EP0720644B1 - Melanges detergents et produits de lavage ou de nettoyage a proprietes ameliorees de dissolution - Google Patents

Melanges detergents et produits de lavage ou de nettoyage a proprietes ameliorees de dissolution Download PDF

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Publication number
EP0720644B1
EP0720644B1 EP94928353A EP94928353A EP0720644B1 EP 0720644 B1 EP0720644 B1 EP 0720644B1 EP 94928353 A EP94928353 A EP 94928353A EP 94928353 A EP94928353 A EP 94928353A EP 0720644 B1 EP0720644 B1 EP 0720644B1
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Prior art keywords
weight
mixtures
detergent
carbon atoms
alkyl
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EP94928353A
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German (de)
English (en)
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EP0720644A1 (fr
Inventor
Karl Schmid
Andreas Syldath
Ditmar Kischkel
Thomas Krohnen
Michael Neuss
Hubert Pawelczyk
Monika Böcker
Herman-Josef Welling
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BASF Personal Care and Nutrition GmbH
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Henkel AG and Co KGaA
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Priority claimed from DE19934332373 external-priority patent/DE4332373C2/de
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    • 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
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • C11D17/065—High-density particulate detergent compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—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
    • C11D1/146—Sulfuric 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
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols

Definitions

  • the invention relates to anhydrous detergent mixtures which contain long-chain and short-chain alkyl sulfates in selected mixing ratios and hydrophobic structure breakers, and to the use of these mixtures for the production of solid detergents.
  • Anionic surfactants in particular alkyl sulfates or fatty alcohol sulfates, are important components of detergents, dishwashing detergents and cleaning agents.
  • nonionic surfactants which have an inverse solubility behavior and, as a result of hydrogen bonds, are more soluble in cold water than in warm water
  • anionic ones Conventional surfactants, i. H. their solubility increases more or less linearly with temperature until the solubility product is reached.
  • anionic surfactants which have a sufficient solubility even in cold water.
  • the best-known hydrotropes undoubtedly include the short-chain alkylarylsulfonates, such as, for example, toluene, xylene or cumene sulfonate. They are suitable, for example, as solubilizers for anionic and nonionic surfactants in the production of liquid detergents.
  • solubilizers for anionic and nonionic surfactants in the production of liquid detergents The improved solubility is probably due to advantageous mixed micelle formation.
  • solubility in cold water in particular of fatty alcohol sulfates
  • hydrotrope surfactants with high HLB values, for example highly ethoxylated polyglycol ethers (tallow alcohol 40 EO adduct) or the like.
  • HLB values for example highly ethoxylated polyglycol ethers (tallow alcohol 40 EO adduct) or the like.
  • solid detergents with high bulk density and improved solubility are obtained by adding mixtures of anionic and nonionic surfactants to polyethylene glycol ethers with a molecular weight in the range from 200 to 12000, preferably from 200 to 600, and then dries and / or solidifies.
  • a detergent preparation containing C 12 -C 18 fatty alcohol sulfate, C 12 -C 18 fatty alcohol 5 EO and C 16 -C 18 tallow fatty alcohol 5 EO adduct and - based on the nonionic surfactants - is not less than 45 wt .-% polyethylene glycol with a molecular weight of about 400 is disclosed, which is extruded after homogenization and processed into granules.
  • the rate of dissolution of the resulting solid detergents is still unsatisfactory.
  • the presence of the large amounts of polymer required is not desirable.
  • spray-dried detergent compositions are disclosed in general form which, in addition to anionic surfactants, contain nonionic surfactants, polyacrylates and polyethylene glycol ethers with an average molecular weight in the range from 1000 to 20,000.
  • the teaching of this document is that the dispersibility of anionic surfactants can be improved by adding nonionic surfactants, polyethylene glycol ether (PEG) and polyacrylates.
  • the only exemplary embodiment describes a mixture comprising alkylbenzenesulfonate and fatty alcohol sulfate, to which a C 12 -C 13 -oxoalcohol-6.5 EO adduct, sodium polyacrylate and polyethylene glycol with a molecular weight of approx. 8000 are added.
  • the weight ratio between nonionic surfactant and PEG is 1: 1.
  • DE-A-21 24 526 relates to detergent and cleaning agent mixtures with controlled foam behavior.
  • compositions which contain tallow alcohol sulfate, alkylbenzenesulfonate and polyethylene glycol with a molecular weight of approximately 20,000.
  • Solid detergents are known, for example, from international patent application WO-A-92/09676 (Henkel), which are obtained by treating aqueous alkyl sulfate pastes with soda and zeolites and then extruding them. The document does not reveal anything about the dissolution rate of the solids.
  • the premix is preferably fed continuously to a 2-screw extruder with a co-rotating or counter-rotating screw guide, the housing and the extruder pelletizing head of which can be heated to the predetermined extrusion temperature.
  • the premix is compressed, plasticized, extruded in the form of fine strands through the perforated die plate in the extruder head and finally, under pressure, which is preferably at least 25 bar, but can also be lower at extremely high throughputs depending on the apparatus used the extrudate is preferably reduced to approximately spherical to cylindrical granules by means of a rotating knife.
  • the hole diameter of the perforated nozzle plate and the strand cut length are matched to the selected granulate dimension.
  • the production of granules of an essentially uniformly predeterminable particle size succeeds, wherein in particular, the absolute particle sizes can be adapted to the intended use. In general, particle diameters up to at most 0.8 cm are preferred.
  • Important embodiments provide for the production of uniform granules in the millimeter range, for example in the range from 0.5 to 5 mm and in particular in the range from approximately 0.8 to 3 mm.
