EP0164703A2 - Additive for washing - Google Patents

Additive for washing Download PDF

Info

Publication number
EP0164703A2
EP0164703A2 EP85107057A EP85107057A EP0164703A2 EP 0164703 A2 EP0164703 A2 EP 0164703A2 EP 85107057 A EP85107057 A EP 85107057A EP 85107057 A EP85107057 A EP 85107057A EP 0164703 A2 EP0164703 A2 EP 0164703A2
Authority
EP
European Patent Office
Prior art keywords
carbon atoms
washing additive
additive according
water
washing
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
EP85107057A
Other languages
German (de)
French (fr)
Other versions
EP0164703B1 (en
EP0164703A3 (en
Inventor
Klaus Dr. Köster
Franz-Josef Dr. Carduck
Heinz-Manfred Wilsberg
Rolf Dr. Puchta
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
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP0164703A2 publication Critical patent/EP0164703A2/en
Publication of EP0164703A3 publication Critical patent/EP0164703A3/en
Application granted granted Critical
Publication of EP0164703B1 publication Critical patent/EP0164703B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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
    • 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
    • C11D17/044—Solid 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
    • 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
    • C11D3/3935—Bleach activators or bleach catalysts granulated, coated or protected
    • 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. The heating of the washing liquor and the textiles is associated with an 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 such an extent that such stains are no longer removed.
  • bleach activators are added to detergents to increase the bleaching effect, which intensify the bleaching effect of the per compounds and allow the effect to be used even at lower washing temperatures.
  • 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 only immediately before use of the wash liquor
  • 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, chelating agents, soil suspending agents, optical brighteners, bactericides, anti-opacifiers, enzymes, fabric softeners, fragrances.
  • a further improvement in the washing performance of laundry 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, has, in addition to a bleach activator, further laundry detergent components, namely a combination of an alkoxylated nonionic surfactant and a cationic surfactant with one Contains 8 to 20 carbon atoms and otherwise short residues with 1 to 4 carbon atoms releasable on a substrate.
  • a similar proposal to use detergent ingredients e.g. B. a surfactant to apply to a substrate in dispensable form is known from DE-OS 28 12 663.
  • a foam made of water-insoluble polyurethane foam is described as the substrate, which contains the active ingredients to be released in its pores.
  • a pore-free, water-insoluble substrate that is used as a depot for active ingredients, e.g. B. detergents or detergents is the subject of German Offenlegungsschriften 23 47 299 and 31 03 499.
  • the substrates described there are water-containing or water-free foils made of polyurethane gel.
  • a disadvantage of the additives mentioned is that after washing, the water-insoluble substrate must be sorted out of the washed textiles.
  • the active substances are generally only partially released from the substrate. It has therefore been proposed to use detergent combinations which improve washing power in bags made of water-soluble film (German patent application No.
  • the aim of the present invention is to provide a washing additive for increasing the washing performance of textile detergents with a content of detergent-enhancing active substances which does not require a substrate which has to be sorted out of the washed textiles after washing.
  • the washing additive according to the invention comprises a mixture of detergent constituents and optionally auxiliaries which are releasably embedded in organic, flexible, film-forming, water-soluble polymers.
  • the mixture contains at least two of the following active ingredients: a) at least one nonionic surfactant, optionally together with an anti-gel agent for the nonionic surfactant, b) at least one activator for per compounds, c) at least one nitrogen-containing compound from the quaternary ammonium compounds with a long-chain alkyl or Alkenyl radical with 10 to 20 carbon atoms and otherwise alkyl radicals with 1 to 4 carbon atoms, addition products of 1 to 6 mol of ethylene oxide with 1 mol of a primary fatty amine with a long-chain alkyl or alkenyl radical with 10 to 16 carbon atoms, compounds of the formula R-NH-CH 2 -CH 2 -COONa, in which R denotes an alkyl or alkenyl radical having 10 to 18 carbon atoms,
  • Suitable nonionic surfactants are, in particular annealing - products of ethylene oxide with fatty or oxo alcohols particularly suitable which 12 to 18, preferably having 14 to 15 carbon atoms. 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.
  • the content of nonionic surfactants in the washing additive according to the invention primarily promotes the removal of greasy or oily soiling during washing. In many cases it is advisable to add foam regulators; in most cases, the development of foam must be dampened.
  • Suitable foam suppressants are, for example, the silicone oils known as foam inhibitors.
  • N-acyl and I-acyl compounds are suitable as activators for per compounds.
  • Acetyl compounds have proven particularly useful. Examples include tetraacetylglycoluril or pentaacetylglucose or in particular tetraacetylethylenediamine.
  • the bleach activators mentioned lead to improved removal of bleachable textile soiling.
  • Suitable nitrogen-containing compounds are, for example, quaternary ammonium compounds with a 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 identical or different 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.
  • 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.
  • a compound of the formula R-NH-OH 2 -CH 2 -COONa can also be used.
  • a compound in which R is a cocoalkyl radical is preferred.
  • the washing additive for complexing any interfering heavy metal ions can contain small amounts of chelating agents.
  • the washing additive according to the invention optionally contains an anti-gel agent for the nonionic surfactant.
  • an anti-gelling agent must be able to prevent the known gelling of the nonionic surfactant upon contact with water.
  • Suitable antigelling agents are preferably polyhydric alcohols having 2 to 4 carbon atoms, which are intimately mixed with the nonionic 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 C 10 to C 20 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 with 3 moles of ethylene oxide, which contains approximately 70% C 12 -fatty alcohol ethoxylate to C14 fatty alcohols t hox y la t, is suitable as an anti-gelling agent.
  • a good anti-gelling effect is obtained if the weight ratio of nonionic surfactant to polyhydric alcohol is in the range from about 1: 1 to 1: 2. If, on the other hand, a mixture of polyhydric alcohol and fatty alcohol ethoxylate is used, very good results are obtained if the weight ratio of nonionic surfactant to polyhydric alcohol to fatty alcohol ethoxylate in the range from (7 to 12) to (5 to 16) to (0.5 to 4 ) lies.
  • the antigelling effect of the antigelling agent can be increased further if, in addition to the antigelling agents described so far, it is easily dissolved in water.
  • the active ingredient mixture can additionally contain adducts of 15 to 25 moles of ethylene oxide with 1 mole of fatty alcohol as auxiliaries.
  • Polyvinyl alcohol which is readily soluble in cold water and has a degree of saponification of between 70 and 90%, preferably between 78 and 88%, is suitable as the material in which the active compounds are embedded according to the invention; Particularly good results are obtained with polyvinyl alcohol which, in addition to this degree of saponification, is also characterized by a degree of polymerization from 225 to 2250, in particular from 500 to 1000. This corresponds to a molecular weight of approximately 10,000 to 100,000, in particular approximately 10,000 to 50,000. With such a polyvinyl alcohol, the rapid addition of the washing additive according to the invention is ensured during the washing cycle in automatic washing machines even when the washing is carried out with relatively little Wash liquor is washed.
  • water-soluble film-forming polymers other than polyvinyl alcohol are also suitable as carriers for the washing-power-increasing active ingredient combination. What is decisive for their suitability is that the films produced from them dissolve completely in cold water and in cold wash liquors under the conditions of washing in automatic washing machines within a maximum of 15 minutes. In many cases, a mixture of several different water-soluble polymers is more soluble than each of the polymers forming the mixture per se.
  • plasticizers to the preferred polyvinyl alcohol.
  • Polyhydric alcohols preferably glycerol and / or polyethylene glycol, are suitable as such. If the foils are to be elastic and surface rough after drying, which means that they are easily carried away by the laundry items when they are circulated in the washing machine, they are used up to 15% by weight, based on the amount of polyvinyl alcohol, methyl cellulose and / or Cellulose fibers too.
  • a particularly effective and therefore preferred washing additive according to the invention contains a combination of at least one nonionic surfactant together with an anti-gel agent, at least one activator for per compounds, at least one nitrogen-containing compound from the quaternary ammonium compounds with a long-chain alkyl or alkenyl radical with 10 to 20 carbon atoms and the rest Alkyl radicals with 1 to 4 carbon atoms, adducts of 1 to 6 moles of ethylene oxide with 1 mole of a primary fatty amine with a long-chain alkyl or alkenyl radical with 10 to 16 carbon atoms, compounds of the formula R-NH-GH 2 -CH 2 -COONa in which R is an alkyl or alkenyl radical having 10 to 18 carbon atoms, in particular having 14 carbon atoms, comprising a group and a water-soluble salt of an alkane polyphosphonic acid.
  • a method for producing the washing additive according to the invention is a further subject of the present invention.
  • This process is characterized in that the active ingredients and auxiliaries, ie the nonionic surfactant, the activator for the per-compound, the nitrogen-containing compound, the anti-gel agent, in what This readily soluble sodium salt or sugar, adducts of 15 to 25 moles of ethylene oxide with 1 mole of fatty alcohol, the water-soluble salt of an alkane polyphosphonic acid and optionally water at elevated temperature, preferably at 40 to 60 ° C, with a water-soluble, film-forming polymer, to which one may add
  • auxiliaries ie optionally adding the polyhydric alcohol and optionally methyl cellulose and / or cellulose fibers, are mixed, a weight ratio of (active ingredients + auxiliaries) to (polymers) from 1:10 to 5: 1, preferably from 1.5: 1 to 3 , 0: 1 sets.
  • This water-containing mixture of all components of the washing additive forms a highly viscous, sticky mass; it is shaped into films which are so thick that, after drying at 60 to 80 ° C., they have a residual water content of 2 to 10% by weight, based on the water-free film containing the active substance and auxiliary, if necessary after being rolled out, Are 4 to 1.5 mm thick. On the one hand, this thickness ensures adequate mechanical stability, on the other hand, sufficient security of dissolution when using the washing additive in the washing machine.
  • the shaping into foils takes place under water evaporation, for example on a preheated roller mill. After the residual water content has been reached and the rolls have cooled to about 35 to 40 ° C., the elastic film can be removed and, if necessary, rolled out to the thickness mentioned.
  • the film can also be formed by extrusion from a nozzle with subsequent calendering and drying.
  • washing additives are obtained, for example, by applying the active ingredient combination to a film of water-soluble polymers and covering the active ingredients with a further water-soluble film in such a way that the active compound combination is firmly anchored between the films and is only released when the film is dissolved.
  • the two foils are glued or welded to one another at the edges or flat.
  • Mixture C was placed on a roller mill heated to 70 ° C., the roller gap of which was set to 0.7 mm. After 3 minutes of treatment on the roller mill, the residual water content was 6% by weight.
  • the roller mill was cooled to 40 ° C. and a 0.7 mm thick film was pulled off the roller. The film was cut into pieces measuring 25 x 16 cm.
  • polyvinyl alcohol granules (molecular weight approx. 15,000, degree of saponification 83%) and 515 g of an internally plasticized polyvinyl alcohol granulate were suspended in 1,195 g of deionized, cold water and 375 g of glycerol in a heatable stirred vessel and by heating the mixture to 80 ° C solved.
  • the mass produced in this way had a viscosity of 9,650 mPa.s (Brookfield viscometer, 60 C).
  • the mixture was placed on a roller mill preheated to 70 ° C., on which the water was evaporated to a residual content of 7% by weight.
  • a film was formed within 3 minutes, the thickness of which was set to 0.8 mm over the nip. After the roller mill had been cooled to 40 ° C., the film was pulled off and cut into pieces measuring 24 ⁇ 15 cm, which contained the amount of active compound sufficient to improve the washing effect.
  • the films produced in this way dissolved completely in a Miele household washing machine with a 30 ° C wash program within 15 minutes.
  • the soiled laundry washed with it was, despite the 2/3 nominal dosage of a single detergent, significantly cleaner than without the addition of the washing power amplifier according to the invention.
  • an active substance film according to the invention was produced by suspending the polyvinyl alcohol granules in 500 ml of water and introducing heat during the dissolving process by introducing direct steam.
  • a 40% by weight aqueous glycerol-containing polyvinyl alcohol solution was prepared by condensation of the steam and was mixed with the other active ingredients and auxiliaries as in Example 2.
  • a compound of active substance produced according to the recipe described in Example 2 was knife-coated onto a metal plate with a hand knife to form a 0.9 mm thick film. This film was dried in a forced-air drying cabinet at 80 C for 60 minutes. A film was formed which corresponded to the rolled-out film of Example 2 in its dissolving and washing-enhancing properties.
  • Example 2 200 kg of an active ingredient composition were prepared which contained 23% water. This was concentrated using a thin-film evaporator (type Filmtruder HS, Luwa company) at 50 mbar and 1 bar steam heating to a residual water content of 6% by weight. The cut-resistant mass obtained in this way was extruded at 70 ° C. through a slot die into a rolling mill (roller head system, from Berstorff) and processed into a 0.9 mm thick film which has the performance properties described in Example 2.
  • a thin-film evaporator type Filmtruder HS, Luwa company
  • the cut-resistant mass obtained in this way was extruded at 70 ° C. through a slot die into a rolling mill (roller head system, from Berstorff) and processed into a 0.9 mm thick film which has the performance properties described in Example 2.
  • Example 2 an active substance film was produced which contained 35 g of urea instead of sodium chloride.
  • the film had the same elastic and application properties as that described in Example 2.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

