WO1998055574A1 - Granulares waschmittel - Google Patents

Granulares waschmittel Download PDF

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Publication number
WO1998055574A1
WO1998055574A1 PCT/EP1998/003109 EP9803109W WO9855574A1 WO 1998055574 A1 WO1998055574 A1 WO 1998055574A1 EP 9803109 W EP9803109 W EP 9803109W WO 9855574 A1 WO9855574 A1 WO 9855574A1
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WIPO (PCT)
Prior art keywords
acid
weight
organic acids
agent
citric acid
Prior art date
Application number
PCT/EP1998/003109
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German (de)
English (en)
French (fr)
Inventor
Eduard Smulders
Peter Sandkühler
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
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Application filed by Henkel Kommanditgesellschaft Auf Aktien filed Critical Henkel Kommanditgesellschaft Auf Aktien
Priority to EP98930735A priority Critical patent/EP0986629B2/de
Priority to DE59805713T priority patent/DE59805713D1/de
Priority to JP50142599A priority patent/JP2002502457A/ja
Priority to AT98930735T priority patent/ATE224942T1/de
Publication of WO1998055574A1 publication Critical patent/WO1998055574A1/de

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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, in particular citric acid, to support the removal of bleachable stains on textiles in granular detergents which are essentially free of bleach.
  • the invention also relates to granular detergents with bulk densities above 600 g / l, which have separately or subsequently admixed organic acids, in particular citric acid, and are particularly suitable for cleaning colored textiles, and to a process for producing the granular detergents.
  • the use of the agents in machine washing processes at temperatures up to a maximum of 60 ° C is claimed.
  • Citric acid has long been known as a detergent ingredient. It primarily served to lower the pH of the mostly strongly alkaline agents in the aqueous liquor, the additional benefit being achieved that both citric acid and the citrate (co) builder obtained by neutralizing the citric acid have properties.
  • German patent application DE-A-28 27 571 already describes detergents which contain a granular alkaline, in particular carbonate-containing, slower-dissolving component and 5 to 30% by weight of a separate organic acid, preferably citric acid.
  • a separate organic acid preferably citric acid.
  • the liquor is already softened at temperatures of 25 ° C. by the citric acid that is already dissolving at these temperatures, so that the liquor at temperatures of around 40 ° C.
  • the international patent application WO-A-91/17232 also describes detergents which, as builders, contain 20 to 30% by weight of zeolite, 5 to 20% by weight of alkali metal carbonate and 1 to 3% by weight of alkali metal silicate and 4 to 10% by weight of citric acid sen.
  • Other ingredients are, for example, peroxy bleaching agents such as perborate.
  • the citric acid which the pH in 1% solution in water at 20 ° C to values between 7 and 9.3 should be added subsequently, since if the citric acid were also sprayed into the spray-dried slurry, the neutralization of the citric acid would already take place in the slurry and not - as desired - in the aqueous washing liquor.
  • the particle size distribution of the separately added citric acid is again irrelevant. Due to the relatively low pH in the aqueous liquor, the colors of colored textiles should be better preserved.
  • Granular detergents or cleaning agents with a bulk density of 650 to 1100 g / l which contain anionic and / or nonionic surfactants as well as builder materials etc. Containing 5 to 30 wt .-% sodium carbonate and / or bicarbonate and / or sesquicarbonate, according to the teaching of the European patent EP-B-0 534 525 (Henkel) show good dispersing properties in the aqueous liquor when they are used as further component 1 contain up to 15% by weight of citric acid added subsequently, said citric acid having to have at least 80% by weight of particles with a particle size of 350 and 1500 ⁇ m. Both smaller particle sizes and coarser granules do not lead to the desired effect of increased dispersion in an aqueous liquor. Peroxy bleaching agents are contained in the agents as further usual constituents.
  • bleaching agents not only have the effect of removing bleachable stains from textiles, they also frequently attack colored textiles, in particular in the case of oxidation-sensitive qualities of textile dyes, so that the intensity of the textile colors diminishes over time and the textiles look "washed out"
  • the use of bleaching agents can also lead to point-like color removals on the textiles, the so-called pinhole spotting effect.
  • Detergents that are explicitly used for colored textiles have therefore been on the market for some time and therefore have 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 for hygienic purposes; the risk of color removal or staining of the textiles by the bleaching agent can then almost be excluded. Nevertheless, the removal of stains from colored textiles is still a problem today.
  • the invention therefore relates to the use of organic acids, in particular citric acid, as a separate or subsequently admixed component in detergent which is essentially bleach-free to assist in removing bleachable stains.