  • the length / diameter ratio of the chopped-off primary granules is in the range from about 1: 1 to about 3: 1.
  • edges present on the crude extrudate are rounded off, so that ultimately spherical to approximately spherical extrudate grains can be obtained.
  • small amounts of dry powder for example zeolite powder such as zeolite NaA powder, can also be used in this step. This shape can be done in standard rounding machines. Care should be taken to ensure that only small amounts of fine grain are produced in this stage.
  • the extrudates are then preferably fed to a drying step, for example a fluidized bed dryer.
  • the extruded granules which may also contain peroxy bleaching agents, for example perborate monohydrate, can be dried at supply air temperatures between 80 and 150 ° C. without loss of active oxygen.
  • peroxy bleaching agents for example perborate monohydrate
  • the extrudates can then be mixed with other constituents of washing or cleaning agents.
  • the object of the invention has now been to provide alkyl sulfates in such a form of supply that, after mixing with other detergent ingredients and mechanical solidification, they result in detergents or cleaning agents which are readily soluble even in cold water and whose production is free from the disadvantages described is.
  • the invention therefore relates in a first embodiment to a detergent mixture
  • a detergent mixture comprising a) alkyl and / or alkenyl sulfates of the formula (I) in which R 1 is a linear or branched aliphatic R 1 OSO 3 X (I) Hydrocarbon radical having 16 to 18 carbon atoms and X is an alkali or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium, b) alkyl and / or alkenyl sulfates of the formula (II) in which R 2 is a linear or branched aliphatic hydrocarbon R 2 OSO 3 X (II) material residue with 12 to 14 carbon atoms and X as above, wherein the detergent mixture is essentially anhydrous, the components a) and b) in a weight ratio of 90: 10 to 70: 30 and c) hydrophobic structure breaker of the formula (III) in which R 4 for a linear
  • essentially water-free means that the individual solid ingredients can still contain residual amounts of water from their production, but no water is additionally added in the preparation of the detergent mixture according to the invention and the total amount of water in the detergent mixture is at values of less than 10% by weight, preferably not more than 5% by weight.
  • detergent mixture always means a mixture of the components (I), (II) and (III), as long as it is not expressly defined that a further ingredient is present in this mixture.
  • the detergent mixtures according to the invention can be mixed with further powdered detergent or cleaning agent ingredients and, after mechanical solidification, in particular extrusion, give solid detergents which have a significantly improved dissolution rate and show advantages in the washing-up behavior in the washing machine.
  • the invention includes the knowledge that only the combination of different features, namely the use of hydrophobic structure breakers and the mixing of alkyl sulfates of different C chain lengths, results in a synergistic improvement in the dissolution behavior.
  • the weight ratio of the different alkyl sulfate types to one another has proven to be a further critical feature, since an improvement in the dissolution rate should not be bought by a deterioration in the washing properties.
  • the alkyl sulfates used are usually prepared by sulfating alcohols with gaseous sulfur trioxide or chlorosulfonic acid and subsequent neutralization with bases. These alcohols are preferably derived from alcohols from renewable raw materials. These are, in particular, fatty alcohols which only have even-numbered C chain numbers. However, if alcohols of other origin are also used, alcohols with odd C chain numbers can also occur. In this case, however, it should apply that C 15 alkyl sulfates should not be contained alone, but only in mixtures with other alkyl sulfates of the formula (I) and / or of the formula (II).
  • the described ratio of components a) and b) can be achieved in that mixtures of this type are produced specifically from C 12 -C 14 alkyl sulfates and C 16 -C 18 alkyl sulfates.
  • mixtures which, for example, contain C 12 -C 18 alkyl sulfates, that is to say already contain components a) and b), and the ratio of a) to b) described, if appropriate - if it is not already present in the mixture - by adding the appropriate shorter or longer chain alkyl sulfates.
  • the alcohols are linear and saturated and, like the fatty alcohols, are obtained from renewable raw materials.
  • alkyl sulfates with C chain numbers below 12 not in amounts above 20% by weight, preferably not in amounts above 10% by weight
  • alk (en) yl sulfates with C chain numbers above 18 also not in amounts above 20% by weight, preferably not in amounts above 10% by weight.
  • the quantities given relate to the total of the total alk (en) yl sulfates present.
  • Alk (en) yl sulfate mixtures which contain a maximum of 5% by weight of alkyl sulfates with C chain numbers below 12 and are preferably free of these and a maximum of 5% by weight of alk (en) yl sulfates with C are particularly advantageous -Chain chain numbers above 18 and in particular are free of these.
  • the quantitative data in turn relate to the sum of the total alk (en) yl sulfates present.
  • alkyl sulfates that make up component a) are cetyl sulfate, stearyl sulfate and oleyl sulfate and their technical mixtures based on C 16 -C 18 tallow alcohol or artificial blends of comparable chain length.
  • Typical examples of alkyl sulfates that make up component b) are lauryl sulfate and myristyl sulfate and their technical mixtures based on C 12 -C 14 coconut or palm kernel alcohol or artificial blends of comparable chain length.
  • the hydrophobic structure breakers are fatty alcohols or their adducts with a few moles of ethylene oxide. Typical examples are lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, linolenyl alcohol and their technical mixtures and their adducts with 1 to 5 moles of ethylene oxide.
  • the alkoxylation products can have both a conventional and, in particular, a narrow homolog distribution.
  • hydrophobic structure breakers of the formula (III) are preferred in which R 4 represents a linear alkyl radical having 12 to 14 carbon atoms and n represents 0 or numbers from 1 to 3.
