primary alcohols having 12 to 24, preferably 12 to 18 carbon atoms and 3 to 20, in particular 4 to 15, ethylene glycol ether groups.
  • Suitable alcohols from which the present ethoxylation products are derived are, for example, those of natural origin, such as coconut oil or tallow fatty alcohols or oleyl alcohol, furthermore oxo alcohols or synthetic alcohols obtained by ethylene polymerization.
  • nonionic surfactants are ethoxylation products of secondary alcohols and vicinal diols each having 12 to 18 carbon atoms and of alkylphenols with 6 to 12 carbon atoms in the alkyl radical, the number of glycol ether groups likewise being 3 to 20, preferably 4 to 15.
  • the abovementioned ethoxylated alcohols and alkylphenols can also be replaced in whole or in part by those which are prepared with 0.5 to 3 mol of propylene oxide per mol of starting compound and only in 2. Stage the prospective amount of ethylene oxide is deposited.
  • those nonionic surfactants which are derived from the abovementioned compounds and which have ethylene glycol and propylene glycol ether groups in a different order may also be present, for example alcohols with 10 to 30 ethylene glycol ether groups and 3 to 30 propylene glycol ether groups; also ethoxylation products of mercaptans, fatty acid amides and fatty acids.
  • the water-soluble, 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol can also be used
  • the compounds mentioned usually contain 1 to 5 ethylene glycol units per propylene glycol unit.
  • Nonionic compounds of the amine oxide and sulfoxide type which can optionally also be ethoxylated, can also be used.
  • Suitable structural substances are the polymer phosphates of sodium and potassium.
  • the pentasodium triphosphate is particularly suitable as the polymer phosphate, which may be present in a mixture with its hydrolysis products, the mono- and diphosphates, and also more highly condensed phosphates, for example the tetraphosphates.
  • These aluminosilicates generally have a grain size of 0.1 to 20 ⁇ and are preferably crystalline.
  • the skeleton salts also include salts of complexing aminopolycarboxylic acids, in particular alkali salts of nitrilotriacetic acid and ethylenediaminotetraacetic acid.
  • the higher homologs of the aminopolycarboxylic acids mentioned are also suitable.
  • Salts are also nitrogen-free polycarboxylic acids which form complex salts with calcium ions, which also include polymers containing carboxyl groups suitable. Examples are citric acid, tartaric acid, benzene hexacarboxylic acid and tetrahydrofuran tetracarboxylic acid.
  • Polycarboxylic acids containing carboxymethyl ether groups can also be used, such as 2,2'-oxydisuccinic acid and polyhydric alcohols or hydroxycarboxylic acids partially or completely etherified with glycolic acid, for example triscarboxymethylglycerol, biscarboxymethylglyceric acid and carboxymethyloxysuccinic acid.
  • complexing polyphosphonic acid salts can be present, for example the alkali salts of aminopolyphosphonic acids, in particular aminotri- (methylenephosphonic acid), 1-hydroxyethane-1,1-diphosphonic acid, phenylhydroxymethane diphosphonic acid, methylene diphosphonic acid and salts of the higher homologues of the polyphosphonic acids mentioned. Mixtures of the aforementioned complexing agents can also be used.
  • Suitable washing alkalis are alkali carbonates, bicarbonates, borates and silicates with a Na 2 0: Si0 2 ratio of 1: 1 to 1: 3.5.
  • Sodium sulfate and sodium chloride are suitable as neutral salts.
  • Graying inhibitors are compounds from the class of cellulose ethers in amounts of from 0.1 to 5 percent by weight, in particular nonionic compounds, such as methyl cellulose, hydroxyethyl cellulose, methyl hydroxyethyl cellulose and methyl hydroxypropyl cellulose. Mixtures of the aforementioned cellulose ethers or mixed ethers can also be used,
  • bleaching agents may be present, preferably per compounds such as sodium percarbonate, but in particular sodium perborate tetrahydrate.
  • suitable ingredients are foam inhibitors, in particular polydimethylsiloxanes, proteolytic or amylolytic enzymes, and bleach activators, such as tetraacetylethylene diamine or tetraacetylglycoluril.
  • the enzymes and bleach activators can be coated with water-soluble or dispersible coating substances.
  • the agents can also be in liquid form and contain water or organic solvents, such as low molecular weight alcohols, glycols, glycol ethers and ether alcohols.
  • Hydrotropic substances such as the alkali metal salts of toluene, xylene, ethylbenzene and cumene sulfonic acid or alkyl sulfates or alkyl sulfonates having 4 to 8 carbon atoms, may also be present.
  • the preparation of powdered or granular laundry detergent may be conducted in a known manner, for example by G ranulation or spray drying, with the present invention concomitantly polysaccharide ether can be added to verstäubenden Waschstoffbrei (slurry) to the.
  • the textile detergents are suitable for use in the delicates range (20 - 40 ° C) and for cottons (90 - 98 ° C), but especially for the treatment of so-called "easy-care textiles" in the 40 - 60 ° C range. They are suitable for washing textiles made of cellulose fibers (cotton, linen), refined cellulose (wash-andwear equipment) as well as those made of synthetic fibers or blended fabrics.
  • Powdery to granular detergents can have the following general composition (in percent by weight):
  • Liquid laundry detergents can have the following composition (in percent by weight):
  • the textile detergents according to the invention are not only distinguished by their high washability but also by valuable finishing and stiffening properties. This manifests itself in an increased bending stiffness and an improved surface smoothness of the washed textiles. These effects are known per se as a result of a finishing treatment, but so far a separate aftertreatment which increases the water consumption and is time-consuming has always been necessary for this. In contrast, the use of the agents according to the invention leads to a simplification of the washing process or to savings in water and energy.
  • a detergent of the following composition was used (in percent by weight):
  • curtain tape and bleaching nettle were used as textile material.
  • the washing treatment was carried out in an automatic washing machine having a horizontally mounted drum at 40 O C ( "easy-care program").
  • the detergent concentration was 8.4 g / l, the liquor ratio (kg of laundry to liter of wash liquor) 1:20, the water hardness 16 ° dH and the washing time 20 minutes.
  • the change in tensile resistance was measured on the curtain tapes, and the change in stiffness and static or sliding friction on the nettle fabric after 1 and 3 washing treatments (abbreviation 1 W and 3 W, respectively).