  • the invention also relates to a granular detergent with a bulk density of 650 g / 1 to 1100 g / l, containing anionic and / or nonionic surfactants and builder substances including 1 to 15% by weight of a separately or subsequently admixed organic acid, the agent being substantially free of bleach.
  • the organic acids used are preferably those which are known to also have a significant builder effect. These organic acids include all that are already listed in German patent application DE 28 27 571.
  • the polyhydroxy-dicarboxylic acids mentioned in international patent application WO-A-94/04650 can also be used. Citric acid, tartaric acid, succinic acid, maleic acid and / or malic acid are particularly preferred.
  • acid anhydrides are also organic acids in the context of the present invention; succinic anhydride and maleic anhydride are particularly preferred here. Citric acid is used with particular preference.
  • citric acid has a better bleaching performance than, for example, tartaric acid over a wide variety of soils, although tartaric acid can achieve better results in the bleaching area than citric acid.
  • the organic acids are used as raw material, i.e. not in the form of a processed compound, and are therefore present in the agents according to the invention as separate or subsequently admixed component.
  • “Separately admixed” is understood to mean that the organic acid is mixed as one of several components with the other components to form the detergent. Depending on the manufacturing process, it is also possible that all other components are first prepared and optionally premixed with one another and possibly further shaping steps the mixed components take place and the organic acid is only added afterwards, that is to say “subsequently added”.
  • the organic acids can be mixed with the other components in their commercially available form.
  • a commercially available citric acid quality has a particle size distribution in which at least 80% by weight of the particles are between 350 and 1500 ⁇ m. But finer grades with at least 80% by weight smaller than 350 ⁇ m or coarser qualities with at least 80% by weight larger than 1500 ⁇ m are also available. Above all, 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.
  • 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, for example granules or extrudates, which may or may not be rounded and at least 80% by weight of particles with a particle diameter above 400 microns and especially those that have an average particle diameter of 0.8 to 1.4 mm.
  • a preferred coarser product of organic acids, in particular citric acid consists of at least 80% by weight of particles with a particle size between 1500 and 2000 ⁇ m. In principle, even more finely divided goods (80% by weight less than 350 ⁇ m) can be used. However, it then preferably serves to powder off the granular components and should advantageously not be present as a separate component in the compositions.
  • this finely divided product with particle diameters of at least 80% by weight less than 350 ⁇ m is also used.
  • Granular detergents are understood to mean particulate detergents which consist of at least 60% by weight of particles with a particle size above 350 ⁇ m and preferably contain at least one component which have at least 80% by weight of a particle size above 350 ⁇ m.
  • the granular compositions consist of at least 60% by weight, preferably 70 to 100% by weight, of components which have at least 80% by weight of a particle size above 350 ⁇ m.
  • the bulk density of the compositions is of less importance since the effect according to the invention is not dependent on the bulk density.
  • compact detergents or so-called concentrates with bulk densities above 600 g / l are preferred.
  • Granular detergents with 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 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% by weight. If finely divided qualities with particle diameters of at least 80% by weight less than 350 ⁇ m are used, their proportion based on the total agent is preferably not more than 2% by weight and in particular not more than 1% by weight. In the preferred embodiment of the invention, which comprises agents which contain both coarse-grained (at least 80% by weight greater than 1500 ⁇ m) and fine-particle (at least 80% by weight less than 350 ⁇ m) organic acids, the proportion of the fine-particle organic acids is Acids in the total amount of organic acids used are 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 being understood to mean “essentially free of” 0 to 10% by weight.
  • the agents are absolutely free of bleaching agents
  • the customary peroxy bleaching agents such as perborate monohydrate, perborate tetrahydrate and / or percarbonate are preferred.
  • the essential ingredients of the 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 a terminal 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.
  • the esters of ⁇ -sulfofatty acids esters of ⁇ -sulfofatty acids (ester sulfonates), for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids
  • Suitable anionic surfactants are sulfonated fatty acid glycene nests, which are monoesters, diesters and testers, and mixtures thereof, such as those produced by esterification by a monoglycene with 1 to 3 mols of fatty acid or in the transesterification of T ⁇ glycerides with 0.3 to 2 moles of glycines be preserved
