EP0184099A2 - Means and process for after-treating washed laundry - Google Patents

Means and process for after-treating washed laundry Download PDF

Info

Publication number
EP0184099A2
EP0184099A2 EP85114926A EP85114926A EP0184099A2 EP 0184099 A2 EP0184099 A2 EP 0184099A2 EP 85114926 A EP85114926 A EP 85114926A EP 85114926 A EP85114926 A EP 85114926A EP 0184099 A2 EP0184099 A2 EP 0184099A2
Authority
EP
European Patent Office
Prior art keywords
weight
percent
salts
quaternary ammonium
composition according
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
EP85114926A
Other languages
German (de)
French (fr)
Other versions
EP0184099A3 (en
EP0184099B1 (en
Inventor
Norbert Dr. Schindler
Hans Dr. Nüsslein
Edgar Dr. Köppelmann
Jörg Poethkow
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
Priority to AT85114926T priority Critical patent/ATE59677T1/en
Publication of EP0184099A2 publication Critical patent/EP0184099A2/en
Publication of EP0184099A3 publication Critical patent/EP0184099A3/en
Application granted granted Critical
Publication of EP0184099B1 publication Critical patent/EP0184099B1/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
    • C11D3/3947—Liquid 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
    • C11D1/38—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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/042—Acids
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/046—Salts
    • 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
    • C11D3/3937—Stabilising agents

Definitions

  • the laundry treatment generally requires several operations for "acidifying” (neutralizing) and “antichlorinating” (reducing) as well as softening or antibacterial treatment.
  • Agents and processes with which acidification and antichlorination of freshly washed laundry * as well as post-treatment with textile softeners or antibacterial agents can be carried out in a single operation are therefore a considerable disadvantage of the post-washing treatment for commercial laundries.
  • liquid aftertreatment agents which can be produced, for example, by dissolving powdery agents into a stock solution, usually fails because of the poor solubility or the insufficient stability of the solution or dispersion of the - because of the metering devices for liquid agents usually present on commercial washing machines known aftertreatment agents intended for use in commercial laundries.
  • Known liquid agents do not have acidifying, antichlorinating and softening properties at the same time.
  • DE-OS 32 05 317 describes a liquid laundry aftertreatment agent which simultaneously combines textile softening, acidifying and antichlorinating properties.
  • the textile treatment agents disclosed here contain, in addition to quaternary ammonium compounds with textile softening action, hydrogen peroxide or organic percarboxylic acids as reducing agents for chlorine and chlorine compounds with positive value and additionally stabilizers for the peroxy compounds, especially the hydrogen peroxide.
  • acidifying agents in particular phosphoric acid or acidic salts of phosphoric acid, but also other inorganic and / or organic acids or salts
  • the pH of the agent is lowered so that it is at most 4.
  • These agents of DE-OS 32 05 317 can also contain other usual additives, for example antibacterial agents. Examples of other additives are dispersants, foam regulators, and colorants and fragrances. Water may be used as the liquid carrier, with additions of organic water-miscible solvents.
  • the invention is based on the task of further improving the means described last.
  • the invention aims to extend the shelf life and thus the useful life of such agents.
  • the substance mixtures of the type described contain per-compounds, in particular hydrogen peroxide, as an essential constituent.
  • hydrogen peroxide quaternary ammonium compounds and an acidic agent, in particular phosphoric acid or phosphoric acid salts
  • an acidic agent in particular phosphoric acid or phosphoric acid salts
  • the invention relates in a first embodiment to liquid laundry aftertreatment agents with textile-softening, acidifying and antichlorizing properties, containing hydrogen peroxide or an organic percarboxylic acid, stabilizers for peroxy compounds, textile-softening quaternary ammonium compounds and acidifying agents and, if desired, other additives which are customary .
  • the new teaching is characterized in that hexafluorosilicic acid and / or its water-soluble salts are present at least partially as acidifying agents.
  • the amount of hexafluorosilicic acid and / or its water-soluble salts in the laundry treatment composition is preferably about 1 to 25 percent by weight, in particular about 5 to 20 percent by weight.
  • the hexafluorosilicic acid or its salts are the sole or predominant constituent for acidifying the treatment agent, it also being preferred here not to set pH values above 4 in the aqueous aftertreatment agent.
  • Suitable water-soluble salts of hexafluorosilicic acid are, for example, corresponding salts from the first to third groups of the periodic system, the ammonium salt of the acid mentioned or the corresponding amine and / or quaternary ammonium salts.
  • particularly suitable acidifying components can be their sodium, potassium and / or ammonium salts, the magnesium and / or zinc salt, the magnesium salt being preferred because of its excellent acidifying and peroxide-stabilizing action.
  • Particularly suitable amounts of these acidifying agents are in the range from about 8 to 18 weight percent.
  • the quaternary ammonium compounds with preferably two long-chain, preferably saturated aliphatic radicals each having 14 to 26, preferably 16 to 20 carbon atoms and at least one quaternary nitrogen atom in the molecule are suitable as fabric softening agents.
  • the long-chain aliphatic radicals can be straight-chain or branched and can accordingly be derived from fatty acids, or from fatty amines, Guerbetamines, or from the alkylamines obtainable by reduction of nitroparaffins.
  • These quaternary ammonium compounds are, in particular, derivatives of ammonia, ie the quaternary salts obtainable by alkylation of long-chain secondary amines, such as, for. B. the compounds distearyldimethylammonium chloride or di.
  • the tallow alkyl dimethyl ammonium chloride or the imidazoline compounds obtainable by reacting 1 mole of an aminoalkyl ethylenediamine or hydroxyalkyl ethylenediamine with 2 moles of a long-chain C 12 -C 26 fatty acid or its ester, which are then converted into the quaternary imidazolinium compounds by alkylation.
  • the anion generally consists of the acid residue which has arisen from the alkylating agent used in the quaternization.
  • chloride, bromide, methyl sulfate, ethyl sulfate, methane, ethane or toluenesulfonate are suitable as anions.
  • the condensates of 1-3 mols of fatty acid alkyl ester or 1/3-1 mol of fatty acid triglyceride with 1Nol of a hydroxyalkylpolyamine, for example hydroxyethylethylenediamine or hydroxyethyldiethyle-n-triamine are also suitable as fabric softeners. Particularly suitable is obtained by reacting 1 mol of a fatty acid triglyceride, particularly hydrogenated tallow, with 1 mol of hydroxyethylethylene d.iamin at 90-150 C d available product.
  • These active ingredients lead to a uniform, striking improvement in the treated textiles with simultaneous antistatic finishing without staining.
  • the agent according to the invention preferably contains hydrogen peroxide (H 2 O 2 ) as an antichlorinating component.
  • H 2 O 2 acts as a reducing agent compared to the stronger oxidizing agent hypochlorite.
  • organic percarboxylic acids such as. B. diperazelaic acid or diperisophthalic acid can be used.
  • the hydrogen peroxide is preferred because of its easy accessibility and because it is converted to the water which is present anyway upon reduction. Another advantage of H 2 O 2 is that it cannot form any solid deposits.
  • the agent contains a heavy metal complexing agent.
  • Suitable complexing agents are e.g. B. alkane polyphosphonic acids, amino and hydroxyalkane polyphosphonic acids and phosphonocarboxylic acids, such as. B. the compounds methanediphosphonic acid, 1-aminoethane-1,1-diphosphonic acid, aminotrimethylene triphosphonic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid and 1-hydroxyethane-1,1-diphosphonic acid or aminopolycarboxylic acids such as. B.
  • nitrilotriacetic acid ethylenediaminetetraacetic acid or hydroxyethylethylenediaminetriacetic acid or its alkali metal salts.
  • Such heavy metal complexing agents also counteract a yellowing tendency of the laundry caused by heavy metal ions in the rinse water.
  • 1-Hydroxyethane-1,1-diphosphonic acid and its alkali salts have a particularly good stabilizing effect.
  • inorganic and / or organic acids or corresponding acid salts can also be used. Especially when working with hydrogen peroxide, the choice of additional acids or acid salts is preferred, which do not in turn interact with the peroxide.
  • Orthophosphoric acid and / or its acidic salts for example sodium dihydrogen phosphate, are particularly suitable.
  • the agents according to the invention can contain customary further additives.
  • Antimicrobial agents are an example of this.
  • bactericidal or bacteriostatic or fungicidal or fungistatic compounds are understood. These active ingredients are said to be water-soluble either as such or in the form of their salts.
  • the antimicrobial agents suitable as additives are e.g. For example, such quaternary ammonium compounds which, in addition to a long-chain aliphatic and two short-chain aliphatic hydrocarbon radicals, contain an aromatic radical linked via an aliphatic carbon atom to the nitrogen atom, or an aliphatic organic radical having double bonds in the molecule.
  • antimicrobial quaternary ammonium compounds are the following: dimethyl-benzyl-dodecylammonium chloride, dimethyl-benzyl-tetradecylammonium chloride, dimethyl- (ethylbenzyl) -dodecyl-ammonium chloride, dimethyl-benzyl-decylammonium bromide, diethyl-benzyl-dodecylammylium diethylammonium ammonium chloride, dibutylallyl, methyl-ethyl-benzyl, ethyl-cyclohexyl-allyl, ethyl-crotyl-diethylaminoethyl-dodecyl-ammonium chloride and in particular cocoalkyldimethylbenzylammonium chloride. Dimethyldidecylammonium chloride is also effective.
  • antimicrobial agents can also be used, provided they are stable in the presence of per compounds in an acidic medium.
  • betaines such as. B. Dodecyl-di (aminoethyl) glycine.
  • Other useful antimicrobial agents are e.g. B. hexamethylene bis (chlorophenyl) biguanide digluconate or dihydrochloride and dodecylglycine.
  • nonionic surfactants are particularly suitable as dispersants, as they can be contained in liquid textile aftertreatment agents according to the invention. These include products that owe their hydrophilic properties to the presence of polyether chains, amine oxide, sulfoxide or phosphine oxide groups, alkylolar groups or, in general, an accumulation of hydroxyl groups.
  • nonionics contain at least one hydrophobic radical with 8-26, preferably 10-20 and in particular 12-18 carbon atoms in the molecule, and at least one nonionic, water-solubilizing group.
  • the preferably saturated hydrophobic residue is usually aliphatic, possibly also alicyclic in nature; it can be connected to the water-solubilizing groups directly or via intermediate links.
  • intermediate links come z. B. benzene rings, carboxylic acid ester or carbonamide groups, ether or ester-bonded residues of polyhydric alcohols, such as. B. that of ethylene glycol, propylene glycol, glycerol or corresponding polyether radicals in question.
  • Typical nonionics preferred as dispersants are e.g. B. the adducts of about 9 moles of ethylene oxide with N o -nylphenol or with dodecyl alcohol, polyethylene glycols up to 50-ethoxy units or polyethoxy-polypropoxy-glycols with up to 20 ethoxy or propoxy units.
  • quaternary ammonium compound which softens the textile preference is given in particular to the compounds which are used to a large extent, dimethylditalgalkylammonium chloride or dimethyldistearylammonium chloride, of which dirzethyldistearylammonium chloride is particularly preferred.
  • Quaternary ammonium compounds are preferred as antibacterial active substances, in particular coconut alkyldimethylbenzylammonium chloride.
  • Hydrogen peroxide which has sufficient stability in the presence of heavy metal complexing agents, is used in particular for the antichlorination.
  • Suitable heavy metal complexing agents by means of which both the hydrogen peroxide is stabilized and discoloration of the laundry is counteracted by the use of washing water and rinsing water with an intrinsically disruptive content of heavy metal ions, are above all alkane polyphosphonic acids and aminopolycarboxylic acids, especially hydroxyethylenediamino-t R acetic acid and / or 1-hydroxyethanl, 1-diphosphonic acid b between their alkali salts.
  • Agents according to the invention contain especially when large amounts of textile-softening quaternary ammonium compounds are used to achieve a pronounced softening effect, expediently small amounts, for example 0.5-5% by weight of nonionic surfactants as dispersants.
  • This substance mixture which corresponds to the teaching of DE-OS 32 05 317, is compared with regard to its degree of hydrogen peroxide conservation during storage for 12 weeks at 40 ° C. compared to the active substance mixtures according to the invention summarized in the following table under numbers 2 to 5.
  • magnesium hexafluorosilicate! Is used as an acidifying agent.
  • the superior effect of the active ingredient mixtures according to the invention with regard to the degree of H 2 0 2 conservation after storage at 40 ° C. for 12 weeks can be seen from the corresponding numerical values.
  • the numerical values of the mixtures according to 2, 4, 5 and 6 are in the range 79-88% H 2 0 2 Conservation compared to 28.5% for the active ingredient mixture according to the prior art.
  • Even the active ingredient mixture 3 used for comparison which contains no complexing agent but contains magnesium fluorosilicate, is still significantly better in terms of the H 2 0 2 degree of preservation than the substance mixture of the prior art used for comparison.
  • the active ingredient mixtures according to the invention are generally placed in the last rinsing bath of a commercial washing machine - depending on the implementation of the previous washing process, i.e. of the remaining residual alkali or the desired softening or microbicidal effect - in an amount of 1 to 5 g / l to the rinse water (temperature approx. 25 ° C) and treat the washed and bleached with hypochlorite laundry for approx. 2 minutes. After this treatment liquor has been spun off, it can be determined by measuring the pH of the adhering moisture that alkaline detergent residues on the laundry are neutralized. The laundry does not smell of chlorine. After drying, it has a soft full grip.

