EP0888450B2 - Additif pour produits de lavage ou de nettoyage, et procede de fabrication associe - Google Patents

Additif pour produits de lavage ou de nettoyage, et procede de fabrication associe Download PDF

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Publication number
EP0888450B2
EP0888450B2 EP97933648A EP97933648A EP0888450B2 EP 0888450 B2 EP0888450 B2 EP 0888450B2 EP 97933648 A EP97933648 A EP 97933648A EP 97933648 A EP97933648 A EP 97933648A EP 0888450 B2 EP0888450 B2 EP 0888450B2
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EP
European Patent Office
Prior art keywords
additive
weight
bleach
granular
granules
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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EP97933648A
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German (de)
English (en)
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EP0888450A2 (fr
EP0888450B1 (fr
Inventor
Kathrin Schnepp-Hentrich
Adolf Wiche
Eric Schumacher
Josef Markiefka
Bernd Larson
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Priority claimed from DE1996127427 external-priority patent/DE19627427A1/de
Priority claimed from DE1996132284 external-priority patent/DE19632284A1/de
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP0888450A2 publication Critical patent/EP0888450A2/fr
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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
    • 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
    • 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

Definitions

  • the invention relates to a detergent or cleaning agent additive, which in particular customary admixing components contains modern washing or cleaning agents, as well as a process for its preparation and the by adding detergents or cleaning agents available from these additives.
  • modern Detergents or cleaning agents are understood to mean those which have bulk densities of at least 500 g / l.
  • Granular detergents or cleaning agents with bulk densities above 500 g / l are now safe State of the art.
  • the products available on the market usually consist of at least one Compound or several compounds, from one basic granulate or several basic granules and further admixing components, either because of their temperature sensitivity or their sensitivity to water or because of undesirable interactions with other ingredients are not used in the manufacturing process of the base granules can be.
  • These are, in particular, solid ingredients such as bleach activators, so-called soil repellents, foam inhibitors, but also enzymes.
  • anionic surfactants which are not suitable, for example, To be used in higher quantities in a slurry for spray drying have already been described as compounds which have been subsequently mixed with other compounds or basic granules.
  • These solids can be finely divided to granular. Usually they differ in their weight, their grain shape and / or in their particle size distribution both with respect to one another and with respect to the base granules or Base granules.
  • the individually blended components have a significantly lower bulk density as the base granules or the base granules as well as not only different grain sizes, but also different ones Grain shapes and other surface properties than the basic granules.
  • the blended components for this reason generally lead to a reduction in the bulk density of the finished product with the bulk weight of the basic granules or the basic granules.
  • Another problem is the homogeneous distribution of the small solid components, i.e. those Ingredients that are only added to the basic granules in amounts of about 0.1 to 4% by weight.
  • the large-scale Manufacturing is precisely the admixture and homogeneous distribution of these small components in the mixture understandably with a relatively high error.
  • the invention was therefore based on the object of granular washing or cleaning agents with bulk weights of at least 500 g / l, which do not have the disadvantages mentioned above.
  • the invention therefore relates to a granular additive with a bulk density of at least 500 g / l, for use in granular washing or cleaning agents with bulk weights of at least 500 g / l is suitable, this additive one or more anionic surfactants and at least one further Contains ingredient that is usually added later in the manufacture of detergents or cleaning agents with the proviso that the additive 20 to 60 wt .-% anionic surfactant (s) and at least one component selected from bleach activator, bleach catalyst and pre-made foam inhibitor, the pre-made Foam inhibitor is preferred.
  • the subject of the invention is a method for the production a granular additive containing 20 to 60 wt .-% anionic surfactant (s) with a bulk density of at least 500 g / l, which is suitable for use in granular washing or Detergents with a bulk density of at least 500 g / l is suitable, a composition, Grain size and grain shape uniform additive is produced by granulating, compacting or extruding and one or more anionic surfactant (s) and at least one further constituent are used to prepare the additive, which is usually subsequently mixed in the manufacture of detergents or cleaning agents, with which Provided that in addition to the anionic surfactant (s) at least one component selected from bleach activator, Bleach catalyst and pre-assembled foam inhibitor is used, but at least one component is mandatory is introduced into the process in a pre-assembled form.
  • anionic surfactant (s) at least one component selected from bleach activator, Bleach catalyst and pre-assembled foam inhibitor is used, but at least one component
  • Another object of the invention is a granular washing or cleaning agent with a bulk density of at least 500 g / l, which usual ingredients including anionic surfactants and foam inhibitors as well optionally contains bleaching agents, bleach activators and / or bleaching catalysts, the agent consisting of at least 2 granular compounds and one compound is an additive which anionic surfactant (s) and at least contains another ingredient, which is usually retrofitted in the manufacture of detergents or cleaning agents is admixed, with the proviso that the additive 20 to 60 wt .-% anionic surfactant (s) and at least one Component selected from bleach activator, bleach catalyst and pre-assembled foam inhibitor.
  • the additive according to the invention has at least one further component usually contained in detergents or cleaning agents.
  • the additives there are additives preferred which anionic surfactant (s), pre-assembled foam inhibitor and bleach activator and / or bleach catalyst contain.
  • the additive according to the invention is preferably not of a certain grain size, grain shape and certain Surface properties and limited to a certain bulk density, but can be made so that there is a (admixture) in bulk density, grain size and grain shape adapted to the basic granules or the basic granules Represents granules.
  • a common test for measuring the flow behavior is that 1 liter of the sample to be measured in each case filled a powder funnel initially closed at its outlet direction and then the outlet time of the samples compared to dry sea sand.
  • the expiry time of the dry sea sand after opening the outlet opening (13 seconds) is set to 100%.
  • the flow behavior of the samples to be examined is expressed in%, based on 100% (measured on sea sand).
  • the trickle behavior - determined according to the test described above the additive adjusted so that it does not accumulate more than 20 percentage points, preferably not more than 10% points from the flow behavior of the base granules or the sum of the base granules different.
  • the additive according to the invention contains at least anionic surfactants, preferably alkyl sulfates (further description For possible surfactants, see below in the general description section), and preferably as usually in Detergent or cleaning agents contain foam inhibitors in pre-assembled solid form; Further
