EP0160254A2 - Additive for a washing bath - Google Patents

Additive for a washing bath Download PDF

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Publication number
EP0160254A2
EP0160254A2 EP85104801A EP85104801A EP0160254A2 EP 0160254 A2 EP0160254 A2 EP 0160254A2 EP 85104801 A EP85104801 A EP 85104801A EP 85104801 A EP85104801 A EP 85104801A EP 0160254 A2 EP0160254 A2 EP 0160254A2
Authority
EP
European Patent Office
Prior art keywords
mixture
additive according
washing additive
washing
alcohol
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP85104801A
Other languages
German (de)
French (fr)
Other versions
EP0160254B1 (en
EP0160254A3 (en
Inventor
Heinz-Manfred Wilsberg
Rolf Dr. Puchta
Klaus Dr. Köster
Franz-Josef Dr. Carduck
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
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Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Priority to AT85104801T priority Critical patent/ATE36556T1/en
Publication of EP0160254A2 publication Critical patent/EP0160254A2/en
Publication of EP0160254A3 publication Critical patent/EP0160254A3/en
Application granted granted Critical
Publication of EP0160254B1 publication Critical patent/EP0160254B1/en
Expired legal-status Critical Current

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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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds
    • 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
    • C11D1/66—Non-ionic compounds
    • C11D1/835—Mixtures of non-ionic with cationic compounds
    • 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
    • C11D1/88—Ampholytes; Electroneutral compounds
    • C11D1/94—Mixtures with anionic, cationic or non-ionic compounds
    • 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
    • C11D17/042—Water soluble or water disintegrable containers or substrates containing cleaning compositions or additives for cleaning compositions
    • C11D17/043—Liquid or thixotropic (gel) compositions
    • 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
    • C11D1/02—Anionic compounds
    • C11D1/04—Carboxylic acids or salts thereof
    • C11D1/10—Amino carboxylic acids; Imino carboxylic acids; Fatty acid condensates thereof
    • 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
    • C11D1/42—Amino alcohols or amino ethers
    • C11D1/44—Ethers of polyoxyalkylenes with amino alcohols; Condensation products of epoxyalkanes with amines
    • 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
    • C11D1/62—Quaternary ammonium compounds
    • 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
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols

Definitions

  • the present invention relates to a washing additive which can be added to washing liquors to increase the washing effect.
  • the addition of the additive according to the invention improves the removal of bleachable soiling and of grease / oil and pigment soiling from the textiles to be washed.
  • the washing liquor When washing textiles, the washing liquor is generally heated to a temperature which is higher than room temperature. This measure significantly increases the washing performance of the detergents used. However, heating the washing liquor and the textiles is associated with increased energy expenditure during washing.
  • some textiles, in particular textiles made of wool or synthetic fibers cannot be washed at elevated temperature for various reasons, attempts have repeatedly been made to achieve good washing results when washing at low temperatures. At low washing temperatures, however, the effect of the per compounds frequently used to remove bleachable stains is in some cases considerably reduced or even weakened to the extent that such stains can no longer be removed. For this reason, detergents are added to increase the bleaching effect, so-called bleach activators, which increase the bleaching effect of the per compounds and allow the effect to be used even at lower washing temperatures.
  • DE-OS 27 44 642 describes a detergent additive which contains an organic bleach activator in water-releasable combination with a non-particulate substrate.
  • the detergent additive of DE-OS 27 44 642 can also contain other additives, such as. B.
  • foam modifiers By separating the bleach activator and the bleaching per-compound bi immediately before use, the problems that bj the joint storage of per-compounds and bleach activators can ent stand, be avoided.
  • a further improvement in the washing performance of detergents based on anionic surfactants and inorganic persalts is made possible by an additive which, according to the teaching of DE-OS 28 57 153, in addition to a bleach activator, is a combination of an alkoxylated nonionic surfactant and a cationic surfactant with 8 to 20 carbon atoms containing residue and otherwise short residues with 1 to 4 carbon atoms on a substrate.
  • a disadvantage of the additives mentioned is that the user of these additives comes into contact with the active ingredients when the additives are removed from the packaging and when the additives are added to the detergent liquor, which, apart from a sometimes unpleasant feeling, can lead to skin irritation.
  • Another disadvantage of the additives mentioned is that after washing, the water-insoluble substrate has to be sorted out from the washed textiles.
  • the aim of the present invention is therefore to provide a washing additive for increasing the washing performance of detergents, in which the user does not come into contact with the active ingredients of the additive and whose substrate does not need to be sorted out from the washed textiles after washing.
  • Addition products of ethylene oxide with fatty alcohols or, in particular, oxo alcohols, which have 12 to 18, preferably 14 to 15, carbon atoms are particularly suitable as nonionic surfactants.
  • the best effects are achieved with oxo alcohol ethoxylates which contain 3 to 10, preferably 6 to 8 and in particular about 7 moles of ethylene oxide per mole of alcohol.
  • foam regulators most of the time, the development of foam must be dampened.
  • Suitable foam suppressants are, for example, the known silicone oils.
  • the content of certain quaternary ammonium compounds and / or ethylene oxide adducts of primary fatty amines and / or of ⁇ -aminoalkyl / alkenyl-propionic acid salts of the formula R-NH-CH -CH is used in the agents according to the invention ⁇ COONa;
  • Suitable quaternary ammonium compounds contain as long-chain alkyl or alkenyl radical with 10 to 20, preferably alkyl groups with 10 to 16 and in particular about 14 carbon atoms.
  • the suitable quaternary ammonium compounds contain 3 of the same alkyl groups with 1 to 4 carbon atoms. In particular, these short alkyl groups are methyl groups.
  • a particularly suitable and therefore preferred quaternary ammonium compound is tetradecyltrimethylammonium bromide. All or part of the quaternary ammonium compound can be replaced by the above-mentioned fatty amine ethoxylate.
  • An example of a particularly suitable fatty amine ethoxylate is the adduct of 2 moles of ethylene oxide with primary coconut alkyl amine; this product is therefore also preferred.
  • N-acyl and 0-acyl compounds are suitable as activators for per compounds.
  • Acetyl compounds have proven particularly useful. Examples of this are tetraacetylglycoluril or pentaacetylglucose or in particular tetraacetylethylenediamine.
  • the bleach activators mentioned lead to improved removal of bleachable textile soiling.
  • the detergent additive according to the invention contains polyhydric alcohols which are able to prevent the known gelling of the nonionic surfactant on contact with water.
  • Suitable antigelling agents are preferably polyhydric alcohols having 2 to 4 carbon atoms, which are intimately mixed with the non-ionic surfactant.
  • the antigelling effect of the polyhydric alcohol can be enhanced if instead of the polyhydric alcohol alone a mixture of a polyhydric alcohol and condensation products of C10 to C20 fatty alcohols with 1 to 4 moles of ethylene oxide per mole of fatty alcohol is used.
  • Polyhydric alcohols which can be used as antigelling agents are, for example, 1,2-propylene glycol, ethylene glycol or glycerol or mixtures of the alcohols mentioned.
  • An example of a particularly suitable fatty alcohol ethoxylate which can be used in a mixture with the polyhydric alcohol to enhance the anti-gelling effect is tallow alcohol ethoxylate with 2 moles of ethylene oxide; but also C12 to C14 fatty alcohol ethoxylate with 3 moles of ethylene oxide, which contains approx. 70% C12 fatty alcohol ethoxylate, is suitable as an anti-gelling agent.
  • the antigelling effect of the antigelling agent can be increased further if, in addition to the antigelling agents described hitherto, compounds which are readily soluble in water, in particular sodium borate, sodium chloride, sodium sulfate, sodium acetate or else sugar, are used.
  • a viscosity of the bag contents in the range of 1,000 to 100,000 mPas is important for good dissolution behavior.
  • a number of different additives can be used as viscosity regulators, for example water-insoluble zeolite, in particular of the zeolite A type, highly disperse silica, sheet silicates, in particular swellable sheet silicates of the bentonite and hectorite type, but also water-soluble salts, and the like
  • Sugar, polyglycols or fatty alcohol ethoxylates with a high proportion of ethylene oxide A high proportion of ethylene oxide in fatty alcohol ethoxylates for the purposes of the present invention means that the fatty alcohol ethoxylate contains about 15 to 25 moles of ethylene oxide per mole of fatty alcohol.
  • the washing additive advantageously contains small amounts of chelating agents.
  • Water-soluble salts of alkane polyphosphonic acid from the group of the phosphonoalkane polycarboxylic acids and the amino and hydroxy-substituted alkane polyphosphonic acids, in particular the alkali salts of amino-tris (methylenephosphonic acid), dimethyleneaminomethane diphosphonic acids, 1-hydroxyethane-1,1-diphosphonic acid, 1-phosphonoethane-1,2-dicarboxylic acid, 2-phosphonobutane-1,2, 3-tricarboxylic acid and especially the hexasodium salt of ethylenediaminotetramethylenephosphonic acid.
  • a polyvinyl alcohol film which meets these requirements is the subject of EP-OS 79 712. According to the teaching of this patent application, are solved Films made of polyvinyl alcohol in borate-containing washing liquors quickly and completely if the polyvinyl alcohol has a molecular weight below about 50,000 and / or if the polyvinyl alcohol contains a polyhydroxy compound with a certain binding constant with borate and / or if the polyvinyl alcohol contains an acid with a certain dissociation constant.
  • the demand for rapid dissolution in washing liquors containing borate arises from the perborate usually used in detergents as a bleaching active ingredient.
  • a film with satisfactory dissolving properties consists of polyvinyl alcohol with a molecular weight of approximately 10,000.
  • the polyvinyl alcohol is 88% hydrolyzed and makes up 71% by weight of the film.
  • the film also contains small amounts of glycerin, trimethylolpropane, sorbitol and water.
  • the washing additive according to the invention is produced, for example, by heating the nonionic surfactant and mixing it with the foam inhibitor. When heated, the anti-gel agent and optionally the complexing agent are mixed in. The powdered viscosity regulators are then suspended with intensively acting mixing elements and the suspension is cooled. 14an receives a paste which is filled into a bag in an amount sufficient to increase the washing performance of commercially available detergents. The bags are closed by thermal welding or by moistening the edges with water and allowing them to dry while being compressed. A method of making the Washing additive is another object of the invention.
  • This process is characterized in that the nonionic surfactant, if appropriate, is heated together with the foam inhibitor to 40 to 75 ° C., the antigelling agent and, if appropriate, the complexing agent are mixed with it, the activator for per compounds, the quaternary ammonium compound and / or the amine derivative and / or the Compound of the formula R-NH-CH 2 -CH 2 -COONa together with the viscosity regulators while introducing high shear forces suspended in the premix, then cooled to room temperature and covered with a bag-like structure made of a film based on polyvinyl alcohol which is readily soluble in borate-containing aqueous solutions.
  • 35.9 g of this paste were in a bag (edge length 7.5 x 7.5 cm) made of a 65 ⁇ m thick film made of 71% by weight polyvinyl alcohol (molecular weight approx. 10,000, degree of hydrolysis 88%), 6% by weight glycerin, 6% by weight trimethylolpropane, 7.5% by weight sorbitol, balance water, filled; the bag was closed by thermal welding.
  • Bags produced in this way were used to determine the dissolution behavior and the detergent-increasing effect.
  • Example 1 Analogously to Example 1, an active substance paste was produced which additionally contained 0.720 kg of sorbitol, but no highly disperse silica and no sodium sulfate.
  • the dissolving behavior and the washing-strengthening effect of the paste filled into bags as in Example 1 corresponded the product of Example 1.
  • Example 1 A paste analogous to Example 1, which contained magnesium aluminum silicate (Veegum HV (R) ) in equal quantities instead of the polyethylene glycol and the highly disperse silica, showed a behavior analogous to that of Example 1.
  • magnesium aluminum silicate Veegum HV (R)
  • Example 6 is an example of a non-inventive paste. If a paste was only prepared from the nonionic surfactant, the quaternary ammonium compound, the activator for per compounds and the complexing agent and the foam regulator from Example 1, a paste was obtained which, upon contact with water, gelled to form a lump which did not separate within 15 minutes dissolved in the wash liquor.

