EP1445301B1 - Dispersions aqueuses liquides détergentes - Google Patents

Dispersions aqueuses liquides détergentes Download PDF

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Publication number
EP1445301B1
EP1445301B1 EP04001425.0A EP04001425A EP1445301B1 EP 1445301 B1 EP1445301 B1 EP 1445301B1 EP 04001425 A EP04001425 A EP 04001425A EP 1445301 B1 EP1445301 B1 EP 1445301B1
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Prior art keywords
weight
liquid detergent
aqueous liquid
alkyl
detergent dispersion
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EP04001425.0A
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German (de)
English (en)
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EP1445301A1 (fr
Inventor
Johannes Dr. Himmrich
Ulrike Reploeg
Werner Di. Skrypzak
Dennis Dr. Miller
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Clariant Produkte Deutschland GmbH
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Clariant Produkte Deutschland GmbH
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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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/65—Mixtures of anionic with cationic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/143—Sulfonic acid esters
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/62—Quaternary ammonium compounds

Definitions

  • Aqueous-based liquid detergent dispersions containing surfactants, quaternary alkyldimethylhydroxyethylammonium salt and / or alkylmethylbishydroxyethylammonium salt, one or more electrolytes and one or more builders By adding hydroxyethyl quats to an aqueous solution of surfactants, electrolytes and builders, a very stable dispersion with good detergency and favorable viscosity behavior is obtained.
  • Liquid detergents have some performance advantages over solid, powdered or particulate products. They are easy to measure, dissolve quickly in the wash water and can be applied in concentrated solutions or dispersions on soiled areas of the textiles to be washed. In addition, it is possible to incorporate into liquid detergent formulations substances which would decompose during drying processes and are unsuitable for solid detergents. In clear liquid detergent formulations only limited amounts of soluble ingredients such as builders and surfactants can be incorporated due to limited solubility and accordingly must be higher doses in the wash to ensure a good wash performance even at high water hardness and corresponding partial inactivation of anionic surfactants. In liquid detergent dispersions much larger amounts of ingredients can be used and thus a reduction in the dosage per wash can be achieved.
  • liquid detergent dispersions allow the use of only poorly water-soluble ingredients. Furthermore, liquid detergent dispersions generally have significantly higher viscosities than clear liquid detergent formulations. Liquid detergent dispersions, on the other hand, tend to phase separate for longer storage times and greater temperature fluctuations.
  • Some products for example, undergo separation during storage, others during cooling and are not easily redispersible. In some cases, the viscosity of the product changes, becoming either too thick and no longer flowable or appearing too watery thin.
  • the object was to prepare liquid-disperse detergent formulations which show not only a good cleaning power over long periods of time and even with large temperature fluctuations no phase separation, have a favorable rheological behavior and can be produced inexpensively.
  • liquid detergents containing a surfactant system which is free of linear alkylbenzenesulfonates contain a selected quaternary ammonium surfactant and an anionic surfactant selected from the group consisting of alkyl alkoxy sulfates and alkyl sulfates.
  • aqueous-based disperse liquid detergents are claimed containing linear alkyl benzene sulphonate, potassium or sodium tripolyphosphate and a solid builder.
  • the formulations are characterized in that in the presence of the electrolyte, the solubility of the surfactant is reduced in water and this is dispersed due to the salting-out effect in the aqueous phase.
  • Our own investigations show that surfactants with better water solubility compared to alkylbenzenesulfonate, for example sec. Alkanesulfonates, in the presence of electrolytes show a low salting-out effect and consequently can not be formulated in the same way as dispersions.