  • R 4 represents a linear alkyl radical having 12 to 14 carbon atoms and n represents 0 or numbers from 1 to 3.
  • C 12 -C 14 coconut fatty alcohol or its 2EO adduct is particularly advantageous.
  • the essentially water-free detergent mixtures can contain the hydrophobic structure breakers in amounts of 1 to 50, preferably 5 to 20% by weight, based on the mixtures.
  • non-ethoxylated fatty alcohol having 12 to 18 carbon atoms is used as the hydrophobic structure breaker.
  • Typical examples of this are, as indicated above, lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, linolyl alcohol, linolenyl alcohol or their technical mixtures, in particular C 12 -C 14 -, C 16 -C 18 - or C 12 -C 18 fatty alcohol mixtures.
  • the unsulfonated portion (US) contained in the alkyl sulfates, i.e. the free fatty alcohol, in the further processing to solid detergents or cleaning agents, in particular in the particularly preferred extrudates, in contrast to the additionally used fatty alcohol have the effect that, with a constant ratio between components a) and b), the dissolving rate of the increasing US content Detergent or cleaning agent decreases again.
  • this effect can be compensated for by increasing the proportion of the shorter-chain component b) within the stated limits.
  • a preferred embodiment of the invention therefore relates to anhydrous detergent mixtures which contain components a) and b) in a weight ratio of 90:10 to 80:20 and in which the unsulfonated components in the Components a) and b) make up a total of less than 2% by weight, based on components a) and b).
  • a further advantageous embodiment relates to anhydrous detergent mixtures which contain components a) and b) in a weight ratio of 70:30 to 75:25 and in which the unsulfonated components in components a) and b) total less than 4.5% by weight. % - based on components a) and b) - make up.
  • Purified alk (en) yl sulfate mixtures which no longer contain unsulfated constituents can also be used and may even be particularly preferred for the reasons mentioned.
  • Purified alk (en) yl sulfate mixtures of this type can be obtained, for example, by superheated steam drying.
  • the anhydrous detergent mixtures used according to the invention preferably contain the non-ethoxylated alcohols in amounts of 1 to 50% by weight, in particular in amounts of up to 20% by weight, based in each case on the detergent mixtures.
  • the detergent mixtures used according to the invention 1 to 20% by weight, advantageously 2 to 15% by weight, of linear alcohols with up to 16 carbon atoms and in particular 2 to 12% by weight.
  • % Of fatty alcohols with 12 and / or 14 carbon atoms are present in the detergent mixtures used according to the invention.
  • the content of C 18 alcohol is not more than 2% by weight and in particular not more than 1.5% by weight, in each case based on the detergent mixture.
  • the alcohol content with a C chain number above 15 is not more than 10% by weight, preferably not more than 5% by weight and in particular not more than 3% by weight, in each case on the detergent mixture.
  • the surfactant grain has to be structured, for which incorporation and homogeneous distribution of the optionally solidified structure breaker is required. This can be done in several ways.
  • a particularly simple embodiment of the method consists in presenting the alkyl sulfates (components a and b) in powder form and intimately mixing them with the required amount of the structure breaker which may have solidified.
  • Components such as mixers from Eirich or shovel mixers from Lödige or in particular spray mixers from Schugi are advantageous for this process, in which the anionic surfactant is placed in the mixing chamber and the hydrophobic structure breaker is optionally sprayed together with a polymeric solidifying agent. It is also possible to carry out the drying of the anionic surfactant pastes and the mixing simultaneously in a fluidized bed dryer. Dry, readily soluble powders are obtained, which are subsequently subjected to further customary, solid powder detergent additives, for example spray-dried compounds, and can be processed, for example, to detergent extrudates.
  • the invention further relates to a process for the preparation of anhydrous detergent mixtures, in which mixtures of alkyl and / or alkenyl sulfates of the formulas (I) and (II) are impregnated with the hydrophobic structure breakers (III).
  • the structure breakers in question are liquid under normal conditions, the question arises as to how it can be ensured that the structure breaker remains in the alkyl sulfate grain, structures it permanently and does not "bleed out".
  • a large number of investigations carried out by the applicant have surprisingly shown that the dry grain of anionic surfactants has an amazing absorption power compared to the liquid structure breakers mentioned. For example, 5 to 10, in some cases even up to 15% by weight of the liquid structure breakers can be processed with the anionic surfactants to form a solid, easily soluble product without the structure breaker gradually bleeds out and the rate of dissolution slows down with prolonged storage.
  • Polyethylene glycol ethers with an average molecular weight of 12,000 to 100,000 are suitable for this purpose. Typical examples are polyethylene glycols with an average molecular weight of 12,000 to 35,000.
  • the water-free detergent mixtures can contain the polymeric strengthening agents in amounts of 1 to 5, preferably 2 to 4% by weight, based on the hydrophobic structure breaker.
  • Another object of the invention relates to the use of the essentially water-free detergent mixtures according to the invention for the production of solid detergents or cleaning agents by customary methods by mixing with further powdery to granular detergent ingredients or compounds and preferably by subsequent mechanical consolidation.
  • detergent additives that can be used are, for example, other surfactants and builder substances such as zeolites, phosphates, polycarboxylates, water glass, soda, sodium sulfate and the like.
  • component b) can also be mixed into a spray-dried compound and this mixture can in turn be added to the anhydrous mixture of components a) and c).
  • the alkyl sulfates are mixed in powder form with the optionally solidified structure breakers and the mixture is homogenized and solidified in a screw press.