  • anionic surfactants preferably alkyl sulfates (further description For possible surfactants, see below in the general description section)
  • Detergent or cleaning agents contain foam inhibitors in pre-assembled solid form;
  • possible constituents are also peroxy bleaching agents, but also, for example, enzymes and so-called soil repellents.
  • Suitable anionic surfactants which are used in the additive according to the invention are, in particular, alk (en) yl sulfates, including 2,3-alkyl sulfates and alkylbenzenesulfonates (for a more detailed description, see below). They too are preferably used in prefabricated, in particular in granular form, anionic surfactant compounds with active substance contents above 60% by weight being particularly preferred. Examples of these are alkyl sulfate compounds with 70 to 90% by weight (optionally also above) active substance which contain sodium sulfate and / or sodium carbonate, unsulfonated constituents and water as other constituents and were produced in particular in the fluidized bed.
  • the anionic surfactants in the additives according to the invention, in particular in pre-assembled form, are 20 to 60% by weight and in particular at least 30% by weight.
  • 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 different 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 used in pre-assembled and solid form, these preferably being bound to a granular, water-soluble or dispersible carrier substance. Mixtures of paraffins and bistearylethylenediamides are particularly preferred.
  • the content of solid foam inhibitor compounds in the additives according to the invention is preferably 1 to 25% by weight and in particular 5 to 20% by weight.
  • the weight ratio of anionic surfactants to pre-assembled foam inhibitor can be in the inventive Additives vary widely. It is also possible that the weight ratio of anionic surfactants prefabricated foam inhibitor is less than 1. In an advantageous embodiment of the invention the additives, however, anionic surfactants and pre-assembled foam inhibitors in a weight ratio of 5: 1 to a maximum of 1: 1, preferably from 4: 1 to 1.5: 1 and in particular from 3.5: 1 to 2: 1. It is particularly preferred that the additives of the invention 30 to 70 wt .-% of a highly concentrated anionic surfactant compound and 10 to 30% by weight, advantageously 12 to 25% by weight of a pre-assembled foam inhibitor.
  • the additives according to the invention can also Contain bleach activators or bleach catalysts.
  • Compounds which are aliphatic peroxocarboxylic acids under perhydrolysis conditions can be used as bleach activators with preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or optionally substituted Perbenzoic acid result are used.
  • Substances containing the O- and / or N-acyl groups of the abovementioned are suitable 0 atom number and / or optionally substituted benzoyl groups.
  • Multi-acylated alkylenediamines are preferred, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, especially tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, especially n-nonanoyl or isononanoyloxybenzene sulfonate (n- or iso-NOBS), carboxylic anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate, 2,5-diacetoxy-2,5-dihydrofuran and those from the German patent applications DE19616 6
  • hydrophilically substituted acylacetals known from German patent application DE 196 16 769 and those in German patent application DE 196 16 770 and international patent application WO 95/14075 Acyl lactams are also preferred. Also that from German patent application DE 44 43 177 known combinations of conventional bleach activators can be used. Such bleach activators are in the usual range of amounts, preferably in amounts of 1% by weight to 10% by weight, in particular 2% by weight up to 8 wt .-%, based on the total average.
  • the content of the additive according to the invention is Bleach activator, preferably on prefabricated bleach activator, advantageously 10 to 50% by weight, in particular at least 20% by weight.
  • the transition metal compounds in question include in particular those from the German Patent application DE195 29 905 known manganese, iron, cobalt, ruthenium or molybdenum salt complexes and their N-analog compounds known from German patent application DE 196 20 267, which are known from the German patent application DE 195 36 082 known manganese, iron, cobalt, ruthenium or molybdenum carbonyl complexes, the manganese, iron, cobalt, ruthenium, described in German patent application DE 196 05 688, Molybdenum, titanium, vanadium and copper complexes with nitrogen-containing tripod ligands, derived from the German Patent application DE 196 20 411 known cobalt, iron, copper and ruthenium-amine complexes, which in the German patent application DE 44 16 438 manganese, copper and cobalt complexes described in the European patent application EP 0 272 030 described cobalt complexes resulting from the European patent application EP 0 693 550 known manga
  • Combinations of bleach activators and transition metal bleach catalysts are for example from the German patent application DE 196 13 103 and the international patent application WO 95/27775 known.
  • Bleach-enhancing transition metal complexes especially with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru are used in conventional amounts, preferably in an amount of up to 1% by weight, in particular from 0.0025% by weight to 0.25% by weight and particularly preferably from 0.01% by weight to 0.1% by weight, each based on the entire mean.
  • Their content in the additives according to the invention can, for example 0.5 to 5% by weight, preferably less than 3% by weight.
  • the bleach activator in the process in a pre-assembled form Manufacture of the additive to bring.
  • the bleach activator can thus be coated with coating substances in a known manner or, optionally using auxiliaries, in particular methyl celluloses and / or carboxymethyl celluloses, have been granulated or extruded / pelletized before use and, if desired, other additives, for example dye.
  • auxiliaries in particular methyl celluloses and / or carboxymethyl celluloses
  • Such granules preferably contain more than 70% by weight, in particular of 90 to 99% by weight bleach activator.
  • the additive according to the invention preferably contains a bleach activator, which is under Washing conditions forms peracetic acid.
  • the weight ratio (based on Active substance contents) of anionic surfactants to bleach activators and optionally bleach catalysts 0.5: 1 to 2: 1 and in particular 0.9: 1 to 1.5: 1.
  • one according to the invention contains Additive 30 to 60 wt .-% of a highly concentrated anionic surfactant compound and 25 to 40 wt .-% of one also highly concentrated bleach activator compounds.
  • Soil is one of the other possible ingredients of the compounds according to the invention repellents, but also superplasticizers, known substances that contribute to solubility improvement, color and Fragrances, possibly also enzymes and parts of the builder system, which are usually present in amounts up to a maximum 10% by weight, preferably up to a maximum of 8% by weight and in particular in amounts below 5% by weight, based on the finished product.
  • soil repellents components can be contained which have oil and fat washability made of textiles. This effect is particularly evident when a textile that is already soiled previously washed several times with a detergent according to the invention, which contains this oil and fat-dissolving component has been.
  • 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 methoxyl groups from 15 to 30% by weight and of hydroxypropoxyl groups from 1 to 15% by weight, based in each case on the nonionic cellulose ether, and the polymers of phthalic acid and / or terephthalic acid known from the prior art or of their derivatives, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives of these. Of these, they are particularly preferred the sulfonated derivatives of phthalic acid and terephthalic acid polymers.