  • the invention relates to aqueous liquid detergent dispersions which 5 to 35, preferably 5 to 25, in particular 5 to 20 wt .-% anionic surfactant consisting of sec. alkanesulfonate, 10 to 50, preferably 10 to 40, in particular 10 to 30 wt .-% builder, 0 to 10, preferably 0 to 7, in particular 0 to 4 wt .-% of electrolytes and 0.1 to 10 wt .-% quaternary alkylhydroxyethylammonium salt consisting of C 12 -C 14 alkyl dimethyl hydroxyethyl ammonium chloride or methosulfate, wherein the wt .-% - ratio of anionic surfactant to quaternary Alkylhydroxyethylammoniumsalz 50: 1 to 2: 1, preferably 30: 1 to 2: 1, in particular 15: 1 to 2: 1.
  • Secondary alkanesulfonates are surfactants of the formula R-SO 3 M, whose alkyl group R is saturated or unsaturated, linear or branched and which can also carry hydroxyl groups, wherein the terminal carbon atoms of the alkyl chain have no sulfonate group.
  • Counterion M may be sodium, potassium, ammonium, mono-, di- or tri-alkanol ammonium, calcium, magnesium ion or mixtures thereof.
  • the disperse liquid detergents according to the invention contain one or more builders as further component.
  • Suitable organic and inorganic builders are neutral or, in particular, alkaline salts which precipitate or complex calcium ions.
  • Builders such as orthophosphates and condensed phosphates, eg pyrophosphates, triphosphates, tetraphosphates, polyphosphates and metaphosphates, as well as fine crystalline, synthetic hydrous zeolites are preferred.
  • Particularly suitable are alkali metal phosphates, which may be in the form of their alkaline, neutral or acidic sodium or potassium salts.
  • Examples of these are trisodium phosphate, tetrasodium diphosphate, disodium dihydrogen phosphate, pentasodium triphosphate, so-called sodium hexametaphosphate, oligomeric trisodium phosphate with degrees of oligomerization of from 5 to 1000, in particular from 5 to 50, and mixtures of sodium and potassium salts.
  • phosphates and zeolites it is also preferred to use sheet silicates and amorphous silicates, as well as carbonates and bicarbonates.
  • Useful organic builders are, for example, citric acid, nitriloacetate (NTA) and ethylenediaminetetraacetic acid, which are preferably used in the form of their salts, and phosphonic and polyphosphonic acids.
  • NTA nitriloacetate
  • ethylenediaminetetraacetic acid which are preferably used in the form of their salts, and phosphonic and polyphosphonic acids.
  • polymeric carboxylates and their salts include, for example, the salts of homopolymeric or copolymeric polyacrylates, polymethacrylates and in particular copolymers of acrylic acid with maleic acid, preferably those of 50% to 10% maleic acid, as well as polyaspartic acid and also polyvinylpyrrolidone and urethanes.
  • the molecular weight of the homopolymers is generally between 1000 and 100,000, those of the copolymers between 2000 and 200,000, preferably 50,000 to 120,000, based on the free acid, in particular water-soluble polyacrylates are suitable, for example, about 1% of a Polyallylethers of sucrose are cross-linked and have a molecular weight above one million. Examples of these are the polymers available under the name Carbopol 940 and 941. Examples of suitable phosphonates are acetodiphosphonates, aminotrismethylene phosphonates and ethylene tetramethylene phosphonates.
  • electrolytes non-interfacially active, water-soluble, ionic compounds that reduce the solubility or micelle concentration of surfactants in the aqueous formulation and cause a “salting out” effect.
  • Suitable are alkali or ammonium chlorides, nitrates, phosphates, - carbonates, sulfates, silicates, acetates, citrates or polyphosphates.
  • Preferably used are potassium chloride, potassium sulfate, potassium carbonate, pentasodium triphosphate and Pentakaliumtriphosphat.
  • the disperse liquid detergents according to the invention may contain, in addition to the anionic surfactants, nonionic, amphoteric, but also cationic surfactants.
  • Preferred nonionic surfactants are fatty alcohol ethoxylates containing from about 1 to about 25 moles of ethylene oxide.
  • the alkyl chain of the aliphatic alcohols may be linear or branched, primary or secondary, and generally contains from 8 to 22 carbon atoms. Particularly preferred are the condensation products of alcohols containing an alkyl chain of 10 to 20 carbons with 2 to 18 moles of ethylene oxide per mole of alcohol.