  • the extrusion is carried out via a perforated disc, so that press strands are formed which can be mechanically comminuted to extrudates or needles of the desired shape and dimension by known processes. Extrudates this form show a particularly high dissolving speed and very good washing-up behavior in the washing machine.
  • the invention therefore relates to the use of the detergent mixtures mentioned for the production of detergents or cleaning agents, a non-ethoxylated alcohol having 12 to 18 carbon atoms (n equal to 0) now being used as the hydrophobic structure breaker c) and the proportion of C 18 alcohol does not exceed 3% by weight, based on the detergent mixture of (I), (II) and (III).
  • extruded detergents or cleaning agents which contain essentially water-free detergent mixtures which a) alkyl and / or alkenyl sulfates of the formula (I), in which R 1 is a linear or R 1 OSO 3 X (I) branched aliphatic hydrocarbon radical having 16 to 18 carbon atoms and X is an alkali or alkaline earth metal, ammonium, alkylammonium or glucammonium, b) alkyl and / or alkenyl sulfates of the formula (II), in which R 2 is R 2 OSO 3 X (II) is a linear or branched aliphatic hydrocarbon radical having 12 to 14 carbon atoms and X is as above, and c) hydrophobic structure breakers of the formula (III) in which R 4 is a linear or branched alkyl and / or alkenyl radical having 12 to 18 R 4 O (CH 2 CH 2 O)
  • the detergent mixtures which have non-ethoxylated alcohols as the hydrophobic structure breaker when used according to the invention for the production of extrudates which are active in washing or cleaning, have advantages over detergent mixtures which, as the hydrophobic structure breaker, instead have ethoxylated alcohols, in particular low ethoxylated alcohols such as a C 12 -C 14 - Contain fatty alcohol with 3 E0 or a C 12 -C 18 fatty alcohol with 5 E0 or 7 E0.
  • Polyethylene glycol ethers with an average molecular weight of 12,000 to 100,000 are particularly suitable as polymeric solidifying agents that can be used.
  • the essentially water-free mixtures of the different alk (en) yl sulfates, fatty alcohols and polymeric solidifying agents can be used in the latter, for example in amounts of 1 to 5% by weight, preferably in amounts of 2 to 4% by weight, based in each case on the total Mixture.
  • the extruded washing or cleaning agents are then used in the production of the extruded washing or cleaning agents, and are used as a component of the solid and free-flowing premix.
  • the extruded washing or cleaning agents and the special process for their preparation are also the subject of this invention.
  • the premix is then - as described, for example, in international patent application WO-A-91/02047 - extruded in a rope shape under a pressure of preferably at least 25 bar.
  • the premix has a consistency such that the strand can be cut to the predetermined size of the granulate directly after it emerges from a hole shape by means of a cutting device.
  • the extrudates can contain all the usual ingredients of washing or cleaning agents, including ethoxylated alcohols, in particular ethoxylated fatty alcohols, which are used as nonionic surfactants in addition to and separately from the detergent mixtures.
  • these common ingredients primarily include other surfactants such as anionic, cationic, zwitterionic or amphoteric, but also other nonionic surfactants.
  • the finished washing or cleaning agents or the extrudates contain, for example, the known alkylbenzenesulfonates, olefin sulfonates, alkanesulfonates, sulfated fatty acid glycerol esters and / or methyl ⁇ -sulfofatty acid or their corresponding salts as anionic surfactants.
  • the extrudates contain no more than 15% and especially no more than 10% by weight of these additional anionic surfactants.
  • Extrudates which contain only the alk (en) yl sulfates mentioned, in particular alkyl sulfates, as anionic surfactants are very particularly preferred.
  • the extrudates can additionally contain soaps in amounts of 0.5 to 5% by weight.
  • Saturated fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, palmitic acid or stearic acid, and in particular soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids.
  • Unsaturated fatty acid soaps which are derived, for example, from oleic acid, may also be present, but their proportion of the soaps should not exceed 50% by weight.
  • the anionic surfactants and soaps can be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine.
  • the anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
  • the content of anionic surfactants including alkyl sulfates and soaps in the washing or cleaning agents, including the extrudates, is generally between 5 and 40% by weight.
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (E0) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2 position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
  • alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow fat or oleyl alcohol, and an average of 2 to 8 E0 per mole of alcohol are particularly preferred.
  • the preferred ethoxylated alcohols include, for example, C 12 -C 14 alcohols with 3 E0 or 4 E0, C 9 -C 11 alcohol with 7 E0, C 13 -C 15 alcohols with 3 E0, 5 E0, 7 E0 or 8 E0, C 12 -C 18 alcohols with 3 E0, 5 E0 or 7 E0 and mixtures thereof, such as mixtures of C 12 -C 14 alcohol with 3 E0 and C 12 -C 18 alcohol with 5 E0.
  • the degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 E0 can also be used. Examples include tallow fatty alcohol with 14 E0, 25 E0, 30 E0 or 40 E0.
  • alkyl glycosides of the general formula RO (G) x can also be used as further nonionic surfactants, in which R denotes a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, C atoms and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
  • the degree of oligomerization x, indicating the distribution of monoglycosides and oligoglycosides is any number between 1 and 10; x is preferably 1.2 to 1.4.
  • Suitable surfactants are polyhydroxy fatty acid amides of the formula (IV), in which R 5 CO for an aliphatic acyl radical having 6 to 22 carbon atoms, R 6 for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups stands.
  • the proportion of nonionic surfactants in the compositions is generally 2 to 25% by weight.
  • anionic and nonionic surfactant mixtures it is particularly preferred for their use in extrudates that the weight ratio of anionic surfactant: nonionic surfactant is approximately 15: 1 to 1: 1 and in particular 10: 1 to 1: 1.5.