  • Additives of such soil repellents (optionally in pre-assembled form), which are usually produced Agents are used in amounts of 0.2 to less than 5 wt .-%, in amounts of 1 to 8 wt .-% and especially in amounts of 2 to 6 wt .-%.
  • the known flow agents can be used in particular to improve the flow behavior Silicas, silicic acid derivatives, but also aluminosilicates such as zeolite A, X and / or P can be used. Their content in the additives is preferably not more than 3% by weight.
  • Organic builder substances are further ingredients of the additives according to the invention, especially those that are not suitable for spray drying.
  • the hydrolysis can be carried out by customary methods, for example acid-catalyzed or enzyme-catalyzed Procedures are carried out. It is preferably hydrolysis products with average molecular weights in Range from 400 to 500000.
  • DE dextrose equivalent
  • Both maltodextrins can be used with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called Yellow dextrins and white dextrins with higher molar masses in the range from 2000 to 30000.
  • a preferred dextrin is in British patent application 94 19 091.
  • the oxidized derivatives of such dextrins act are their reaction products with oxidizing agents which are capable of at least one alcohol function or to oxidize an aldehyde function of the saccharide ring to the carboxylic acid function.
  • oxidizing agents capable of at least one alcohol function or to oxidize an aldehyde function of the saccharide ring to the carboxylic acid function.
  • Such oxidized dextrins and Methods of their production are, for example, from European patent applications EP-A-0 232 202, EP-A-0 427 349, EP-A-0 472 042 and EP-A-0 542 496 as well as international patent applications WO-A-92/18542, WO-A-93/08251, WO-A-94/28030, WO-A-95/07303, WO-A-95/12619 and WO-A-95/20608 are known.
  • One at C6 of the saccharide ring oxidized product can be particularly advantageous.
  • Suitable builder substances are oxidation products of carboxyl-containing polyglucosans and / or their water-soluble salts, as described, for example, in international patent application WO-A-93/08251 are described or their production, for example, in international patent application WO-A-93/16110 is described.
  • Oxidized oligosaccharides according to the older German are also suitable Patent application DE-A-19 600 018.
  • the additives can also be oxydisuccinates and others Derivatives of disuccinates, preferably ethylenediamine disuccinate, contain.
  • disuccinates preferably ethylenediamine disuccinate
  • glycerol disuccinates and glycerol trisuccinates such as those found in the United States Patents US 4,524,009, US 4,639,325, in European patent application EP-A-0 150 930 and the Japanese patent application JP 93/339896.
  • Suitable amounts are those containing zeolite and / or formulations containing silicate at 3 to 15% by weight.
  • organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their Salts, which may also be in lactone form and which have at least 4 carbon atoms and contain at least one hydroxy group and a maximum of two acid groups.
  • Such cobuilders are, for example described 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 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 to contain 50 to 90 wt .-% acrylic acid and 50 to 10 wt .-% maleic acid. Your 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.
  • the (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution, 20 to 55% by weight aqueous solutions are preferred; in the latter case they serve as granulation aids (see below).
  • Biodegradable polymers of more than two different monomer units are also particularly preferred, for example those which according to DE-A-43 00 772 as monomers salts of acrylic acid and Maleic acid and vinyl alcohol or vinyl alcohol derivatives or according to DE-C-42 21 381 as monomers salts of Acrylic acid and 2-alkylallylsulfonic acid as well as sugar derivatives.
  • copolymers are those described in German patent applications DE-A-43 03 320 and DE-A-44 17 734 and as monomers preferably acrolein and acrylic acid / acrylic acid salts or Have acrolein and vinyl acetate.
  • the content of (co) polymeric polycarboxylates in the finished, optionally dried additive is preferably 1 to 5% by weight. If desired, the content of these organic cobuilders can also be higher. Amounts which exceed this 5% by weight are advantageously in solid form and not in excess of Granulating liquid introduced into the additive.
  • further preferred builder substances are polymeric aminodicarboxylic acids, to name their salts or their precursors. Polyaspartic acids are particularly preferred or their salts and derivatives, of which disclosed in German patent application DE-A-195 40 086 is that, in addition to cobuilder properties, they also have a bleach-stabilizing effect.
  • polyacetals which are obtained by reacting dialdehydes with polyolcarboxylic acids, which have 5 to 7 carbon atoms and at least 3 hydroxyl groups, for example as in the European patent application EP-A-0 280 223 described can be obtained.
  • Preferred polyacetals will be from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyolcarboxylic acids such as gluconic acid and / or glucoheptonic acid.
  • the additives can also include, for example, the polycarboxylic acids which can be replaced 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 that such use is not objectionable for ecological reasons is, and mixtures of these contain.
  • 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 acids themselves can also be used.
  • the acids typically have also the property of an acidifying component and thus also serve to set a lower one and milder pH of detergents or cleaning agents.
  • citric acid succinic acid
  • glutaric acid adipic acid
  • gluconic acid any mixtures of these.
  • the content of organic builder substances in the additives according to the invention is preferably 0.1 to 15% by weight.
  • Further ingredients are preferably phosphonates, which are usually present in finished compositions in amounts of 0.1 to normally not more than 2.5% by weight are used.
  • Their content in the additives according to the invention is preferably more than 1 wt .-% and in particular 1.5 to 5 wt .-%.
  • the additives can also be equipped with colors and fragrances, but then usually applied in liquid form.
  • Enzymes in particular include those from the class of hydrolases, such as proteases, esterases, Lipases or lipolytic enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned in question. All of these hydrolases contribute to the removal of stains such as stains containing protein, fat or starch, and graying. Cellulases and other glycosyl hydrolases can remove pilling and microfibrils to maintain color and increase the softness of the skin Textiles contribute. Oxidoreductases can also be used for bleaching or for inhibiting color transfer.
  • hydrolases such as proteases, esterases, Lipases or lipolytic enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned in question. All of these hydrolases contribute to the removal of stains such as stains containing protein, fat or starch, and graying. Cellulases and other glycosyl hydrolases can
  • Bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus and Humicola insolens enzymatic active substances obtained.
  • Proteases are preferred of the subtilisin type and in particular proteases which are obtained from Bacillus lentus.
  • Enzyme mixtures for example of 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, in particular, however, mixtures or mixtures containing protease and / or lipase lipolytic enzymes of particular interest.
