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EP0528900A1 - Activators for inorganic percompounds. - Google Patents

Activators for inorganic percompounds.

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Publication number
EP0528900A1
EP0528900A1 EP91909256A EP91909256A EP0528900A1 EP 0528900 A1 EP0528900 A1 EP 0528900A1 EP 91909256 A EP91909256 A EP 91909256A EP 91909256 A EP91909256 A EP 91909256A EP 0528900 A1 EP0528900 A1 EP 0528900A1
Authority
EP
European Patent Office
Prior art keywords
weight
mixtures
group
compounds
carbon atoms
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
EP91909256A
Other languages
German (de)
French (fr)
Other versions
EP0528900B1 (en
Inventor
Beatrix Kottwitz
Thomas Merz
Rudolf Lehmann
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Publication of EP0528900A1 publication Critical patent/EP0528900A1/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—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
    • C11D3/391—Oxygen-containing compounds

Definitions

  • the present invention relates to the use of 2,5-diacyloxy-2,5-dihydrofurans as activators for inorganic peroxides and detergents, cleaners and disinfectants which contain such activators.
  • Inorganic per-compounds in particular hydrogen peroxide and solid per-compounds, which dissolve in water with the release of hydrogen peroxide, such as sodium perborate and sodium carbonate perhydrate, have long been used as oxidizing agents for disinfection and bleaching purposes.
  • the oxidation effect of these substances in dilute solutions depends strongly on the temperature; For example, with H2O2 or perborate in alkaline bleaching liquors, sufficiently quick bleaching of soiled textiles can only be achieved at temperatures above about 80 ° C.
  • the oxidation effect of the inorganic per-compounds can be improved by the addition of so-called activators, for which numerous suggestions, especially from the classes of the N- or O-acyl compounds, for example multiple acylated alkylenediamines, especially tetraacetylethylene diamine, acylated glycolurils, especially tetraacetylglycoluril, N Acylated hydantoins, hydrazides, triazoles, urazoles, diketopiperazines, sulfurylaids and cyanurates, and also carboxylic acid anhydrides, in particular phthalic anhydride, carboxylic acid esters, in particular sodium iononanoylphenylsulfonate and acylated sugar derivatives, such as pentaacetyl glucose, have become known .
  • activators for which numerous suggestions, especially from the classes of the N- or O-acyl compounds, for example multiple acylated alkylenediamine
  • the present invention aims to improve the oxidation and bleaching effect of inorganic per-compound at low temperatures below 80 ° C., in particular in the temperature range from approximately 15 ° C. to 45 ° C.
  • R represents an alkyl radical having 1 to 8 carbon atoms or the phenyl radical, and mixtures thereof are selected. Particularly preferred are the compounds of formula (I) with R »C - to C alkyl and mixtures thereof.
  • the present invention further relates to detergents, cleaning agents and disinfectants which contain such activators and a process for activating inorganic per-compounds.
  • the 2,5-diacyloxy-2,5-dihydrofurans according to formula (I) to be used according to the invention can be oxidized by chemical or electrochemical means. by F ran according to methods known in principle, as described, for example, in German published patent application DT 2601543, British patent specifications GB 642277 and GB 703297, by N. Elraing and N. Clauson-Kaas in Acta Che Scand. £ (1952), 535 or by A.J. Baggaley and R. Brettle in J. Che Soc. (C) 1968. 969.
  • such compounds can be used as activators wherever a particular increase in the oxidation effect of inorganic per-compounds at low temperatures is important, for example in the bleaching of textiles, hair or hard surfaces, in the oxidation of organic or inorganic intermediates and in disinfection.
  • the use according to the invention is to create conditions under which hydrogen peroxide and 2,5-diacyloxy-2,5-dihydrofuran can react with one another with the aim of obtaining secondary products which have a stronger oxidizing action.
  • Such conditions exist in particular when both reactants meet in aqueous solution.
  • This can be done by adding the per compound and the activator separately to a solution which may contain detergents or cleaning agents.
  • the method according to the invention is particularly advantageously carried out using a washing, cleaning or disinfecting agent according to the invention which contains the activator and, if appropriate, a peroxidic oxidizing agent.
  • the per compound can also be added to the solution separately, in bulk or as a preferably aqueous solution or suspension, if a peroxide-free agent is used.
  • the conditions can be varied widely depending on the intended use.
  • mixtures of water and suitable organic solvents are also suitable as the reaction medium.
  • the amounts of per compounds used are generally chosen so that the solutions contain between 10 ppm and 10% active oxygen, preferably between 50 and 5000 ppm active oxygen.
  • the amount of activator used also depends on the application. Depending on the desired degree of activation, 0.03-1 mol, preferably 0.1-0.5 mol, of activator are used per mol of inorganic per-compound, but in special cases these limits can also be exceeded or fallen short of.
  • a washing, cleaning or disinfecting agent according to the invention preferably contains 0.2% by weight to 30% by weight, in particular 1% by weight to 20% by weight, of the activator according to the invention.
  • the activator used can be in Known principle adsorbed on carriers and / or embedded in coating substances.
  • the detergents, cleaning agents and disinfectants according to the invention which may be present as powdery solids, homogeneous solutions or suspensions, can, in addition to the activator according to the invention in the form of a compound of the formula (I) or mixtures of such compounds, in principle all known and in Such ingredients contain the usual ingredients.
  • the washing and cleaning agents according to the invention can in particular builder substances, surface-active surfactants, inorganic per-compounds, water-miscible organic solvents, enzymes, sequestering agents, electrolytes, pH regulators and other auxiliaries, such as optical brighteners, graying inhibitors, foam regulators, additional peroxide activators, Dyes and fragrances.
  • a cleaning agent according to the invention for hard surfaces can also contain abrasive components, in particular from the group comprising quartz powders, wood powders, plastic powders, chalks and microglass balls and mixtures thereof.
  • Abrasives are preferably not contained in the cleaning agents according to the invention in excess of 20% by weight, in particular from 1% by weight to 10% by weight.
  • a disinfectant according to the invention can contain customary antimicrobial active ingredients in addition to the ingredients mentioned hitherto in order to enhance the disinfectant action against special germs.
  • Such anti-microbial additives are preferably not contained in the disinfectants according to the invention in excess of 10% by weight, in particular from 0.1% by weight to 5% by weight.
  • the agents according to the invention contain one or more surfactants, in particular anionic surfactants, nonionic surfactants and mixtures thereof.
  • Suitable nonionic surfactants are in particular alkyl glycosides and ethoxylation and / or propoxylation products of alkyl glycosides or linear or branched alcohols each having 12 to 18 carbon atoms in the alkyl part and 3 to 20, preferably 4 to 10, alkyl ether groups.
