EP1322744A1 - Sels enduits et granuleux de n-alkylammoniumacetonitrile et leur utilisation en tant qu'activeurs de blanchiment - Google Patents

Sels enduits et granuleux de n-alkylammoniumacetonitrile et leur utilisation en tant qu'activeurs de blanchiment

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Publication number
EP1322744A1
EP1322744A1 EP01969797A EP01969797A EP1322744A1 EP 1322744 A1 EP1322744 A1 EP 1322744A1 EP 01969797 A EP01969797 A EP 01969797A EP 01969797 A EP01969797 A EP 01969797A EP 1322744 A1 EP1322744 A1 EP 1322744A1
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EP
European Patent Office
Prior art keywords
acid
coated
group
sodium
granular
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.)
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Application number
EP01969797A
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German (de)
English (en)
Inventor
Arend Jouke Kingma
Axel Kistenmacher
Gregor Schürmann
Michael SCHÖNHERR
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BASF SE
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BASF SE
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Publication of EP1322744A1 publication Critical patent/EP1322744A1/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
    • C11D3/3917—Nitrogen-containing compounds
    • C11D3/3925—Nitriles; Isocyanates or quarternary ammonium nitriles
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules

Definitions

  • the present invention relates to N-alkylammonium acetonitrile salts of the formula
  • Bleach activators have been used in modern washing and cleaning agents for some time. They serve to activate the compounds usually used as bleaching agents so that the decomposition of these compounds occurs completely and / or even at low temperatures, thus achieving the desired bleaching effect.
  • the bleach activators are often provided with a layer that envelops them, which makes them easier to dose and handle and often results in better washing results.
  • they are less easily subject to hydrolysis in coated form, which is generally easy in the usual detergent and cleaning agent formulations due to the detergent substances which have an alkaline pH.
  • a known class of bleach activators are N-alkylammonium acetonitrile salts of the general formula
  • R 1 is a - to C 4 -alkyl group which can be interrupted by non-adjacent oxygen atoms or can additionally carry hydroxyl groups, a C 4 - to C 24 -cycloalkyl group, a C 7 - to C 24 -alkaryl group or a grouping of the formula -CR 4 R 5 means -CN,
  • R 2 and R 3 each independently of one another have the meaning of R 1 or together represent a saturated four- to nine-membered ring with at least one carbon atom and at least one further hetero atom from the group consisting of oxygen, sulfur and nitrogen,
  • R 4 and R 5 each independently of one another are hydrogen, a - to C 24 -alkyl group which can be interrupted by non-adjacent oxygen atoms or can additionally carry hydroxyl groups, a C 4 - to C 24 -cycloalkyl group or a C 7 - to C 24 -alkaryl group means and
  • Y stands for a suitable anion.
  • This group of bleach activators is described in patent applications EP-A 303 520 (Kao Corporation, earliest priority date August 14, 1987), WO 96/40661 (Clorox Company, priority date June 7, 1995) and applications EP-A 790 244 (Hoechst AG, priority date February 15, 1996) and DE-A 197 40 669 (Clariant GmbH, filing date September 17, 1997).
  • This last-mentioned application also describes the coating (coating) of the compounds with a suitable substance.
  • BASF AG describes a process which provides these nitrile salts in granular, granular form.
  • the respective nitrile which is present as the salt of the methyl sulfate, is evaporated to a melt at a temperature of 80 to 250 ° C. and a pressure of 10 mbar to 2 bar, which is then allowed to solidify.
  • customary carrier materials and / or auxiliaries are added and the nitrile thus obtained, which is present as sulfate or hydrogen sulfate, is converted into the crystalline state.
  • R 1 is a C to C 24 alkyl group which is not adjacent
  • Oxygen atoms may be interrupted or may additionally carry hydroxyl groups, a C 4 - to C 4 cycloalkyl group, a C 7 - to C 24 alkaryl group or a group of formula -CR 4 R 5 -CN,
  • R 2 and R 3 each independently of one another have the meaning of R 1 or, together with the nitrogen atom to which they are attached, a saturated four- to nine-membered ring having at least one carbon atom and at least one further heteroatom from the group consisting of oxygen and sulfur and represent nitrogen,
  • R 4 and R 5 are each independently hydrogen, a Q to C 24 alkyl group which can be interrupted by non-adjacent oxygen atoms or can additionally carry hydroxyl groups, a C 4 to C 24 cycloalkyl group or a C 7 to C 24 Alkaryl group means and
  • Y represents a sulfate or bisulfate anion in the corresponding stochiometric amount, wherein the salts of formula (I) are coated with a material which is selected from the group consisting of organic, inorganic, hydrophilic and hydrophobic substances.
  • N-alkylammomumacetonitrile salts of the formula (I) coated according to the invention are prepared in a manner known per se by coating the granules obtained after evaporation and transfer of the salts into a granular form in accordance with the process disclosed in the application with the file number 199 13 995.4 manufactured. Both inorganic and organic, hydrophilic and hydrophobic substances serve as coating materials.
  • organic, hydrophilic coating materials include fatty alcohols (also in a mixture with aluminum stearate), ethoxylated fatty alcohols and oxo alcohols, for example C 8 -C 31 fatty alcohol polyalkoxylates with 1 to 150 moles of ethylene oxide, fatty acids, for example lauric acid, myristic acid, stearic acid and their Na, K, Ca and ammonium salts, fatty acid esters, waxes, for example paraffin waxes, montan ester wax, montanic acid wax, polyethylene wax, oxidized polyethylene wax, ethylene / acrylic acid copolymer wax, ethylene / vinyl acetate copolymer wax, polyalkyl vinyl ether wax, dispersions of suitable polymers, for example of alkyl acrylate, styrene , Alkyl acrylate / (meth) acrylic acid copolymers, maleic acid / olefin copolymers, vinyl chloride / ethylene copolymers
  • organic, hydrophilic coating materials include polyethylene glycols with a molecular weight of 1,000 to 50,000, and block copolymers and statistical copolymers of ethylene glycol and propylene glycol.
