EP0888450B1 - 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
EP0888450B1
EP0888450B1 EP97933648A EP97933648A EP0888450B1 EP 0888450 B1 EP0888450 B1 EP 0888450B1 EP 97933648 A EP97933648 A EP 97933648A EP 97933648 A EP97933648 A EP 97933648A EP 0888450 B1 EP0888450 B1 EP 0888450B1
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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
EP0888450B2 (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 is particularly conventional Mixing components of modern detergents or cleaning agents contains, as well a process for its preparation and those obtainable by admixing these additives Detergents or cleaning agents.
  • a detergent or cleaning agent additive which is particularly conventional Mixing components of modern detergents or cleaning agents contains, as well a process for its preparation and those obtainable by admixing these additives Detergents or cleaning agents.
  • modern washing or cleaning agents understood those that have bulk densities of at least 500 g / l.
  • Granular detergents or cleaning agents with bulk weights above 500 g / l belong today to the secure state of technical knowledge.
  • the products available on the market usually consist of at least one compound or several compounds, from one base granulate or several base granules and further admixing components, either because of their temperature sensitivity or their sensitivity to water or because of undesirable interactions with other ingredients in the manufacturing process of the basic granules can be used.
  • This is in particular solid ingredients such as bleach activators, so-called soil repellents, foam inhibitors, but also enzymes.
  • anionic surfactants which, for example, are not are suitable for use in higher quantities in a slurry for spray drying, have already been described as compounds, the later other compounds or basic granules were added.
  • These solids can be finely divided to granular available. Usually they differ in their weight, their grain shape and / or in their particle size distribution both among one another and with respect to that Base granules or the base granules. So have the individually blended components usually a significantly lower bulk density than 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 For this reason, components generally lead to a reduction the bulk density of the finished product compared to the bulk weight of the base granulate or the base granules.
  • Another problem is the homogeneous distribution of the solid small components, that is, of those ingredients that only contain the basic granules in amounts of about 0.1 up to 4 wt .-% are added.
  • admixing is just the thing and the homogeneous distribution of these small components in the mixture is understandable with a relatively high error.
  • the invention was therefore based on the object of granular detergents or cleaning agents with bulk densities of at least 500 g / l to provide the above Do not have disadvantages.
  • the invention therefore relates to a granular additive with a bulk density of at least 500 g / l, which is suitable for use in granular washing or cleaning agents with bulk weights of at least 500 g / l is suitable, wherein this additive contains one or more anionic surfactants and at least one further constituent contains, which is usually retrofitted in the manufacture of detergents or cleaning agents is admixed, with the proviso that the additive in addition to the anionic surfactant (s) at least one component selected from bleach activator, bleach catalyst and contains a prefabricated foam inhibitor, the prefabricated foam inhibitor is preferred.
  • this additive contains one or more anionic surfactants and at least one further constituent contains, which is usually retrofitted in the manufacture of detergents or cleaning agents is admixed, with the proviso that the additive in addition to the anionic surfactant (s) at least one component selected from bleach activator, bleach catalyst and contains a prefabricated foam inhibitor, the prefabricated foam inhibitor is preferred.
  • the invention relates to a method in a further embodiment of the invention for the production of a granular additive with a bulk density of at least 500 g / l, for use in granular washing or cleaning agents with a bulk density of at least 500 g / l is suitable, with a composition, grain size and Granular additive produced by granulating, compacting or extruding is and for the preparation of the additive one or more anionic surfactant (s) and at least another ingredient can be used in the manufacture of washing or Detergents are usually added subsequently, with the proviso that in addition to the anionic surfactant (s) has at least one component selected from bleach activator, Bleaching catalyst and pre-assembled foam inhibitor is mandatory however, at least one component is introduced into the process in a pre-assembled form becomes.
  • Another object of the invention is a granular washing or cleaning agent a bulk density of at least 500 g / l, which includes common ingredients Anionic surfactants and foam inhibitors and optionally bleaches, bleach activators and / or bleach catalysts, the agent consisting of at least 2 granular compounds exists and that a compound is an additive, which anionic surfactant (s) and at least contains another ingredient that is commonly used in the manufacture of Detergents or cleaning agents are subsequently mixed, with the proviso that the Additive in addition to the anionic surfactant (s) selected from at least one component Bleach activator, bleach catalyst and pre-assembled foam inhibitor contains.
