EP0840780B1 - Produit granule de lavage ou de nettoyage a masse volumique apparente elevee - Google Patents

Produit granule de lavage ou de nettoyage a masse volumique apparente elevee Download PDF

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Publication number
EP0840780B1
EP0840780B1 EP96922901A EP96922901A EP0840780B1 EP 0840780 B1 EP0840780 B1 EP 0840780B1 EP 96922901 A EP96922901 A EP 96922901A EP 96922901 A EP96922901 A EP 96922901A EP 0840780 B1 EP0840780 B1 EP 0840780B1
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Prior art keywords
weight
extruded
detergent
component
surfactant
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EP96922901A
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German (de)
English (en)
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EP0840780A1 (fr
Inventor
Kathrin Schnepp
Josef Markiefka
Adolf Wiche
Eric Schumacher
Manfred Greger
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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 one composed of several granular components Detergent or cleaning agent with high bulk density and an extrusion process for Manufacture of intermediate products used in the manufacture of such agents become.
  • European patent EP-B-0 486 592 describes granular or extruded washing or detergents with bulk densities above 600 g / l, which are anionic and / or nonionic surfactants in amounts of at least 15% by weight and up to about 35 % By weight. They are manufactured using a process in which a solid, free-flowing Premix containing a plasticizer and / or lubricant at high Pressures between 25 and 200 bar extruded and the extrudate exits the hole shape by means of a cutting device to the predetermined granule dimension is cut and then rounded using a rounding device. The so produced extrudates can be subsequently mixed with other granules, in an advantageous embodiment, the proportion of extrudates in the finished Washing or cleaning agents is more than 60% by weight.
  • German patent application DE 43 35 966 also relates to a further development of the mentioned process, in that alkyl sulfates with 8 to 14th Carbon atoms alone or in a mixture in the form of one in a fluidized bed incorporated granulated granules into the premix to be extruded.
  • nonionic surfactants, sodium silicate and salts of copolymers of acrylic acid and maleic acid as a plasticizer or lubricant is in this document also disclosed.
  • a detergent with a Bulk density above 600 g / l from at least two different granular components build up, at least one extruded and at least one not extruded the extruded component (s) in amounts of 30% by weight to 85% by weight, based on the total agent in which agent is (are) the content of the extruded Component (s) of surfactant is less than 15 wt .-% and at least one Non-extruded granular and surfactant-containing components contained in the amounts on average is that by this component at least 1 wt .-%, based on the total agent, of surfactants is provided.
  • the relatively low-surfactant extruded components of the above-mentioned German patent application 195 19 139 only allows the bulk density to increase above a value of about 750 g / l, if you want to accept a lower grain stability of the extruded component.
  • This lower grain stability manifests itself in the fact that when mixed with the others granular components or, in extreme cases, directly afterwards in the rounding step at the extrusion the extruded component disintegrates and - possibly by the loss of their approximately spherical shape to irregular granules and thus - to a reduction in the bulk weight of the entire composition as well Deterioration of its trickle and pour behavior.
  • the invention accordingly relates to a granular washing or Detergent with a bulk density above 600 g / l, containing an extruded Component as well as anionic and / or nonionic surfactants in amounts of at least 15% by weight, with at least two different granular components in the agent are included, of which at least one is extruded and at least one is not extruded is, the extruded component (s) in amounts of 30 to 85 wt .-%, based to the entire medium, which contains (are) and at least one non-extruded Granular and surfactant-containing components included in the amounts on average is that by this component at least 1 wt .-%, based on the total agent, of surfactants is provided, the content of the extruded component (s) Surfactants 0 to less than 35 wt .-%, in particular 5 wt .-% to 24 wt .-%, based to the respective extruded component, and at least one
  • structure breaker follows from that in German Patent application DE 41 24 701 used use of this term with the Exception that water in the sense of the present invention is not a structure breaker is understood. However, this also applies to the extruded components here strive for the lowest possible free water content.
  • Another object of the invention is therefore a method for manufacturing a preliminary product that is suitable for the production of granular detergents and cleaning agents with a bulk density above 600 g / l, whose surfactant content is 0 to less than 35% by weight and which has a bulk density of at least 760 g / l, preferably in the range from 770 g / l to 870 g / l and in particular in the range from 790 g / l up to 850 g / l, by extrusion of a premix, which preferably by Extrusion of a pre-mix containing tower powder is produced and characterized is that it is free from structural breakers and non-surfactant organic plasticizers and there is inorganic neutral salt contained in it in amounts of, in each case based on the neutral salt content in the preliminary product, 10% by weight to 65% by weight.