  • the alkyl chain can be saturated or unsaturated.
  • the alcohol ethoxylates may have a narrow homolog distribution of the ethylene oxide ("narrow range ethoxylates") or a broad homolog distribution of the ethylene oxide ("broad range ethoxylates").
  • nonionic surfactants of this type are Tergitol TM 15-S-9 (condensation product of a C 11 -C 15 linear secondary alcohol with 9 moles of ethylene oxide), Tergitol TM 24-L-NMW (condensation product of a C 12 -C 14 linear primary alcohol with 6 moles of ethylene oxide with narrow molecular weight distribution). Also included in this product class are the Genapol TM brands from Clariant GmbH.
  • nonionic surfactants come into question, such as polyethylene, polypropylene and Polybutylenoxidaddukte of fatty alcohols having 8 to 22 carbon atoms in the alkyl chain and alkylphenols having 6 to 12 carbon atoms in the alkyl chain, addition products of Ethylene oxide with a hydrophobic base, formed from the condensation of propylene oxide with propylene glycol or addition products of ethylene oxide with a Reaction product of propylene oxide and ethylenediamine, but also Fettklarepolyhydroxyamide and fatty acid amido alkoxylates.
  • polyethylene, polypropylene and Polybutylenoxidaddukte of fatty alcohols having 8 to 22 carbon atoms in the alkyl chain and alkylphenols having 6 to 12 carbon atoms in the alkyl chain
  • addition products of Ethylene oxide with a hydrophobic base formed from the condensation of propylene oxide with propylene glycol or addition products of ethylene oxide with a Reaction product of propylene oxide and
  • semipolar nonionic surfactants for example amine oxides of the formula where R 8 is an alkyl, hydroxyalkyl or alkylphenol group or mixtures thereof having a chain length of 8 to 22 carbon atoms; R 9 is an alkylene or hydroxyalkylene group having 2 to 3 carbon atoms or mixtures thereof; R 10 is an alkyl or hydroxyalkyl group with. 1 to 3 carbon atoms or a polyethylene oxide group having 1 to 3 ethylene oxide units.
  • the R 10 / R 9 groups may be linked together via an oxygen or nitrogen atom and thus form a ring.
  • These amine oxides particularly include C 10 -C 18 alkyl dimethyl amine oxides and C 8 -C 12 alkoxyethyl dihydroxyethyl amine oxides.
  • amphoteric surfactants which can be used in the formulations of the present invention are, above all, those which are described as derivatives of aliphatic secondary and tertiary amines in which the aliphatic radical can be linear or branched and in which one of the aliphatic substituents contains between 8 to 18 carbon atoms and contains an anionic, water-soluble group, such as carboxy, sulfonate, sulfate, phosphate or phosphonate.
  • Amphoteric surfactants in this context include amphoteric imidazolinium surfactants as represented by the following formula: wherein R 11 is C 8 -C 22 alkyl or alkenyl, preferably C 12 -C 16 , R 12 is hydrogen or a group of the formula CH 2 CO 2 M, R 13 is a group of the formulas CH 2 CH 2 OH or CH 2 CH 2 OCH 2 CHCOOM, R 14 is hydrogen or a group of the formulas CH 2 CH 2 OH or CH 2 CH 2 OCH 2 CHCOOM, Z is CO 2 M or CH 2 CO 2 M, n is 2 or 3, preferably 2, M is hydrogen or a cation such as alkali metal, alkaline earth metal, ammonia or alkanolammonium.
  • Preferred amphoteric surfactants of the above formula are monocarboxylates and dicarboxylates.
  • Examples of these compounds include cocoamphocarboxypropionate, cocoamidocaboxypropionic acid, cocoamphocarboxyglycinate (also referred to as cocoamphodiacetate), and cocoamphoacetate.