  • 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 oil 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, petrochemical-based straight-chain alkyl radical which have a degradation behavior analogous to that of the appropriate compounds based on oleochemical raw materials from the washing are C 12 -C 16 alkyl sulfates and C 12 -C 15 alkyl sulfates and C 14 - C 15 alkyl sulfates especially preferably 2,3-alkyl sulfates, which patents US 3,234,258 or 5,075,041 be prepared for example according to and as Commercial products from Shell Oil Company under the name DAN (R) are available ignite 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 Cg-C, -, 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 sulfobemstone esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain C 8 -C 18 -fatty alcohol residues or mixtures from these particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below).
  • sulfosuccinates the fatty alcohol residues of which differ from ethoxylated fatty alcohols derived with narrow homolog distribution, particularly preferred. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
  • Fatty acid derivatives of amino acids for example of N-methyl taurine (taurides) and / or of N-methyl glycine (sarcosides) are suitable as further anionic surfactants.
  • the anionic surfactants are preferably used in relatively high amounts, i.e. in amounts above 15% by weight.
  • Anionic surfactants are advantageously present in the compositions in amounts between 16 and 30% by weight, based on the finished compositions.
  • Suitable anionic surfactants also include soaps, which are preferably present in amounts of 0.5 to 3% by weight, based on the finished agent.
  • Saturated fatty acid soaps are particularly suitable, 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.
  • the known alkenylsuccinic acid salts can also be used together with these soaps or as a substitute for soaps.
  • the proportion of soaps and alkenylsuccinic acid salts in the total surfactant system is preferably below 10% by weight and in particular at most 5% by weight.
  • the anionic surfactants can be in the form of their sodium, potassium or ammonium salts and also 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 radical can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
  • alcohol ethoxylates with linear residues from alcohols of native origin with 12 to 18 carbon atoms for example from coconut, palm, palm kernel, tallow or Oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol is preferred.
  • Preferred ethoxylated alcohols include, for example C 12 -C 14 alcohols with 3 EO or 4 EO, C 9 - C ⁇ r alcohols containing 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-coconut alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanol amides can also be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of them.
  • Other suitable surfactants are polyhydroxy fatty acid amides of the formula (I),
  • 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
  • [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)
  • 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
  • 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
  • [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, for example according to the teaching of international patent application WO-A-95/07331, be converted 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. These are generally understood to mean those compounds which have two hydrophilic groups and two hydrophobic groups per molecule. These groups are usually The so-called “spacer” is separated from one another. This spacer is generally a carbon chain which should be long enough that the hydrophilic groups have a sufficient spacing so that they can act independently of one another. Such surfactants are generally distinguished 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 German patent application DE-A-43 21 022 or dimer alcohol bis and trimeral alcohol trisulfates and ether sulfates according to older German patent application P 195 03 061.3.
  • End group-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-polyhydroxyfatty acid amides or poly-polyhydroxyfatty acid amides can also be used.
  • surfactants such as amphoteric surfactants, cationic surfactants and / or zwitterionic surfactants can also be present in the agents according to the invention.
  • cationic surfactants with softening properties can be used to increase the softness of the textiles after the wash or after drying.
  • the content of 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 anionic surfactant which does not consist of soap and at least one nonionic surfactant and if necessary soap is included in the funds.
  • a content of nonionic surfactants above 12% by weight of the agents can in principle lead to a further increase in the performance of the agents, but it has been shown in several cases that the granular agents lose such free flowability and stickiness at such high nonionic surfactant contents can tend to clump. For this reason, amounts of nonionic surfactants above 12% by weight are not particularly preferred.