  • separate admixtures should be used mean that the neutral salt as a single component, for example as Powder, or as a powdery mixture of several neutral salts and not as part of granular components that contain other ingredients, for example Surfactants.
  • the amounts of neutral salt separately mixed in this way are preferably 1% by weight to 5% by weight, based on the premix to be extruded.
  • extruded components are also counted among the granular components. In the Cases where it doesn't matter whether a component is extruded or not therefore the overarching term of the granular component is chosen.
  • the surfactants including soaps, are present in the agents according to the invention in total preferably 15% by weight to 40% by weight and in particular 18% by weight to 30% by weight.
  • Suitable surfactants in the granular components and in particular in the extruded components are both anionic surfactants and mixtures of 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 those obtained from C 12 -C 18 monoolefins with an end or internal double bond by sulfonating Gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products.
  • alkanesulfonates obtained from C 12 -C 18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • esters of ⁇ -sulfo fatty 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 glycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol.
  • Preferred sulfated 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. If one starts from the sulfonation of saturated fatty acids or hardened fatty acid glycerol ester mixtures, 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 C 12 to C 18 fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 to C 20 alcohol 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 - to 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 - to C 18 -alk (en) yl sulfates in combination with lower melting anionic surfactants and in particular with those anionic surfactants which have a lower power point and relative low 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 to C 14 fatty alkyl sulfates or C 12 to C 18 fatty alkyl sulfates with C 16 to C 18 fatty alkyl sulfates or C 12 to C 16 fatty alkyl sulfates with C 16 to 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, for example, according to US Pat. Nos. 3,234,258 or 5,075,041 and sold as Shell Oil Company's commercial product under the Suitable DAN® names are 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 are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially 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, viewed in isolation, are nonionic surfactants as described by unteen.
  • alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
  • the particularly preferred anionic surfactants include alkylbenzenesulfonates and / or both straight-chain as well as branched alkyl sulfates.
  • soaps are also preferred in amounts of 0.1 to 5 wt .-%, based on the total agent.
  • Suitable are, for example, saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, Palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid and in particular from natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived Soap mixtures.
  • the anionic surfactants including the soaps can be in the form of their sodium, potassium or Ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine, available.
  • the anionic surfactants are preferably in the form of their Sodium or potassium salts, especially in the form of the 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 can 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 to C 14 alcohols with 3 EO or 4 EO, C 9 to C 11 alcohols with 7 EO, C 13 to C 15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12 to C 18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C 12 to C 14 alcohol with 3 EO and C 12 to 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 is a primary straight-chain or branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms and G stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
  • the degree of oligomerization x which reflects the statistical distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.
  • nonionic surfactants which either as sole nonionic surfactant or in combination with other nonionic surfactants, used in particular together with alkoxylated fatty alcohols and / or alkyl glycosides are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated Fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters, as described, for example, in the Japanese patent application JP 58/217598 are described or which preferably according to that in the international Patent application WO-A-90/13533 can be prepared.
  • nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can be suitable.
  • the amount of such nonionic surfactants is preferably not more than that of ethoxylated fatty alcohols, especially not more than half of it.