  • lipolytic enzymes are the well-known cutinases. Peroxidases or oxidases have also proven to be suitable in some cases.
  • amylases include in particular ⁇ -amylases, iso-amylases, pullulanases and pectinases.
  • cellulases are preferably cellobiohydrolases, endoglucanases and ⁇ -glucosidases, which are also called cellobiases are used, or mixtures of these. Since the different cellulase types are characterized by their CMCase and Avicelase activities can distinguish the desired activities by targeted mixtures of the cellulases can be set.
  • the enzymes can be adsorbed on carriers and / or embedded in coating substances to counter them to protect premature decomposition. If enzymes are used in the additives according to the invention, the is Proportion of the enzymes, enzyme mixtures or enzyme granules preferably 5 to 30% by weight, in particular 8 to 20% Wt .-%.
  • the bulk density of the additives according to the invention is preferably in a range between 550 and 1000 g / l. In particular, it is preferred that the bulk density of the additive according to the invention does not exceed ⁇ 150 g / l, advantageously not more than 100 g / l from the bulk weight of the base granules or the base granules.
  • the additives are usually in granular form.
  • the particle size distribution can - as with Granules common - cover a wide range.
  • the spectrum of the particle size distribution can also be influenced by the use of pre-assembled ingredients become. As a result, not only the aesthetics of the finished agent can be significantly improved; if the spectrum the particle size of the additives is adapted to the spectrum of the particle size of the base granules also significantly reduce the tendency to segregate in the finished product.
  • the additives according to the invention deviate from the spherical shape by a maximum of 20 area%, in particular a maximum of 10 area%, the Deviation is measured with the method of silhouette projection.
  • This measurement method can be used, for example carry out with the "particle size counter 3" from Zeiss.
  • the deviation from the spherical shape is due to this determines what percentage of the area outside a circle with the same total area as that projected image of the granules lies.
  • the additive contains anionic surfactant (s), pre-assembled foam inhibitor and bleach activator and / or bleach catalyst. It is particularly preferred that in addition to the foam inhibitors also the anionic surfactants and bleach activators or bleach catalysts in prefabricated, preferably granular form can be used.
  • the additives according to the invention accordingly contain Bleach activator and / or bleach catalyst, anionic surfactants, preferably alk (en) yl sulfates including the 2,3-alkyl sulfates and / or alkyl benzene sulfonates (for a more detailed description see below) and foam inhibitors, in particular each in a pre-assembled form.
  • anionic surfactants preferably alk (en) yl sulfates including the 2,3-alkyl sulfates and / or alkyl benzene sulfonates (for a more detailed description see below) and foam inhibitors, in particular each in a pre-assembled form.
  • the additive according to the invention contains all of them usually in solid form to form a basic granulate or a plurality of basic granules, which in total up to 30% by weight, preferably up to 25% by weight and in particular at least 10% by weight of the make up finished detergent or cleaning agent.
  • the additives according to the invention contain Bleach activators and optionally bleach catalysts, anionic surfactants and foam inhibitors in amounts of at least 50% by weight (based on active substance). In particular, it is preferred that 70 to 100 wt .-% of the invention Additives consist of pre-assembled forms of these raw materials. Can be used as "filling materials" the other usually mixed components of detergents or cleaning agents, in particular should repellents and builders (including alkali carbonates and alkali silicates) as well as enzymes, but also inorganic ones Salts such as sodium sulfate are used.
  • the water content of the additives is preferably below 10% by weight and in particular below 8% by weight.
  • Basic granules are understood to mean such compounds that are already used on their own Make up detergent and usually at least surfactants, builder substances and optionally peroxy bleach contain. These ingredients do not have to be contained in a single basic granulate, but can also available on different compounds. A detailed list of the preferred ones Ingredients in the basic granules are added later.
  • the additive according to the invention is preferably prepared by batchwise or continuous granulation of its ingredients, the latter in a mixer / granulator with the addition of a small amount of granulating liquid to a possibly moist granulate, this - if spherical or pearl shape are desired - can compact and round in a rounder and if necessary subsequently, in particular in a fluidized bed, dries.
  • Known apparatus for example granulators from Gebrüder Lödige, Paderborn, can be used as the mixer / granulator.
  • Apparatus suitable for compacting and rounding are also known.
  • An example is the rounder known under the name “Marumerizer (R) ".
  • the mode of operation and the construction of this apparatus are described in GB-PS 1 517 713.
  • Known rounding plates or rounding discs can also be used for rounding.
  • a rotating fluidized bed granulator as described for example in Pietsch, "Size Enlargement by Agglomeration", John Wiley & Sons, 1990, p. 451, is used.
  • a large number of compounds can be used as granulation aids. So connections can from the class of water-soluble cellulose ethers, starch and starch ethers can be used. Carboxymethyl cellulose is preferred here, especially sodium carboxymethyl cellulose.
  • a granulating aid can also Additives such as oxidation-stable complexing agents and stabilizers for per compounds and / or other components of detergents and cleaning agents are added or introduced via the aqueous granulating liquid. Examples of these are salts of polyphosphonic acids, such as 1-hydroxyethane-1,1-diphosphonate, ethylenediamine tetramethylene phosphonate and diethylene triamine pentamethylene phosphonate, each in the form of the sodium salt.
  • More known and suitable additives in the granulating liquid are tallow alcohol sulfates and ethoxylated tallow alcohol sulfates (with up to 100 EO), starch phosphates, soaps and well-known emulsifying agents.
  • copolymers have acrylic acid and maleic acid as well as biodegradable polymers made up of more than 2 monomer units proven suitable.
  • aqueous solutions of, in particular, inorganic salts advantageously aqueous alkali silicate solutions, preferably sodium silicate solutions, silicates having a Na 2 O: SiO 2 ratio of about 1: 2 to 1: 3, in particular up to 1: 2.6, being used.
  • aqueous polymer solutions of the type described above and aqueous alkali silicate solutions have proven particularly useful as granulation aids.
  • the amount of water-containing granulation aid is advantageously such that it follows the granulation does not require drying.
  • water-containing granulation aids are particularly useful not used in amounts above 5 wt .-%, with amounts between 0.1 and 2.5 wt .-% particularly are preferred.
  • the quantities are based on the total amount of moist and undried granules. If drying is added afterwards, the content of the aqueous granulating liquid can be reduced also more than 10 parts by weight, based on 100 parts by weight of the solid mixture to be granulated. It but then usually no more than 15 parts by weight of aqueous granulating liquid are used, with values between 8 and 12 parts by weight can be particularly advantageous.
  • the granulation is anhydrous, that is to say anhydrous Granulation aids carried out.