  • the additive according to the invention has at least one further usually contained in washing or cleaning agents Component on.
  • additives which prefabricate anionic surfactant (s) are preferred Foam inhibitor and bleach activator and / or bleach catalyst included.
  • the additive according to the invention is preferably not of a certain grain size, grain shape and certain surface properties as well as a certain bulk density limited, but can be made so that it has a bulk density, grain size and Grain shape (admixed) granules adapted to the basic granules or the basic granules represents.
  • the flow behavior of the additive essentially corresponds to the flow behavior of the base granulate or to adapt the base granules.
  • a common test for measuring trickle behavior consists in that 1 liter of the sample to be measured in one at its outlet direction first filled powder hopper and then the run-out time of the samples compared to dry sea sand.
  • the drainage time of the dry Sea sand after opening the outlet opening (13 seconds) is set to 100%.
  • the The flow behavior of the samples to be examined is measured in%, based on 100% ( to sea sand).
  • the trickle behavior is determined according to the test described above - the additive adjusted so that this not more than 20 percentage points, preferably not more than 10 percentage points, of the trickle behavior of the base granules or the sum of the base granules.
  • the additive according to the invention contains at least anionic surfactants, preferably alkyl sulfates (For a further description of possible surfactants, see below in the general description section), and preferably as a component usually contained in washing or cleaning agents Foam inhibitors in pre-assembled solid form; other possible components in addition to the preferred bleach activators or bleach catalysts, also peroxy bleaches, but also, for example, enzymes and so-called soil repellents.
  • anionic surfactants preferably alkyl sulfates (For a further description of possible surfactants, see below in the general description section)
  • Foam inhibitors in pre-assembled solid form Foam inhibitors in pre-assembled solid form
  • other possible components in addition to the preferred bleach activators or bleach catalysts, also peroxy bleaches, 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 pre-assembled, in particular in granular form, with anionic surfactant compounds with active substance contents above 60% by weight being particularly preferred. Examples of this are alkyl sulfate compounds with 70 to 90 wt. Of particular interest are C-chain cuts with at least 90% by weight, preferably with at least 95% by weight, of C 12 -C 18 which contain more than 50% by weight of C 16 -C 18 and at least 20% by weight. have less than C 16 .
  • the content of anionic surfactants in the additives according to the invention, in particular in pre-assembled form is preferably 20 to 60 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 bistearylethylenediamide. Mixtures of various foam inhibitors are also used with advantages, for example those made of silicones, paraffins or waxes.
  • the foam inhibitors in particular silicone and / or paraffin-containing foam inhibitors, are 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 Additives according to the invention vary within a wide range. It is also possible that the weight ratio of anionic surfactants to pre-assembled 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 from 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 on. It is particularly preferred that the additives 30 to 70% by weight of a highly concentrated anionic surfactant compound and 10 to 30% by weight, advantageously have 12 to 25% by weight of a pre-assembled foam inhibitor.
  • the foam inhibitors according to the invention also contain bleach activators or bleach catalysts.
  • Peroxocarboxylic acids with preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid can be used.
  • Substances containing O- and / or N-acyl groups with the stated number of 0 atoms are suitable and / or optionally substituted benzoyl groups.
  • acylated alkylenediamines especially tetraacetylethylenediamine (TAED), acylated Triazine derivatives, especially 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated Glycolurils, especially tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, especially n-nonanoyl or Isononanoyloxybenzenesulfonat (n- or iso-NOBS), carboxylic anhydrides, in particular Phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate, 2,5-diacetoxy-2,5-dihydrofuran and those from the German patent applications DE19616 693 and DE
  • the transition metal compounds in question include in particular known from the German patent application DE195 29 905 manganese, iron, cobalt, Ruthenium or molybdenum salt complexes and those from the German patent application DE 196 20 267 known N-analog compounds, which are from the German patent application DE 195 36 082 known manganese, iron, cobalt, ruthenium or molybdenum carbonyl complexes, those described in German patent application DE 196 05 688 Manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and Copper complexes with nitrogenous tripod ligands resulting from the German patent application DE 196 20 411 known cobalt, iron, copper and ruthenium amine complexes, the manganese described in German patent application DE 44 16 438, Copper and cobalt complexes described in European patent application EP 0 272 030 described cobalt complexes, which are from the European patent application EP 0 693 550 known manganese complexes
  • Combinations of bleach activators and transition metal bleaching catalysts are, for example, from the German patent application DE 196 13 103 and 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 in customary amounts, preferably in an amount 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, in each case based on the total average, used.