Abstract

Liquid aftertreatment preparations for laundry having fabric-softening, acidifying and antichlorinating properties which contain, in acidic aqueous solution, hydrogen peroxide or an organic percarboxylic acid, a quaternary ammonium compounds, and hexafluorosilicic acid and/or water-soluble salts thereof, more especially the magnesium salt, as an acidifying agent. Preparations containing magnesium salts of hexafluorosilicic acid are distinguished by particularly high stability of the per compounds.

Description

In gewerblichen Wäschereien werden üblicherweise sehr alkalireiche Waschmittel eingesetzt. Eine Bleiche erfolgt gewöhnlich mit Hypochlorit. Wasch- und Bleichmittelreste, die der gewaschenen Wäsche nach dem letzten Spülvorgang anhaften, sind durch Spülen allein wirtschaftlich nicht zu entfernen. Die Beseitigung dieser Reste ist aber beispielsweise zur Vermeidung von Hautirritationen und zur Beseitigung eines vom Hypochlorit stammenden unangenehmen Chlorgeruchs notwendig. Hypochlorit- bzw. Chlorreste schädigen zudem die Textilfasern.In commercial laundries, very alkaline detergents are usually used. Bleaching is usually done with hypochlorite. Detergent and bleach residues that adhere to the washed laundry after the last rinsing process cannot be removed economically by rinsing alone. The removal of these residues is necessary, for example, to avoid skin irritation and to remove an unpleasant smell of chlorine originating from hypochlorite. Hypochlorite or chlorine residues also damage the textile fibers.

Man setzt deswegen dem letzten Spülbad Mittel mit sauren und/oder reduzierenden Bestandteilen, durch die störende Wasch- und Bleichmittelreste in nicht störende Verbindungen umgewandelt werden, zu. In vielen Fällen ist es weiterhin wünschenswert, daß gewaschene Wäsche nach dem Trocknen einen angenehmen weichen Griff aufweist; besonders trifft dies für Wäsche, die auf der Haut aufliegt, und für Frottierartikel zu. Gelegentlich ist auch eine bakteriostatische Ausrüstung der Textilien, z. B. von Rollenhandtüchern erforderlich.For this reason, agents with acidic and / or reducing constituents are added to the last rinsing bath, through which disruptive detergent and bleach residues are converted into non-disruptive compounds. In many cases it is also desirable that washed laundry has a pleasantly soft feel after drying; this is especially true for laundry that lies on the skin and for terry towels. Occasionally, bacteriostatic finishing of the textiles, e.g. B. roll towels required.

Aus diesem Grunde schließt sich häufig im letzten Spülbad eine Behandlung mit einem textilweichmachenden Mittel und/oder mit antibakteriellen Wirkstoffen in wäßriger Flotte oder beim anschließenden Trocknungsgang in einem automatischen Wäschetrockner an.For this reason, a treatment with a fabric softening agent and / or with antibacterial agents in aqueous liquor or in the subsequent drying cycle in an automatic tumble dryer is often followed in the last rinsing bath.

Die Wäschebehandlung erfordert im allgemeinen mehrere Arbeitsgänge für "Absäuern" (Neutralisieren) und "Antichlorieren" (Reduzieren) sowie Weichmachen bzw. antibakterielle Ausrüstung. Mittel und Verfahren, mit denen gleichzeitig ein Absäuern und Antichlorieren von frisch gewaschener Wäsche *sowie eine Nachbehandlung mit Textilweichmachern bzw. antibakteriellen Wirkstoffen in einem Arbeitsgang möglich ist, stellen daher für gewerbliche Wäschereien eine beträchtliche Versinfacbung der Wäschenachbehandlung dar.The laundry treatment generally requires several operations for "acidifying" (neutralizing) and "antichlorinating" (reducing) as well as softening or antibacterial treatment. Agents and processes with which acidification and antichlorination of freshly washed laundry * as well as post-treatment with textile softeners or antibacterial agents can be carried out in a single operation are therefore a considerable disadvantage of the post-washing treatment for commercial laundries.