  • suitable inorganic coating materials include magnesium sulfate, sodium hexaphosphate, dihydrogen phosphate, pyrophosphate, phosphonic acids, sodium metaborate, sodium metasilicate, water glass,
  • Suitable coating materials must have a melting point which is> 30 ° C, preferably> 40 ° C, in particular> 45 ° C.
  • polyethylene glycols having a molecular weight> 1500, long chain fatty acids, fatty alcohol ethoxylates are used as the shell material (for example of the type Lutensol ® from BASF AG), and block copolymers of ethylene oxide and propylene oxide (for example of the type Pluronic ® from BASF AG).
  • polyethylene glycols having a molecular weight of about 6000 fatty alcohol ethoxylates of the type Lutensol ® AT BASF AG (C 16 -C 18 -Fettalkohol- ethoxylates), ethylene oxide / propylene oxide block copolymers of the Pluronic ® PE 6800 (ethylene oxide Content approx. 80%, molecular weight approx. 8,000) and stearic acid as the coating material.
  • Preferred substances of the formula (I) are those in which R 2 and R 3 together with the nitrogen atom to which they are attached form a six-membered ring which may optionally contain a further N atom or an oxygen atom, and those in which R 1 to R 3 are the same or different and represent a Ci to C 4 alkyl radical.
  • the most preferred substances according to the present invention are N-methyl-Mo holinium acetonitrile sulfate or bisulfate and trimethylammonium acetonitrile sulfate and bisulfate.
  • the coating can be applied from the melt or from solutions or dispersions, the solution or emulsifier being removed by evaporation. It can also be applied as a fine powder, for example using electrostatic techniques.
  • the coating materials can be applied to the granular N-alkylammonium acetonitriles in stirrers, mixers and granulators. The coating materials are preferably applied in a fluidized bed, it being possible for the particles to be sized at the same time. If, under certain circumstances, the coating materials lead to sticky products, it can be useful to additionally coat the coated granular N-alkylammom ' umacetonitrile with fine-particle substances ("powdering").
  • the amount of coating material used for the bleach activator used according to the invention is from 2 to 30% by weight, based on the base granules containing the bleach activator.
  • Preferred amounts of coating material are from 5 to 20% by weight, in particular 5 to 15% by weight, in each case based on the base granules.
  • the average particle size of the coated granular N-alkylammonium acetonitrile according to the invention is in the range from 100 ⁇ m to 3000 ⁇ m, preferably in the range 300 ⁇ m to 2000 ⁇ m, very particularly preferably 500 ⁇ m to 1200 ⁇ m.
  • the granular N-alkylammonium acetonitriles to be coated can also be coated or used in combination with other bleach activators.
  • These are, for example, compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids with preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or optionally substituted perbenzoic acid.
  • These are often bleach activators which contain eyie or more N- or O-acyl groups and / or optionally substituted benzoyl groups, such as substances from the class of anhydrides, esters, imides and acylated imidazoles or oximes.
  • TAED tetraacetylethylenediamine
  • TAMD tetraacetylmethylenediamine
  • TAGU tetraacetylglycoluril
  • TAHD tetraacetylhexylenediamine
  • N-acylimides especially N-nonanoylsuccinimide (NOSI), acylated phenolsulfonoylnonyllononyllonyllonononllnonononllonononllononllononllonllonllonllonllonlononlonononlonononlonononlonononlonononlonononlonononlonononlonononlonononlonononlonononlonononlonononlonononlonononlonononlonononlonononlonononlonononlonononlonononlonononlonononlonon
  • bleach activators from the group consisting of carboxylic acid anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate, 2,5-diacetoxy-2,5-dihydrofuran and those from German patent applications DE 196 16 693 and DE 196 16 767 known enol esters and acetylated sorbitol and mannitol or their mixtures described in European patent application EP 0 525 239 (SORMAN), acylated sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetylfructose, tetraacetylxylose and octaacetyllactose, and also acetone optionally N-alkylated glucamine and gluconolactone, and / or
  • carboxylic acid anhydrides in particular phthalic anhydride
  • transition metal compounds in question include, in particular, the manganese, iron and iron compounds known from German patent application DE 195 29 905.
  • Patent application DE 196 20 267 known N-analog compounds, which from the German
  • Patent application DE 195 36 082 known manganese, iron, cobalt. Ruthenium or
  • Molybdenum-carbonyl complexes the manganese, iron, cobalt, ruthenium, molybdenum, titanium and vanadium and described in the German patent application DE 196 05 688
  • bleach-enhancing transition metal complexes in particular with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, preferably selected from the group of manganese and cobalt salts and complexes, the cobalt (ammin) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt and manganese and of the manganese sulfate are particularly preferably selected.
  • bleach-enhancing transition metal complexes can be used in conventional amounts, preferably in an amount up to 5% by weight, in particular from 0.0025% by weight to 1% by weight and particularly preferably from 0.01% by weight to 0.25 % By weight, based in each case on the total detergent formulation.
  • polyacylated alkylenediamines especially tetraacetylethylenediamine (TAED), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), further glucose pentaacetate (GPA), xylose tetraacetate (TAX), sodium-4-benzoyloxy benzene sulphonate (SBOBS), Natriumtrimethylhexanoyloxy- benzenesulfonate (STHOBS ), Tetraacetylglucoluril (TAGU), tetraacetylcyanoic acid (TACA), di-N-acetyldimethylglyoxime (ADMG), l-phenyl-3-acetylhydantoin (PAH), acylated phenol sulfonates, nonanoylbenzene sulfonate (NOBS), isobenzolonoylbenzene sulfonate (is
  • coated granular N-alkylammonium acetonitriles according to the invention are generally used in combination with the bleaching agents listed below.
  • Alkali metal perborates and their hydrates and alkali metal percarbonates preferably sodium perborate in the form of the mono- or tetrahydrate, or sodium percarbonate and its hydrates being used.