  • Their content in the additives according to the invention can be, for example, 0.5 to 5 % By weight, preferably less than 3% by weight.
  • the bleach activator in a prefabricated form to introduce the process for the preparation of the additive.
  • the bleach activator in in a known manner with coating substances or, optionally using Auxiliaries, especially methyl celluloses and / or carboxymethyl celluloses, before his Insert has been granulated or extruded / pelletized and, if desired, further additives, for example dye.
  • Such granules preferably contain over 70% by weight, in particular from 90 to 99% by weight, of bleach activator.
  • the additive according to the invention contains a bleach activator that works under washing conditions Peracetic acid forms.
  • the weight ratio is (based on active substance contents) of anionic surfactants to bleach activators and optionally Bleaching catalysts 0.5: 1 to 2: 1 and in particular 0.9: 1 to 1.5: 1.
  • the weight ratio contains an additive according to the invention 30 to 60% by weight of a highly concentrated anionic surfactant compound and 25 to 40% by weight also a highly concentrated bleach activator compound.
  • ingredients of the compounds according to the invention include in Primarily soil repellents, but also superplasticizers, known substances, which improve solubility contribute, dyes and fragrances, possibly also enzymes as well Parts of the builder system, which are usually present in amounts up to a maximum of 10% by weight, preferably up to a maximum of 8% by weight and in particular in amounts below 5 % By weight, based in each case on the finished composition, are used.
  • soil repellents components can be included, which the oil and Influencing fat washability from textiles positively. 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 has been.
  • the preferred oil and fat dissolving components include, for example with non-ionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose a proportion of methoxyl groups of 15 to 30 wt .-% 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 known from the prior art Terephthalic acid or its derivatives, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified Derivatives of these.
  • non-ionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose a proportion of methoxyl groups of 15 to 30 wt .-% and of hydroxypropoxyl groups from 1 to 15% by weight, based in each case on the nonionic cellulose ether
  • the sulfonated derivatives are particularly preferred of the phthalic acid and terephthalic acid polymers.
  • a superplasticizer can improve the flow behavior, depending on the requirements in particular the known 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 in particular, are further ingredients of the additives according to the invention Builder substances, especially those which are not suitable for spray drying are considered.
  • the additives advantageously contain dextrins, for example oligomers or polymers of carbohydrates obtained by partial hydrolysis of starches can be.
  • the hydrolysis can be carried out according to customary methods, for example acid-catalyzed or enzyme-catalyzed Procedures are carried out. They are preferably hydrolysis products with average molecular weights in the range of 400 to 500,000.
  • DE dextrose equivalent
  • DE a polysaccharide with a dextrose equivalent
  • DE a customary measure of the reducing effect of a Polysaccharides compared to dextrose, which has a DE of 100.
  • Useful are both maltodextrins 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 higher molecular weights in the range of 2000 to 30,000.
  • a preferred dextrin is in the UK Patent application 94 19 091 described.
  • Dextrins are their reaction products with oxidizing agents, which in are capable of at least one alcohol function or an aldehyde function of the saccharide ring to oxidize to the carboxylic acid function.
  • oxidizing agents which in are capable of at least one alcohol function or an aldehyde function of the saccharide ring to oxidize to the carboxylic acid function.
  • Such oxidized dextrins and processes their manufacture is, 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 ones Polyglucosans and / or their water-soluble salts, such as those in the international patent application WO-A-93/08251 can be described or their preparation described, for example, in international patent application WO-A-93/16110 becomes. Oxidized oligosaccharides according to the older German are also suitable Patent application DE-A-19 600 018.
  • the additives can also be oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate, contain.
  • Glycerol disuccinates are also particularly preferred in this context and glycerol trisuccinates, as described, for example, in the US patents US 4,524,009, US 4,639,325, in European patent application EP-A-0 150 930 and Japanese Patent Application JP 93/339896.
  • Suitable quantities in zeolite-containing and / or silicate-containing formulations are 3 to 15% by weight.
  • organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally also be in lactone form, and which have at least 4 carbon atoms and at least one hydroxyl group and at most contain two acid groups.
  • Such cobuilders are used, for example, in the international Patent application WO-A-95/20029.