Abstract

A washing additive consisting of a bag, filled with a detergent composition, of a polyvinyl-alcohol-based film readily soluble in borate-containing aqueous solutions. The detergent composition is a mixture of a nonionic surfactant, a quaternary ammonium compound containing a long-chain radical, which may be completely or partly replaced by a fatty amine ethoxylate or by a beta -aminoalkyl propionic acid derivative, an activator for per compound, an antigel agent, and a viscosity regulator, wherein the mixture has a viscosity of from 1000 to 100,000 mPas for a shear gradient of from 5 to 500 s-1.

Description

Die vorliegende Erfindung betrifft einen Waschzusatz, welcher Waschflotten zur Steigerung der Waschwirkung beigefügt werden kann. Durch den Zusatz des erfindungsgemäßen Additivs wird die Entfernung von bleichbaren Anschmutzungen sowie von Fett-/O1- und Pigmentschmutz aus den zu waschenden Textilien verbessert.The present invention relates to a washing additive which can be added to washing liquors to increase the washing effect. The addition of the additive according to the invention improves the removal of bleachable soiling and of grease / oil and pigment soiling from the textiles to be washed.

Beim Waschen von Textilien wird die Waschflotte im allgemeinen auf eine gegenüber Raumtemperatur erhöhte Temperatur erwärmt. Durch diese Maßnahme wird die Waschleistung der eingesetzten Waschmittel zum Teil erheblich verstärkt. Die Erwärmung der Waschflotte und der Textilien ist allerdings mit einem erhöhtem Energieaufwand beim Waschen verbunden. Da außerdem manche Textilien, insbesondere Textilien aus Wolle oder synthetischen Fasern aus verschiedenen Gründen bei erhöhter Temperatur nicht gewaschen werden können, sind immer wieder Versuche gemacht worden, gute Waschergebnisse beim Waschen mit niedrigen Temperaturen zu erreichen. Bei niedrigen Waschtemperaturen ist aber die Wirkung der zur Entfernung von bleichbaren Flecken häufig verwendeten Perverbindungen zum Teil erheblich verringert oder sogar soweit abgeschwächt, daß derartige Flecken nicht mehr entfernt werden. Aus diesem Grunde setzt man Waschmitteln zur Erhöhung der Bleichwir kung sogenannte Bleichaktivatoren zu, die die bleichende Wirkung der Perverbindungen verstärken und die Wirkung auch schon bei niedrigeren Waschtemperaturen einsetzen lassen. Die gleichzeitige Anwesenheit von Perverbindungen und Bleichaktivatoren in Waschmitteln verringert aber deren Lagerstabilität, insbesondere, wenn die Materialien während der Lagerung nicht vor Feuchtigkeit geschützt werden können. Versuche zur Verbesserung der Stabilität führten in der Regel zu einer beträchtlichen Verringerung der Bleichwirkung der Waschmittel. Es ist daher bereits vorgeschlagen worden, den Bleichaktivator getrennt von dem die Perverbindung enthaltenden Waschmittel zu lagern und wenigstens einen Teil des Aktivators erst unmittelbar vor Gebrauch der Waschflotte zuzusetzen. Die DE-OS 27 44 642 beschreibt zur Lösung dieses Problems ein Waschmittel-Additiv, das einen organischen Bleichaktivator in wasserfreisetzbarer Kombination mit einem nichtteilchenförmigen Substrat enthält. Außer dem Bleichaktivator und eventuellen Freisetzungshilfsmitteln kann das Waschmittel-Additiv der DE-OS 27 44 642 noch weitere Zusätze, wie z. B. Schaummodifikatoren, Chelat-bildende Mittel, Schmutzsuspendiermittel, optische Aufheller, Bakterizide, Antitrübungsmittel, Enzyme, Textilweichmacher, Duftstoffe enthalten. Durch die Trennung von Bleichaktivator und bleichender Perverbindung bi unmittelbar vor dem Gebrauch können die Proleme, die b j der gemeinsamen Lagerung von Perverbindungen und Bleich :tivatoren entstehen, vermieden werden. Eine weitere Verbesserung der Waschleistung von Waschmitteln auf Basis von Aniontensiden und anorganischen Persalzen ermöglicht ein Additiv, das nach der Lehre der DE-OS 28 57 153 zusätzlich zu einem Bleichaktivator eine Kombination aus einem alkoxylierten nichtionischen Tensid und einem kationischen Tensid mit einem 8 bis 20 Kohlenstoffatome enthaltenden Rest und im übrigen kurzen Resten mit 1 bis 4 Kohlenstoffatomen auf einem Substrat enthält. Ein Nachteil der genannten Additive besteht aber darin, daß der Verwender dieser Additive beim Entnehmen der Additive aus der Verpackung und beim Zusetzen der Additive zu der Waschmittelflotte mit den Wirkstoffen in Berührung kommt, was abgesehen von einem teilweise unangenehmen Gefühl zu Hautirritationen führen kann. Ein weiterer Nachteil der genannten Additve besteht darin, daß nach der Wäsche das wasserunlösliche Substrat aus den gewaschenen Textilien aussortiert werden muß.When washing textiles, the washing liquor is generally heated to a temperature which is higher than room temperature. This measure significantly increases the washing performance of the detergents used. However, heating the washing liquor and the textiles is associated with increased energy expenditure during washing. In addition, since some textiles, in particular textiles made of wool or synthetic fibers, cannot be washed at elevated temperature for various reasons, attempts have repeatedly been made to achieve good washing results when washing at low temperatures. At low washing temperatures, however, the effect of the per compounds frequently used to remove bleachable stains is in some cases considerably reduced or even weakened to the extent that such stains can no longer be removed. For this reason, detergents are added to increase the bleaching effect, so-called bleach activators, which increase the bleaching effect of the per compounds and allow the effect to be used even at lower washing temperatures. However, the simultaneous presence of per compounds and bleach activators in detergents reduces their storage stability, especially if the materials cannot be protected from moisture during storage. Attempts to improve the stability have generally led to a considerable reduction in the bleaching action of the detergents. It has therefore already been proposed to store the bleach activator separately from the detergent containing the per-compound and to add at least part of the activator to the wash liquor only immediately before use. To solve this problem, DE-OS 27 44 642 describes a detergent additive which contains an organic bleach activator in water-releasable combination with a non-particulate substrate. In addition to the bleach activator and any release aids, the detergent additive of DE-OS 27 44 642 can also contain other additives, such as. B. foam modifiers, chelating agents, soil suspending agents, optical brighteners, bactericides, anti-opacifiers, enzymes, fabric softeners, fragrances. By separating the bleach activator and the bleaching per-compound bi immediately before use, the problems that bj the joint storage of per-compounds and bleach activators can ent stand, be avoided. A further improvement in the washing performance of detergents based on anionic surfactants and inorganic persalts is made possible by an additive which, according to the teaching of DE-OS 28 57 153, in addition to a bleach activator, is a combination of an alkoxylated nonionic surfactant and a cationic surfactant with 8 to 20 carbon atoms containing residue and otherwise short residues with 1 to 4 carbon atoms on a substrate. A disadvantage of the additives mentioned, however, is that the user of these additives comes into contact with the active ingredients when the additives are removed from the packaging and when the additives are added to the detergent liquor, which, apart from a sometimes unpleasant feeling, can lead to skin irritation. Another disadvantage of the additives mentioned is that after washing, the water-insoluble substrate has to be sorted out from the washed textiles.