1. A washing additive comprising a mixture of detergent ingredients and, optionally, auxiliaries encapsulated in organic, flexible, film-forming water-soluble polymers, characterized in that the mixture contains a) 2 to 30 parts by weight of a monionic surfactant ; b) 2 to 50 parts by weight of an antigel agent for the nonionic surfactant ; c) 2 to 30 parts by weight of an activator for per compounds ; d) 0.5 to 10 parts by weight of a nitrogen-containing compound from the group consisting of quaternary ammonium compounds containing a long-chain C10-20 alkyl or alkenyl radical and, for the rest, C1-4 alkyl radicals, adducts of 1 to 6 mol ethylene oxide with 1 mol of a primary fatty amine with a long-chain C10-16 alkyl or alkenyl radical, compounds corresponding to the formula R-NH-CH2 -CH2 -COONa, in which R is an alkyl or alkenyl radical containing 10 to 18 carbon atoms and more especially 14 carbon atoms, and the washing additive is readily soluble in cold water and in cold wash liquors.

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-/Öl- 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 erhöhten 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 Bleichwirkung 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 bis unmittelbar vor dem Gebrauch können die Probleme, die bei der gemeinsamen Lagerung von Perverbindungen und Bleichaktivatoren 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 weitere Waschmittelbestandteile, nämlich 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 l bis 4 Kohlenstoffatomen freisetzbar auf einem Substrat enthält. Ein ähnlicher Vorschlag, Waschmittelbestandteile, z. B. ein Tensid, auf einem Substrat in abgebbarer Form aufzubringen, ist aus der DE-OS 28 12 663 bekannt. In dieser Patentanmeldung wird als Substrat ein Schaumstoff aus wasserunlöslichem Polyurethanschaum beschrieben, der in seinen Poren die freizusetzenden Wirkstoffe enthält. Ein porenfreies, wasserunlösliches Substrat, das als Depot für Wirkstoffe, z. B. Detergentien oder Waschmittel dient, ist Gegenstand der deutschen Offenlegungsschriften 23 47 299 und 31 03 499. Die dort beschriebenen Substrate sind wasserhaltige bzw. wasserfreie Folien aus Polyurethangel. Ein Nachteil der genannten Additive besteht darin, daß nach der Wäsche das wasserunlösliche Substrat aus den gewaschenen Textilien aussortiert werden muß. Die Wirkstoffe werden außerdem in der Regel nur unvollständig von dem Substrat abgegeben. Man hat daher vorgeschlagen, waschkraftverbessernde leichtlösliche Wirkstoff-Kombinationen in Beuteln aus wasserlöslicher Folie (deutsche Patentanmeldung Nr. P 34 15 880.4) oder in Form spontan in Wasser zerfallender Tabletten (deutsche Patentanmeldung Nr. P 34 17 820.1) einzusetzen. Aus der US-Patentschrift 4,115,292 ist ein Zusatz für Geschirrspülmittel bekannt, der eine Kombination aus einem Enzym und einem Tensid gegebenenfalls zusammen mit weiteren Geschirrspülmittel-Bestandteilen, eingebettet in einer Folie aus einem wasserlöslichen Polymeren darstellt.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. The heating of the washing liquor and the textiles is associated with an 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 such an extent that such stains are no longer removed. For this Basically, so-called bleach activators are added to detergents to increase the bleaching effect, which intensify 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 only immediately before use of the wash liquor
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 bleaching per-compound until immediately before use, the problems associated with the joint storage of per-compounds and bleaching acti vators arise, are avoided. A further improvement in the washing performance of laundry 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, has, in addition to a bleach activator, further laundry detergent components, namely a combination of an alkoxylated nonionic surfactant and a cationic surfactant with one Contains 8 to 20 carbon atoms and otherwise short residues with 1 to 4 carbon atoms releasable on a substrate. A similar proposal to use detergent ingredients e.g. B. a surfactant to apply to a substrate in dispensable form is known from DE-OS 28 12 663. In this patent application, a foam made of water-insoluble polyurethane foam is described as the substrate, which contains the active ingredients to be released in its pores. A pore-free, water-insoluble substrate that is used as a depot for active ingredients, e.g. B. detergents or detergents is the subject of German Offenlegungsschriften 23 47 299 and 31 03 499. The substrates described there are water-containing or water-free foils made of polyurethane gel. A disadvantage of the additives mentioned is that after washing, the water-insoluble substrate must be sorted out of the washed textiles. In addition, the active substances are generally only partially released from the substrate. It has therefore been proposed to use detergent combinations which improve washing power in bags made of water-soluble film (German patent application No. P 34 15 880.4) or in the form of tablets which disintegrate spontaneously in water (German patent application No. P 34 17 820.1). From US Pat. No. 4,115,292, an additive for dishwashing detergents is known which contains a combination of an enzyme and a surfactant, optionally together with other dishwashing detergents. Components embedded in a film made of a water-soluble polymer.