  • Persulfates and Hydrogen peroxide and typical oxygen bleaching agents such as organic peracids, for example perbenzoic acid, peroxy-alpha-naphthoic acid, peroxylauric acid, peroxystearic acid, phthalimidoperoxycaproic acid, nonylimidperoxysuccinic acid, nonylimidperoxyadipic acid, 1, 32-diperoxydodecanoic acid, 1, 9-dodiacodiacid, 1-9-dodiacodiacid, 1-9-dodiacodoxydiperoxyacid, 1-9-dodiacodiacid, 1-9-dodiacodiacid, 1-9-dodiacodiacid, 1-9-dodiacyldiperoxyacid, 1-9-dodiacid, , Also suitable are cationic peroxy acids, as described in patent applications US 5 422 028, US 5 294 362 and US 5 292 447, and sulfonyl peroxy acids, as described, for example, in patent application US 5 03
  • the peroxyacid bleaching agent is used in amounts that provide an amount of available oxygen between about 0.1% to about 10%, preferably between about 0.5% to about 5%, especially about 1% to 4%.
  • the percentages relate to the total weight of the detergent composition.
  • the proportion of bleaching agents containing peroxide in the detergent compositions according to the invention is between about 0.1% by weight to about 95% by weight and preferably between about 1% by weight and about 60% by weight. If the bleach composition is also fully formulated
  • the proportion of the peroxide-containing bleaching agent is between about 1 wt .-% to about 20 wt .-%.
  • N-alkylammonium acetonitriles coated according to the invention can also be used in combination with so-called bleach boosters. These are substances that further increase the effectiveness of the known bleaching agents.
  • Bleach activators are particularly suitable for the diamines described in DE-A 196 11 992. These are compounds that secondary amine groups
  • NHR 1 Contain NHR 1 and which are low molecular weight, oligomeric or polymeric.
  • they are secondary amino acids of the general formula R 1 NH - [(CR 3 R 4 ) m -NH] n -R 2
  • radicals R 3 and R independently of one another are -C 3 o-, preferably -Cis-hydrocarbyl radicals and the radicals R and R independently of one another are C 1 -C 3 Q-, preferably C 1 -C15-
  • the bleaching power amplifiers disclosed in DE-A 196 11 992 are an integral part of the present invention and are incorporated into this by reference.
  • the N-alkylammonium acetonitrile salts coated according to the invention are used in particular with the bleaching power boosters disclosed in the abovementioned application. Particularly good results are obtained with regard to the effect of the combination bleach activator / bleach booster.
  • the bleaching effect achieved is of course to be mentioned here, which is particularly pronounced and is therefore desirable in principle.
  • the granular N-alkylammonium acetonitriles coated according to the invention can be used as bleach activators for use in detergents, cleaning agents, dishwashing detergents, stain salts, disinfectants, denture cleaners, fiber bleaches, such as. B. the cellulose bleach, the pulp bleach or in the cotton fiber bleaching as well as the hair bleaching. Preferred areas of application are detergents and dishwashing detergents.
  • the bleach activators are preferably used in the formulations intended for these fields of application in amounts of up to 10% by weight, in particular 0.1% by weight to 8% by weight, particularly 0.5 to 8% by weight and particularly preferably 0 , 8 to 5 wt .-% based on the total formulation used.
  • the main areas of application are household and industrial textile detergents and household and industrial dishwashing formulations.
  • the formulations in which the granular N-alkylammonium acetonitriles coated according to the invention can be used are described below by way of example for the fields of application of textile detergents and machine dishwashing detergents.
  • the coating of the invention enables the substances of the formula (I) to be handled easily and safely, and dust formation is practically not observable.
  • the Substances are protected from undesired hydrolysis, which easily occurs in detergent formulations, for example.
  • composition of household textile detergent Composition of household textile detergent
  • the detergent formulations in which the coated granular N-alkylammomum acetonitrile according to the invention can be used are in powder, granule, paste, gel or liquid form, or they are solid detergents. Depending on their intended use, the formulation of the formulations must be adapted to the type of textiles to be washed. They contain conventional detergent ingredients that correspond to the state of the art. Representative examples of such detergent and cleaning agent ingredients are described below.
  • the total concentration of surfactants in the finished detergent formulation can be from 1 to 99% by weight, preferably from 5 to 80% by weight.
  • the surfactants used can be anionic, nonionic, amphoteric or cationic. Mixtures of the surfactants mentioned can also be used.
  • Preferred detergent formulations contain anionic and / or nonionic surfactants and their mixtures with other surfactants.
  • Suitable anionic surfactants are sulfates, sulfonates, carboxylates, phosphates and mixtures thereof.
  • Suitable cations are alkali metals such as sodium or potassium or alkaline earth metals such as. As calcium or magnesium and ammonium, substituted ammonium compounds including mono-, di- or triethanolammonium cations and mixtures thereof.
  • alkyl ester sulfonates, alkyl sulfates, alkyl ether sulfates, alkyl benzene sulfonates, secondary alkane sulfonates and soaps are preferred. These are described below. j
  • Alkyl ester sulfonates include linear esters of C 18 -C 2 o-carboxylic acids (fatty acids) which are sulfonated using gaseous SO 3 , as described, for example, in "The Journal of the American Oil Chemists Society” 52 (1975), p. 323- 329.
  • Suitable starting materials are natural fats such as, for example, tallow, coconut oil and palm oil, but also fats of a synthetic nature
  • Preferred alkyl ester sulfonates are compounds of the formula R 1 - CH- COR
  • R 1 is a C 8 -C 20 hydrocarbon residue, preferably alkyl and R is a Ci-C ⁇ hydrocarbon residue, preferably alkyl.
  • M stands for a cation that forms a water-soluble salt with the alkyl ester sulfonate. Suitable cations are sodium, potassium, lithium or ammonium cations such as monoethanolamine, diethanolamine and triethanolamine.
  • R 1 is preferably C 10 -C 16 alkyl and R is methyl, ethyl or isopropyl. Most preferred are methyl ester sulfonates in which R 1 is C 1 -C 16 -alkyl.
  • Alkyl sulfates are water soluble salts or acids of the formula ROSO 3 M wherein R is a C 10 - C 24 hydrocarbon group, preferably an alkyl or hydroxyalkyl radical having C 10 -C 2 0 - alkyl component, more preferably a C 12 -C 18 - alkyl or Is hydroxyalkyl.
  • M is hydrogen or a suitable cation, such as "umkation an alkali metal cation, preferably sodium, potassium, lithium or ammonium or substituted Ammom, preferably methyl-, dimethyl-, and trimethyl or a quaternary ammonium cations, such as tetramethylammonium and dimethyl and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine and mixtures thereof.