Ziel der vorliegenden Erfindung ist daher, einen Waschzusatz zur Verstärkung der Waschleistung von Waschmitteln zur Verfügung zu stellen, bei dem der Benutzer nicht mit den Wirkstoffen des Additivs in Berührung kommt und dessen Substrat nach der Wäsche aus den gewaschenen Textilien nicht aussortiert zu werden braucht.The aim of the present invention is therefore to provide a washing additive for increasing the washing performance of detergents, in which the user does not come into contact with the active ingredients of the additive and whose substrate does not need to be sorted out from the washed textiles after washing.

Der Waschzusatz nach der vorliegenden Erfindung umfaßt daher

  • a) ein Gemisch aus mehreren Waschmittelbestandteilen,
  • b) ein a) umhüllendes beutelartiges Gebilde aus einer in borathaltigen wäßrigen Lösungen leicht löslichen Folie auf Basis von Polyvinylalkohol,

das dadurch gekennzeichnet ist, daß das Gemisch a) wenigstens ein nichtionisches Tensid, eine quartäre Ammoniumverbindung mit einem langkettigen Alkyl- oder Alkenylrest mit 10 bis 18 Kohlenstoffatomen und im übrigen Alkylresten mit 1 bis 4 Kohlenstoffatomen und/oder ein Anlagerungsprodukt von 1 bis 6 Mol Ethylenoxid an 1 Mol eines primären Fettamins mit einem langkettigen Alkyl-oder Alkenylrest mit 10 bis 18 Kohlenstoffatomen und/oder eine Verbindung der Formel R-NH-CH 2 -CH2-CO0Na, in der R einen Alkyl- oder einen Alkenylrest mit 10 bis 18 Kohlenstoffatomen, insbesondere mit 14 Kohlenstoffatomen bedeutet, einen Aktivator für Perverbindungen und einen mehrwertigen Alkohol als Antigelmittel enthält und soviel an Viskositätsregulator enthält, daß es eine Viskosität von 1 000 bis 100 000 mPas aufweist.The washing additive according to the present invention therefore comprises
  • a) a mixture of several detergent components,
  • b) an a) enveloping bag-like structure made of a film based on polyvinyl alcohol which is readily soluble in borate-containing aqueous solutions,

which is characterized in that the mixture a) at least one nonionic surfactant, a quaternary ammonium compound with a long-chain alkyl or alkenyl radical having 10 to 18 carbon atoms and otherwise alkyl radicals with 1 to 4 carbon atoms and / or an adduct of 1 to 6 moles of ethylene oxide 1 mol of a primary fatty amine with a long-chain alkyl or alkenyl radical having 10 to 18 carbon atoms and / or a compound of the formula R-NH-CH 2 -CH 2 -CO0Na, in which R is an alkyl or an alkenyl radical with 10 to 18 Carbon atoms, in particular with 14 carbon atoms, contains an activator for per compounds and a polyhydric alcohol as an anti-gel agent and contains so much viscosity regulator that it has a viscosity of 1,000 to 100,000 mPas.

Als nichtionische Tenside kommen vor allem Anlagerungsprodukte von Ethylenoxid an Fett- oder insbesondere Oxoalkohole infrage, die 12 bis 18, vorzugsweise 14 bis 15 Kohlenstoffatome aufweisen. Die besten Wirkungen erzielt man mit Oxoalkohol-Ethoxylaten, die 3 bis 10, vorzugsweise 6 bis 8 und insbesondere etwa 7 Mol Ethylenoxid pro Mol Alkohol enthalten. In vielen Fällen ist es zweckmäßig, Schaumregulatoren zuzusetzen; meistens muß die Schaumentwicklung gedämpft werden. Geeignete Schaumdämpfungsmittel sind beispielsweise die bekannten Silikonöle. Durch den Gehalt der erfindungsgemäßen Waschzusätze an nichtionischen Tensiden und vor allem die Entfernung von fett- oder ölartigen erschmutzungen beim Waschen gefördert.Addition products of ethylene oxide with fatty alcohols or, in particular, oxo alcohols, which have 12 to 18, preferably 14 to 15, carbon atoms are particularly suitable as nonionic surfactants. The best effects are achieved with oxo alcohol ethoxylates which contain 3 to 10, preferably 6 to 8 and in particular about 7 moles of ethylene oxide per mole of alcohol. In many cases it is advisable to add foam regulators; most of the time, the development of foam must be dampened. Suitable foam suppressants are, for example, the known silicone oils. The content of nonionic surfactants in the washing additives according to the invention and, above all, the removal of greasy or oily soiling during washing promoted.

