EP0828818B1 - Produit de lavage ou detergent en granules a densite en vrac elevee - Google Patents

Produit de lavage ou detergent en granules a densite en vrac elevee Download PDF

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Publication number
EP0828818B1
EP0828818B1 EP96917393A EP96917393A EP0828818B1 EP 0828818 B1 EP0828818 B1 EP 0828818B1 EP 96917393 A EP96917393 A EP 96917393A EP 96917393 A EP96917393 A EP 96917393A EP 0828818 B1 EP0828818 B1 EP 0828818B1
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EP
European Patent Office
Prior art keywords
extruded
weight
component
detergent
granular
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EP96917393A
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German (de)
English (en)
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EP0828818A1 (fr
Inventor
Peter Sandkühler
Reiner Vogler
Dieter Jung
Eduard Smulders
Peter Krings
Kathrin Schnepp
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • 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

Definitions

  • the invention relates to a granular washing or cleaning agent high bulk densities and improved dissolving properties.
  • European patent EP-B-0 486 592 describes granular or extruded materials Detergents or cleaning agents with bulk densities above 600 g / l are known, which anionic and / or nonionic surfactants in amounts of at least Contain 15 wt .-% and up to about 35 wt .-%. You will be following a procedure manufactured in which a solid, free-flowing premix, which a Contains plasticizers and / or lubricants at high pressures between 25 and 200 bar extruded and the strand after exiting the Hole shape by means of a cutting device to the predetermined granule dimension is cut.
  • the extrudates produced can be retrofitted can be mixed with other granules, whereby in an advantageous Embodiment of the proportion of extrudates in the finished washing or detergents is more than 60% by weight.
  • the invention accordingly relates to a granular washing or Detergent with a bulk density above 600 g / l, containing one extruded component and anionic and / or nonionic surfactants in Amounts of at least 15 wt .-%, the agent at least two different has granular components, at least one of which extruded and at least one is not extruded, the extruded (n) Component (s) in amounts of 30 to 85 wt .-%, based on the total Means, in which means are contained, the content of the extruded Component (s) of surfactants (including soaps) 0 to less than 15 % By weight, based on the respective extruded component, is and at least one non-extruded granular and surfactant-containing component is contained in the amounts on average that at least by this component 1% by weight, based on the total composition, of surfactants becomes.
  • extruded components also become the granular components counted. In all cases where it is immaterial Whether a component is extruded or not is therefore the designation the granular component selected.
  • the total amount of surfactants, including soaps, in the detergents preferably 15 to 40% by weight and in particular 18 to 30% by weight.
  • Surfactants come in the granular components and in particular in the extruded components both anionic and anionic nonionic surfactants.
  • Preferred 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.
  • alkanesulfonates obtained from C 12 -C 18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • esters of ⁇ -sulfofatty acids for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, and their salts.
  • Sulfated fatty acid glycerol esters are also suitable.
  • Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and their mixtures, as obtained in the production by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol.
  • Preferred sulfonated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
  • the sulfonation products are a complex mixture which contains mono-, di- and triglyceride sulfonates with an ⁇ -position and / or internal sulfonic acid grouping.
  • sulfonated fatty acid salts, glyceride sulfates, glycerine sulfates, glycerin and soaps are formed.
  • the proportion of the ⁇ -sulfonated fatty acid disalts can be up to about 60% by weight, depending on the procedure.
  • 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 16 -C 18 alk (en) yl sulfates are particularly preferred from the point of view of washing technology. It can also be particularly advantageous, and particularly advantageous for machine washing agents, to use C 16 -C 18 alk (en) yl sulfates in combination with lower melting anionic surfactants and in particular with those anionic surfactants which have a lower Krafft point and relatively low ones Washing temperatures of, for example, room temperature to 40 ° C. show a low tendency to crystallize.
  • the compositions therefore contain mixtures of short-chain and long-chain fatty alkyl sulfates, preferably mixtures of C 12 -C 14 fatty alkyl sulfates or C 12 -C 18 fatty alkyl sulfates with C 16 -C 18 fatty alkyl sulfates or C 12 -C 16 Fatty alkyl sulfates with C 16 -C 18 fatty alkyl sulfates.
  • saturated alkyl sulfates but also unsaturated alkenyl sulfates with an alkenyl chain length of preferably C 16 to C 22 are used.
  • 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 ethylene oxide such as 2-methyl-branched C 9 -C 11 alcohols with an average of 3.5 mol 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.