  • Alkyl chains with C 12 -C ⁇ 6 are preferred for low washing temperatures (e.g. below about 50 ° C) and alkyl chains with C 6 -C 18 for higher washing temperatures (e.g. above about 50 ° C).
  • Alkyl ether sulfates are water soluble salts or acids of the formula RO (A) m SO 3 M wherein R is an unsubstituted C 1 oC 24 - alkyl or hydroxyalkyl group, preferably a C 12 -C 20 - alkyl or hydroxyalkyl group, particularly preferably a C 1 -C 18 represents alkyl or hydroxyalkyl.
  • A is an ethoxy or propoxy unit
  • m is a number greater than 0, preferably between approximately 0.5 and approximately 6, particularly preferably between approximately 0.5 and approximately 3
  • M is a hydrogen atom or a cation such as, for , As sodium, potassium, lithium, calcium, magnesium, ammonium or a substituted ammonium cation.
  • substituted ammonium cations include methyl, dimethyl, trimethylammonium and quaternary ammonium cations such as tetramethylammonium and dimethylpiperidinium cations, as well as those derived from alkylamines such as ethylamine, diethylamine, triethylamine or mixtures thereof.
  • alkylamines such as ethylamine, diethylamine, triethylamine or mixtures thereof.
  • C 12 -C 8 fatty alcohol ether sulfates called, the content of ethylene oxide units being 1, 2, 2.5, 3 or 4 mol per mol of the fatty alcohol ether sulfate and in which M is sodium or potassium.
  • the alkyl group can either be saturated or unsaturated, branched or linear and optionally substituted with a hydroxyl group.
  • the sulfo group can be at any position on the C chain, the primary methyl groups at the beginning and end of the chain having no sulfonate groups.
  • the preferred secondary alkanesulfonates contain linear alkyl chains with about 9 to 25 carbon atoms, preferably about 10 to about 20 carbon atoms and particularly preferably about 13 to 17 carbon atoms.
  • the cation is, for example, sodium, potassium, ammonium, mono-, di- or triethanolammonium, calcium or magnesium and mixtures thereof. Sodium as the cation is preferred.
  • anionic surfactants are alkenyl or alkylbenzenesulfonates.
  • Alkenyl or alkyl group can be branched or linear and optionally substituted with a hydroxyl group.
  • the preferred alkylbenzenesulfonates contain linear alkyl chains with about 9 to 25 carbon atoms, preferably from about 10 to about 13 carbon atoms, the cation is sodium, potassium, ammonium, mono-, di- or triethanolammonium, calcium or magnesium and mixtures thereof. Magnesium is preferred as the cation for mild surfactant systems, while sodium is preferred for standard washing applications. The same applies to alkenylbenzenesulfonates.
  • anionic surfactants also includes olefin sulfonates which are obtained by sulfonating C 12 -C 24 , preferably C 14 -C 16, ⁇ -olefins with sulfur trioxide and subsequent neutralization. Due to the manufacturing process, these olefin sulfonates can contain small amounts of hydroxyalkanesulfonates and
  • Suitable anionic surfactants are carboxylates, e.g. B. fatty acid soaps and comparable surfactants.
  • the soaps can be saturated or unsaturated and can contain various substituents such as hydroxyl groups or ⁇ -sulfonate groups.
  • Linear saturated or unsaturated hydrocarbon radicals are preferred as the hydrophobic portion with approximately 6 to approximately 30, preferably approximately 10 to approximately 18 carbon atoms.
  • Suitable anionic surfactants are: salts of acylaminocarboxylic acids; the acyl sarcosinates formed by the reaction of fatty acid chlorides with sodium sarcosinate in an alkaline medium; Fatty acid-protein condensation products obtained by reacting fatty acid chlorides with oligopeptides; Salts of alkyl sulfamidocarboxylic acids: salts of alkyl and alkyl aryl ether carboxylic acids; C 8 -C 24 olefin sulfonates; sulfonated polycarboxylic acids, prepared by sulfonating the pyrolysis products of alkaline earth metal citrates, such as. B.
  • alkylglycerol alkylglycerol
  • acylglycerol sulfates alkylphenol; primary paraffin sulfonates; alkyl phosphates; alkyl ether; Isethionates such as acyl isethionates; N-acyl taurides; alkyl succinates; sulfosuccinates; Monoesters of sulfosuccinates (especially saturated and unsaturated Ci 2 -C 8 monoesters) and diesters of sulfosuccinates (especially saturated and unsaturated Ci 2 -C ] 8 diesters); acyl sarcosinates; Sulfates of alkyl polysaccharides such as sulfates of alkyl polyglycosides, branched primary alkyl sulfates and alkyl polyethoxy carboxylates such as those of the formula RO (CH 2 CH 2 ) CH 2 COO " M +
  • Cation is; resin acids or hydrogenated resin acids such as rosin or hydrogenated rosin or tall oil resins and tall oil resin acids Further examples are described in "Surface Active Agents and Detergents” (Vol. I and II, Schwartz, Perry and Berch).
  • Polyethylene, polypropylene and polybutylene oxide condensates of alkylphenols.
  • These compounds include the condensation products of alkylphenols with a C 6 -C. 2 o-alkyl group, which can be either linear or branched, with alkene oxides. Compounds with about 5 to 25 mol of alkene oxide per mol of alkylphenol are preferred.
  • the alkyl chain of the aliphatic alcohols can be linear or branched, primary or secondary and generally contains from about 8 to about 22 carbon atoms.
  • the condensation products of do to C 20 alcohols with about 2 to about 18 moles of ethylene oxide per mole of alcohol are particularly preferred.
  • the alkyl chain can be saturated or unsaturated.
  • the alcohol ethoxylates can have a narrow (“narrow range ethoxylates”) or a broad homolog distribution of the ethylene oxide (“broad range ethoxylates”). Examples of commercially available nonionic surfactants of this type are, for example, the Lutensol ® brands from BASF Aktiengesellschaft.
  • Condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol.
  • the hydrophobic part of these compounds preferably has a molecular weight between approximately 1,500 and approximately 1,800.