Der Verbesserung der Entfernung von Pigmentverschmutzungen aus Textilien dient der Gehalt der erfindungsgemäßen Mittel an bestimmten quartären Ammoniumverbindungen und/oder Ethylenoxid-Addukten von primären Fettaminen und/oder von ß-Aminoalkyl-/alkenyl-propionsäure-Salzen der Formel R-NH-CH -CH―COONa; Geeignete quartäre Ammoniumverbindungen enthalten als langkettigen Alkyl- oder Alkenylrest mit 10 bis 20, vorzugsweise Alkylgruppen mit 10 bis 16 und insbesondere etwa 14 Kohlenstoffatomen. Im übrigen enthalten die geeigneten quartären Ammoniumverbindungen 3 gleiche der verschiedenen Alkylgruppen mit 1 bis 4 Kohlenstoffatomen. Insbesondere handelt es sich bei diesen kurzen Alkylgruppen um Methylgruppen. Eine besonders gut geeignete und daher bevorzugte quartäre Ammoniumverbindung ist Tetradecyltrimethylammoniumbromid. Die quartäre Ammoniumverbindung kann ganz oder teilweise durch das oben genannte Fettamin-Ethoxylat ersetzt werden. Ein Beispiel für ein besonders gut geeignetes Fettamin-Ethoxylat ist das Anlagerungsprodukt von 2 Mol Ethylenoxid an primäres Kokosalkylamin; dieses Produkt ist daher ebenfalls bevorzugt.To improve the removal of pigment soiling from textiles, the content of certain quaternary ammonium compounds and / or ethylene oxide adducts of primary fatty amines and / or of β-aminoalkyl / alkenyl-propionic acid salts of the formula R-NH-CH -CH is used in the agents according to the invention ―COONa; Suitable quaternary ammonium compounds contain as long-chain alkyl or alkenyl radical with 10 to 20, preferably alkyl groups with 10 to 16 and in particular about 14 carbon atoms. In addition, the suitable quaternary ammonium compounds contain 3 of the same alkyl groups with 1 to 4 carbon atoms. In particular, these short alkyl groups are methyl groups. A particularly suitable and therefore preferred quaternary ammonium compound is tetradecyltrimethylammonium bromide. All or part of the quaternary ammonium compound can be replaced by the above-mentioned fatty amine ethoxylate. An example of a particularly suitable fatty amine ethoxylate is the adduct of 2 moles of ethylene oxide with primary coconut alkyl amine; this product is therefore also preferred.

Als Aktivator für Perverbindungen sind N-Acyl- und 0-Acylverbindungen geeignet. Besonders bewährt haben sich Acetylverbindungen. Beispiele hierfür sind Tetraacetylglykoluril bzw. Pentaacetylglucose bzw. insbesondere Tetraacetylethylendiamin. In Verbindung mit Perverbindungen der gebräuchlichen Vollwaschmittel, insbesondere mit dem üblicherweise verwendeten Perborat, führen die genannten Bleichaktivatoren zu einer verbesserten Entfernung bleichbarer Textilverschmutzungen.N-acyl and 0-acyl compounds are suitable as activators for per compounds. Acetyl compounds have proven particularly useful. Examples of this are tetraacetylglycoluril or pentaacetylglucose or in particular tetraacetylethylenediamine. In conjunction with per compounds of the common heavy-duty detergents, in particular with the perborate that is usually used, the bleach activators mentioned lead to improved removal of bleachable textile soiling.

Als Antigelmittel enthält das erfindungsgemäße Waschmittel-Additiv mehrwertige Alkohole, die in der Lage sind, das bekannte Gelieren des nichtionischen Tensids bei Kontakt mit Wasser zu verhindern. Geeignete Antigelmittel sind vorzugsweise mehrwertige Alkohole mit 2 bis 4 Kohlenstoffatomen, die mit dem nichtonischen Tensid innig vermischt werden. Die antigelierende Wirkung des mehrwertigen Alkohols kann noch verstärkt werden, wenn man statt des mehrwertigen Alkohols allein ein Gemisch aus einem mehrwertigen Alkohol und Kondensationsprodukten von C10- bis C20-Fettalkoholen mit 1 bis 4 Mol Ethylenoxid pro Mol Fettalkohol einsetzt. Als Antigeliermittel verwendbare mehrwertige Alkohole sind beispielsweise 1,2-Propylenglykol, Ethylenglykol oder Glycerin oder Mischungen der genannten Alkohole. Ein Beispiel für ein besonders geeignetes Fettalkoholethoxylat, das im Gemisch mit dem mehrwertigen Alkohol zur Verstärkung der Antigelierwirkung verwendet werden kann, ist Talgalkoholethoxylat mit 2 Mol Ethylenoxid; aber auch C12- bis C14-Fettalkoholtethoxylat mit 3 Mol Ethylenoxid, das ca. 70 % C12-Fettalkolol ethoxylat enthält, ist als Antigeliermittel geeignet. Wird ausschließlich ein mehrwertiger Alkohol als Intigeliermittel eingesetzt, erhält man eine gute Antigeliderwirkung, wenn das Gewichtsverhältnis von nichtionischem Tensid zu mehrwertigem Alkohol im Bereich von etwa 1 : 1 bis 1 : 2 liegt. Setzt man dagegen ein Gemisch aus rehrwertigem Alkohol und Fettalkoholethoxylat ein, erhalt man sehr gute Ergebnisse, wenn das Gewichtsverhältnis von nichtionischem Tensid zu mehrwertigem Alkohol zu Fettalkoholethoxylat im Bereich von (7 bis 12) zu (5 bis 16) zu (0,5 bis 4) liegt. Die antigelierende Wirkung des Antigelmittels kann noch gesteigert werden, wenn man zu den bisher beschriebenen Antigeliermitteln zusätzlich in Wasser leicht lösliche Verbindungen, insbesondere Natriumborat, Natriumchlorid, Natriumsulfat, Natriumacetat oder auch Zucker verwendet. Wichtig für ein gutes Auflöseverhalten ist eine Viskosität des Beutelinhalts im Bereich von 1 000 bis 100 000 mPas. Zur Einstellung einer Viskosität in dem genannten Bereich kann eine Reihe unterschiedlicher Zusätze als Viskositätsregulatoren verwendet werden, beispielsweise wasserunlöslicher Zeolith, insbesondere vom Typ Zeolith A, hochdisperse Kieselsäure, Schichtsilikate, insbesondere quellfähige Schichtsilikate vom Typ des Bentonits und des Hectorits, aber auch wasserlösliche Salze, sowie Zucker, Polyglykole oder Fettalkoholethoxylate mit einem hohen Anteil an Ethylenoxid. Ein hoher Anteil an Ethylenoxid in Fettalkoholethoxylaten im Sinne der vorliegenden Erfindung bedeutet, daß das Fettalkoholethoxylat pro Mol Fettalkohol etwa 15 bis 25 Mol Ethylenoxid enthält.As an anti-gel agent, the detergent additive according to the invention contains polyhydric alcohols which are able to prevent the known gelling of the nonionic surfactant on contact with water. Suitable antigelling agents are preferably polyhydric alcohols having 2 to 4 carbon atoms, which are intimately mixed with the non-ionic surfactant. The antigelling effect of the polyhydric alcohol can be enhanced if instead of the polyhydric alcohol alone a mixture of a polyhydric alcohol and condensation products of C10 to C20 fatty alcohols with 1 to 4 moles of ethylene oxide per mole of fatty alcohol is used. Polyhydric alcohols which can be used as antigelling agents are, for example, 1,2-propylene glycol, ethylene glycol or glycerol or mixtures of the alcohols mentioned. An example of a particularly suitable fatty alcohol ethoxylate which can be used in a mixture with the polyhydric alcohol to enhance the anti-gelling effect is tallow alcohol ethoxylate with 2 moles of ethylene oxide; but also C12 to C14 fatty alcohol ethoxylate with 3 moles of ethylene oxide, which contains approx. 70% C12 fatty alcohol ethoxylate, is suitable as an anti-gelling agent. If only a polyhydric alcohol is used as an intigelling agent, a good anti-gelation effect is obtained if the weight ratio of nonionic surfactant to polyhydric alcohol is in the range from about 1: 1 to 1: 2. On the other hand, if you use a mixture of pure alcohol and fatty alcohol ethoxylate, you get very good results if the weight ratio of nonionic surfactant to polyhydric alcohol to fatty alcohol ethoxylate is in the range from (7 to 12) to (5 to 16) to (0.5 to 4). The antigelling effect of the antigelling agent can be increased further if, in addition to the antigelling agents described hitherto, compounds which are readily soluble in water, in particular sodium borate, sodium chloride, sodium sulfate, sodium acetate or else sugar, are used. A viscosity of the bag contents in the range of 1,000 to 100,000 mPas is important for good dissolution behavior. To set a viscosity in the range mentioned, a number of different additives can be used as viscosity regulators, for example water-insoluble zeolite, in particular of the zeolite A type, highly disperse silica, sheet silicates, in particular swellable sheet silicates of the bentonite and hectorite type, but also water-soluble salts, and the like Sugar, polyglycols or fatty alcohol ethoxylates with a high proportion of ethylene oxide. A high proportion of ethylene oxide in fatty alcohol ethoxylates for the purposes of the present invention means that the fatty alcohol ethoxylate contains about 15 to 25 moles of ethylene oxide per mole of fatty alcohol.