Ziel der vorliegenden Erfindung ist, einen Waschzusatz zur Verstärkung der Waschleistung von Textil-Waschmitteln mit einem Gehalt an waschkraftverstärkenden Wirkstoffen zur Verfügung zu stellen, der kein Substrat erfordert, das nach der-Wäsche aus den gewaschenen Textilien aussortiert werden muß.The aim of the present invention is to provide a washing additive for increasing the washing performance of textile detergents with a content of detergent-enhancing active substances which does not require a substrate which has to be sorted out of the washed textiles after washing.

Der erfindungsgemäße Waschzusatz umfaßt ein Gemisch aus Waschmittelbestandteilen und gegebenenfalls Hilfsstoffen, die freisetzbar in organische, flexible, filmbildende, wasserlösliche Polymere eingebettet sind. Das Gemisch enthält wenigstens zwei der folgenden Wirkstoffe: a) wenigstens ein nichtionisches Tensid, gegebenenfalls zusammen mit einem Antigelmittel für das nichtionische Tensid, b) wenigstens einen Aktivator für Perverbindungen, c) wenigstens eine stickstoffhaltige Verbindung aus der quartäre Ammoniumverbindungen mit einem langkettigen Alkyl- oder Alkenylrest mit 10 bis 20 Kohlenstoffatomen und im übrigen Alkylresten mit 1 bis 4 Kohlenstoffatomen, Anlagerungsprodukte von 1 bis 6 Mol Ethylenoxid an 1 Mol eines primären Fettamins mit einem langkettigen Alkyl-oder Alkenylrest mit 10 bis 16 Kohlenstoffatomen, Verbindungen der Formel R-NH-CH2-CH2-COONa, in der R einen Alkyl- oder Alkenylrest mit 10 bis 18 Kohlenstoffatomen, insbesondere mit 14 Kohlenstoffatomen bedeutet, umfassenden Gruppe. Der Waschzusatz ist in kaltem Wasser und in kalten Waschlaugen leicht löslich.The washing additive according to the invention comprises a mixture of detergent constituents and optionally auxiliaries which are releasably embedded in organic, flexible, film-forming, water-soluble polymers. The mixture contains at least two of the following active ingredients: a) at least one nonionic surfactant, optionally together with an anti-gel agent for the nonionic surfactant, b) at least one activator for per compounds, c) at least one nitrogen-containing compound from the quaternary ammonium compounds with a long-chain alkyl or Alkenyl radical with 10 to 20 carbon atoms and otherwise alkyl radicals with 1 to 4 carbon atoms, addition products of 1 to 6 mol of ethylene oxide with 1 mol of a primary fatty amine with a long-chain alkyl or alkenyl radical with 10 to 16 carbon atoms, compounds of the formula R-NH-CH 2 -CH 2 -COONa, in which R denotes an alkyl or alkenyl radical having 10 to 18 carbon atoms, in particular having 14 carbon atoms. The washing additive is easily soluble in cold water and in cold washing liquors.

Als nichtionische Tenside kommen vor allem Anlagerungs- produkte 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. Durch den Gehalt des erfindungsgemäßen Waschzusatzes an nichtionischen Tensiden wird vor allem die Entfernung von fett- oder ölartigen Verschmutzungen beim Waschen gefördert. In vielen Fällen ist es zweckmäßig, Schaumregulatoren zuzusetzen; meistens muß die Schaumentwicklung gedämpft werden. Geeignete Schaumdämpfungsmittel sind beispielsweise die als Schauminhibitoren bekannten Silikonöle.Suitable nonionic surfactants are, in particular annealing - products of ethylene oxide with fatty or oxo alcohols particularly suitable which 12 to 18, preferably having 14 to 15 carbon atoms. 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. The content of nonionic surfactants in the washing additive according to the invention primarily promotes the removal of greasy or oily soiling during washing. In many cases it is advisable to add foam regulators; in most cases, the development of foam must be dampened. Suitable foam suppressants are, for example, the silicone oils known as foam inhibitors.

Als Aktivator für Perverbindungen sind N-Acyl- und I-Acylverbindungen geeignet. Besonders bewährt haben sich Acetyl Verbindungen. Beispiele hierfür sind Tetraacetylglykoluril oder Pentaacetylglucose oder 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 I-acyl compounds are suitable as activators for per compounds. Acetyl compounds have proven particularly useful. Examples include 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.

Geeignete stickstoffhaltige Verbindungen sind beispielsweise quartäre Ammoniumverbindungen mit einem 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 oder verschiedene 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. Anstelle oder gemeinsam mit der quartären Ammoniumverbindung und dem Fettaminderivat kann auch eine Verbindung der Formel R-NH-OH2-CH2-COONa eingesetzt werden. Bevorzugt ist eine Verbindung, in der R ein Kokosalkylrest ist.Suitable nitrogen-containing compounds are, for example, quaternary ammonium compounds with a 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 identical or different 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. Instead of or together with the quaternary ammonium compound and the fatty amine derivative, a compound of the formula R-NH-OH 2 -CH 2 -COONa can also be used. A compound in which R is a cocoalkyl radical is preferred.

Falls erforderlich, kann der Waschzusatz zur Komplexierung eventuell störender Schwermetallionen geringe Mengen an Chelatbildnern enthalten. Besonders bewährt haben sich hierfür wasserlösliche Salze von Alkanpolyphosphonsäuren aus der Gruppe der Phosphonoalkanpolycarbonsäuren und der amino- und hydroxysubstituierten Alkanpolyphosphonsäuren, insbesondere die Alkalisalze der Amino-tris-(methylenphosphonsäure), Dimethylenaminomethandiphosphonsäuren, 1-Hydroxyethan-1,1-diphosphonsäure, 1-Phosphonoethan-1,2-dicarbonsäure, 2-Phosphonobutan-1,2,3-tricarbonsäure und insbesondere das Hexanatriumsalz der Ethylendiaminotetramethylenphosphonsäure.If necessary, the washing additive for complexing any interfering heavy metal ions can contain small amounts of chelating agents. Water-soluble salts of alkane polyphosphonic acids 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, have proven particularly useful for this. 1,2-dicarboxylic acid, 2-phosphonobutane-1,2,3-tricarboxylic acid and in particular the hexasodium salt of ethylenediaminotetramethylenephosphonic acid.

Der erfindungsgemäße Waschzusatz enthält gegebenenfalls ein Antigelmittel für das nichtionische Tensid. Ein derartiges Antigelmittel muß-imstande sein, 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 nichtionischen 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 de-r 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-Fettalkoholethoxylat mit 3 Mol Ethylenoxid, das ca. 70 % C12-Fettalkoholethoxylat enthält, ist als Antigeliermittel geeignet. Wird ausschließlich ein mehrwe-rtiger Alkohol als Antigeliermittel eingesetzt, erhält man eine gute Antigelierwirkung, 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 mehrwertigem Alkohol und Fettalkoholethoxylat ein, erhält 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 lös-1=che Verbindungen, insbesondere Natriumchlorid, Natriumacetat, Magnesiumchlorid, Harnstoff oder auch Zucker verwendet. Durch den Zusatz an Antigelmittel wird nicht nur die problemlose Auflösung des nichtionischen Tensids, sondern auch des wasserlöslichen Polymeren, in den die Wirkstoffe eingebettet sind, gewährleistet. Das Wirkstoffgemisch kann zusätzlich als Hilfsmittel Addukte von 15 bis 25 Mol Ethylenoxid an 1 Mol Fettalkohol enthalten.The washing additive according to the invention optionally contains an anti-gel agent for the nonionic surfactant. Such an anti-gelling agent must be able to prevent the known gelling of the nonionic surfactant upon contact with water. Suitable antigelling agents are preferably polyhydric alcohols having 2 to 4 carbon atoms, which are intimately mixed with the nonionic 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 C 10 to C 20 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 with 3 moles of ethylene oxide, which contains approximately 70% C 12 -fatty alcohol ethoxylate to C14 fatty alcohols t hox y la t, is suitable as an anti-gelling agent. If only a polyhydric alcohol is used as an anti-gelling agent, a good anti-gelling effect is obtained if the weight ratio of nonionic surfactant to polyhydric alcohol is in the range from about 1: 1 to 1: 2. If, on the other hand, a mixture of polyhydric alcohol and fatty alcohol ethoxylate is used, very good results are obtained if the weight ratio of nonionic surfactant to polyhydric alcohol to fatty alcohol ethoxylate in the range from (7 to 12) to (5 to 16) to (0.5 to 4 ) lies. The antigelling effect of the antigelling agent can be increased further if, in addition to the antigelling agents described so far, it is easily dissolved in water. 1 = che compounds, especially sodium chloride, sodium acetate, magnesium chloride, urea or sugar used. The addition of anti-gel agent ensures not only the problem-free dissolution of the nonionic surfactant, but also of the water-soluble polymer in which the active ingredients are embedded. The active ingredient mixture can additionally contain adducts of 15 to 25 moles of ethylene oxide with 1 mole of fatty alcohol as auxiliaries.