  • preferred anionic surfactants are alkylbenzenesulfonates and / or both straight-chain as well as branched alkyl sulfates.
  • soaps also come in, preferably Amounts of 0.1 to 5 wt .-%, based on the total agent, into consideration.
  • saturated fatty acid soaps are 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 anionic surfactants and soaps can be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, Di- or triethanolamine.
  • the anionic are preferably located Surfactants in the form of their sodium or potassium salts, especially in the form of Sodium 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, 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 5 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 include tallow fatty alcohol with 14 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.
  • non-ionic surfactants that either as the sole nonionic surfactant or in combination with others nonionic surfactants, especially together with alkoxylated Fatty alcohols and / or alkyl glycosides are used, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated Fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the Alkyl chain, especially fatty acid methyl esters, as described, for example, in Japanese Patent Application JP 58/217598 are described or the preferably according to that in international patent application WO-A-90/13533 described methods are produced.
  • 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 may be suitable.
  • the amount of this nonionic Surfactants are preferably no more than that of the ethoxylated ones Fatty alcohols, especially not more than half of them.
  • 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 known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
  • the polyhydroxy fatty acid amides are preferably derived from reducing sugars with 5 or 6 carbon atoms, in particular from glucose.
  • the compositions contain at least 2 different granular ones Components whose only difference can be that one Component is extruded while the other component is after another Process was made.
  • the agents contain one or more extruded components, the proportion of extruded component (s) 50 to 80% by weight, based on the total agent, is. It is further preferred that at least one of the existing extruded components or in the event that only one extruded component is present then this extruded component Contains surfactants, the content of each extruded component Surfactants not more than 14% by weight, and preferably 6 to 13% by weight, each based on the extruded component. In another preferred embodiment of the invention, the agents contain surfactants extruded components in quantities such that 0.5 to 10 % By weight, based on the total agent, of surfactants are provided.
  • the extruded components can be by any of the known methods getting produced. However, a method according to is preferred the teaching of the European patent EP-B-0 486 592 or the teaching of the international Patent application WO-A-94/09111.
  • the size of the preferred almost spherical extrudates is advantageously between 0.8 and 2 mm.
  • non-extruded granular and surfactant component Anionic surfactants or anionic and nonionic surfactants preferably in Amounts of 30 to 95 wt .-%, based on the non-extruded granular Component.
  • the non-extruded granular component contains anionic surfactants, but free of non-ionic Is surfactants.
  • anionic surfactants Alkylbenzenesulfonates and / or straight-chain and / or branched Alkyl sulfates used.
  • the non-extruded granular and Surfactant-containing components are preferably in the amounts in the Contain agents that 2.25 to 30 wt .-%, in particular 5 to 25th % By weight, based in each case on the total composition, of surfactants become.
  • the weight ratio extruded component containing tenside: non-extruded component containing tenside granular component greater than 30: 1 to 2: 1 and in particular 25: 1 to 3: 1, with weight ratios between 10: 1 and 5: 1, for example 8.5: 1 to 6: 1 can be particularly preferred.
  • the non-extruded granular component or the other non-extruded granular components, especially the surfactant-containing components, can by any of the methods known today, for example by means of Spray drying, superheated steam drying, spray neutralization or granulation have been produced.
  • they contain anionic surfactants Components preferred by spray neutralization according to the German patent application DE 44 25 968 or by granulation and possibly simultaneous drying in a fluidized bed according to the teaching of international Applications WO-A-93/04162 and WO-A-94/18303 can be obtained.
  • the grain size distribution of the non-extruded surfactant-containing granules should not be fundamentally different from those for reasons of homogeneity Grain size distributions of the other components, so that the grain size spectrum is not widened too much.
  • granules in the fluidized bed can be almost produce any grain size and grain size distribution.
  • Particularly preferred are therefore non-extruded surfactant-containing granules that are almost are spherical and have a grain size distribution that is also approximately the grain size distribution of another granular component, for example an enzyme granulate, a foam inhibitor granulate, one Bleach activator granules and in particular an extruded granulate corresponds.
