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WO1996030482A1 - Activateurs pour composes peroxo et agents les contenant - Google Patents

Activateurs pour composes peroxo et agents les contenant Download PDF

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Publication number
WO1996030482A1
WO1996030482A1 PCT/EP1996/000599 EP9600599W WO9630482A1 WO 1996030482 A1 WO1996030482 A1 WO 1996030482A1 EP 9600599 W EP9600599 W EP 9600599W WO 9630482 A1 WO9630482 A1 WO 9630482A1
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WO
WIPO (PCT)
Prior art keywords
activator
activators
acyl
weight
group
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PCT/EP1996/000599
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German (de)
English (en)
Inventor
Michael Del Grosso
Astrid Dorfer
Heribert Offermanns
Original Assignee
Degussa Aktiengesellschaft
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.)
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Application filed by Degussa Aktiengesellschaft filed Critical Degussa Aktiengesellschaft
Publication of WO1996030482A1 publication Critical patent/WO1996030482A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • 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 invention relates to new, highly effective activators based on phenolic and enolic O-acyl compounds for peroxo compounds containing them
  • Inorganic peroxo compounds are used as oxidizing agents in bleaching, washing, cleaning and disinfecting agents in order to improve the effect of such agents.
  • Peroxo compounds used are in particular hydrogen peroxide and those substances which release hydrogen peroxide in aqueous solution, such as perborates and percarbonates.
  • the effect of the inorganic peroxo compounds depends not only on the pH value, but also on the temperature. While a good effect is achieved when using the peroxo compounds mentioned at temperatures above about 80 ° C., at lower temperatures, in particular around / below 60 ° C. or around / below 40 ° C., the use of so-called activators is necessary.
  • the activators are mostly N-acyl compounds, such as tetraacetylethylene diamine (TAED), or O-acyl compounds, such as n-nonanoyloxybenzenesulfonate (NOBS).
  • TAED tetraacetylethylene diamine
  • NOBS n-nonanoyloxybenzenesulfonate
  • Hydrogen peroxide and the activators by perhydrolysis of the same percarboxylic acids which also have a good washing, cleaning, bleaching and disinfecting effect in the low temperature range.
  • Bleaching agent compositions are known from US Pat. No. 4,412,934 which act as activators of substances of the formula R-CO-L contain, where R is an alkyl group with 5 to 18 carbon atoms, the longest chain R-CO has 6 to 10 carbon atoms, and the acid LH conjugated to the leaving group L has a pK a value of 6 to 13 has.
  • LH stands for phenols, enols and amides.
  • the radical R stands for linear or branched alkyl, preferably (C5 to Cg) alkyl.
  • the phenolic O-acyl activators include the Na salt of n-nonanoyloxybenzenesulfonic acid (NOBS), which is a very effective activator. Compounds with R equal to alkenyl are not disclosed in this document.
  • DE-OS 38 24 901 shows a process for the preparation of acyloxybenzenesulfonic acids and their salts, phenolsulfonic acid or a salt thereof being reacted with a carboxylic acid of the formula R-COOH and acetic anhydride.
  • R can also be C5-C21-. in particular mean C5-Cn-alkenyl. Individual alkenoyloxybenzenesulfonic acids or their salts are not mentioned.
  • Phenols largely depend on their ability to release the percarboxylic acid in the highest possible yield during perhydrolysis: With C2-Cc) -alkanoyl compounds, the perhydrolysis proceeds essentially quantitatively. The yield of percarboxylic acids in the perhydrolysis of C ⁇ o-alkanoyl compounds is already less than satisfactory, but a sudden drop in yield was found for Cn-alkanoyl compounds and a further sudden drop in the case of Ci2- alkanoyl compounds, so that alkanoyl compounds with the same or, in particular, more than 10 C atoms in the
  • EP-B 0 320 219 teaches a detergent composition comprising (a) a surfactant, (b) a bleaching component of a peroxygen bleach and a peracid bleach precursor, and (c) an antioxidant in a glassy PVP carrier.