  • the addition of ethylene oxide to this hydrophobic part leads to an improvement in water solubility.
  • the product is liquid up to a polyoxyethylene content of approx. 50% of the total weight of the condensation product, which corresponds to a condensation with up to approx. 40 mol ethylene oxide.
  • Commercially available examples of this product class are, for example, the Pluronic ® brands from BASF Aktiengesellschaft.
  • the hydrophobic unit of these compounds consists of the reaction product of ethylenediamine with excess propylene oxide and generally has a molecular weight of approximately 2,500 to 3,000. Ethylene oxide is added to this hydrophobic unit up to a content of approx. 40 to approx. 80% by weight polyoxyethylene and a molecular weight of approx. 5,000 to 11,000.
  • Ethylene oxide is added to this hydrophobic unit up to a content of approx. 40 to approx. 80% by weight polyoxyethylene and a molecular weight of approx. 5,000 to 11,000.
  • Tetronic ® brands from BASF Corp.
  • nonionic compounds includes water-soluble amine oxides, water-soluble phosphine oxides and water-soluble sulfoxides, each with an alkyl radical of approximately 10 to approximately 18 carbon atoms.
  • Semipolar nonionic surfactants are also amine oxides of the formula
  • R is an alkyl, hydroxyalkyl or alkylphenol group with a chain length of about 8 to about 22 carbon atoms.
  • R 2 is an alkylene or hydroxyalkylene group with approx. 2 to 3 carbon atoms or mixtures thereof, each radical R is an alkyl or hydroxyalkyl group with approx. 1 to approx. 3 carbon atoms or a polyethylene oxide group with approx. 1 to approx. 3 ethylene oxide units, and x represents a number from 0 to about 10.
  • the R 1 groups can be connected to one another via an oxygen or nitrogen atom and thus form a ring.
  • Amine oxides of this type are especially Cio-Cis-alkyldimethylamine oxides and C 8 -C ⁇ 2 -
  • Fatty acid amides have the formula
  • R is an alkyl group with about 7 to about 21, preferably about 9 to about 17 carbon atoms and R 1 is independently hydrogen, C 1 -C 4 alkyl, C 1 -C 4 hydroxyalkyl or (C 2 H 0)
  • X H means, where x varies from about 1 to about 3.
  • Preferred are C 8 -C 2 o-amides, mono-ethanolamides, diethanolamides and isopropanol ide.
  • nonionic surfactants are alkyl and alkenyl oligoglycosides as well as fatty acid polyglycol esters or fatty amine polyglycol esters each having 8 to 20, preferably 12 to 18 carbon atoms in the fatty alkyl radical, alkoxylated triglycamides, mixed ethers or mixed formals, alkyl oligoglycosides, alkenyl oligoglycosides, fatty acid-N-alkylgloxoxides, fatty acid-N-alkyl sulfoxides, and fatty acid-N-alkyl sulfoxides protein.
  • Typical examples of amphoteric or zwitterionic surfactants are alkyl betaines, alkylamide betaines, aminopropionates, aminoglycinates or amphoteric imidazolinium compounds of the formula
  • R 1 is C 8 -C 22 alkyl or alkenyl
  • R 2 is hydrogen or CH 2 CO 2 M
  • R 3 CH 2 CH 2 OH or CH 2 CH 2 ⁇ CH 2 CH 2 CO 2 M
  • R 4 is hydrogen, CH 2 CH 2 OH or CH 2 CH 2 COOM
  • n 2 or 3 preferably 2
  • M is hydrogen or a cation such as an alkali metal, alkaline earth metal, ammonium or alkanolammonium cation.
  • Preferred amphoteric surfactants of this formula are monocarboxylates and dicarboxylates. Examples include cocoamphocarboxypropionate, cocoamidocarboxypropionic acid, cocoamphocarboxyglycinate (also known as cocoamphodiacetate) and cocoamphoacetate.
  • amphoteric surfactants are alkyldimethylbetaines and alkyldipolyethoxybetaines with an alkyl radical with about 8 to about 22 carbon atoms which can be linear or branched, preferably with 8 to 18 carbon stolen atoms and particularly preferably with 12 to 18 carbon atoms.
  • Suitable cationic surfactants are substituted or unsubstituted straight-chain or branched quaternary ammonium salts of the type R 1 N (CH 3 ) 3 " 'X, R I R 2 N (CH 3 ) 2 ', X,
  • R 1 R 2 R 3 N (CH 3 ) + X " or R 1 R 2 RR 4 N I X.
  • the radicals R 1 , R 2 , R 3 and R 4 are, independently of one another, preferably unsubstituted alkyl having a chain length of 8 to 24
  • Carbon atoms in particular from 10 to 18 carbon atoms, hydroxyalkyl with 1 to 4 carbon atoms,
  • X is a suitable anion known to those skilled in the art.
  • Other detergent and cleaning agent ingredients that may be included in the present invention include inorganic and / or organic builders to reduce the hardness of the water.
  • Inorganic builders include, for example alkali metal, ammonium and Alkanolammom 'umsalze of polyphosphates such as tripolyphosphates, pyrophosphates, and glassy polymeric meta-phosphates, phosphonates, silicates, carbonates, including bicarbonates and sesquicarbonates, sulfates, and aluminosilicates.
  • silicate builders are the alkali metal silicates, in particular those with a SiO 2 : Na 2 O ratio between 1.6: 1 and 3.2: 1, and sheet silicates, for example the sodium sheet silicates described in US Pat. No. 4,664,839, available from Clariant GmbH under the brand name SKS ® .
  • SKS -6 ® is a particularly preferred layered silicate builder.
  • Aiuminosilicate builders are particularly preferred for the present invention. These are in particular zeolites with the formula Na z [(AlO 2 ) z (SiO 2 ) ⁇ ] .xH 2 O, where z and y are integers of at least 6, the ratio of z to y of about 1, 0 to 0.5 and x is an integer from 15 to 264.