Als Material, in das die Wirkstoffe erfindungsgemäß eingebettet sind, ist vorzugsweise in kaltem Wasser leichtlöslicher Polyvinylalkohol mit einem Verseifungsgrad zwischen 70 und 90 %, vorzugsweise zwischen 78 und 88 %, geeignet; besonders gute Resultate erhält man mit Polyvinylalkohol, der außer durch diesen Verseifungsgrad zusätzlich durch einen Polymerisationsgrad von 225 bis 2250, insbesondere von 500 bis 1000 charakterisiert ist. Dem entspricht ein Molekulargewicht von ca. 10 000 bis 100 000, insbesondere von ca. 10 000 bis 50 000. Mit einem derartigen Polyvinylalkohol ist die rasche Auflösung des erfindungsgemäßen Waschzusatzes während des Waschgangs in automatischen Waschmaschinen auch dann gewährleistet, wenn die Wäsche mit verhältnismäßig wenig Waschlauge gewaschen wird. Aber auch andere wasserlösliche filmbildende Polymere als Polyvinylalkohol sind geeignet als Träger für die waschkraftsteigernde Wirkstoff-Kombination. Entscheidend für ihre Eignung ist, daß daraus hergestellte Folien sich in kaltem Wasser und in kalten Waschlaugen unter den Bedingungen des Waschens in automatischen Waschmaschinen innerhalb von höchstens 15 Minuten vollständig auflösen. In vielen Fällen ist ein Gemisch aus mehreren verschiedenen wasserlöslichen Polymeren besser löslich als jedes der das Gemisch bildenden Polymeren für sich.Polyvinyl alcohol which is readily soluble in cold water and has a degree of saponification of between 70 and 90%, preferably between 78 and 88%, is suitable as the material in which the active compounds are embedded according to the invention; Particularly good results are obtained with polyvinyl alcohol which, in addition to this degree of saponification, is also characterized by a degree of polymerization from 225 to 2250, in particular from 500 to 1000. This corresponds to a molecular weight of approximately 10,000 to 100,000, in particular approximately 10,000 to 50,000. With such a polyvinyl alcohol, the rapid addition of the washing additive according to the invention is ensured during the washing cycle in automatic washing machines even when the washing is carried out with relatively little Wash liquor is washed. However, water-soluble film-forming polymers other than polyvinyl alcohol are also suitable as carriers for the washing-power-increasing active ingredient combination. What is decisive for their suitability is that the films produced from them dissolve completely in cold water and in cold wash liquors under the conditions of washing in automatic washing machines within a maximum of 15 minutes. In many cases, a mixture of several different water-soluble polymers is more soluble than each of the polymers forming the mixture per se.

Um dem erfindungsgemäßen Waschzusatz eine gewisse Weichheit zu verleihen, ist es zweckmäßig, dem bevorzugten Polyvinylalkohol Weichmacher zuzusetzen. Als solche kommen mehrwertige Alkohole, vorzugsweise Glycerin und/oder Polyethylenglykol in Betracht. Falls die Folien nach dem Trocknen elastisch und oberflächlich rauh sein sollen, wodurch sie von den Wäschestücken leicht beim Umwälzen in der Waschmaschine mitgenommen werden, setzt man ihnen bis zu je 15 Gew.-%, bezogen auf die Menge an Polyvinylalkohol, Methylcellulose und/oder Cellulosefasern zu.In order to impart a certain softness to the washing additive according to the invention, it is expedient to add plasticizers to the preferred polyvinyl alcohol. Polyhydric alcohols, preferably glycerol and / or polyethylene glycol, are suitable as such. If the foils are to be elastic and surface rough after drying, which means that they are easily carried away by the laundry items when they are circulated in the washing machine, they are used up to 15% by weight, based on the amount of polyvinyl alcohol, methyl cellulose and / or Cellulose fibers too.

Ein besonders wirksamer und daher bevorzugter erfindungsgemäßer Waschzusatz enthält eine Kombination aus wenigstens einem nichtionischen Tensid zusammen mit einem Antigelmittel, wenigstens einem Aktivator für Perverbindungen, wenigstens einer stickstoffhaltigen Verbindung aus der quartäre Ammoniumverbindungen mit einem langkettigen Alkyl- oder Alkenylrest mit 10 bis 20 Kohlenstoffatomen und im übrigen Alkylresten mit 1 bis 4 Kohlenstoffatomen, Anlagerungsprodukte von 1 bis 6 Mol Ethylenoxid an 1 Mol eines primären Fettamins mit einem langkettigen Alkyl-oder Alkenylrest mit 10 bis 16 Kohlenstoffatomen, Verbindungen der Formel R-NH-GH2-CH2-COONa, in der R einen Alkyl- oder Alkenylrest mit 10 bis 18 Kohlenstoffatomen, insbesondere mit 14 Kohlenstoffatomen bedeutet, umfassenden Gruppe und einem wasserlöslichen Salz einer Alkanpolyphosphonsäure.A particularly effective and therefore preferred washing additive according to the invention contains a combination of at least one nonionic surfactant together with an anti-gel agent, at least one activator for per compounds, at least one nitrogen-containing compound from the quaternary ammonium compounds with a long-chain alkyl or alkenyl radical with 10 to 20 carbon atoms and the rest Alkyl radicals with 1 to 4 carbon atoms, adducts of 1 to 6 moles of ethylene oxide with 1 mole of a primary fatty amine with a long-chain alkyl or alkenyl radical with 10 to 16 carbon atoms, compounds of the formula R-NH-GH 2 -CH 2 -COONa in which R is an alkyl or alkenyl radical having 10 to 18 carbon atoms, in particular having 14 carbon atoms, comprising a group and a water-soluble salt of an alkane polyphosphonic acid.

Ein Verfahren zur Herstellung des erfindungsgemäßen Waschzusatzes ist ein weiterer Gegenstand der vorliegenden Erfindung. Dieses Verfahren ist dadurch gekennzeichnet, daß man die Wirk- und Hilfsstoffe, d. h. das nichtionische Tensid, den Aktivator für die Perverbindung, die stickstoffhaltige Verbindung, das Antigelmittel, in Wasser leichtlösliche Natriumsalze oder Zucker, Addukte von 15 bis 25 Mol Ethylenoxid an 1 Mol Fettalkohol, das wasserlösliche Salz einer Alkanpolyphosphonsäure sowie gegebenenfalls Wasser bei erhöhter Temperatur, vorzugsweise bei 40 bis 60 °C, mit einem wasserlöslichen, filmbildenden Polymeren, dem man die eventuell zuzusetzenden Hilfsstoffe, d. h. gegebenenfalls den mehrwertigen Alkohol sowie gegebenenfalls Methylcellulose und/oder Cellulosefasern zusetzt, vermischt, wobei man ein Gewichtsverhältnis von (Wirkstoffe + Hilfsstoffe) zu (Polymere) von 1 : 10 bis 5 : 1, vorzugsweise von 1,5 : 1 bis 3,0 : 1 einstellt. Dieses wasserhaltige Gemisch aller Komponenten des Waschzusatzes bildet eine hochviskose, klebrige Masse; sie wird zu Folien verformt, die so dick sind, daß sie nach dem Trocknen bei 60 bis 80 °C auf einen Restwassergehalt von 2 bis 10 Gew.-%, bezogen auf die wasserfreie wirkstoff- und hilfsstoffhaltige Folie, gegebenenfalls nach Auswalzen, 0,4 bis 1,5 mm dick sind. Diese Dicke gewährleistet einerseits eine ausreichende mechanische Stabilität, andererseits eine genügende Auflösesicherheit bei der Anwendung des Waschzusatzes in der Waschmaschine. Die Verformung zu Folien erfolgt unter Wasserverdampfung, beispielsweise auf einem vorgeheizten Walzenstuhl. Nach Erreichen des Restwassergehaltes und Abkühlen der Walzen auf ca. 35 bis 40 °C kann die elastische Folie abgezogen-und gegebenenfalls auf die genannte Dicke ausgewalzt werden.A method for producing the washing additive according to the invention is a further subject of the present invention. This process is characterized in that the active ingredients and auxiliaries, ie the nonionic surfactant, the activator for the per-compound, the nitrogen-containing compound, the anti-gel agent, in what This readily soluble sodium salt or sugar, adducts of 15 to 25 moles of ethylene oxide with 1 mole of fatty alcohol, the water-soluble salt of an alkane polyphosphonic acid and optionally water at elevated temperature, preferably at 40 to 60 ° C, with a water-soluble, film-forming polymer, to which one may add Auxiliaries, ie optionally adding the polyhydric alcohol and optionally methyl cellulose and / or cellulose fibers, are mixed, a weight ratio of (active ingredients + auxiliaries) to (polymers) from 1:10 to 5: 1, preferably from 1.5: 1 to 3 , 0: 1 sets. This water-containing mixture of all components of the washing additive forms a highly viscous, sticky mass; it is shaped into films which are so thick that, after drying at 60 to 80 ° C., they have a residual water content of 2 to 10% by weight, based on the water-free film containing the active substance and auxiliary, if necessary after being rolled out, Are 4 to 1.5 mm thick. On the one hand, this thickness ensures adequate mechanical stability, on the other hand, sufficient security of dissolution when using the washing additive in the washing machine. The shaping into foils takes place under water evaporation, for example on a preheated roller mill. After the residual water content has been reached and the rolls have cooled to about 35 to 40 ° C., the elastic film can be removed and, if necessary, rolled out to the thickness mentioned.