Abstract

This invention relates to detergent compositions comprising at least one nonionic and/or zwitterionic tenside and from about 0.5 to 10 percent by weight of polysaccharide amino ethers having quaternary ammonium groups. Builder salts and other conventionally used detergent compositions may also be present. These detergent compositions have sizing and stiffening properties and make a secondary treatment of washed textiles unnecessary.

Description

Gegenstand der Erfindung ist ein Textilwaschmittel, das während des Waschprozesses eine appretierende bzw. steifende Wirkung auf die gewaschenen Textilien ausübt, so daß sich ein gesonderter, meist nach.dem letzten Spülgang angeschlossener Nachbehandlungsprozeß erübrigt,The invention relates to a textile detergent which exerts a finishing or stiffening effect on the washed textiles during the washing process, so that a separate aftertreatment process, usually after the last rinse cycle, is unnecessary.

Das erfindungsgemäße, appretierend wirkende, nichtionische und/oder zwitterionische Tenside enthaltende Textilwaschmittel ist gekennzeichnet durch einen Gehalt von 0,5 bis 10 Gewichtsprozent an in Wasser löslichen, quartäre Ammoniumgruppen aufweisenden Aminoethern von Poly- sacchariden.According to the invention, appretierend acting, nonionic and / or zwitterionic surfactants containing laundry detergent is characterized by a content of 0.5 to 10 percent by weight of water-soluble, quaternary ammonium group-containing amino-ethers of P oly- saccharides.

Als quartäre Gruppen aufweisende Ether von Polysacchariden kommen insbesondere Ether von Polygalactomannan und der Stärke in Frage. Polygalactomannan ist bekanntlich Hauptbestandteil des Guar-Mehls und ist aus Trisaccharid-Einheiten folgender Struktur aufgebaut:

Figure imgb0001
Suitable quaternary group ethers of polysaccharides are in particular ethers of polygalactomannan and starch. As is known, polygalactomannan is the main component of guar flour and is made up of trisaccharide units with the following structure:
Figure imgb0001

Die Ethergruppen können sich an den -CH20H-Gruppen ausbilden, wobei der Substitutionsgrad im Bereich von 0,05 bis 0,2, vorzugsweise von 0,07 bis 0,15 Ethergruppen pro vorstehend dargestellter Anhydrogalactomannan-Einheit liegt. Bei den Stärkeethern beträgt der Substitutionsgrad 0,05 bis 0,12, vorzugsweise 0,07 bis 0,1 Ethergruppen pro Anhydroglucose-Einheit.The ether groups can form on the -CH 2 0H groups, the degree of substitution being in the range from 0.05 to 0.2, preferably from 0.07 to 0.15, ether groups per anhydrogalactomannan unit shown above. The degree of substitution for starch ethers is 0.05 to 0.12, preferably 0.07 to 0.1 ether groups per anhydroglucose unit.