  • Weight ratios of anionic surfactants: nonionic surfactants of at least 1: 1, preferably of 2.5: 1 to 1.1: 1, have proven to be particularly advantageous, especially when 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 builder substances in customary amounts. For example, 10 to 30% by weight of additional builder substances can be included 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 0 2x + ⁇ "yH 2 0, where M is sodium or hydrogen, x is a number from 1, 9 to 4 and y is a number from 0 to Is 20 and preferred values for x are 2, 3 or 4.
  • Such crystalline layered silicates are used in 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.
  • both ⁇ - and ⁇ -sodium disilicates Na 2 Si2 ⁇ 5-yH 2 0 are preferred.
  • the preferred builder substances also include amorphous sodium silicates with a modulus Na 2 0: Si0 2 of 1: 2 to 1: 3.3, preferably 1: 2 to 1: 2.8 and in particular 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.
  • the sodium salts of orthophosphates, pyrophosphates and in particular tripolyphosphates are particularly suitable. Their content is generally not more than 25% by weight, preferably not more than 20% by weight, based in each case on the finished composition. In some cases, it has been shown that tripolyphosphates in particular in small 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 monoalkali metal salts and dialkali metal salts of carbonic acid as well as sesquicarbonates can be included in the compositions as carbonates.
  • Preferred alkali metal ions are sodium and / or potassium ions.
  • the carbonate content or the bicarbonate content of the agents is preferably 5 to 20% by weight, although in one embodiment it may be preferred that the carbonate and / or bicarbonate at least partially as further Mix component separately or subsequently.
  • Compounds made of, for example, carbonate, silicate and optionally other auxiliaries such as anionic surfactants or other, in particular organic builder substances, can also be present as separate components in the finished compositions.
  • Another component which can be mixed in subsequently is silicate, for example metasilicate and / or crystalline layered disilicate.
  • the above-mentioned components but especially carbonate, bicarbonate, metasilicate - as described above for citric acid - in coarse-grained form, it being particularly advantageous if carbonate, bicarbonate and / or metasilicate to at least 50% by weight .-% have a particle size above 1 mm and in particular at least 50% by weight above 1.2 mm.
  • the constituents which have an alkaline reaction are mixed or mixed separately, in particular carbonate, bicarbonate and / or metasilicate and / or crystalline layered disilicate, in amounts of 1 to 15% by weight, advantageously in amounts from 2 to 10% by weight.
  • Usable organic builders are, for example, the polycarboxylic acids that can be used in the form of their sodium salts, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), as long as such use is not objectionable for ecological reasons, and mixtures of these.
  • Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.
  • the salts of the polycarboxylic acids can be contained 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 processes, for example acid-catalyzed or enzyme-catalyzed. It is preferably hydrolysis pro- Products with average molecular weights in the range from 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 contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups.
  • Such cobuilders 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 with a relative molecular weight of 800 to 150,000 (based on acid).
  • Suitable copolymeric polycarboxylates are, in particular, those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of malic acid have proven to be particularly suitable.
  • Their relative molecular weight, based on free acids is generally 5,000 to 200,000, preferably 10,000 to 120,000 and in particular 50,000 to 100,000.
  • 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 are also particularly preferred, for example those which, according to DE-A-43 00 772, are monomers as salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or according to DE-C-42 21 381 contain as monomers salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives.
  • Further preferred copolymers are those which are described in German patent applications DE-A-43 03 320 and DE-A-44 17 734 and which preferably contain acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers.
  • Suitable builder substances are oxidation products of carboxyl group-containing polyglucosans and / or their water-soluble salts, as are described, for example, in international patent application WO-A-93/08251 or whose preparation is described, for example, in international patent application WO-A-93/16110. Oxidized oligosaccha de according to German patent application DE 196 00 018 are also suitable.
  • builder substances are polymeric aminodicarboxylic acids, their salts or their precursor substances.
  • 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 carbon 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 their mixtures and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
  • the agents can also contain components which have a positive influence on the oil and fat washability from textiles. This effect becomes particularly clear when a textile is soiled that has already been washed several times beforehand with a detergent according to the invention which contains this oil and fat-dissolving component.