  • Suitable ion exchangers based on aluminosilicate are commercially available. These aluminosilicates can be crystalline or amorphous in structure and can be naturally occurring or synthetic. Methods for the production of ion exchangers based on aluminosilicate are described, for example, in US Pat. Nos. 3,985,669 and 4,605,509. Preferred ion exchangers based on synthetic crystalline aluminosilicates are available under the names Zeolite A, Zeolite P (B) (including those disclosed in EP-A-0 384 070) and Zeolite X. Preferred are aluminosilicates with a particle diameter between 0.1 and 10 ⁇ .
  • Suitable organic builders include polycarboxyl compounds such as ether polycarboxylates and oxydisuccinates as described, for example, in US-3,128,287 and US-3,635,830.
  • the TMS / TDS builders known from US 4,663,071 are also suitable.
  • Other suitable builders include the ether hydroxypolycarboxylates, copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1,3,5-trihydroxybenzene-2,4,6-trisulfonic acid and carboxymethyloxy succinic acid, the alkali, ammonium and substituted ammonium salts of polyacetic acids such as e.g. B.
  • ethylenediaminetetraacetic acid and nitrilotriacetic acid and polycarboxylic acids such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene-1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid and their soluble salts.
  • Citrate-based builders e.g. B. citric acid and its soluble salts, especially the sodium salt, are preferred polycarboxylic acid builders, which can also be used in granulated formulations, in particular together with zeolites and / or layered silicates.
  • phosphorus-based builders When phosphorus-based builders can be used, and especially when hand soap formulations are to be formulated, various alkali metal phosphates such as sodium tripolyphosphate, sodium pyrophosphate and sodium orthophosphate can be used. Phosphonate builders such as ethane-l-hydroxy-l, l-diphosphonate and other known phosphonates, as described, for example, in US Pat. Nos. 3,159,581, 3,213,030, 3,422,021, 3,400,148 and US Pat. 3,422,137 are used.
  • the detergent ingredients used with the salts of the formula (I) coated according to the invention will be selected from components typical of detergents, such as surface-active substances and builders.
  • the detergent ingredients can contain one or more cleaning aids or other materials that enhance the cleaning effect, serve to treat or care for the object to be cleaned or change the performance properties of the detergent composition.
  • Suitable cleaning aids in detergent compositions include, for example, the substances mentioned in US 3,936,537.
  • the cleaning aids that can be used in the cleaning agent compositions of the present invention include, for example, enzymes, in particular proteases, lipases and cellulases, foam boosters, foam brakes, tarnishing and / or corrosion protection agents, Suspending agents, dyes, fillers, optical brighteners, disinfectants, alkalis, hydrotropic compounds, antioxidants, enzyme stabilizers, perfumes, solvents, solubilizers, redeposition inhibitors, dispersants, color transfer inhibitors, e.g. B.
  • enzymes in particular proteases, lipases and cellulases
  • foam boosters foam boosters
  • foam brakes foam brakes
  • tarnishing and / or corrosion protection agents Suspending agents, dyes, fillers, optical brighteners, disinfectants, alkalis, hydrotropic compounds, antioxidants, enzyme stabilizers, perfumes, solvents, solubilizers, redeposition inhibitors, dispersants, color transfer inhibitors, e.g. B.
  • Polyamine N-oxides such as poly- (4-vinylpyridine-N-oxide), polyvinylpyrrolidone, poly-N-vinyl-N-methylacetamide and copolymers of N-vinylimidazole and N-vinylpyrrolidone, processing aids, plasticizers and antistatic aids.
  • the detergent compositions can contain one or more conventional enzymes, such as proteases, amylases, lipases and cellulases.
  • a particularly preferred enzyme is cellulase.
  • the cellulase used here can be obtained from bacteria or fungi and should have an optimal pH range between 5 and 9.5. Suitable cellulases are disclosed in US 4,435,307.
  • Suitable cellulases are also disclosed in GB-A-2.075.028, GB-A-2.085.275 and DE-OS-2.247.832.
  • the detergent compositions according to the invention contain enzymes in amounts of up to about 50 mg, preferably from about 0.01 mg to about 10 mg, per gram of the detergent composition. Based on the weight of the detergent composition
  • Detergent compositions are at least 0.001% by weight, preferably between about 0.001% by weight and about 5% by weight, in particular from about 0.001% by weight to about 1% by weight, especially about 0.01% to about 1% by weight.
  • Composition of machine dishwashers are at least 0.001% by weight, preferably between about 0.001% by weight and about 5% by weight, in particular from about 0.001% by weight to about 1% by weight, especially about 0.01% to about 1% by weight.
  • Water-soluble and water-insoluble builders can be used whose main task is to bind calcium and magnesium. Common builders, which can be present between 10 and 90% by weight based on the entire preparation, are listed below.
  • Phosphates such as alkali phosphates and polymeric alkali phosphates, which can be in the form of their alkaline, neutral or acidic sodium or potassium salts. Examples include trisodium phosphate, tetrasodium diphosphate,
  • These phosphates are preferably used in the range from 25% by weight to 65% by weight, based on the overall formulation, and calculated as an anhydrous active substance.
  • Low molecular weight carboxylic acids and their salts e.g. Alkali citrates (such as anhydrous trisodium citrate or trisodium citrate dihydrate), alkali succinates, alkali monononates, fatty acid sulfonates, oxydisuccinates, alkyl or alkenyl disuccinates, gluconic acids, oxadiacetates, carboxymethyloxysuccinate, tartrate monosuccinate oxidate, tartrate monosuccinate oxidate acetic acid, tartrate monosuccinate monoxide succinate acetic acid, homo- and copolymeric polycarboxylic acids and their salts, e.g.
  • Alkali citrates such as anhydrous trisodium citrate or trisodium citrate dihydrate
  • alkali succinates alkali monononates
  • fatty acid sulfonates oxydisuccinates
  • oxydisuccinates alkyl or alkenyl
  • Polyacrylic acid Polymethacrylic acid, copolymer maleic acid / acrylic acid, copolymer maleic acid / acrylic acid / vinyl acetate; Graft polymers of monoethylenically unsaturated mono- and / or dicarboxylic acids on monosaccharides, oligosaccharides, polysaccharides or polyaspartic acid; On iopolycarboxylate and polyaspartic acid; Carbonates such as sodium carbonate and sodium bicarbonate.