  • the liquids which are liquid at the processing temperature are particularly suitable nonionic surfactants (detailed list see below), especially ethoxylated (fatty) alcohols with a melting point below 40 ° C, but also polyethylene glycols with molecular weights between 200 and 100,000, where the latter can advantageously be used in combination with nonionic surfactants or in aqueous solution / dispersion.
  • the additives mentioned above in particular an aqueous solution of a granulation aid, or other ingredients of washing and cleaning agents when rounding the moist granules added simultaneously, e.g. B. are injected.
  • no liquid is added in this process step.
  • the surface of the Granules can also be treated with finely divided to dusty components, which reduces the flow behavior the granules can be further improved.
  • Agents for the surface treatment are, for example, aluminosilicates such as amorphous and / or crystalline zeolite and / or calcium stearate and / or silicas.
  • the fine and / or coarse fractions are sieved off and guided, if appropriate after drying after crushing the coarse fractions for granulation.
  • the additive according to the invention By mixing one or more basic granules as defined above with a detergent or cleaning agent is obtained in the additive according to the invention, in which the admixing components are evenly distributed and remain evenly distributed and which has a visually uniform appearance and also can also have an increased bulk density.
  • An increased bulk density is understood here that the bulk density of the agent according to the invention is higher than that of an agent with the same composition and the same basic granulate (s), but in which the admixing components are not added in compounded form become.
  • the base granules contain, in particular, surfactants, especially anionic surfactants, nonionic surfactants, if appropriate also cationic surfactants, amphoteric surfactants and / or zwitterionic surfactants, also builder substances, peroxy bleaching agents.
  • surfactants especially anionic surfactants, nonionic surfactants, if appropriate also cationic surfactants, amphoteric surfactants and / or zwitterionic surfactants, also builder substances, peroxy bleaching agents.
  • a basic granulate with 10 up to 40% by weight of an additive according to the invention, it being particularly preferred that these the two components not more than 10% by weight, advantageously less than 5% by weight of further constituents all enzymes.
  • Embodiments have proven to be particularly advantageous in which the base granules are in extruded form and part of the anionic surfactants according to the teaching of the German application DE-A-195 19 139 can now be admixed with the additives according to the invention.
  • Anionic surfactants used are, for example, those of the sulfonate and sulfate type.
  • 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 an end 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 ⁇ -sulfo fatty acids e.g. the ⁇ -sulfonated methyl ester of hydrogenated coconut, palm kernel or tallow fatty acids.
  • Suitable anionic surfactants are sulfonated fatty acid glycerol esters, which are mono-, di- and triesters as well their mixtures represent how they are in the preparation by esterification by a monoglycerol with 1 to 3 mol Fatty acid or in the transesterification of triglycerides with 0.3 to 2 mol of glycerol can be obtained.
  • the sulfonation products represent a complex mixture, the mono-, di- and triglyceride sulfonates with ⁇ -and / or internally Contains sulfonic acid grouping.
  • sulfonated fatty acid salts As by-products, sulfonated fatty acid salts, glyceride sulfates, glycerol sulfates, Glycerin and soaps.
  • glyceride sulfates As by-products, sulfonated fatty acid salts, glyceride sulfates, glycerol sulfates, Glycerin and soaps.
  • the proportion of ⁇ -sulfonated fatty acid disalts can, depending on the procedure, well up to about 60% 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 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).
  • sulfosuccinates the fatty alcohol residues of which are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are 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.
  • the alk (en) yl sulfates are the alkali and in particular the sodium salts of the sulfuric acid half esters of 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. Also preferred are 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 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 and in particular C 12 -C 16 -Fatty alkyl sulfates with C 16 -C 18 fatty alkyl sulfates.
  • not only saturated alkyl sulfates but also unsaturated alkenyl sulfates with an alkenyl chain length of preferably C 16 to C 22 are used.
  • Mixtures of saturated sulfated fatty alcohols consisting predominantly of C 16 and unsaturated sulfated fatty alcohols consisting predominantly of C 18 are particularly preferred, for example those derived from solid or liquid fatty alcohol mixtures of the HD-Ocenol (R) type (commercial product of the applicant) , Weight ratios of alkyl sulfates to alkenyl sulfates from 10: 1 to 1: 2 and in particular from about 5: 1 to 1: 1 are preferred.
  • Mixtures in which the proportion of the alkyl radicals are 15 to 40% by weight on C 12 , 5 to 15% by weight on C 14 , 15 to 25% by weight on C 16 and 30 find a preferred use up to 60% by weight on C 18 and less than 1% by weight on C 10 .
  • the total alk (en) yl sulfate content of the detergents is preferably 15 to 25% by weight.
  • 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.
  • anionic surfactants include, in particular, soaps, preferably in amounts of 0.2 to 5% by weight, into consideration.
  • 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 anionic surfactants 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, are present.
  • the anionic surfactants are preferably present 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 linearly or preferably 2-branched methyl 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 -C 14 alcohols with 3 EO or 4 EO, C 9 -C 11 alcohols with 7 EO, C 13 -C 15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12 -C 18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C 12 -C 14 alcohol with 3 EO and C 12 -C 18 alcohol with 7 EO.
  • the degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples of these are (tallow) fatty alcohols with 14 EO, 16 EO, 20 EO, 25 EO, 30 EO or 40 EO.
  • alkyl glycosides of the general formula RO (G) X can also be used as further nonionic surfactants, in which R denotes a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, C atoms and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.
  • nonionic surfactants which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, in particular together with alkoxylated fatty alcohols and / or alkyl glycosides, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters, as described, for example, in Japanese patent application JP 58/217598 or which are preferably prepared by the process described in international patent application WO-A-90/13533.
  • nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may be suitable.
  • the amount of this nonionic surfactants are preferably no more than that of the ethoxylated fatty alcohols, especially not more than half of it.
  • Suitable surfactants are polyhydroxy fatty acid amides of the formula (I), in the R 2 CO for an aliphatic acyl radical having 6 to 22 carbon atoms, R 3 for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups stands.
  • the polyhydroxy fatty acid amides are preferably derived from reducing sugars with 5 or 6 carbon atoms, in particular from glucose.
  • the group of polyhydroxy fatty acid amides also includes compounds of the formula (II) in which R 3 is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R 4 is a linear, branched or cyclic alkyl radical or an aryl radical is 2 to 8 carbon atoms and R 5 is a linear, branched or cyclic alkyl radical or Aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, C 1 -C 4 -alkyl or phenyl radicals being preferred, and [Z] for a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this radical.