  • Suitable surfactants are fatty acid polyhydroxyamides 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 components, the only difference being that one component is extruded, while the other component was made by a different process.
  • the extruded component (s) and the non-extruded (n) differ Component (s) but also in their composition.
  • the agents contain one or more extruded component (s), the proportion of the extruded component (s) 50 to 80 % By weight, based on the total average. It is further preferred that at least one of the existing extruded components or in the event that only there is an extruded component that then contains the extruded component surfactants, the surfactant content of each extruded component being less than 15% by weight, in particular not more than 14% by weight and preferably 6 to 13% by weight, in each case based on the extruded component.
  • the agents contain surfactant-containing extruded components in the amounts that thereby 0.5 wt .-% to 30 wt .-%, in particular 6 wt .-% to 25% by weight, based in each case on the total composition, of surfactants are provided.
  • the extruded components can be by any of the known methods getting produced. However, a method according to the teaching of European patent EP-B-0 486 592 or the teaching of the international patent application WO-A-94/09111.
  • the size of the almost spherical extrudates thus produced is preferably between 0.8 mm and 2 mm.
  • the non-extruded granular and surfactant-containing component contains anionic surfactants or a combination of anionic and nonionic surfactants, preferably in amounts of 30 up to 95% by weight, based on the non-extruded granular component. It is preferred that the non-extruded granular component contains anionic surfactants, but largely free of nonionic surfactants. Alkylbenzenesulfonates are advantageously used as anionic surfactants and / or straight-chain and / or branched alkyl sulfates are used.
  • non-extruded granular and surfactant-containing components are preferred contained in the amounts in the agents that through them 2 wt .-% to 30 wt .-%, in particular 5 wt .-% to 25 wt .-%, each based on the total agent, of surfactants to be provided.
  • surfactant-containing extrusions are extruded Components and surfactant-containing non-extruded granular components used, the weight ratio of surfactant-containing extruded component to Non-extruded granular component containing surfactant 6: 1 to 2: 1 and in particular 5: 1 is up to 3: 1
  • non-extruded granular component or the further non-extruded granular component Components can be added to any of the processes known today, for example by means of spray drying, hot steam drying, Spray neutralization or granulation.
  • anionic surfactants granular components preferred by spray neutralization according to the German patent application DE 44 25 968 or by granulation and optionally simultaneous drying in a fluidized bed according to the teaching of international Patent applications WO-A-93/04162 and WO-A-94/18303 can be obtained.
  • the grain size distribution The non-extruded granules containing surfactants should be used for reasons of homogeneity not fundamentally different from the grain size distributions of the other components be, so that the grain size spectrum is not broadened too much.
  • granules in the fluidized bed of produce almost any grain size and grain size distribution.
  • Particularly preferred are therefore non-extruded granules containing surfactants that are almost spherical and one Have grain size distribution that is roughly the same as the grain size distribution of another granular component, for example an enzyme granulate, a foam inhibitor granulate, a bleach activator granulate and in particular an extruded granulate corresponds.
  • Enzymes which may be present in agents according to the invention are used the class of proteases, lipases, cutinases, amylases, pullulanases, cellulases, Oxidases, peroxidases or mixtures thereof in question. Particularly suitable are from bacterial strains or fungi, such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus and Humicola insolens enzymatic active ingredients obtained. Proteases of the subtilisin type and in particular proteases which are preferred Bacillus lentus are used.
  • enzyme mixtures for example from protease and amylase or protease and lipase or lipolytic acting enzymes or protease and cellulase or from cellulase and lipase or lipolytically active enzymes or from protease, amylase and lipase or lipolytically active enzymes or protease, lipase or lipolytic enzymes and cellulase, but especially protease and / or Mixtures containing lipase or mixtures with lipolytic agents Enzymes of special interest.
  • lipolytic enzymes are known cutinases.
  • the enzymes are preferably adsorbed on carriers and / or embedded in coating substances to protect them against premature decomposition.
  • the amount of the enzymes, enzyme mixtures or enzyme granules can, for example, about 0.1% by weight to 5 wt .-%, preferably 0.1 wt .-% to about 2 wt .-%.
  • 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 bistearylethylenediarnide. Mixtures of different foam inhibitors are also used with advantages, for example those made of silicone, 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.