Die aus den US-Patentschriften 3 193 505, 3 676 353, .3 925 230, 3 984 335, 4 053 423, 4 089 786, 4 115 281 und der deutschen Patentanmeldung P 29 04 876.8 bekannten Mittel und Verfahren erfüllen die Forderung nach einer gleichermaßen guten Weichmachung bzw. antibakteriellen Ausrüstung, Absäuerung und Antichlorierung in einem Arbeitsgang nicht oder nur unvollkommen, oder die Mittel lassen sich schlecht automatisch dosieren, da sie als , Pulver vorliegen. Das an sich - wegen der an gewerblichen Waschmaschinen üblicherweise vorhandenen Dosiereinrichtungen für flüssige Mittel - wünschenswerte Arbeiten mit flüssigen Nachbehandlungsnitteln, die man beispielsweise durch Auflösen von pulverförmigen Mitteln zu einer Vorratslösung herstellen könnte, scheitert meist an der schlechten Löslichkeit oder der ungenügenden Lösungs-oder Dispersionsstabilität der bekannten, für den Einsatz in gewerblichen Wäschereien vorgesehenen Nachbehandlungsmittel. Bekannte flüssige Mittel weisen nicht gleichzeitig absäuernde, antichlorierende und weichmachende Eigenschaften auf.The means and methods known from US Pat. Nos. 3,193,505, 3,676,353, .3,925,230, 3,984,335, 4,053,423, 4,089,786, 4,115,281 and German Patent Application P 29 04 876.8 meet the requirement an equally good softening or antibacterial treatment, acidification and antichlorination in one operation, or only incompletely, or the agents are difficult to dose automatically, since they are present as a powder. The desirable work with liquid aftertreatment agents, which can be produced, for example, by dissolving powdery agents into a stock solution, usually fails because of the poor solubility or the insufficient stability of the solution or dispersion of the - because of the metering devices for liquid agents usually present on commercial washing machines known aftertreatment agents intended for use in commercial laundries. Known liquid agents do not have acidifying, antichlorinating and softening properties at the same time.

In der DE-OS 32 05 317 ist ein flüssiges Wäschenachbehandlungsmittel beschrieben, das gleichzeitig textilweichmachende, absäuerende und antichlorierende Eigenschaften miteinander verbindet.. Die hier offenbarten Textilbehandlungsmittel enthalten neben quartären Ammoniumverbindungen mit textilweichmachender Wirkung Wasserstoffperoxid oder organische Percarbonsäuren als Reduktionsmittel für Chlor und Chlorverbindungen mit positiver Wertigkeit und zusätzlich Stabilisatoren für die Peroxi- Verbindungen, insbesondere das Wasserstoffperoxid. Durch Zugabe von Säuerungsmitteln, insbesondere Phosphorsäure oder saurer Salze der Phosphorsäure, aber auch andere anorganische und/oder organische Säuren bzw. Salze, wird der pH-wert des Mittels soweit gesenkt, daß er bei höchstens 4 liegt. Diese Mittel der DE-OS 32 05 317 können darüberhinaus übliche weitere Zusatzstoffe,beispielsweise antibakterielle Wirkstoffe enthalten. Beispiele für andere Zusatzstoffe sind Dispergatoren, Schaumregulatoren sowie Farb" und Duftstoffe. Als flüssiger Träger kommt Wasser evtl, mit Zusätzen organischer wassermischbarer Lösungsmittel in Betracht.DE-OS 32 05 317 describes a liquid laundry aftertreatment agent which simultaneously combines textile softening, acidifying and antichlorinating properties. The textile treatment agents disclosed here contain, in addition to quaternary ammonium compounds with textile softening action, hydrogen peroxide or organic percarboxylic acids as reducing agents for chlorine and chlorine compounds with positive value and additionally stabilizers for the peroxy compounds, especially the hydrogen peroxide. By adding acidifying agents, in particular phosphoric acid or acidic salts of phosphoric acid, but also other inorganic and / or organic acids or salts, the pH of the agent is lowered so that it is at most 4. These agents of DE-OS 32 05 317 can also contain other usual additives, for example antibacterial agents. Examples of other additives are dispersants, foam regulators, and colorants and fragrances. Water may be used as the liquid carrier, with additions of organic water-miscible solvents.

Die Erfindung geht von der Aufgabe aus die zuletzt geschilderten Mittel weiterhin zu verbessern. Insbesondere will die Erfindung die Lagerstabilität und damit die Gebrauchsdauer solcher Mittel verlängern.The invention is based on the task of further improving the means described last. In particular, the invention aims to extend the shelf life and thus the useful life of such agents.

Die Stoffgemische der geschilderten Art enthalten als einen wesentlichen Bestandteil Per-Verbindungen, insbesondere Wasserstoffperoxid. Mit Wasserstoffperoxid, quartären Ammoniumver- bindungen und einem sauren Agens, insbesondere Phosphorsäure bzw. Phosphorsäuresalzen, lassen sich bei gleichzeitiger Gegenwart eines Komplex bildners für Schwermetallionen bereits außerordentlich stabile Lösungen konfektionieren. Weiterführande Untersuchungen haben nun aber überraschender Weise gezeigt, daß bei Einsatz bzw. Mitverwendung ganz bestimmter Säuerungsmittel nochmals eine substantielle Veränderung der Lagerstabilität und damit der Gebrauchsdauer von Mitteln der geschilderten Art erreicht werden kann.The substance mixtures of the type described contain per-compounds, in particular hydrogen peroxide, as an essential constituent. With hydrogen peroxide, quaternary ammonium compounds and an acidic agent, in particular phosphoric acid or phosphoric acid salts, extremely stable solutions can already be assembled in the presence of a complexing agent for heavy metal ions. Further studies have now surprisingly shown that when using or using certain acidulants, there is again a substantial change in storage stability and thus the Service life of means of the type described can be achieved.

Gegenstand der Erfindung sind dementsprechend in einer ersten Ausführungsform flüssige Wäschenachbehandlungsmittel mit textilweichmachenden, absäuernden und antichlorierenden Eigenschaften, enthaltend in sauer eingestellter wäßriger Lösung Wasserstoffperoxid oder eine organische Percarbonsäure, Stabilisatoren für Peroxi-Verbindungen, textilweichmachende quartäre Ammoniumver- bindungen und Säuerungsmittel sowie gewünschtenfalls weitere !übliche Zusatzstoffe. Das Kennzeichen der neuen Lehre liegt darin, idaß als Säuerungsmittel wenigstens anteilsweise Hexafluorkieselsäure und/oder ihre wasserlöslichen Salze vorliegen. Bevorzugt beträgt die Menge der Hexafluorkieselsäure und/oder ihrer wasserlöslichen Salze im Wäschebehandlungsmittel etwa 1 bis 25 Gewichtsprozent, insbesondere etwa 5 bis 20 Gewichtsprozent. In einer wichtigen Ausführungsform der Erfindung sind die Hexafluorkieselsäure bzw. ihre Salze alleiniger oder überwiegender Be-;standteil zur Säuerung des Behandlungsmittels, wobei es auch hier bevorzugt ist im wäßrigen Nachbehandlungsmittel pH-Werte inicht oberhalb 4 einzustellen. Geeignete wasserlösliche Salze der Hexafluorkieselsäure sind beispielsweise entsprechende Salze der ersten bis dritten Gruppe des Periodischen Systems, das Ammoniumsalz der genannten Säure bzw. die entsprechenden amin- und/oder quartären Ammoniumsalze. Besonders geeignete Säuerungskomponenten können neben der Hexafluorkieselsäure ihre Natrium-, Kalium und/oder Ammoniumsalze, das Magnesium- und/oder das Zinksalz sein, wobei das Magnesiumsalz wegen seiner hervorragenden absäuernden und peroxidstabilisierenden Wirkung bevorzugt ist, Ganz besonders geeignete Mengen dieser Säuerungsmittel liegen im Bereich von etwa 8 bis 18 Gewichtsprozent.Accordingly, the invention relates in a first embodiment to liquid laundry aftertreatment agents with textile-softening, acidifying and antichlorizing properties, containing hydrogen peroxide or an organic percarboxylic acid, stabilizers for peroxy compounds, textile-softening quaternary ammonium compounds and acidifying agents and, if desired, other additives which are customary . The new teaching is characterized in that hexafluorosilicic acid and / or its water-soluble salts are present at least partially as acidifying agents. The amount of hexafluorosilicic acid and / or its water-soluble salts in the laundry treatment composition is preferably about 1 to 25 percent by weight, in particular about 5 to 20 percent by weight. In an important embodiment of the invention, the hexafluorosilicic acid or its salts are the sole or predominant constituent for acidifying the treatment agent, it also being preferred here not to set pH values above 4 in the aqueous aftertreatment agent. Suitable water-soluble salts of hexafluorosilicic acid are, for example, corresponding salts from the first to third groups of the periodic system, the ammonium salt of the acid mentioned or the corresponding amine and / or quaternary ammonium salts. In addition to hexafluorosilicic acid, particularly suitable acidifying components can be their sodium, potassium and / or ammonium salts, the magnesium and / or zinc salt, the magnesium salt being preferred because of its excellent acidifying and peroxide-stabilizing action. Particularly suitable amounts of these acidifying agents are in the range from about 8 to 18 weight percent.