Die Einführung der Ethergruppe kann in an sich bekannter Weise, beispielsweise durch Umsetzung des Polygalactomannans beziehungsweise der Stärke mit Ethylenimin (vergleiche US-PS 3 303 184) und anschließende teilweise oder vollständige Quaternierung der Aminogruppe erfolgen. Vorzugsweise werden jedoch solche Ether verwendet, die beispielsweise durch Umsetzung von Polygalactomannan beziehungsweise Stärke mit 2,3-Epoxypropyltrialkylammoniumsalzen oder 3-Chlor-2-hydroxypropyltrimethylammoniumsalzen, insbesondere mit 2,3-Epoxypropyltrimethylammoniumchlorid, erhalten werden. Derartige Umsetzungsprodukte sind beispielsweise in der GB-PS 1 136 842 beschrieben und sind als Zusätze bei der Papierherstellung beziehungsweise als Flockungsmittel bekannt.The ether group can be introduced in a manner known per se, for example by reacting the polygalactomannan or starch with ethyleneimine (compare US Pat. No. 3,303,184) and then partially or completely quaternizing the amino group. However, preference is given to using ethers which are obtained, for example, by reacting polygalactomannan or starch with 2,3-epoxypropyltrialkylammonium salts or 3-chloro-2-hydroxypropyltrimethylammonium salts, in particular with 2,3-epoxypropyltrimethylammonium chloride. Such reaction products are described for example in GB-PS 1 136 842 and are known as additives in paper manufacture or as flocculants.

Die Quartärsalze können als Halogenide, insbesondere Chloride, Sulfate, Alkylsulfate, Nitrate, Phosphate und als Salze organischer Säuren, zum Beispiel als Acetate, Citrate oder Lactate vorliegen.The quaternary salts can be present as halides, in particular chlorides, sulfates, alkyl sulfates, nitrates, phosphates and as salts of organic acids, for example as acetates, citrates or lactates.

Der Gehalt der Waschmittel an den vorgenannten, quartäre Ammoniumgruppen aufweisenden Ethern beträgt vorzugsweise 1 bis 5 Gewichtsprozent.The detergent content of the aforementioned quaternary ammonium ether is preferably 1 to 5 percent by weight.

Die Waschmittel enthalten als weitere Bestandteile mindestens ein nichtionisches oder zwitterionisches Tensid sowie Calciumionen bindende Gerüstsalze. Sie können ferner übliche Waschmittelbestandteile, wie Waschalkalien, Neutralsalze, Vergrauungsinhibitoren, Bleichmittel sowie Stabilisatoren beziehungsweise Aktivatoren für Bleichmittel, Enzyme, Farb- und Duftstoffe enthalten. Verbin- dungen mit anionischem Charakter, die mit den quartären Polysaccharid-Estern unter Bildung schwer- beziehungsweise unlöslicher Elektroneutralsalze reagieren können, sollen in den Mitteln nicht enthalten sein.The detergents contain at least one nonionic or zwitterionic surfactant and calcium ion-binding skeleton salts as further constituents. They can also contain conventional detergent components, such as washing alkalis, neutral salts, graying inhibitors, bleaching agents and stabilizers or activators for bleaching agents, enzymes, dyes and fragrances. Con - compounds with anionic character, can react with the quaternary sparingly polysaccharide to form esters or insoluble electroneutral salts are not to be included in the media.

Brauchbare zwitterionische Verbindungen sind solche mit Betainstruktur, wie Carboxylat-Betaine, Sulfat-Betaine und Sulfobetaine, enthaltend einen geradkettigen Kohlenwasserstoffrest mit 12 bis 18 Kohlenstoffatomen, wie sie beispielsweise durch Umsetzung von tertiären Aminen mit Halogencarbonsäuren (zum Beispiel Monochloressigsäure), Halogenalkylschwefelsäureestern, Halogenalkylsulfonsäuren oder Sultonen (zum Beispiel Propansulton) erhältlich sind.Useful zwitterionic compounds are those with a betaine structure, such as carboxylate betaines, sulfate betaines and sulfobetaines, containing a straight-chain hydrocarbon radical having 12 to 18 carbon atoms, such as, for example, by reacting tertiary amines with halocarboxylic acids (for example monochloroacetic acid), haloalkylsulfonic acid esters, haloalkylsulfonic acids or sultones (for example propane sultone) are available.

Vorzugsweise besteht die Tensidkomponente aus nichtionischen Verbindungen. Der Gehalt der Textilwaschmittel an nichtionischen Tensiden beträgt allgemein 1 - 30 Gewichtsprozent. In pulverförmigen bis körnigen Waschmitteln ist der maximale Gehalt etwas niedriger, d.h. er übersteigt 25 Gewichtsprozent im allgemeinen nicht und beträgt vorzugsweise 3 - 15 Gewichtsprozent.The surfactant component preferably consists of nonionic compounds. The content of nonionic surfactants in the laundry detergent is generally 1 to 30 percent by weight. The maximum content is slightly lower in powdery to granular detergents, i.e. it generally does not exceed 25 percent by weight and is preferably 3-15 percent by weight.