  • amphoteric surfactants are alkyl dimethyl betaines, alkylamido betaines and alkyl dipolyethoxy betaines having an alkyl radical which may be linear or branched having from 8 to 22 carbon atoms, preferably from 8 to 18 carbon atoms and most preferably from 12 to 18 carbon atoms. These compounds are e.g. marketed by Clariant GmbH under the trade name Genagen®.
  • cationic surfactants are quaternary ammonium compounds and ester quats, especially quaternized fatty acid alkanolamine ester salts and dialkylaminopropylamine ester salts.
  • the liquid detergents according to the invention may contain the auxiliaries and additives customary for these products, for example bleach activators, bleach catalysts, optical brighteners, grayness inhibitors, dye transfer inhibitors, Solubilizers, hydrotropes, enzymes, enzyme stabilizers, thickeners, preservatives, fragrances and dyes, pearlescing agents, foam inhibitors, sequestering agents, corrosion inhibitors and antioxidants.
  • auxiliaries and additives customary for these products for example bleach activators, bleach catalysts, optical brighteners, grayness inhibitors, dye transfer inhibitors, Solubilizers, hydrotropes, enzymes, enzyme stabilizers, thickeners, preservatives, fragrances and dyes, pearlescing agents, foam inhibitors, sequestering agents, corrosion inhibitors and antioxidants.
  • bleach activators include N, N, N ', N'-tetraacetylethylenediamine (TAED), nonanoyl-caprolactam phenylsulfonate ester (APES), glucose pentaacetate (GPA), xylose tetraacetate (TAX), acyloxybenzenesulfonates (eg nonanoyloxybenzenesulfonate (NOBS), sodium 4-benzoyloxybenzenesulfonate ( SBOBS), sodium trimethylhexanoyloxybenzenesulfonate (STHOBS)), diacetyldioxohexahydrotriazine (DADHT), tetraacetylglucoluril (TAGU), tetraacetylcyanoic acid (TACA), di-N-acetyldimethylglyoxine (ADMG) and 1-phenyl-3-acetylhydantoin (PAH)
  • Examples include perborate monohydrate, perborate tetrahydrate, percarbonates, alkali persulfates, persilicates and percitrates, with sodium being the preferred alkali metal, as well as hydrogen peroxide adducts of urea or amine oxides.
  • peroxycarboxylic acids for example dodecanedioic acid or phthalimidopercarboxylic acids, which may optionally be substituted on the aromatic, may be present.
  • bleach stabilizers such as phosphonates, borates, or metaborates and metasilicates, and magnesium salts such as magnesium sulfate may be advantageous.
  • the agents may contain as optical brighteners derivatives of Diaminostilbendisulfonklare and their alkali metal salts. Suitable examples are salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of similar construction, which instead of the morpholino group a Diethanolamino group, a methylamino group, an anilino group or a 2-Methoxyethylamino distr carry.
  • substituted diphenylstyryls for example alkali metal salts of 4,4'-bis (2-sulfostyryl) -diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) -diphenyl or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl).
  • the maximum content of brighteners in the compositions according to the invention is 0.5% by weight, preferably amounts of 0.02 to 0.25% by weight are used.
  • Graying inhibitors have the task of keeping the loosened soil suspended in the liquor.
  • Water-soluble colloids of mostly organic nature are suitable for this purpose, for example starch and cellulose and their derivatives, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
  • water-soluble polyamides containing acidic groups are suitable for this purpose.
  • starch derivatives can be used, for example aldehyde starches.
  • cellulose ethers such as carboxymethylcellulose (Na salt), methylcellulose, hydroxyalkylcellulose and mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose, in amounts of from 0.3% by weight to 5% by weight, based on the finished composition.
  • Suitable color transfer inhibitors are polyvinylpyrrolidones, polyvinylimidazoles, polymeric N-oxides such as poly (vinylpyridine-N-oxide) and copolymers of vinylpyrrolidone with vinylimidazole.
  • color protective additives such as e.g. quaternary polyamine derivatives, cationic methylolamides or formaldehyde condensation products can be used.
