EP0986629B2 - Detergent granule - Google Patents

Detergent granule Download PDF

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Publication number
EP0986629B2
EP0986629B2 EP98930735A EP98930735A EP0986629B2 EP 0986629 B2 EP0986629 B2 EP 0986629B2 EP 98930735 A EP98930735 A EP 98930735A EP 98930735 A EP98930735 A EP 98930735A EP 0986629 B2 EP0986629 B2 EP 0986629B2
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EP
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Prior art keywords
acid
weight
composition
organic acid
organic
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German (de)
English (en)
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EP0986629A1 (fr
EP0986629B1 (fr
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Eduard Smulders
Peter Sandkühler
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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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
    • C11D1/66—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
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2082—Polycarboxylic acids-salts thereof
    • 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
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2086—Hydroxy carboxylic acids-salts thereof

Definitions

  • the invention relates to granular detergents having bulk densities above 600 g / l, which separately or subsequently admixed organic acids, in particular citric acid, and are particularly suitable for cleaning colored textiles, and a method for producing the granular detergent. Furthermore, the use of the agents in machine washing processes at temperatures up to 60 ° C claimed.
  • Citric acid has long been known as a detergent ingredient. It was used primarily to reduce the pH of the mostly strong alkaline agent in the aqueous liquor, the added benefit was achieved that both the citric acid and obtained by the neutralization of citric acid citrate (Co) have builder properties.
  • German Patent Application DE-A-28 27 571 generally describes laundry detergents which comprise a granular alkaline, in particular carbonate-containing, slower-dissolving component and from 5 to 30% by weight of a separate organic acid, preferably citric acid.
  • a separate organic acid preferably citric acid.
  • This is achieved as part of an "acid prewash" in commercial household washing machines already at temperatures of 25 ° C by already dissolving at these temperatures citric acid softening of the liquor, so that at temperatures around 40 ° C at the beginning of dissolution of the alkaline component, the liquor already softened so that the risk of the formation of calcium carbonate and thus the formation of calcium carbonate residues on the textiles is largely minimized.
  • Other components of the means include, but are not limited to: Peroxy bleach such as perborates.
  • the citric acid which adjusts the pH in 1% solution in water at 20 ° C to between 7 and 9.3 should be lowered, added later, as in Mitversprühung the citric acid in the spray-dried slurry, the neutralization of the citric acid would already be in the slurry and not - as desired - would take place in the aqueous wash liquor.
  • the particle size distribution of the separately added citric acid again plays no role. Due to the relatively low pH in the aqueous liquor, the colors of colored textiles should be better preserved.
  • Granular detergents having a bulk density of 650 to 1100 g / l, which anionic and / or nonionic surfactants and as builder materials u.a. Contain 5 to 30 wt .-% sodium carbonate and / or bicarbonate and / or sesquicarbonate, according to the teaching of European Patent EP-B-0 534 525 (Henkel) good dispersing properties in the aqueous liquor, if they are used as further component contain up to 15 wt .-% subsequently added citric acid, said citric acid must have at least 80 wt .-% of particles having a particle size of 350 and 1500 microns. Both smaller particle sizes and coarser granules do not lead to the desired effect of increased dispersion in aqueous liquor.
  • Other common ingredients include peroxy bleaches in the compositions.
  • bleach and especially peroxy bleach such as perborate or percarbonate in detergents usually in amounts of 15 wt .-% and above used to remove bleachable stains from textiles.
  • Bleaching agents however, not only have the effect of removing bleachable stains from textiles, they also often attack colored fabrics, especially in the oxidation-sensitive grades of textile dyes, so that over time the intensity of the textile dyes diminishes and the fabrics look "washed out” .
  • the use of bleaching agents can also lead to punctiform color removal on the textiles, the so-called pinhole spotting effect.
  • detergents are commercially available which are explicitly used for colored textiles and therefore have no or only small amounts, for example less than 10 wt .-%, based on the total agent, of bleaching agents. With such small amounts, the bleaching agent is for hygienic purposes only; the risk of color removal or staining of the textiles by the bleach are then almost impossible. Nonetheless, stain removal from colored textiles is still a problem.
  • the invention therefore provides a granular detergent as defined in claim 1.
  • the invention also provides a process for the preparation of a granular detergent having the features defined in claim 4.
  • organic acids it is preferred to use those which are known to also have a significant builder effect. These organic acids include all those which are already listed in the German patent application DE 28 27 571.
  • the polyhydroxydicarboxylic acids mentioned in international patent application WO-A-94/04650 can also be used. Particularly preferred are citric acid, tartaric acid, succinic acid, maleic acid and / or malic acid. But also acid anhydrides count in the context of the present invention to the organic acids; Here, especially succinic anhydride and maleic anhydride are preferred. With particular preference, citric acid is used.
  • citric acid has a better bleaching performance over a wide variety of stains than, for example, tartaric acid, although tartaric acid can achieve better results on targeted stains in the bleaching area than citric acid.
  • the organic acids / organic acid anhydrides are used as raw material, ie not in the form of a processed compound and are therefore present in the inventive compositions as a separate or subsequently admixed component.
  • syntheticly admixed is meant that the organic acid is mixed as one of several components with the other components to the detergent.
  • all other components are first prepared and optionally premixed with each other and possibly further shaping steps of the mixed components are carried out and the organic acid is added afterwards, ie "subsequently added”.
  • the organic acids can be mixed in their commercial form with the other components.
  • Finer-particle grades with at least 80% by weight smaller than 350 ⁇ m or coarser qualities with at least 80% by weight greater than 1500 ⁇ m are available.
  • the coarser product with particle diameters of at least 80 wt .-% greater than 1500 microns is used in the inventive compositions without sacrificing performance.
  • This coarser article may even be aesthetically advantageous when blended into components which also have a coarser grain spectrum, for example granules or extrudates, which may optionally be rounded, and at least 80% by weight of particles having a particle diameter above 400 microns, and in particular those having an average particle diameter of 0.8 to 1.4 mm.
  • a coarser product of organic acids, as defined in claim 4, in particular citric acid, consists of at least 80 wt .-% of particles having a particle size between 1500 and 2000 microns. Even more finely divided product (80 wt .-% less than 350 microns) can be used in principle. However, it then preferably serves for dusting off the granular components and should advantageously not be present as a separate component in the agents. According to claim 1, in addition to the above-mentioned coarse-grained quality with at least 80 wt .-% of particles having a particle diameter greater than 1500 microns and this finely divided product with particle diameters of at least 80 wt .-% less than 350 microns.
  • Granular detergents are understood to mean particulate detergents which comprise at least 60% by weight of particles having a particle size of more than 350 ⁇ m and preferably contain at least one component which has at least 80% by weight a particle size of more than 350 ⁇ m.
  • the granular agents consist of at least 60% by weight, preferably from 70 to 100% by weight, of components which have at least 80% by weight of a particle size of more than 350 ⁇ m.
  • the bulk density of the funds is of less importance, since the effect of the invention is not dependent on the bulk density.
  • compact detergents or so-called concentrates having bulk densities above 600 g / l are preferred.
  • Granular detergents having bulk densities between 650 and 1100 g / l are claimed according to the invention, bulk densities above 700 g / l and in particular above 750 g / l being particularly preferred.
  • the organic acids / organic acid anhydrides are used in the inventive compositions in amounts of from 1 to 15 wt .-%, but preferably in amounts of less than 10 wt .-% and in particular in amounts of 2 to 6 wt .-%.
  • Finely divided qualities with particle diameters of at least 80% by weight of less than 350 ⁇ m, based on the total composition, are preferably not more than 2% by weight and in particular not more than 1% by weight.
  • both coarse (at least 80 wt .-% greater than 1500 microns) and finely divided (at least 80 wt .-% less than 350 microns) contain organic acids, the proportion of finely divided organic acids the total amount
  • the organic acids used preferably at most 50 wt .-% and in particular 5 to 30 wt .-%.
  • compositions according to the invention contain less than 10% bleach and are in particular substantially free from peroxy bleach, being understood in the context of this invention to be “substantially free of” from 0 to 10% by weight.
  • the agents are absolutely free of bleaches.
  • the usual Peroxyblleichstoff such as, perborate tetrahydrate and / or percarbonate are preferred.
  • compositions of the invention also include anionic and / or nonionic surfactants, wherein it is particularly preferred if the agents contain both anionic and nonionic surfactants.
  • anionic surfactants of the sulfonate type are preferably C 9 -C 13 alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as they are, for example, from C 12 -C 18 monoolefins with terminal or internal double bond by sulfonation with gaseous Sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation obtained.
  • the use of said alkylbenzenesulfonates is particularly preferred.
  • esters of ⁇ -sulfo fatty acids e.g. the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.
  • Suitable anionic surfactants are sulfated fatty acid glycerol esters, which are mono-, di- and triesters and mixtures thereof, as in the preparation by esterification by a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol to be obtained.
  • alk (en) ylsulfates are the alkali metal salts and, in particular, the sodium salts of the sulfuric monoesters of C 12 -C 18 fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -C 20 oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred.
  • alk (en) ylsulfates of said chain length which contain a synthetic, produced on a petrochemical basis straight-chain alkyl radical, which have an analogous degradation behavior as the adequate compounds based on oleochemical raw materials.
  • C 12 -C 16 -alkyl sulfates and C 12 -C 15 -alkyl sulfates and C 14 -C 15 -alkyl sulfates are particularly preferred.
  • 2,3-Alkyl sulfates which are prepared, for example, according to US Pat. Nos. 3,234,258 or 5,075,041 and can be obtained as commercial products of Shell Oil Company under the name DAN (R), are suitable anionic surfactants.
  • sulfuric acid monoesters of the straight-chain or branched C 7 -C 21 -alcohols ethoxylated with from 1 to 6 mol of ethylene oxide such as 2-methyl-branched C 9 -C 11 -alcohols having on average 3.5 mol of ethylene oxide (EO) or C 12 -C 18 Fatty alcohols containing 1 to 4 EO are suitable. They are used in detergents due to their high foaming behavior only in relatively small amounts, for example in amounts of 1 to 5 wt .-%.
  • Preferred anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • alcohols preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain C 8 to C 18 fatty alcohol residues or mixtures of these.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols, which in themselves constitute nonionic surfactants (see description below).
  • Sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are again particularly preferred.
  • alk (en) ylsuccinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
  • Suitable further anionic surfactants are fatty acid derivatives of amino acids, for example N-methyltaurine (Tauride) and / or N-methylglycine (sarcosides). Particularly preferred are the sarcosides or the sarcosinates and here especially sarcosinates of higher and optionally monounsaturated or polyunsaturated fatty acids such as oleyl sarcosinate.
  • the anionic surfactants are preferably used in relatively high amounts, i. in amounts above 15 wt .-% used.
  • Anionic surfactants are advantageously present in amounts of between 16 and 30% by weight, based on the finished compositions, in the compositions.
  • Suitable anionic surfactants also include soaps, which are preferably present in amounts of from 0.5 to 3% by weight, based on the finished compositions.
  • Particularly suitable are saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular of natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures. Together with these soaps or as a substitute for soaps, it is also possible to use the known alkenylsuccinic acid salts.
  • the proportion of soaps and alkenylsuccinic acid salts in the total surfactant system is preferably below 10% by weight and in particular at a maximum of 5% by weight.
  • the anionic surfactants including the soaps may 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 nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten.
  • alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, palm kernel, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred.
  • the preferred ethoxylated alcohols include, for example, C 12 -C 14 -alcohols with 3 EO or 4 EO, C 9 -C 11 -alcohols with 7 EO, C 13 -C 15 -alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12 -C 18 -alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 12 -C 14 -alcohol with 3 EO and C 12 -C 18 -alcohol with 7 EO.
  • the degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples include (tallow) fatty alcohols with 14 EO, 16 EO, 20 EO, 25 EO, 30 EO or 40 EO.
  • nonionic surfactants and alkyl glycosides of the general formula RO (G) x can be used in which R is a primary straight-chain or methyl-branched, especially in the 2-position methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol which represents a glycose unit having 5 or 6 C atoms, preferably glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1.2 to 1.4.
  • nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants, in particular together with alkoxylated fatty alcohols and / or alkyl glycosides, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably from 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl esters, as described for example in Japanese Patent Application JP 58/217598 or which are preferably prepared according to the method described in International Patent Application WO-A-90/13533.
  • Particularly preferred are C 12 -C 18 fatty acid methyl esters having an average of 3 to 15 EO, in particular having an average of 5 to 12 EO.
  • Nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.
  • polyhydroxy fatty acid amides of the formula (I) in R 2 CO is an aliphatic acyl radical having 6 to 22 carbon atoms
  • R 3 is hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms
  • [Z] is a linear or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups stands.
  • the polyhydroxy fatty acid amides are preferably derived from reducing sugars having 5 or 6 carbon atoms, in particular from glucose.
  • the group of polyhydroxy fatty acid amides also includes compounds of the formula (II) in the R 3 is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
  • R 4 is a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms
  • R 5 is a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, with C 1 -C 4 -alkyl or phenyl radicals being preferred
  • [Z] is also obtained here preferably by reductive amination of a sugar such as glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • a sugar such as glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • the N-alkoxy- or N-aryloxy-substituted compounds can then be converted into the desired polyhydroxy fatty acid amides, for example according to the teaching of international patent application WO-A-95/07331, by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
  • gemini surfactants are so-called gemini surfactants. These are generally understood as meaning those compounds which have two hydrophilic groups and two hydrophobic groups per molecule. These groups are usually separated by a so-called “spacer”. This spacer is usually a carbon chain that should be long enough for the hydrophilic groups to be spaced sufficiently apart for them to act independently of each other. Such surfactants are generally characterized by an unusually low critical micelle concentration and the ability to greatly reduce the surface tension of the water. In exceptional cases, however, the term gemini surfactants is understood to mean not only dimeric but also trimeric surfactants.
  • Suitable gemini surfactants are, for example, sulfated hydroxy mixed ethers according to the German patent application DE-A-43 21 022 or dimer alcohol bis- and trimeralcohol trissulfates and ether sulfates according to the earlier German patent application P 195 03 061.3.
  • End-capped dimeric and trimeric mixed ethers according to the earlier German patent application P 195 13 391.9 are distinguished in particular by their bi-and multifunctionality.
  • the end-capped surfactants mentioned have good wetting properties and are low foaming, so that they are particularly suitable for use in machine washing or cleaning processes.
  • gemini polyhydroxy fatty acid amides or poly-polyhydroxy fatty acid amides as described in international patent applications WO-A-95/19953, WO-A-95/19954 and WO95-A- / 19955.
  • surfactants such as amphoteric surfactants, cationic surfactants and / or zwitterionic surfactants may be included in the inventive compositions.
  • cationic surfactants having scavenging properties can be used to increase the softness of the fabrics after washing or after drying.
  • the content of anionic and / or nonionic surfactants in the compositions according to the invention is preferably 15 to 40% by weight, in particular 20 to 35% by weight, advantageously at least one nonionic anionic surfactant and at least one nonionic surfactant and optionally soap contained in the funds.
  • a content of nonionic surfactants above 12 wt .-% may in principle lead to a further increase in the performance of the funds, however, it has been found in several cases that the granular agents with such high Niotensidiere increasingly lose flowability and sticking can tend to clumping. For this reason, amounts of nonionic surfactants above 12 wt .-% are not particularly preferred.
  • Nonionic surfactants of at least 1: 1, preferably of 2.5: 1 to 1.1: 1, have proven to be particularly advantageous, in particular if the soap content, based on the total surfactant content, is at most 5% by weight ,
  • the agents according to the invention normally contain customary further inorganic and / or organic builders in conventional amounts. In this case, for example, 10 to 30 wt .-% of additional builders may be included in the agents.
  • the inorganic builders include above all zeolites, crystalline phyllosilicates, carbonates, amorphous silicates and, to a lesser extent, phosphates.
  • the fine crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P.
  • zeolite P for example, zeolite MAP (R) (commercial product of Crosfield) may be contained in the agents.
  • zeolite X and mixtures of A, X and / or P are also suitable.
  • the zeolite can be used as spray-dried powder or else as undried, still moist, stabilized suspension of its preparation.
  • the zeolite may contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3 wt .-%, based on zeolite, of ethoxylated C 12 -C 18 fatty alcohols having 2 to 5 ethylene oxide groups , C 12 -C 14 fatty alcohols having 4 to 5 ethylene oxide groups or ethoxylated isotridecanols.
  • Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution, measuring method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22 wt .-% of bound water.
  • Suitable substitutes or partial substitutes for phosphates and zeolites are crystalline, layered sodium silicates of the general formula NaMSi x O 2x + 1 .yH 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 is up to 20 and preferred values for x are 2, 3 or 4.
  • Such crystalline sheet silicates are described, for example, in European Patent Application EP-A-0 164 514.
  • Preferred crystalline layered silicates of the formula given are those in which M is sodium and x assumes the values 2 or 3. In particular, both ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 O 5 .yH 2 O are preferred.
  • the preferred builder substances also include amorphous sodium silicates having a modulus Na 2 O: SiO 2 of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2, 6, which are delay-delayed and have secondary washing properties.
  • the dissolution delay compared with conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction / densification or by overdrying.
  • the term "amorphous” is also understood to mean "X-ray amorphous”.
  • the silicates do not yield sharp X-ray reflections typical of crystalline substances in X-ray diffraction experiments, but at most one or more maxima of the scattered X-rays having a width of several degrees of diffraction angle. However, it may well even lead to particularly good builder properties if the silicate particles provide blurred or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline regions of size 10 to a few hundred nm, values of up to max. 50 nm and in particular up to max. 20 nm are preferred.
  • Such so-called X-ray amorphous silicates which likewise have a dissolution delay compared with the conventional water glasses, are described, for example, in German patent application DE-A-44 00 024. Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates.
  • phosphates as builders are possible, unless such use should not be avoided for environmental reasons.
  • Particularly suitable are the sodium salts of orthophosphates, pyrophosphates and in particular tripolyphosphates.
  • Their content is generally not more than 25 wt .-%, preferably not more than 20 wt .-%, each based on the finished composition.
  • tripolyphosphates even in smaller amounts, for example up to a maximum of 10% by weight, based on the finished composition, in combination with other builder substances lead to a synergistic improvement in the secondary washing power.
  • both the monoalkali metal salts and the dialkali metal salts of carbonic acid as well as sesquicarbonates can be contained in the compositions.
  • Preferred alkali metal ions are sodium and / or potassium ions.
  • the carbonate content or the bicarbonate content of the compositions is preferably 5 to 20% by weight, although in one embodiment it may be preferred to separate the carbonate and / or bicarbonate at least partially as a further component or to be added later.
  • Compounds of, for example, carbonate, silicate and optionally other auxiliaries such as, for example, anionic surfactants or other, in particular organic builders, may be present as a separate component in the finished compositions.
  • silicate for example metasilicate and / or crystalline layered disilicate.
  • silicate for example metasilicate and / or crystalline layered disilicate.
  • carbonate, bicarbonate, metasilicate - as described above for the citric acid - in coarse-grained form, it being particularly advantageous if carbonate, bicarbonate and / or metasilicate to at least 50 wt .-% have a particle size above 1 mm and in particular at least 50 wt .-% above 1.2 mm.
  • the alkaline liquor in aqueous liquor admixed or separately admixed components, in particular carbonate, bicarbonate and / or metasilicate and / or crystalline layered disilicate, in amounts of 1 to 15 wt .-%, advantageously in amounts from 2 to 10% by weight.
  • Useful organic builders are, for example, usable in the form of their sodium salts polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such use is not objectionable for environmental reasons, and mixtures thereof.
  • Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures thereof.
  • the salts of the polycarboxylic acids may be included in the agents in addition to the organic acids; however, their presence in the agents is less preferred.
  • dextrins for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches.
  • the hydrolysis can be carried out by customary, for example acid or enzyme catalyzed processes. Preference is given to hydrolysis products having average molecular weights in the range from 400 to 500,000.
  • a polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30 is preferred, DE being a customary measure of the reducing one Effect of a polysaccharide compared to dextrose, which has a DE of 100.
  • DE dextrose equivalent
  • Suitable co-builders are oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate.
  • organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally also be present in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups.
  • Such co-builders are described, for example, in International Patent Application WO-A-95/20029.
  • Suitable polymeric polycarboxylates are, for example, the sodium salts of polyacrylic acid or polymethacrylic acid, for example those having 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 from 5000 to 200,000, preferably from 10,000 to 120,000 and in particular from 50,000 to 100,000.
  • the (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution, with 20 to 55% by weight aqueous solutions being preferred.
  • Polymers of more than two different monomer units for example those which according to DE-A-43 00 772 as monomers are salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or according to DE-C-42 21 381, are also particularly preferred as monomers, salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives.
  • copolymers are those which are described in the German patent applications DE-A-43 03 320 and DE-A-44 17 734 and preferably have as monomers acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.
  • oxidation products of carboxyl-containing polyglucosans and / or their water-soluble salts are oxidation products of carboxyl-containing polyglucosans and / or their water-soluble salts, as described, for example, in International Patent Application WO-A-93/08251 or the preparation of which is described, for example, in International Patent Application WO-A-93/16110.
  • oxidized oligosaccharides according to the German patent application DE 196 00 018.
  • polymeric aminodicarboxylic acids their salts or their precursors.
  • polyaspartic acids or their salts and derivatives are particularly preferred.
  • polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 C atoms and at least 3 hydroxyl groups, for example as described in European Patent Application EP-A-0 280 223.
  • Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
  • compositions may also contain components that positively affect oil and grease washability from fabrics. This effect is particularly evident when a textile is dirty, which has been previously washed several times 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 cellulose and methyl hydroxypropyl cellulose having a methoxyl group content of 15 to 30% by weight and hydroxypropoxyl groups of 1 to 15% by weight, respectively based on the nonionic cellulose ether, and the known from the prior art polymers of phthalic acid and / or terephthalic acid or derivatives thereof, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionic and / or nonionic modified derivatives thereof. Particularly preferred of these are the sulfonated derivatives of phthalic and terephthalic acid polymers.
  • compositions may contain known additives conventionally used in detergents, for example foam inhibitors, salts of polyphosphonic acids, optical brighteners, enzymes, enzyme stabilizers, grayness inhibitors, small amounts of neutral filler salts and dyes and fragrances.
  • foam inhibitors for example foam inhibitors, salts of polyphosphonic acids, optical brighteners, enzymes, enzyme stabilizers, grayness inhibitors, small amounts of neutral filler salts and dyes and fragrances.
  • foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of C 18 -C 24 fatty acids.
  • Suitable non-surfactant foam inhibitors are, for example, organopolysiloxanes and mixtures thereof with microfine, optionally silanized silica and paraffins, waxes, microcrystalline waxes and mixtures thereof with silanated silica or bistearylethylenediamide. With advantages also mixtures of different foam inhibitors are used, eg those from silicones, paraffins or To grow.
  • the foam inhibitors in particular silicone and / or paraffin-containing foam inhibitors, are bound to a granular, water-soluble or dispersible carrier substance.
  • a granular, water-soluble or dispersible carrier substance In particular, mixtures of paraffins and bisstearylethylenediamides are preferred.
  • the salts of polyphosphonic acids used are preferably the neutral-reacting sodium salts of, for example, 1-hydroxyethane-1,1-diphosphonate, diethylenetriamine penta-methylenephosphonate or ethylenediamine tetramethylenephosphonate in amounts of from 0.1 to 1.5% by weight.
  • Suitable enzymes are, in particular, those from the class of the hydrolases, such as the proteases, esterases, lipases or lipolytic enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases in the wash contribute to the removal of stains such as proteinaceous, greasy or starchy stains, and graying. Cellulases and other glycosyl hydrolases can contribute to color retention and increase the softness of the fabric by removing pilling and microfibrils. It is also possible to use oxidoreductases for bleaching or inhibiting color transfer.
  • subtilisin-type proteases and in particular proteases derived from Bacillus lentus are used.
  • enzyme mixtures for example from protease and amylase or protease and lipase or lipolytic enzymes or protease and cellulase or from cellulase and lipase or lipolytic enzymes or from protease, amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic enzymes and cellulase, but in particular protease and / or lipase-containing mixtures or mixtures with lipolytic enzymes of particular interest.
  • lipolytic enzymes are the known cutinases. Peroxidases or oxidases have also proved suitable in some cases.
  • Suitable amylases include in particular ⁇ -amylases, iso-amylases, pullulanases and pectinases.
  • As cellulases are preferably cellobiohydrolases, endoglucanases and ⁇ -glucosidases, which are also called cellobiases, or mixtures thereof used. Since the different cellulase types differ by their CMCase and avicelase activities, targeted mixtures of the cellulases can be used to set the desired activities.
  • the enzymes may be adsorbed to carriers and / or embedded in encapsulants to protect against premature degradation.
  • the proportion of enzymes, enzyme mixtures or enzyme granules may be, for example, about 0.1 to 5 wt .-%, preferably 0.1 to about 2 wt .-%.
  • the agents may contain, for example, from 0.5 to 1% by weight of sodium formate. It is also possible to use proteases which are stabilized with soluble calcium salts and a calcium content of preferably about 1.2% by weight, based on the enzyme. In addition to calcium salts, magnesium salts also serve as stabilizers. However, it is particularly advantageous to use boron compounds, for example boric acid, boron oxide, borax and other alkali metal borates, such as the salts of orthoboric acid (H 3 BO 3 ), metaboric acid (HBO 2 ) and pyroboric acid (tetraboric acid H 2 B 4 O 7 ).
  • boron compounds for example boric acid, boron oxide, borax and other alkali metal borates, such as the salts of orthoboric acid (H 3 BO 3 ), metaboric acid (HBO 2 ) and pyroboric acid (tetraboric acid H 2 B 4 O 7 ).
  • Grayness inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being rebuilt.
  • Water-soluble colloids of mostly organic nature are suitable for this purpose, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or of cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
  • water-soluble polyamides containing acidic groups are suitable for this purpose.
  • soluble starch preparations and other than the above-mentioned starch products can be used, e.g. degraded starch, aldehyde levels, etc. Also polyvinylpyrrolidone is useful.
  • cellulose ethers such as carboxymethylcellulose (sodium salt), methylcellulose, hydroxyalkylcellulose and mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof, and polyvinylpyrrolidone, for example, in amounts of from 0.1 to 5% by weight, based on the compositions, used.
  • the agents may contain as optical brighteners derivatives of Diaminostilbendisulfonklare or their 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 similarly constructed compounds which, instead of the morpholino group, a diethanolamino group , a methylamino group, an anilino group or a 2-methoxyethylamino group. Furthermore, brighteners of the substituted diphenylstyrene type may be present, e.g.
  • compositions according to the invention or the compositions prepared according to the invention have significant advantages, in particular on bleachable stains.
  • advantages can also be found, for example, in enzymatic soiling, while the primary washing performance is to be classified as equal to greasy and pigment-containing stains on average.
  • the advantages occur especially at the bleachable stains even at washing temperatures of 60 ° C and below.
  • compositions according to the invention or the compositions according to the invention in a mechanical washing process at temperatures up to 60 ° C, preferably at temperatures below 60 ° C and in particular in washing programs with temperatures up to 40 ° C claimed , Also in the hand wash at 30 ° C or to 40 ° C, the compositions of the invention show advantages.
  • the performance testing of the primary washing capacity was carried out under practical conditions in household washing machines (Miele Novotronic W918).
  • the machines were charged with 3.5 kg of clean filling laundry and 0.5 kg of test fabric.
  • the test fabrics were cotton and impregnated with the natural and artificial soils detailed below.
  • the stains showed an aging of 5 to 6 days.
  • red wine red wine
  • tea Messmer, TEE
  • instant coffee Neescafé, IK
  • currant juice Eden, J
  • blueberry juice Eden, H
  • compositions had the following compositions (in parts by weight).
  • the basic granulate 1 was prepared in accordance with the teaching of European patent EP-B-0 486 592 and had essentially the following composition: 14% by weight of anionic surfactants (alkylbenzenesulfonate and fatty alkylsulfate), in addition 2% by weight of soap, 8% by weight. % ethoxylated fatty alcohols, 40 wt .-% zeolite (based on anhydrous active substance), 7 wt .-% trisodium citrate dihydrate, 5.5 wt .-% copolymer of acrylic acid and maleic acid, 8 wt .-% sodium carbonate, 2 wt.
  • anionic surfactants alkylbenzenesulfonate and fatty alkylsulfate
  • soap 8% by weight.
  • % ethoxylated fatty alcohols 40 wt .-% zeolite (based on anhydrous active substance)
  • the base extrudate 2 was prepared according to the teaching of EP-A-0931137 and had essentially the following composition: 23% by weight of anionic surfactants (alkylbenzenesulfonate and fatty alkylsulfate), in addition 1% by weight of soap, 8% by weight of ethoxylated fatty alcohols, 27.5 wt .-% zeolite (based on anhydrous active substance), 12 wt .-% trisodium citrate dihydrate, 5.5 wt .-% copolymer of acrylic acid and maleic acid, 6.5 wt .-% sodium carbonate and 5 wt. -% polyethylene glycol with a molecular weight of 4000.
  • the bulk density was about 800 g / l.
  • the enzyme granules contained protease, amylase and cellulase in the weight ratio 1: 1: 1.
  • the "coarse” grades of citric acid and citrate had more than 50% by weight of particles with a particle diameter above 1.5 mm.
  • the foam inhibitor granules were a paraffin frother on soda as a carrier.

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Claims (6)

  1. Agent de lavage granulé présentant une densité apparente de 650 g/l à 1100 g/l, contenant des agents tensioactifs anioniques et/ou non ioniques ainsi que des substances de type builder, y compris 1 à 15% en poids d'un acide organique/anhydride d'acide organique qui y est mélangé séparément ou ultérieurement, caractérisé en ce que l'agent, par rapport à la totalité de l'agent, contient moins de 10% en poids d'agent de blanchiment et les acides organiques/anhydrides d'acide organique présentent une répartition granulométrique selon laquelle au moins 80% en poids des particules sont supérieures à 1500 µm, des acides organiques/anhydrides d'acide organique finement divisés, avec des grosseurs de particules dont au moins 80% en poids sont inférieurs à 350 µm étant également contenus en plus.
  2. Agent selon la revendication 1, caractérisé en ce qu'il contient comme acide organique/anhydride d'acide organique de l'acide citrique, de l'acide tartrique, de l'acide succinique, de l'anhydride de l'acide succinique, de l'acide maléique, de l'anhydride de l'acide maléique et/ou de l'acide malique, en particulier de l'acide citrique.
  3. Agent selon l'une des revendications 1 ou 2, caractérisé en ce qu'il contient, en plus de l'acide organique/anhydride d'acide organique, au moins un constituant à réaction alcaline dans un bain aqueux, sous une forme mélangée ultérieurement ou séparément, les constituants à réaction alcaline dans le bain aqueux, mélangés ultérieurement ou séparément, en particulier du carbonate, du bicarbonate et/ou du métasilicate et/ou du disilicate cristallin en forme de couches se trouvant en des quantités de 1 à 15% en poids, avantageusement en des quantités de 2 à 10% en poids.
  4. Procédé pour la préparation d'un agent de lavage granulé présentant une densité apparente de 650 g/l à 1100 g/l, contenant des agents tensioactifs anioniques et/ou non ioniques ainsi que des substances de type builder, y compris 1 à 15% en poids d'acides organiques/d'anhydrides d'acide organique présentant une répartition granulométrique selon laquelle au moins 80% en poids des particules présentent une grosseur entre 1 500 et 2 000 µm, ainsi que, par rapport à la totalité de l'agent, moins de 10% en poids d'agent de blanchiment, caractérisé en ce que l'agent est préparé selon des procédés usuels tels que le séchage par pulvérisation, la granulation, le compactage, la pelletisation, l'extrusion en combinaison avec un ou plusieurs processus de traitement ultérieurs, qui comprennent des étapes de façonnage, de séchage ou de modification de surface avec des substances liquides à cireuses ou solides et des processus de mélange, au moins l'acide organique/anhydride d'acide organique, en particulier l'acide citrique, le cas échéant toutefois également d'autres composants y étant mélangé(s) séparément ou ultérieurement et on prépare ainsi un agent qui contient les acides organiques/anhydrides d'acide organique dans le produit fini sous forme de composant séparé.
  5. Procédé selon la revendication 4, caractérisé en ce que l'agent est préparé par un procédé de granulation ou d'extrusion, le procédé de granulation ou d'extrusion étant modifié de telle manière qu'on prépare d'abord un mélange préalable solide, qui contient différentes matières premières et/ou des compounds, qui se trouvent à température ambiante et à une pression de 1 bar sous forme solide et qui présentent un point de fusion ou de ramollissement qui n'est pas inférieur à 45°C ainsi que le cas échéant jusqu'à 10% en poids d'agents tensioactifs non ioniques liquides à des températures inférieures à 45°C et une pression de 1 bar, et on transforme avec utilisation de forces de compactage à des températures d'au moins 45°C en un grain et on transforme ultérieurement et traite le cas échéant consécutivement, à condition que
    - le prémélange soit essentiellement exempt d'eau et
    - dans le prémélange, au moins une matière première ou compound qui se trouve à une pression de 1 bar et à des températures inférieures à 45°C sous forme solide, mais qui se trouve sous forme de masse fondue dans les conditions de transformation, cette masse fondue servant de liant polyfonctionnel soluble dans l'eau, qui exerce lors de la préparation de l'agent tant une fonction de lubrifiant qu'une fonction d'adhésif pour les- compounds ou les matières premières d'agent de lavage ou de nettoyage solide, mais qui agit par contre avec un effet de désintégration lors de la redissolution de l'agent dans un bain aqueux et
    - on mélange dans l'étape de traitement au moins les acides organiques/anhydrides d'acide organique sous forme de composant séparé.
  6. Utilisation d'un agent selon l'une quelconque des revendications 1 à 3 ou d'un agent préparé selon l'une quelconque des revendications 4 ou 5 dans un procédé de lavage en machine à des températures jusqu'au maximum 60°C, de préférence à des températures inférieures à 60°C et en particulier dans des programmes de lavage à des températures jusqu'à 40°C.
EP98930735A 1997-06-05 1998-05-27 Detergent granule Expired - Lifetime EP0986629B2 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19723616 1997-06-05
DE19723616A DE19723616A1 (de) 1997-06-05 1997-06-05 Granulares Waschmittel
PCT/EP1998/003109 WO1998055574A1 (fr) 1997-06-05 1998-05-27 Detergent granule

Publications (3)

Publication Number Publication Date
EP0986629A1 EP0986629A1 (fr) 2000-03-22
EP0986629B1 EP0986629B1 (fr) 2002-09-25
EP0986629B2 true EP0986629B2 (fr) 2007-05-16

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EP98930735A Expired - Lifetime EP0986629B2 (fr) 1997-06-05 1998-05-27 Detergent granule

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EP (1) EP0986629B2 (fr)
JP (1) JP2002502457A (fr)
AT (1) ATE224942T1 (fr)
DE (2) DE19723616A1 (fr)
ES (1) ES2183384T5 (fr)
WO (1) WO1998055574A1 (fr)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19854083A1 (de) * 1998-11-24 2000-05-25 Henkel Kgaa Citronensäurehaltiges Waschmittel
GC0000084A (en) * 1998-12-12 2004-06-30 Lg Household & Health Care Ltd Process for preparing laundry powder detergents.
GB0006037D0 (en) 2000-03-13 2000-05-03 Unilever Plc Detergent composition
GB0115552D0 (en) 2001-05-16 2001-08-15 Unilever Plc Particulate laundry detergent composition containing zeolite
DE10242222A1 (de) * 2002-09-12 2004-03-25 Henkel Kgaa Unter Druck kompaktiertes Wasch- oder Reinigungsmittel
US7863237B2 (en) * 2004-03-08 2011-01-04 Ecolab Inc. Solid cleaning products
KR100817687B1 (ko) 2004-09-10 2008-03-27 주식회사 엘지생활건강 산성형태의 수용성 고분자와 유기산을 함유하는 저밀도분말세제 조성물 및 그의 제조방법
WO2020109227A1 (fr) 2018-11-28 2020-06-04 Unilever N.V. Grosses particules

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US4110262A (en) † 1976-03-08 1978-08-29 The Procter & Gamble Company Liquid detergent composition
JPS6262899A (ja) † 1985-09-13 1987-03-19 花王株式会社 高密度粒状洗剤組成物
EP0523681A2 (fr) † 1991-07-17 1993-01-20 Johannes Dr. Behrensdorf Composition détergente pour le lavage automatique de la vaisselle et méthode pour sa production
US5378388A (en) † 1993-06-25 1995-01-03 The Procter & Gamble Company Granular detergent compositions containing selected builders in optimum ratios
WO1995004125A1 (fr) † 1993-07-31 1995-02-09 Henkel Kommanditgesellschaft Auf Aktien Agents de lavage a composants acides
EP0990697A1 (fr) † 1996-03-11 2000-04-05 Kao Corporation Composition detergente granulaire pour vetements

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DE3812455A1 (de) * 1987-04-15 1988-10-27 Sandoz Ag Bleichmittelersatz fuer waschmittel
GB8906089D0 (en) * 1989-03-16 1989-04-26 Monsanto Europe Sa Improved detergent compositions
DE69121460D1 (de) * 1990-05-08 1996-09-26 Procter & Gamble Niedrig-pH-Waschmittelgranulate enthaltend Aluminiumsilikat, Zitronensäure und Carbonatbuilder
DE4024759A1 (de) * 1990-08-03 1992-02-06 Henkel Kgaa Bleichaktivatoren in granulatform
GB9120657D0 (en) * 1991-09-27 1991-11-06 Unilever Plc Detergent powders and process for preparing them
DE4402051A1 (de) * 1994-01-25 1995-07-27 Henkel Kgaa Gerüststoff für Wasch- oder Reinigungsmittel
GB2288187A (en) * 1994-03-31 1995-10-11 Procter & Gamble Detergent composition
DE19638599A1 (de) * 1996-09-20 1998-03-26 Henkel Kgaa Verfahren zur Herstellung eines teilchenförmigen Wasch- oder Reinigungsmittels

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4110262A (en) † 1976-03-08 1978-08-29 The Procter & Gamble Company Liquid detergent composition
JPS6262899A (ja) † 1985-09-13 1987-03-19 花王株式会社 高密度粒状洗剤組成物
EP0523681A2 (fr) † 1991-07-17 1993-01-20 Johannes Dr. Behrensdorf Composition détergente pour le lavage automatique de la vaisselle et méthode pour sa production
US5378388A (en) † 1993-06-25 1995-01-03 The Procter & Gamble Company Granular detergent compositions containing selected builders in optimum ratios
WO1995004125A1 (fr) † 1993-07-31 1995-02-09 Henkel Kommanditgesellschaft Auf Aktien Agents de lavage a composants acides
EP0990697A1 (fr) † 1996-03-11 2000-04-05 Kao Corporation Composition detergente granulaire pour vetements

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DE59805713D1 (de) 2002-10-31
EP0986629A1 (fr) 2000-03-22
DE19723616A1 (de) 1998-12-10
ES2183384T3 (es) 2003-03-16
JP2002502457A (ja) 2002-01-22
EP0986629B1 (fr) 2002-09-25
WO1998055574A1 (fr) 1998-12-10
ES2183384T5 (es) 2007-11-16
ATE224942T1 (de) 2002-10-15

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