  • Enzymes come from the class of proteases, lipases or lipolytic acting enzymes, amylases, cellulases or their mixtures in Question.
  • Bacterial strains or fungi such as are particularly well suited Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus and Humicola insolens obtained enzymatic active substances.
  • Bacillus subtilis Bacillus licheniformis
  • Streptomyces griseus and Humicola insolens obtained enzymatic active substances.
  • Subtilisin-type proteases and in particular proteases derived from Bacillus lentus are used.
  • enzyme mixtures for example from protease and amylase or protease and lipase or lipolytic enzymes or protease and cellulase or from Cellulase and lipase or lipolytically active enzymes or from protease, Amylase and lipase or lipolytic 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.
  • lipolytic enzymes are the well-known cutinases. Also Peroxidases or oxidases have proven to be suitable in some cases.
  • the enzymes are preferably adsorbed on carriers and / or embedded in coating substances to prevent them from premature decomposition protect.
  • the proportion of enzymes, enzyme mixtures or enzyme granules can for example about 0.1 to 5% by weight, preferably 0.1 to about 2% by weight be.
  • 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 and thus form a further granular component of the agents according to the invention.
  • a granular, water-soluble or dispersible carrier substance and thus form a further granular component of the agents according to the invention.
  • Mixtures of paraffins and bistearylethylenediamides and mixtures of paraffins and silicones on inorganic carriers are particularly preferred.
  • Granules which contain mixtures of paraffins and silicones in a weight ratio of 1: 1 to 3: 1 are particularly preferred.
  • bleach activators can be incorporated into the preparations.
  • these are N-acyl or O-acyl compounds which form organic peracids with H 2 O 2 , preferably N, N'-tetraacylated diamines, p- (alkanoyloxy) benzenesulfonates, furthermore carboxylic acid anhydrides and esters of polyols such as glucose pentaacetate.
  • Other known bleach activators are acetylated mixtures of sorbitol and mannitol, as described, for example, in European patent application EP-A-0 525 239.
  • bleach activators are N, N, N ', N'-tetraacetylethylene diamine (TAED), 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine (DADHT) and acetylated sorbitol-mannitol mixtures (SORMAN).
  • the bleach activators contain bleach activators in the usual range.
  • the bleach activators are introduced in granular form, that is to say as a further granular component, in the compositions according to the invention in amounts such that the compositions contain 1 to 10% by weight and preferably 3 to 8% by weight, in each case based on the total composition Bleach activator included.
  • ingredients of the agents according to the invention are preferably inorganic and organic builder substances, bleaches, substances, which have a positive effect on oil and fat washability, graying inhibitors, optionally substances which increase solubility and Dissolving speed of the individual granular components and / or the entire Improve agents, fabric softening agents, optical brighteners, Dyes and fragrances as well as alkaline and / or neutral salts in the form of their Sodium and / or potassium salts.
  • Suitable inorganic builder substance is, for example, fine crystalline, synthetic and bound water-containing zeolite in detergent quality.
  • Zeolite A and / or P and, if appropriate, zeolite X and mixtures of A, X and / or P are particularly 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. Zeolites can be contained both in the extruded components and in the non-extruded granular components.
  • 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.
  • both ⁇ - and ⁇ -sodium disilicate Na 2 Si 2 O 5 .yH 2 O are preferred, wherein ⁇ -sodium disilicate can be obtained, for example, by the method described in international patent application WO-A-91/08171.
  • Crystalline layered sodium silicates can be contained both in the extruded and in the non-extruded granular components. However, they are preferably introduced into the composition in non-extruded granular form.
  • Amorphous silicates so-called X-ray amorphous silicates, which do not give sharp X-ray reflections in X-ray diffraction experiments, 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, can have secondary washing power and as builder substances be used. It can even lead to particularly good builder properties if the silicate particles provide 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.
  • Spray-dried sodium carbonate-sodium silicate compounds are also particularly preferred, which may additionally contain surfactants, in particular anionic surfactants such as alkylbenzenesulfonates or alkyl sulfates, including the 2,3-alkyl sulfates.
  • Amorphous silicates and silicate compounds such as the above-mentioned silicate-carbonate compounds can also be contained in the extruded as well as in the non-extruded granular components.
  • Sodium silicate with a molar ratio Na 2 O: SiO 2 of 1: 1 to 1: 4.5 is primarily used as the amorphous silicate, and preferably from 1: 2 to 1: 3.0 as the amorphous silicate.
  • the content of sodium carbonate and / or sodium bicarbonate in the agents is preferably up to 20% by weight, advantageously between 5 and 15% by weight.