Die Folienbildung kann aber auch durch Extrusion aus einer Düse mit nachfolgender Kalandrierung und Trocknung erfolgen.The film can also be formed by extrusion from a nozzle with subsequent calendering and drying.

Andere Arten erfindungsgemäßer Waschzusätze erhält man, indem man beispielsweise die Wirkstoff-Kombination auf eine Folie aus wasserlöslichen Polymeren aufträgt und die Wirkstoffe mit einer weiteren wasserlöslichen Folie so bedeckt, daß die Wirkstoff-Kombination fest zwischen den Folien verankert ist und erst beim Auflösen freigesetzt wird. Zu diesem Zweck verbindet man, d. h. zum Beispiel verklebt oder verschweißt man die beiden Folien an den Rändern oder flächig miteinander.Other types of washing additives according to the invention are obtained, for example, by applying the active ingredient combination to a film of water-soluble polymers and covering the active ingredients with a further water-soluble film in such a way that the active compound combination is firmly anchored between the films and is only released when the film is dissolved. For this purpose one connects, d. H. For example, the two foils are glued or welded to one another at the edges or flat.

Vor der Verwendung wird die Folie in Stücke von einer Größe geschnitten oder gestanzt, die eine für die Steigerung der Waschleistung von handelsüblichen Waschmitteln bei der Wäsche ausreichende Menge an Wirkstoffen enthalten; dies sind etwa 10 bis 50 g für Haushaltswaschmaschinen. Die Wirkstoffe sind in dem erfindungsgemäßen Waschzusatz vorzugsweise in folgendem Gewichtsverhältnis enthalten:

  • 2 bis 30 Gew.-Teile nichtionsches Tensid,
  • 2 bis 30 Gew.-Teile Aktivator für Perverbindungen,
  • 0,5 bis 10 Gew.-Teile stickstoffhaltige Verbindung,
  • 0 bis 5 Gew.-Teile Chelatbildner.
Before use, the film is cut or punched into pieces of a size which contain a sufficient amount of active ingredients to increase the washing performance of commercially available detergents; this is about 10 to 50 g for household washing machines. The active ingredients are preferably contained in the washing additive according to the invention in the following weight ratio:
  • 2 to 30 parts by weight of nonionic surfactant,
  • 2 to 30 parts by weight activator for per compounds,
  • 0.5 to 10 parts by weight of nitrogenous compound,
  • 0 to 5 parts by weight of chelating agent.

Hinzu kommen 2 bis 50 Gew.-Teile Antigelmittel für das nichtionische Tensid.In addition there are 2 to 50 parts by weight of anti-gel agent for the nonionic surfactant.

B e i s p i e l eExample Beispiel 1example 1

In einem heizbaren Rührwerk wurden 90 g Wasser, 39 g Polyvinylalkohol (Molekulargewicht ca. 15 000, Verseifungsgrad 83 %) und 39 g Polyvinylalkohol (durch Copolymerisation innerlich weichgemacht; Molekulargewicht ca. 22 000, Verseifungsgrad 86 %) bei 100 °C gelöst. Hierzu gab man 20 g Glycerin, 4 g Polyethylenglykol (Molekulargewicht 4 000), 4 g Methylcellulose und 4 g Cellulosefasern, Länge max. 1 mm (= Mischung A).90 g of water, 39 g of polyvinyl alcohol (molecular weight approx. 15,000, degree of saponification 83%) and 39 g of polyvinyl alcohol (internally softened by copolymerization; molecular weight approx. 22,000, degree of saponification 86%) were dissolved at 100 ° C. in a heatable stirrer. To this were added 20 g glycerol, 4 g polyethylene glycol (molecular weight 4,000), 4 g methyl cellulose and 4 g cellulose fibers, length max. 1 mm (= mixture A).

In einem weiteren Mischaggregat wurden 97 g Tetraacetylethylendiamin, 104 g C14/C15-Oxoalkohol + 7 Mol Ethylenoxid, 37 g Tetradecyltrimethylammoniumbromid, 12 g einer 50-gewichtsprozentigen wäßrigen Lösung des Hexanatriumsalzes der Ethylendiaminotetramethylenphosphonsäure, 37 g 1,2-Propylenglykol, 37 g Glycerin, 11 g Oleyl-/Cetylalkohol + 2 Mol Ethylenoxid und 6 g Polydimethylsiloxan bei 50 °C zu einer Paste vermischt (= Mischung B).In a further mixing unit, 97 g of tetraacetylethylene diamine, 104 g of C 14 / C 15 oxo alcohol + 7 mol of ethylene oxide, 37 g of tetradecyl trimethyl ammonium bromide, 12 g of a 50% strength by weight aqueous solution of the hexasodium salt of ethylenediaminotetramethylene phosphonic acid, 37 g of 37 g of 1,2-propylene glycol Glycerin, 11 g oleyl / cetyl alcohol + 2 mol ethylene oxide and 6 g polydimethylsiloxane mixed to a paste at 50 ° C (= mixture B).

In einem Zick-Zack-Kneter wurden dann Mischung A und Mischung B bei 40 °C 20 Minuten lang homogenisiert (= Mischung C). Mischung C wurde auf einen auf 70 C erhitzten Walzenstuhl gegeben, dessen Walzenspalt auf 0,7 mm eingestellt war. Nach 3-minütiger Behandlung auf dem Walzenstuhl betrug der Rest-Wassergehalt 6 Gew.-%. Der Walzenstuhl wurde auf 40 °C abgekühlt und eine 0,7 mm dicke Folie von der Walze abgezogen. Die Folie wurde in Stücke von 25 x 16 cm Größe zerschnitten. Diese Stücke enthielten eine für die gewünschte Verbesserung der Waschwirkung ausreichende Menge an Wirkstoffen: Wenn die Folien-Stücke der Waschflotte einer automatischen Haushaltswaschmaschine zusätzlich zu der für eine Wäschefüllung vorgeschriebenen Menge Waschmittel hinzugegeben wurden, erhielt man eine bessere Waschleistung als ohne den Zusatz des erfindungsgemäßen Waschzusatzes.Mixture A and mixture B were then homogenized at 40 ° C. for 20 minutes in a zigzag kneader (= mixture C). Mixture C was placed on a roller mill heated to 70 ° C., the roller gap of which was set to 0.7 mm. After 3 minutes of treatment on the roller mill, the residual water content was 6% by weight. The roller mill was cooled to 40 ° C. and a 0.7 mm thick film was pulled off the roller. The film was cut into pieces measuring 25 x 16 cm. These pieces contained a sufficient amount of active ingredients for the desired improvement in the washing effect: If the film pieces of the washing liquor were added to an automatic household washing machine in addition to the amount of detergent prescribed for laundry, a better washing performance was obtained than without the addition of the washing additive according to the invention.

Beispiel 2Example 2

In einem beheizbaren Rührgefäß wurden 515 g Polyvinylalkohol-Granulat (Molekulargewicht ca. 15 000, Verseifungsgrad 83 %) und 515 g eines innerlich weichgemachten Polyvinylalkohol-Granulates in 1 195 g entionisiertem, kaltem Wasser und 375 g Glycerin suspendiert und durch Aufheizen der Mischung auf 80 °C gelöst. Zu dieser Lösung wurden unter Rühren 619 g C14/C15-Oxoalkohol + 7 Mol Ethylenoxid, 330 g 1,2-Propylenglykol, 61,7 g 01eyl-/Cetylalkohol + 2 Mol Ethylenoxid, 35,2 g Polydimethylsiloxan, 146 g einer 50-gewichtsprozentigen wäßrigen Lösung des Hexanatriumsalzes der Ethylendiaminotetramethylenphosphonsäure sowie je 53 g Polyethylenglykol (Molekulargewicht 4 000), Methylcellulose und Cellulosefasern (Länge bis 1 mm) gegeben. Die Lösung kühlte sich dabei auf etwa 60 °C ab. In dieser warmen Masse wurden 222 g Tetradecyltrimethylammoniumbromid, 575 g Tetraacetylethylendiamin, 222 g hochdisperse Fällungs-Kieselsäure, 35 g Natriumchlorid sowie 0,09 g eines blauen Farbstoffes suspendiert.515 g of polyvinyl alcohol granules (molecular weight approx. 15,000, degree of saponification 83%) and 515 g of an internally plasticized polyvinyl alcohol granulate were suspended in 1,195 g of deionized, cold water and 375 g of glycerol in a heatable stirred vessel and by heating the mixture to 80 ° C solved. 619 g of C14 / C15 oxo alcohol + 7 mol of ethylene oxide, 330 g of 1,2-propylene glycol, 61.7 g of 01eyl / cetyl alcohol + 2 mol of ethylene oxide, 35.2 g of polydimethylsiloxane, 146 g of a 50- weight percent aqueous solution of the hexasodium salt of ethylenediaminotetramethylenephosphonic acid and 53 g of polyethylene glycol (molecular weight 4,000), methyl cellulose and cellulose fibers (length up to 1 mm). The solution cooled to about 60 ° C. In this warm mass, 222 g of tetradecyltrimethylammonium bromide, 575 g of tetraacetylethylene diamine, 222 g of highly dispersed precipitated silica, 35 g of sodium chloride and 0.09 g of a blue dye were suspended.