  • Corresponding ethoxylation and / or Propoxylation products of N-alkylamines, vicinal diols and fatty acids which correspond to the long-chain alcohol derivatives mentioned with regard to the alkyl part, and of alkylphenols having 5 to 12 carbon atoms in the alkyl radical, can be used.
  • Suitable anionic surfactants are, in particular, soaps and those which contain sulfate or sulfonate groups with preferably alkali ions as cations.
  • Usable soaps are preferably the alkali salts of saturated or unsaturated fatty acids with 12 to 18 carbon atoms. Such fatty acids can also be used in a form that is not completely neutralized.
  • the useful surfactants of the sulfate type include the salts of the sulfuric acid half-esters of fatty alcohols with 12 to 18 carbon atoms and the sulfation products of the nonionic surfactants mentioned with a low degree of ethoxylation.
  • the surfactants of the sulfonate type include linear alkylbenzenesulfonates with 9 to 14 carbon atoms in the alkyl part, alkanesulfonates with 12 to 18 carbon atoms, and olefin sulfonates with 12 to 18 carbon atoms, which are used in the reaction of corresponding monoolefins with sulfur ⁇ trioxide, as well as alpha-sulfofatty acid esters, which result from the sulfonation of fatty acid methyl or ethyl esters.
  • Such surfactants are contained in the cleaning or washing agents according to the invention in proportions of preferably 5% by weight to 50% by weight, in particular 8% by weight to 30% by weight, while the agents according to the invention disinfectants preferably contain 0.1% by weight to 20% by weight, in particular from 0.2% by weight to 5% by weight of surfactants.
  • Suitable per compounds are in particular hydrogen peroxide and inorganic salts which give off hydrogen peroxide under the cleaning conditions, such as perborate, percarbonate and / or persilicate. If solid per compounds are to be used, they can be used in the form of powders or granules, which can also be coated in a manner known in principle. The per compounds can be added to the cleaning liquor as such or in the form of compositions containing them, which in principle can contain all the usual detergent, cleaning agent or disinfectant components. Hydrogen peroxide in the form of aqueous solutions which contain 3 to 10% by weight of hydrogen peroxide is preferably used.
  • a washing or cleaning agent according to the invention contains per compounds, these are present in amounts of preferably not more than 50% by weight, in particular 5% by weight to 30% by weight, while in the disinfectants according to the invention preferably 0 5% by weight to 40% by weight, in particular from 5% by weight to 20% by weight, of per compounds are contained.
  • Suitable builder substances are those from the classes of polycarboxylic acids, in particular polymers of acrylic acid, methacrylic acid and maleic acid, and their copolymers, aminopolycarboxylic acids, in particular nitrilotriacetic acid and ethylenediaminetetraacetic acid, polyphosphonic acids, in particular aminotri- (methylenephosphonic) acid), ethylenediaminetetra- (methylenephosphonic acid) and 1-hydroxyethane-1,1-diphosphonic acid, polyphosphates, in particular sodium triphosphate, phyllosilicates, in particular bentonites, and aluminosilicates, in particular zeolites and, in particular, those of the NaA or NaX type.
  • polycarboxylic acids in particular polymers of acrylic acid, methacrylic acid and maleic acid, and their copolymers, aminopolycarboxylic acids, in particular nitrilotriacetic acid and ethylenediaminetetraacetic acid, polyphosphonic
  • the abovementioned acids are usually used in the form of their alkali metal salts, in particular their sodium or potassium salts.
  • Such builder substances are preferably not contained in the washing or cleaning agents according to the invention in excess of 60% by weight, in particular from 5% by weight to 40% by weight, while the disinfectants according to the invention are preferably free from only the components of the water hardness are complexing builder substances and preferably not more than 20% by weight, in particular from 0.1% by weight to 5% by weight, of substances which are difficult to complex, preferably from the group comprising aminopolycarboxylic acids, aminopolyphosphonic acids and hydroxypolyphosphonic acids and their water-soluble salts and mixtures thereof.
  • Enzymes from the class of proteases, lipases and amylases as well as their mixtures are possible. Enzymatic active ingredients obtained from fungi or bacterial strains such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus are particularly suitable.
  • the enzymes used can be adsorbed on carriers and / or embedded in coating substances in order to protect them against premature inactivation. They are in the detergents, cleaning agents and disinfectants according to the invention preferably not more than 1% by weight, in particular from 0.2% by weight to 0.7% by weight.
  • the organic solvents which can be used in the agents according to the invention include alcohols having 1 to 4 carbon atoms, in particular methanol, ethanol, isopropanol and tert-butanol, diols having 2 to 4 carbon atoms -Atoms, especially ethylene glycol and propylene glycol, and their mixtures.
  • Such water-miscible solvents are preferably not present in the washing, cleaning and disinfecting agents according to the invention in excess of 30% by weight, in particular from 6% by weight to 20% by weight.
  • the agents according to the invention can be systemic and non-proprietary acids, in particular citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid and / or adipic acid, but also mineral acids, in particular sulfuric acid, or bases, in particular ammonium or alkali metal hydroxides.
  • Such pH regulators are preferably not contained in the agents according to the invention in excess of 20% by weight, in particular from 1.2% by weight to 17% by weight.
  • the preparation of the solid agents according to the invention does not present any difficulties and can be carried out in a manner known in principle, for example by spray drying or granulation, the per compound and activator possibly being added separately later. Washing, cleaning or disinfecting agents according to the invention in the form of solutions containing aqueous or other conventional solvents are particularly advantageously produced by simply mixing the ingredients, which can be added in bulk or as a solution to an automatic mixer. Examples
  • liquid detergents Hl, H2 and the liquid detergents W3 and W4 additionally containing 2,5-diacetoxy-2,5-dihydrofuran were prepared by simply mixing their constituents in the proportions given in Table 1.
  • 2,5-diacetoxy-2,5-dihydrofuran 2,5-dibutyroxy-2,5-dihydrofuran (H5), 2,5-dipentanoyloxy-2,5-dihydrofuran (W6 ) or 2,5-dibenzoyloxy-2,5-dihydrofuran (H7).
  • Aqueous solutions each containing 0.9 g of the specified detergent and 2 ml of red wine per 100 ml, were examined by UV / Vis spectroscopy (measuring wavelength 460 nm). After every 30 minutes of reaction time at 30 ° C., the decreases in the dye concentration given in Table 2 (5c) were observed.
  • Soiling A: red wine on cotton; B: tea on cotton; C:
  • the bleach activator content of the liquid detergents according to the invention shown in the table below was determined by testing the decolorization capacity of brilliant green. For this purpose, 100 ⁇ l of a 0.1% by weight solution (100 ml of aqueous solution containing 0.9 g of a detergent listed in Table 4 and 2% by weight of H2O2) were added to the process described in Example 2 ( Water / ethanol 1: 1) of brilliant green (Aldrich) added. The bleach activator content in the respective detergent was determined by UV / Vis spectroscopic measurement of the decrease in the dye concentration.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (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)
  • Detergent Compositions (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