  • Suitable polymeric polycarboxylates are, for example, the sodium salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight from 800 to 150,000 (based on acid).
  • Suitable copolymeric polycarboxylates are in particular those of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid have been found to be particularly suitable Maleic acid proved to be 50 to 90 wt .-% acrylic acid and 50 to 10 wt .-% maleic acid contain.
  • Their relative molecular weight, based on free acids is in general 5000 to 200000, preferably 10000 to 120000 and in particular 50000 to 100000.
  • the (co) polymeric polycarboxylates can be either as a powder or as an aqueous solution are used, 20 to 55% by weight aqueous solutions being preferred; in the latter In this case they serve as granulation aids (see below).
  • biodegradable polymers made from more than two different ones Monomer units, for example those which according to DE-A-43 00 772 as Monomeric salts of acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives or according to DE-C-42 21 381 as monomer salts of acrylic acid and 2-alkylallylsulfonic acid as well as sugar derivatives.
  • copolymers are those described in the German patent applications DE-A-43 03 320 and DE-A-44 17 734 are described and preferably as monomers Have acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.
  • the additive is preferably 1 to 5% by weight. If desired, the content of these organic cobuilders are also higher. Quantities exceeding this 5% by weight but are advantageously in solid form and not via the granulating liquid introduced into the additive.
  • Polymers are also another preferred builder substance Aminodicarboxylic acids, their salts or their precursors. Especially preferred are polyaspartic acids or their salts and derivatives, of which in German patent application DE-A-195 40 086 discloses that in addition to cobuilder properties also have a bleach-stabilizing effect.
  • polyacetals which are obtained by reacting dialdehydes with polyol carboxylic acids, which have 5 to 7 carbon atoms and at least 3 hydroxyl groups have, for example as in European patent application EP-A-0 280 223 described, can be obtained.
  • Preferred polyacetals are made from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
  • the additives can also be, for example, in the form of their sodium salts replaceable polycarboxylic acids, such as citric acid, adipic acid, succinic acid, glutaric acid, Tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if provided such use is not objectionable for ecological reasons, as well as mixtures contained from these.
  • Preferred salts are the salts of polycarboxylic acids such as Citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and Mixtures of these.
  • the acids themselves can also be used.
  • the acids have a builder effect typically also the property of an acidifying component and serve thus also for setting a lower and milder pH value of washing or Detergents.
  • citric acid succinic acid, glutaric acid, Adipic acid, gluconic acid and any mixtures of these.
  • the content of organic builders in the additives according to the invention is preferably 0.1 to 15% by weight.
  • ingredients are preferably phosphonates, which are usually in finished products in amounts of 0.1 to normally not more than 2.5% by weight. you In contrast, the content of the additives according to the invention is preferably more than 1 % By weight and in particular 1.5 to 5% by weight.
  • the additives can also be equipped with dyes and fragrances, which are then usually applied in liquid form.
  • Proteases of the subtilisin type and in particular are preferred Proteases obtained from Bacillus lentus are used.
  • enzyme mixtures for example from protease and amylase or protease and lipase or lipolytic acting enzymes or protease and cellulase or from cellulase and lipase or lipolytically active enzymes or from protease, amylase and lipase or lipolytically acting enzymes or protease, lipase or lipolytically acting enzymes and Cellulase, in particular, however, mixtures or mixtures containing protease and / or lipase with lipolytic enzymes of particular interest.
  • the well-known cutinases are lipolytic enzymes. Peroxidases or Oxidases have been found to be suitable in some cases.
  • amylases include in particular ⁇ -amylases, iso-amylases, pullulanases and pectinases.
  • cellulases are preferably cellobiohydrolases, endoglucanases and ⁇ -glucosidases that also called cello bias, or mixtures of these are used. Since the distinguish different cellulase types by their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases become.
  • the enzymes can be adsorbed on carriers and / or embedded in coating substances to protect them against premature decomposition. If enzymes in the invention Additives are used, the proportion of enzymes, enzyme mixtures or enzyme granules preferably 5 to 30% by weight, in particular 8 to 20% by weight.
  • the bulk density of the additives according to the invention is preferably in a range between 550 and 1000 g / l.
  • the bulk density of the invention Additive not more than ⁇ 150 g / l, advantageously not more than 100 g / l deviates from the bulk density of the base granules or the base granules.
  • the additives are usually in granular form.