Als textilweichmachende Wirkstoffen eignen sich die quartören Ammoniiumverbindungen mit vorzugsweise zwei langkettigen, vorzugsweise ge-!sättigten aliphatischen Resten mit je 14 bis 26, vorzugsweise 16 bis j 20 Kohlenstoffatomen und wenigstens einem quartärem Stickstoffatom im Molekül.The quaternary ammonium compounds with preferably two long-chain, preferably saturated aliphatic radicals each having 14 to 26, preferably 16 to 20 carbon atoms and at least one quaternary nitrogen atom in the molecule are suitable as fabric softening agents.

Die langicettigen aliphatischen Reste können geradkettig oder verzweigt sein und dementsprechend von Fettsäuren, bzw. von Fettaminen, Guerbetaminen, oder aus den durch Reduktion von Nitroparaffinen erhältlichen Alkylaminen abstammen. Bei diesen quartären Ammoniumverbindungen handelt es sich insbesondere um Derivate des Ammoniaks, d. h. um die durch Alkylierung von langkettigen sekundären Aminen erhältlichen quartären Salze, wie z. B. die Verbindungen Distearyldimethylammoniumchlorid bzw. Di- . talgalkyldimethylammoniumchlorid, oder um die durch Umsetzung von 1 Mol eines Aminoalkylethylendiamins oder Hydroxyalkylethylendiamins mit 2 Mol einer langkettigen C12-C26-Fettsäure oder deren Ester erhältlichen Imidazolinverbindungen, die anschließend durch Alkylierung in die quartären Imidazoliniumverbindungen überführt werden. In diesen quartären Ammoniumverbindungen besteht das Anion im allgemeinen aus dem Säurerest, der aus dem bei der Quaternierung verwendeten Alkylierungsmittel entstanden ist. Beispielsweise kommt als Anion daher Chlorid, Bromid, Methylsulfat, Ethylsulfat, Methan-, Ethan- oder Toluolsulfonat in Betracht. Neben diesen quartären Ammoniumverbindungen kommen als Textilweich-,macher auch die Kondensationsprodukte aus 1 - 3 Mol Fettsäurealkylester oder 1/3 - 1 Mol Fettsäuretriglycerid mit 1Nol eines Hydroxyalkylpo'yamins, beispielsweise Hydroxyethylethylendiamin oder Hydroxyethyldiethyle-n-triamin, in Betracht. Besonders geeignet ist das durch Umsetzung von 1 Mol eines Fettsäuretriglycerids, insbesondere gehärtetem Talg, mit 1 Mol Hydroxyethylethylen-d.iamin bei 90 - 150 dC erhältliche Produkt. Vorzugsweise wird als Textilweichmacher eine quartäre Ammoniunverbindung des Ammoniaktyps mit 2 C16-C20-Alkyl- oder Alkenylgruppen und 2 Methylgruppen im Molekül, und mit dem Chlorid-, Bromid- oder Methylsulfat-Anion, insbesondere das Distearyldimethylammoniumchlorid oder Ditalgalkyldimethylammoniumchlorid eingesetzt. Diese Wirkstoffe führen bei den behandelten Textilien zu einer gleichmäßigen markanten Griffverbesserung bei gleichzeitiger antistatischer Ausrüstung ohne Fleckenbildung.The long-chain aliphatic radicals can be straight-chain or branched and can accordingly be derived from fatty acids, or from fatty amines, Guerbetamines, or from the alkylamines obtainable by reduction of nitroparaffins. These quaternary ammonium compounds are, in particular, derivatives of ammonia, ie the quaternary salts obtainable by alkylation of long-chain secondary amines, such as, for. B. the compounds distearyldimethylammonium chloride or di. tallow alkyl dimethyl ammonium chloride, or the imidazoline compounds obtainable by reacting 1 mole of an aminoalkyl ethylenediamine or hydroxyalkyl ethylenediamine with 2 moles of a long-chain C 12 -C 26 fatty acid or its ester, which are then converted into the quaternary imidazolinium compounds by alkylation. In these quaternary ammonium compounds, the anion generally consists of the acid residue which has arisen from the alkylating agent used in the quaternization. For example, chloride, bromide, methyl sulfate, ethyl sulfate, methane, ethane or toluenesulfonate are suitable as anions. In addition to these quaternary ammonium compounds, the condensates of 1-3 mols of fatty acid alkyl ester or 1/3-1 mol of fatty acid triglyceride with 1Nol of a hydroxyalkylpolyamine, for example hydroxyethylethylenediamine or hydroxyethyldiethyle-n-triamine, are also suitable as fabric softeners. Particularly suitable is obtained by reacting 1 mol of a fatty acid triglyceride, particularly hydrogenated tallow, with 1 mol of hydroxyethylethylene d.iamin at 90-150 C d available product. A quaternary ammonium compound of the ammonia type with 2 C 16 -C 20 alkyl or alkenyl groups and 2 methyl groups in the molecule, and with the chloride, bromide or methyl sulfate anion, in particular the distearyldimethylammonium chloride or ditalgalkyldimethylammonium chloride, is preferably used as the textile softener. These active ingredients lead to a uniform, striking improvement in the treated textiles with simultaneous antistatic finishing without staining.

Wäsche, die mit einem Bleichmittel auf Hypochlorit-Basis behandelt wurde, haftet häufig ein schwacher Chlorgeruch an. Zur Beseitigung dieses Chlorgeruchs der Wäschestücke enthält das erfindungsgemäße Mittel vorzugsweise Wasserstoffperoxid (H2O2) als antichlorierenden Bestandteil. Das H2O2 wirkt gegenüber dem stärkeren Oxidationsmittel Hypochlorit als Reduktionsmittel. Anstelle von H2O2 können auch organische Percarbonsäuren wie z. B. Diperazelainsäure oder Diperisophthalsäure eingesetzt werden.Laundry that has been treated with a hypochlorite-based bleach often has a slight smell of chlorine. To eliminate this chlorine odor from the laundry, the agent according to the invention preferably contains hydrogen peroxide (H 2 O 2 ) as an antichlorinating component. The H 2 O 2 acts as a reducing agent compared to the stronger oxidizing agent hypochlorite. Instead of H 2 O 2 , organic percarboxylic acids such as. B. diperazelaic acid or diperisophthalic acid can be used.

Das Wasserstoffperoxid ist wegen seiner leichten Zugänglichkeit und weil es bei der Reduktion zu dem ohnehin anwesenden Wasser umgewandelt wird, bevorzugt. Ein weiterer Vorteil des H2O2 besteht darin, daß es keine festen Abla- gerungen bilden kann.The hydrogen peroxide is preferred because of its easy accessibility and because it is converted to the water which is present anyway upon reduction. Another advantage of H 2 O 2 is that it cannot form any solid deposits.

Zur Stabilisierung des erfindungsgemäßen Mittels gegenüber Schwermetall-; insbesondere Kupfer- und/oder Eisenionen enthält das Mittel einen Schwermetallkomplexbildner. Geeignete Komplexbildner sind z. B. Alkanpolyphosphonsäuren, Amino- und Hydroxyalkanpolyphosphonsäuren und Phosphonocarbonsäuren, wie z. B. die Verbindungen Methandiphosphonsäure, 1-Aminoethan-1,1-diphosphonsäure, Aminotrimethylentriphosphonsäure, 2-Phosphonobu-tan-1,2,4-tricarbonsäure und 1-Hydroxyethan-1,1-diphosphonsäure oder Aminopolycarbonsäuren wie z. B. Nitrilotriessigsäure, Ethylendiamintetraessigsäure oder Hydroxyethylethylendiamintriessigsäure bzw. deren Alkalisalze. Derartige Schwermetallkomplexbildner wirken auch einer durch Schwermetallionen im Spülwasser verursachten Vergilbungstendenz der Wäsche entgegen. Besonders gute stabilisierende Wirkung weist 1-Hydroxyethan-1,1-diphosphonsäure bzw. deren Alkalisalze auf.To stabilize the agent according to the invention against heavy metal; in particular copper and / or iron ions, the agent contains a heavy metal complexing agent. Suitable complexing agents are e.g. B. alkane polyphosphonic acids, amino and hydroxyalkane polyphosphonic acids and phosphonocarboxylic acids, such as. B. the compounds methanediphosphonic acid, 1-aminoethane-1,1-diphosphonic acid, aminotrimethylene triphosphonic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid and 1-hydroxyethane-1,1-diphosphonic acid or aminopolycarboxylic acids such as. B. nitrilotriacetic acid, ethylenediaminetetraacetic acid or hydroxyethylethylenediaminetriacetic acid or its alkali metal salts. Such heavy metal complexing agents also counteract a yellowing tendency of the laundry caused by heavy metal ions in the rinse water. 1-Hydroxyethane-1,1-diphosphonic acid and its alkali salts have a particularly good stabilizing effect.