  • Peroxyacid precursors of the formula AC-L, L can represent a ⁇ - to C 2 o ⁇ alkyl or alkenyl radical; compounds with a specific alkenyl group are not disclosed, nor are any advantages of such compounds indicated.
  • activators are known based on a (Cg-C2 ⁇ ) fatty acyl mono- or diester of a hexose or pentose or an alkyl glycoside, the fatty acyl group being saturated or mono- or polyunsaturated.
  • the sugars have an acyl group with a saturated or unsaturated (C7-C19) hydrocarbon radical and 1 to 4 short-chain acyl or aroyl groups; oleoyl and 10-undecenoyl are mentioned among the unsaturated acyl radicals.
  • acylated sugars can only be produced with great technical effort;
  • the long- or medium-chain acyl group is in the right place - for hexoses this is the C ⁇ atom and not the C 6 atom.
  • Another problem with activators based on acylated sugar is their often insufficient solubility, which reduces the effectiveness of the activator.
  • an activator for peroxo compounds based on an O-acyl compound of the general formula R ⁇ -CO-L, in which L is a leaving group bonded to R ⁇ -CO via an O atom of L, the O atom mentioned is bound to a C atom of a CC double bond of L and the acid LH corresponding to L has a pK a value in the range from 1 to 13 and R- 1 - an aliphatic one
  • Is hydrocarbon radical the longest carbon chain comprises at least 5 carbon atoms, which is characterized in that Rl is a decenyl group with a central or terminal CC double bond or an alkadienyl group with 5 to 17 carbon atoms.
  • R 1 is preferably decenyl, the C chain advantageously being unbranched.
  • the double bond of decenyl can be terminal or middle;
  • R 1 is particularly preferably n-decenyl with a terminal double bond.
  • Activators with an alkenoyl group with more than 11 carbon atoms are also more effective than the corresponding alkanoyl compounds. It is assumed that the completely different percarboxylic acid release of undec-10-enoyl compared to analog n-undecanoyl compounds is due to different micelle formation.
  • R 1 alkadienyl radical
  • R 1 unbranched or only slightly branched radical
  • the longest C chain in R 1 here preferably has 5 to 13, in particular 8 to 10, C atoms.
  • the two double bonds of R 1 can be conjugated or isolated.
  • the acyl group is bonded to an oxygen atom of the leaving group L and said oxygen atom in turn to a one C atom of a CC double bond of L.
  • the leaving group L is generally a phenolic or enolic one Leaving group.
  • this expediently has the general formula (I):
  • Y is a solubilizing group from the series -SO3M, -OSO3M, -COOM, -N + R 3 A ⁇ , -NRJ ⁇ O, n is an integer between 0 and 4 and Z is H, Cl, Y or C ⁇ -bis C_j-alkyl, M is H, alkali metal or ammonium, R 4 alkyl having 1 to 4 C atoms and A ⁇ an anion from the series Cl “ , OH “ , SO4 2 " , PO4 3" , HPO4 2 "
  • this expediently has the general formula (II):
  • R 2 is H or C ] _ to C4 ⁇ alkyl and R 3 is H, Ci to C4 alkyl, vinyl, Cl, CN or COOM, where M has the meaning given above.
  • phenolic leaving groups L preference is given to those in which n is the number 0 or 1, Z is hydrogen and Y is a sulfonic acid or carboxyl group or a salt, in particular a water-soluble salt, such as the sodium or potassium salt, of these acidic groups .
  • LH p- or / and o-hydroxybenzenesulfonic acid or its sodium or potassium salt is particularly preferred.
  • Activators which are both one of the preferred leaving groups L and a preferred acyl group R ⁇ -CO are particularly effective.
  • the acid LH corresponding to the leaving group L has one or more pK a values, depending on whether the molecule contains other acidic functions in addition to the acidic phenolic or enolic hydroxyl group. If Y in the general formula (I) is a sulfonic acid or carboxyl group and R 3 in the general formula (II) is a carboxyl group, these activators have two pK a values, the first pK a value between 1 and 5 and the second pK a is between 6 and 13. The second pK a value of preferred activators is usually between 8 and 10.
  • the activators according to the invention can be used to activate peroxo compounds.
  • the pH of which is between 4 and 13, preferably between 8 and 12
  • perhydrolysis of the activator forms an unsaturated percarboxylic acid which has a bleaching and disinfecting effect;