  • R 3 is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
  • R 4 is a linear, branched or cyclic alkyl radical or an
  • [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 such Compounds understood that have two hydrophilic groups and two hydrophobic groups per molecule. These groups are usually separated from one another by a so-called "spacer". This spacer is in the Usually a carbon chain that should be long enough that the hydrophilic groups are spaced sufficiently have so that they can act independently of each other. Such surfactants are generally characterized by a unusually low critical micelle concentration and the ability to keep the surface tension of water strong to reduce from. In exceptional cases, however, Gemini surfactants are not only dimeric, but also also understood trimeric surfactants.
  • Suitable gemini surfactants are, for example, sulfated hydroxy mixed ethers according to the German patent application DE-A-43 21 022 or dimer alcohol bis and trimer alcohol tris sulfates and ether sulfates according to the older one German patent application P 195 03 061.3.
  • End group capped dimeric and trimeric mixed ethers according to the Older German patent application P 195 13 391.9 are particularly characterized by their bi- and multifunctionality out.
  • the end group-closed surfactants mentioned have good wetting properties and are low-foaming, so that they are particularly suitable for use in machine washing or cleaning processes.
  • Gemini polyhydroxy fatty acid amides or poly polyhydroxy fatty acid amides can also be used. as described in international patent applications WO-A-95/19953, WO-A-95/19954 and W095-A- / 19955 become.
  • the finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P.
  • zeolite P zeolite MAP (R) (commercial product from Crosfield) and zeolite NaP (commercial product from Degussa) are particularly preferred.
  • 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 in the event that the zeolite is used as a suspension, it can contain small additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C 12 -C 18 fatty alcohols with 2 to 5 ethylene oxide groups , C 12 -C 14 fatty alcohols with 4 to 5 ethylene oxide groups or ethoxylated isotridecanols.
  • Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.
  • Suitable substitutes or partial substitutes for phosphates and zeolites are crystalline, layered sodium silicates of the general formula NaMSi x O 2x + 1 .yH 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4.
  • Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514.
  • Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3. In particular, both ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 O 5 .yH 2 O are preferred.
  • the preferred builder substances also include amorphous sodium silicates with a modulus Na 2 O: SiO 2 from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2, 6, which are delayed release and have secondary washing properties.
  • the delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying.
  • the term “amorphous” also means “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 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.
  • 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 organic builder substances already mentioned can - at least for Part - be included in the base granules.
  • 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, phthaloiminoperic 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, advantageously using perborate monohydrate or percarbonate.
  • Suitable ingredients of the agents are water-soluble inorganic salts such as bicarbonates, carbonates, amorphous silicates or mixtures of these; in particular, alkali carbonate and amorphous alkali silicate, especially sodium silicate with a molar ratio Na 2 O: SiO 2 of 1: 1 to 1: 4.5, preferably of 1: 2 to 1: 3.5, are used.
  • the sodium carbonate content of the agents is preferably up to 20% by weight, advantageously between 5 and 15% by weight.
  • the content of normal sodium silicate (water glass) is generally up to 10% by weight and preferably between 2 and 8% by weight.
  • Graying inhibitors have the task of suspending the dirt detached from the fiber in the liquor to keep and thus prevent the dirt from re-opening.
  • water-soluble colloids are usually more organic Naturally suitable, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of Ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters cellulose or starch.
  • Water-soluble polyamides containing acidic groups are also suitable for this purpose suitable.
  • Soluble starch preparations and starch products other than those mentioned above can also be used, e.g. 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 carboxymethyl cellulose and mixtures thereof, and Polyvinylpyrrolidone, for example in amounts of 0.1 to 5 wt .-%, based on the agent used.
  • the agents can be derivatives of diaminostilbenedisulfonic acid or its alkali metal salts contain. Are suitable for.
  • Brighteners can also be used of the substituted diphenyl styrene type, e.g.
  • the basic granules can be produced by any of the known processes, such as spray drying, granulation or compacting (Roller compaction, pelleting, extrusion). Is a spray-dried basic granulate is present, then this with another base granulate, which is produced in another way and which contains the peroxy bleach contains, mixed.
  • the washing or cleaning agents according to the invention preferably contain no base granules, which were produced by spray drying.
  • the washing or cleaning agent consists of a basic granulate and an admixed inventive Additive.
  • the basic granules can also be obtained by extrusion of a premix with subsequent shaping can be produced, as described in more detail for example in WO-A-91/02047.
  • almost spherical base granules in particular extruded base granules with almost spherical, rounded or rounded additives to a heavy granular washing or cleaning agent with bulk densities of preferably above 700 g / l mixed.
  • the (comparative) agent 1 had a bulk density of about 750 g / l.
  • the sieve analysis (sieves 0.8 mm and 0.4 mm) showed that 74% by weight were 0.8 mm on the sieve and 26% by weight were 0.4 mm on the sieve.
  • Im used Base extrudate was only 10% by weight on the 0.4 mm sieve; by mixing these became finer Shares more than doubled!
  • Agent 2 according to the invention had only a negligible reduction in bulk density 740 g / l to about 750 g / l.
  • the sieve analysis (sieves 0.8 mm and 0.4 mm) showed that 85% by weight on the sieve 0.8 mm and only 15% by weight were on the sieve 0.4 mm.
  • the fraction was on the 0.4 mm sieve again 10% by weight; the granulation reduced the finer fractions compared to agent 1, Accordingly, the aesthetics of the product are significantly improved.
  • Agent 2 according to the invention also pointed a higher degree of whiteness (measured according to Berger and Ganz) than the (comparative) mean 1.
  • the agent 2 according to the invention also had an improved dissolution rate after 1.5 minutes in comparison with the dissolving speed of the (comparative) agent 1.
  • Agent 2 according to the invention also showed significantly less segregation than (comparative) agent 1. This was investigated as follows: 3 filled 1.5 kg packets each were emptied with measuring spoons, each sample being 100 g. Of the 15 samples in each package, every third sample was analyzed for anionic surfactant content (AT), perborate monohydrate content (PBMH) and bleach activator content (TAED). The values obtained (in each case in% by weight) clearly show that the use of the additive according to the invention made it possible to achieve a substantially better homogeneity in the package.
  • AT anionic surfactant content
  • PBMH perborate monohydrate content
  • TAED bleach activator content