  • the sodium silicate content of the compositions is generally up to 30% by weight and preferably between 2 and 25% by weight.
  • Useful organic builder substances are preferred, for example polycarboxylic acids 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), provided such use is not objectionable for ecological reasons, as well as mixtures from these.
  • Preferred salts are the salts of polycarboxylic acids such as citric acid, Adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.
  • Suitable polymeric polycarboxylates are, for example, the sodium salts 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 acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid have proven particularly suitable proven that 50 to 90 wt .-% acrylic acid and 50 to 10 wt .-% maleic acid contain.
  • Their relative molecular mass, 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.
  • Ter- and Quadropolymers for example those which according to DE-A-43 00 772 as Monomeric salts of 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.
  • Suitable builder systems are oxidation products from carboxyl-containing polyglucosans and / or their water-soluble Salts such as those used in the international patent application WO-A-93/08251 are described or their production, for example, in of international patent application WO-A-93/16110.
  • polyacetals which by reaction of dialdehydes with polyol carboxylic acids, which have 5 to 7 carbon atoms and have at least 3 hydroxyl groups, for example as in European Patent application EP-A-0 280 223 can be obtained.
  • Preferred polyacetals are derived from dialdehydes such as glyoxal, glutaraldehyde, Terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
  • the organic builder substances can be used both in the extruded and can also be used in the non-extruded granular components, use in the extruded component being preferred.
  • bleaching agents which can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid or diperdodecanedioic acid.
  • the bleaching agent content of the agents is preferably 5 to 25% by weight and in particular 10 to 20% by weight, with perborate monohydrate being advantageously used.
  • the bleaching agents can be contained both in the extruded and in the non-extruded components of the agent. It is preferred to introduce perborates into the composition via extruded components, while percarbonates are preferably used in the form of almost spherical, non-extruded granules.
  • the agents can also contain components which and grease washability from textiles positively. This effect becomes particularly clear when a textile that is already soiled is soiled previously several times with a detergent according to the invention that this oil and contains fat-dissolving component, is washed.
  • nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion on methoxyl groups from 15 to 30% by weight and on hydroxypropoxyl groups from 1 to 15% by weight, based in each case on the nonionic Cellulose ether, as well as the polymers known from the prior art Phthalic acid and / or terephthalic acid or their derivatives, in particular Polymers made from ethylene terephthalates and / or polyethylene glycol terephthalates or anionic and / or nonionic modified derivatives of these. These substances can be extruded as well also be included in the non-extruded granular components, where their content in the non-extruded granular components is preferred is.
  • Graying inhibitors have the task of removing the fiber To keep dirt suspended in the fleet and thus the rewinding of the To prevent dirt.
  • water-soluble colloids are usually more organic Suitable in nature, for example the water-soluble polymeric salts Carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids the starch or the cellulose or salts of acidic sulfuric acid esters cellulose or starch.
  • water-soluble, acidic Group-containing polyamides are suitable for this purpose.
  • Polyvinyl pyrrolidone is useful.
  • cellulose ethers are preferred, such as carboxymethyl cellulose (Na salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers, such as methylhydroxyethyl cellulose, Methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and their Mixtures and polyvinylpyrrolidone, for example in amounts from 0.1 to 5 % By weight, based on the composition.
  • carboxymethyl cellulose Na salt
  • methyl cellulose methyl cellulose
  • hydroxyalkyl cellulose and mixed ethers, such as methylhydroxyethyl cellulose, Methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and their Mixtures and polyvinylpyrrolidone, for example in amounts from 0.1 to 5 % By weight, based on the composition.
  • polyvinylpyrrolidone for example in amounts from 0.1 to 5 % By weight, based on the composition.
  • the agents can also contain components which increase the dissolution rate of the individual granular components and / or of the entire agent.
  • the components preferably used include, in particular, C 8 -C 18 alcohols with 10 to 80 moles of ethylene oxide per mole of alcohol, for example tallow fatty alcohol with 30 EO and tallow fatty alcohol with 40 EO, but also fatty alcohols with 14 EO, and polyethylene glycols with a relative molecular weight between 200 and 2000.
  • Other suitable substances are described, for example, in international patent application WO-A-93/02176.