  • Activators are particularly preferred which are capable of forming a linear percarboxylic acid with a total of 11 carbon atoms and a terminal or medium-sized, preferably terminal, double bond.
  • Another object of the invention is based on
  • Activator compositions which, in addition to at least one activator according to the invention, additionally contain one or more activators not according to the invention.
  • activators not according to the invention are in particular those based on N-acyl and
  • O-acyl compounds with 2 to 18 carbon atoms, preferably 2 to 11 carbon atoms in the acyl group.
  • exemplary representatives of these activators are O-acylated sugars and phenols, such as nonanoyloxybenzenesulfonate (NOBS), and N-acylated polyamines, such as tetraacetylethylene diamine (TAED), as well short-chain or medium-chain N-acyl compounds of cyclic amides, such as hytandoin, 2, 5-diketopiperazine, succinimide, caprolactam and pyrrolidinone and their derivatives.
  • NOBS nonanoyloxybenzenesulfonate
  • TAED tetraacetylethylene diamine
  • the activators according to the invention and activators not according to the invention can in the.
  • Activator composition can be present in any mixing ratio per se, but a weight ratio in the range between 95 to 5 to 5 to 95 is expedient.
  • the mixing ratio between activator according to the invention and activator not according to the invention is preferably in the range between 90 to 10 and 10 to 90.
  • Particularly expedient it is, in addition to an activator according to the invention, in particular 4-undec-10-enoyl-oxybenzenesulfonate-Na (UDOBS), to use an activator according to the invention which is short-chain in perhydrolysis
  • UOBS 4-undec-10-enoyl-oxybenzenesulfonate-Na
  • Percarboxylic acid especially peracetic acid forms - TAED is particularly suitable for this.
  • activator combinations in detergents, bleaching agents, cleaning agents and disinfectants are notable for the fact that the costs for the activator combination are often lower than when an activator according to the invention is used alone.
  • Another very effective activator mixture consists essentially of the above-mentioned UDOBS and n-heptanoyloxybenzenesulfonate-Na, the two activators being present in any quantitative ratio, but preferably in a molar ratio of about 1 to 1.
  • the advantage of the last-mentioned activator mixture results from the fact that the carboxylic acids on which the two activators are based are easily obtainable as a mixture by pyrolysis of ricinoleic acid and subsequent oxidation.
  • the acid mixture can be converted into the acid chloride using, for example, thionyl chloride, and this can be reacted in a manner known per se with ortho and / or para-hydroxybenzenesulfonic acid Na salt to give the desired activator mixture.
  • the pure activators according to the invention can be prepared in principle in the same way by reacting the mono- or di-unsaturated carboxylic acid chloride with a phenol or enol or a phenolate or enolate to form the phenol or enol ester according to the invention and, if required, the reaction product in the desired acid or salt form is transferred.
  • that of DE-OS 38 24 901 is also suitable.
  • the invention further relates to oxidizing agents, bleaching agents, cleaning agents and disinfectants which contain hydrogen peroxide or a peroxo compound which releases hydrogen peroxide in the aqueous phase or an enzyme-substrate combination which forms hydrogen peroxide in situ in the aqueous phase and at least one activator according to the invention or one contain activator composition according to the invention.
  • Suitable peroxo compounds which in the aqueous phase under the usual washing, bleaching, cleaning and
  • Disinfection conditions are hydrogen peroxide in particular inorganic salts such as perborates, in particular sodium perborate monohydrate, sodium perborate tetrahydrate and superoxidized sodium perborate and sodium percarbonate, in particular sodium percarbonate of the general formula 2 Na2C ⁇ 3 • 3 H2O2 .
  • inorganic salts such as perborates, in particular sodium perborate monohydrate, sodium perborate tetrahydrate and superoxidized sodium perborate and sodium percarbonate, in particular sodium percarbonate of the general formula 2 Na2C ⁇ 3 • 3 H2O2 .