Geeignete nichtionische Tenside sind insbesondere Ethoxylierungsprodukte von gesättigten oder einfach ungesättigten aliphatischen primären Alkoholen mit 12 bis 24, vorzugsweise 12 bis 18 Kohlenstoffatomen und 3 bis 20, insbesondere 4 bis 15 Ethylenglykolethergruppen. Geeignete Alkohole, von denen sich die vorliegenden Ethoxylierungsprodukte ableiten, sind beispielsweise solche natürlichen Ursprungs, wie Cocos- oder Talgfettalkohole bzw. Oleylalkohol, ferner Oxoalkohole oder durch Ethylenpolymerisation gewonnene Synthesealkohole.Suitable nonionic surfactants are, in particular, ethoxylation products of saturated or monounsaturated aliphatic primary alcohols having 12 to 24, preferably 12 to 18 carbon atoms and 3 to 20, in particular 4 to 15, ethylene glycol ether groups. Suitable alcohols from which the present ethoxylation products are derived are, for example, those of natural origin, such as coconut oil or tallow fatty alcohols or oleyl alcohol, furthermore oxo alcohols or synthetic alcohols obtained by ethylene polymerization.

Weitere geeignete nichtionische Tenside sind Ethoxylierungsprodukte von sekundären Alkoholen und vicinalen Diolen mit jeweils 12 bis 18 Kohlenstoffatomen sowie von Alkylphenolen mit 6 bis 12 Kohlenstoffatomen im Alkylrest, wobei die Zahl der Glykolethergruppen ebenfalls 3 bis 20, vorzugsweise 4 bis 15 beträgt. Die vorstehend genannten ethoxylierten Alkohole und Alkylphenole können auch ganz oder teilweise durch solche ersetzt sein, bei deren Herstellung mit O,5 bis 3 Mol Propylenoxid pro Mol Ausgangsverbindung und erst in '2. Stufe die in Aussicht genommmene Menge an Ethylenoxid angelagert wird.Further suitable nonionic surfactants are ethoxylation products of secondary alcohols and vicinal diols each having 12 to 18 carbon atoms and of alkylphenols with 6 to 12 carbon atoms in the alkyl radical, the number of glycol ether groups likewise being 3 to 20, preferably 4 to 15. The abovementioned ethoxylated alcohols and alkylphenols can also be replaced in whole or in part by those which are prepared with 0.5 to 3 mol of propylene oxide per mol of starting compound and only in 2. Stage the prospective amount of ethylene oxide is deposited.

Gegebenenfalls können auch solche nichtionischen Tenside anwesend sein, die sich von den vorgenannten Verbindungen ableiten und die Ethylenglykol- als auch Propylenglykolethergruppen in anderer Reihenfolge aufweisen, beispielsweise Alkohole mit 10 bis 30 Ethylenglykolethergruppen und 3 bis 30 Propylenglykolethergruppen; ferner Ethoxylierungsprodukte von Mercaptanen, Fettsäureamiden und Fettsäuren. Brauchbar sind auch die wasserlöslichen, 20 bis 250 Ethylenglykolethergruppen und 10 bis 100 Propylenglykolethergruppen enthaltenden Polyethylenoxidaddukte an Polypropylenglykol, Ethylendiaminopolypropylenglykol und Alkylpolypropylenglykol mit 1 bis 10 Kohlenstoffatomen in der Alkylkette. Die genannten Verbindungen enthalten üblicherweise pro Propylenglykol-Einheit 1 bis 5 Ethylenglykoleinheiten. Auch nichtionische Verbindungen vom Typ der Aminoxide und Sulfoxide, die gegebenenfalls auch ethoxyliert sein können, sind verwendbar.If appropriate, those nonionic surfactants which are derived from the abovementioned compounds and which have ethylene glycol and propylene glycol ether groups in a different order may also be present, for example alcohols with 10 to 30 ethylene glycol ether groups and 3 to 30 propylene glycol ether groups; also ethoxylation products of mercaptans, fatty acid amides and fatty acids. The water-soluble, 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol can also be used Polyethylene oxide adducts containing ether groups on polypropylene glycol, ethylenediaminopolypropylene glycol and alkylpolypropylene glycol with 1 to 10 carbon atoms in the alkyl chain. The compounds mentioned usually contain 1 to 5 ethylene glycol units per propylene glycol unit. Nonionic compounds of the amine oxide and sulfoxide type, which can optionally also be ethoxylated, can also be used.

Geeignete Gerüstsubstanzen sind die Polymerphosphate des Natriums und Kaliums. Als Polymerphosphat kommt insbesondere das Pentanatriumtriphosphat in Frage, das im Gemisch mit seinen Hydrolyseprodukten, den Mono- und Diphosphaten, sowie höherkondensierten Phosphaten, zum Beispiel den Tetraphosphaten, vorliegen kann. Brauchbar sind ferner zum Kationenaustausch befähigte, wasserhaltige Alumosilikate des Kaliums oder insbesondere des Natriums der allgemeinen Formel (Na2O)x . Al2O3 . (SiO2)y . (H2O) Z mit x = 0,9 bis 1,5,. y = 1,3 bis 4,0 und z = 1 bis 6. Diese Alumosilikate weisen allgemein eine Korngröße von 0,1 bis 20µ auf und sind vorzugsweise kristallin.Suitable structural substances are the polymer phosphates of sodium and potassium. The pentasodium triphosphate is particularly suitable as the polymer phosphate, which may be present in a mixture with its hydrolysis products, the mono- and diphosphates, and also more highly condensed phosphates, for example the tetraphosphates. Water-containing aluminosilicates of potassium or, in particular, of sodium of the general formula (Na 2 O) x capable of cation exchange can also be used. Al 2 O 3 . (SiO 2 ) y . (H 2 O) Z with x = 0.9 to 1.5. y = 1.3 to 4.0 and z = 1 to 6. These aluminosilicates generally have a grain size of 0.1 to 20μ and are preferably crystalline.