Comme activateurs pour des percomposés anorganiques dans des solutions d'oxydation, de lavage, de nettoyage ou de désinfection, on utilise des 2,5-diacyloxy-2,5-dihydrofurannes correspondant à la formule générale (I) dans laquelle R désigne un reste alkyle de 1 à 8 atomes de carbone ou un reste phényle. Les agents de lavage et de nettoyage selon l'invention renferment de 0,2 à 30 % en poids de tels activateurs.As activators for inorganic percompounds in oxidation, washing, cleaning or disinfection solutions, 2,5-diacyloxy-2,5-dihydrofurans corresponding to the general formula (I) in which R denotes a residue are used. alkyl of 1 to 8 carbon atoms or a phenyl residue. The washing and cleaning agents according to the invention contain from 0.2 to 30% by weight of such activators.

Description

"Aktivatoren für anorganische Perverbindungen" "Activators for inorganic per-compounds"
Die vorliegende Erfindung betrifft die Verwendung von 2,5-Diacyloxy-2,5- dihydrofuranen als Aktivatoren für anorganische Peroxide und Wasch-, Rei- nigungs- und Desinfektionsmittel, die derartige Aktivatoren enthalten.The present invention relates to the use of 2,5-diacyloxy-2,5-dihydrofurans as activators for inorganic peroxides and detergents, cleaners and disinfectants which contain such activators.
Anorganische Perverbindungen, insbesondere Wasserstoffperoxid und feste Perverbindungen, die sich in Wasser unter Freisetzung von Wasserstoff¬ peroxid lösen, wie Natriumperborat und Natriu carbonat-Perhydrat, werden seit langem als Oxidationsmittel zu Desinfektions- und Bleichzwecken ver¬ wendet. Die Oxidationswirkung dieser Substanzen hängt in verdünnten Lö¬ sungen stark von der Temperatur ab; so erzielt man beispielsweise mit H2O2 oder Perborat in alkalischen Bleichflotten erst bei Temperaturen oberhalb von etwa 80 °C eine ausreichend schnelle Bleiche verschmutzter Textilien. Bei niedrigeren Temperaturen kann die Oxidationswirkung der anorganischen Perverbindungen durch Zusatz sogenannter Aktivatoren verbessert werden, für die zahlreiche Vorschläge, vor allem aus den Stoffklassen der N- oder O-AcylVerbindungen, beispielsweise mehrfach acylierte Alkylendiamine, insbesondere Tetraacetylethylendia in, acylierte Glykolurile, insbesondere Tetraacetylglykoluril, N-acylierte Hydantoine, Hydrazide, Triazole, Ura- zole, Diketopiperazine, Sulfuryla ide und Cyanurate, außerdem Carbon¬ säureanhydride, insbesondere Phthalsäureanhydrid, Carbonsäureester, ins¬ besondere Natriu -isononanoyl-phenylsulfonat und acylierte Zuckerderivate, wie Pentaacetylglukose, in der Literatur bekannt geworden sind. Durch Zu¬ satz dieser Substanzen kann die Bleichwirkung wäßriger Peroxidflotten so weit gesteigert werden, daß bereits bei 60 °C nahezu die gleichen Wir¬ kungen wie mit der Peroxidflotte allein bei 95 °C eintreten.Inorganic per-compounds, in particular hydrogen peroxide and solid per-compounds, which dissolve in water with the release of hydrogen peroxide, such as sodium perborate and sodium carbonate perhydrate, have long been used as oxidizing agents for disinfection and bleaching purposes. The oxidation effect of these substances in dilute solutions depends strongly on the temperature; For example, with H2O2 or perborate in alkaline bleaching liquors, sufficiently quick bleaching of soiled textiles can only be achieved at temperatures above about 80 ° C. At lower temperatures, the oxidation effect of the inorganic per-compounds can be improved by the addition of so-called activators, for which numerous suggestions, especially from the classes of the N- or O-acyl compounds, for example multiple acylated alkylenediamines, especially tetraacetylethylene diamine, acylated glycolurils, especially tetraacetylglycoluril, N Acylated hydantoins, hydrazides, triazoles, urazoles, diketopiperazines, sulfurylaids and cyanurates, and also carboxylic acid anhydrides, in particular phthalic anhydride, carboxylic acid esters, in particular sodium iononanoylphenylsulfonate and acylated sugar derivatives, such as pentaacetyl glucose, have become known . By adding these substances, the bleaching effect of aqueous peroxide liquors can be increased to such an extent that almost the same effects occur at 60 ° C as with the peroxide liquor alone at 95 ° C.
Im Bemühen um energiesparende Wasch- und Bleichverfahren gewinnen in den letzten Jahren auch Anwendungstemperaturen deutlich unterhalb 60 °C, ins¬ besondere unterhalb 45 °C bis herunter zur Kaltwassertemperatur an Bedeu¬ tung. Bei diesen niedrigen Temperaturen läßt allerdings die Wirkung der bisher bekannten Aktivatoren deutlich nach. Es hat deshalb nicht an Bestrebungen gefehlt, für diesen Temperaturbereich wirksamere Aktivatoren zu entwik- keln, ohne daß bis heute ein überzeugender Erfolg zu verzeichnen gewesen wäre. Auch die vorliegende Erfindung hat die Verbesserung der Oxidations- und Bleichwirkung anorganischer Perverbindung bei niedrigen Temperature unterhalb von 80 °C, insbesondere im Temperaturbereich von etwa 15 °C bi 45 °C, zum Ziel.In the effort to save energy in washing and bleaching, in recent years application temperatures well below 60 ° C., in particular below 45 ° C. down to the cold water temperature, have become more important. At these low temperatures, however, the effect of the activators known hitherto decreases significantly. There has been no shortage of efforts to develop more effective activators for this temperature range without convincing success to date. The present invention also aims to improve the oxidation and bleaching effect of inorganic per-compound at low temperatures below 80 ° C., in particular in the temperature range from approximately 15 ° C. to 45 ° C.
Es wurde nun gefunden, daß bei Verwendung bestimmter 2,5-Diacyloxy-2,5 dihydrofurane als Aktivatoren in diesem Temperaturbereich eine außeror dentliche Steigerung der Oxidations- und Bleichwirkung anorganische Perverbindungeπ in Oxidations-, Bleich- und Waschflotten erreicht wird. E handelt sich bei diesen Aktivatoren um Stoffe, die aus den Verbindunge nach Formel (I),It has now been found that when certain 2,5-diacyloxy-2,5-dihydrofurans are used as activators in this temperature range, an extraordinary increase in the oxidation and bleaching effect of inorganic compounds is achieved in oxidation, bleaching and washing liquors. E these activators are substances which are derived from the compounds of the formula (I),
in der R für einen Alkyirest mit 1 bis 8 C-Atomen oder den Phenylres steht, sowie deren Gemischen ausgewählt werden. Besonders bevorzugt sin die Verbindungen nach Formel (I) mit R » C - bis C -Alkyl und deren Gemi sche. Weiterhin betrifft die vorliegende Erfindung Wasch-, Reinigungs- un Desinfektionsmittel, die derartige Aktivatoren enthalten und ein Verfahr zur Aktivierung anorganischer Perverbindungen.in which R represents an alkyl radical having 1 to 8 carbon atoms or the phenyl radical, and mixtures thereof are selected. Particularly preferred are the compounds of formula (I) with R »C - to C alkyl and mixtures thereof. The present invention further relates to detergents, cleaning agents and disinfectants which contain such activators and a process for activating inorganic per-compounds.
Die erfindungsgemäß zu verwendenden 2,5-Diacyloxy-2,5-dihydrofurane gem Formel (I) können durch chemische oder elektrochemische Oxidatior. von F ran nach im Prinzip bekannten Verfahren, wie sie beispielsweise in d deutschen Offenlegungsschrift DT 2601543, den britischen Patentschrift GB 642277 und GB 703297, von N. Elraing und N. Clauson-Kaas in Acta Che Scand. £ (1952), 535 oder von A.J. Baggaley und R. Brettle in J. Che Soc. (C) 1968. 969 beschrieben sind, hergestellt werden.The 2,5-diacyloxy-2,5-dihydrofurans according to formula (I) to be used according to the invention can be oxidized by chemical or electrochemical means. by F ran according to methods known in principle, as described, for example, in German published patent application DT 2601543, British patent specifications GB 642277 and GB 703297, by N. Elraing and N. Clauson-Kaas in Acta Che Scand. £ (1952), 535 or by A.J. Baggaley and R. Brettle in J. Che Soc. (C) 1968. 969.