  • the agents can, as optical brighteners, derivatives of diaminostilbenedisulfonic acid or their alkali metal salts. Suitable are e.g. Salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or similarly constructed connections that instead the morpholino group is a diethanolamino group, a methylamino group, carry an anilino group or a 2-methoxyethylamino group. Brighteners of the substituted diphenylstyryl type may also be present be, e.g.
  • sulfates optionally and in particular, can be used as neutral salts Chlorides may also be present in cleaning agents.
  • Fine-grained components are understood to mean those which have a particle size have less than 0.2 mm. For reasons of homogeneity and around Such fine grain fractions are preferred to avoid separations however only in amounts not above 10% by weight and in particular not above 5% by weight in the compositions.
  • Some fine grain components can also be used to make existing ones To powder granules, thereby stickiness of the granules, for example to reduce and the bulk densities of the individual granules as well to increase total funds.
  • Suitable such surface modifiers are known from the prior art.
  • the bulk density of the granular washing or cleaning agents is above 600 g / l, preferably between 650 and 900 g / l. Because of the high Shares in spherical granules, the phenomenon occurs that the density of the granular agent after scooping with a currently commercially available Ladle from a commercial package, the so-called ladle density, is higher than the initially determined bulk density.
  • the scooping density of the agents is above 650 g / l, in particular between 680 and 950 g / l.
  • not more than 20% by weight and in particular not more than 15% by weight of the granular components and any existing fine grain contents a bulk density of less than 600 g / l.
  • agents according to the invention are particularly suitable for producing the agents according to the invention such procedures in which several sub-components, of which at least one is extruded, with non-extruded granular components, for example spray-dried and / or granulated components together can be mixed. It is also possible that spray-dried or granulated components afterwards in the preparation, for example with nonionic surfactants, especially ethoxylated fatty alcohols, be applied according to the usual procedures.
  • nonionic surfactants especially ethoxylated fatty alcohols
  • composition in% by weight (a) C 9 -C 13 alkylbenzenesulfonate 6.54 (b) Granules of 85% by weight of the sodium salts of coconut fatty alcohol sulfate and tallow fatty alcohol sulfate in a weight ratio of 1: 1, 12% by weight of sodium sulfate, the rest unsulfated components and water; produced by granulation and simultaneous drying in the fluidized bed 14.11 (c) C 12 -C 18 fatty alcohol with 7 EO 2.90 (d) Tallow fatty alcohol with 5 EO 0.47 (e) C 12 -C 18 fatty acid soap 0.80 (f) Caustic soda 0.36 (G) Zeolite A 18.47 (H) sodium 7.75 (i) Sodium silicate (Na 2 O: SiO 2 1: 3.0) 1.45 (j) Copolymer sodium salt of acrylic acid 4.95 (k) Perborate monohydrate 14.02 (l) Tetraacetylethylenedi
  • Agent M1 contained one according to the teaching of the European one Patent EP-B-0 486 592 extrudate made from the ingredients (a), (c) to (k), (m), (o) to (r) and (s). Component (o) was used for subsequent powdering of the extruded granules. The granular components (b), (l), (n) and (q) were mixed in afterwards.
  • the comparative agent V1 contained the same components with the difference that that component (b) was coextruded and only the components (l), (n) and (q) were subsequently mixed.
  • the surfactant content of both agents was thus 21.9% by weight without soap and 22.7% by weight with soap.
  • M1 were 9.9 wt .-% without soap and 10.7 % By weight of surfactants, including soap, are introduced via the extrudate and 12 % By weight of surfactants subsequently mixed in via component (b). In V1 however, the entire amount of surfactant was introduced via the extrudate.
  • the bulk density of agents M1 and V1 were 700 g / l and 710 g / l, respectively.
  • the induction behavior of both agents via the induction chambers is more commercially available Household washing machines was excellent.
  • the grain spectrum of both agents was such that 99% by weight of all particles were not larger than 1.6 mm and more than 90% by weight of all particles were larger than 0.4 mm. Showed differences in a modified hand wash test in the dissolution behavior of the agents in water .
  • agent M1 according to the invention did not gel when water was added; the visual grading of the wrung-out towel was correspondingly good.
  • the comparative detergent V1 gelled under the same test conditions and gave worse values in the visual grading of the towel.
  • visual grading of agents M1 and V1 (tendency to gel) Bowl test towel M1 Grade 1-2 Grade 1-2 V1 Grade 4 Grade 3-4
  • compositions V2 and V3 demonstrate the influence of the surfactant content in the extruded component on the gelling when the agent is redissolved in water.
  • the surfactant content in the extruded component was increased compared to M1, and the proportion of the surfactant blended was reduced via component (b) (Table 2).
  • the total surfactant content was 21.9% by weight without soap and 22.7% by weight with soap.
  • Table 3 shows the results of the bowl test described in more detail above.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Cosmetics (AREA)