  • All of the previously commonly used builder substances can be used as inorganic builder substances. These include in particular zeolites, crystalline layered silicates, even phosphates, if their use should not be avoided for ecological reasons. Their content can usually be 10 to 60% by weight.
  • the finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite NaA in detergent quality. However, zeolite NaX and zeolite P and mixtures of A, X and / or P are also suitable.
  • the zeolite can be used as a spray-dried powder or as an undried stabilized suspension which is still moist from its production.
  • the zeolite in the event that the zeolite is used as a suspension, it can contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C 12 -C 18 fatty alcohols with 2 to 5 ethylene oxide groups, C 12 -C 14 fatty alcohols with 4 to 5 ethylene oxide groups or ethoxylated isotridecanols.
  • Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.
  • Suitable substitutes or partial substitutes for phosphates and zeolites are crystalline, layered sodium silicates of the general formula NaMSi z O 2z + 1 .yH 2 O, where M is sodium or hydrogen, z is a number from 1.9 to 4 and y is a number from 0 is to 20 and preferred values for z are 2, 3 or 4.
  • Such crystalline layered silicates are described, for example, in European patent application EP-AO 164 514.
  • Preferred crystalline layered silicates are those in which M is sodium and z is 2 or 3. In particular, both ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 O 5 .yH 2 O are preferred.
  • Usable organic builders are, for example, the polycarboxylic acids preferably used in the form of their sodium salts, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), as long as such use is not objectionable for ecological reasons, and mixtures of these .
  • Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.
  • Suitable polymeric polycarboxylates are, for example, the sodium salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 800 to 150,000 (based on acid).
  • Suitable copolymeric polycarboxylates are, in particular, those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable.
  • Their relative molecular weight, based on free acids is generally 5,000 to 200,000, preferably 10,000 to 120,000 and in particular 50,000 to 100,000. Terpolymers are also particularly preferred.
  • oxidation products of carboxyl group-containing polyglucosans and / or their water-soluble salts are described, for example, in international patent application WO-A-93/08251 or whose preparation is described, for example, in international patent application WO-A-93/16110.
  • the agents can also contain components which have a positive influence on the oil and fat washability from textiles. This effect becomes particularly clear when a textile is soiled that has already been washed several times beforehand with a detergent according to the invention which contains this oil and fat-dissolving component.
  • the preferred oil- and fat-dissolving components include, for example, nonionic cellulose ethers such as methyl hydroxypropyl cellulose with a proportion of methoxyl groups of 15 to 30% by weight and of hydroxypropoxyl groups of 1 to 15% by weight, based in each case on the nonionic cellulose ether. and the polymers of phthalic acid and / or terephthalic acid or known from the prior art. of their derivatives, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates.
  • Suitable ingredients of the agents are water-soluble inorganic salts such as bicarbonates, carbonates, amorphous silicates or mixtures of these;
  • alkali carbonate and amorphous alkali silicate especially sodium silicate with a molar ratio Na 2 O: SiO 2 of 1: 1 to 1: 4.5, preferably of 1: 2 to 1: 3.5, are used.
  • the content of sodium carbonate in the compositions is preferably up to about 20% by weight, advantageously between 5 and 15% by weight.
  • the sodium silicate content of the agents is generally up to 10% by weight and preferably between 2 and 8% by weight.
  • the alkali silicates are at least partially in the form of an aqueous solution, for example in the form of a 10 to 45 wt .-% aqueous water glass solution to introduce into the process.
  • alkali metal carbonates can also be replaced by sulfur-free, 2 to 11 carbon atoms and, if appropriate, a further carboxyl and / or amino group and amino acids and / or their salts.
  • the alkali metal carbonates are partially or completely replaced by glycine or glycinate.
  • bleaching agents which serve as bleaching agents and supply H 2 O 2 in water
  • sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • Further bleaching agents which can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracid salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid or diperdodecanedioic acid.
  • the bleaching agent content of the agents is preferably 5 to 25% by weight and in particular 10 to 20% by weight, with perborate monohydrate being advantageously used.
  • bleach activators can be incorporated into the preparations.
  • these are N-acyl or O-acyl compounds which form organic peracids with H 2 O 2 , preferably N, N'-tetra-acylated diamines, furthermore carboxylic acid anhydrides and esters of polyols such as glucose pentaacetate.
  • Other known bleach activators are acetylated mixtures of sorbitol and mannitol, as described, for example, in European patent application EP-A-0 525 239.
  • the bleach activators contain bleach activators in the usual range, preferably between 1 and 10% by weight and in particular between 3 and 8% by weight.
  • bleach activators are N, N, N ', N'-tetraacetylethylene diamine (TAED), 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine (DADHT) and acetylated sorbitol-mannitol mixtures (SORMAN).
  • TAED N, N, N ', N'-tetraacetylethylene diamine
  • DADHT 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine
  • SORMAN acetylated sorbitol-mannitol mixtures
  • Suitable as foam inhibitors Soaps of natural or synthetic origin, for example, which have a high proportion of C 18 -C 24 fatty acids.
  • Suitable non-surfactant-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica or bistearylethylenediamide. Mixtures of various foam inhibitors are also used with advantages, for example those made of silicones, paraffins or waxes.
  • the foam inhibitors, in particular silicone or paraffin-containing foam inhibitors are preferably bound to a granular, water-soluble or dispersible carrier substance. Mixtures of paraffins and bistearylethylenediamides are particularly preferred.