ERSATZBLATT Bei dem erfindungsgemäßen Verfahren können derartige Verbindungen als Ak¬ tivatoren überall dort eingesetzt werden, wo es auf eine besondere Stei¬ gerung der Oxidationswirkung anorganischer Perverbindungen bei niedrigen Temperaturen ankommt, beispielsweise bei der Bleiche von Textilien, Haaren oder harten Oberflächen, bei der Oxidation organischer oder anorganischer Zwischenprodukte und bei der Desinfektion.REPLACEMENT LEAF In the method according to the invention, such compounds can be used as activators wherever a particular increase in the oxidation effect of inorganic per-compounds at low temperatures is important, for example in the bleaching of textiles, hair or hard surfaces, in the oxidation of organic or inorganic intermediates and in disinfection.
Die erfindungsgemäße Verwendung besteht darin, Bedingungen zu schaffen, unter denen Wasserstoffperoxid und 2,5-Diacyloxy-2,5-dihydrofuran mitei¬ nander reagieren können, mit dem Ziel, stärker oxidierend wirkende Folge¬ produkte zu erhalten. Solche Bedingungen liegen insbesondere dann vor, wenn beide Reaktionspartner in wäßriger Lösung aufeinander treffen. Dies kann durch separate Zugabe der Perverbindung und des Aktivators zu einer gegebenenfalls wasch- oder reinigungsmittelhaltigen Lösung geschehen. Be¬ sonders vorteilhaft wird das erfindungsgemäße Verfahren jedoch unter Ver¬ wendung eines erfindungsgemäßen Wasch-, Reinigungs- oder Desinfektions¬ mittels, das den Aktivator und gegebenenfalls ein peroxidisches Oxidati- onsmittel enthält, durchgeführt. Die Perverbindung kann auch separat, in Substanz oder als vorzugsweise wäßrige Lösung oder Suspension, zur Lösung zugegeben werden, wenn ein peroxidfreies Mittel verwendet wird.The use according to the invention is to create conditions under which hydrogen peroxide and 2,5-diacyloxy-2,5-dihydrofuran can react with one another with the aim of obtaining secondary products which have a stronger oxidizing action. Such conditions exist in particular when both reactants meet in aqueous solution. This can be done by adding the per compound and the activator separately to a solution which may contain detergents or cleaning agents. However, the method according to the invention is particularly advantageously carried out using a washing, cleaning or disinfecting agent according to the invention which contains the activator and, if appropriate, a peroxidic oxidizing agent. The per compound can also be added to the solution separately, in bulk or as a preferably aqueous solution or suspension, if a peroxide-free agent is used.
Je nach Verwendungszweck können die Bedingungen weit variiert werden. So kommen neben rein wäßrigen Lösungen auch Mischungen aus Wasser und geeig¬ neten organischen Lösungsmitteln als Reaktionsmedium in Frage. Die Ein¬ satzmengen an Perverbindungen werden im allgemeinen so gewählt, daß in den Lösungen zwischen 10 ppm und 10 % Aktivsauerstoff, vorzugsweise zwischen 50 und 5000 ppm Aktivsauerstoff vorhanden sind. Auch die verwendete Menge an Aktivator hängt vom Anwendungszweck ab. Je nach gewünschtem Aktivie¬ rungsgrad werden 0,03 - 1 Mol, vorzugsweise 0,1 - 0,5 Mol Aktivator pro Mol anorganischer Perverbindung verwendet, doch können in besonderen Fäl¬ len diese Grenzen auch über- oder unterschritten werden.The conditions can be varied widely depending on the intended use. In addition to purely aqueous solutions, mixtures of water and suitable organic solvents are also suitable as the reaction medium. The amounts of per compounds used are generally chosen so that the solutions contain between 10 ppm and 10% active oxygen, preferably between 50 and 5000 ppm active oxygen. The amount of activator used also depends on the application. Depending on the desired degree of activation, 0.03-1 mol, preferably 0.1-0.5 mol, of activator are used per mol of inorganic per-compound, but in special cases these limits can also be exceeded or fallen short of.
Ein erfindungsgemäßes Wasch-, Reinigungs- oder Desinfektionsmittel enthält vorzugsweise 0,2 Gew.-% bis 30 Gew.-%, insbesondere 1 Gew.-% bis 20 Gew.-% des erfindungsgemäßen Aktivators. Der verwendete Aktivator kann in im Prinzip bekannter Weise an Trägerstoffen adsorbiert und/oder in Hüllsub- stanzen eingebettet sein.A washing, cleaning or disinfecting agent according to the invention preferably contains 0.2% by weight to 30% by weight, in particular 1% by weight to 20% by weight, of the activator according to the invention. The activator used can be in Known principle adsorbed on carriers and / or embedded in coating substances.
Die erfindungsgemäßen Wasch-, Reinigungs- und Desinfektionsmittel, die als pulverförmige Feststoffe, homogene Lösungen oder Suspensionen vorliegen können, können außer dem erfindungsgemäßen Aktivator in Form einer Ver¬ bindung gemäß Formel (I) oder Mischungen derartiger Verbindungen im Prin¬ zip alle bekannten und in derartigen Mitteln üblichen Inhaltsstoffe ent¬ halten. Die erfindungsgemäßen Wasch- und Reinigungsmittel können insbe¬ sondere Buildersubstanzen, oberflächenaktive Tenside, anorganische Perverbindungen, wassermischbare organische Lösungsmittel, Enzyme, Seque¬ strierungsmittel, Elektrolyte, pH-Regulatoren und weitere Hilfsstoffe, wie optische Aufheller, Vergrauungsinhibitoren, Schaumregulatoren, zusätzliche Peroxid-Aktivatoren, Färb- und Duftstoffe, enthalten.The detergents, cleaning agents and disinfectants according to the invention, which may be present as powdery solids, homogeneous solutions or suspensions, can, in addition to the activator according to the invention in the form of a compound of the formula (I) or mixtures of such compounds, in principle all known and in Such ingredients contain the usual ingredients. The washing and cleaning agents according to the invention can in particular builder substances, surface-active surfactants, inorganic per-compounds, water-miscible organic solvents, enzymes, sequestering agents, electrolytes, pH regulators and other auxiliaries, such as optical brighteners, graying inhibitors, foam regulators, additional peroxide activators, Dyes and fragrances.
Ein erfindungsgemäßes Reinigungsmittel für harte Oberflächen kann darüber hinaus abrasiv wirkende Bestandteile, insbesondere aus der Gruppe umfas¬ send Quarzmehle, Holzmehle, Kunststoffmehle, Kreiden und Mikroglaskugeln sowie deren Gemische, enthalten. Abrasivstoffe sind in den erfindungsge¬ mäßen Reinigungsmitteln vorzugsweise nicht über 20 Gew.-%, insbesondere von 1 Gew.-% bis 10 Gew.-%, enthalten.A cleaning agent according to the invention for hard surfaces can also contain abrasive components, in particular from the group comprising quartz powders, wood powders, plastic powders, chalks and microglass balls and mixtures thereof. Abrasives are preferably not contained in the cleaning agents according to the invention in excess of 20% by weight, in particular from 1% by weight to 10% by weight.
Ein erfindungsgemäßes Desinfektionsmittel kann zur Verstärkung der Desin¬ fektionswirkung gegenüber speziellen Keimen zusätzlich zu den bisher ge¬ nannten Inhaltsstoffeπ übliche antimikrobielle Wirkstoffe enthalten. Der¬ artige anti ikrobielle Zusatzstoffe sind in den erfindungsgemäßen Desin¬ fektionsmitteln vorzugsweise nicht über 10 Gew.-%, insbesondere von 0,1 Gew.-% bis 5 Gew.-%, enthalten.A disinfectant according to the invention can contain customary antimicrobial active ingredients in addition to the ingredients mentioned hitherto in order to enhance the disinfectant action against special germs. Such anti-microbial additives are preferably not contained in the disinfectants according to the invention in excess of 10% by weight, in particular from 0.1% by weight to 5% by weight.