  • Mixtures of paraffins and bistearylethylenediamide 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, bleaching agents, substances that reduce the oil and fat washability positively influence graying inhibitors, possibly substances which the solubility and the rate of dissolution of the individual granular components and / or improve the total agent, textile softening substances, 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 and 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 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 Is 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 disilicates Na 2 Si 2 O 5 ⁇ yH 2 O are preferred, with ⁇ -sodium can be obtained for example by the method / described in the international patent application WO-A-91 08171 as.
  • 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 are used in X-ray diffraction experiments do not provide sharp X-ray reflections as they do for crystalline substances are typical, 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 secondary washing ability own and are used as builder substances. It can even lead to particularly good builder properties if the silicate particles contribute Electron diffraction experiments blurred or even sharp diffraction maxima deliver.
  • 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 sodium carbonate and / or sodium bicarbonate content of the agents is preferably up to 20% by weight, advantageously between 5% by weight and 15% by weight.
  • the sodium silicate content of the agents is generally up to 30% by weight and preferably between 2% by weight and 25% by weight.
  • Usable organic builders are, for example, the preferred ones in the form of their Sodium salts used polycarboxylic acids, such as citric acid, adipic acid, succinic acid, Glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided that such use is not objectionable for ecological reasons, and mixtures of these.
  • Preferred salts are the salts of polycarboxylic acids such as Citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and Mixtures of these.
  • Suitable polymeric polycarboxylates are, for example, the sodium salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight from 800 to 150,000 (based on acid).
  • Suitable copolymeric polycarboxylates are in particular those of acrylic acid with methacrylic acid and acrylic acid or Methacrylic acid with maleic acid. Copolymers of Acrylic acid with maleic acid, 50 to 90 wt .-% acrylic acid and 50 to 10 % By weight of maleic acid.
  • Their relative molecular mass, based on free acids, is generally 5,000 to 200,000, preferably 10,000 to 120,000, and especially 50,000 to 100,000.
  • terpolymers and quadropolymers for example those which according to the German patent application DE-A-43 00 772 as Monomeric salts of acrylic acid and maleic acid as well as vinyl alcohol respectively Vinyl alcohol derivatives or according to German patent DE-C-42 21 381 as monomers Contain salts of acrylic acid and 2-alkylallylsulfonic acid as well as sugar derivatives.
  • Suitable builder systems are oxidation products of carboxyl-containing ones Polyglucosans and / or their water-soluble salts, such as those used in the international Patent application WO-A-93/08251 can be described or their preparation is described, for example, in international patent application WO-A-93/16110.
  • Also known as other preferred builder substances are the known polyaspartic acids or to name their salts and derivatives.
  • polyacetals which are obtained by reacting dialdehydes with polyol carboxylic acids, which have 5 to 7 carbon atoms and at least 3 hydroxyl groups have, for example, as in European patent application EP-A-0 280 223 can be obtained.
  • Preferred polyacetals are made from Dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and obtained from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
  • the organic builder substances can be found both in the extruded and in the non-extruded granular components are used, the use in the extruded component is preferred.
  • sodium perborate tetrahydrate and sodium perborate monohydrate and sodium percarbonate are of particular importance.
  • Other useful bleaching agents are, for example, peroxypyrophosphates, citrate perhydrates and 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% by weight to 20% by weight, advantageously using perborate monohydrate and / or percarbonate.
  • 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 that make oil and fat washable made of textiles. This effect is particularly evident if a textile is soiled, which has previously been repeatedly with an inventive Detergent containing this oil and fat-dissolving component is washed.
  • the preferred oil- and fat-dissolving components include, for example, nonionic Cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of Methoxyl groups from 15 to 30 wt .-% and hydroxypropoxyl groups from 1 to 15 %
  • nonionic Cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of Methoxyl groups from 15 to 30 wt .-% and hydroxypropoxyl groups from 1 to 15 %
  • Graying inhibitors have the task of removing the dirt detached from the fiber in the Keep the liquor suspended and thus prevent the dirt from re-opening.