  • the preferred oil and fat-dissolving components include, for example, non-ionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxy groups from 15 to 30% by weight and of hydroxypropoxyl groups from 1 to 15% by weight.
  • the detergents can contain known additives commonly used in detergents, for example foam inhibitors, salts of polyphosphonic acids, optical brighteners, enzymes, enzyme stabilizers, graying inhibitors, small amounts of neutral filler salts and colorants and fragrances.
  • Suitable foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of C 18 -C 2 fatty acids.
  • Suitable non-surfactant-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, possibly signed silica, and paraffins, waxes, microcrystalline waxes and their mixtures with signed 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 which are preferably used are the neutral sodium salts of, for example, 1-hydroxyethane-1J-diphosphonate, diethylenetriaminepentamethylenephosphonate or ethylenediaminetetramethylenephosphonate in amounts of 0.1 to 1.5% by weight.
  • Particularly suitable enzymes are those from the class of hydrolases, such as proteases, esterases, lipases or lipolytically active enzymes, amylases, cellulases or other glycosyl hydrolases, and mixtures of the enzymes mentioned. All of these hydrolases contribute to the removal of stains, such as stains containing protein, fat or starch, and graying in the laundry. By removing pilling and microfibrils, cellulases and other glycosyl hydrolases can help maintain color and increase the softness of the textile. Oxidoreductases can also be used for bleaching or for inhibiting color transfer.
  • hydrolases such as proteases, esterases, lipases or lipolytically active enzymes, amylases, cellulases or other glycosyl hydrolases, and mixtures of the enzymes mentioned. All of these hydrolases contribute to the removal of stains, such as stains containing protein, fat or starch, and graying in the laundry. By removing pilling
  • Enzymatic active substances obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus and Humicola insolens are particularly suitable.
  • Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used.
  • enzyme mixtures for example of protease and amylase or protease and lipase or lipolytically active enzymes or protease and cellulase or of cellulase and lipase or lipolytically active enzymes or of protease, amylase and lipase or lipolytically active enzymes or protease, lipase or lipolytic enzymes and cellulase, but especially protease- and / or lipase-containing mixtures or mixtures with lipolytic enzymes of particular interest.
  • Known cutinases are examples of such lipolytically active enzymes.
  • Peroxidases or oxidases have also proven to be suitable in some cases.
  • Suitable amylases include in particular ⁇ -amylases, iso-amylases, pullulanases and pectinases.
  • Cellobiohydrolases, endoglucanases and ⁇ -glucosidases, which are also called cellobiases, or mixtures thereof, are preferably used as cellulases. Since the different cellulase types differ in their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases.
  • the enzymes can be adsorbed on carriers and / or embedded in coating substances in order to protect them against premature decomposition.
  • the proportion of the enzymes, enzyme mixtures or enzyme granules can be, for example, approximately OJ to 5% by weight, preferably 0.1 to approximately 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 B0 3 ), metaboric acid (HB0 2 ) and pyrobic acid (tetraboric acid H 2 B 4 0 7 ), is particularly advantageous.
  • Graying inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being re-absorbed.
  • Water-soluble colloids of mostly organic nature are suitable for this, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
  • Water-soluble polyamides containing acidic groups are also suitable for this purpose. Soluble starch preparations and other starch products than those mentioned above can also be used, eg degraded starch, Aldehyde starches, etc. Polyvinylpyrrolidone can also be used.
  • cellulose ethers such as carboxymethyl cellulose (sodium salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers, such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethylceilulose and mixtures thereof, and also polyvinylpyrrolidone, for example in amounts of from 0 to 5% by weight, based on the composition, are preferably used.
  • the agents can contain derivatives of diaminostilbenedisulfonic acid or its alkali metal salts. Suitable are e.g. Salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-thazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of similar structure which, instead of the morpholino group, have a diethanolamino group , a methylamino group, an anilino group or a 2-methoxyethylamino group.
  • brighteners of the substituted diphenylstyryl type may be present, e.g.
  • the granular detergents according to the invention can be produced by any known process, such as spray drying, granulation, compacting, pelleting, extrusion in combination with one or more downstream preparation processes, which include shaping steps, drying or surface modification with liquid to waxy or solid substances and mixing processes, wherein at least the organic acid, in particular the citric acid, but optionally also other components, are mixed separately or subsequently, and an agent is thus produced which contains the organic acids in the finished product as a separate component.