Werden neben der Hexafluorkieselsäure und/ihren wasserlöslichen Salzen weitere sauere Komponenten eingesetzt, so können anorganische und/oder organische Säuren bzw. entsprechende saure Salze mitverwendet werden. Insbesondere beim Arbeiten mit Wasserstoffperoxid ist die Auswahl von zusätzlichen Säuren bzw. sauren Salzen bevorzugt, die nicht ihrerseits mit dem Peroxid in Interaktion treten. Geeignet sind insbesondere die Orthophosphorsäure und/oder ihre sauren Salze, beispielsweise Natrium-dihydrogenphosphat.If, in addition to hexafluorosilicic acid and / or its water-soluble salts, further acidic components are used, inorganic and / or organic acids or corresponding acid salts can also be used. Especially when working with hydrogen peroxide, the choice of additional acids or acid salts is preferred, which do not in turn interact with the peroxide. Orthophosphoric acid and / or its acidic salts, for example sodium dihydrogen phosphate, are particularly suitable.

Die erfindungsgemäßen Mittel können übliche weitere Zusatzstoffe enthalten. Ein Beispiel hierfür sind antimikrobielle Wirkstoffe. Darunter werden hier bakterizid oder bakteriostatisch bzw. fungizid oder fungistatisch wirkende Verbindungen verstanden. Diese Wirkstoffe sollen entweder als solche oder in Form ihrer Salze wasserlöslich sein. Bei den als Zusätze geeigneten antimikrobiellen Wirkstoffen handelt es sich z. B. um solche quartären Ammoniumverbindungen, die neben einem langkettigen aliphatischen und zwei kurzkettigen aliphatischen Kohlenwasserstoffresten einen aromatischen, über ein aliphatisches Kohlenstoffatom mit dem Stickstoffatom verknüpften, oder einen aliphatischen, Doppelbindungen aufweisenden organischen Rest im Molekül enthalten. Beispiele für derartige antimikrobielle quartäre Ammoniumverbindungen sind die folgenden: Dimethyl-benzyl-dodecylammoniumchlorid, Dimethyl-benzyl-tetradecylammoniumchlorid, Dimethyl-(ethylbenzyl)-dodecyl-ammoniumchlorid, Dimethyl-benzyl-decylammoniumbromid, Diethyl-benzyl-dodecylammoniumehlorid, Diethyl-benzyl-octyl-ammoniumchlorid, Dibutylallyl-, Methyl-ethyl-benzyl-, Ethyl-cyclohexyl-allyl-, Ethyl-crotyl-diethylaminoethyl-dodecyl-ammoniumchlorid und insbesondere Kokosalkyldimethylbenzylammoniumchlorid. Auch Dimethyldidecylammoniumchlorid ist wirksam.The agents according to the invention can contain customary further additives. Antimicrobial agents are an example of this. Here, bactericidal or bacteriostatic or fungicidal or fungistatic compounds are understood. These active ingredients are said to be water-soluble either as such or in the form of their salts. The antimicrobial agents suitable as additives are e.g. For example, such quaternary ammonium compounds which, in addition to a long-chain aliphatic and two short-chain aliphatic hydrocarbon radicals, contain an aromatic radical linked via an aliphatic carbon atom to the nitrogen atom, or an aliphatic organic radical having double bonds in the molecule. Examples of such antimicrobial quaternary ammonium compounds are the following: dimethyl-benzyl-dodecylammonium chloride, dimethyl-benzyl-tetradecylammonium chloride, dimethyl- (ethylbenzyl) -dodecyl-ammonium chloride, dimethyl-benzyl-decylammonium bromide, diethyl-benzyl-dodecylammylium diethylammonium ammonium chloride, dibutylallyl, methyl-ethyl-benzyl, ethyl-cyclohexyl-allyl, ethyl-crotyl-diethylaminoethyl-dodecyl-ammonium chloride and in particular cocoalkyldimethylbenzylammonium chloride. Dimethyldidecylammonium chloride is also effective.

Daneben sind auch andere antimikrobielle Wirkstoffe einsetzbar, soweit sie in Gegenwart von Perverbindungen in saurem Medium beständig sind. Hierzu gehören beispielsweise Betaine, wie z. B. Dodecyl-di(aminoethyl)-glycin. Andere brauchbare antimikrobielle Wirkstoffe sind z. B. Hexamethylen-bis-(chlorphenyl)-biguanid-diglu-conat bzw. -dihydrochlorid und Dodecylglycin.In addition, other antimicrobial agents can also be used, provided they are stable in the presence of per compounds in an acidic medium. These include, for example, betaines, such as. B. Dodecyl-di (aminoethyl) glycine. Other useful antimicrobial agents are e.g. B. hexamethylene bis (chlorophenyl) biguanide digluconate or dihydrochloride and dodecylglycine.

Als Dispergatoren, wie sie in rlen erfindungsgemäßen flüssigen Textilnachbehandlungsmitteln enthalten sein können, eignen sich insbesondere die nichtionischen Tenside ("Nonionics"). Dazu gehören Produkte, die ihre hydrophilen Eigenschaften der Anwesenheit von Polyetherketten, Aminoxid, Sulfoxid- oder Phosphinoxidgruppen, Alkylolaraidgruppierungen oder ganz allgemein einer Häufung von Hydroxylgruppen verdanken. Derartige Nonionics enthalten im Molekül wenigstens einen hydrophoben Rest mit 8 - 26, .vorzugsweise 10 - 20 und insbesondere 12 - 18 Kohlenstoffatomen, und wenigstens eine nichtionische, wasserlöslichmachende Gruppe. Der vorzugsweise gesättigte hydrophobe Rest ist meist aliphatischer, gegebenenfalls auch alicyclischer Natur; er kann mit den wasserlöslichmachenden Gruppen direkt oder über Zwischenglieder verbunden sein. Als Zwischenglieder kommen z. B. Benzolringe, Carbonsäureester- oder Carbonamidgruppen, ether- oder esterartig gebundene Reste mehrwertiger Alkohole, wie z. B. die des Ethylenglykols, des Propylenglykols, des Glycerins oder entsprechender Polyetherreste infrage. Typische, als Dispergatoren bevorzugte Nonionics sind z. B. die Anlagerungsprodukte von ca. 9 Mol Ethylenoxid an No-nylphenol oder an Dodecylalkohol, Polyethylenglykole mit bis zu 50-Ethoxy-Einheiten oder Polyethoxy-polypropoxy-glykole mit bis zu 20 Ethoxy- bzw. Propoxy-Einheiten.The nonionic surfactants ("nonionics") are particularly suitable as dispersants, as they can be contained in liquid textile aftertreatment agents according to the invention. These include products that owe their hydrophilic properties to the presence of polyether chains, amine oxide, sulfoxide or phosphine oxide groups, alkylolar groups or, in general, an accumulation of hydroxyl groups. Such nonionics contain at least one hydrophobic radical with 8-26, preferably 10-20 and in particular 12-18 carbon atoms in the molecule, and at least one nonionic, water-solubilizing group. The preferably saturated hydrophobic residue is usually aliphatic, possibly also alicyclic in nature; it can be connected to the water-solubilizing groups directly or via intermediate links. As intermediate links come z. B. benzene rings, carboxylic acid ester or carbonamide groups, ether or ester-bonded residues of polyhydric alcohols, such as. B. that of ethylene glycol, propylene glycol, glycerol or corresponding polyether radicals in question. Typical nonionics preferred as dispersants are e.g. B. the adducts of about 9 moles of ethylene oxide with N o -nylphenol or with dodecyl alcohol, polyethylene glycols up to 50-ethoxy units or polyethoxy-polypropoxy-glycols with up to 20 ethoxy or propoxy units.

Der Gehalt der erfindungsgemäßen Mittel an den erfindungswesentlichen Bestandteilen liegt je nach dem Schwerpunkt der Anwendung, d. h. je nach dem, ob die Mittel besonders ausgeprägte textilweichmachende oder absäuernde oder antichlorierende ( = Hypochlorit reduzierende) Eigenschaften oder besonders ausgeprägte Kombinationen dieser Eigenschaften aufweisen sollen, im Bereich folgender Mengen:

  • a) 1-- 25 Gewichtsprozent Wasserstoffperoxid oder organische Percarbonsäure
  • b) 0,1 - 10 Gewichtsprozent Stabilisatoren
  • c) 1 - 25 Gewichtsprozent Hexafluorkieselsäure und/oder ihre wasserlöslichen Salze
  • d) 1 - 20 Gewichtsprozent textilweichmachende quartäre Ammoniumverbindungen
  • e) 0 - 25 Gewichtsprozerit weitere saure Verbindungen
  • f) 0 - 15 Gewichtsprozent antimikrobiell wirksame Substanzen und zum Rest Wasser sowie gegebenenfalls geringe Mengen Dispergatoren, Schaumregulatoren oder andere übliche Zusatzstoffe.
The content of the inventive constituents of the constituents essential to the invention, depending on the focus of the application, that is to say depending on whether the detergents should have particularly pronounced textile softening or acidifying or antichlorizing (= hypochlorite reducing) properties or particularly pronounced combinations of these properties, are in the range below Amounts:
  • a) 1-- 25 weight percent hydrogen peroxide or organic percarboxylic acid
  • b) 0.1-10 percent by weight of stabilizers
  • c) 1-25% by weight of hexafluorosilicic acid and / or its water-soluble salts
  • d) 1 - 20 percent by weight quaternary ammonium compounds which soften the textile
  • e) 0 - 25 percent by weight of other acidic compounds
  • f) 0 - 15 percent by weight of antimicrobial substances and the rest water and optionally small amounts of dispersants, foam regulators or other conventional additives.