  • Water-soluble colloids of mostly organic nature are suitable for this purpose, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic Sulfuric acid esters of cellulose or starch.
  • water-soluble, acidic groups containing polyamides are suitable for this purpose.
  • soluble ones Use starch preparations and starch products other than the above, for example degraded starch and aldehyde starches. Polyvinyl pyrrolidone can also be used.
  • cellulose ethers such as carboxymethyl cellulose (sodium salt), methyl cellulose, Hydroxyalkyl cellulose and mixed ethers, such as methylhydroxyethyl cellulose, methyl hydroxypropyl cellulose, Methyl carboxymethyl cellulose and mixtures thereof, and polyvinyl pyrrolidone for example in amounts of 0.1 to 5% by weight, based on the composition, used.
  • These substances can also be used both in the extruded and in the non-extruded granular components may be included.
  • the agents can be derivatives of diaminostilbenedisulfonic acid or whose alkali metal salts contain. Suitable are e.g. Salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or similar built-up compounds that instead of the morpholino group a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group wear. Brighteners of the substituted diphenylstyryl type may also be present be, e.g.
  • fine-grained components are understood to be those which have a particle size smaller than 0.2 mm. Out Such fine grain fractions are reasons of homogeneity and to avoid separations however, preferably only in amounts not above 10% by weight and in particular not above 5% by weight in the compositions.
  • Some fine-grained components can also be used to make existing granules to powder, thereby reducing stickiness of the granules and the Increase bulk densities of the individual granules as well as the entire agent.
  • Suitable such surface modifiers are, for example, from the international patent application WO-A-994/01526 known.
  • the bulk density of the granular washing or cleaning agents is preferably above 600 g / l at least 725 g / l and in particular in the range from 745 g / l to 950 g / l. Due to the high proportion of 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 density of the agents is preferably included Values above 790 g / l, especially in the range from 800 g / l to 820 g / l. To be like that To achieve high densities of the entire agent, it is necessary that the individual and in particular the granular components already have high bulk densities.
  • Suitable processes for the preparation of the agents according to the invention are, in particular, 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 can be mixed together. It is also there possible that spray-dried or granulated components subsequently in the preparation ready for sale, for example with nonionic surfactants, in particular ethoxylated fatty alcohols can be applied according to the usual procedures.
  • the agent for example carbonates, citrate or Citric acid or other polycarboxylates or polycarboxylic acids, polymers Polycarboxylates, zeolite and / or layered silicates, for example layered crystalline ones Disilicates, are added, with the proportion of fine grain on average, that is Particles with a particle size below 0.2 mm, not above 15% by weight, in particular should not be above 5% by weight, based in each case on the total agent.
  • the proportion of fine grain on average that is Particles with a particle size below 0.2 mm, not above 15% by weight, in particular should not be above 5% by weight, based in each case on the total agent.
  • the agents listed in Table 1 above each contained an extrudate ( VE1 , VE2 , ME1 and ME2 ) prepared according to the teaching of the European patent EP-B-0 486592 mentioned from the components (a) to (f), (l) and (m) in the stated proportions, each based on the finished product.
  • Component (k) was used for subsequent powdering of the extruded granules.
  • the granular components (g) to (j) were mixed in subsequently.
  • the tower powders TP1 and TP2 (components a and b) were produced by spray-drying aqueous slurries and consisted of the ingredients given in Table 2 below in the respective amounts (based on tower powder): Composition [% by weight] of the tower powder TP1 TP2 C 9 -C 13 alkylbenzenesulfonate 13.9 15.6 5-fold ethoxylated tallow alcohol 1.0 1.1 Soap 1.7 1.9 Zeolite Na-A 35.9 42.0 sodium 16.5 6.3 Sodium sulfate 7.3 8.2 Sodium silicate (Na 2 O: SiO 2 1: 3.0) 3.0 3.4 Copolymer Na salt of acrylic acid 5.4 6.0 Water and salts from solutions Rest to 100
  • Agents M1 and M2 according to the invention contained no structure breaker and no non-surfactant organic pastifying agent (component e) in the extrudates ( ME1 or ME2 ).
  • Table 3 shows the bulk densities of the extruded components VE1 , VE2 , ME1 and ME2 as well as the compositions V1 , V2 , M1 and M2 produced from them . It can be seen that only in the absence of the non-surfactant plasticizer or structural breaker (component e) can extrudates with high grain stability and high bulk density be produced, which lead to finished compositions with a high bulk density.
  • the dissolving behavior of agents M1 and M2 according to the invention and of comparative agents V1 and V2 was good without a significant difference.
  • Bulk weights [g / l] composition Bulk density VE1 760 V1 681 VE2 798 V2 676 ME1 810 M1 736 ME2 812 M2 775