  • the particle size distribution can cover a wide range - as is usual with granules. However, it has shown and this is a particular advantage of the invention that the particle size distribution depends on the type and quantity of the pre-assembled raw materials. The rougher already The prefabricated raw materials used are, the more the particle size distribution be shifted to the higher range; the mostly undesirable The proportion of fine grains is reduced accordingly. Also the spectrum of the particle size distribution can be influenced by the use of pre-assembled ingredients.
  • Another particularly preferred embodiment is that the invention Additives of at most 20 area%, in particular at most 10 area%, deviate from the spherical shape, the deviation using the method of Silhouette projection is measured.
  • This measurement method can be used, for example, with the Perform "Particle Size Counter 3" from Zeiss.
  • the deviation from the spherical shape is determined here by what percentage of the area outside a Circle with the same total area as the projected image of the granules.
  • the additive contains anionic surfactant (s), prefabricated Foam inhibitor and bleach activator and / or bleach catalyst. It is special preferred that in addition to the foam inhibitors also the anionic surfactants and bleach activators or bleaching catalysts in pre-assembled, preferably granular form be used.
  • the additives according to the invention contain accordingly 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, especially in each case 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, especially in each case pre-assembled form.
  • the invention contains Additive all usually in solid form to one or more basic granules admixed components, which in total up to 30 wt .-%, preferably up to 25% by weight and in particular at least 10% by weight of the finished washing or detergent.
  • the invention contain Additive bleach activators and optionally bleach catalysts, anionic surfactants and foam inhibitors in amounts of at least 50% by weight (based on active substance).
  • Additive bleach activators and optionally bleach catalysts, anionic surfactants and foam inhibitors in amounts of at least 50% by weight (based on active substance).
  • 70 to 100 wt .-% of the additives according to the invention consist of pre-assembled forms of these raw materials.
  • “Filling materials” can be the other components of Detergents or cleaning agents, especially soil repellents and builders (including Alkali carbonates and alkali silicates) and enzymes, but also inorganic salts such as Serve sodium sulfate.
  • the water content of the additives is preferably below 10% by weight. and especially below 8% by weight.
  • Basic granules are understood to mean compounds of this type that already stand alone make up a detergent and usually at least tensides, builder substances and optionally contain peroxy bleach. These ingredients need not be contained in a single basic granulate, but can also be in different Compounds are distributed. 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 batch or continuous Granulate its ingredients here, the latter in a mixer / granulator with the addition of a small amount of granulating liquid to an optionally wet granulate processed, this - if spherical or pearl shape desired are - compact and round in a rounder and if necessary then, especially 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 can Compounds from the class of water-soluble cellulose ethers, starches and starch ethers be used. Carboxymethyl cellulose, in particular sodium carboxymethyl cellulose, is preferred here. Additives can also be used as granulation aids such as oxidation-stable complexing agents and stabilizers for per compounds and / or other constituents of detergents and cleaning agents mixed in or via the aqueous Granulation liquid are introduced. 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.
  • 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.
  • tallow alcohol sulfates and ethoxylated tallow alcohol sulfates are tallow alcohol sulfates and ethoxylated tallow alcohol sulfates (with up to 100 EO), starch phosphates, soaps and known Emulsifying agents.
  • an aqueous granulation aid is used Solution of (co) polymeric polycarboxylates used, as already described above were.
  • copolymers of acrylic acid and maleic acid have been found as well as biodegradable polymers from more than 2 monomer units as suitable proven.
  • 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 granulating aid is advantageously such that no drying is required after the granulation.
  • the granulation is anhydrous, So performed with anhydrous pelletizers.
  • the non-ionic surfactants that are liquid at the processing temperature (detailed list see below), especially ethoxylated (fatty) alcohols with a melting point below of 40 ° C, but also polyethylene glycols with molecular weights between 200 and 100,000, the latter advantageously in combination with nonionic surfactants or in aqueous Solution / dispersion are used.
  • the additives mentioned above in particular an aqueous solution of a Granulation aid, or other ingredients of detergents and cleaning agents at Rounding the moist granules added at the same time, e.g. B. be injected.
  • a advantageous embodiment of the invention is not in this process stage Liquid added.
  • the surface of the granules can also be finely divided up dusty parts are treated, which reduces the flow behavior of the granules can be further improved.
  • agents for surface treatment are Aluminosilicates such as amorphous and / or crystalline zeolite and / or calcium stearate and / or silicas.