Vorzugsweise haben die erfindungsgemäßen Flittel die folgende Zusammensetzung:

  • a) 1 - 15 Gewichtsprozent Wasserstoffperoxid
  • b) 0,2 - 3 Gewichtsprozent Schwermetalkomplexbildner als Stabilisatoren
  • c) 5 - 20 Gewichtsprozent Hexafluorkieselsäure und/oder ihre wasserlöslichen Salze
  • d) 2 - 7 Gewichtsprozent einer textilweichmachenden quartären Ammoniumverbindung
  • e) 0,5 - 7 Gewichtsprozent eines antibakteriellen Wirkstoffes sowie

zum Rest Wasser und gegebenenfalls Dispergatoren in geringen Mengen.The fluxes according to the invention preferably have the following composition:
  • a) 1 - 15 weight percent hydrogen peroxide
  • b) 0.2-3 percent by weight of heavy metal complexing agents as stabilizers
  • c) 5-20 percent by weight of hexafluorosilicic acid and / or its water-soluble salts
  • d) 2-7 percent by weight of a textile softening quaternary ammonium compound
  • e) 0.5 - 7 percent by weight of an antibacterial agent and

the rest water and optionally dispersants in small quantities.

Bevorzugt wird als textilweichmachende quartäre Hmnoniumverbindung insbesondere die in großem Umfang eingesetzten Verbindungen Dimethylditalgalkylammoniumchlorid oder Dimethyldistearylammoniumchlorid verwendet, wovon Dirzethyldistearylammoniumchlorid besonders bevorzugt ist. Als antibakterielle Wirkstoffe werden quartäre Ammoniumverbindungen bevorzugt, insbesondere Kokosalkyldimethylbenzylammoniumchlorid. Zur Antichlorierung verwendet man insbesondere Wasserstoffperoxid, das in Gegenwart von Schwermetallkomplexbildnern ausreichende Stabilität besitzt. Geeignete Schwermetallkomplexbildner, durch welche sowohl das Wasserstoffperoxid stabilisiert wird als auch einer Verfärbung der Wäsche durch die Verwendung von Wasch-, und Spülwasser mit einem an sich :störenden Gehalt an Schwermetallionen entgegengewirkt wird, sind vor allem Alkanpolyphosphon.säuren und Aminopolycarbonsäuren, insbesondere Hydroxyethylendiamino-triessigsäure und/oder 1-Hydroxyethanl,1-diphosphonsäure bzw. deren Alkalisalze. Erfindungsgemäße Mittel enthalten insbesondere dann, wenn größere Mengen textilweichmachende quartäre Ammoniumverbindungen zur Erzielung einer ausgeprägten weichmachenden Wirkung eingesetzt werden, zweckmäßigerweise geringe Mengen, beispielsweise 0,5 - 5 Gewichtsprozent nichtionische Tenside als Dispergator.As the quaternary ammonium compound which softens the textile, preference is given in particular to the compounds which are used to a large extent, dimethylditalgalkylammonium chloride or dimethyldistearylammonium chloride, of which dirzethyldistearylammonium chloride is particularly preferred. Quaternary ammonium compounds are preferred as antibacterial active substances, in particular coconut alkyldimethylbenzylammonium chloride. Hydrogen peroxide, which has sufficient stability in the presence of heavy metal complexing agents, is used in particular for the antichlorination. Suitable heavy metal complexing agents, by means of which both the hydrogen peroxide is stabilized and discoloration of the laundry is counteracted by the use of washing water and rinsing water with an intrinsically disruptive content of heavy metal ions, are above all alkane polyphosphonic acids and aminopolycarboxylic acids, especially hydroxyethylenediamino-t R acetic acid and / or 1-hydroxyethanl, 1-diphosphonic acid b between their alkali salts. Agents according to the invention contain especially when large amounts of textile-softening quaternary ammonium compounds are used to achieve a pronounced softening effect, expediently small amounts, for example 0.5-5% by weight of nonionic surfactants as dispersants.

Figure imgb0001
Figure imgb0001

BEISPIELEXAMPLE

In einem Gefäß wurden mit einem intensiv wirkenden Mischer die folgenden Komponenten miteinander vermischt:

  • a) 3,75 Gewichtsprozent Dimethyldistearylammoniumchlorid
  • b) 3 Gewichtsprozent Wasserstoffperoxid (eingesetzt als 35 gewichtsprozentige wäßrige Lösung)
  • c) 15 Gewichtsprozent Orthophosphorsäure
  • d) 0, 6 Gewichtsprozent 1-Hydroxyethan-1,1-diphosphonsäure
    Rest Wasser
The following components were mixed together in a vessel using an intensive mixer:
  • a) 3.75 percent by weight of dimethyldistearylammonium chloride
  • b) 3 percent by weight of hydrogen peroxide (used as a 35 percent by weight aqueous solution)
  • c) 15 weight percent orthophosphoric acid
  • d) 0.6% by weight of 1-hydroxyethane-1,1-diphosphonic acid
    Rest of water

Dieses der Lehre der DE-OS 32 05 317 entsprechende Stoffgemisch wird bezüglich seines Wasserstoffperoxiderhaltungsgrades bei der Lagerung für 12 Wochen bei 40 °C verglichen mit den in der nachfolgenden Tabelle unter Ziffern 2 bis 5 zusammengefaßten Wirkstoffgemischen gemäß der Erfindung. Hier ist anstelle der Phosphorsäure als Säuerungsmittel Magnesiumhexafluorsilikat !eingesetzt. Die überlegene Wirkung der erfindungsgemäßen Wirkstoffgemische bezüglich des H202-Erhaltungsgrades nach der Lagerung bei 40 °C für 12 Wochen ist aus den entsprechenden Zahlenwerten ersichtlich. Die Zahlenwerte der Stoffgemische gemäß 2, 4, 5 und 6 liegen im Bereich von 79 bis 88 % H202-Erhaltung gegenüber 28,5 % bei der Wirkstoffmischung gemäß des Standes der Technik. Selbst das zum Vergleich eingesetzte Wirkstoffgemisch 3, das keinen Komplexbildner jedoch Magnesiumfluorsilikat enthält, ist im H202-Erhaltungsgrad noch deutlich besser ,als das zum Vergleich herangezogene Stoffgemisch des Standes der :Technik.

Figure imgb0002
This substance mixture, which corresponds to the teaching of DE-OS 32 05 317, is compared with regard to its degree of hydrogen peroxide conservation during storage for 12 weeks at 40 ° C. compared to the active substance mixtures according to the invention summarized in the following table under numbers 2 to 5. Instead of phosphoric acid, magnesium hexafluorosilicate! Is used as an acidifying agent. The superior effect of the active ingredient mixtures according to the invention with regard to the degree of H 2 0 2 conservation after storage at 40 ° C. for 12 weeks can be seen from the corresponding numerical values. The numerical values of the mixtures according to 2, 4, 5 and 6 are in the range 79-88% H 2 0 2 Conservation compared to 28.5% for the active ingredient mixture according to the prior art. Even the active ingredient mixture 3 used for comparison, which contains no complexing agent but contains magnesium fluorosilicate, is still significantly better in terms of the H 2 0 2 degree of preservation than the substance mixture of the prior art used for comparison.
Figure imgb0002

Die erfindungsgemäßen Wirkstoffgemische setzt man in der Regel dem letzten Spülbad einer gewerblichen Waschmaschine - je nach Durchführung des vorausgegangenen Waschprozesses, d.h. des verbliebenen Restalkalis beziehungsweise der gewünschten Avivage oder mikrobiziden Wirkung - in einer Menge von 1 bis 5 g/l dem Spülwasser (Temperatur ca. 25 °C) zu und behandelt damit die gewaschene und mit Hypochlorit gebleichte Wäsche ca. 2 Minuten lang. Nach dem Abschleudern dieser Behandlungsflotte ist durch pH-Messung der anhaftenden Feuchtigkeit festzustellen, daß alkalische Waschmittelreste auf der Wäsche neutralisiert sind. Die Wäsche weist keinen Chlorgeruch auf. Nach dem Trocknen besitzt sie einen weichen vollen Griff.The active ingredient mixtures according to the invention are generally placed in the last rinsing bath of a commercial washing machine - depending on the implementation of the previous washing process, i.e. of the remaining residual alkali or the desired softening or microbicidal effect - in an amount of 1 to 5 g / l to the rinse water (temperature approx. 25 ° C) and treat the washed and bleached with hypochlorite laundry for approx. 2 minutes. After this treatment liquor has been spun off, it can be determined by measuring the pH of the adhering moisture that alkaline detergent residues on the laundry are neutralized. The laundry does not smell of chlorine. After drying, it has a soft full grip.