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Claims (13)

  1. Additif granulaire présentant une densité en vrac d'au moins 500 g/l pour utilisation dans des produits de lavage ou de nettoyage granulaires présentant une densité en vrac d'au moins 500 g/l, caractérisé en ce qu'il renferme un ou plusieurs surfactifs anioniques et au moins un autre constituant, qui est additionné d'ordinaire par mélangage postérieurement lors de la fabrication de produits de lavage ou de nettoyage, à condition que l'additif renferme 20 à 60% en poids de surfactifs anioniques et au moins un constituant sélectionné parmi un activateur de blanchiment, un catalyseur de blanchiment et un inhibiteur de mousse préconfectionné.
  2. Additif selon la revendication 1, caractérisé en ce qu'il renferme le ou les surfactifs anioniques et un inhibiteur de mousse préconfectionné, ainsi que de préférence un activateur de blanchiment en plus.
  3. Additif selon la revendication 1 ou 2, caractérisé en ce qu'il constitue un produit de granulation pour adjonction par mélangeage, dont la densité en vrac, la grosseur et la forme des grains sont adaptées au granulé ou aux granulés de base.
  4. Additif selon une des revendications 1 à 3, caractérisé en ce qu'il renferme tant l'inhibiteur de mousse que les surfactifs anioniques et les activateurs de blanchiment présents dans la forme de réalisation préférée sous forme préconfectionnée.
  5. Additif selon une des revendications 1 à 4, caractérisé en ce qu'il est constitué à raison de 70 à 100 % en poids de formes préconfectionnées des constituants activateur de blanchiment et/ou catalyseur de blanchiment, surfactifs anioniques et inhibiteurs de mousse.
  6. Additif selon une des revendications 1 à 5, caractérisé en ce qu'il présente une densité en vrac, qui ne s'écarte pas de ± 150 g/l, avantageusement de ± 100 g/l, de celle du granulé ou des granulés de base.
  7. Additif selon la revendication 6, caractérisé en ce qu'il ne s'écarte de la forme sphérique que de 20 % de la surface au maximum, en particulier de 10 % de la surface au maximum.
  8. Produit de lavage ou de nettoyage granulaire présentant une densité en vrac d'au moins 500 g/l, qui renferme des constituants usuels, y compris des surfactifs anioniques et des inhibiteurs de mousse, ainsi que, le cas échéant, des agents de blanchiment, des activateurs de blanchiment et/ou des catalyseurs de blanchiment, caractérisé en ce que le produit étant constitué d'au moins 2 compounds granulaires, un des compounds étant un additif, qui renferme 20 à 60% en poids de surfactifs anioniques et au moins un autre constituant, qui est ajouté d'ordinaire par mélangeage postérieurement lors de la fabrication de produits de lavage ou de nettoyage, à condition que l'additif renferme outre le ou les surfactifs anioniques, au moins un constituant sélectionné parmi un activateur de blanchiment, un catalyseur de blanchiment et un inhibiteur de mousse préconfectionné.
  9. Produit selon la revendication 8, caractérisé en ce qu'il ne renferme pas de granulés de base séchés par pulvérisation.
  10. Produit selon la revendication 8 ou 9, caractérisé en ce que 60 à 90 % en poids d'un granulé de base sont préparés avec 10 à 40 % en poids d'un additif selon une des revendications 1 à 7, auquel cas il est préférable que ces deux composants n'aient pas été additionnés de plus de 10 % en poids, avantageusement de plus de 5 % en poids d'autres constituants, surtout des enzymes.
  11. Procédé de production d'un additif granulaire, qui renferme 20 à 60% en poids de surfactifs anioniques présentant une densité en vrac d'au moins 500 g/l selon une des revendications 1 à 7, qui est approprié à l'utilisation dans des produits de lavage ou de nettoyage granulaires présentant une densité en vrac d'au moins 500 g/l, caractérisé en ce qu'un additif uniforme en matière de composition, de grosseur et de forme de grain est produit par granulation, compactage ou extrusion, et un ou plusieurs surfactifs anioniques et au moins un autre constituant, qui est additionné d'ordinaire par mélangeage postérieurement lors de la fabrication de produite de lavage et de nettoyage, sont mis en oeuvre pour la production de l'additif, à condition qu'outre le ou les surfactifs anioniques, au moins un constituant sélectionné parmi un activateur de blanchiment, un catalyseur de blanchiment et un inhibiteur de mousse préconfectionné soit mis en oeuvre, au moins un constituant sous forme préconfectionnée devant impérativement être incorporé dans le procédé.
  12. Procédé selon la revendication 11, caractérisé en ce que l'additif est produit par granulation discontinue ou continue de ses constituants, en transformant ces damiers en un granulé, éventuellement humide, dans un mélangeur/granulateur, sous adjonction d'une faible proportion de liquide de granulation, on peut compacter et arrondir ledit granulé dans un arrondisseur, au cas où on souhaite une forme sphérique ou perlée, et on le sèche éventuellement à la suite, en particulier dans un lit fluidisé.
  13. Procédé de production d'un produit de lavage ou de nettoyage granulaire selon une des revendications 8 à 10, caractérisé en ce que l'on mélange des granulés de base quasiment sphériques, en particulier des granulés de base extrudés, avec des additifs quasiment sphériques, arrondis ou fabriqués en les arrondissant, en un produit de lavage ou de nettoyage granulaire lourd présentant une densité en vrac de préférence supérieure à 700 g/l.
EP97933648A 1996-07-08 1997-07-02 Additif pour produits de lavage ou de nettoyage, et procede de fabrication associe Expired - Lifetime EP0888450B2 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
DE1996127427 DE19627427A1 (de) 1996-07-08 1996-07-08 Wasch- oder Reinigungsmitteladditiv sowie ein Verfahren zu seiner Herstellung
DE19627427 1996-07-08
DE1996132284 DE19632284A1 (de) 1996-08-09 1996-08-09 Wasch- oder Reinigungsmitteladditiv sowie ein Verfahren zu seiner Herstellung
DE19632284 1996-08-09
PCT/EP1997/003468 WO1998001531A2 (fr) 1996-07-08 1997-07-02 Additif pour produits de lavage ou de nettoyage, et procede de fabrication associe