Claims (8)

  1. Produit de lavage ou de nettoyage granulaire à densité en vrac supérieure à 600 g/l, renfermant un composant extrudé ainsi que des tensioactifs anioniques et/ou non ioniques en proportions d'au moins 15 % en poids, caractérisé en ce que le produit renferme au moins deux composants granulaires différents, dont au moins un est extrudé et au moins un n'est pas extrudé, le ou les composants extrudés étant contenu(s) dans le produit en proportions de 30 à 85 % en poids (par rapport à la totalité du produit), la concentration du ou des composants extrudés en tensioactifs (y compris des savons) atteignant 0 à moins de 15 % en poids, par rapport au composant extrudé respectif, et au moins un composant granulaire non extrudé et à contenu tensioactif étant présent dans le produit en quantités telles que ce composant met à disposition au moins 1 % en poids de tensioactifs par rapport à la totalité du produit.
  2. Produit selon la revendication 1, caractérisé en ce que le composant granulaire non extrudé et à contenu tensioactif renferme des surfactifs anioniques ou des tensioactifs anioniques et non ioniques, en proportions de 30 à 95 % en poids par rapport au composant granulaire non extrudé.
  3. Produit selon la revendication 2, caractérisé en ce que le composant granulaire non extrudé renferme comme surfactifs anioniques, des alkylbenzènesulfonates et/ou des alkylsulfates à chaíne droite et/ou ramifiée, en étant toutefois de préférence exempt de tensioactifs non ioniques.
  4. Produit selon une des revendications 1 à 3, caractérisé en ce que des composants granulaires non extrudés et à contenu tensioactif sont contenus dans les produits dans des proportions telles qu'elles mettent à disposition 2,25 à 30 % en poids, en particulier 5 à 25 % en poids de tensioactifs, dans chaque cas par rapport à la totalité du produit.
  5. Produit selon une des revendications 1 à 4, caractérisé en ce qu'il renferme un ou plusieurs composants extrudés, dont un au moins contient des tensioactifs, la concentration en surfactifs de chaque composant extrudé ne dépassant pas 14 % en poids et étant comprise de préférence entre 6 et 13 % en poids, dans chaque cas par rapport au composant extrudé respectif.
  6. Produits selon une des revendications 1 à 5, caractérisé en ce qu'ils renferment des composants extrudés à contenu tensioactif en proportions telles qu'elles mettent à disposition 0,5 à 10 % en poids de tensioactifs par rapport à la totalité du produit.
  7. Produits selon une des revendications 1 à 6, caractérisé en ce que les composants extrudés, de préférence les composants extrudés à contenu tensioactif, sont contenus dans la totalité du produit à raison de 50 à 80 % en poids.
  8. Produits selon une des revendications 1 à 7, caractérisé en ce que le rapport pondéral entre le composant extrudé à contenu tensioactif et le composant granulaire non extrudé à contenu tensioactif est supérieur à 30:1 à 2:1, de préférence à 25:1 à 3:1 et en particulier, à 10:1 à 5:1.
EP96917393A 1995-05-30 1996-05-22 Produit de lavage ou detergent en granules a densite en vrac elevee Expired - Lifetime EP0828818B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19519139 1995-05-30
DE19519139A DE19519139A1 (de) 1995-05-30 1995-05-30 Granulares Wasch- oder Reinigungsmittel mit hoher Schüttdichte
PCT/EP1996/002186 WO1996038530A1 (fr) 1995-05-30 1996-05-22 Produit de lavage ou detergent en granules a densite en vrac elevee