Zur Komplexierung von störenden Schwermetallionen enthält der Waschzusatz zweckmäßigerweise geringe Mengen von Chelatbildnern. Besonders geeignet haben sich hierfür wasserlösliche Salze von Alkanpolyphosphonsäure aus der Gruppe der Phosphonoalkanpolycarbonsäuren und der amino-und hydroxysubstituierten Alkanpolyphosphonsäuren, insbesondere die Alkalisalze der Amino-tris-(methylen- phosphonsäure), Dimethylenaminomethandiphosphonsäuren, 1-Hydroxyethan-1,1-diphosphonsäure, 1-Phosphono- ethan-1,2-dicarbonsäure, 2-Phosphonobutan-1,2,3-tricarbonsäure und insbesondere das Hexanatriumsalz der Ethylendiaminotetramethylenphosphonsäure.In order to complex disruptive heavy metal ions, the washing additive advantageously contains small amounts of chelating agents. Water-soluble salts of alkane polyphosphonic acid from the group of the phosphonoalkane polycarboxylic acids and the amino and hydroxy-substituted alkane polyphosphonic acids, in particular the alkali salts of amino-tris (methylenephosphonic acid), dimethyleneaminomethane diphosphonic acids, 1-hydroxyethane-1,1-diphosphonic acid, 1-phosphonoethane-1,2-dicarboxylic acid, 2-phosphonobutane-1,2, 3-tricarboxylic acid and especially the hexasodium salt of ethylenediaminotetramethylenephosphonic acid.

Erfindungsgemäße Waschzusätze enthalten in wasserlöslichen Beuteln dickflüssige bis pastöse Gemische folgender Wirkstoffe:

  • 2 bis 30 Gew.-Teile nichtionisches Tensid,
  • 0,5 bis 10 Gew.-Teile quartäre Ammoniumverbindung und/oder Fettaminderivat und/oder eine Verbindung der Formel R-NH-CH2-CH2-COONa,
  • 2 bis 30 Gew.-Teile Aktivatör für Perverbindungen,
  • 0 bis 5 Gew.-Teile Schwermetallkomplexbildner. Hinzu kommen
  • 2 bis 50 Gew.-Teile Antigelmittel,
  • 5 bis 20 Gew.-Teile Viskositätsregulatoren,
  • Rest Gew.-Teile schaumregulierende Mittel, Farbstoffe in geringen Mengen.
Washing additives according to the invention contain viscous to pasty mixtures of the following active ingredients in water-soluble bags:
  • 2 to 30 parts by weight of nonionic surfactant,
  • 0.5 to 10 parts by weight of quaternary ammonium compound and / or fatty amine derivative and / or a compound of the formula R-NH-CH 2 -CH 2 -COONa,
  • 2 to 30 parts by weight of activator for per compounds,
  • 0 to 5 parts by weight of heavy metal complexing agents. Add to that
  • 2 to 50 parts by weight of anti-gel agent,
  • 5 to 20 parts by weight of viscosity regulators,
  • Remaining parts by weight of foam-regulating agents, dyes in small quantities.

Die genannten Wirkstoff-Kombination wird von einem Beutel aus wasserlöslicher Folie auf Basis von Polyvinylalkohol umhüllt. Damit sich der Beutel in der Waschmaschine beim Waschen, insbesondere beim Waschen mit kurzem Flottenverhältnis (= Verhältnis von Wäsche zu Wasser), schnell und vollständig auflöst, werden an das Beutelmaterial besondere Anforderungen gestellt. Eine Polyvinylalkohol-Folie, die diesen Anforderungen genügt, ist Gegenstand der EP-OS 79 712. Nach der Lehre dieser Patentanmeldung lösen sich Folien aus Polyvinylalkohol in borathaltigen Waschflotten schnell und vollständig, wenn der Polyvinylalkohol ein Molgewicht unterhalb etwa 50 000 hat und/oder wenn der Polyvinylalkohol eine Polyhydroxyverbindung mit einer bestimmten Bindungskonstanten mit Borat enthält und/oder wenn der Polyvinylalkohol eine Säure mit einer bestimmten Dissoziationskonstanten enthält. Die Forderung nach schneller Auflösung in borathaltigen Waschflotten ergibt sich aus dem üblicherweise in Waschmitteln verwendeten Perborat als bleichendem Wirkstoff.The active ingredient combination mentioned is enveloped in a bag made of water-soluble film based on polyvinyl alcohol. So that the bag in the washing machine dissolves quickly and completely during washing, especially when washing with a short liquor ratio (= ratio of laundry to water), special requirements are placed on the bag material. A polyvinyl alcohol film which meets these requirements is the subject of EP-OS 79 712. According to the teaching of this patent application, are solved Films made of polyvinyl alcohol in borate-containing washing liquors quickly and completely if the polyvinyl alcohol has a molecular weight below about 50,000 and / or if the polyvinyl alcohol contains a polyhydroxy compound with a certain binding constant with borate and / or if the polyvinyl alcohol contains an acid with a certain dissociation constant. The demand for rapid dissolution in washing liquors containing borate arises from the perborate usually used in detergents as a bleaching active ingredient.

Eine Folie mit zufriedenstellenden Löseeigenschaften besteht aus Polyvinylalkohol mit einem Molgewicht von ca. 10 000. Der Polyvinylalkohol ist zu 88 % hydrolysiert und macht 71 Gew.-% der Folie aus. Zusätzlich enthält die Folie Glycerin, Trimethylolpropan, Sorbit und Wasser in geringen Mengen.A film with satisfactory dissolving properties consists of polyvinyl alcohol with a molecular weight of approximately 10,000. The polyvinyl alcohol is 88% hydrolyzed and makes up 71% by weight of the film. The film also contains small amounts of glycerin, trimethylolpropane, sorbitol and water.

Die Herstellung des erfindungsgemäßen Waschzusatzes erfolgt beispielsweise, indem man das nichtionische Tensid erwärmt und mit dem Schauminhibitor vermischt. In erwärmtem Zustand mischt man das Antigelmittel und gegebenenfalls den Komplexbildner ein. Anschließend suspendiert man mit intensiv wirkenden Mischorganen die pulverförmigen Viskositätsregulatoren und kühlt die Suspension ab. 14an erhält eine Paste, die man in einen Beutel in einer Menge füllt, die für die Steigerung der Waschleistung von handelsüblichen Waschmitteln ausreicht. Die Beutel verschließt man durch thermisches Verschweißen oder durch Befeuchten der Kanten mit Wasser und trocknen lassen unter Zusammendrücken. Ein Verfahren zur Herstellung des Waschzusatzes ist ein weiterer Gegenstand der Erfindung.The washing additive according to the invention is produced, for example, by heating the nonionic surfactant and mixing it with the foam inhibitor. When heated, the anti-gel agent and optionally the complexing agent are mixed in. The powdered viscosity regulators are then suspended with intensively acting mixing elements and the suspension is cooled. 14an receives a paste which is filled into a bag in an amount sufficient to increase the washing performance of commercially available detergents. The bags are closed by thermal welding or by moistening the edges with water and allowing them to dry while being compressed. A method of making the Washing additive is another object of the invention.

Dieses Verfahren ist dadurch gekennzeichnet, daß man das nichtionische Tensid gegebenenfalls zusammen mit dem Schauminhibitor auf 40 bis 75 °C erwärmt, das Antigelmittel und gegebenenfalls den Komplexbildner damit vermischt, den Aktivator für Perverbindungen, die quartäre Ammoniumverbindung und/oder das Aminderivat und/oder die Verbindung der Formel R-NH-CH2-CH2-COONa zusammen mit den Viskositätsregulatoren unter Einleiten hoher Scherkräfte in dem Vorgemisch suspendiert, anschließend auf Raumtemperatur abkühlt und mit einem beutelartigen Gebilde aus einer in borathaltigen wäßrigen Lösungen leichtlöslichen Folie auf Basis von Polyvinylalkohol umhüllt.This process is characterized in that the nonionic surfactant, if appropriate, is heated together with the foam inhibitor to 40 to 75 ° C., the antigelling agent and, if appropriate, the complexing agent are mixed with it, the activator for per compounds, the quaternary ammonium compound and / or the amine derivative and / or the Compound of the formula R-NH-CH 2 -CH 2 -COONa together with the viscosity regulators while introducing high shear forces suspended in the premix, then cooled to room temperature and covered with a bag-like structure made of a film based on polyvinyl alcohol which is readily soluble in borate-containing aqueous solutions.

BEISPIELEEXAMPLES

Die folgenden Beispiele 1 bis 5 beschreiben die Zusammensetzung und die Herstellung von erfindungsgemäßen Waschzusätzen.The following Examples 1 to 5 describe the composition and the preparation of washing additives according to the invention.