Publications (3)

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EP0888450A2 EP0888450A2 (fr) 1999-01-07
EP0888450B1 EP0888450B1 (fr) 2000-05-24
EP0888450B2 true EP0888450B2 (fr) 2003-01-15

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EP97933648A Expired - Lifetime EP0888450B2 (fr) 1996-07-08 1997-07-02 Additif pour produits de lavage ou de nettoyage, et procede de fabrication associe

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EP (1) EP0888450B2 (fr)
JP (1) JPH11513074A (fr)
AT (1) ATE193322T1 (fr)
DE (1) DE59701763D1 (fr)
ES (1) ES2148999T5 (fr)
WO (1) WO1998001531A2 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
MXPA04010775A (es) 2002-05-02 2005-03-07 Procter & Gamble Composiciones detergentes y componentes de las mismas.

Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4486327A (en) † 1983-12-22 1984-12-04 The Procter & Gamble Company Bodies containing stabilized bleach activators
US4590237A (en) † 1984-01-02 1986-05-20 Henkel Kommanditgesellschaft Auf Aktien Foam regulators containing paraffin hydrocarbons and hydrophobic silica
EP0266863A1 (fr) † 1986-08-12 1988-05-11 Unilever Plc Agent antimousseux
EP0373743A2 (fr) † 1988-10-14 1990-06-20 The Clorox Company Détergent contenant des granulés stables d'activateur de blanchiment
US4997590A (en) † 1988-12-22 1991-03-05 The Procter & Gamble Company Process of coloring stabilized bleach activator extrudates
WO1992006162A1 (fr) † 1990-09-28 1992-04-16 The Procter & Gamble Company Detergent contenant des tensioactifs de sulfate d'alkyle et d'amide de l'acide gras de polyhydroxy
US5334324A (en) † 1990-08-03 1994-08-02 Henkel Kommanditgesellschaft Auf Aktien Bleach activators in granular form
EP0342985B1 (fr) † 1988-05-20 1994-11-30 Unilever Plc Additif anti-mousse
EP0639639A1 (fr) † 1993-08-17 1995-02-22 The Procter & Gamble Company Compositions détergentes contenant des percarbonates comme agents de blanchiment
EP0639638A1 (fr) † 1993-08-18 1995-02-22 The Procter & Gamble Company Procédé de préparation de compositions détergentes
US5516449A (en) † 1992-04-03 1996-05-14 The Procter & Gamble Company Detergent compositions
WO1997016519A1 (fr) † 1995-11-03 1997-05-09 The Procter & Gamble Company Composant granule suppresseur de mousses

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Publication number Priority date Publication date Assignee Title
GB8811447D0 (en) * 1988-05-13 1988-06-15 Procter & Gamble Granular laundry compositions
DE4127323A1 (de) * 1991-08-20 1993-02-25 Henkel Kgaa Verfahren zur herstellung von tensidgranulaten
DE4221736A1 (de) * 1992-07-02 1994-01-05 Henkel Kgaa Feste waschaktive Zubereitung mit verbessertem Einspülverhalten
CA2141587A1 (fr) * 1992-08-01 1994-02-17 Anthony Dovey Compositions detergentes peu gelifiantes et methode pour les preparer
WO1995004124A1 (fr) * 1993-08-02 1995-02-09 Henkel Kommanditgesellschaft Auf Aktien Granule regulateur du moussage et son procede de preparation
DE19521365A1 (de) * 1995-06-12 1996-12-19 Henkel Kgaa Feste und hochverdichtete waschaktive Zubereitungen mit verbesserter Löslichkeit auch schon bei niederen Flottentemperaturen

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4486327A (en) † 1983-12-22 1984-12-04 The Procter & Gamble Company Bodies containing stabilized bleach activators
US4590237A (en) † 1984-01-02 1986-05-20 Henkel Kommanditgesellschaft Auf Aktien Foam regulators containing paraffin hydrocarbons and hydrophobic silica
EP0266863A1 (fr) † 1986-08-12 1988-05-11 Unilever Plc Agent antimousseux
EP0342985B1 (fr) † 1988-05-20 1994-11-30 Unilever Plc Additif anti-mousse
EP0373743A2 (fr) † 1988-10-14 1990-06-20 The Clorox Company Détergent contenant des granulés stables d'activateur de blanchiment
US4997590A (en) † 1988-12-22 1991-03-05 The Procter & Gamble Company Process of coloring stabilized bleach activator extrudates
US5334324A (en) † 1990-08-03 1994-08-02 Henkel Kommanditgesellschaft Auf Aktien Bleach activators in granular form
WO1992006162A1 (fr) † 1990-09-28 1992-04-16 The Procter & Gamble Company Detergent contenant des tensioactifs de sulfate d'alkyle et d'amide de l'acide gras de polyhydroxy
US5516449A (en) † 1992-04-03 1996-05-14 The Procter & Gamble Company Detergent compositions
EP0639639A1 (fr) † 1993-08-17 1995-02-22 The Procter & Gamble Company Compositions détergentes contenant des percarbonates comme agents de blanchiment
EP0639638A1 (fr) † 1993-08-18 1995-02-22 The Procter & Gamble Company Procédé de préparation de compositions détergentes
WO1997016519A1 (fr) † 1995-11-03 1997-05-09 The Procter & Gamble Company Composant granule suppresseur de mousses

Also Published As

Publication number Publication date
EP0888450A2 (fr) 1999-01-07
ATE193322T1 (de) 2000-06-15
WO1998001531A3 (fr) 1998-04-09
WO1998001531A2 (fr) 1998-01-15
JPH11513074A (ja) 1999-11-09
ES2148999T5 (es) 2003-05-01
EP0888450B1 (fr) 2000-05-24
DE59701763D1 (de) 2000-06-29
ES2148999T3 (es) 2000-10-16

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