Zu den Gerüstsalzen zählen ferner Salze von komplexierend wirkenden Aminopolycarbonsäuren, insbesondere Alkalisalze der Nitrilotriessigsäure und Ethylendiaminotetraessigsäure. Geeignet sind ferner die'höheren Homologen der genannten Aminopolycarbonsäuren. Auch Salze stickstofffreier, mit Calciumionen Komplexsalze bildender Polycarbonsäuren, wozu auch Carboxylgruppen enthaltende Polymerisate zählen, sind geeignet. Beispiele sind Citronensäure, Weinsäure, Benzolhexacarbonsäure und Tetrahydrofurantetracarbonsäure. Auch Carboxymethylethergruppen enthaltende Polycarbonsäuren sind brauchbar, wie 2,2'-Oxydibernsteinsäure sowie mit Glykolsäure teilweise oder vollständig veretherte mehrwertige Alkohole oder Hydroxycarbonsäuren, beispielsweise Triscarboxymethylglycerin, Biscarboxymethylglycerinsäure und Carboxymethyl-oxybernsteinsäure.The skeleton salts also include salts of complexing aminopolycarboxylic acids, in particular alkali salts of nitrilotriacetic acid and ethylenediaminotetraacetic acid. The higher homologs of the aminopolycarboxylic acids mentioned are also suitable. Salts are also nitrogen-free polycarboxylic acids which form complex salts with calcium ions, which also include polymers containing carboxyl groups suitable. Examples are citric acid, tartaric acid, benzene hexacarboxylic acid and tetrahydrofuran tetracarboxylic acid. Polycarboxylic acids containing carboxymethyl ether groups can also be used, such as 2,2'-oxydisuccinic acid and polyhydric alcohols or hydroxycarboxylic acids partially or completely etherified with glycolic acid, for example triscarboxymethylglycerol, biscarboxymethylglyceric acid and carboxymethyloxysuccinic acid.

Weiterhin können komplexierend wirkende polyphosphonsaure Salze anwesend sein, zum Beispiel die Alkalisalze von Aminopolyphosphonsäuren, insbesondere Aminotri-(methylen- phosphonsäure), 1-Hydroxyethan-1,1-diphosphonsäure, Phenylhydroxymethandiphosphonsäure, Methylendiphosphonsäure sowie Salze der höheren Homologen der genannten Polyphosphonsäuren. Auch Gemische der vorgenannten Komplexierungsmittel sind verwendbar.Furthermore, complexing polyphosphonic acid salts can be present, for example the alkali salts of aminopolyphosphonic acids, in particular aminotri- (methylenephosphonic acid), 1-hydroxyethane-1,1-diphosphonic acid, phenylhydroxymethane diphosphonic acid, methylene diphosphonic acid and salts of the higher homologues of the polyphosphonic acids mentioned. Mixtures of the aforementioned complexing agents can also be used.

Geeignete Waschalkalien sind Alkalicarbonate, -bicarbonate, -borate und -silikate mit einem Na20 : Si02-Verhältnis von 1 : 1 bis 1 : 3,5. Als Neutralsalze kommen Natriumsulfat und Natriumchlorid in Betracht.Suitable washing alkalis are alkali carbonates, bicarbonates, borates and silicates with a Na 2 0: Si0 2 ratio of 1: 1 to 1: 3.5. Sodium sulfate and sodium chloride are suitable as neutral salts.

Als Vergrauungsinhibitoren kommen Verbindungen aus der Klasse der Celluloseether in Mengen von-0,1 bis 5 Gewichtsprozent in Betracht, insbesondere nichtionische Verbindungen, wie Methylcellulose, Hydroxyethylcellulose, Methylhydroxyethylcellulose und Methyl-hydroxypropylcellulose. Auch Gemische der vorgenannten Celluloseether beziehungsweise Mischether können eingesetzt werden,Graying inhibitors are compounds from the class of cellulose ethers in amounts of from 0.1 to 5 percent by weight, in particular nonionic compounds, such as methyl cellulose, hydroxyethyl cellulose, methyl hydroxyethyl cellulose and methyl hydroxypropyl cellulose. Mixtures of the aforementioned cellulose ethers or mixed ethers can also be used,