Beispiel 1example 1

1,35 kg C14-/C15-0xoalkohol + 7 Mol Ethylenoxid wurden mit 0,077 kg schauminhibierendem Siliconöl unter Erwärmen vermischt. Zu dieser Mischung wurden 0,483 kg Propylenglykol-1,2, 0,483 kg Glycerin und 0,133 kg Oleyl-/Cetylalkohol + 2 Mol Ethylenoxid hinzugegeben und auf 60 °C erwärmt. Nach der Homogenisierung wurden 0,720 kg Polyethylenglykol (Molgewicht ca. 4 000) in fester Form zugesetzt und in dem Gemisch aufgeschmolzen. Hierzu fügte man 0,315 kg des Hexanatriumsalzes von Ethylendiamintetramethylenphosphonat als 50 gew.-%ige wäßrige Lösung. Mit einer Dissolverscheibe wurden dann 0,483 kg Tetradecyltrimethylammoniumbromid, 1,253 kg Tetraacetylethylendiamin, 0,238 kg hochdisperse Kieselsäure und 1,463 kg Natriumsulfat in dem erhaltenen flüssigen Gemisch suspendiert und die Suspension in einer Zahnkolloidmühle naß vermahlen. Nach dem Abkühlen auf 30 bis 35 °C erhielt man eine paste mit einer Dichte von 1,29 g/cm3 und einer Viskosität (nach DIN 114, Contraves-Rotatlonsviskosimeter) von 65 000 mPas (Schergefälle D = 5,6 s-1 ) bzw.1.35 kg of C14 / C15-0xoalcohol + 7 moles of ethylene oxide were mixed with 0.077 kg of foam-inhibiting silicone oil while heating. 0.483 kg of 1,2-propylene glycol, 0.483 kg of glycerol and 0.133 kg of oleyl / cetyl alcohol + 2 moles of ethylene oxide were added to this mixture and heated to 60.degree. After homogenization, 0.720 kg of polyethylene glycol (molecular weight approx. 4,000) was added in solid form and melted in the mixture. For this, 0.315 kg of the hexasodium salt of ethylenediaminetetramethylenephosphonate was added as a 50% strength by weight aqueous solution. 0.483 kg of tetradecyltrimethylammonium bromide, 1.253 kg of tetraacetylethylene diamine, 0.238 kg of highly disperse silica and 1.463 kg of sodium sulfate were then suspended in the liquid mixture obtained with a dissolver disc and the suspension was wet-ground in a toothed colloid mill. After cooling to 30 to 35 ° C., a paste with a density of 1.29 g / cm 3 and a viscosity (according to DIN 114, Contraves Rotatlon viscometer) of 65,000 mPas (shear rate D = 5.6 s -1) was obtained ) respectively.

6 200 mPas (D = 500 s-1).6,200 mPas (D = 500 s -1 ).

35,9 g dieser Paste wurden in einem Beutel (Kantenlänge 7,5 x 7,5 cm) aus einer 65 µm dicken Folie aus 71 Gew.-% Polyvinylalkohol (Molgewicht ca. 10 000, Hydrolysegrad 88 %), 6 Gew.-% Glycerin, 6 Gew.-% Trimethylolpropan, 7,5 Gew.-% Sorbit, Rest Wasser, gefüllt; durch thermisches Verschweißen wurde der Beutel geschlossen.35.9 g of this paste were in a bag (edge length 7.5 x 7.5 cm) made of a 65 µm thick film made of 71% by weight polyvinyl alcohol (molecular weight approx. 10,000, degree of hydrolysis 88%), 6% by weight glycerin, 6% by weight trimethylolpropane, 7.5% by weight sorbitol, balance water, filled; the bag was closed by thermal welding.

So hergestellte Beutel wurden zur Bestimmung des Auflöseverhaltens und der waschkraftsteigernden Wirkung verwendet.Bags produced in this way were used to determine the dissolution behavior and the detergent-increasing effect.

Zur Prüfung des Auflöseverhaltens wurde ein Beutel zusammen mit Textilien in einen Waschautomaten (Typ Miele De Luxe W 433) gegeben, bei 30 °C gewaschen und nach 5, 10 und 15 Minuten Waschdauer geprüft, ob noch Rückstände des Waschzusatzes an den Waschmaschinenteilen, die mit der Waschflotte in Berührung kommen, bzw. ob Reste des Waschzusatzes in der Wäsche festgestellt werden können. Dieser Versuch wurde 25 mal durchgeführt. In 19 Fällen wurden bereits nach 5 Minuten keine Rückstände mehr festgestellt, nach weiteren 5 Minuten waren in 24 von 25 Versuchen keine Rückstände mehr feststellbar und nach insgesamt 15 Minuten waren die Waschzusätze in allen Fällen vollständig aufgelöst. Verwendete man keine oder nicht erfindungsgemäße Antigelmittel, waren stets Rückstände des Beutelinhalts oder sogar der gesamte Beutelinhalt an den Maschinenteilen und/oder auf der Wäsche feststellbar. Der erfindungsgemäße Waschzusatz löste sich bei höheren Wassertemperaturen als 30 °C noch schneller auf.To test the dissolution behavior, a bag was placed together with textiles in an automatic washing machine (type Miele De Luxe W 433), washed at 30 ° C and after 5, 10 and 15 minutes of washing, it was checked whether residues of the washing additive on the washing machine parts containing the come into contact with the washing liquor or whether residues of the washing additive can be found in the laundry. This experiment was carried out 25 times. In 19 cases no residues were found after only 5 minutes, after a further 5 minutes no residues were detectable in 24 of 25 experiments and after a total of 15 minutes the washing additives were completely dissolved in all cases. If no or no anti-gel agents according to the invention were used, residues of the contents of the bag or even the entire contents of the bags were always found on the machine parts and / or on the laundry. The washing additive according to the invention dissolved even faster at water temperatures higher than 30 ° C.

Zur Prüfung der Waschkraftverbesserung durch den erfindungsgemäßen Waschzusatz wurden in einem Waschautomaten (Miele De Luxe W 433) mit Pigmentschutz, mit 01/Fett und bleichbaren Anschmutzungen angeschmutzte Prüftextilien bei 60 °C zusammen mit 3 kg sauberer Füllwäsche und einem Waschzusatz nach Beispiel 1 30 Minuten lang gewaschen. Als Waschmittel wurde ein Billigwaschmittel mit 2/3 Soll-Dosierung verwendet. Es wurde eine sehr deutliche Entfernung der Anschmutzungen festgestellt, die derjenigen entsprach, die man enthielt, wenn man ein handelsübliches Waschkraftverstärkertuch, das die Wirkstoffe auf seiner Oberfläche trug und nach dem Waschen aus der Wäsche aussortiert werden mußte, verwendete.To test the improvement in washing power by the washing additive according to the invention, in an automatic washing machine (Miele De Luxe W 433) with pigment protection, with 01 / fat and bleachable soils soiled test textiles at 60 ° C together with 3 kg of clean laundry and a washing additive according to Example 1 for 30 minutes. A cheap detergent with 2/3 target dosage was used as the detergent. A very clear removal of the soiling was found, which corresponded to that which was present when using a commercially available detergent intensifier cloth which carried the active ingredients on its surface and had to be removed from the laundry after washing.

Beispiel 2Example 2

Analog Beispiel 1 wurde eine Wirkstoffpaste hergestellt, die zusätzlich 0,720 kg Sorbit, aber keine hochdisperse Kieselsäure und kein Natriumsulfat enthielt. Auf das in Beispiel 1 beschriebene Naßvermahlen wurde bei diesem Beispiel verzichtet. Die Paste hatte nach dem Abkühlen auf 27 °C eine Viskosität von 80 000 mPas (D = 5,6 s die durch eine Scherbelastung auf niedrigere Werte reduziert werden konnte. Das Auflöseverhalten und die waschkraftverstärkende Wirkung der wie in Beispiel 1 in Beutel abgefüllten Paste entsprach dem Produkt von Beispiel 1.Analogously to Example 1, an active substance paste was produced which additionally contained 0.720 kg of sorbitol, but no highly disperse silica and no sodium sulfate. The wet grinding described in Example 1 was dispensed with in this example. After cooling to 27 ° C., the paste had a viscosity of 80,000 mPas (D = 5.6 s, which could be reduced to lower values by a shear stress. The dissolving behavior and the washing-strengthening effect of the paste filled into bags as in Example 1 corresponded the product of Example 1.