  • inorganic salts such as perborates, in particular sodium perborate monohydrate, sodium perborate tetrahydrate and superoxidized sodium perborate and sodium percarbonate, in particular sodium percarbonate of the general formula 2 Na2C ⁇ 3 • 3 H2O2 .
  • inorganic support materials such as silicas and silicates
  • sodium perborates and sodium percarbonate are the most important peroxo compounds in the agents mentioned.
  • the enzyme-substrate combinations which form hydrogen peroxide in situ in the aqueous phase are understood to be those which contain both an enzyme, for example glucose oxidase, urea oxidase, D-amino acid oxidase, alcohol oxidase and xanthine oxidase, and the corresponding substrate, that is to say glucose, urea, amino acids, alcohols or xanthine contain.
  • the aforementioned activators according to the invention and not according to the invention can be used individually or in the form of a previously prepared activator mixture in the washing, bleaching, cleaning and disinfecting agents according to the claims.
  • the activator mixture can be in the form of a powder, granules, extrudate or coated particles, or in the form of a paste of the mixture and a liquid medium.
  • the activators and inorganic peroxygen compounds can be used not only in the purely aqueous phase but also in the aqueous-organic phase.
  • the usual washing, bleaching and cleaning liquors have a purely aqueous environment.
  • An aqueous organic environment can be used in disinfection applications as well as be useful in technical oxidation processes.
  • the pH of the aqueous medium is generally between about 4 and 13; but preferably in the alkaline range, usually at pH 8 to 12, since both the in situ formation of the organic peracid proceeds well and the stability of the peroxo compounds is satisfactory.
  • Detergents, bleaching agents, cleaning agents and disinfectants according to the invention contain, in addition to at least one activator according to the invention and a peroxo compound or an enzyme-substrate combination which forms H2O 2, customary components of such compositions.
  • these agents are dissolved in an aqueous medium and form the washing, bleaching or cleaning liquor.
  • the agents expediently contain pH-regulating components in order to maintain the pH value which is most favorable for washing, bleaching, cleaning and disinfecting and to favorably influence the in situ formation of the organic peracid from the peroxo compound and the activator and their stability in the environment.
  • the main components of the detergents and bleaches are builders and surfactants.
  • the builders include, in particular, crystalline detergent-grade sodium aluminosilicates, in particular zeolite A, P and optionally X.
  • Effective organic builder substances are amino polycarboxylic acids, such as ethylenediaminetetraacetic acid and Nitrilotriacetic acid, polyphosphonic acids, in particular 1-hydroxyethane-l, 1-diphosphonic acid and ethylenediaminetetra- (methylenephosphonic acid), furthermore polycarboxylic acids, such as citric acid and sugar acids, and also polymeric polycarboxylic acids and polyoxycarboxylic acids, such as those known from DE-OS 43 03 320.
  • amino polycarboxylic acids such as ethylenediaminetetraacetic acid and Nitrilotriacetic acid
  • polyphosphonic acids in particular 1-hydroxyethane-l, 1-diphosphonic acid and ethylenediaminetetra- (methylenephosphonic acid)
  • polycarboxylic acids such as citric acid and sugar acids
  • polymeric polycarboxylic acids and polyoxycarboxylic acids such as those known from DE-OS 43 03 320.
  • the agents according to the invention contain one or more surfactants from the series of cationic, anionic, non-ionic, amphoteric and ampholytic surfactants.
  • the agents preferably contain nonionic surfactants, such as fatty alcohol and alkylphenol polyethylene glycol ethers and long-chain alkylglycosides, and anionic surfactants, such as alkylbenzenesulfonates and sulfates of fatty alcohol and polyethylene glycol monoethers.
  • washing, bleaching, cleaning and disinfecting agents according to the claims can contain alkaline and neutral electrolytes, such as alkanolamines, silicates, carbonates and sulfates; further additional components of such agents are pH regulators, stabilizers, foam regulators, graying inhibitors, anti-redeposition agents and enzymes such as oxidases, cellulases, peroxidases, proteases, amylases and lipases.