  • the fine and / or coarse fractions are preferably sieved, if appropriate after drying and, after crushing the coarse fractions, leads them back to the granulation.
  • the base granules contain in particular surfactants, especially anionic surfactants, nonionic surfactants, optionally also cationic surfactants, amphoteric surfactants and / or zwitterionic surfactants, in addition Builder substances, peroxy bleach.
  • surfactants especially anionic surfactants, nonionic surfactants, optionally also cationic surfactants, amphoteric surfactants and / or zwitterionic surfactants, in addition Builder substances, peroxy bleach.
  • a base granulate processed with 10 to 40 wt .-% of an additive according to the invention wherein it it is particularly preferred that no more than 10% by weight of these two components, advantageously less than 5% by weight of further constituents, especially enzymes, are admixed become.
  • Embodiments have proven to be particularly advantageous in which the basic granules are in extruded form and a part of the anionic surfactants the teaching of the German application DE-A-195 19 139 now on the inventive Additives are added.
  • Anionic surfactants are, for example, those of the sulfonate and sulfate type used.
  • Preferred surfactants of the sulfonate type are C 9 -C 13 alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates such as are obtained, for example, from C 12 -C 18 monoolefins with a terminal or internal double bond by sulfonating with gaseous Sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products is considered.
  • alkanesulfonates obtained from C 12 -C 18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • esters of ⁇ -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 and their mixtures represent how they are produced by esterification by a monoglycerin with 1 to 3 moles of fatty acid or in the transesterification of triglycerides can be obtained with 0.3 to 2 mol of glycerol.
  • the sulfonation products represent a complex Mixture, the mono-, di- and triglyceride sulfonates with ⁇ -and / or contains internal sulfonic acid grouping.
  • Sulfonated form as by-products Fatty acid salts, glyceride sulfates, glycerine sulfates, glycerin and soaps. If you go to the Sulfation of saturated fatty acids or hardened fatty acid glycerol ester mixtures , the proportion of ⁇ -sulfonated fatty acid disalts can vary depending on the procedure can be 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 represent monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain C 8 to C 18 fatty alcohol residues or mixtures thereof.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below).
  • alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
  • alk (en) yl sulfates the alkali and in particular the sodium salts of the sulfuric acid half-esters of the C 12 -C 18 fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -C 20 oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred.
  • alk (en) yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical prepared on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials.
  • C 16 -C 18 alk (en) yl sulfates are particularly preferred from the point of view of washing technology. It can also be particularly advantageous, and particularly advantageous for machine washing agents, to use C 16 -C 18 -alk (en) yl sulfates in combination with lower melting anionic surfactants and in particular with those anionic surfactants which have a lower Krafft point and relatively low ones Washing temperatures of, for example, room temperature to 40 ° C. show a low tendency to crystallize.
  • the compositions therefore contain mixtures of short-chain and long-chain fatty alkyl sulfates, preferably mixtures of C 12 -C 14 fatty alkyl sulfates or C 12 -C 18 fatty alkyl sulfates with C 16 -C 18 fatty alkyl sulfates 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 predominantly consisting of C 16 and unsaturated sulfated fatty alcohols predominantly consisting of C 18 are particularly preferred, for example those derived from solid or liquid HD-Ocenol (R) fatty alcohol mixtures (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 quantities from 0.2 to 5% by weight.
  • 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 as well as soluble salts of organic bases, such as mono-, di- or triethanolamine.
  • the anionic surfactants are preferably in the form of their sodium or potassium salts, in particular 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 may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
  • EO ethylene oxide
  • alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow fat or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred.
  • the preferred ethoxylated alcohols include, for example, C 12 -C 14 alcohols with 3 EO or 4 EO, C 9 -C 11 alcohols with 7 EO, C 13 -C 15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12 -C 18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C 12 -C 14 alcohol with 3 EO and C 12 -C 18 alcohol with 7 EO.
  • the degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples of these are (tallow) fatty alcohols with 14 EO, 16 EO, 20 EO, 25 EO, 30 EO or 40 EO.
  • alkyl glycosides of the general formula RO (G) x can also be used as further nonionic surfactants, in which R denotes a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, C atoms and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.
  • nonionic surfactants which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, in particular together with alkoxylated fatty alcohols and / or alkyl glycosides, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters, as described for example in Japanese patent application JP 58/217598 or which are preferably prepared by the process described in international patent application WO-A-90/13533.
  • nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than that 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 represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R 4 represents a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R 5 represents a linear, branched or cyclic alkyl radical or Aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, C 1 -C 4 -alkyl or phenyl radicals being preferred, and [Z] for a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this radical.
  • R 3 represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
  • R 4 represents a linear, branched or cyclic alkyl radical or an
  • [Z] is also preferably obtained here by reductive amination of a sugar such as glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • a sugar such as glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • the N-alkoxy- or N-aryloxy-substituted compounds can then, 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.
  • the two hydrophilic groups and two hydrophobic Have groups per molecule are usually identified by a so-called "Spacer" separated from each other. This spacer is usually a carbon chain, which should be long enough that the hydrophilic groups have a sufficient Have a distance so that they can act independently of each other.
  • Such surfactants are generally characterized by an unusually low critical micelle concentration and the ability to greatly reduce the surface tension of the water.
  • Gemini surfactants does not only refer to dimeric, but 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 earlier German patent application P 195 03 061.3.
  • End-capped dimeric and trimeric mixed ethers according to the older one German patent application P 195 13 391.9 are characterized in particular by their bi and multifunctionality. So the end-capped surfactants mentioned good network properties and are low-foaming, so that they are particularly suitable for 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 can be described.
  • the basic granules contain builder substances, especially inorganic ones preferably zeolites and / or silicates, but optionally also "and / or" usual Phosphates, especially tripolyphosphates.
  • builder substances especially inorganic ones preferably zeolites and / or silicates, but optionally also "and / or" usual Phosphates, especially tripolyphosphates.
  • the latter lead in quantities up to 10 wt .-%, based on the total, to significant improvements in the Washing performance when used in combination with zeolite and / or silicates.
  • 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 may contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C 12 -C 18 fatty alcohols with 2 to 5 ethylene oxide groups , C 12 -C 14 fatty alcohols with 4 to 5 ethylene oxide groups or ethoxylated isotridecanols.
  • Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.
  • Suitable substitutes or partial substitutes for phosphates and zeolites are crystalline, layered sodium silicates of the general formula NaMSi x O 2x + 1 .yH 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4.
  • Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514.
  • Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3. In particular, both ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 O 5 .yH 2 O are preferred.
  • the preferred builder substances also include amorphous sodium silicates with a modulus Na 2 O: SiO 2 of 1: 2 to 1: 3.3, preferably 1: 2 to 1: 2.8 and in particular 1: 2 to 1: 2, 6, which are delayed release and have secondary washing properties.
  • the delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying.
  • the term “amorphous” is also understood to mean “X-ray amorphous”.
  • silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle.
  • it can very well lead to particularly good builder properties if the silicate particles deliver washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred.
  • Such so-called X-ray amorphous silicates which also have a delay in dissolution compared to conventional water glasses, are described, for example, in German patent application DE-A-44 00 024. Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.
  • organic builder substances already mentioned can also be used - at least in part - contained in the basic granules.
  • sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • Further bleaching agents which can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracid salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.
  • the bleach 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;
  • 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) in the agents is generally up to 10% by weight and preferably between 2 and 8% by weight.
  • 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, 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 polyvinyl pyrrolidone for example in amounts of 0.1 to 5 wt .-%, based on the agent used.
  • the agents can be derivatives of diaminostilbenedisulfonic acid or their Contain alkali metal salts. Suitable are e.g. Salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or similar connections, which instead of the morpholino group is a diethanolamino group, a methylamino group, carry an anilino group or a 2-methoxyethylamino group.
  • Farther brighteners of the substituted diphenylstyryl type may be present, e.g.
  • alkali salts 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl, or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl) -diphenyls.
  • Mixtures of the aforementioned brighteners can be used.
  • the basic granules can be prepared by any of the known processes such as spray drying, granulation, Compacting (roller compacting, pelleting, extrusion) can be produced. If a spray-dried basic granulate is available, then this is combined with another produced further base granules which contain the peroxy bleach, mixed.
  • the washing or cleaning agents according to the invention preferably contain but no base granules, which were produced by spray drying. In one particularly preferred embodiment of the invention is the washing or cleaning agent from a base granulate and a mixed additive according to the invention.
  • the basic granules can also be obtained by extrusion of a premix with the following one Shaping can be produced, as described, for example, in WO-A-91/02047 is executed.