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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)

Claims (10)

  1. Procédé de fabrication d'un produit intermédiaire convenant pour la fabrication de produits de lavage et de nettoyage granulaires ayant une densité apparente supérieure à 600 g/litre, dont la teneur en agents tensioactifs est comprise entre 0 et moins de 35 % en poids, et qui présente une densité apparente d'au moins 760 g/litre, par extrusion d'un mélange intermédiaire,
    caractérisé en ce qu'
    il est dépourvu de rupteurs de structure et de plastifiants organiques non tensioactifs, et on ajoute au mélange intermédiaire à extruder le sel neutre inorganique qui y est contenu à des quantités, toujours par rapport à la teneur en sel neutre dans le produit intermédiaire, de 10 % en poids à 65 % en poids par un mélange séparé, et à 100 % en poids comme constituant de composants granulaires qui contiennent les autres ingrédients.
  2. Procédé selon la revendication 1,
    caractérisé en ce que
    le produit intermédiaire présente une densité apparente de 770 g/litre à 870 g/litre, en particulier de 790 g/litre à 850 g/litre.
  3. Procédé selon la revendication 1 ou 2,
    caractérisé en ce qu'
    on ajoute au mélange intermédiaire le sel neutre inorganique contenu dans le produit intermédiaire, à des quantités de 30 % en poids à 65 % en poids, toujours par rapport à la teneur en sel neutre dans le produit extrudé, par ajout séparé au mélange.
  4. Procédé selon la revendication 3,
    caractérisé en ce qu'
    on extrude un mélange intermédiaire contenant de la poudre de colonne.
  5. Produit de lavage ou de nettoyage granulaire ayant une densité apparente supérieure à 600 g/litre, contenant un composant extrudé ainsi que des agents tensioactifs anioniques et/ou non ioniques en quantités d'au moins 15 % en poids, dans lequel
    au moins deux composants granulaires différents sont contenus dans le produit, dont au moins un est extrudé et au moins un est non extrudé,
    le ou les composants extrudés sont en quantités de 30 à 85 % en poids, par rapport à l'ensemble du produit, et au moins un composant granulaire contenant un agent tensioactif non extrudé est contenu dans le produit en quantités telles que de par ses composants on ait au moins 1 % en poids, par rapport à l'ensemble du produit, en agents tensioactifs,
    la teneur du ou des composants extrudés en agents tensioactifs s'élève de 0 à moins de 35 % en poids, par rapport au composant extrudé à chaque fois, et
    on trouve au moins un produit intermédiaire fabriqué selon le procédé de la revendication 1.
  6. Produit selon la revendication 5,
    caractérisé en ce que
    sa densité apparente se situe à au moins 725 g/litre, en particulier dans un intervalle de 745 g/litre à 950 g/litre.
  7. Produit selon la revendication 5 ou 6,
    caractérisé en ce que
    des composants granulaires non extrudés et contenant des agents tensioactifs sont contenus dans le produit en quantités telles que l'on obtient ainsi de 2 % en poids à 30 % en poids, de préférence de 5 % en poids à 25 % en poids, toujours par rapport à l'ensemble des produits, d'agents tensioactifs.
  8. Produit selon l'une quelconque des revendications 5 à 7,
    caractérisé en ce que
    les produits contiennent des composants extrudés contenant des agents tensioactifs en quantités telles que l'on obtient ainsi de 0,5 % en poids à 30 % en poids, en particulier de 6 % en poids à 25 % en poids, par rapport à l'ensemble du produit, d'agents tensioactifs.
  9. Produit selon l'une quelconque des revendications 5 à 8,
    caractérisé en ce que
    les composants extrudés, de préférence des composants extrudés contenant des agents tensioactifs, sont contenus à raison de 50 % en poids à 80 % en poids dans l'ensemble du produit.
  10. Produit selon l'une quelconque des revendications 5 à 9,
    caractérisé en ce que
    le rapport pondéral du composant extrudé contenant un agent tensioactif au composant non extrudé granulaire contenant un agent tensioactif s'élève à 6:1 à 2:1, en particulier à 5:1 à 3:1.
EP96922901A 1995-07-12 1996-07-03 Produit granule de lavage ou de nettoyage a masse volumique apparente elevee Expired - Lifetime EP0840780B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19524722 1995-07-12
DE19524722A DE19524722A1 (de) 1995-07-12 1995-07-12 Granulares Wasch- oder Reinigungsmittel mit hoher Schüttdichte
PCT/EP1996/002905 WO1997003181A1 (fr) 1995-07-12 1996-07-03 Produit granule de lavage ou de nettoyage a masse volumique apparente elevee