  • Cleaning agents often contain additional abrasive substances and disinfectants, organic
  • Preferred detergents and bleaches according to the invention contain 2 to 35% by weight of one or more inorganic peroxo compounds, 0.2 to 20% by weight of activators, including at least one activator according to the invention or an activator composition according to the invention, 5 to 30% by weight anionic and / or non-ionic surfactants, 5 to 60 wt .-% inorganic builders, 0 to 20 wt .-% organic Builders as well as ad 100% by weight of customary auxiliaries in effective amounts and water.
  • activators including at least one activator according to the invention or an activator composition according to the invention, 5 to 30% by weight anionic and / or non-ionic surfactants, 5 to 60 wt .-% inorganic builders, 0 to 20 wt .-% organic Builders as well as ad 100% by weight of customary auxiliaries in effective amounts and water.
  • agents according to the invention are so-called bleach additives, which advantageously contain 5 to 50% by weight of inorganic peroxo compounds, 2 to 30% by weight of activators, including at least one activator according to the invention or one activator composition according to the invention, 0 to 5% by weight peroxide stabilizers, 0 up to 40% by weight of pH regulating agents and ad 100% by weight of customary auxiliaries and water.
  • the agents according to the invention for washing, bleaching, cleaning and disinfecting are used in a conventional manner, for example by producing a washing, bleaching, cleaning and disinfectant liquor, contacting the material to be treated with this liquor, rinsing with water and drying.
  • activator compositions are distinguished by an extraordinarily good activator activity.
  • Activators are quickly and completely perhydrolyzed and form a very bleaching medium-chain unsaturated percarboxylic acid.
  • the property profile of the activators according to the invention exceeds that of numerous known activators and, when used alone, corresponds at least to that of the currently most effective known activator NOBS.
  • a mixture according to the invention and an activator not according to the invention are distinguished by a surprisingly higher activator activity than was known even from the best known activators.
  • the activators according to the invention are also accessible with less technical effort than activators based on sugars with at least one medium-chain unsaturated acyl group. example 1
  • UDOBS was produced according to example 1.
  • HOBS was prepared analogously to Example 1 from 4-hydroxybenzenesulfonate Na and heptanoic acid chloride.
  • the activator test was carried out in each case using a mixture of 1.5 g sodium perborate monohydrate, 0.5 g activator and 8 g base powder of a detergent composition containing zeolite, free of enzymes, bleaches and activators per 1 water.
  • the peracid content formed at 30 ° C became dependent determined by the reaction time: 100 ml samples were taken at the times shown in Table 1, these were immediately added to a mixture of 250 g of ice and 15 ml of glacial acetic acid and then titrated with 0.1N sodium thiosulfate solution and starch as an indicator after the addition of potassium iodide . Only the peracids formed in situ were recorded under the specified conditions. The results - content of equivalent peracid as a function of time - follow from Table 1.
  • Detergents containing anionic surfactants, zeolite A,
  • Test fabric cotton Test stains: coffee, wfk 10 K; Tea wfk CFT BC-1; Bell pepper wfk 10 N; Curry wfk
  • Example 4 Activator effect of activator mixtures compared to individual components.
  • the washing tests were carried out analogously to Example 4 in a Launder-O-meter at 30 ° C. using the soiled test fabrics specified in Example 4 (but soiling tea with CFT-BC-3 instead of CFT-BC-1).
  • Activator UDOBS more effective than NOBS.
  • the effectiveness of the activator mixture UDOBS / HOBS corresponds essentially to UDOBS and NOBS.
  • Activator mixtures from TAED and UDOBS are better bleaching than NOBS at a mixing ratio of 1: 4.