  • Base granules in particular extruded base granules, with almost spherical, rounded ones or rounding additives to a heavy granular washing or detergent mixed with bulk weights of preferably above 700 g / l.
  • 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 on the sieve 0.8 mm and 26% by weight were 0.4 mm on the sieve. In the basic extrudate used, the fraction was 0.4 mm sieve only 10% by weight; by mixing these finer parts became more than doubled!
  • the agent 2 according to the invention showed only a negligible reduction in the Bulk density from 740 g / l to about 750 g / l.
  • Sieve analysis (sieves 0.8 mm and 0.4 mm) showed that 85% by weight on the sieve was 0.8 mm and only 15% by weight on the sieve 0.4 mm.
  • the fraction on the 0.4 mm sieve was again 10% by weight; the granulation compared the finer fractions Means 1 reduced, the aesthetics of the product accordingly improved considerably.
  • the Agent 2 according to the invention also had a higher degree of whiteness (measured according to Berger and after Ganz) as the (comparative) agent 1.
  • the one according to the invention had Agent 2 also 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 (AT), perborate monohydrate (PBMH) and bleach activator (TAED) content. The values obtained (indicated in each case in% by weight) clearly show that by using the additive according to the invention it was possible to achieve a substantially better homogeneity in the package.
  • AT anionic surfactant
  • PBMH perborate monohydrate
  • TAED bleach activator

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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 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.
  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 un ou des 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 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 produits 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 derniers 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

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

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Family Applications (1)

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

Country Status (6)

Country Link
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.

Family Cites Families (18)

* 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
DE3400008A1 (de) † 1984-01-02 1985-07-11 Henkel KGaA, 4000 Düsseldorf Zur verwendung in tensidhaltigen mitteln geeignetes schaumregulierungsmittel
GB8619634D0 (en) † 1986-08-12 1986-09-24 Unilever Plc Antifoam ingredient
US5002691A (en) † 1986-11-06 1991-03-26 The Clorox Company Oxidant detergent containing stable bleach activator granules
GB8811447D0 (en) * 1988-05-13 1988-06-15 Procter & Gamble Granular laundry compositions
GB8811954D0 (en) † 1988-05-20 1988-06-22 Unilever Plc Antifoam ingredients
US4997590A (en) † 1988-12-22 1991-03-05 The Procter & Gamble Company Process of coloring stabilized bleach activator extrudates
DE4024759A1 (de) † 1990-08-03 1992-02-06 Henkel Kgaa Bleichaktivatoren in granulatform
KR0184850B1 (ko) † 1990-09-28 1999-05-01 자코버스 코넬리스 라써 알킬 설페이트 및 폴리하이드록시 지방산 아미드 계면활성제 함유 세제
DE4127323A1 (de) * 1991-08-20 1993-02-25 Henkel Kgaa Verfahren zur herstellung von tensidgranulaten
US5516449A (en) † 1992-04-03 1996-05-14 The Procter & Gamble Company Detergent compositions
DE4221736A1 (de) * 1992-07-02 1994-01-05 Henkel Kgaa Feste waschaktive Zubereitung mit verbessertem Einspülverhalten
AU4777993A (en) * 1992-08-01 1994-03-03 Procter & Gamble Company, The Low gelling detergent compositions and a process for making such compositions
ES2109720T3 (es) * 1993-08-02 1998-01-16 Henkel Kgaa Granulado regulador de la espuma y procedimiento para su fabricacion.
EP0639639B2 (fr) † 1993-08-17 2010-07-28 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
DE19521365A1 (de) * 1995-06-12 1996-12-19 Henkel Kgaa Feste und hochverdichtete waschaktive Zubereitungen mit verbesserter Löslichkeit auch schon bei niederen Flottentemperaturen
EP0771864A1 (fr) † 1995-11-03 1997-05-07 The Procter & Gamble Company Granule supprimant la mousse

Also Published As

Publication number Publication date
ATE193322T1 (de) 2000-06-15
ES2148999T5 (es) 2003-05-01
WO1998001531A3 (fr) 1998-04-09
DE59701763D1 (de) 2000-06-29
JPH11513074A (ja) 1999-11-09
EP0888450A2 (fr) 1999-01-07
ES2148999T3 (es) 2000-10-16
WO1998001531A2 (fr) 1998-01-15
EP0888450B2 (fr) 2003-01-15

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