Claims (11)

1. Flüssiges Wäschenachbehandlungsmittel mit textilweichmachenden, absäuernden und antichlorierenden Eigenschaften, enthaltend in sauer eingestellter wäßriger Lösung Wasserstoffperoxid oder eine organische Percarbonsäure, Stabilisatoren für Peroxidverbindungen, textilweichmachende quartäre Ammoniumver- bindungen und Säuerungsmittel sowie gewünschtenfalls weitere übliche Zusatzstoffe,dadurch gekennzeichnet, daß als Säuerungsmittel wenigstens anteilsweise Hexafluorkieselsäure und/oder ihre wasserlöslichen Salze vorliegen.1. Liquid laundry aftertreatment agent with fabric softening, acidifying and antichlorizing properties, containing hydrogen peroxide or an organic percarboxylic acid, stabilizers for peroxide compounds, fabric softening quaternary ammonium compounds and acidifying agents and, if desired, other customary additives, characterized in that the acidifying agent contains at least some of the acidifying agent and / or their water-soluble salts are present. 2. Mittel nach Anspruch 1, dadurch gekennzeichnet, daß die Hexafluorkieselsäure und/oder ihre Salze in Mengen von 1 bis 25 Gewichtsprozent, vorzugsweise in Mengen von 5 bis 20 Gewichtsprozent vorliegen.2. Composition according to claim 1, characterized in that the hexafluorosilicic acid and / or its salts are present in amounts of 1 to 25 percent by weight, preferably in amounts of 5 to 20 percent by weight. 3. Mittel nach Ansprüchen 1 und 2, dadurch gekennzeichnet, daß beim Einsatz von Salzen der Hexafluorkieselsäure ihre wasserlöslichen ' Salze mit Metallen der ersten bis dritten Gruppe des Periodischen Systems, insbesondere das Magnesiumsalz, ferner das Ammoniumsalz bzw. entsprechende Amin- und/oder quartäre Ammoniumsalze vorliegen.3. Composition according to claims 1 and 2, characterized in that when using salts of hexafluorosilicic acid their water-soluble 'salts with metals of the first to third groups of the periodic system, in particular the magnesium salt, furthermore the ammonium salt or corresponding amine and / or quaternary Ammonium salts are present. 4. Mittel nach Ansprüchen 1 bis 3,dadurch gekennzeichnet, daßsie andere anorganische und/oder organische Säuren und/oder ihre sauren Salze als zusätzliches Säuerungsmittel enthalten.4. Composition according to claims 1 to 3, characterized in that they contain other inorganic and / or organic acids and / or their acid salts as an additional acidifying agent. 5. Mittel nach Ansprüchen 1 bis 4,dadurch gekennzeichnet, daß sie a) 1 bis 25 Gewichtsprozent Wasserstoffperoxid oder organische Percärbonsäuren b) 0,1 bis 10 Gewichtsprozent Stabilisatoren c) 1 bis 25 Gewichtsprozent Hexafluorkieselsäure und,fcdcr ihre wasserlöslichen Salze d) 1 bis 20 Gewichtsprozent textilweichmachende quartäre Ammoniumverbindungen e) 0 bis 25 Gewichtsprozent an zusätzlichen Säuerungsmitteln f) 0 bis 15 Gewichtsprozent antimikrobiell wirksame Kompo- ; neten
und zum Rest Wasser sowie gegebenenfalls geringe Mengen Dispergatoren, Schaumregulatoren oder andere übliche Zusatzstoffe enthalten.5. Composition according to claims 1 to 4, characterized in that it a) 1 to 25 weight percent hydrogen peroxide or organic percarboxylic acids b) 0.1 to 10 weight percent stabilizers c) 1 to 25 weight percent hexafluorosilicic acid and, fcdcr their water-soluble salts d) 1 to 20 percent by weight quaternary ammonium textile softening agents e) 0 to 25 percent by weight of additional acidulants f) 0 to 15 percent by weight of antimicrobial compo; nets
and the rest water and optionally small amounts of dispersants, foam regulators or other conventional additives. 6. Mittel nach Ansprüchen 1 - 5, dadurch gekennzeichnet, daß als textilweichmachende quartäre Ammoniumverbindungen Dimethylditalgalkylammoniumchlorid oder Dimethyldistearylammoniumchlorid vorliegen.6. Composition according to claims 1-5, characterized in that dimethylditalgalkylammonium chloride or dimethyldistearylammonium chloride are present as textile-softening quaternary ammonium compounds. 7. Mittel nach Ansprüchen 1 - 6, dadurch gekennzeichnet, daß als textilweichmachende quartäre Ammoniumverbindungen Dimethylditalgalkylammoniumchiorid oder Dimethyldistearylammoniumchlorid vorliegen.7. Composition according to claims 1-6, characterized in that dimethylditalgalkylammonium chloride or dimethyldistearylammonium chloride are present as textile-softening quaternary ammonium compounds. 8. Mittel nach Ansprüchen 1 - 7, dadurch gekennzeichnet, daß als antibakterielle Wirkstoffe quartäre Ammoniumverbindungen, vorzugsweise Benzyl-dimethyl-alkylammonium-chloride, insbesondere Benzyl-dimethyl-kokosalkyl. , ammoniumchlorid, vorliegen.8. Composition according to claims 1-7, characterized in that as antibacterial agents quaternary ammonium compounds, preferably benzyl-dimethyl-alkylammonium chloride, especially benzyl-dimethyl-cocoalkyl. , ammonium chloride. 9. Mittel nach Ansprüchen 1 - 8, dadurch gekennzeichnet, daß sie als Stabilisatoren Komplexbildner für Schwermetalle, insbesondere aus der Gruppe der Alkanpolyphosphonsäuren und/oder der Aminopolycarbonsäuren enthalten.9. Composition according to claims 1-8, characterized in that they contain complexing agents for heavy metals, in particular from the group of alkane polyphosphonic acids and / or aminopolycarboxylic acids as stabilizers. 10. Mittel nach Ansprüchen 1 - 9, daß sie geringe Mengen nichtionischer Tenside als Dispergatoren enthalten.10. Compositions according to claims 1-9 that they contain small amounts of nonionic surfactants as dispersants. 11. Verfahren zum gleichzeitigen Weichmachen, Neutralisieren alkalischer Waschmittelreste, Entfernen von Aktivchlor und gegebenenfalls zum anitmikrobiellen Ausrüsten frisch gewaschener Wäsche in wässriger Flotte, dadurch gekennzeichnet, daß man die Wäsche beim Spülen unter Zusatz von 0,5 bis 20 Gramm des Mittels nach Ansprüchen 1 bis 10 pro i Liter Spülbad 0,5 bis 5 Minuten lang unter ständiger Bewegung behandelt und anschließend die Nachbehandlungsflotte durch Abquetschen oder Zentrifugieren bis auf eine Restfeuchte von ca. 10 bis ca. 100 Gewichtsprozent - bezogen auf das Trockengewicht der Wäsche - von der Wäsche abtrennt.11. A process for simultaneous softening, neutralizing alkaline detergent residues, removing active chlorine and optionally for antimicrobial finishing of freshly washed laundry in an aqueous liquor, characterized in that the laundry during rinsing with the addition of 0.5 to 20 grams of the agent according to claims 1 to 10 per i liter of rinsing bath for 0.5 to 5 minutes with constant movement and then the aftertreatment liquor is separated from the laundry by squeezing or centrifuging to a residual moisture content of about 10 to about 100 percent by weight, based on the dry weight of the laundry.
EP85114926A 1984-12-03 1985-11-25 Means and process for after-treating washed laundry Expired - Lifetime EP0184099B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT85114926T ATE59677T1 (en) 1984-12-03 1985-11-25 MEANS AND PROCESSES FOR POST-TREATMENT OF LAUNDRY.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19843444068 DE3444068A1 (en) 1984-12-03 1984-12-03 AGENT AND METHOD FOR TREATING WASHED LAUNDRY
DE3444068 1984-12-03

Publications (3)

Publication Number Publication Date
EP0184099A2 true EP0184099A2 (en) 1986-06-11
EP0184099A3 EP0184099A3 (en) 1988-05-25
EP0184099B1 EP0184099B1 (en) 1991-01-02

Family

ID=6251782

Family Applications (1)

Application Number Title Priority Date Filing Date
EP85114926A Expired - Lifetime EP0184099B1 (en) 1984-12-03 1985-11-25 Means and process for after-treating washed laundry