  • Granulation and extrusion methods are advantageously used to achieve the high bulk density.
  • An extrusion process is particularly preferred, which is described, for example, in European patents and international patent applications EP-B-0 486 592, WO-A-94/091 11, WO-A-96/38530.
  • the granules or extrudates are produced in accordance with the teaching of German patent application P 196 38 599.7, the granulation or extrusion process being modified in such a way that a solid premix is first prepared which comprises individual raw materials and / or contains compounds which are present as a solid at room temperature and a pressure of 1 bar and have a melting point or softening point not below 45 ° C, and optionally up to 10% by weight at temperatures below 45 ° C and a pressure of 1 bar contains liquid non-ionic surfactants, and using compression forces at temperatures of at least 45 ° C converted into a grain and optionally subsequently processed or processed, with the provisos that the premix is essentially water-free and in the premix at least one raw material or compound which at a pressure of 1 bar and temperatures below 45 ° C.
  • melt serving as a polyfunctional, water-soluble binder which, in the preparation of the compositions, functions both as a lubricant and as an adhesive function for the solid detergent or cleaning agent compounds or exerts raw materials, on the other hand has a disintegrating effect when the agent is redissolved in an aqueous liquor and at least the organic acids are mixed in as a separate component in the treatment step.
  • the agents according to the invention or the agents produced according to the invention have significant advantages, particularly on bleachable soiling. However, further advantages can also be found, for example, on enzymatic soiling, while the primary washing performance compared to fatty and pigment-containing soiling can be classified as the same on average. Surprisingly, the advantages of bleachable soiling occur even at washing temperatures of 60 ° C and below.
  • the use of the agents according to the invention or the agents produced according to the invention is therefore claimed in a machine washing process at temperatures up to a maximum of 60 ° C., preferably at temperatures below 60 ° C. and in particular in washing programs with temperatures up to 40 ° C. .
  • the agents according to the invention also show advantages in hand washing at 30 ° C. or up to 40 ° C.
  • the application-related testing of the primary washing ability was carried out under practical conditions in household washing machines (Miele Novotronic W918).
  • the machines were loaded with 3.5 kg of clean laundry and 0.5 kg of test fabric.
  • the test fabrics consisted of cotton and were impregnated with the natural and artificial stains explained in more detail below.
  • the soiling showed an aging of 5 to 6 days.
  • red wine R
  • tea Messmer, TEE
  • instant coffee Nescafe, IK
  • currant juice Eden, J
  • blueberry juice Eden, H
  • compositions had the following compositions (in parts by weight). M1 V V1 M2 V2 V3
  • the base granulate 1 was produced in accordance with the teaching of the European patent EP-B-0 486 592 and essentially had the following composition: 14% by weight anionic surfactants (alkylbenzenesulfonate and fatty alkyl sulfate), additionally 2% by weight 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 (rest: water and salts from solutions).
  • the bulk density was 780 to 800 g / l.
  • a base granulate which had been produced by conventional granulation / compaction and had approximately the same composition and the same bulk density gave comparable results.
  • the base extrudate 2 was produced in accordance with the teaching of German patent application P 196 38 599.7 and essentially had the following composition: 23% by weight of anionic surfactants (alkylbenzenesulfonate and fatty alkyl sulfate), 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 of trisodium citrate dihydrate, 5.5% by weight of copolymer of acrylic acid and maleic acid, 6.5% by weight of sodium carbonate and 5% by weight .-% 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 a weight ratio of 1: 1: 1.
  • the "coarse" qualities of citric acid and citrate contained 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.
  • the primary washing results are summarized (in part) in Tables 1 to 6.
  • the abbreviation AW always means "initial value of the test soiling". All tables show that the agents according to the invention have clear advantages over bleachable soils (in particular at 40 ° C.), and in some cases also for enzymatic soils. There were fatty soils and pigment-containing soils on average, the results were comparable both at 40 ° C. and at 60 ° C. In the case of cosmetic soiling, clear advantages were again achieved in certain cases for the agents according to the invention (not listed in tables).
  • Examples M1 and V1 were repeated with organic acids other than citric acid: succinic anhydride, tartaric acid and malic acid.
  • succinic anhydride succinic anhydride
  • tartaric acid tartaric acid
  • malic acid succinic anhydride