Die erfindungsgemäßen Mittel enthalten ein Tensid oder mehrere Tenside, wobei insbesondere anionische Tenside, nichtionische Tenside und deren Gemische in Frage kommen. Geeignete nichtionische Tenside sind insbeson¬ dere Alkylglykoside und Ethoxylierungs- und/oder Propoxylierungsprodukte von Alkylglykosiden oder linearen oder verzweigten Alkoholen mit jeweils 12 bis 18 C-Atomen im Alkylteil und 3 bis 20, vorzugsweise 4 bis 10 Alkylethergruppen. Weiterhin sind entsprechende Ethoxylierungs-und/oder Propoxylierungsprodukte von N-Alkyl-aminen, vicinalen Diolen und Fettsäu- rea iden, die hinsichtlich des Alkylteils den genannten langkettigen Al¬ koholderivaten entsprechen, sowie von Alkylphenolen mit 5 bis 12 C-Atomem im Alkyirest brauchbar.The agents according to the invention contain one or more surfactants, in particular anionic surfactants, nonionic surfactants and mixtures thereof. Suitable nonionic surfactants are in particular alkyl glycosides and ethoxylation and / or propoxylation products of alkyl glycosides or linear or branched alcohols each having 12 to 18 carbon atoms in the alkyl part and 3 to 20, preferably 4 to 10, alkyl ether groups. Corresponding ethoxylation and / or Propoxylation products of N-alkylamines, vicinal diols and fatty acids which correspond to the long-chain alcohol derivatives mentioned with regard to the alkyl part, and of alkylphenols having 5 to 12 carbon atoms in the alkyl radical, can be used.
Geeignete anionische Tenside sind insbesondere Seifen und solche, die Sulfat- oder Sulfonat-Gruppen mit bevorzugt Alkaliionen als Kationen ent¬ halten. Verwendbare Seifen sind bevorzugt die Alkalisalze der gesättigten oder ungesättigten Fettsäuren mit 12 bis 18 C-Atomen. Derartige Fettsäuren können auch in nicht vollständig neutralisierter Form eingesetzt werden. Zu den brauchbaren Tensiden des Sulfat-Typs gehören die Salze der Schwe¬ felsäurehalbester von Fettalkoholen mit 12 bis 18 C-Atomen und die Sulfa- tierungsprodukte der genannten nichtionischen Tenside mit niedrigem Ethoxylierungsgrad. Zu den verwendbaren Tensiden vom Sulfonat-Typ gehören lineare Alkylbenzolsulfonate mit 9 bis 14 C-Atomen im Alkylteil, Alkan- sulfonate mit 12 bis 18 C-Atomen, sowie Olefinsulfonate mit 12 bis 18 C- Atomen, die bei der Umsetzung entsprechender Monoolefine mit Schwefel¬ trioxid entstehen, sowie alpha-Sulfofettsäureester, die bei der Sulfonie- rung von Fettsäuremethyl- oder -ethylestern entstehen.Suitable anionic surfactants are, in particular, soaps and those which contain sulfate or sulfonate groups with preferably alkali ions as cations. Usable soaps are preferably the alkali salts of saturated or unsaturated fatty acids with 12 to 18 carbon atoms. Such fatty acids can also be used in a form that is not completely neutralized. The useful surfactants of the sulfate type include the salts of the sulfuric acid half-esters of fatty alcohols with 12 to 18 carbon atoms and the sulfation products of the nonionic surfactants mentioned with a low degree of ethoxylation. The surfactants of the sulfonate type that can be used include linear alkylbenzenesulfonates with 9 to 14 carbon atoms in the alkyl part, alkanesulfonates with 12 to 18 carbon atoms, and olefin sulfonates with 12 to 18 carbon atoms, which are used in the reaction of corresponding monoolefins with sulfur ¬ trioxide, as well as alpha-sulfofatty acid esters, which result from the sulfonation of fatty acid methyl or ethyl esters.
Derartige Tenside sind in den erfindungsgemäßen Reinigungs- oder Wasch¬ mitteln in Mengenanteilen von vorzugsweise 5 Gew.-% bis 50 Gew.-%, insbe¬ sondere von 8 Gew.-% bis 30 Gew.-%, enthalten, während die erfindungsge¬ mäßen Desinfektionsmittel vorzugsweise 0,1 Gew.-% bis 20 Gew.-%, insbe¬ sondere von 0,2 Gew.-% bis 5 Gew.-% Tenside, enthalten.Such surfactants are contained in the cleaning or washing agents according to the invention in proportions of preferably 5% by weight to 50% by weight, in particular 8% by weight to 30% by weight, while the agents according to the invention disinfectants preferably contain 0.1% by weight to 20% by weight, in particular from 0.2% by weight to 5% by weight of surfactants.
Ais geeignete Perverbindungen kommen insbesondere Wasserstoffperoxid und unter den Reinigungsbedingungen Wasserstoffperoxid abgebende anorganische Salze, wie Perborat, Percarbonat und/oder Persilikat, in Betracht. Sofern feste Perverbindungen eingesetzt werden sollen, können diese in Form von Pulvern oder Granulaten verwendet werden, die auch in im Prinzip bekannter Weise umhüllt sein können. Die Perverbindungen können als solche oder in Form diese enthaltender Mittel, die prinzipiell alle üblichen Wasch-, Reinigungs- oder Desinfektionsmittelbetandteile enthalten können, zu der Reinigungslauge zugegeben werden. Vorzugsweise wird Wasserstoffperoxid in Form wäßriger Lösungen, die 3 bis 10 Gew.-% Wasserstoffperoxid enthalten, eingesetzt. Falls ein erfindungsgemäßes Wasch- oder Reinigungsmittel Per¬ verbindungen enthält, sind diese in Mengen von vorzugsweise nicht über 50 Gew.- , insbesondere von 5 Gew.-% bis 30 Gew.-%, vorhanden, während in den erfindungsgemäßen Desinfektionsmitteln vorzugsweise von 0,5 Gew.-% bis 40 Gew.-%, insbesondere von 5 Gew.-% bis 20 Gew.-%, an Perverbindungen enthalten sind.Suitable per compounds are in particular hydrogen peroxide and inorganic salts which give off hydrogen peroxide under the cleaning conditions, such as perborate, percarbonate and / or persilicate. If solid per compounds are to be used, they can be used in the form of powders or granules, which can also be coated in a manner known in principle. The per compounds can be added to the cleaning liquor as such or in the form of compositions containing them, which in principle can contain all the usual detergent, cleaning agent or disinfectant components. Hydrogen peroxide in the form of aqueous solutions which contain 3 to 10% by weight of hydrogen peroxide is preferably used. If a washing or cleaning agent according to the invention contains per compounds, these are present in amounts of preferably not more than 50% by weight, in particular 5% by weight to 30% by weight, while in the disinfectants according to the invention preferably 0 5% by weight to 40% by weight, in particular from 5% by weight to 20% by weight, of per compounds are contained.
Geeignete Buildersubstanzen sind, einzeln oder in Gemischen, solche aus den Klassen der Polycarbonsäuren, insbesondere Polymere der Acrylsäure, der Methacrylsäure und der Maleinsäure sowie deren Copoly ere, Aminopoly- carbonsäuren, insbesondere Nitrilotriessigsäure und Ethylendiamintetra- essigsäure, Polyphosphonsäuren, insbesondere Aminotri-(methylenphosphon- säure), Ethylendiamintetra-(methylenphosphonsäure) und 1-Hydroxyethan- 1,1-diphosphonsäure, Polyphosphate, insbesondere Natriumtriphosphat, Schichtsilikate, insbesondere Bentonite, und Alumosilikate, insbesondere Zeolithe und unter diesen insbesondere solche des NaA- oder NaX-Typs. Die vorgenannten Säuren werden üblicherweise in Form ihrer Alkalisalze, ins¬ besondere ihrer Natrium- oder Kaliumsalze, eingesetzt. Derartige Builder¬ substanzen sind in den erfindungsgemäßen Wasch- oder Reinigungsmitteln vorzugsweise nicht über 60 Gew.-%, insbesondere von 5 Gew.-% bis 40 Gew.-%, enthalten, während die erfindungsgemäßen Desinfektionsmittel vorzugsweise frei von den lediglich die Komponenten der Wasserhärte komplexierenden Buildersubstanzen sind und bevorzugt nicht über 20 Gew.-%, insbesondere von 0,1 Gew.-% bis 5 Gew.-%, an schwer eta11komplexierenden Stoffen, vorzugsweise aus der Gruppe umfassend Aminopolycarbonsäuren, Aminopolyphosphonsäuren und Hydroxypolyphosphonsäuren und deren wasser¬ lösliche Salze sowie deren Gemische, enthalten.Suitable builder substances, individually or in mixtures, are those from the classes of polycarboxylic acids, in particular polymers of acrylic acid, methacrylic acid and maleic acid, and their copolymers, aminopolycarboxylic acids, in particular nitrilotriacetic acid and ethylenediaminetetraacetic acid, polyphosphonic acids, in particular aminotri- (methylenephosphonic) acid), ethylenediaminetetra- (methylenephosphonic acid) and 1-hydroxyethane-1,1-diphosphonic acid, polyphosphates, in particular sodium triphosphate, phyllosilicates, in particular bentonites, and aluminosilicates, in particular zeolites and, in particular, those of the NaA or NaX type. The abovementioned acids are usually used in the form of their alkali metal salts, in particular their sodium or potassium salts. Such builder substances are preferably not contained in the washing or cleaning agents according to the invention in excess of 60% by weight, in particular from 5% by weight to 40% by weight, while the disinfectants according to the invention are preferably free from only the components of the water hardness are complexing builder substances and preferably not more than 20% by weight, in particular from 0.1% by weight to 5% by weight, of substances which are difficult to complex, preferably from the group comprising aminopolycarboxylic acids, aminopolyphosphonic acids and hydroxypolyphosphonic acids and their water-soluble salts and mixtures thereof.