Die so hergestellte Masse hatte eine Viskosität von 9 650 mPa.s (Brookfield-Viskosimeter, 60 C). Die Mischung wurde auf einen auf 70 °C vorgewärmten Walzenstuhl gegeben, auf dem das Wasser bis auf einen Restanteil von 7 Gew.-% ausgedampft wurde. Dabei bildete sich innerhalb von 3 Minuten eine Folie, deren Dicke über dem Walzenspalt auf 0,8 mm eingestellt wurde. Die Folie wurde nach Kühlung des Walzenstuhles auf 40 °C abgezogen und in 24 x 15 cm große Stücke zerschnitten, die die für die gewünschte Verbesserung der Waschwirkung ausreichende Wirkstoffmenge enthielten.The mass produced in this way had a viscosity of 9,650 mPa.s (Brookfield viscometer, 60 C). The mixture was placed on a roller mill preheated to 70 ° C., on which the water was evaporated to a residual content of 7% by weight. A film was formed within 3 minutes, the thickness of which was set to 0.8 mm over the nip. After the roller mill had been cooled to 40 ° C., the film was pulled off and cut into pieces measuring 24 × 15 cm, which contained the amount of active compound sufficient to improve the washing effect.

Die so hergestellten Folien lösten sich innerhalb von 15 Minuten in einem Miele-Haushalts-Waschautomaten mit 30 °C-Waschprogramm rückstandslos auf. Die damit gewaschene angeschmutzte Wäsche war trotz 2/3-Solldosierung eines Einfach-Waschmittels deutlich sauberer als ohne Zusatz des erfindungsgemäßen Waschkraftverstärkers.The films produced in this way dissolved completely in a Miele household washing machine with a 30 ° C wash program within 15 minutes. The soiled laundry washed with it was, despite the 2/3 nominal dosage of a single detergent, significantly cleaner than without the addition of the washing power amplifier according to the invention.

Beispiel 3Example 3

Entsprechend Beispiel 2 wurde eine erfindungsgemäße Wirkstofffolie dadurch hergestellt, daß das Polyvinylalkohol-Granulat in 500 ml Wasser suspendiert wurde und die Wärmezufuhr beim Lösevorgang durch Direktdampf-Einleitung erfolgte. Durch Kondensation des Dampfes wurde eine 40-gewichtsprozentige wäßrige glycerinhaltige Polyvinylalkohol-Lösung hergestellt, die wie in Beispiel 2 mit den übrigen Wirk- und Hilfsstoffen vermischt wurde.In accordance with Example 2, an active substance film according to the invention was produced by suspending the polyvinyl alcohol granules in 500 ml of water and introducing heat during the dissolving process by introducing direct steam. A 40% by weight aqueous glycerol-containing polyvinyl alcohol solution was prepared by condensation of the steam and was mixed with the other active ingredients and auxiliaries as in Example 2.

Beispiel 4Example 4

Eine nach der in Beispiel 2 beschriebenen Rezeptur hergestellte Wirkstoffmasse wurde mit einem Handrakel auf eine Metallplatte zu einem 0,9 mm dicken Film ausgerakelt. Dieser Film wurde in einem Umlufttrockenschrank 60 Minuten bei 80 C getrocknet. Es bildete sich eine Folie, die in ihren löse- und waschverstärkenden Eigenschaften der ausgewalzten Folie von Beispiel 2 entsprach.A compound of active substance produced according to the recipe described in Example 2 was knife-coated onto a metal plate with a hand knife to form a 0.9 mm thick film. This film was dried in a forced-air drying cabinet at 80 C for 60 minutes. A film was formed which corresponded to the rolled-out film of Example 2 in its dissolving and washing-enhancing properties.

Beispiel 5Example 5

Nach der in Beispiel 2 beschriebenen Rezeptur wurden 200 kg einer Wirkstoffmasse-hergestellt, die 23 % Wasser enthielt. Diese wurde mit Hilfe eines Dünnschichtverdampfers (Typ Filmtruder HS, Firma Luwa) bei 50 mbar und 1 bar-Dampfheizung auf einen Restwassergehalt von 6 Gew.-% konzentriert. Die so erhaltene schnittfeste Masse wurde bei 70 °C über eine Breitschlitzdüse in ein Walzwerk extrudiert (Roller Head Anlage, Fa. Berstorff) und zu einer 0,9 mm dicken Folie verarbeitet, die die im Beispiel 2 beschriebenen anwendungstechnischen Eigenschaften hat.According to the recipe described in Example 2, 200 kg of an active ingredient composition were prepared which contained 23% water. This was concentrated using a thin-film evaporator (type Filmtruder HS, Luwa company) at 50 mbar and 1 bar steam heating to a residual water content of 6% by weight. The cut-resistant mass obtained in this way was extruded at 70 ° C. through a slot die into a rolling mill (roller head system, from Berstorff) and processed into a 0.9 mm thick film which has the performance properties described in Example 2.

Beispiel 6Example 6

Nach dem in Beispiel 2 beschriebenen Verfahren wurde eine Wirkstofffolie hergestellt, die statt Natriumchlorid 35 g Harnstoff enthielt. Die Folie hatte die gleichen elastischen und anwendungstechnischen Eigenschaften wie die im Beispiel 2 beschriebene.According to the process described in Example 2, an active substance film was produced which contained 35 g of urea instead of sodium chloride. The film had the same elastic and application properties as that described in Example 2.

Claims (17)