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
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PCT/EP1998/003109 1997-06-05 1998-05-27 Granulares waschmittel WO1998055574A1 (de)

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EP98930735A EP0986629B2 (de) 1997-06-05 1998-05-27 Granulares waschmittel
DE59805713T DE59805713D1 (de) 1997-06-05 1998-05-27 Granulares waschmittel
JP50142599A JP2002502457A (ja) 1997-06-05 1998-05-27 粒状洗剤
AT98930735T ATE224942T1 (de) 1997-06-05 1998-05-27 Granulares waschmittel

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DE19723616A DE19723616A1 (de) 1997-06-05 1997-06-05 Granulares Waschmittel

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6573231B2 (en) 2000-03-13 2003-06-03 Unilever Home & Personal Care Division Of Conopco, Inc. Detergent compositions
US6908895B2 (en) 2001-05-16 2005-06-21 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Particulate laundry detergent composition containing zeolite
WO2020109227A1 (en) 2018-11-28 2020-06-04 Unilever N.V. Large particles

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* 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.
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

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DE3812455A1 (de) * 1987-04-15 1988-10-27 Sandoz Ag Bleichmittelersatz fuer waschmittel
EP0388389A2 (en) * 1989-03-16 1990-09-19 Monsanto Europe S.A./N.V. Improved detergent compositions
WO1991017232A1 (en) * 1990-05-08 1991-11-14 The Procter & Gamble Company Low ph granular laundry detergent compositions containing aluminosilicate, citric acid and carbonate builders
WO1992002608A1 (de) * 1990-08-03 1992-02-20 Henkel Kommanditgesellschaft Auf Aktien Bleichaktivatoren in granulatform
EP0534525A2 (en) * 1991-09-27 1993-03-31 Unilever N.V. Detergent powders and process for preparing them
WO1995020029A1 (de) * 1994-01-25 1995-07-27 Henkel Kommanditgesellschaft Auf Aktien Gerüststoff für wasch- oder reinigungsmittel
WO1995027027A1 (en) * 1994-03-31 1995-10-12 The Procter & Gamble Company Detergent composition comprising zeolite map builder
WO1998012299A1 (de) * 1996-09-20 1998-03-26 Henkel Kommanditgesellschaft Auf Aktien Verfahren zur herstellung eines teilchenförmigen wasch- oder reinigungsmittels

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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
DE4223265A1 (de) † 1991-07-17 1993-03-18 Behrensdorf Johannes Maschinengeschirrspuelmittel und verfahren zu seiner herstellung
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
ID16213A (id) † 1996-03-11 1997-09-11 Kao Corp Komposisi deterjen butiran untuk mencuci pakaian

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Publication number Priority date Publication date Assignee Title
DE3812455A1 (de) * 1987-04-15 1988-10-27 Sandoz Ag Bleichmittelersatz fuer waschmittel
EP0388389A2 (en) * 1989-03-16 1990-09-19 Monsanto Europe S.A./N.V. Improved detergent compositions
WO1991017232A1 (en) * 1990-05-08 1991-11-14 The Procter & Gamble Company Low ph granular laundry detergent compositions containing aluminosilicate, citric acid and carbonate builders
WO1992002608A1 (de) * 1990-08-03 1992-02-20 Henkel Kommanditgesellschaft Auf Aktien Bleichaktivatoren in granulatform
EP0534525A2 (en) * 1991-09-27 1993-03-31 Unilever N.V. Detergent powders and process for preparing them
WO1995020029A1 (de) * 1994-01-25 1995-07-27 Henkel Kommanditgesellschaft Auf Aktien Gerüststoff für wasch- oder reinigungsmittel
WO1995027027A1 (en) * 1994-03-31 1995-10-12 The Procter & Gamble Company Detergent composition comprising zeolite map builder
WO1998012299A1 (de) * 1996-09-20 1998-03-26 Henkel Kommanditgesellschaft Auf Aktien Verfahren zur herstellung eines teilchenförmigen wasch- oder reinigungsmittels

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6573231B2 (en) 2000-03-13 2003-06-03 Unilever Home & Personal Care Division Of Conopco, Inc. Detergent compositions
US6908895B2 (en) 2001-05-16 2005-06-21 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Particulate laundry detergent composition containing zeolite
WO2020109227A1 (en) 2018-11-28 2020-06-04 Unilever N.V. Large particles

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

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