  • Complexing agents and phosphonates and their salts such as, for example, nitrilotriacetic acid, ethylenediaminetetraacetic acid, diethylenetiaminepentaacetic acid, hydroxyethylethylenediaminetriacetic acid, methylglycinediacetic acid, 2-phosphono-l, 2,4-butanetricarboxylic acid, aminotri- (methylenephosphonic acid), 1-hydroxy acid, 1-hydroxy acid, 1-hydroxy acid Ethylene diamine tetramethylene phosphonic acid, hexamethylene diamine teti amethylene phosphonic acid and diethylene triamine pentamethylene phosphonic acid.
  • Silicates such as sodium disilicate and sodium metasilicate.
  • Water-insoluble builders include the zeolites and crystalline layered silicates, the latter in particular corresponding to the general formula NaMSi x O 2x + ⁇ * y H 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 22, preferably 1.9 to 4, and y represents a number from 0 to 33.
  • M sodium or hydrogen
  • x is a number from 1.9 to 22, preferably 1.9 to 4
  • y represents a number from 0 to 33.
  • Known examples of this are in particular ⁇ -Na 2 Si 2 05, ⁇ -Na 2 Si 2 0 5 , ⁇ -Na 2 Si 2 0 5 .
  • Mixtures of the abovementioned builder substances also count. Trisodium citrate and / or are preferred
  • Alkali carriers can be present as further components. Alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogen carbonates, alkali metal sesquicarbonates, alkali silicates, alkali metal silicates and mixtures of the abovementioned substances are considered as alkali carriers, alkali metal carbonates, in particular sodium carbonate, sodium hydrogen carbonate or sodium sesquicarbonate, being preferably used. Preferred combinations of builder and alkali carrier are mixtures of tripolyphosphate and sodium carbonate or tripolyphosphate, sodium carbonate and sodium disilicate.
  • Low-foaming or low-foaming nonionic surfactants are preferably used in proportions of 0.1 to 20% by weight (preferably 0.1-10% by weight, 0.25-4% by weight). These are for example surfactants from the group of fatty alcohol ethoxylates, such as those available commercially for example under the product Plurafac ® (BASF Aktiengesellschaft) or Dehypon ® (Cognis). Further, di- and multiblock copolymers can be built up from ethylene oxide and propylene oxide, as they are commercially available for example under the name Pluronic ® (BASF Aktiengesellschaft) or Tetronic ® (BASF Corporation).
  • Reaction products of sorbitan esters with ethylene oxide and / or propylene oxide can also be used.
  • Amine oxides or alkyl glycosides are also suitable.
  • An overview of suitable nonionic surfactants is given, for example, by EP-A 0851 023 and DE-A 198 19 187.
  • the formulation can also contain anionic or zwitterionic surfactants, preferably in a mixture with nonionic surfactants. Suitable anionic and zwitterionic surfactants are also mentioned in the documents EP-A 0851 023 and DE-A 198 19 187. Typical bleaching agents which can be used in combination with the salts of the formula (I) used according to the invention are described above.
  • Corrosion inhibitors In particular, silver protection agents from the group of the triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes can be used. Benzotriazole and / or alkylaminotriazole are particularly preferably to be used.
  • active chlorine-containing agents are often found in cleaner formulations, which can significantly reduce the corroding of the silver surface. In chlorine-free cleaners, oxygen and nitrogen-containing organic redox-active compounds, such as di- and trihydric phenols, e.g.
  • Hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucin, pyrogallol or derivatives of these classes of compounds are used.
  • Salt-like and complex-like inorganic compounds such as salts of the metals Mn, Ti, Zr Hf, V, Co and Ce, are also frequently used.
  • Preferred here are the transition metal salts which are selected from the group consisting of the manganese and cobalt salts and their complexes, particularly preferably the
  • Cobalt (amrnin) complexes the cobalt (acetate) complex
  • the cobalt (acetate) complex the cobalt (acetate) complex
  • Manganese sulfate Zinc compounds or bismuth compounds can also be used to prevent corrosion on the wash ware.
  • Enzymes Between 0 and 5% by weight of enzymes based on the entire preparation can be added to the cleaning agent in order to increase the performance of the cleaning agents or to guarantee the same quality of cleaning performance under milder conditions.
  • the most commonly used enzymes include lipases, amylases, cellulases and proteases. Esterases, pectinases, lactases and peroxidases can also be used.
  • Preferred proteases are, for example, BLAP ® 140 from the company Biozym, Optimase ® M-440 and Opticlean ® M 50 from Solvay Enzymes..; Maxacal ® CX and Maxapem ® or Esperase ® from Gist Brocades or Savinase ® from Novo or Purafect OxP from Genencor. Particularly suitable cellulases and lipases are Celluzym ® 0.7T and Lipolase ® 30T from Novo Nordisk.
  • the coated granular N-alkylammonium acetonitriles according to the invention can be used in detergent formulations both for the household sector and for the commercial sector.
  • Commercial cleaner types usually contain a builder system based on pentasodium triphosphate and / or sodium citrate and / or complexing agents such as nitrilotriacetate.
  • sodium hydroxide solution or potassium hydroxide solution is often used as an alkali carrier.
  • the coated granular N-alkylammonium acetonitriles according to the invention can be used both in liquid, gel-like, powdery, granular and tablet-shaped dishwashing detergents. It is possible to incorporate the coated granular N-alkylammonium acetonitriles according to the invention, if appropriate with other formulation components, into special compartments, such as e.g. Microcapsules, gel capsules. Furthermore, the copolymers according to the invention can also be installed in special compartments within dishwashing detergent tablets, which may show different dissolution behavior compared to the other tablet compartments. These can be both certain tablet layers and certain shaped bodies let into the tablet, glued to the tablet or enveloped by the tablet.
  • the coarse material larger than 1600 microns was ground and then sieved again. Thus, granular granules with a content of about 60 wt .-% of N-methylmorpholinium-acetonit ⁇ il hydrogensuifat was obtained.
  • Examples 6-16 were coated analogously to examples 3-5:
  • Test formulation The detergent formulation used to test the spotting behavior is composed as follows:
  • the procedure was carried out as a standard washing test in a Launder-o-Meter.