Publications (2)

Publication Number Publication Date
EP0840780A1 EP0840780A1 (fr) 1998-05-13
EP0840780B1 true EP0840780B1 (fr) 2000-11-15

Family

ID=7766220

Family Applications (1)

Application Number Title Priority Date Filing Date
EP96922901A Expired - Lifetime EP0840780B1 (fr) 1995-07-12 1996-07-03 Produit granule de lavage ou de nettoyage a masse volumique apparente elevee

Country Status (5)

Country Link
EP (1) EP0840780B1 (fr)
AT (1) ATE197606T1 (fr)
DE (2) DE19524722A1 (fr)
ES (1) ES2153114T3 (fr)
WO (1) WO1997003181A1 (fr)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9711356D0 (en) 1997-05-30 1997-07-30 Unilever Plc Particulate detergent composition
GB9825558D0 (en) 1998-11-20 1999-01-13 Unilever Plc Granular detergent components and particulate detergent compositions containing them
GB9825563D0 (en) 1998-11-20 1999-01-13 Unilever Plc Particulate laundry detergent compositions containing anionic surfactant granules
GB9825560D0 (en) 1998-11-20 1999-01-13 Unilever Plc Particulate laundry detergent compositons containing nonionic surfactant granules
GB0006037D0 (en) 2000-03-13 2000-05-03 Unilever Plc Detergent composition
GB0115552D0 (en) 2001-05-16 2001-08-15 Unilever Plc Particulate laundry detergent composition containing zeolite

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995023207A1 (fr) * 1994-02-25 1995-08-31 Henkel Kommanditgesellschaft Auf Aktien Produit detergent ou nettoyant granulaire
WO1996010070A1 (fr) * 1994-09-27 1996-04-04 Henkel Kommanditgesellschaft Auf Aktien Amelioration apportee a un procede d'extrusion pour la production de detergents
WO1996038530A1 (fr) * 1995-05-30 1996-12-05 Henkel Kommanditgesellschaft Auf Aktien Produit de lavage ou detergent en granules a densite en vrac elevee

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4399049A (en) * 1981-04-08 1983-08-16 The Procter & Gamble Company Detergent additive compositions
DK0486592T3 (da) * 1989-08-09 1994-07-18 Henkel Kgaa Fremstilling af kompakterede granulater til vaskemidler
DE4325500A1 (de) * 1993-07-29 1995-02-02 Henkel Kgaa Verfahren zur Herstellung wasch- oder reinigungsaktiver Extrudate
DE4335955A1 (de) * 1993-10-21 1995-04-27 Henkel Kgaa Verfahren zur Herstellung wasch- oder reinigungsaktiver Extrudate mit verbessertem Redispergiervermögen

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995023207A1 (fr) * 1994-02-25 1995-08-31 Henkel Kommanditgesellschaft Auf Aktien Produit detergent ou nettoyant granulaire
WO1996010070A1 (fr) * 1994-09-27 1996-04-04 Henkel Kommanditgesellschaft Auf Aktien Amelioration apportee a un procede d'extrusion pour la production de detergents
WO1996038530A1 (fr) * 1995-05-30 1996-12-05 Henkel Kommanditgesellschaft Auf Aktien Produit de lavage ou detergent en granules a densite en vrac elevee

Also Published As

Publication number Publication date
ES2153114T3 (es) 2001-02-16
WO1997003181A1 (fr) 1997-01-30
DE19524722A1 (de) 1997-01-16
ATE197606T1 (de) 2000-12-15
EP0840780A1 (fr) 1998-05-13
DE59606146D1 (de) 2000-12-21

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