1. Waschzusatz, umfassend ein Gemisch aus Waschmittelbestandteilen und gegebenenfalls Hilfsstoffen, eingebettet in organische, flexible, filmbildende, wasserlösliche Polymere, dadurch gekennzeichnet, daß das Gemisch wenigstens zwei der folgenden Wirkstoffe a) wenigstens ein nichtionisches Tensid gegebenenfalls zusammen mit einem Antigelmittel, b) wenigstens einen Aktivator für Perverbindungen, c) wenigstens eine stickstoffhaltige Verbindung aus der quartäre Ammoniumverbindungen mit einem langkettigen Alkyl- oder Alkenylrest mit 10 bis 20 Kohlenstoffatomen und im übrigen Alkylresten mit 1 bis 4-Kohlenstoffatomen, Anlagerungsprodukte von 1 bis 6 Mol Ethylenoxid an 1 Mol eines primären Fettamins mit einem langkettigen Alkyl- oder Alkenylrest mit 10 bis 16 Kohlenstoffatomen, Verbindungen der Formel R-NH-CH2-CH2-COONa, in der R einen Alkyl- oder Alkenylrest mit 10 bis 18 Kohlenstoffatomen, insbesondere mit 14 Kohlenstoffatomen bedeutet, umfassenden Gruppe,
enthält und der Waschzusatz in kaltem Wasser und in kalten Waschlaugen leicht löslich ist.1. washing additive comprising a mixture of detergent constituents and optionally auxiliary substances, embedded in organic, flexible, film-forming, water-soluble polymers, characterized in that the mixture comprises at least two of the following active substances a) at least one nonionic surfactant, optionally together with an anti-gel agent, b) at least one activator for per-compounds, c) at least one nitrogen-containing compound from the quaternary ammonium compounds with a long-chain alkyl or alkenyl radical having 10 to 20 carbon atoms and, moreover, alkyl radicals with 1 to 4 carbon atoms, addition products of 1 to 6 mol of ethylene oxide with 1 mol of a primary fatty amine with a long-chain alkyl - or alkenyl radical with 10 to 16 carbon atoms, compounds 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,
contains and the washing additive is easily soluble in cold water and cold wash liquors. 2. Waschzusatz nach Anspruch 1, dadurch gekennzeichnet, daß er als 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.2. Washing additive according to claim 1, characterized in that it is a non-ionic surfactant a fatty alcohol - or especially oxo alcohol ethoxylate with 12 to 18, preferably 14 to 15 carbon atoms and 3 to 10, preferably 6 to 8 and in particular about 7 moles of ethylene oxide per mole of alcohol and optionally contains a foam suppressant. 3. Waschzusatz nach den Ansprüchen l oder 2, dadurch gekennzeichnet, daß er als Aktivator für Perverbindungen N-Acyl- oder 0-Acylverbindungen, vorzugsweise Tetraacetylethylendiamin enthält.3. A washing additive according to claims 1 or 2, characterized in that it contains N-acyl or 0-acyl compounds, preferably tetraacetylethylene diamine, as an activator for per compounds. 4. Waschzusatz nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß er 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.4. A washing additive according to one of claims 1 to 3, characterized in that it contains 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 preferably tetradecyltrimethylammonium bromide . 5. Waschzusatz nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß er als Antigelmittel einen mehrwertigen Alkohol mit 2 bis 4 Kohlenstoffatomen enthält.5. Washing additive according to one of claims 1 to 4, characterized in that it contains a polyhydric alcohol having 2 to 4 carbon atoms as an anti-gel agent. 6: Waschzusatz nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß er als Antigelmittel ein Gemisch aus einem mehrwertigen Alkohol und Kondensationsprodukten von C10 - bis C20 -Fettalkoholen mit 1 bis 4 Mol Ethylenoxid pro Mol Fettalkohol enthält.6: washing additive according to any one of claims 1 to 5, characterized in that it contains, as an anti-gel agent, a mixture of a polyhydric alcohol and condensation products of C 10 to C 20 fatty alcohols with 1 to 4 moles of ethylene oxide per mole of fatty alcohol. 7. Waschzusatz nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß das Gewichtsverhältnis von nichtionischem Tensid zu mehrwertigem Alkohol im Bereich von 1 1 bis 1 : 2 liegt.7. washing additive according to one of claims 1 to 6, characterized in that the weight ratio of nonionic surfactant to polyhydric alcohol is in the range of 1 1 to 1: 2. 8. Waschzusatz nach Anspruch 6, dadurch gekennzeichnet, daß das Gewichtsverhältnis von nichtionischem Tensid zu mehrwertigem Alkohol zu Fettalkoholethoxylat-Addukt im Bereich von (7 bis 12) zu (5 bis 16) zu (0,5 bis 4) liegt.8. Washing additive according to claim 6, characterized in that the weight ratio of nonionic surfactant to polyhydric alcohol to fatty alcohol ethoxylate adduct is in the range from (7 to 12) to (5 to 16) to (0.5 to 4). 9. Waschzusatz nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, daß er zusätzlich in Wasser leicht lösliche Verbindungen, vorzugsweise aus der Natriumchlorid, Natriumacetat, Magnesiumchlorid, Harnstoff und Zucker umfassenden Gruppe enthält.9. Washing additive according to one of claims 1 to 8, characterized in that it additionally contains water-soluble compounds, preferably from the group comprising sodium chloride, sodium acetate, magnesium chloride, urea and sugar. 10. Waschzusatz nach einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, daß er zusätzlich Addukte von 15 bis 25 Mol Ethylenoxid an 1 Mol Fettalkohol enthält.10. Washing additive according to one of claims 1 to 9, characterized in that it additionally contains adducts of 15 to 25 moles of ethylene oxide with 1 mole of fatty alcohol. 11. Waschzusatz nach einem der Ansprüche 1 bis 10, dadurch gekennzeichnet, daß er zusätzlich ein wasserlösliches Salz einer Alkanpolyphosphonsäure enthält.11. washing additive according to one of claims 1 to 10, characterized in that it additionally contains a water-soluble salt of an alkane polyphosphonic acid. 12. Waschzusatz nach einem der Ansprüche 1 bis 11, dadurch gekennzeichnet, daß das filmbildende Polymere Polyvinylalkohol mit einem Verseifungsgrad zwischen 70 und 90 %, vorzugsweise zwischen 78 und 88 % ist.12. Washing additive according to one of claims 1 to 11, characterized in that the film-forming polymer is polyvinyl alcohol with a degree of saponification between 70 and 90%, preferably between 78 and 88%. 13. Waschzusatz nach einem der Ansprüchel bis 12, dadurch gekennzeichnet, daß der Polyvinylalkohol ein Molekulargewicht von 10 000 bis 100 000, vorzugsweise von 10 000 bis 50 000 hat.13. washing additive according to one of claims to 12, characterized in that the polyvinyl alcohol has a molecular weight of 10,000 to 100,000, preferably from 10,000 to 50,000. 14. Waschzusatz nach einem der Ansprüche 1 bis 13, dadurch gekennzeichnet, daß der Polyvinylalkohol mehrwertige Alkohole, vorzugsweise Glycerin und/oder Polyethylenglykol enthält.14. Washing additive according to one of claims 1 to 13, characterized in that the polyvinyl alcohol contains polyhydric alcohols, preferably glycerol and / or polyethylene glycol. 15. Waschzusatz nach einem der Ansprüche 1 bis 14, dadurch gekennzeichnet, daß der Polyvinylalkohol bis zu je 15 Gew.-%, bezogen auf den Polyvinylalkohol, Cellulosefasern und/oder Methylcellulose enthält.15. washing additive according to one of claims 1 to 14, characterized in that the polyvinyl alcohol contains up to 15 wt .-%, based on the polyvinyl alcohol, cellulose fibers and / or methyl cellulose. 16. Waschzusatz nach einem der Ansprüche 1 bis 15,'dadurch gekennzeichnet, daß das Gemisch aus Waschmittelbestandteilen wenigstens ein nichtionisches Tensid in Kombination mit einem Antigelmittel, wenigstens einen Aktivator für Perverbindungen und wenigstens eine stickstoffhaltige Verbindung aus der quartäre Ammöniumverbindungen mit einem langkettigen Alkyl- oder Alkenylrest mit 10 bis 20 Kohlenstoffatomen und im übrigen Alkylresten mit 1 bis 4 Kohlenstoffatomen, Anlagerungsprodukte von 1 bis 6 Mol Ethylenoxid an l Mol eines primären Fettamins mit einem langkettigen Alkyl-oder Alkenylrest mit 10 bis 16 Kohlenstoffatomen, Verbindungen der Formel R-NN-CH2-CH2-COONa, in der R einen Alkyl- oder Alkenylrest mit 10 bis 18 Kohlenstoffatomen, insbesondere mit 14 Kohlenstoffatomen bedeutet, umfassenden Gruppe und ein wasserlösliches Salz einer Alkanpolyphosphonsäure enthält.16. Washing additive according to one of claims 1 to 15, 'characterized in that the mixture of detergent components at least one nonionic surfactant in combination with an anti-gel agent, at least one activator for per compounds and at least one nitrogen-containing compound from the quaternary ammonium compounds with a long-chain alkyl or Alkenyl radical with 10 to 20 carbon atoms and otherwise alkyl radicals with 1 to 4 carbon atoms, addition products of 1 to 6 moles of ethylene oxide with 1 mole of a primary fatty amine with a long-chain alkyl or alkenyl radical with 10 to 16 carbon atoms, compounds of the formula R-NN-CH 2 -CH 2 -COONa, in which R denotes an alkyl or alkenyl radical having 10 to 18 carbon atoms, in particular having 14 carbon atoms, comprising a group and a water-soluble salt of an alkane polyphosphonic acid. 17. Verfahren zur Herstellung eines Waschzusatzes nach einem der Ansprüche 1 bis 16, dadurch gekennzeichnet, daß man die Wirk- und Hilfsstoffe nach den Ansprüchen 1 bis 11, gegebenenfalls unter Zusatz von Wasser, bei erhöhter Temperatur mit einem wasserlöslichen, filmbildenden Polymeren und den Hilfsstoffen nach den Ansurüchen 14 und 15 in einem Verhältnis (Wirkstoff + Hilfsstoffe) zu (Polymere) von 1 : 10 bis 5 : 1, vorzugsweise von 1,5 : 1 bis 3,0 : 1 vermischt und das Gemisch zu Folien formt, die so dick sind, daß sie nach dem anschließenden Trocknen bei 60 bis 80 °C auf einen Wassergehalt von 2 bis 10 Gew.-%, bezogen auf die wasserfreie, wirkstoff- und hilfsstoffhaltige Folie, gegebenenfalls unter Auswalzen, eine Dicke von 0,4 bis 1,5 mm aufweisen.17. A process for the preparation of a washing additive according to one of claims 1 to 16, characterized in that the active ingredients and auxiliaries according to claims 1 to 11, optionally with the addition of water, at elevated temperature with a water-soluble, film-forming polymer and the auxiliaries according to the An suruchen 14 and 15 in a ratio (active ingredient + excipients) to (polymers) of 1:10 to 5: 1, preferably from 1.5: 1 to 3.0: 1 mixed and the mixture is formed into films that are so thick that after the subsequent drying at 60 to 80 ° C to a water content of 2 to 10 wt .-%, based on the water-free, active ingredient and auxiliary-containing film, optionally with rolling, a thickness of 0.4 to 1.5 mm.
EP85107057A 1984-06-14 1985-06-07 Additive for washing Expired - Lifetime EP0164703B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3422055 1984-06-14
DE19843422055 DE3422055A1 (en) 1984-06-14 1984-06-14 WASHING ADDITIVE

Publications (3)

Publication Number Publication Date
EP0164703A2 true EP0164703A2 (en) 1985-12-18
EP0164703A3 EP0164703A3 (en) 1986-04-02
EP0164703B1 EP0164703B1 (en) 1990-01-17

Family

ID=6238323

Family Applications (1)

Application Number Title Priority Date Filing Date
EP85107057A Expired - Lifetime EP0164703B1 (en) 1984-06-14 1985-06-07 Additive for washing

Country Status (5)