  • compositions according to the invention may contain, as foam inhibitors, fatty acid alkyl ester alkoxylates, organopolysiloxanes and mixtures thereof with microfine, optionally silanized silica and paraffins, waxes, microcrystalline waxes and mixtures thereof with silanated silica.
  • foam inhibitors fatty acid alkyl ester alkoxylates, organopolysiloxanes and mixtures thereof with microfine, optionally silanized silica and paraffins, waxes, microcrystalline waxes and mixtures thereof with silanated silica.
  • mixtures of various foam inhibitors may also be used, e.g. those made of silicone oil, paraffin oil or waxes.
  • the desired viscosity of the agents can be adjusted by adding water and / or organic solvents or by adding a combination of organic solvents and thickeners.
  • organic solvents all mono- or polyhydric alcohols are suitable as organic solvents.
  • Alcohols having 1 to 4 carbon atoms, such as methanol, ethanol, propanol, isopropanol, straight-chain and branched butanol, glycerol and mixtures of the alcohols mentioned are preferably used.
  • Further Preferred alcohols are polyethylene glycols having a molecular weight below 2000.
  • polyethylene glycol having a molecular weight of between 200 and 600 and in amounts of up to 45% by weight and of polyethylene glycol having a molecular weight of between 400 and 600 in amounts of 5 to 25 wt .-% preferred.
  • An advantageous mixture of solvents consists of monomeric alcohol, for example ethanol and polyethylene glycol in a ratio of 0.5: 1 to 1.2: 1, wherein the liquid detergent according to the invention may contain 8 to 12 wt .-% of such a mixture.
  • suitable solvents include triacetin (glycerol triacetate) and 1-methoxy-2-propanol.
  • Preferred thickeners are hardened castor oil, salts of long-chain fatty acids, preferably in amounts of from 0 to 5% by weight and in particular in amounts of from 0.5 to 2% by weight, for example sodium. Potassium, aluminum, magnesium and titanium stearates or the sodium and / or potassium salts of behenic acid, and also polysaccharides, in particular xanthan gum, guar guar, agar agar, alginates and tyloses, carboxymethyl cellulose and hydroxyethyl cellulose, and also higher molecular weight polyethylene glycol mono- and diesters of fatty acids, polyacrylates, polyvinyl alcohol and polyvinylpyrrolidone. Also suitable are copolymers based on acryloyldimethyltaurine, as in EP 10 60142 . EP 10 28129 . EP 11 16 733 and Hostacerin® AMPS.
  • Suitable hydrotropes are, for example, sodium toluene sulphonate, sodium cumulosulphonate, sodium xylene sulphonate, alkanephosphonic acids and alkenyldicarboxylic acids and also their anhydrides.
  • Suitable enzymes are those from the class of proteases, lipases, amylases and cellulases or mixtures thereof. Their proportion can be 0.2 to 3 wt .-%.
  • the enzymes can be adsorbed to carrier substances and / or embedded in encapsulating substances.
  • the salts of polyphosphoric acids such as 1-hydroxyethane-1,1-diphosphonic acid (HEDP), Ethylenediamine tetramethylenephosphonic acid (EDTMP) and Diethylentriaminpentamethylenphosphonklare (DTPMP) can be used.
  • HEDP 1-hydroxyethane-1,1-diphosphonic acid
  • ETMP Ethylenediamine tetramethylenephosphonic acid
  • DTPMP Diethylentriaminpentamethylenphosphonklare
  • Suitable preservatives are, for example, phenoxyethanol, formaldehyde solution, parabens, isothiazolinones, pentanediol or sorbic acid.
  • Suitable pearlescing agents are, for example, glycol distearate esters, such as ethylene glycol distearate, but also fatty acid monoglycol esters.
  • the preparation of the liquid detergents according to the invention can be carried out by simply mixing the ingredients, which can be added in bulk or as a solution in an automatic mixer.