  • Suitable enzymes are those from the class of proteases, lipases, amylases, cellulases or mixtures thereof. Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus are particularly suitable. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used.
  • enzyme mixtures for example of protease and amylase or protease and lipase or protease and cellulase or of cellulase and lipase or of protease, amylase and lipase or protease, lipase and cellulase, but in particular mixtures containing cellulase, are of particular interest.
  • Peroxidases or oxidases have also proven to be suitable in some cases.
  • the enzymes can be adsorbed on carriers and / or embedded in coating substances in order to protect them against premature decomposition.
  • the proportion of the enzymes, enzyme mixtures or enzyme granules can be, for example, about 0.1 to 5% by weight, preferably 0.1 to about 2% by weight.
  • HEDP 1-hydroxyethane-1,1-diphosphonic acid
  • DETPMP diethylenetriaminepentamethylenephosphonic acid
  • ETMP ethylenediaminetetramethylenephosphonic acid
  • Graying inhibitors have the task of keeping the dirt detached from the fibers suspended in the liquor and thus preventing graying.
  • Water-soluble colloids mostly of an organic nature, are suitable for this, for example the water-soluble salts of polymeric carboxylic acids, 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 also suitable for this purpose. Soluble starch preparations and starch products other than those mentioned above can also be used, e.g. degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone can also be used.
  • cellulose ethers such as carboxymethyl cellulose (sodium salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers, such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof, and also polyvinylpyrrolidone, for example in amounts of 0.1 to 5% by weight, based on the composition, used.
  • the agents can contain derivatives of diaminostilbenedisulfonic acid or its alkali metal salts. Suitable are e.g. Salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of similar structure which, instead of the morpholino group, have a diethanolamino group , a methylamino group, an anilino group or a 2-methoxyethylamino group.
  • brighteners of the substituted diphenylstyryl type may be present, e.g.
  • the finished washing or cleaning agents can be built up uniformly from extrudates which contain the above-mentioned ingredients, including the detergent mixtures, which are also extruded as a component of the premix.
  • the extrudates are processed with further ingredients of washing or cleaning agents. This can be such that the washing or cleaning agents are obtained from a mixture of several different granules, of which the extrudates according to the invention are the main component form.
  • Bleach activators for example N, N'-tetraacylated diamines such as N, N, N ', N'-tetraacetylethylenediamine, enzyme granules containing enzymes, in particular protease and / or lipase and / or cellulase and / or amylase, with mixtures of 2 or 3 enzymes can be particularly beneficial, and perfume added afterwards.
  • the extrudates can also be prepared with further finely divided dry powders before the enzymes and the other components are added. Examples include zeolite, silicas and salts of fatty acids, for example calcium stearate, bleach activator or mixtures of zeolite with one of the other powders mentioned.
  • the foaming behavior for detergents can be positively influenced if the foam inhibitor, for example organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica or bistearylethylenediamide, at least partially does not extrude , but is subsequently mixed with the extrudate.
  • the surface of the extrudate according to the invention is first covered, for example, with zeolite or a mixture containing zeolite and then with a foam inhibitor. Such measures make it possible to further improve the flushing behavior of the extrudates.
  • the bulk density of the extrudates produced according to the invention is preferably between 600 and 1200 g / l, bulk densities between 700 and 1000 g / l and in particular between 750 and 950 g / l being particularly preferred.
  • the proportions can be found in Tab. 1.
  • the anhydrous detergent mixtures were mixed with other customary detergent ingredients.
  • the homogenized mixture was then first extruded in a screw press and then through a perforated disc (diameter of the holes 1.1 mm). The resulting strands were then processed into granular granules.
  • the composition of the extrudates is shown in Table 1.
  • C 12/14 -FAS C 12/14 fatty alcohol sulfate sodium salt spray dried
  • C 12/14 -FA2 C 12/14 fatty alcohol 2E0 adduct
  • C 16/18 -FA40 C 16/18 fatty alcohol 40E0 adduct
  • a 35% by weight aqueous sodium silicate solution (1: 3.0) was used as the plasticizer and / or lubricant.
  • M1 a mixture of 9 parts FAS-M with 1 part FA was first produced in a Lödige mixer. This was then incorporated into the premix. The finished extrudates were dried and mixed with TAED and the enzyme.
  • Table 3 Compositions of the extrudate R3 according to the invention and of the comparative extrudate V5 (in% by weight) R3 V5 SECTION ---- 18th FAS-M 18th ---- FA 2.2 ---- NOK ---- 2.2 Soap 1 1 TA40 2.5 2.5 Zeolite 28 28 CP5 4th 4th soda 5 5 Sil3.0 2nd 2nd By 20th 20th TAED 6 6 SIK 0.6 0.6 enzyme 1.2 1.2 Water and salts from raw materials rest rest rest rest
  • the extrudates were tested in household drum washing machines with an induction drawer at a water pressure of 0.5 bar. Test machines were Miele W918 and Jo Privileg 1100. 5 determinations were carried out in each machine. The mean value given below was then formed from the 10 results. For this purpose, 80 g of the extrudates were added to the induction chamber per wash. The tap water with which the extrudates were washed into the respective machine, which was loaded with 3.5 kg of dry laundry, had a water hardness from 16 ° d. After the wash-in was completed, the detergent residues from the wash-in drawer and the wash-in chamber were placed separately on a watch glass with a rubber wiper and weighed out. 30% moisture was subtracted from these moist residues. The "dry residues" from the drawer and chamber were added and the mean was formed from the sum, which is given in Table 4 for R3 and V5.
  • the table shows that both the flushing-in behavior and the residue behavior of the extrudates in the hand-washing test are significantly better with the extrudate R3 according to the invention than with the comparative example V5.

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Claims (20)

  1. Mélange de détergents renfermant :
    a) des alkyl et/ou alkénylsulfates de formule

            R1OSO3X     (I)

    dans laquelle R1 représente un radical hydrocarboné aliphatique linéaire ou ramifié ayant de 16 à 18 atomes de carbone et X représente un métal alcalin ou alcalinoterreux, un ammonium, un alkylamnonium, un alkanolammonium ou un glucammonium,
    b) des alkyl et/ou alkenylsulfates de formule (II),

            R2OSO3X     (II)

    dans laquelle R2 représente un radical hydrocarboné aliphatique linéaire ou ramifié, ayant de 12 à 14 atomes de carbone et X représente un métal alcalin ou alcalino-terreux, un ammonium, un alkylammonium , un alkanolamnonium ou un glucammonium,
    caractérisé en ce que
    le mélange de détergents est essentiellement anhydre et renferme les composants a) et b) dans un rapport pondéral de 90:10 à 70:30 ainsi que,
    c) un agent de rupture de la structure hydrophobe de formule (III)

            R4O(CH2CH2O)nH     (III)

    dans laquelle R4 représente un radical alkyl et/ou alkényle linéaire ou ramifié ayant de 12 à 18 atomes de carbone et n représente 0 ou des nombres allant de 1 à 5.
  2. Mélange de détergents selon la revendication 1,
    caractérisé en ce que
    les composants a) et b) sont contenus dans un rapport pondéral de 90:10 à 80:20, et que les fractions non sulfatées dans les composants a) et b) dans l'ensemble représentent moins de 4,5 % en poids, de préférence moins de 3 % en poids et en particulier moins de 2 % en poids, à chaque fois rapporté au mélange d'alk(en)ylsultates produit industriellement.
  3. Mélanges de détergents selon l'une des revendications 1 ou 2,
    caractérisé en ce qu'
    ils renferment comme agent de rupture de la structure hydrophobe, des substances de formule (III) dans laquelle R4 représente un radical alkyle linéaire ayant de 12 à 18 atomes de carbone et n représente 0 ou des nombres allant de 1 à 3.
  4. Mélanges de détergents selon l'une des revendications 1 à 3,
    caractérisés en ce qu'
    ils renferment les agents de rupture de la structure hydrophobes en quantités allant de 1 à 50 % en poids, rapporté aux mélanges.
  5. Mélanges de détergents selon l'une des revendications 1 à 4,
    caractérisés en ce qu'
    ils renferment comme agent de solidification polymère, un éther de polyéthylèneglycol ayant un poids moléculaire moyen dans la zone de 12000 à 100.000.
  6. Mélanges de détergents selon l'une des revendications 1 à 5,
    caractérisés en ce qu'
    ils renferment les agents de solidification polymères en quantités allant de 1 à 5 % en poids, rapporté aux agents de rupture de la structure hydrophobes.
  7. Procédé de préparation de mélanges de détergents conformément à l'une des revendications 1 à 6,
    dans lequel des mélanges d'alkyl et/ou d'alkénylsulfates de formules (I) et (II) sont imprégnés d'agents de rupture de la structure (III) hydrophobes.
  8. Utilisation des mélanges de détergents conformément à l'une des revendications 1 à 6, en vue de la fabrication d'agents de lavage ou de nettoyage par mélange avec des ingrédients supplémentaires pulvérulents de produits de lavage ou de nettoyage et de préférence solidification mécanique subséquente.
  9. Utilisation de mélanges de détergents conformément à la revendication 8,
    caractérisée en ce que
    comme agent de rupture de la structure c) hydrophobe on utilise un alcool non éthoxylé ayant de 12 à 18 atomes de carbone et en ce que la quantité d'alcool en C18 ne dépasse pas 3 % en poids, rapporté au mélange de détergents à base de a), de b) et de c).
  10. Utilisation des mélanges de détergents conformément aux revendications 8 ou 9,
    caractérisée en ce que
    les mélanges de détergents sont utilisés qui renferment des alkylsulfates ayant des nombres d'atomes de carbone dans la chaîne en dessous de 12, en quantités qui ne sont pas en dessous de 20 % en poids, et de préférence en quantités qui ne sont pas au-dessus de 10 % en poids, à chaque fois rapporté à la somme des alk(en)ylsulfates présents au total.
  11. Utilisation des mélanges de détergents selon l'une des revendications 8 à 10,
    caractérisé en ce qu'
    on utilise des mélanges de détergents qui renferment des alk(en)ylsulfates, de préférence des alkylsulfates ayant un nombre d'atomes de carbone dans la chaîne au-dessus de 18, en quantités qui ne sont pas au-dessus de 20 % en poids et de préférence en quantités qui ne sont pas au dessus de 10% en poids, à chaque fois rapporté à la somme des alk(en)ylsulfates présents au total.
  12. Utilisation de mélanges de détergents selon l'une des revendications 8 à 11,
    caractérisée en ce qu'
    on utilise des mélanges de détergents qui renferment des mélanges d'alkylsulfates avec une quantité maximale de 5 % en poids d'alkylsulfates avec des nombres d'atomes de carbone dans la chaîne en dessous de 12, et qui sont de préférence dépourvus de ceux-ci.
  13. Utilisation de mélanges de détergents selon l'une des revendications 8 à 12,
    caractérisée en ce qu'
    on utilise des mélanges de détergents qui renferment des mélanges d'alk(en)ylsulfates ayant au maximum 5 % en poids d'alk(en)ylsulfates avec des nombres d'atomes de carbone dans la chaîne au-dessus de 18 et de préférence qui sont dépourvus de ceux-ci.
  14. Utilisation de mélanges de détergents selon l'une des revendications 8 à 13,
    caractérisée en ce qu'
    on utilise des mélanges de détergents qui renferment des mélanges d'alk(en)ylsulfates produits industriellement qui ne renferment compte tenu des quantités des fractions non sulfatées pas plus de 4,5 % en poids, de préférence moins de 3 % en poids et en particulier moins de 2 % en poids, à chaque fois rapporté au mélange d'alk(en)ylsulfates produit industriellement.
  15. Utilisation de mélanges de détergents selon l'une des revendications 8 à 14,
    caractérisée en ce qu'
    on utilise des mélanges de détergents qui ne renferment pas plus de 2 % en poids, de préférence pas plus de 1,5 % en poids, rapporté au mélange de détergents, d'alcools en C18.
  16. Utilisation de mélanges de détergents selon l'une des revendications 8 à 15,
    caractérisée en ce qu'
    on utilise des mélanges de détergents qui possèdent des alcools ayant des nombres d'atomes de carbone au-dessus de 15 en quantités qui ne sont pas supérieures a 10 % en poids, de préférence en quantités qui ne sont pas supérieures à 5 % en, poids, et en particulier qui ne sont pas supérieures à 3 % en poids, à chaque fois rapporté au mélange de détergents.
  17. Utilisation de mélanges de détergents selon l'une des revendications 8 à 16,
    caractérisée en ce qu'
    on utilise des mélanges de détergents qui contiennent en supplément aux fractions non sulfatées déjà présentes le cas échéant à cause de fabrication industrielle, de 1 à 20 % en poids rapporté au mélange de détergents, de préférence de 2 à 15 % en poids d'alcools linéaires ayant jusqu'à 14 atomes de carbone et en particulier de 2 à 12 % en poids d'alcools gras ayant 12 et/ou 14 atomes de carbone.
  18. Produits de lavage ou de nettoyage extrudé qui renferment des mélanges de détergents essentiellement anhydres, qui possède,
    a) des alkyl et/ou alkénylsulfates de formule (I)

            R1OSO3X     (I)

    dans laquelle R1 représente un radical hydrocarboné aliphatique linéaire ou ramifié ayant de 16 à 18 atomes de carbone et X représente un métal alcalin ou alcalino-terreux, un ammonium, un alkylammonium, un alkanolammonium ou un glucamnonium,
    b) des alkyl et/ou alkenylsulfates de formule (II),

            R2OSO3X     (II)

    dans laquelle R2 représente un radical hydrocarboné aliphatique linéaire ou ramifié, ayant de 12 à 14 atomes de carbone et X a la signification comme ci-dessus,
    et c) des agents de rupture de la structure hydrophobes de formule (III)

            R4O(CH2CH2O)nH     (III)

    dans laquelle R4 représente un radical alkyl et/ou alkényle linéaire ou ramifié ayant de 12 à 18 atomes de carbone et n représente 0 ou des nombres allant de 1 à 5, avec la réserve qu'ils renferment les composants a) et b) dans un rapport pondéral de 90:10 à 70:30, qu'on ment en oeuvre comme agent de rupture de la structure c) hydrophobe un alcool non éthoxylé ayant de 12 à 18 atomes de carbone, et que la fraction d'alcool en C18 rapporté au mélange de détergents, ne dépasse pas 3 % en poids.
  19. Procédé de fabrication d'extrudats actifs pour le lavage ou le nettoyage ayant une densité élevée, dans lequel un pré-mélange solide et apte au ruissellement qui contient un agent de plastification et/ou de glissement, est comprimé sous pression, sous forme de filament et dans lequel le filament est découpé après sortie d'une forme perforée à l'aide d'un dispositif de coupe, à la dimension de granulé prédéterminée,
    caractérisé en ce qu'
    on met en oeuvre des mélanges de détergents qui contiennent :
    a) des alkyl et/ou alkénylsulfates de formule (I)

            R1OSO3X     (I)

    dans laquelle R1 représente un radical hydrocarboné aliphatique linéaire ou ramifié ayant de 16 à 18 atomes de carbone et X représente un métal alcalin ou alcalino-terreux, un ammonium, un alkylammonium, un alkanolammonium ou un glucammonium,
    b) des alkyl et/ou alkenylsulfates de formule (II),

            R2OSO3X     (II)

    dans laquelle R2 représente un radical hydrocarboné aliphatique linéaire ou ramifié, ayant de 12 à 14 atomes de carbone et X a les significations comme ci-dessus,
    et c) des agents de rupture de la structure hydrophobes de formule (III)

            R4O(CH2CH2O)nH     (III)

    dans laquelle R4 représente un radical alkyl et/ou alkényle linéaire ou ramifié ayant de 12 à 18 atomes de carbone et n représente 0,
    en ce que le mélange de détergents est essentiellement anhydre, en ce qu'il renferme les composants a) et b) dans un rapport pondéral de 90:10 à 70:30, et en ce que la fraction d'alcool en C18, ne dépasse pas 3 % en poids, rapporté au mélange de détergents.
  20. Procédé selon la revendication 19,
    caractérisé en ce que
    les extrudats produits sont fabriqués avec d'autres ingrédients de produits de lavage ou de nettoyage.
EP94928353A 1993-09-23 1994-09-14 Melanges detergents et produits de lavage ou de nettoyage a proprietes ameliorees de dissolution Revoked EP0720644B1 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
DE19934332373 DE4332373C2 (de) 1993-09-23 1993-09-23 Wasserfreie Detergensgemische
DE4332373 1993-09-23
DE4403323A DE4403323A1 (de) 1993-09-23 1994-02-03 Extrudierte Wasch- oder Reinigungsmittel mit verbesserten Löseeigenschaften
DE4403323 1994-02-03
PCT/EP1994/003077 WO1995008616A1 (fr) 1993-09-23 1994-09-14 Melanges detergents et produits de lavage ou de nettoyage a proprietes ameliorees de dissolution

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EP0720644B1 true EP0720644B1 (fr) 1997-12-17

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EP0525239B1 (fr) * 1991-07-31 1997-07-09 AUSIMONT S.p.A. Procédé pour augmenter l'efficacité de blanchiment d'un persel inorganique
DE4127323A1 (de) * 1991-08-20 1993-02-25 Henkel Kgaa Verfahren zur herstellung von tensidgranulaten
DE4134914A1 (de) * 1991-10-23 1993-04-29 Henkel Kgaa Wasch- und reinigungsmittel mit ausgewaehlten builder-systemen
CA2083331C (fr) * 1991-11-26 1998-08-11 Johannes H. M. Akkermans Compositions pour detergent
DE4203031A1 (de) * 1992-02-04 1993-08-05 Henkel Kgaa Verfahren zur herstellung fester wasch- und reinigungsmittel mit hohem schuettgewicht und verbesserter loesegeschwindigkeit
DE4203923A1 (de) * 1992-02-11 1993-08-12 Henkel Kgaa Verfahren zur herstellung von polycarboxylaten auf polysaccharid-basis
DE4235646A1 (de) * 1992-10-22 1994-04-28 Henkel Kgaa Verfahren zur Herstellung wasch- und reinigungsaktiver Extrudate
DE4242185A1 (de) * 1992-12-15 1994-06-16 Henkel Kgaa Granulare Wasch- und Reinigungsmittel mit hohem Tensidgehalt
DE4300772C2 (de) * 1993-01-14 1997-03-27 Stockhausen Chem Fab Gmbh Wasserlösliche, biologisch abbaubare Copolymere auf Basis von ungesättigten Mono- und Dicarbonsäuren, Verfahren zu ihrer Herstellung und ihre Verwendung
US5415806A (en) * 1993-03-10 1995-05-16 Lever Brothers Company, Division Of Conopco, Inc. Cold water solubility for high density detergent powders
DE4319578A1 (de) * 1993-06-14 1994-12-15 Henkel Kgaa Waschmittel, enthaltend Aminosäuren und/oder deren Salze
US5478580A (en) * 1994-01-21 1995-12-26 Coors Brewing Company Method for the production of a purified iso-alpha-acid concentrate from hop extract

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DE4403323A1 (de) 1995-08-10
ATE161283T1 (de) 1998-01-15
ES2110784T3 (es) 1998-02-16
WO1995008616A1 (fr) 1995-03-30
EP0720644A1 (fr) 1996-07-10
DE59404837D1 (de) 1998-01-29
US5668100A (en) 1997-09-16

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