Country Link
EP (1) EP0164703B1 (en)
JP (1) JPS6112796A (en)
CA (1) CA1242949A (en)
DE (2) DE3422055A1 (en)
ES (1) ES8604299A1 (en)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0223175A2 (en) * 1985-11-18 1987-05-27 Henkel Kommanditgesellschaft auf Aktien Process for encapsulating textile-conditioning agents
EP0244796A1 (en) * 1986-05-09 1987-11-11 Henkel Kommanditgesellschaft auf Aktien Process for the preliminary treatment of dirty textiles
US5800755A (en) * 1995-09-19 1998-09-01 Warwick International Group Limited Agglomerated active with controlled release
WO2002026928A1 (en) * 2000-09-28 2002-04-04 The Dow Chemical Company Polymer composite structures useful for controlled release systems
WO2003010266A1 (en) * 2001-07-24 2003-02-06 Unilever N.V. Polymer products
DE20313248U1 (en) * 2003-08-27 2005-01-05 Melitta Haushaltsprodukte Gmbh & Co Kommanditgesellschaft Cleaning agent for spectacle lenses comprises water-soluble film containing embedded tensides which are released as film dissolves
WO2006124483A1 (en) * 2005-05-13 2006-11-23 The Procter & Gamble Company Bleaching product

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2533763B2 (en) * 1986-10-27 1996-09-11 忠生 白石 Bath salts containing film-like components
TW399096B (en) 1996-07-03 2000-07-21 Kao Corp The sheet-like article for laundry
DE19709991C2 (en) 1997-03-11 1999-12-23 Rettenmaier & Soehne Gmbh & Co Detergent compact and process for its manufacture
DE19710254A1 (en) * 1997-03-13 1998-09-17 Henkel Kgaa Shaped or active cleaning moldings for household use
EP1048722B1 (en) * 1998-07-23 2005-06-08 Kao Corporation Sheet-form laundering article
EP1436376B1 (en) * 2001-10-09 2010-04-21 Arrow Coated Products Limited Method of manufacturing of embedded water-soluble film system
CN1421519A (en) * 2001-11-23 2003-06-04 吕秀娟 Lamelliform sanitory washing article and its making process and use
WO2019056336A1 (en) 2017-09-25 2019-03-28 The Procter & Gamble Company Unitary laundry detergent article
KR102642620B1 (en) 2019-01-15 2024-03-05 더 프록터 앤드 갬블 캄파니 Multilayer dissolvable solid article with apertures or holes
CN112004650A (en) 2019-03-25 2020-11-27 宝洁公司 Multilayer dissolvable solid article and method of making same
EP4065064A1 (en) 2019-11-29 2022-10-05 The Procter & Gamble Company Flexible, porous, dissolvable solid sheet articles having large pores and method of making same
CN117442517A (en) 2020-02-20 2024-01-26 宝洁公司 Flexible porous dissolvable solid sheet article comprising cationic surfactant
BR112023005054A2 (en) 2020-10-09 2023-04-18 Procter & Gamble MULTILAYER DISOLUBLE SOLID ARTICLE CONTAINING SOLID PARTICLES FOR ITS PRODUCTION

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2367114A1 (en) * 1976-10-06 1978-05-05 Procter & Gamble LAUNCHING ADDITIVES.
US4115292A (en) * 1977-04-20 1978-09-19 The Procter & Gamble Company Enzyme-containing detergent articles
EP0000226A1 (en) * 1977-06-29 1979-01-10 THE PROCTER & GAMBLE COMPANY Laundry additive substrate for stain removal
EP0070474A1 (en) * 1981-07-17 1983-01-26 Henkel Kommanditgesellschaft auf Aktien Process for the production of enveloped granular bleaching activators
EP0079712A1 (en) * 1981-11-10 1983-05-25 The Clorox Company Borate solution soluble polyvinyl alcohol films
EP0106634A1 (en) * 1982-10-08 1984-04-25 THE PROCTER & GAMBLE COMPANY Bodies containing bleach activators
EP0118191A1 (en) * 1983-02-03 1984-09-12 The Procter & Gamble Company Laundry additive compositions

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2367114A1 (en) * 1976-10-06 1978-05-05 Procter & Gamble LAUNCHING ADDITIVES.
US4115292A (en) * 1977-04-20 1978-09-19 The Procter & Gamble Company Enzyme-containing detergent articles
EP0000226A1 (en) * 1977-06-29 1979-01-10 THE PROCTER & GAMBLE COMPANY Laundry additive substrate for stain removal
EP0070474A1 (en) * 1981-07-17 1983-01-26 Henkel Kommanditgesellschaft auf Aktien Process for the production of enveloped granular bleaching activators
EP0079712A1 (en) * 1981-11-10 1983-05-25 The Clorox Company Borate solution soluble polyvinyl alcohol films
EP0106634A1 (en) * 1982-10-08 1984-04-25 THE PROCTER & GAMBLE COMPANY Bodies containing bleach activators
EP0118191A1 (en) * 1983-02-03 1984-09-12 The Procter & Gamble Company Laundry additive compositions

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0223175A2 (en) * 1985-11-18 1987-05-27 Henkel Kommanditgesellschaft auf Aktien Process for encapsulating textile-conditioning agents
EP0223175A3 (en) * 1985-11-18 1989-07-05 Henkel Kommanditgesellschaft auf Aktien Process for encapsulating textile-conditioning agents
EP0244796A1 (en) * 1986-05-09 1987-11-11 Henkel Kommanditgesellschaft auf Aktien Process for the preliminary treatment of dirty textiles
US5800755A (en) * 1995-09-19 1998-09-01 Warwick International Group Limited Agglomerated active with controlled release
WO2002026928A1 (en) * 2000-09-28 2002-04-04 The Dow Chemical Company Polymer composite structures useful for controlled release systems
WO2003010266A1 (en) * 2001-07-24 2003-02-06 Unilever N.V. Polymer products
DE20313248U1 (en) * 2003-08-27 2005-01-05 Melitta Haushaltsprodukte Gmbh & Co Kommanditgesellschaft Cleaning agent for spectacle lenses comprises water-soluble film containing embedded tensides which are released as film dissolves
WO2006124483A1 (en) * 2005-05-13 2006-11-23 The Procter & Gamble Company Bleaching product

Also Published As

Publication number Publication date
EP0164703B1 (en) 1990-01-17
EP0164703A3 (en) 1986-04-02
ES8604299A1 (en) 1986-01-16
JPS6112796A (en) 1986-01-21
DE3422055A1 (en) 1985-12-19
ES544107A0 (en) 1986-01-16
CA1242949A (en) 1988-10-11
DE3575440D1 (en) 1990-02-22

Similar Documents

Publication Publication Date Title
EP0164703B1 (en) Additive for washing
EP0160254B1 (en) Additive for a washing bath
EP0170791B1 (en) Process for the production of a washing additive in the form of tablets
EP1148868B1 (en) Detergent mixtures
DE2636673C2 (en)
DE3728256A1 (en) NON-AQUEOUS LIQUID BLENDER-REINFORCING COMPOSITION
DE3727727A1 (en) Dirt-releasing PET-POET COPOLYMER METHOD FOR PRODUCING AND APPLYING THE SAME IN DETERGENTS
DE2604990A1 (en) LIQUID DETERGENT COMPOSITIONS
DE2336291A1 (en) LIQUID DETERGENT AND DETERGENT
EP1592762A1 (en) Detergents or cleaning agents comprising a water-soluble building block system and a cellulose derivative with dirt dissolving properties
DE1467613C3 (en) Low-foaming detergent
EP1099748A2 (en) Surfactant containing detergent compositions
DE3609345A1 (en) LIQUID TEXTILE DETERGENT AND BLENDER
DE3402437A1 (en) POWDERED SOFT SOFT DETERGENT, METHOD FOR THE PRODUCTION THEREOF AND DETERGENT CONTAINING THIS
WO2000031227A1 (en) Aqueous bleach concentrate
DE2349323A1 (en) Antimicrobial cleaning compsn. - contg. anionic and cationic surfactants
DE10163578A1 (en) Laundry pretreatment agents
DE19606765A1 (en) Process for the production of dishwasher tablets
DE2653259A1 (en) SOFTENING AND DETERGENT MIXTURES
DE19704229A1 (en) Cobuilder-containing additive for detergents or cleaning agents
DE19822391A1 (en) High viscosity, aqueous, liquid, hydrogen peroxide-containing bleaching or pre-spotting agent
EP1084224B1 (en) Aqueous bleaching agent with viscose structure
EP0264825A2 (en) Pasty formulation containing little water
DE10032588A1 (en) Increasing viscosity stability of thickened aqueous liquid bleach or prewash compositions based on hydrogen peroxide comprises increasing the pH
DE2430245C3 (en) Washing and cleaning agents containing anionic and cationic surfactants

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Designated state(s): AT BE CH DE FR GB IT LI LU NL SE

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): AT BE CH DE FR GB IT LI LU NL SE

17P Request for examination filed

Effective date: 19860911

17Q First examination report despatched

Effective date: 19871109

RBV Designated contracting states (corrected)

Designated state(s): DE

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): DE

REF Corresponds to:

Ref document number: 3575440

Country of ref document: DE

Date of ref document: 19900222

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Effective date: 19910301