Gegebenenfalls können Bleichmittel anwesend sein, vorzugsweise Perverbindungen, wie Natriumpercarbonat, insbesondere jedoch Natriumperborat-tetrahydrat. Weitere geeignete Bestandteile sind Schauminhibitoren, insbesondere Polydimethylsiloxane, proteolytische beziehungsweise am amylolytische Enzyme sowie Bleichaktivatoren, wie Tetraacetylethylendiamin oder Tetraacetylglykoluril. Zum Schutz gegen Zersetzung oder Wechselwirkungen mit den übrigen Pulverbestandteilen des Waschmittels können die Enzyme und Bleichaktivatoren mit in Wasser löslichen beziehungsweise dispergierbaren Hüllsubstanzen überzogen sein,If necessary, bleaching agents may be present, preferably per compounds such as sodium percarbonate, but in particular sodium perborate tetrahydrate. Other suitable ingredients are foam inhibitors, in particular polydimethylsiloxanes, proteolytic or amylolytic enzymes, and bleach activators, such as tetraacetylethylene diamine or tetraacetylglycoluril. To protect against decomposition or interactions with the other powder components of the detergent, the enzymes and bleach activators can be coated with water-soluble or dispersible coating substances.

Die Mittel können auch in flüssiger Form vorliegen und Wasser beziehungsweise organische Lösungsmittel, wie niedermolekulare Alkohole, Glykole, Glykolether und Etheralkohole enthalten. Ebenso können hydrotrope Stoffe, wie die Alkalimetallsalze der Toluol-, Xylol-, Ethylbenzol-und Cumolsulfonsäure beziehungsweise Alkylsulfate oder Alkylsulfonate mit 4 bis 8 Kohlenstoffatomen anwesend sein.The agents can also be in liquid form and contain water or organic solvents, such as low molecular weight alcohols, glycols, glycol ethers and ether alcohols. Hydrotropic substances, such as the alkali metal salts of toluene, xylene, ethylbenzene and cumene sulfonic acid or alkyl sulfates or alkyl sulfonates having 4 to 8 carbon atoms, may also be present.

Die Herstellung pulverförmiger beziehungsweise körniger Textilwaschmittel kann in bekannter Weise durchgeführt werden, beispielsweise durch Granulation oder Sprühtrocknung, wobei die erfindungsgemäß mitzuverwendenden Polysaccharidether dem zu verstäubenden Waschmittelbrei (Slurry) zugesetzt werden können.The preparation of powdered or granular laundry detergent may be conducted in a known manner, for example by G ranulation or spray drying, with the present invention concomitantly polysaccharide ether can be added to verstäubenden Waschmittelbrei (slurry) to the.

Die Textilwaschmittel eignen sich zur Verwendung im Feinwaschbereich (20 - 40 °C) und für Kochwäsche (90 - 98 °C), insbesondere jedoch zur Behandlung von sogenannten "Pflegeleicht-Textilien" im 40 - 60 °C-Waschbereich. Sie sind sowohl zum Waschen von Textilien aus Cellulosefasern (Baumwolle, Leinen), aus veredelter Cellulose (wash-andwear-Ausrüstung) als auch von solchen aus Synthesefasern beziehungsweise Mischgeweben geeignet.The textile detergents are suitable for use in the delicates range (20 - 40 ° C) and for cottons (90 - 98 ° C), but especially for the treatment of so-called "easy-care textiles" in the 40 - 60 ° C range. They are suitable for washing textiles made of cellulose fibers (cotton, linen), refined cellulose (wash-andwear equipment) as well as those made of synthetic fibers or blended fabrics.

Pulverförmige bis körnige Waschmittel können folgende allgemeine Zusammensetzung aufweisen (in Gewichtsprozent):

Figure imgb0002
Flüssige Textilwaschmittel können die folgende Zusammensetzung aufweisen (in Gewichtsprozent):
Figure imgb0003
Powdery to granular detergents can have the following general composition (in percent by weight):
Figure imgb0002
Liquid laundry detergents can have the following composition (in percent by weight):
Figure imgb0003

Die erfindungsgemäßen Textilwaschmittel zeichnen sich außer durch ihr hohes Waschvermögen auch durch wertvolle appretierende und steifende Eigenschaften aus. Dies äußert sich in einer erhöhten Biegesteifigkeit und einer verbesserten Oberflächenglätte der gewaschenen Textilien. An sich sind diese Effekte als Folgen einer Appretierbehandlung bekannt, nur war hierzu bisher stets eine gesonderte, den Wasserverbrauch erhöhende und zeitlich aufwendigere Nachbehandlung erforderlich. Die Anwendung der erfindungsgemäßen Mittel führt demgegenüber zu einer Vereinfachung des Waschprozesses beziehungsweise zu Einsparungen an Wasser und Energie.The textile detergents according to the invention are not only distinguished by their high washability but also by valuable finishing and stiffening properties. This manifests itself in an increased bending stiffness and an improved surface smoothness of the washed textiles. These effects are known per se as a result of a finishing treatment, but so far a separate aftertreatment which increases the water consumption and is time-consuming has always been necessary for this. In contrast, the use of the agents according to the invention leads to a simplification of the washing process or to savings in water and energy.