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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)

Abstract

La présente invention concerne de nouveaux activateurs très efficaces à base de composés phénoliques ou énoliques O-acyle pour composés peroxo, des compositions activatrices et des agents de lavage, décolorants, nettoyants et désinfectants contenant ces activateurs. L'effet activateur des composés phénoliques O-alcanoyle est considérablement réduit si la chaîne du groupe alcanoyle contient plus de 9 à 10 atomes de C. Les activateurs phénoliques et énoliques selon l'invention contiennent le radical undécénoyle ou un groupe alcadiénoyle avec 5 à 17 atomes C en tant que groupe O-acyle. L'activateur acide 4-undéc-10-énoyloxybenzolsulfonique ou un sel de celui-ci soluble l'eau est sensiblement plus efficace que l'activateur correspondant avec un groupe undécanoyle. Les mélanges d'activateurs comprenant un activateur selon l'invention et un activateur à base d'un composé O-acyle ou N-acyle présentent une efficacité synergique.
PCT/EP1996/000599 1995-03-24 1996-02-13 Activateurs pour composes peroxo et agents les contenant WO1996030482A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19510813.2 1995-03-24
DE1995110813 DE19510813A1 (de) 1995-03-24 1995-03-24 Aktivatoren für Peroxoverbindungen und sie enthaltende Mittel

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WO1996030482A1 true WO1996030482A1 (fr) 1996-10-03

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WO (1) WO1996030482A1 (fr)

Families Citing this family (1)

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DE19616693A1 (de) * 1996-04-26 1997-11-06 Henkel Kgaa Enolester als Bleichaktivatoren für Wasch- und Reinigungsmittel

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EP0140648A2 (fr) * 1983-10-26 1985-05-08 Interox Chemicals Limited Compositions de péroxyde d'hydrogène
EP0150532A1 (fr) * 1983-12-22 1985-08-07 The Procter & Gamble Company Activateurs de blanchiment à base de péroxydes et compositions de blanchiment
WO1991010719A1 (fr) * 1990-01-22 1991-07-25 Novo Nordisk A/S Composition detergente de blanchissage
CS515290A3 (en) * 1990-10-23 1992-04-15 Univ Komenskeho N-/2(10-undecenoyl)ethyl/-n,n,n-alkyldimethylammonium bromides and process for preparing thereof
DE4231466A1 (de) * 1992-09-19 1994-03-24 Henkel Kgaa Aktivatoren für anorganische Perverbindungen

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DE3824901A1 (de) 1988-07-22 1990-02-15 Hoechst Ag Verfahren zur herstellung von acyloxibenzolsulfonsaeuren oder deren salzen
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GB8910725D0 (en) * 1989-05-10 1989-06-28 Unilever Plc Bleach activation and bleaching compositions
DE3927758A1 (de) 1989-08-23 1991-02-28 Saarberg Interplan Gmbh Vorrichtung zum verhindern des austretens von fuellgasen waehrend des einfahrens von kohlekuchen in horizontale verkokungskammern
YU221490A (sh) 1989-12-02 1993-10-20 Henkel Kg. Postupak za hidrotermalnu izradu kristalnog natrijum disilikata
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DE3003351A1 (de) * 1980-01-31 1981-08-06 Basf Ag, 6700 Ludwigshafen Verwendung von enolestern als kaltbleichaktivatoren fuer aktivsauerstoff abgebende verbindungen enthaltende wasch- und reinigungsmittel
EP0140648A2 (fr) * 1983-10-26 1985-05-08 Interox Chemicals Limited Compositions de péroxyde d'hydrogène
EP0150532A1 (fr) * 1983-12-22 1985-08-07 The Procter & Gamble Company Activateurs de blanchiment à base de péroxydes et compositions de blanchiment
WO1991010719A1 (fr) * 1990-01-22 1991-07-25 Novo Nordisk A/S Composition detergente de blanchissage
CS515290A3 (en) * 1990-10-23 1992-04-15 Univ Komenskeho N-/2(10-undecenoyl)ethyl/-n,n,n-alkyldimethylammonium bromides and process for preparing thereof
DE4231466A1 (de) * 1992-09-19 1994-03-24 Henkel Kgaa Aktivatoren für anorganische Perverbindungen

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DE19549358A1 (de) 1996-09-26
DE19510813A1 (de) 1996-09-26
EP0733701A1 (fr) 1996-09-25

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