Als Enzyme kommen solche aus der Klasse der Proteasen, Lipasen und Amyl- asen sowie deren Gemische in Frage. Besonders geeignet sind aus Pilzen oder Bakterienstämmen, wie Bacillus subtilis, Bacillus licheniformis und Streptomyces griseus gewonnene enzy atische Wirkstoffe. Die verwendeten Enzyme können an Trägerstoffen adsorbiert und/oder in Hüllsubstanzen ein¬ gebettet sein, um sie gegen vorzeitige Inaktivierung zu schützen. Sie sind in den erfindungsgemäßen Wasch-, Reinigungs- und Desinfektionsmitteln vorzugsweise nicht über 1 Gew.-%, insbesondere von 0,2 Gew.-% bis 0,7 Gew.-%, enthalten.Enzymes from the class of proteases, lipases and amylases as well as their mixtures are possible. Enzymatic active ingredients obtained from fungi or bacterial strains such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus are particularly suitable. The enzymes used can be adsorbed on carriers and / or embedded in coating substances in order to protect them against premature inactivation. They are in the detergents, cleaning agents and disinfectants according to the invention preferably not more than 1% by weight, in particular from 0.2% by weight to 0.7% by weight.
Zu den in den erfindungsgemäßen Mitteln, insbesondere wenn sie in flüs¬ siger Form vorliegen, verwendbaren organischen Lösungsmitteln gehören Al¬ kohole mit 1 bis 4 C-Atomen, insbesondere Methanol, Ethanol, Isopropanol und tert.-Butanol, Diole mit 2 bis 4 C-Atomen, insbesondere Ethylenglykol und Propylenglykol, sowie deren Gemische. Derartige wassermischbare Lö¬ sungsmittel sind in den erfindungsgemäßen Wasch-, Reinigungs- und Desin¬ fektionsmitteln vorzugsweise nicht über 30 Gew.-%, insbesondere von 6 Gew.-% bis 20 Gew.-%, vorhanden.The organic solvents which can be used in the agents according to the invention, in particular if they are in liquid form, include alcohols having 1 to 4 carbon atoms, in particular methanol, ethanol, isopropanol and tert-butanol, diols having 2 to 4 carbon atoms -Atoms, especially ethylene glycol and propylene glycol, and their mixtures. Such water-miscible solvents are preferably not present in the washing, cleaning and disinfecting agents according to the invention in excess of 30% by weight, in particular from 6% by weight to 20% by weight.
Zur Einstellung eines gewünschten, sich durch die Mischung der übrigen Komponenten nicht von selbst ergebenden pH-Werts können die erfindungsge¬ mäßen Mittel syste - und umweitvertragliehe Säuren, insbesondere Zitro¬ nensäure, Essigsäure, Weinsäure, Äpfelsäure, Milchsäure, Glykolsäure, Bernsteinsäure, Glutarsäure und/oder Adipinsäure, aber auch Mineralsäuren, insbesondere Schwefelsäure, oder Basen, insbesondere Ammonium- oder Alka- lihydroxide, enthalten. Derartige pH-Regulatoren sind in den erfindungs¬ gemäßen Mitteln vorzugsweise nicht über 20 Gew.-%, insbesondere von 1,2 Gew.-% bis 17 Gew.-%, enthalten.In order to set a desired pH value which does not result from the mixture of the other components, the agents according to the invention can be systemic and non-proprietary acids, in particular citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid and / or adipic acid, but also mineral acids, in particular sulfuric acid, or bases, in particular ammonium or alkali metal hydroxides. Such pH regulators are preferably not contained in the agents according to the invention in excess of 20% by weight, in particular from 1.2% by weight to 17% by weight.
Die Herstellung der erfindungsgemäßen festen Mittel bietet keine Schwie¬ rigkeiten und kann in im Prinzip bekannter Weise, zum Beispiel durch Sprühtrocknen oder Granulation, erfolgen, wobei Perverbindung und Akti¬ vator gegebenenfalls später getrennt zugesetzt werden. Erfindungsgemäße Wasch-, Reinigungs- oder Desinfektionsmittel in Form wäßriger oder son¬ stige übliche Lösungsmittel enthaltender Lösungen werden besonders vor¬ teilhaft durch einfaches Mischen der Inhaltsstoffe, die in Substanz oder als Lösung in einen automatischen Mischer gegeben werden können, herge¬ stellt. BeispieleThe preparation of the solid agents according to the invention does not present any difficulties and can be carried out in a manner known in principle, for example by spray drying or granulation, the per compound and activator possibly being added separately later. Washing, cleaning or disinfecting agents according to the invention in the form of solutions containing aqueous or other conventional solvents are particularly advantageously produced by simply mixing the ingredients, which can be added in bulk or as a solution to an automatic mixer. Examples
Beispiel 1: Herstellung der AktivatorenExample 1: Preparation of the activators
1. 2,5-Diacetoxy-2,5-dihydrofuran1. 2,5-diacetoxy-2,5-dihydrofuran
Unter Rühren wurden zu einer Mischung von 180 ml Eisessig und 115 ml Acetanhydrid bei 50 °C 97,5 g Blei(IV)acetat portionsweise zugegeben. Nach Zugabe von 14,9 g Furan wurde das Reaktionsgemisch 1,5 Stunden auf 60 °C bis 65 °C erhitzt. Anschließend wurde das Lösungsmittel im Vakuum (ca. 10 Torr, Badtemperatur 60 °C) weitgehend entfernt. Der Rückstand wurde mit 400 ml wasserfreiem Diethylether versetzt und nach Filtrieren und Abziehen des Lösungsmittels fraktionierend destilliert. Man erhielt im Siedebereich von 81 °C bis 85 °C bei 0,01 Torr 24,5 g 2,5-Diacetoxy-2,5-dihydrofuran als laut Gaschromatographie 99-prozentige Flüssigkeit mit dem Brechungs¬ index n§5 = 1,4538.While stirring, 97.5 g of lead (IV) acetate were added in portions to a mixture of 180 ml of glacial acetic acid and 115 ml of acetic anhydride at 50 ° C. After adding 14.9 g of furan, the reaction mixture was heated at 60 ° C. to 65 ° C. for 1.5 hours. The solvent was then largely removed in vacuo (approx. 10 torr, bath temperature 60 ° C.). 400 ml of anhydrous diethyl ether were added to the residue and, after filtering and stripping off the solvent, fractionally distilled. In the boiling range from 81 ° C. to 85 ° C. at 0.01 Torr, 24.5 g of 2,5-diacetoxy-2,5-dihydrofuran were obtained as a 99% liquid according to gas chromatography with the refractive index n§ 5 = 1, 4538.
2. 2,5-Dipropionyloxy-2,5-dihydrofuran2. 2,5-dipropionyloxy-2,5-dihydrofuran
Eine Mischung aus 130 ml Propionsäure, 51,3 g Blei(IV)propionat (herge¬ stellt in Analogie zu dem von D.H. Hey, C.J.M. Stirling und G.H. Williams in J. Chem. Soc. 1954. 2747 angegebenen Verfahren) und 7,0 g Furan wurde 35 Minuten auf 55 °C bis 60 °C und 45 Minuten auf 60 °C bis 65 °C erhitzt. Anschließende fraktionierende Destillation ergab im Siedebereich von 110 °C bis 116 °C bei 0,5 Torr 12,0 g 2,5-Dipropionyloxy-2,5-dihydrofuran als laut Gaschromatographie 98-prozentige Flüssigkeit mit dem Brechungs¬ index n§5 = 1,4525.A mixture of 130 ml of propionic acid, 51.3 g of lead (IV) propionate (prepared in analogy to the method given by DH Hey, CJM Stirling and GH Williams in J. Chem. Soc. 1954, 2747) and 7.0 g Furan was heated at 55 ° C to 60 ° C for 35 minutes and at 60 ° C to 65 ° C for 45 minutes. Subsequent fractional distillation in the boiling range from 110 ° C to 116 ° C at 0.5 Torr gave 12.0 g of 2,5-dipropionyloxy-2,5-dihydrofuran as 98% liquid according to gas chromatography with the refractive index n§5 = 1.4525.
3. 2,5-Dibutyroxy-2,5-dihydrofuran3. 2,5-dibutyroxy-2,5-dihydrofuran