B e i s p i e l eExample

Es wurde ein Waschmittel folgender Zusammensetzung verwendet (in Gewichtsprozent):

Figure imgb0004
A detergent of the following composition was used (in percent by weight):
Figure imgb0004

Der Polysaccharid-Ether bestand aus

  • A) Polygalactomannan-ether, hergestellt durch Umsetzung von Guarmehl mit 2,3-Epoxypropyl-trimethylammoniumchlorid, Substitutionsgrad = 0,1 quartäre Ethergruppen pro Anhydrogalactomannan-Einheit,
  • B) Polygalactomannan-ether, hergestellt wie Produkt (A), Substitutionsgrad = 0,15 quartäre Ethergruppen pro Anhydrogalactomannan-Einheit,
  • C) Stärkeether, hergestellt durch Umsetzung von Stärke mit 2,3-Epoxypropyl-trimethylammoniumchlorid, Substitutionsgrad = 0,085 quartäre Ethergruppen pro Anhydroglycose-Einheit.
The polysaccharide ether consisted of
  • A) polygalactomannan ether, prepared by reacting guar flour with 2,3-epoxypropyltrimethylammonium chloride, degree of substitution = 0.1 quaternary ether groups per anhydrogalactomannan unit,
  • B) polygalactomannan ether, prepared as product (A), degree of substitution = 0.15 quaternary ether groups per anhydrogalactomannan unit,
  • C) Starch ether, produced by reacting starch with 2,3-epoxypropyltrimethylammonium chloride, degree of substitution = 0.085 quaternary ether groups per anhydroglycose unit.

Im Vergleichsversuch wurde der Polysaccharidether durch Natriumsulfat ersetzt.In the comparative experiment, the polysaccharide ether was replaced by sodium sulfate.

Als Textilmaterial wurde Gardinenband und Bleichnessel verwendet. Die Waschbehandlung erfolgte in einer automatischen Waschmaschine mit horizontal gelagerter Trommel bei 40 OC ("Pflegeleicht-Programm"). Die Waschmittelkonzentration betrug 8,4 g/l, das Flottenverhältnis (kg Wäsche zu Liter Waschlauge) 1 : 20, die Wasserhärte 16° dH und die Waschdauer 20 Minuten. Nach Entfernung der Waschlauge wurde dreimal mit Wasser nachgespült und getrocknet. An den Gardinenbändern wurde die Veränderung des Zugwiderstandes, am Nesselgewebe die der Biegesteifigkeit und der Haft- beziehungsweise Gleitreibung nach jeweils 1 und 3 Waschbehandlungen (Abkürzung 1 W beziehungsweise 3 W) gemessen. Eine Erhöhung des Zugwiderstandes und der Biegesteifigkeit entspricht einer Gebrauchswerterhöhung; eine Erniedrigung der Haftreibung und Gleitreibung entspricht einer (erwünschten) Verbesserung der Oberflächenglätte. Die in der folgenden Tabelle aufgeführten Testergebnisse (angegeben in cN) belegen die Überlegenheit der erfindungsgemäßen Mittel.Curtain tape and bleaching nettle were used as textile material. The washing treatment was carried out in an automatic washing machine having a horizontally mounted drum at 40 O C ( "easy-care program"). The detergent concentration was 8.4 g / l, the liquor ratio (kg of laundry to liter of wash liquor) 1:20, the water hardness 16 ° dH and the washing time 20 minutes. After the wash liquor had been removed, it was rinsed three times with water and dried. The change in tensile resistance was measured on the curtain tapes, and the change in stiffness and static or sliding friction on the nettle fabric after 1 and 3 washing treatments (abbreviation 1 W and 3 W, respectively). An increase in tensile resistance and bending stiffness corresponds to an increase in use value; a reduction in static friction and sliding friction corresponds to a (desired) improvement in surface smoothness. The test results listed in the following table (given in cN) demonstrate the superiority of the agents according to the invention.

An Babywindeln aus veredelter Baumwolle, die in der gleichen Weise bei einer Waschtemperatur von 60 °C gewaschen wurden, war eine deutliche Abnahme der Oberflächenreibung bzw. der Haftreibung festzustellen.