Beispiel 3Example 3

Eine Paste analog Beispiel 1, die statt des Polyethylenglykols und der hochdispersen Kieselsäure mengengleich Magnesiumaluminiumsilikat (Veegum HV(R)) enthielt, zeigte ein der Paste von-Beispiel 1 analoges Verhalten.A paste analogous to Example 1, which contained magnesium aluminum silicate (Veegum HV (R) ) in equal quantities instead of the polyethylene glycol and the highly disperse silica, showed a behavior analogous to that of Example 1.

Beispiel 4Example 4

Eine Paste, entsprechend Beispiel 1 hergestellt, die statt des Polyethylenglykol 480 g Cetylstearylalkohol enthielt und vor dem Abfüllen bei 50 Torr entgast wurde, hatte eine Konsistenz, die anders als die Paste von Beispiel 1 weitgehend unabhängig von den Scherbedingungen war.A paste prepared in accordance with Example 1, which contained 480 g of cetylstearyl alcohol instead of the polyethylene glycol and was degassed at 50 torr before filling, had a consistency which, unlike the paste of Example 1, was largely independent of the shear conditions.

Beispiel 5Example 5

Eine von den Scherbedingungen weitgehend unabhängige Konsistenz wies auch eine Paste analog Beispiel 1 auf, bei der das Polyethylenglykol nur zur Hälfte durch Cetylstearylalkohol ersetzt war.A consistency largely independent of the shear conditions also had a paste analogous to Example 1, in which only half of the polyethylene glycol was replaced by cetylstearyl alcohol.

Beispiel 6Example 6

Beispiel 6 ist ein Beispiel für eine nichterfindungsgemäße Paste. Stellte man eine Paste nur aus dem nichtionischen Tensid, der quartären Ammoniumverbindung, dem Aktivator für Perverbindungen und dem Komplexbildner und dem Schaumregulator von Beispiel 1 her, erhielt man eine Paste, die beim Kontakt mit Wasser zu einem Klumpen gelierte, der sich innerhalb 15 Minuten nicht in der Waschflotte auflöste.Example 6 is an example of a non-inventive paste. If a paste was only prepared from the nonionic surfactant, the quaternary ammonium compound, the activator for per compounds and the complexing agent and the foam regulator from Example 1, a paste was obtained which, upon contact with water, gelled to form a lump which did not separate within 15 minutes dissolved in the wash liquor.

Claims (13)

1. Wasch-Zusatz, umfassend a) ein Gemisch aus mehreren Waschmittelbestandteilen b) ein a) umhüllendes beutelartiges Gebilde aus einer in borathaltigen wäßrigen Lösungen leichtlöslichen Folie auf Basis von Polyvinylalkohol,
dadurch gekennzeichnet, daß das Gemisch a) wenigstens ein nichtionisches Tensid, eine quartäre Ammoniumverbindung mit einem langkettigen Alkyl- oder Alkenylrest mit 10 bis 20 Kohlenstoffatomen und im übrigen Alkylresten mit 1 bis 4 Kohlenstoffatomen und/oder ein Anlagerungsprodukt von 1 bis 6 Mol Ethylenoxid an 1 Mol eines primären Fettamins mit einem langkettigen Alkyl-oder Alkenylrest mit 10 bis 16 Kohlenstoffatomen und/oder eine Verbindung der Formel
R-NH-CH2-CH2-COONa,
in der R einen Alkyl- oder Alkenylrest mit 10 bis 18 Kohlenstoffatomen, insbesondere mit 14 Kohlenstoffatomen bedeutet, einen Aktivator für Perverbindungen und einen mehrwertigen Alkohol als Antigelmittel und soviel an Viskositätsregulatoren enthält, daß es eine Viskosität von 1 000 bis 100 000 mPas bei einem Schergefälle zwischen 5 und 500 s-1.1. Washing additive, comprehensive a) a mixture of several detergent ingredients b) an a) enveloping bag-like structure made of a film based on polyvinyl alcohol which is readily soluble in borate-containing aqueous solutions,
characterized in that the mixture a) at least one nonionic surfactant, a quaternary ammonium compound with a long-chain alkyl or alkenyl radical with 10 to 20 carbon atoms and otherwise alkyl radicals with 1 to 4 carbon atoms and / or an adduct of 1 to 6 mol ethylene oxide with 1 Mol of a primary fatty amine with a long-chain alkyl or alkenyl radical having 10 to 16 carbon atoms and / or a compound of the formula
R-NH-CH 2 -CH 2 -COONa,
in which R denotes an alkyl or alkenyl radical with 10 to 18 carbon atoms, in particular with 14 carbon atoms, an activator for per-compounds and a polyhydric alcohol as an anti-gel agent and contains enough viscosity regulators that it has a viscosity of 1,000 to 100,000 mPas at a shear rate between 5 and 500 s- 1 . 2. Wasch-Zusatz nach Anspruch 1, dadurch gekennzeichnet, daß das Gemisch a) als Antigelmittel einen mehrwertigen Alkohol mit 2 bis 4 Kohlenstoffatomen enthält.2. Washing additive according to claim 1, characterized in that the mixture a) contains a polyhydric alcohol having 2 to 4 carbon atoms as an anti-gel agent. 3. Wasch-Zusatz nach Anspruch 2, dadurch gekennzeichnet, daß das Gemisch a) als Antigelmittel ein Gemisch aus einem mehrwertigen Alkohol und Kondensationsprodukten von C10-C20-Fettalkoholen mit 1 bis 4 Mol Ethylenoxid pro Mol Fettalkohol enthält.3. Washing additive according to claim 2, characterized in that the mixture a) contains as the anti-gel agent a mixture of a polyhydric alcohol and condensation products of C10-C20 fatty alcohols with 1 to 4 moles of ethylene oxide per mole of fatty alcohol. 4. Wasch-Zusatz nach Anspruch 2, dadurch gekennzeichnet, daß das Gewichtsverhältnis von nichtionischem Tensid zu mehrwertigem Alkohol im Bereich von 1 : 1 bis 1 : 2 liegt.4. washing additive according to claim 2, characterized in that the weight ratio of nonionic surfactant to polyhydric alcohol is in the range of 1: 1 to 1: 2. 5. Wasch-Zusatz nach Anspruch 3, dadurch gekennzeichnet, daß das Gewichtsverhältnis von nichtionischem Tensid zu mehrwertigem Alkohol zu Fettalkohol/Ethylenoxid-Addukt im Bereich von (7 bis 12) zu (5 bis 16) zu (0,5 bis 4) liegt.5. Washing additive according to claim 3, characterized in that the weight ratio of nonionic surfactant to polyhydric alcohol to fatty alcohol / ethylene oxide adduct is in the range from (7 to 12) to (5 to 16) to (0.5 to 4) . 6. Wasch-Zusatz nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß das Gemisch a) zusätzlich in Wasser leicht lösliche Verbindungen, vorzugsweise aus der Natriumborat, Natriumchlorid, Natriumacetat und Zucker umfassenden Gruppe enthält.6. Washing additive according to one of claims 1 to 5, characterized in that the mixture a) additionally contains water-soluble compounds, preferably from the group comprising sodium borate, sodium chloride, sodium acetate and sugar. 7. Wasch-Zusatz nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß das Gemisch a) zusätzlich in Wasser unlösliche Stoffe, vorzugsweise aus der Zeolith A, hochdisperse Kieselsäure, Schichtsilikate umfassenden Gruppe enthält.7. Washing additive according to one of claims 1 to 6, characterized in that the mixture a) additionally contains water-insoluble substances, preferably from the zeolite A, highly disperse silica, layered silicates group. 8. Wasch-Zusatz nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß das Gemisch a) zusätzlich Polyglykole und/oder Addukte von 15 bis 25 Mol Ethylenoxid an 1 Mol Fettalkohol enthält.8. Washing additive according to one of claims 1 to 7, characterized in that the mixture a) additionally contains polyglycols and / or adducts of 15 to 25 moles of ethylene oxide with 1 mole of fatty alcohol. 9. Wasch-Zusatz nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, daß das Gemisch a) als waschkraftverstärkendes nichtionisches Tensid ein Fettalkohol- oder insbesondere Oxoalkoholethoxylat mit 12 bis 18, vorzugsweise 14 bis 15 Kohlenstoffatomen und 3 bis 10, vorzugsweise 6 bis 8 und insbesondere etwa 7 Mol Ethylenoxid pro Mol Alkohol und gegebenenfalls ein Schaumdämpfungsmittel enthält.9. Washing additive according to one of claims 1 to 8, characterized in that the mixture a) as a washing power-enhancing nonionic surfactant is a fatty alcohol or in particular oxo alcohol ethoxylate having 12 to 18, preferably 14 to 15 carbon atoms and 3 to 10, preferably 6 to 8 and especially contains about 7 moles of ethylene oxide per mole of alcohol and optionally a foam suppressant. 10. Wasch-Zusatz nach einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, daß das Gemisch a) eine quartäre Ammoniumverbindung, deren langkettiger Alkylrest oder Alkenylrest 10 bis 20, vorzugsweise 10 bis 16 und insbesondere etwa 14 Kohlenstoffatome und im übrigen drei Methylgruppen aufweist und vorzugsweise Tetradecyltrimethylammoniumbromid ist, enthält.10. Washing additive according to one of claims 1 to 9, characterized in that the mixture a) has a quaternary ammonium compound, the long-chain alkyl radical or alkenyl radical of 10 to 20, preferably 10 to 16 and in particular about 14 carbon atoms and the other three methyl groups and is preferably tetradecyltrimethylammonium bromide. 11. Wasch-Zusatz nach einem der Ansprüche 1 bis 10, dadurch gekennzeichnet, daß es als Aktivator für Perverbindungen Tetraacetylethylendiamin enthält.11. Washing additive according to one of claims 1 to 10, characterized in that it contains tetraacetylethylenediamine as an activator for per compounds. 12. Wasch-Zusatz nach einem der Ansprüche 1 bis 11, dadurch gekennzeichnet, daß das Gemisch a) zusätzlich wasserlösliche Salze von Alkanpolyphosphonsäuren aus der Gruppe der Phosphonolalkanpolycarbonsäuren und der amino- und hydroxysubstituierten Alkanpolyphosphonsäuren, insbesondere die Alkalisalze der Amino-tris-(me- thylenphosphonsäure), Dimethylenaminomethandiphosphonsäuren, 1-Hydroxyethan-1,1-diphosphonsäure, 1-Phos- phonoethan-1,2-diearbonsäure, 2-Phosphonobutan-1,2,4-tricarbonsäure und vorzugsweise das Hexanatriumsalz der Ethylendiaminotetramethylenphosphonsäure enthält.12. Washing additive according to one of claims 1 to 11, characterized in that the mixture a) additionally water-soluble salts of alkane polyphosphonic acids from the group of the phosphonolalkane polycarboxylic acids and the amino- and hydroxy-substituted alkane polyphosphonic acids, in particular the alkali metal salts of the amino-tris (me- contains thylenephosphonic acid), dimethyleneaminomethane diphosphonic acids, 1-hydroxyethane-1,1-diphosphonic acid, 1-phosphonoethane-1,2-diearbonic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid and preferably the hexasodium salt of ethylenediaminotetramethylenephosphonic acid. 13. Verfahren zur Herstellung eines Waschzusatzes nach einem der Ansprüche 1 bis 12, dadurch gekennzeichnet, daß man das nichtionische Tensid gegebenenfalls zusammen mit dem Schauminhibitor auf 40 bis 75 °C erwärmt, das Antigelmittel und gegebenenfalls den Komplexbildner damit vermischt, den Aktivator für Perverbindungen, die quartäre Ammoniumverbindung und/oder das Aminderivat und/oder die Verbindung der Formel R-NH-CH2-CH2-COONa zusammen mit den Viskositätsregulatoren unter Einleiten hoher Scherkräfte in dem Vorgemisch suspendiert, anschließend auf Raumtemperatur abkühlt und mit einem beutelartigen Gebilde aus einer in borathaltigen wäßrigen Lösungen leichtlöslichen Folie auf Basis von Polyvinylalkohol umhüllt.13. A process for the preparation of a washing additive according to any one of claims 1 to 12, characterized in that the nonionic surfactant is optionally heated together with the foam inhibitor to 40 to 75 ° C, the antigelling agent and optionally the complexing agent are mixed with it, the activator for per compounds, the quaternary ammonium compound and / or the amine derivative and / or the compound of the formula R-NH-CH 2 -CH 2 -COONa together with the viscosity regulators while introducing high shear forces are suspended in the premix, then cooled to room temperature and with a bag-like structure from one wrapped in borate-containing aqueous solutions easily soluble film based on polyvinyl alcohol.
EP85104801A 1984-04-28 1985-04-20 Additive for a washing bath Expired EP0160254B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT85104801T ATE36556T1 (en) 1984-04-28 1985-04-20 WASH ADDITIVE.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3415880 1984-04-28
DE19843415880 DE3415880A1 (en) 1984-04-28 1984-04-28 WASHING ADDITIVE