Analog zu dem unter Punkt 2 angegebenen Verfahren erhielt man aus 36,5 g Blei(IV)butyrat, 135 ml Buttersäure und 4,5 g Furan im Siedebereich von 104 °C bis 108 °C bei 0,2 Torr 2,5-Dibutyroxy-2,5-dihydrofuran als laut Gaschromatographie 98-prozentige Flüssigkeit mit dem Brechungsindex = 1,4496. 4. 2,5-Dibenzoyloxy-2,5-dihydrofuranAnalogously to the process given under point 2, 36.5 g of lead (IV) butyrate, 135 ml of butyric acid and 4.5 g of furan were obtained in the boiling range from 104 ° C. to 108 ° C. at 0.2 Torr 2,5-dibutyroxy -2,5-dihydrofuran as 98% liquid according to gas chromatography with the refractive index = 1.4496. 4. 2,5-dibenzoyloxy-2,5-dihydrofuran
Eine Mischung aus 100 g Benzoesäure, 67,5 g Blei(IV)benzoat (hergestellt nach dem in J. Che . Soc. 1954, 2747 angegebenen Verfahren) und 10,2 g Furan wurde 1 Stunde auf 50 °C und 3 Stunden auf 75 °C erhitzt. Nach Ab¬ kühlen auf Raumtemperatur, Filtrieren und Entfernen überschüssigen Furans im Vakuum kristallisierten aus dem Rückstand nach Zugabe von 100 ml Dioxan und Kühlen auf ca. 0 °C 26 g 2,5-Dibenzoyloxy-2,5-dihydrofuran mit dem Schmelzpunkt 190 - 196 °C aus.A mixture of 100 g of benzoic acid, 67.5 g of lead (IV) benzoate (prepared according to the process given in J. Che. Soc. 1954, 2747) and 10.2 g of furan was heated at 50 ° C. for 1 hour and for 3 hours Heated to 75 ° C. After cooling to room temperature, filtering and removing excess furan in vacuo, 26 g of 2,5-dibenzoyloxy-2,5-dihydrofuran with a melting point of 190- crystallized from the residue after addition of 100 ml of dioxane and cooling to about 0 ° C. 196 ° C.
5. 2,5-Dipentanoyloxy-2,5-dihydrofuran5. 2,5-dipentanoyloxy-2,5-dihydrofuran
Analog zu dem unter Punkt 4 angegebenen Verfahren erhielt man aus 68,2 g Blei(IV)valerat, 100 ml Valeriansäure und 7,6 g Furan 17,3 g 2,5-Dipenta- noyloxy-2,5-dihydrofuran mit dem Schmelzpunkt 30 - 35 °C.Analogously to the process given under point 4, 17.3 g of 2,5-dipentanoyloxy-2,5-dihydrofuran with the melting point were obtained from 68.2 g of lead (IV) valerate, 100 ml of valeric acid and 7.6 g of furan 30 - 35 ° C.
Beispiel 2Example 2
Durch einfaches Mischen ihrer Bestandteile in den in Tabelle 1 angegebenen Mengenanteilen wurden die Flüssigwaschmittel Hl, H2 und die zusätzlich 2,5-Diacetoxy-2,5-dihydrofuran enthaltenden Flüssigwaschmittel W3 und W4 hergestellt. Statt dem Bleichaktivator 2,5-Diacetoxy-2,5-dihydrofuran wurde in ansonsten dem Waschmittel H4 entsprechende Formulierungen 2,5- Dibutyroxy-2,5-dihydrofuran (H5), 2,5-Dipentanoyloxy-2,5-dihydrofuran (W6) oder 2,5-Dibenzoyloxy-2,5-dihydrofuran (H7) eingearbeitet. The liquid detergents Hl, H2 and the liquid detergents W3 and W4 additionally containing 2,5-diacetoxy-2,5-dihydrofuran were prepared by simply mixing their constituents in the proportions given in Table 1. Instead of the bleach activator 2,5-diacetoxy-2,5-dihydrofuran, 2,5-dibutyroxy-2,5-dihydrofuran (H5), 2,5-dipentanoyloxy-2,5-dihydrofuran (W6 ) or 2,5-dibenzoyloxy-2,5-dihydrofuran (H7).
Tabelle 1 : Waschmittelzusammensetzung [Gew.-%]Table 1: Detergent composition [% by weight]
Wäßrige Lösungen, die jeweils 0,9 g der angegebenen Waschmittel und 2 ml Rotwein auf 100 ml enthielten, wurden UV/Vis-spektroskopisch untersucht (Meßwellenlänge 460 nm). Man beobachtete nach jeweils 30 Minuten Reakti¬ onszeit bei 30 °C die in Tabelle 2 angegebenen Abnahmen der Farbstoffkon- zentration (5c). In einem Launderometer, Typ Atlas Standard (250 ml Flottenvolumen, Wasserhärte 17 °dH), wurden unter Verwendung des Wasch¬ mittels H2 (9,25 Gramm pro Liter Waschlösung) jeweils 2,1 g der mit den in Tabelle 3 angegebenen Testanschmutzungen verunreinigten Gewebe mit jeweils 6,3 g sauberem Füllgewebe aus weißer Baumwolle bei 40 °C oder 60 °C je¬ weils 30 Minuten (einschließlich Aufheizzeit (3°C/Minute)) gewaschen und anschließend 3 Mal je 30 Sekunden gespült (Spalte I). Nach dem Trocknen wurde die Remission der augenscheinlich sauberen Testgewebe, bezogen auf BaSθ4 = 100 %, photometrisch bestimmt (Meßwellenlänge 460 nm). Zum Ver¬ gleich wurde eine gleiche Waschlösung, der 2 Gew.-% Wasserstoffperoxid, berechnet als 100-prozentige Substanz, zugesetzt worden waren (Spalte II) und eine Waschlösung, die 9,25 Gramm pro Liter des Waschmittels H4 und 2 Gew.-% Wasserstoffperoxid (Spalte III) unter den gleichen Bedingungen getestet.Aqueous solutions, each containing 0.9 g of the specified detergent and 2 ml of red wine per 100 ml, were examined by UV / Vis spectroscopy (measuring wavelength 460 nm). After every 30 minutes of reaction time at 30 ° C., the decreases in the dye concentration given in Table 2 (5c) were observed. In a Launderometer, type Atlas Standard (250 ml liquor volume, water hardness 17 ° dH), 2.1 g of the tissue soiled with the test soils indicated in Table 3 were used using the detergent H2 (9.25 grams per liter of wash solution) washed with 6.3 g of clean white cotton fill fabric at 40 ° C or 60 ° C for 30 minutes each (including heating time (3 ° C / minute)) and then rinsed 3 times for 30 seconds each (column I). After drying, the reflectance of the apparently clean test tissue, based on BaSO 4 = 100%, was determined photometrically (measuring wavelength 460 nm). For comparison, an identical washing solution to which 2% by weight hydrogen peroxide, calculated as a 100% substance, had been added (column II) and a washing solution containing 9.25 grams per liter of detergent H4 and 2% by weight. % Hydrogen peroxide (column III) tested under the same conditions.
Tabelle 2: Abnahme der FarbstoffkonzentrationTable 2: Decrease in dye concentration
Tabelle 3 : Remissionswerte [%]Table 3: Remission values [%]
Anschmutzungen : A : Rotwein auf Baumwolle; B : Tee auf Baumwolle; C :Soiling: A: red wine on cotton; B: tea on cotton; C:
Kaffee auf Baumwolle; D : Rotwein auf veredelter Baumwolle; E : Tee auf veredelter Baumwolle; F : Rotwein auf Bau wolle/Polyester-Mischgewebe; G : Tee auf Bau wolle/Polyester-Mischgewebe. Aus den in Tabelle 3 wiedergegebenen Rem ssionswerten geht die überlegene leichwirkung der den erfindungsgemäßen Aktivator enthaltenden Formulierung im Vergleich zum aktivatorfreien und peroxidfreien Waschmittel (Spalte I) und zum aktivatorfreien, aber peroxidhaltigen Waschmittel (Spalte II) hervor.Coffee on cotton; D: red wine on refined cotton; E: tea on refined cotton; F: red wine on cotton / polyester blend; G: Tea on construction wool / polyester blend. The reflection values shown in Table 3 show the superior ease of action of the formulation containing the activator according to the invention in comparison with the activator-free and peroxide-free detergent (column I) and the activator-free but peroxide-containing detergent (column II).
Beispiel 3: Prüfung der LagerstabilitätExample 3: Checking the storage stability
Nach 14 Tagen Lagerung bei Raumtemperatur wurde der Gehalt der in der nachfolgenden Tabelle angegebenen erfindungsgemäßen Flüssigwaschmittel an Bleichaktivator durch den Test des Entfärbungsvermögens von Brillantgrün bestimmt. Dazu wurde in Analogie zu dem in Beispiel 2 beschriebenen Ver¬ fahren zu jeweils 100 ml wäßriger, 0,9 g eines in Tabelle 4 angegebenen Waschmittels und 2 Gew.-% H2O2 enthaltender Lösung 100 μl einer 0,1-ge- wichtsprozentigen Lösung (Wasser/Ethanol 1:1) von Brillantgrün (Aldrich) zugegeben. Durch UV/Vis-spektroskopische Messung der Abnahme der Farb¬ stoffkonzentration wurde der Gehalt an Bleichaktivator im jeweiligen Waschmittel bestimmt.After 14 days of storage at room temperature, the bleach activator content of the liquid detergents according to the invention shown in the table below was determined by testing the decolorization capacity of brilliant green. For this purpose, 100 μl of a 0.1% by weight solution (100 ml of aqueous solution containing 0.9 g of a detergent listed in Table 4 and 2% by weight of H2O2) were added to the process described in Example 2 ( Water / ethanol 1: 1) of brilliant green (Aldrich) added. The bleach activator content in the respective detergent was determined by UV / Vis spectroscopic measurement of the decrease in the dye concentration.
Tabelle 4 :Table 4:

Claims

Patentansprüche Claims
1. Verwendung eines 2,5-Diacyloxy-2,5-dihydrofurans, ausgewählt aus d Verbindungen nach Formel (I),1. Use of a 2,5-diacyloxy-2,5-dihydrofuran selected from d compounds of the formula (I),
in der R einen Alkyirest mit 1 bis 8 C-Atomen oder einen Phenylre bedeutet, und Gemischen derartiger Verbindungen als Aktivator für a organische Perverbindungen in Oxidations-, Wasch-, Reinigungs- od Desinfektionslösungen.in which R is an alkyl radical having 1 to 8 carbon atoms or a phenylene, and mixtures of such compounds as an activator for organic per compounds in oxidation, washing, cleaning or disinfecting solutions.
2. Verwendung nach Anspruch 1, dadurch gekennzeichnet, daß die Aktivi rung in überwiegend wäßriger, tensidhaltiger Lösung erfolgt.2. Use according to claim 1, characterized in that the activation takes place in predominantly aqueous, surfactant-containing solution.
3. Verwendung nach Anspruch 2 zur Aktivierung eines peroxidisch Bleichmittels während der Wäsche von Textilien.3. Use according to claim 2 for activating a peroxidic bleaching agent during the washing of textiles.
4. Verwendung nach Anspruch 2 zur Aktivierung eines Peroxids bei de Reinigung und/oder Desinfektion fester Oberflächen.4. Use according to claim 2 for activating a peroxide in the cleaning and / or disinfection of solid surfaces.
5. Verwendung einer Verbindung gemäβ Formel (I) zur Herstellung v Wasch-, Reinigungs- oder Desinfektionsmitteln.5. Use of a compound according to formula (I) for the production of washing, cleaning or disinfecting agents.
6. Verwendung nach einem der Ansprüche 1 bis 5, dadurch gekennzeichne daβ der Aktivator aus den Verbindungen der Formel (I), in der R ein Alkyirest mit 1 bis 4 C-Atomen bedeutet, ausgewählt wird.6. Use according to one of claims 1 to 5, characterized in that the activator is selected from the compounds of the formula (I) in which R is an alkyl radical having 1 to 4 carbon atoms.
7. Verwendung nach einem der Ansprüche 1 bis 6, dadurch gekennzeichne daβ das zu aktivierende Peroxid aus der Gruppe umfassend Hasserstof peroxid, Perborat und Percarbonat sowie deren Gemische ausgewäh wird.7. Use according to one of claims 1 to 6, characterized in that the peroxide to be activated is selected from the group consisting of hydrogen peroxide, perborate and percarbonate and mixtures thereof.
ERSATZBLATT REPLACEMENT LEAF
8. Tensidhaltiges Wasch-, Reinigungs- oder Desinfektionsmittel, enthal tend ein 2,5-Diacyloxy-2,5-dihydrofuran nach Formel (I),8. detergent, detergent or disinfectant containing surfactants, containing a 2,5-diacyloxy-2,5-dihydrofuran according to formula (I),
in der R einen Alkyirest mit 1 bis 8 C-Atomen oder einen Phenylres bedeutet.in which R is an alkyl radical having 1 to 8 carbon atoms or a phenyl radical.
9. Mittel nach Anspruch 8, dadurch gekennzeichnet, daß das 2,5-Di acyloxy-2,5-dihydrofuraπ aus den Verbindungen nach Formel (I), in de R einen Alkyirest mit 1 bis 4 C-Atomen bedeutet, ausgewählt wird.9. Composition according to claim 8, characterized in that the 2,5-di acyloxy-2,5-dihydrofuraπ from the compounds of formula (I) in which R is an alkyl radical having 1 to 4 carbon atoms, is selected.
10. Mittel nach einem der Ansprüche 8 oder 9, dadurch gekennzeichnet, da es10. Agent according to one of claims 8 or 9, characterized in that it
0,2 - 30 Gew.-%, insbesondere 1 - 20 Gew.-* Aktivator nach Formel (I)0.2-30% by weight, in particular 1-20% by weight * activator according to formula (I)
5 - 50 Gew.-*, insbesondere 8 - 30 Gew.-* anionisches und/ode nichtionisches Tensid,5 - 50% by weight, in particular 8 - 30% by weight, anionic and / or nonionic surfactant,
0 - 60 Gew.-*, insbesondere 5 - 40 Gew.-* Buildersubstanz aus de Gruppe umfassend Polycarbonsäuren, Aminopolycarbon säuren, Polyphosphonsäuren, Polyphosphate, Schich silikate und AlumosiUkate, insbesondere Zeolith sowie deren Gemische,0 to 60% by weight, in particular 5 to 40% by weight builder substance from the group comprising polycarboxylic acids, aminopolycarbon acids, polyphosphonic acids, polyphosphates, layered silicates and aluminosilicates, in particular zeolite and mixtures thereof,
0 - 1 Gew.-*, insbesondere 0,2 - 0,7 Gew.-*, Enzym,0-1% by weight *, in particular 0.2-0.7% by weight *, enzyme,
0 - 30 Gew.-*, insbesondere 6 - 20 Gew.-*, organisches Lösungsmi tel aus der Gruppe umfassend Alkohole mit 1 bis C-Atomen, Diole mit 2 bis 4 C-Atomen sowie der Gemische,0 - 30% by weight *, in particular 6 - 20% by weight *, organic solvent from the group comprising alcohols with 1 to C atoms, diols with 2 to 4 C atoms and the mixtures,
0 - 20 Gew.-*, insbesondere 1,2 - 17 Gew.-* pH-Regulator, enthält.0 - 20 wt .- *, in particular 1.2 - 17 wt .- * pH regulator.
11. Waschmittel nach Anspruch 10, dadurch gekennzeichnet, daβ es zusät lich zu den genannten Bestandteilen nicht Ober 50 Gew.-*, vorzugswei von 5 Gew.-* bis 30 Gew.-* Perverbindung, ausgewählt aus der Grup11. Detergent according to claim 10, characterized in that it does not add up to the above-mentioned constituents above 50% by weight, preferably from 5% to 30% by weight, per compound selected from the group
ERSATZBLATT umfassend Wasserstoffperoxid, Perborat und Percarbonat sowie deren Gemische, enthält.REPLACEMENT LEAF comprising hydrogen peroxide, perborate and percarbonate and mixtures thereof.
12. Reinigungsmittel nach Anspruch 10, dadurch gekennzeichnet, daß es zu¬ sätzlich nicht über 20 Gew.-%, insbesondere 1 - 10 Gew.-% Abrasivstoff aus der Gruppe umfassend Quarzmehle, Holzmehle, Kunststoffmehle, Kreiden und Mikroglaskugeln sowie deren Gemische, enthält.12. Cleaning agent according to claim 10, characterized in that it additionally does not contain more than 20% by weight, in particular 1-10% by weight, of abrasive from the group comprising quartz flours, wood flours, plastic flours, chalks and micro-glass balls and mixtures thereof .
13. Reinigungsmittel nach Anspruch 12, dadurch gekennzeichnet, daß es zu¬ sätzlich nicht über 50 Gew.-%, insbesondere von 5 Gew.-% bis 30 Gew.-% Perverbindung, ausgewählt aus der Gruppe umfassend Wasserstoffperoxid, Perborat und Percarbonat sowie deren Gemische, enthält.13. Cleaning agent according to claim 12, characterized in that it additionally does not contain more than 50% by weight, in particular from 5% by weight to 30% by weight, of the per compound selected from the group comprising hydrogen peroxide, perborate and percarbonate and their Mixtures contains.
14. Desinfektionsmittel nach einem der Ansprüche 8 oder 9, dadurch ge¬ kennzeichnet, daß es14. Disinfectant according to one of claims 8 or 9, characterized in that it
0,2 - 30 Gew.-%, insbesondere 1 - 20 Gew.-% Aktivator nach Formel (I),0.2-30% by weight, in particular 1-20% by weight of activator according to formula (I),
0,5 - 40 Gew.-%, insbesondere 5 - 20 Gew.-% Perverbindung, ausgewählt aus der Gruppe umfassend Wasserstoffperoxid, Perborat und Percarbonat sowie deren Gemische,0.5 to 40% by weight, in particular 5 to 20% by weight per compound, selected from the group comprising hydrogen peroxide, perborate and percarbonate and mixtures thereof,
0,1 - 20 Gew.-%, insbesondere 0,2 - 5 Gew.-% anionisches und/oder nichtionisches Tensid, 0 - 20 Gew.-%, insbesondere 0,1 - 5 Gew.-% Komplexbildner aus der Gruppe umfassend A inopolycarbonsäuren, A inopoly- phosphonsäuren und Hydroxypolyphosphonsäuren sowie deren Gemische, 0 - 1 Gew.-%, insbesondere 0,2 - 0,7 Gew.-%, Enzym, 0 - 30 Gew.-%, insbesondere 6 - 20 Gew.-%, organisches Lösungsmittel aus der Gruppe umfassend Alkohole mit 1 bis 4 C-Ato¬ men, Diole mit 2 bis 4 C-Atomen sowie deren Gemische, insbesondere 1,2 - 17 Gew.-% pH-Regulator, insbesondere 0,1 - 5 Gew.-%, zusätzlichen anti- ikrobiellen Wirkstoff 0.1-20% by weight, in particular 0.2-5% by weight of anionic and / or nonionic surfactant, 0-20% by weight, in particular 0.1-5% by weight of complexing agents from the group comprising A inopolycarboxylic acids, A inopolyphosphonic acids and hydroxypolyphosphonic acids and their mixtures, 0-1% by weight, in particular 0.2-0.7% by weight, enzyme, 0-30% by weight, in particular 6-20% by weight. %, organic solvent from the group comprising alcohols with 1 to 4 carbon atoms, diols with 2 to 4 carbon atoms and mixtures thereof, in particular 1.2-17% by weight pH regulator, in particular 0.1 - 5 wt .-%, additional anti-microbial agent
15. Verfahren zur Aktivierung anorganischer Perverbindungen in im wesent¬ lichen wäßrigen Oxidations-, Wasch-, Reinigungs- oder Desinfektionslösungen, dadurch gekennzeichnet, daß zur Lösung ein Ak tivator, ausgewählt aus der Gruppe umfassend die Verbindungen nac Formel (I),15. Process for the activation of inorganic per-compounds in essentially aqueous oxidation, washing, cleaning or Disinfection solutions, characterized in that for the solution an activator selected from the group comprising the compounds of formula (I),
in der R einen Alkyirest mit 1 bis 8 C-Atomen oder einen Phenylres bedeutet, und deren Gemische, zugegeben wird.in which R is an alkyl radical having 1 to 8 carbon atoms or a phenyl radical, and mixtures thereof is added.
ERSATZBLATT REPLACEMENT LEAF
EP91909256A 1990-05-17 1991-05-08 Activators for inorganic percompounds Expired - Lifetime EP0528900B1 (en)

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DE4015859 1990-05-17
DE4015859A DE4015859A1 (en) 1990-05-17 1990-05-17 ACTIVATORS FOR INORGANIC PERCENTAGES
PCT/EP1991/000864 WO1991018082A2 (en) 1990-05-17 1991-05-08 Activators for inorganic percompounds

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EP0528900B1 EP0528900B1 (en) 1994-08-10

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EP0866116A3 (en) * 1997-03-22 1999-05-12 Henkel Kommanditgesellschaft auf Aktien Bisacylacetal derivatives as bleach activators for laundry and detergent compositions

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Publication number Priority date Publication date Assignee Title
GB9116939D0 (en) * 1991-08-06 1991-09-18 Unilever Plc Bleach precursors and bleaching compositions
DE4424005A1 (en) * 1994-07-07 1996-01-11 Henkel Kgaa Powdery bleach and detergent
US5720897A (en) * 1995-01-25 1998-02-24 University Of Florida Transition metal bleach activators for bleaching agents and detergent-bleach compositions
DE19616769A1 (en) * 1996-04-26 1997-11-06 Henkel Kgaa Acylacetals as bleach activators for detergents and cleaning agents
DE60040317D1 (en) * 1999-06-30 2008-11-06 Kao Corp Germicidal detergent composition
MX349265B (en) 2010-05-20 2017-07-20 Ecolab Usa Inc Rheology modified low foaming liquid antimicrobial compositions and methods of use thereof.

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US4107065A (en) * 1975-11-05 1978-08-15 Colgate-Palmolive Company Activated peroxy compound bleaching compositions and bleaching detergent compositions
GB8304990D0 (en) * 1983-02-23 1983-03-30 Procter & Gamble Detergent ingredients
US4483778A (en) * 1983-12-22 1984-11-20 The Procter & Gamble Company Peroxygen bleach activators and bleaching compositions

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Cited By (1)

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Publication number Priority date Publication date Assignee Title
EP0866116A3 (en) * 1997-03-22 1999-05-12 Henkel Kommanditgesellschaft auf Aktien Bisacylacetal derivatives as bleach activators for laundry and detergent compositions

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WO1991018082A2 (en) 1991-11-28
US5273674A (en) 1993-12-28
ES2057894T3 (en) 1994-10-16
DE59102515D1 (en) 1994-09-15
EP0528900B1 (en) 1994-08-10
DE4015859A1 (en) 1991-11-21

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