Figure imgb0005
On baby diapers made from refined cotton, which were washed in the same way at a washing temperature of 60 ° C, there was a significant decrease in surface friction or static friction.
Figure imgb0005

Claims (6)

1. Appretierend wirkendes Textilwaschmittel mit einem Gehalt an nichtionischen und/oder zwitterionischen Tensiden, gekennzeichnet durch einen Gehalt von 0,5 bis 10 Gewichtsprozent an in Wasser löslichen, quartäre Ammoniumgruppen aufweisenden Aminoethern von Polysacchariden.1. Textile detergent with a finishing action, containing nonionic and / or zwitterionic surfactants, characterized by a content of 0.5 to 10 percent by weight of water-soluble amino ethers of polysaccharides containing quaternary ammonium groups. 2. Mittel nach Anspruch 1, gekennzeichnet durch einen Gehalt an quartäre Ammoniumgruppen aufweisenden Polygalactomannanethern mit einem Substitutionsgrad von 0,05 bis 0,2 Ethergruppen pro Anhydrogalactomannan-Einheit.2. Composition according to claim 1, characterized by a content of quaternary ammonium groups containing polygalactomannan ethers with a degree of substitution of 0.05 to 0.2 ether groups per anhydrogalactomannan unit. 3. Mittel nach Anspruch 1, gekennzeichnet durch einen Gehalt an quartäre Ammoniumgruppen aufweisenden Stärkeethern mit einem Substitutionsgrad von 0,05 bis 0,12 Ethergruppen pro Anhydroglucose-Einheit.3. Composition according to claim 1, characterized by a content of quaternary ammonium starch ethers with a degree of substitution of 0.05 to 0.12 ether groups per anhydroglucose unit. 4. Mittel nach Anspruch 1 bis 3, gekennzeichnet durch einen Gehalt an Ethern, erhältlich durch Umsetzung von Polygalactomannan (Guar) und/oder Stärke mit 2,3-Epoxypropyltrimethylammoniumsalzen.4. Composition according to claim 1 to 3, characterized by a content of ethers, obtainable by reacting polygalactomannan (guar) and / or starch with 2,3-epoxypropyltrimethylammonium salts. 5. Mittel nach Anspruch 1 bis 4, gekennzeichnet durch einen Gehalt von 1 bis 5 Gewichtsprozent an quartäre Ammoniumgruppen aufweisenden Ethern.5. Composition according to claim 1 to 4, characterized by a content of 1 to 5 percent by weight of quaternary ammonium-containing ethers. 6. Mittel nach Anspruch 1 bis 5, gekennzeichnet durch einen Gehalt an nichtionischen Tensiden von 1 bis 30 Gewichtsprozent.6. Composition according to claim 1 to 5, characterized by a content of nonionic surfactants from 1 to 30 percent by weight.
EP80101534A 1979-03-26 1980-03-24 Textile detergent acting as a finishing agent Expired EP0017120B2 (en)

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WO1987003682A1 (en) * 1985-12-03 1987-06-18 Hoffmann's Stärkefabriken Ag Laundry care product
US5150312A (en) * 1989-06-16 1992-09-22 International Business Machines Corporation Animation processor method and apparatus
EP0607529A2 (en) * 1993-01-20 1994-07-27 Hüls Aktiengesellschaft Aqeous softeners for the treatment of textiles
WO2005105965A1 (en) 2004-04-30 2005-11-10 Henkel Kommanditgesellschaft Auf Aktien Fabric care product containing a cellulose ether comprising amine groups
WO2009016060A1 (en) * 2007-07-31 2009-02-05 Henkel Ag & Co. Kgaa Textile care agent having cellulose ether comprising amine groups

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GB8334159D0 (en) * 1983-12-22 1984-02-01 Unilever Plc Perfume
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DE4411681A1 (en) * 1994-04-05 1995-10-12 Hoechst Ag Process for the preparation of low molecular weight polysaccharide ethers
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US6180582B1 (en) * 1997-09-26 2001-01-30 Colgate-Palmolive Co. Liquid cleaning compositions
GB2342358A (en) * 1998-10-09 2000-04-12 Procter & Gamble Detergent compositions comprising cationic polymers
US6281172B1 (en) 1999-04-07 2001-08-28 Akzo Nobel Nv Quaternary nitrogen containing amphoteric water soluble polymers and their use in drilling fluids
AU1152601A (en) * 1999-10-22 2001-05-08 Reckitt Benckiser France Compositions and their use
US6849586B2 (en) 2001-10-26 2005-02-01 S. C. Johnson & Son, Inc. Hard surface cleaners containing chitosan
US20060217287A1 (en) * 2005-03-22 2006-09-28 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Fabric softening composition
US20060223739A1 (en) * 2005-04-05 2006-10-05 Unilever Home And Personal Care Usa, Division Of Conopco, Inc. Fabric softening composition with cationic polymer, soap, and amphoteric surfactant
US10273434B2 (en) * 2010-06-18 2019-04-30 Rhodia Operations Protection of the color of textile fibers by means of cationic polysacchrides
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DE2911857A1 (en) 1980-10-16
ATE1248T1 (en) 1982-07-15
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EP0017120B2 (en) 1985-09-04
BR8001788A (en) 1980-11-18
US4289642A (en) 1981-09-15
EP0017120B1 (en) 1982-06-23

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