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EP0160254A2 true EP0160254A2 (en) 1985-11-06
EP0160254A3 EP0160254A3 (en) 1986-03-26
EP0160254B1 EP0160254B1 (en) 1988-08-17

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EP (1) EP0160254B1 (en)
JP (1) JPS60235899A (en)
AT (1) ATE36556T1 (en)
CA (1) CA1241889A (en)
DE (2) DE3415880A1 (en)
ES (1) ES8607381A1 (en)

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EP0244796A1 (en) * 1986-05-09 1987-11-11 Henkel Kommanditgesellschaft auf Aktien Process for the preliminary treatment of dirty textiles
EP0253151A2 (en) * 1986-06-27 1988-01-20 Henkel Kommanditgesellschaft auf Aktien Liquid washing agent and process for its production
EP0291198A2 (en) * 1987-05-14 1988-11-17 The Clorox Company Films from PVA modified with nonhydrolyzable anionic comonomers containing additives
WO2001029172A1 (en) * 1999-10-21 2001-04-26 Henkel Kommanditgesellschaft Auf Aktien Dishwasher detergent portion
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EP0234867A2 (en) * 1986-02-20 1987-09-02 The Clorox Company Concentrated non-phosphate detergent paste compositions
EP0234867A3 (en) * 1986-02-20 1989-04-26 The Clorox Company Concentrated non-phosphate detergent paste compositions
EP0244796A1 (en) * 1986-05-09 1987-11-11 Henkel Kommanditgesellschaft auf Aktien Process for the preliminary treatment of dirty textiles
EP0253151A3 (en) * 1986-06-27 1990-06-13 Henkel Kommanditgesellschaft auf Aktien Liquid washing agent and process for its production
EP0253151A2 (en) * 1986-06-27 1988-01-20 Henkel Kommanditgesellschaft auf Aktien Liquid washing agent and process for its production
EP0291198A2 (en) * 1987-05-14 1988-11-17 The Clorox Company Films from PVA modified with nonhydrolyzable anionic comonomers containing additives
EP0291198A3 (en) * 1987-05-14 1990-03-28 The Clorox Company Films from pva modified with nonhydrolyzable anionic comonomers in the form of pouches containing cleaning compositions
US6281183B1 (en) 1999-03-17 2001-08-28 Unilever Home & Personal Care, Division Of Conopco, Inc. Process for producing a water soluble package
US6378274B1 (en) * 1999-03-17 2002-04-30 Unilever Home & Personal Care Usa Division Of Conopco, Inc. Process for producing a water soluble package
WO2001029172A1 (en) * 1999-10-21 2001-04-26 Henkel Kommanditgesellschaft Auf Aktien Dishwasher detergent portion
US6451750B2 (en) 2000-04-14 2002-09-17 Unilever Home & Personal Care Usa Division Of Conopco, Inc. Water soluble package and liquid contents thereof
US6479448B2 (en) 2000-05-15 2002-11-12 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Liquid detergent composition
US7674761B2 (en) 2001-03-16 2010-03-09 Unilever Home & Personal Care, Division Of Conopco, Inc. Water soluble sachet with a dishwashing enhancing particle
US8367599B2 (en) 2001-03-16 2013-02-05 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Dishwashing composition with particles
WO2002102956A1 (en) * 2001-06-18 2002-12-27 Unilever Plc Water soluble package and liquid contents thereof

Also Published As

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JPS60235899A (en) 1985-11-22
US4610799A (en) 1986-09-09
ES8607381A1 (en) 1986-06-01
DE3564448D1 (en) 1988-09-22
EP0160254B1 (en) 1988-08-17
EP0160254A3 (en) 1986-03-26
ES542592A0 (en) 1986-06-01
DE3415880A1 (en) 1985-10-31
ATE36556T1 (en) 1988-09-15
CA1241889A (en) 1988-09-13

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