  • the test fabric was fabric of the type EMPA 114, which had been treated with red wine for staining, or fabric of the type EMPA 167 (origin: EMPA Testgewebe, St. Gallen, Switzerland), the ⁇ for staining Tea had been added.
  • the reflectance is measured using an Elrepho measuring device from Zeiss.
  • the detergent had the following composition:
  • Nonionic surfactants (C13-15 -oxoalcohol-7EO) 4.7%
  • Example 17 The procedure was as in Example 17, the fabric was EMPA 132, which had been dyed with direct black 122.
  • the color loss was measured using a Zeiss type Ehepho, the color loss [%] was calculated as follows:

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Abstract

L'invention concerne des sels granuleux et enduits de N-alkylammoniumacétonitrile de formule générale (I) R<2>R<3>N R<1>-CR<4>R<5>-CN<+>Y<-> dans laquelle R<1> signifie un groupe alkyle C1 à C24, pouvant être interrompu par des atomes d'oxygène non voisins ou pouvant porter en plus des groupes hydroxyle, un groupe cycloalkyle C4 à C24, un groupe alkaryle C7 à C24, ou un groupe de formule CR<4>R<5>-CN, R<2> et R<3> ont chacun, indépendamment l'un de l'autre, la signification de R<1> ou, ensemble, dans l'atome d'azote auquel ils sont liés, désignent un anneau saturé de quatre à neuf chaînons avec au moins un atome C et au moins un autre hétéroatome du groupe oxygène, soufre et azote, R<4> et R<5> représentent chacun, indépendamment l'un de l'autre, hydrogène, un groupe alkyle C1 à C24, pouvant être interrompu par des atomes d'oxygène non voisins ou pouvant porter en plus des groupes hydroxyle, un groupe cycloalkyle C4 à C24 ou un groupe alkaryle C7 à C24, et Y signifie un anion de sulfate ou de sulfate d'hydrogène dans la quantité stoechiométrique correspondante. Ces éléments sont enduits d'un matériau sélectionné dans le groupe comprenant des substances organiques, inorganiques, hydrophiles et hydrophobes.
EP01969797A 2000-09-28 2001-09-28 Sels enduits et granuleux de n-alkylammoniumacetonitrile et leur utilisation en tant qu'activeurs de blanchiment Withdrawn EP1322744A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE2000149237 DE10049237A1 (de) 2000-09-28 2000-09-28 Beschichtete, körnige N-Alkylammoniumacetonitril-Salze und deren Verwendung als Bleichaktivator
DE10049237 2000-09-28
PCT/EP2001/011290 WO2002026927A1 (fr) 2000-09-28 2001-09-28 Sels enduits et granuleux de n-alkylammoniumacetonitrile et leur utilisation en tant qu'activeurs de blanchiment

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DE10159388A1 (de) * 2001-12-04 2003-06-12 Henkel Kgaa Verfahren zur Herstellung von umhüllten Bleichaktivatorgranulaten
DE10161766A1 (de) * 2001-12-15 2003-06-26 Clariant Gmbh Bleichaktivator-Co-Granulate
WO2003101940A2 (fr) 2002-05-31 2003-12-11 Henkel Kommanditgesellschaft Auf Aktien Desodorisation de derives d'acetonitriles cationiques
DE10314442A1 (de) * 2003-03-31 2004-11-04 Henkel Kgaa MGSM mit speziell konfektionierten Bleichaktivatoren III
EP1572851B1 (fr) 2002-12-20 2007-03-21 Henkel Kommanditgesellschaft auf Aktien Produits de lavage et de nettoyage contenant un agent de blanchiment
DE50210897D1 (de) * 2002-12-24 2007-10-25 Dalli Werke Gmbh & Co Kg Optimiertes Wasch- und Reinigungsmittelsystem für eine verbesserte Bleichwirkung bei niedrigeren Temperaturen
ES2285421T3 (es) 2003-02-10 2007-11-16 Henkel Kommanditgesellschaft Auf Aktien Agente de lavado o de limpieza, que continen un agente de blanqueo, con sistema adyuvante, soluble en agua, y un derivado de la celulosa con capacidad para el desprendimiento de la suciedad.
DE10351325A1 (de) 2003-02-10 2004-08-26 Henkel Kgaa Wasch- oder Reinigungsmittel mit wasserlöslichem Buildersystem und schmutzablösevermögendem Cellulosederivat
DE102004012568A1 (de) * 2004-03-12 2005-12-08 Henkel Kgaa Bleichaktivatoren und Verfahren zu ihrer Herstellung
DE102005026522B4 (de) 2005-06-08 2007-04-05 Henkel Kgaa Verstärkung der Reinigungsleistung von Waschmitteln durch Polymer
DE102006029344A1 (de) * 2006-06-23 2007-12-27 Henkel Kgaa Zahnbehandlungsmittel mit verstärkter Bleichwirkung
DE102007062519A1 (de) 2007-12-20 2009-06-25 Henkel Ag & Co. Kgaa Reinigungsmittel
WO2018044273A1 (fr) * 2016-08-30 2018-03-08 Colgate-Palmolive Company Composition dentifrice blanchissante stable contenant des particules contenant un colorant

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US5888419A (en) * 1995-06-07 1999-03-30 The Clorox Company Granular N-alkyl ammonium acetontrile compositions
US5814242A (en) * 1995-06-07 1998-09-29 The Clorox Company Mixed peroxygen activator compositions
DE19611992A1 (de) * 1996-03-26 1997-10-02 Basf Ag Bleichkraftverstärker für Bleichmittel- und Textilwaschmittelzusammensetzungen
DE19740671A1 (de) * 1997-09-16 1999-03-18 Clariant Gmbh Bleichaktivator-Granulate
DE19740669A1 (de) * 1997-09-16 1999-03-18 Clariant Gmbh Gecoatete Ammoniumnitril-Bleichaktivatorgranulate

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BR0114325A (pt) 2003-10-07
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AU2001289940A1 (en) 2002-04-08
DE10049237A1 (de) 2002-04-11
MXPA03002615A (es) 2004-04-02
CN1471572A (zh) 2004-01-28
WO2002026927A1 (fr) 2002-04-04

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