Publications (2)

Publication Number Publication Date
EP0828818A1 EP0828818A1 (fr) 1998-03-18
EP0828818B1 true EP0828818B1 (fr) 1999-08-25

Family

ID=7762810

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Application Number Title Priority Date Filing Date
EP96917393A Expired - Lifetime EP0828818B1 (fr) 1995-05-30 1996-05-22 Produit de lavage ou detergent en granules a densite en vrac elevee

Country Status (6)

Country Link
EP (1) EP0828818B1 (fr)
AT (1) ATE183772T1 (fr)
DE (2) DE19519139A1 (fr)
DK (1) DK0828818T3 (fr)
ES (1) ES2137700T3 (fr)
WO (1) WO1996038530A1 (fr)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19524722A1 (de) * 1995-07-12 1997-01-16 Henkel Kgaa Granulares Wasch- oder Reinigungsmittel mit hoher Schüttdichte
PL337039A1 (en) 1997-05-30 2000-07-31 Unilever Nv Particulate granular detergent compositions
GB9711350D0 (en) * 1997-05-30 1997-07-30 Unilever Plc Granular detergent compositions and their production
GB9711356D0 (en) * 1997-05-30 1997-07-30 Unilever Plc Particulate detergent composition
GB9711359D0 (en) 1997-05-30 1997-07-30 Unilever Plc Detergent powder composition
IN243977B (fr) 1998-09-25 2010-11-19 Procter & Gamble
DE19915320A1 (de) * 1999-04-03 2000-10-05 Henkel Kgaa Wasch- und Reinigungsmittelformkörper mit speziellen Tensidgranulaten
KR100462265B1 (ko) * 1999-08-10 2004-12-17 더 프록터 앤드 갬블 캄파니 전해질 농도가 저하된 계면활성제 입자를 함유하는 입상세제 조성물
AU2010240944B2 (en) 2009-04-24 2013-01-10 Unilever Plc Manufacture of high active detergent particles
DE102015002877A1 (de) 2015-03-09 2016-09-15 Henkel Ag & Co. Kgaa Granulares Wasch- oder Reinigungsmittel mit verbesserter Lösegeschwindigkeit

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8811447D0 (en) * 1988-05-13 1988-06-15 Procter & Gamble Granular laundry compositions
JPH05500076A (ja) * 1989-08-09 1993-01-14 ヘンケル・コマンディットゲゼルシャフト・アウフ・アクチェン 洗剤中で使用する高密度顆粒の製造方法
DE4127323A1 (de) * 1991-08-20 1993-02-25 Henkel Kgaa Verfahren zur herstellung von tensidgranulaten
DE4203031A1 (de) * 1992-02-04 1993-08-05 Henkel Kgaa Verfahren zur herstellung fester wasch- und reinigungsmittel mit hohem schuettgewicht und verbesserter loesegeschwindigkeit
GB9205189D0 (en) * 1992-03-10 1992-04-22 Procter & Gamble Granular detergent compositions
DE4235646A1 (de) * 1992-10-22 1994-04-28 Henkel Kgaa Verfahren zur Herstellung wasch- und reinigungsaktiver Extrudate
DE4304062A1 (de) * 1993-02-11 1994-08-18 Henkel Kgaa Verfahren zur Herstellung von Tensidgranulaten
DE4406210A1 (de) * 1994-02-25 1995-08-31 Henkel Kgaa Granulares Wasch- oder Reinigungsmittel

Also Published As

Publication number Publication date
DE19519139A1 (de) 1996-12-05
WO1996038530A1 (fr) 1996-12-05
DK0828818T3 (da) 2000-02-14
ATE183772T1 (de) 1999-09-15
EP0828818A1 (fr) 1998-03-18
DE59602883D1 (de) 1999-09-30
ES2137700T3 (es) 1999-12-16

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