Country Status (7)

Country Link
US (1) US4704212A (en)
EP (1) EP0184099B1 (en)
JP (1) JPS61138770A (en)
AT (1) ATE59677T1 (en)
DE (2) DE3444068A1 (en)
DK (1) DK551885A (en)
ES (1) ES8706811A1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0288812B1 (en) * 1987-04-30 1991-08-07 Hoechst Aktiengesellschaft Use of an inhibitor of corrosion on ceramic surfaces
WO1994000548A1 (en) * 1992-06-19 1994-01-06 Laporte E.S.D. Limited Compositions containing organic peracid and quaternary ammonium compound

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8822206D0 (en) * 1988-09-21 1988-10-26 Unilever Plc Fabric treatment composition
US5173214A (en) * 1989-02-01 1992-12-22 Union Oil Company Of California Precursor composition for sols and gels
DE4111040C1 (en) * 1991-04-05 1992-06-17 Deutsche Granini Gmbh & Co Kg, 4800 Bielefeld, De
GB2285051A (en) * 1993-12-23 1995-06-28 Procter & Gamble Rinse aid composition
US5460736A (en) * 1994-10-07 1995-10-24 The Procter & Gamble Company Fabric softening composition containing chlorine scavengers
JP2001519706A (en) * 1995-06-07 2001-10-23 バイオ−ラボ・インコーポレーテッド Treatment of water with hydrogen peroxide and polyquaternary ammonium stabilizer
US6262013B1 (en) 1999-01-14 2001-07-17 Ecolab Inc. Sanitizing laundry sour
US6436445B1 (en) 1999-03-26 2002-08-20 Ecolab Inc. Antimicrobial and antiviral compositions containing an oxidizing species
US6855328B2 (en) * 2002-03-28 2005-02-15 Ecolab Inc. Antimicrobial and antiviral compositions containing an oxidizing species
CA2544198C (en) * 2003-10-29 2011-07-26 Mallinckrodt Baker, Inc. Alkaline, post plasma etch/ash residue removers and photoresist stripping compositions containing metal-halide corrosion inhibitors
WO2013116734A1 (en) * 2012-02-01 2013-08-08 Gurtler Industries, Inc. Composition and method for removing stains derived from chlorhexidine gluconate

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3329609A (en) * 1965-03-22 1967-07-04 Wyandotte Chemicals Corp Compositions containing quaternary ammonium salts
US4115281A (en) * 1975-01-30 1978-09-19 Basf Wyandotte Corporation Compositions for souring and softening laundered textile materials, method of preparing the same, and stock solutions prepared therefrom
DE3142767A1 (en) * 1980-10-28 1982-07-08 Société d'Applications de Procédés Industriels et Chimiques S.A.P.I.C., 92600 Asnières, Seine STABILIZED AQUEOUS HYDROGEN PEROXIDE SOLUTIONS AND METHOD FOR THEIR PRODUCTION
EP0086423A2 (en) * 1982-02-15 1983-08-24 Henkel Kommanditgesellschaft auf Aktien Means and process for the aftertreatment of washed linen

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3193505A (en) * 1961-09-20 1965-07-06 Wyandotte Chemicals Corp Antimicrobial laundry sour composition
US3676353A (en) * 1971-02-16 1972-07-11 Basf Wyandotte Corp Nonflouride laundry sour containing fumaric acid
US3925230A (en) * 1973-12-26 1975-12-09 Procter & Gamble Non-caking laundry sour
US3984335A (en) * 1975-01-16 1976-10-05 Basf Wyandotte Corporation Compositions for souring and softening laundered textile materials and stock solutions prepared therefrom
DE2904876A1 (en) * 1979-02-09 1980-08-21 Henkel Kgaa Compsn. for rinsing wet laundry - contains textile softener, sodium bi:sulphite and sodium hexa:fluorosilicate

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3329609A (en) * 1965-03-22 1967-07-04 Wyandotte Chemicals Corp Compositions containing quaternary ammonium salts
US4115281A (en) * 1975-01-30 1978-09-19 Basf Wyandotte Corporation Compositions for souring and softening laundered textile materials, method of preparing the same, and stock solutions prepared therefrom
DE3142767A1 (en) * 1980-10-28 1982-07-08 Société d'Applications de Procédés Industriels et Chimiques S.A.P.I.C., 92600 Asnières, Seine STABILIZED AQUEOUS HYDROGEN PEROXIDE SOLUTIONS AND METHOD FOR THEIR PRODUCTION
EP0086423A2 (en) * 1982-02-15 1983-08-24 Henkel Kommanditgesellschaft auf Aktien Means and process for the aftertreatment of washed linen

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0288812B1 (en) * 1987-04-30 1991-08-07 Hoechst Aktiengesellschaft Use of an inhibitor of corrosion on ceramic surfaces
WO1994000548A1 (en) * 1992-06-19 1994-01-06 Laporte E.S.D. Limited Compositions containing organic peracid and quaternary ammonium compound

Also Published As

Publication number Publication date
JPS61138770A (en) 1986-06-26
DK551885A (en) 1986-06-04
DK551885D0 (en) 1985-11-28
ES8706811A1 (en) 1987-07-01
EP0184099A3 (en) 1988-05-25
EP0184099B1 (en) 1991-01-02
DE3581068D1 (en) 1991-02-07
DE3444068A1 (en) 1986-06-05
US4704212A (en) 1987-11-03
ES549515A0 (en) 1987-07-01
ATE59677T1 (en) 1991-01-15

Similar Documents

Publication Publication Date Title
DE2407708C2 (en) Aqueous fabric softening agent for use in rinsing baths in washing processes
DE2334899C2 (en) Granular detergent containing builders for washing and softening textiles at the same time
DE2318324C3 (en) Fabric softener mixtures for textiles
DE3112854C2 (en)
EP0086423B1 (en) Means and process for the aftertreatment of washed linen
DE2352955A1 (en) SOFTENING MIXTURES
EP0184099B1 (en) Means and process for after-treating washed laundry
DE3641314A1 (en) LAUNDRY TREATMENT AGENT BASED ON LAYERED SILICATE
DE1619043B2 (en) AGENT FOR SOFTENING TEXTILES AND AT THE SAME TIME PROVIDING GOOD ABSORPTION
EP0346634A1 (en) Liquid aqueous composition for the aftertreatment of laundry
EP0085933A2 (en) Concentrated laundry softening agents
DE3402437A1 (en) POWDERED SOFT SOFT DETERGENT, METHOD FOR THE PRODUCTION THEREOF AND DETERGENT CONTAINING THIS
DE2060849A1 (en) Detergent for cleaning and softening at the same time
DE1901194C3 (en) Detergent-compatible aqueous softening agent and its use for softening fabrics during washing or during rinsing
CH638829A5 (en) CONCENTRATED SOFT SOFT COIL COMPOSITION, METHOD FOR THE PRODUCTION AND USE THEREOF.
DE2925859A1 (en) Textile rinsing compsn. improving softness and absorption capacity - contg. quat. ammonium salt and water soluble quat. ammonium gp.-contg. poly:galactomannan ether
EP0056151B1 (en) Process for the microbicidal finishing of textiles
DE1619182C3 (en) Process for softening textiles
DE1919622A1 (en) Fabric softeners and processes for their manufacture
EP1497402A1 (en) Washing-softening rinsing formulations containing betaine ester derivatives and method for improving the washing performance of washing agents
DE2424855C2 (en) Anti-yellowing fabric softener
DE2243806C3 (en) Aqueous agent for softening textiles
EP0018630A1 (en) Washing agent for textiles
DE2357278B2 (en) Ampholytes, processes for their production and detergents, cleaning agents and disinfectants containing them
DE3211175A1 (en) TWO-STAGE PROCESS FOR WASHING AND TREATING TEXTILES

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

Kind code of ref document: A2

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

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 NL

17P Request for examination filed

Effective date: 19881111

17Q First examination report despatched

Effective date: 19890612

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

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

REF Corresponds to:

Ref document number: 59677

Country of ref document: AT

Date of ref document: 19910115

Kind code of ref document: T

REF Corresponds to:

Ref document number: 3581068

Country of ref document: DE

Date of ref document: 19910207

ET Fr: translation filed
ITF It: translation for a ep patent filed

Owner name: STUDIO JAUMANN

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 19911023

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19911028

Year of fee payment: 7

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

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: AT

Payment date: 19911104

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19911107

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19911115

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 19911130

Year of fee payment: 7

26N No opposition filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 19920107

Year of fee payment: 7

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Effective date: 19921125

Ref country code: AT

Effective date: 19921125

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Effective date: 19921130

Ref country code: CH

Effective date: 19921130

Ref country code: BE

Effective date: 19921130

BERE Be: lapsed

Owner name: HENKEL K.G.A.A.

Effective date: 19921130

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Effective date: 19930601

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee
GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19921125

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Effective date: 19930730

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Effective date: 19930803

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST