EP0986629B1 - Detergent granule - Google Patents

Detergent granule Download PDF

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Publication number
EP0986629B1
EP0986629B1 EP98930735A EP98930735A EP0986629B1 EP 0986629 B1 EP0986629 B1 EP 0986629B1 EP 98930735 A EP98930735 A EP 98930735A EP 98930735 A EP98930735 A EP 98930735A EP 0986629 B1 EP0986629 B1 EP 0986629B1
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EP
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Prior art keywords
acid
organic
weight
detergent
organic acids
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EP98930735A
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German (de)
English (en)
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EP0986629B2 (fr
EP0986629A1 (fr
Inventor
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 the use of organic acids / organic acid anhydrides, in particular citric acid, to support the removal of bleachable soiling on textiles in the essential bleach-free granular detergents.
  • the invention also relates granular detergents with bulk weights above 600 g / l, which can be used separately or subsequently admixed organic acids, especially citric acid, and especially are suitable for cleaning colored textiles, and a manufacturing process granular detergent.
  • Citric acid has long been known as a detergent ingredient. It was mainly used for Lowering the pH of the mostly strongly alkaline agents in the aqueous liquor, the added benefit was achieved that both the citric acid and that by Neutralize the citric acid obtained citrate (co) builder properties.
  • German patent application DE-A-28 27 571 (Akzo) already describes this in general Detergent, which is a granular alkaline, especially carbonate-containing slower solvent component and 5 to 30 wt .-% of a separate organic acid, preferably Citric acid.
  • a separate organic acid preferably Citric acid.
  • the citric acid that is already dissolving at these temperatures softens the liquor reached so that at temperatures around 40 ° C when the alkaline component begins to dissolve, the liquor is already softened such that the risk of calcium carbonate and This largely minimizes the formation of calcium carbonate residues on the textiles becomes.
  • Other components of the funds include et al Peroxy bleaches such as perborates.
  • Detergents are also used in international patent application WO-A-91/17232 (P&G) described, which as a builder 20 to 30 wt .-% zeolite, 5 to 20 wt .-% alkali metal carbonate and 1 to 3% by weight of alkali metal silicate and 4 to 10% by weight of citric acid.
  • Other ingredients are, for example, peroxy bleaching agents such as perborate.
  • the granular agents for the formation of a bulk density of 500 to 600 g / l usually be spray-dried and also contain the carbonate in the spray-dried portion the citric acid which values the pH in 1% solution in water at 20 ° C should drop between 7 and 9.3, subsequently mixed in, as the Citric acid in the spray-dried slurry already neutralizes the citric acid 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 plays again not matter. Due to the relatively low pH in the aqueous liquor, the colors should of colored textiles are better preserved.
  • Other common ingredients are in the Agents contain peroxy bleach.
  • bleaching agents have not only the effect that bleachable soiling from textiles removed, they also often catch - especially in the case of those sensitive to oxidation Qualities of textile dyes - colored textiles, so that over time the intensity the textile colors wear off and the textiles look "washed out”. It can also Use of bleaching agents for spot color removals on the textiles so-called pinhole spotting effect. Detergents have therefore been in use for some time Trade that are explicitly used for colored textiles and therefore no or only small amounts, for example less than 10% by weight, based on the total agent Have bleaching agents. With such small amounts, the bleach is only used hygienic purposes; the risk of color removal or staining of the textiles the bleaching agent can then almost be excluded. Nevertheless, it is precisely that Stain removal from colored textiles remains a problem to this day.
  • the invention therefore relates to the use of organic acids / organic acid anhydrides, in particular citric acid, as separate or subsequently admixed Component in detergents which contain less than 10% by weight of bleaching agent, based on the total detergent, as a support the removal of bleachable stains.
  • the invention also relates to a granular detergent with a bulk density from 650 g / l to 1100 g / l, containing anionic and / or nonionic surfactants and builder substances including 1 to 15 wt .-% of a separately or subsequently mixed organic acid, the agent being less than 10% by weight Contains bleach and a particle size distribution of organic acids / organic Has acid anhydrides of at least 80% of the particles larger than 1500 microns.
  • organic acids preference is given to those which are poor in that they also have a significant builder effect. These include organic acids all of which are already listed in German patent application DE 28 27 571. Also the polyhydroxydicarboxylic acids mentioned in the international patent application WO-A-94/04650 can be used. Citric acid is particularly preferred, 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 succinic anhydride and maleic anhydride are preferred. Under special Citric acid is preferred.
  • the organic acids / organic acid anhydrides are used as raw material, i.e. not in the form of a processed compound used and are therefore in the agents according to the invention as separate or subsequently admixed component.
  • "separately admixed” means that the organic acid as one of several components with the other components is mixed to the detergent.
  • all other components are first manufactured and if necessary together premixed and possibly further shaping steps of the mixed components take place and the organic acid only afterwards, ie "subsequently mixed in” becomes.
  • the organic acids can be in their commercial form with the others Components are mixed.
  • the coarser goods with particle diameters of at least 80 % By weight greater than 1500 ⁇ m can be used in the agents according to the invention without loss of performance be used.
  • This coarser product can even be advantageous from an aesthetic point of view if it is mixed into components, which also have a coarser grain spectrum have, for example granules or extrudates, which may be rounded can be and at least 80 wt .-% of particles with a particle diameter above 400 ⁇ m and especially those that have an average particle diameter have 0.8 to 1.4 mm.
  • a preferred coarser commodity of organic Acids, especially citric acid consist of at least 80% by weight of particles of one Particle size between 1500 and 2000 ⁇ m. Even more finely divided goods (80% by weight less than 350 ⁇ m) can be used in principle. But then it is preferably used for powdering of the granular components and should advantageously not be used as a separate component available in the funds.
  • this fine-particle product Particle diameters of at least 80 wt .-% less than 350 microns used.
  • Granular detergents mean particulate detergents which include at least 60 wt .-% consist of particles with a particle size above 350 microns and preferably contain at least one component which is at least 80% by weight have a particle size above 350 microns.
  • the bulk density of the agents is of less importance because the effect according to the invention is not dependent on the bulk weight.
  • Claimed according to the invention granular detergents with bulk weights between 650 and 1100 g / l, bulk densities above 700 g / l and especially above 750 g / l particularly are preferred.
  • the organic acids / organic acid anhydrides are used in the agents according to the invention in amounts of 1 to 15 % By weight, but preferably in amounts of less than 10% by weight and in particular in Amounts of 2 to 6 wt .-% used.
  • which means includes both coarse (at least 80 wt .-% greater than 1500 microns) and fine particles contain (at least 80 wt .-% less than 350 microns) organic acids, the proportion of the finely divided organic acids in the total amount of organic acids used Acids preferably at most 50% by weight and in particular 5 to 30% by weight.
  • the agents according to the invention are essentially free of bleaching agents and in particular essentially free of peroxy bleaching agents, in the context of this invention under "im is understood to be essentially free from "0 to 10% by weight.
  • the agents are absolutely free of bleach.
  • the usual peroxy bleaching agents such as perborate monohydrate, Perborate tetrahydrate and / or percarbonate are preferred.
  • agents according to the invention also include anionic and / or nonionic surfactants, it being particularly preferred if the agents contain both anionic and nonionic surfactants.
  • Preferred anionic surfactants of the sulfonate type are C 9 -C 13 alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates, and disulfonates such as are obtained, for example, from C 12 -C 18 monoolefins with an end or internal double bond by sulfonating with gaseous Sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products is considered.
  • the use of the alkylbenzenesulfonates mentioned is particularly preferred.
  • esters of ⁇ -sulfo fatty acids e.g. the ⁇ -sulfonated Methyl ester of hydrogenated coconut, palm kernel or tallow fatty acids.
  • Suitable anionic surfactants are sulfonated fatty acid glycerol esters, which are mono-, di- and Triester and their mixtures represent how they are produced by esterification by a monoglycerin with 1 to 3 moles of fatty acid or in the transesterification of triglycerides can be obtained with 0.3 to 2 mol of glycerol.
  • alk (en) yl sulfates the alkali and in particular the sodium salts of the sulfuric acid half-esters of the C 12 -C 18 fatty alcohols, for example from 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) yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical prepared on a petrochemical basis and which have a degradation behavior analogous to that of 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 from the point of view of washing technology.
  • 2,3-Alkyl sulfates which are produced, for example, according to US Pat. Nos. 3,234,258 or 5,075,041 and can be obtained as commercial products from the Shell Oil Company under the name DAN (R), are also suitable anionic surfactants.
  • the sulfuric acid monoesters of the straight-chain or branched C 7 -C 21 alcohols ethoxylated with 1 to 6 mol of ethylene oxide such as 2-methyl branched C 9 -C 11 alcohols with an average of 3.5 mol of ethylene oxide (EO) or C 12 -C 18 -Fatty alcohols with 1 to 4 EO are suitable. Because of their high foaming behavior, they are used in detergents only in relatively small amounts, for example in amounts of 1 to 5% by weight.
  • Preferred anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which represent monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain C 8 to C 18 fatty alcohol residues or mixtures thereof.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below).
  • alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
  • anionic surfactants are fatty acid derivatives of amino acids, for example of N-methyl taurine (tauride) and / or of N-methyl glycine (sarcoside).
  • the sarcosides or sarcosinates are particularly preferred, and above all Sarcosinates of higher and optionally mono- or polyunsaturated fatty acids such as oleyl sarcosinate.
  • the anionic surfactants are preferably used in relatively high amounts, i.e. in quantities above 15% by weight.
  • Anionic surfactants are advantageously in amounts between 16 and 30 wt .-%, based on the finished agent, included in the agents.
  • Suitable anionic surfactants also include soaps, preferably in quantities from 0.5 to 3 wt .-%, based on the finished agent, are included.
  • soaps preferably in quantities from 0.5 to 3 wt .-%, based on the finished agent.
  • 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 from 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 you can also use them known alkenyl succinic acid salts are used.
  • the proportion of soaps and alkenyl succinic acid salts 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 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 and / or potassium salts.
  • 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 (EO) 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.
  • EO ethylene oxide
  • alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, palm kernel, tallow fat or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly 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 thereof, 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 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 EO can also be used. Examples of these are (tallow) fatty alcohols with 14 EO, 16 EO, 20 EO, 25 EO, 30 EO or 40 EO.
  • 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 which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.
  • nonionic surfactants which are 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 with 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters, as described for example in Japanese patent application JP 58/217598 or which are preferably prepared by the process described in international patent application WO-A-90/13533.
  • nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half from that.
  • Suitable surfactants are polyhydroxy fatty acid amides of the formula (I), in the R 2 CO for an aliphatic acyl radical having 6 to 22 carbon atoms, R 3 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 polyhydroxy fatty acid amides are preferably derived from reducing sugars with 5 or 6 carbon atoms, in particular from glucose.
  • the group of polyhydroxy fatty acid amides also includes compounds of the formula (II) in which R 3 represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R 4 represents a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R 5 represents a linear, branched or cyclic alkyl radical or Aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, C 1 -C 4 -alkyl or phenyl radicals being preferred, and [Z] for a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this radical.
  • R 3 represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
  • R 4 represents a linear, branched or cyclic alkyl radical or an
  • [Z] is also preferably obtained here 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, for example according to the teaching of international patent application WO-A-95/07331, into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
  • gemini surfactants can be considered as further surfactants.
  • the two hydrophilic groups and two hydrophobic Have groups per molecule are usually identified by a so-called "Spacer" separated from each other. This spacer is usually a carbon chain, which should be long enough that the hydrophilic groups have a sufficient Have a distance so that they can act independently.
  • 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, under the term Gemini surfactants, not only dimeric but also also understood 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 trimer alcohol trissulfates and ether sulfates according to the earlier German patent application P 195 03 061.3.
  • End group capped dimeric and trimeric mixed ethers according to the older German Patent application P 195 13 391.9 is particularly characterized by its bi- and multifunctionality out.
  • the end group-capped surfactants 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 can also be used. as described in international patent applications WO-A-95/19953, WO-A-95/19954 and WO95-A- / 19955 can be described.
  • surfactants such as amphoteric surfactants, cationic surfactants and / or zwitterionic surfactants can be contained in the agents according to the invention.
  • Cationic surfactants with softening properties can be used to improve the softness of the textiles after the wash cycle or after drying.
  • the anionic and / or nonionic surfactants in the agents according to the invention is preferably 15 to 40% by weight, in particular 20 to 35% by weight, advantageously at least one non-soap anionic surfactant and at least one nonionic surfactant and possibly soap are included in the funds.
  • Agents with a nonionic content have proven to be particularly powerful Surfactants of at least 2% by weight, preferably of at least 4% by weight, have, for example, at least 5% by weight, the contents of the finished product being at nonionic surfactants between 5 and 12 wt .-% are particularly preferred, in particular when the agents are used at low temperatures below 50 ° C become.
  • the content of the agents in nonionic surfactants can exceed 12% by weight in principle lead to a further increase in the performance of the funds, but it has in Several cases have shown that the granular agents are at such high levels of nonionic surfactants increasingly lose their flowability and tend to stick to clumping can. For this reason, amounts of nonionic surfactants above 12% by weight are not special prefers.
  • Weight ratios of anionic surfactants: nonionic surfactants of at least 1: 1, preferably of 2.5: 1 up to 1.1: 1, have proven to be particularly advantageous, especially if the Soap content, based on the total surfactant content, is a maximum of 5% by weight.
  • Acids in the agents according to the invention normally contain customary inorganic and / or organic builder substances in customary amounts. For example 10 to 30% by weight of additional builder substances can be contained in the compositions.
  • the inorganic builder substances include above all zeolites, crystalline layered silicates, Carbonates, amorphous silicates and, to a lesser extent, also phosphates.
  • the finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P.
  • Zeolite P can contain, for example, zeolite MAP (R) (commercial product from Crosfield) in the compositions.
  • zeolite X 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 may 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 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 to 20 and preferred values for x are 2, 3 or 4.
  • Such crystalline layered 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 represents 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 with a modulus Na 2 O: SiO 2 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 delayed release and have secondary washing properties.
  • the delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying.
  • the term “amorphous” is also understood to mean “X-ray amorphous”.
  • silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle.
  • it can very well lead to particularly good builder properties if the silicate particles deliver washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred.
  • Such so-called X-ray amorphous silicates which also have a delay in dissolution compared to conventional water glasses, are described, for example, in German patent application DE-A-44 00 024. Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.
  • phosphates are also used as builder substances possible if such use is not avoided for ecological reasons should be.
  • the sodium salts of orthophosphates, pyrophosphates are particularly suitable and especially the tripolyphosphates.
  • Your salary in general no longer than 25% by weight, preferably not more than 20% by weight, in each case based on the finished product Medium.
  • tripolyphosphates in particular are already in smaller amounts, for example up to a maximum of 10% by weight, based on the finished agent, in combination with other builder substances to a synergistic improvement of the Secondary washing power.
  • Both the monoalkali metal salts and the dialkali metal salts of the Carbon dioxide as well as sesquicarbonates can be included in the funds.
  • Preferred alkali metal ions represent sodium and / or potassium ions.
  • the carbonate content or the bicarbonate content the average is preferably 5 to 20% by weight, in one embodiment may be preferred, the carbonate and / or bicarbonate at least partially as further Mix component separately or subsequently.
  • compounds from, for example Carbonate, silicate and optionally other auxiliary substances such as anionic surfactants or other, especially organic builder substances, can be used as separate Component present in the finished funds.
  • Another component, which is retrofitted can be admixed is silicate, for example metasilicate and / or crystalline layered disilicate.
  • the additives mentioned subsequently Components but especially carbonate, bicarbonate, metasilicate - as above described for the citric acid - to mix in coarse-grained form, being particularly it is advantageous if carbonate, bicarbonate and / or metasilicate to at least 50 wt .-% a particle size above 1 mm and in particular at least 50% by weight have above 1.2 mm.
  • carbonate, bicarbonate and / or metasilicate to at least 50 wt .-% a particle size above 1 mm and in particular at least 50% by weight have above 1.2 mm.
  • those which have an alkaline reaction in aqueous liquor are mixed or mixed separately Components, in particular carbonate, bicarbonate and / or metasilicate and / or crystalline layered disilicate, in amounts of 1 to 15% by weight, advantageously in amounts of 2 to 10% by weight.
  • Useful organic builders are, for example, those in the form of their sodium salts usable 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 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 from these.
  • the salts of the polycarboxylic acids can be in addition to the organic ones Acids may be included in the agents; however, their presence in the media is less prefers.
  • dextrins for example oligomers or polymers of carbohydrates obtained by partial hydrolysis of starches can be.
  • the hydrolysis can be carried out according to customary methods, for example acid-catalyzed or enzyme-catalyzed Procedures are carried out. They are preferably hydrolysis products with average molecular weights in the range of 400 to 500,000.
  • DE dextrose equivalent
  • Suitable cobuilders 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 in lactone form, and which have at least 4 carbon atoms and at least one hydroxyl group and at most contain two acid groups.
  • Such cobuilders are used, for example, in the 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 with a relative molecular weight from 800 to 150,000 (based on acid).
  • Suitable copolymeric polycarboxylates are in particular those of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid have been found to be particularly suitable Maleic acid proved to be 50 to 90 wt .-% acrylic acid and 50 to 10 wt .-% maleic acid contain.
  • Their relative molecular weight, based on free acids is in general 5000 to 200000, preferably 10000 to 120000 and in particular 50000 to 100000.
  • the (co) polymeric polycarboxylates can be either as a powder or as an aqueous solution are used, 20 to 55% by weight aqueous solutions being preferred.
  • Polymers composed of more than two different monomer units are also particularly preferred, for example those which, according to DE-A-43 00 772, are monomers as salts acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives or according to DE-C-42 21 381 as monomer salts of acrylic acid and 2-alkylallylsulfonic acid as well as sugar derivatives.
  • copolymers are those described in German patent applications DE-A-43 03 320 and DE-A-44 17 734 are described and preferably as monomers Have acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.
  • Suitable builder substances are oxidation products of carboxyl-containing ones Polyglucosans and / or their water-soluble salts, such as those in the international patent application WO-A-93/08251 can be described or their preparation described, for example, in international patent application WO-A-93/16110 becomes.
  • Oxidized oligosaccharides according to the German are also suitable Patent application DE 196 00 018.
  • further preferred builder substances are polymeric aminodicarboxylic acids, to name their salts or their precursors.
  • Polyaspartic acids are particularly preferred or their salts and derivatives.
  • polyacetals which are obtained by reacting dialdehydes with polyol carboxylic acids, which have 5 to 7 carbon atoms and at least 3 hydroxyl groups have, for example as in European patent application EP-A-0 280 223 described, can be obtained.
  • Preferred polyacetals are made from dialdehydes such as Glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
  • the agents can also contain components that make the oil and fat washable made of textiles. This effect is particularly evident when a textile is soiled that has already been washed several times with an inventive one Detergent containing this oil and fat-dissolving component has been washed.
  • non-ionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxyl groups from 15 to 30% by weight and from 1 to 15% by weight of hydroxypropoxyl groups, in each case based on the nonionic cellulose ether and those from the prior art known polymers of phthalic acid and / or terephthalic acid or of their Derivatives, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives of these. Of these, particular preference is given to the sulfonated derivatives of phthalic acid and Terephthalic acid polymers.
  • the agents can usually be found in detergents additives used, for example foam inhibitors, salts of polyphosphonic acids, optical brighteners, enzymes, enzyme stabilizers, graying inhibitors, contain small amounts of neutral filling salts as well as colors and fragrances.
  • Suitable 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-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 and / or paraffin-containing foam inhibitors are preferably bound to a granular, water-soluble or dispersible carrier substance. Mixtures of paraffins and bisstearylethylenediamides are particularly preferred.
  • the salts of polyphosphonic acids are preferably the neutral sodium salts for example 1-hydroxyethane-1,1-diphosphonate, diethylenetriaminepentamethylenephosphonate or ethylenediaminetetramethylene phosphonate in amounts of 0.1 to 1.5 % By weight used.
  • hydrolases such as proteases, Esterases, lipases or lipolytic enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned in question. All these Hydrolases contribute to the removal of stains, such as protein, fat or in the laundry starchy stains and graying. Cellulases and other glycosyl hydrolases can remove color and microf
  • Proteases of the subtilisin type and in particular are preferred Proteases obtained from Bacillus lentus are used.
  • enzyme mixtures for example from protease and amylase or protease and lipase or lipolytic acting enzymes or protease and cellulase or from cellulase and lipase or lipolytic enzymes or from protease, amylase and lipase or lipolytic acting enzymes or protease, lipase or lipolytically acting enzymes and cellulase, in particular, however, mixtures or mixtures containing protease and / or lipase with lipolytic enzymes of particular interest.
  • lipolytic acting enzymes are the well-known cutinases. Also peroxidases or oxidases have proven to be suitable in some cases.
  • Suitable amylases include in particular ⁇ -amylases, iso-amylases, pullulanases and pectinases.
  • As cellulases are preferably cellobiohydrolases, endoglucanases and ⁇ -glucosidases, which also Cellobiases are called, or mixtures of these are used. Because the different Distinguish cellulase types by their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases become.
  • the enzymes can be adsorbed on carriers and / or embedded in coating substances, to protect them against premature decomposition.
  • the proportion of enzymes, enzyme mixtures or enzyme granules can, for example, about 0.1 to 5 wt .-%, preferably 0.1 to about 2% by weight.
  • the agents can contain, for example, 0.5 to 1% by weight of sodium formate as enzyme stabilizers. 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.
  • 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 pyrobic acid (tetraboric acid H 2 B 4 O 7 ), is particularly advantageous.
  • Graying inhibitors have the task of removing the dirt detached from the fiber in the Keep the liquor suspended and thus prevent the dirt from re-opening.
  • 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 cellulose or salts of acidic sulfuric acid esters cellulose or starch. Also water-soluble containing acidic groups Polyamides are suitable for this purpose. Soluble starch preparations can also be used and use starch products other than the above, e.g. degraded starch, Aldehyde starches, etc. Polyvinylpyrrolidone can also be used.
  • Cellulose ethers such as carboxymethyl cellulose (Na salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as methylhydroxyethyl cellulose, methyl hydroxypropyl cellulose, Methyl carboxymethyl cellulose and mixtures thereof, and also polyvinyl pyrrolidone, for example in amounts of 0.1 to 5% by weight, based on the composition.
  • the agents can be derivatives of diaminostilbenedisulfonic acid or their Contain 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 similar connections, which instead of the morpholino group is a diethanolamino group, a methylamino group, carry an anilino group or a 2-methoxyethylamino group. Can continue Present brighteners of the substituted diphenylstyryl type, e.g.
  • the agents according to the invention or the agents produced according to the invention have in particular significant advantages in bleachable soiling.
  • Other benefits can but can also be found on enzymatic soiling, for example the primary washing performance compared to greasy and pigmented soiling in the Average is to be classified as the same.
  • the advantages occur in particular on the bleachable stains even at wash temperatures of 60 ° C and below.
  • the use of the agents according to the invention or those produced according to the invention Agent in a machine washing process at temperatures up to a maximum of 60 ° C, preferably at temperatures below 60 ° C and especially in washing programs Temperatures up to 40 ° C. Also for hand washing at 30 ° C or up to 40 ° C the agents according to the invention show advantages.
  • the application-related testing of the primary washing ability was carried out under practical Conditions in household washing machines (Miele Novotronic W918).
  • the Machines loaded with 3.5 kg of clean laundry and 0.5 kg of test fabric.
  • the test fabric were made of cotton and were made with the natural and impregnated artificial soiling. The soiling showed an aging of 5 up 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 produced in accordance with the teaching of the European patent EP-B-0 486 592 produced and essentially had the following composition: 14 wt .-% anionic surfactants (Alkyl benzene sulfonate and fatty alkyl sulfate), additionally 2% by weight of soap, 8% by weight ethoxylated fatty alcohols, 40% by weight zeolite (based on anhydrous active substance), 7 % By weight trisodium citrate dihydrate, 5.5% by weight copolymer of acrylic acid and maleic acid, 8% by weight sodium carbonate, 2% by weight polyvinylpyrrolidone (balance: water and salts from solutions).
  • the bulk density was 780 to 800 g / l.
  • the basic extrudate 2 was made according to the teaching of EP-A-0931137 produced and essentially had the following composition: 23 % By weight of anionic surfactants (alkylbenzenesulfonate and fatty alkylsulfate), additionally 1% by weight of soap, 8 % By weight of ethoxylated fatty alcohols, 27.5% by weight of zeolite (based on anhydrous active substance), 12% by weight trisodium citrate dihydrate, 5.5% by weight copolymer of acrylic acid and of maleic acid, 6.5% by weight of sodium carbonate and 5% by weight of polyethylene glycol with a relative molecular mass of 4000.
  • the bulk density was about 800 g / l.
  • the enzyme granules contained protease, amylase and cellulase in a weight ratio of 1: 1: 1.
  • the "coarse" qualities of citric acid and citrate indicated more than 50 % By weight of particles with a particle diameter above 1.5 mm.
  • the foam inhibitor granulate was a paraffin defoamer on soda as a carrier.

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  • Detergent Compositions (AREA)

Claims (10)

  1. Utilisation d'acides organiques ou d'anhydrides d'acides organiques comme composant séparé ou ajouté postérieurement par mélangeage dans des produits de lavage, qui contiennent, par rapport à la totalité du mélange, moins de 10 % en poids d'agents de blanchiment, pour faciliter l'élimination des salissures blanchissables.
  2. Utilisation selon la revendication 1, caractérisée en ce que l'on utilise comme acide organique ou comme 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. Utilisation selon la revendication 1 ou 2, caractérisée en ce que l'on utilise les acides organiques ou les anhydrides d'acide organique, en particulier l'acide citrique, avec une répartition granulométrique selon laquelle au moins 80 % en poids des particules présentent une grosseur comprise entre 1500 et 2000 µm.
  4. Utilisation selon la revendication 3, caractérisée en ce qu'en plus des acides organiques ou des anhydrides d'acides organiques à gros grains, on utilise également des acides organiques ou des anhydrides d'acides organiques en fines particules présentant une grosseur inférieure à 350 µm dans une proportion d'au moins 80 % en poids.
  5. Produit de lavage en granulés possédant une densité en vrac compris entre 650 et 1100 g/l, contenant des tensioactifs anioniques et/ou non ioniques ainsi que des substances adjuvantes, y compris 1 à 15 % en poids d'un acide organique ou d'un anhydride d'acide organique ajouté séparément ou postérieurement par mélangeage, caractérisé en ce que le produit contient moins de 10 % en poids d'agents de blanchiment (par rapport à la totalité du produit) et que les acides organiques ou les anhydrides d'acides organiques présentent une répartition granulométrique selon laquelle au moins 80 % en poids des particules présentent une grosseur supérieure à 1500 µm, auquel cas des acides organiques ou des anhydrides d'acides organiques en fines particules présentant une grosseur inférieure à 350 µm dans une proportion d'au moins 80 % en poids sont également contenus en plus le cas échéant.
  6. Produit selon la revendication 5, caractérisé en ce qu'il contient comme acide organique ou comme 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.
  7. Produit selon une des revendications 1 à 6, caractérisé en ce qu'il contient en plus de l'acide organique ou de l'anhydride d'acide organique, au moins un constituant à réaction alcaline dans un bain aqueux, sous une forme ajoutée par mélangeage postérieurement ou séparément, auquel cas les constituants à réaction alcaline dans un bain aqueux ajoutés postérieurement ou séparément, en particulier le carbonate, le bicarbonate et/ou le métasilicate et/ou le disllicate lamellaire cristallin, sont présents en proportions comprises entre 1 et 15 % en poids, avantageusement en proportions situées entre 2 et 10 % en poids.
  8. Procédé de production d'un produit de lavage en granulés présentant une densité en vrac comprise entre 650 et 1100 g/l, renfermant des tensioactifs anioniques et/ou non ioniques ainsi que des substances adjuvantes, y compris 1 à 15 % en poids d'acides organiques ou d'anhydrides d'acides organiques, ainsi que, par rapport à la totalité du produit, moins de 10 % en poids d'agents de blanchiment, caractérisé en ce que le produit est fabriqué selon des méthodes usuelles telles que séchage par pulvérisation, granulation, compactage, transformation en boulettes, extrusion, en association avec une ou plusieurs opérations de traitement intercalées à la suite, qui comprennent des étapes de formage, de séchage ou de modification superficielle par des matières liquides à cireuses ou solides et des opérations de mélangeage, auquel cas au moins l'acide organique ou l'anhydride d'acide organique, en particulier l'acide citrique, toutefois éventuellement d'autres composants également, est/sont ajouté(s) par mélangeage séparément ou postérieurement, et on obtient ainsi un produit qui renferme les acides organiques ou les anhydrides d'acides organiques comme composant séparé dans le produit fini.
  9. Procédé selon la revendication 8, caractérisé en ce que le produit est fabriqué par un procédé de granulation ou d'extrusion, ledit procédé de granulation ou d'extrusion étant modifié de telle manière que l'on fabrique tout d'abord un prémélange solide, qui contient les matières premières individuelles et/ou les compounds qui sont présents comme matière solide à température ambiante et à une pression de 1 bar et dont le point de fusion ou de ramollissement n'est pas inférieur à 45 °C, ainsi qu'éventuellement jusqu'à 10 % en poids de tensioactifs non ioniques liquides à des températures inférieures à 45 °C et à une pression de 1 bar, et qui est transformé en utilisant des forces de densification à des températures d'au moins 45°C en un granulé, lequel fait éventuellement ensuite l'objet d'une transformation ultérieure ou d'un traitement, à condition que
    le mélange soit essentiellement anhydre et que
    dans le prémélange, au moins une matière première ou un compound, qui est présent sous forme solide à une pression de 1 bar et à des températures inférieures à 45 °C, soit toutefois contenu comme masse fondue dans les conditions de transformation, ladite masse fondue servant de liant polyfonctionnel, soluble dans l'eau, qui remplit dans la fabrication des produits aussi bien une fonction de lubrifiant qu'une fonction d'adhésif pour les compounds ou les matières premières solides de produits de lavage ou de nettoyage, mais exerce en revanche une action désintégrante lors de la remise en solution du produit dans un bain aqueux, et que les acides organiques ou les anhydrides d'acides organiques soient ajoutés par mélangeage comme composant séparé dans l'étape de traltement
  10. Utilisation d'un produit conforme à une des revendications 5 à 7 ou d'un produit fabriqué selon une des revendications 8 ou 9 dans un procédé de lavage en machine, à des températures atteignant 60 °C au maximum, de préférence à des températures inférieures à 60 °C et en particulier, dans des programmes de lavage avec une température atteignant 40 °C au maximum.
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 true EP0986629B1 (fr) 2002-09-25
EP0986629B2 EP0986629B2 (fr) 2007-05-16

Family

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Application Number Title Priority Date Filing Date
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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Publication number Priority date Publication date Assignee Title
GB1569617A (en) † 1976-03-08 1980-06-18 Procter & Gamble 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
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
EP0456315B1 (fr) * 1990-05-08 1996-08-21 The Procter & Gamble Company Compositions détergentes granulaires pour le linge ayant un pH bas et contenant des renforcateurs d'aluminosilicate, d'acide citrique et de carbonate
DE4024759A1 (de) * 1990-08-03 1992-02-06 Henkel Kgaa Bleichaktivatoren in granulatform
DE59209547D1 (de) † 1991-07-17 1998-12-10 Behrensdorf Johannes Maschinengeschirrspülmittel und Verfahren zu seiner Herstellung
GB9120657D0 (en) * 1991-09-27 1991-11-06 Unilever Plc Detergent powders and process for preparing them
US5378388A (en) † 1993-06-25 1995-01-03 The Procter & Gamble Company Granular detergent compositions containing selected builders in optimum ratios
DE4325787A1 (de) † 1993-07-31 1995-02-02 Henkel Kgaa Waschmittel mit saurer Komponente
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
ID16213A (id) † 1996-03-11 1997-09-11 Kao Corp Komposisi deterjen butiran untuk mencuci pakaian
DE19638599A1 (de) * 1996-09-20 1998-03-26 Henkel Kgaa Verfahren zur Herstellung eines teilchenförmigen Wasch- oder Reinigungsmittels

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JP2002502457A (ja) 2002-01-22
WO1998055574A1 (fr) 1998-12-10
DE59805713D1 (de) 2002-10-31
DE19723616A1 (de) 1998-12-10
ES2183384T5 (es) 2007-11-16
EP0986629B2 (fr) 2007-05-16
EP0986629A1 (fr) 2000-03-22
ATE224942T1 (de) 2002-10-15
ES2183384T3 (es) 2003-03-16

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