  • the optical brightener is first pasted with the nonionic surfactant Genapol UD 030 with a glass rod, then mixed if necessary alkyl sulfate and TEA and then the Hostapur SAS 60 also stirred with a glass rod (mixture 1).
  • the clear mixture 2 is then stirred into the mixture 1 with a glass rod until no more particles of the surfactant phase are on the wall of the beaker.
  • the resulting mixture is further stirred with a magnetic stirrer until a homogeneous dispersion is formed. It will be the rest Amount of STPP or PTPP (3% or 5%) and then added the sodium disilicate.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
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Claims (11)

  1. Dispersions aqueuses liquides détergentes, qui contiennent 5% en poids à 35% en poids d'agent tensioactif anionique, constitué de sec-alcanesulfonate,
    10% en poids à 50% en poids de builders,
    0% en poids à 10% en poids d'électrolytes et
    0,1% en poids à 10% en poids de sel d'alkylhydroxyéthylammonium quaternaire,
    constitué de chlorure ou de méthosulfate de C12-C14-alkyldiméthylhydroxyéthylammonium, le rapport des pourcentages en poids d'agent tensioactif anionique au sel d'alkylhydroxyéthylammonium quaternaire valant 50:1 à 2:1.
  2. Dispersions aqueuses liquides détergentes selon la revendication 1, contenant un sel sodique de (C13-C17-sec-alcane)sulfonate comme agent tensioactif anionique.
  3. Dispersions aqueuses liquides détergentes selon la revendication 1, caractérisées en ce qu'elles contiennent 5 à 25% en poids d'agent tensioactif anionique.
  4. Dispersions aqueuses liquides détergentes selon la revendication 1, caractérisées en ce qu'elles contiennent 5 à 20% en poids d'agent tensioactif anionique.
  5. Dispersions aqueuses liquides détergentes selon la revendication 1, caractérisées en ce qu'elles contiennent 10 à 40% en poids de builders.
  6. Dispersions aqueuses liquides détergentes selon la revendication 1, caractérisées en ce qu'elles contiennent 10 à 30% en poids de builders.
  7. Dispersions aqueuses liquides détergentes selon la revendication 1, caractérisées en ce qu'elles contiennent 0 à 7% en poids d'électrolyte.
  8. Dispersions aqueuses liquides détergentes selon la revendication 1, caractérisées en ce qu'elles contiennent 0 à 4% en poids d'électrolyte.
  9. Dispersions aqueuses liquides détergentes selon la revendication 1, caractérisées en ce que le rapport pondéral d'agent tensioactif anionique au sel d'alkylhydroxyéthylammonium quaternaire vaut 30:1 à 2:1.
  10. Dispersions aqueuses liquides détergentes selon la revendication 1, caractérisées en ce que le rapport pondéral d'agent tensioactif anionique au sel d'alkylhydroxyéthylammonium quaternaire vaut 15:1 à 2:1.
  11. Dispersions aqueuses liquides détergentes selon la revendication 1, caractérisées en ce qu'elles contiennent les adjuvants et additifs usuels.
EP04001425.0A 2003-01-28 2004-01-23 Dispersions aqueuses liquides détergentes Expired - Lifetime EP1445301B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10303130A DE10303130A1 (de) 2003-01-28 2003-01-28 Wässrige Flüssigwaschmittel-Dispersionen
DE10303130 2003-01-28

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EP1445301B1 true EP1445301B1 (fr) 2013-11-27

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EP (1) EP1445301B1 (fr)
JP (1) JP4592294B2 (fr)
DE (1) DE10303130A1 (fr)
ES (1) ES2442219T3 (fr)

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JP2004231959A (ja) 2004-08-19
EP1445301A1 (fr) 2004-08-11
JP4592294B2 (ja) 2010-12-01
DE10303130A1 (de) 2004-07-29
US6949501B2 (en) 2005-09-27
ES2442219T3 (es) 2014-02-10
US20040204336A1 (en) 2004-10-14

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