EP1036158B1 - Procede de production de melanges de matieres premieres de masse volumique apparente elevee - Google Patents

Procede de production de melanges de matieres premieres de masse volumique apparente elevee Download PDF

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Publication number
EP1036158B1
EP1036158B1 EP98963490A EP98963490A EP1036158B1 EP 1036158 B1 EP1036158 B1 EP 1036158B1 EP 98963490 A EP98963490 A EP 98963490A EP 98963490 A EP98963490 A EP 98963490A EP 1036158 B1 EP1036158 B1 EP 1036158B1
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Prior art keywords
weight
raw material
binder
process according
solid
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German (de)
English (en)
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EP1036158A1 (fr
Inventor
Wilfried Rähse
Norbert Kühne
Wolfgang Seiter
Kathleen Paatz
Kathrin Schnepp-Hentrich
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3707—Polyethers, e.g. polyalkyleneoxides
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • C11D17/065—High-density particulate detergent compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2093—Esters; Carbonates

Definitions

  • the invention relates to a process for the preparation of granular raw material compounds from the field of detergents or cleaners, especially the laundry detergent, which have a high bulk density and still a good, improved solubility even in cold water and which are free of dust and fines. Furthermore, the present invention relates to detergents or cleaners containing such raw material compounds.
  • Particulate detergents or cleaning agents with bulk densities above 600 g / l have been part of the state of the art for quite some time. In recent years, was associated with the increase in bulk density and a concentration of the washing and cleaning active ingredients, so that the consumer had to dose not only less volume, but also less mass per washing or cleaning process. The increase in bulk density and, in particular, once again the higher concentration of the agents on washing or cleaning-active substances was generally paid for by a subjectively worse, slower dissolution rate of the agent used from the point of view of the consumer. This undesirable dissolution delay is triggered inter alia by the fact that a number of anionic and nonionic surfactants which are customary in practice and, above all, corresponding surfactant mixtures tend to form gel phases when dissolved in water.
  • Such gelling agents can already occur at surfactant contents of 10% by weight, based on the total agent, that is to say surfactant quantities which are quite customary in detergents or cleaners.
  • surfactant quantities which are quite customary in detergents or cleaners.
  • the tendency to form gels also increases with the increasingly compact grain structure of the particles.
  • EP-B-0 486 592 describes granular or extruded detergents or cleaning compositions having bulk densities above 600 g / l and containing anionic and / or nonionic surfactants in amounts of at least 15% by weight and up to about 35% by weight , she are prepared by a process in which a solid, free-flowing premix containing a plasticizer and / or lubricant of preferably aqueous surfactant pastes and / or aqueous polymer solutions, extruded at high pressures between 25 and 200 bar strand and the strand after leaving the Hole shape is cut by means of a cutting device to the predetermined granule dimension and rounded.
  • the premix consists, at least in part, of solid ingredients to which liquid ingredients such as liquid nonionic surfactants which are liquid at room temperature are optionally added.
  • liquid ingredients such as liquid nonionic surfactants which are liquid at room temperature are optionally added.
  • aqueous formulations are used as plasticizers and / or lubricants in preferred embodiments.
  • plasticizers and / or lubricants in preferred embodiments.
  • organic liquids optionally in turn in admixture with water, in question.
  • the patent does not disclose process conditions to be followed in the case of anhydrous extrusion.
  • the extrudates produced can either already be used as detergents or cleaners or else subsequently be treated with other granules or powder components to form finished detergents or cleaners.
  • a further solution to the above problems can be achieved by using at least two granular components in granular detergents or cleaners having a bulk density above 600 g / l, of which at least one extruded, wherein the extruded component in amounts of from 30 to 85 wt .-%, based on the agent, in the agent and from 0 to less than 15% by weight, based on the extruded component, of surfactants, while at least one further surfactant-containing component is provided by which further surfactants are provided in the composition.
  • anhydrous or nearly anhydrous methods are not described.
  • surfactant granules according to WO-A-93/04162, if they contain, for example, over 90 wt .-% of surfactants.
  • Such granules are due to their other positive physical properties and due to their high concentration of - especially anionic - surfactants highly suitable as admixing components to concentrated detergents or cleaning agents; however, it would be desirable if the dissolution rate of such raw material compounds could be improved.
  • polymer compounds which have at least one amphiphilic polymer, in particular polyester, and an increased mechanical stability and storage stability (no sticking). They contain 10-97 wt .-% of polymers having a softening temperature above 35 ° C and also 3 to 90 wt .-% of inorganic solids such as zeolite, silicate, carbonate, sulfate, which have particle sizes of not more than 500 microns. Polymer and inorganic solids are both heated separately to a temperature above the softening temperature and mixed at this temperature.
  • the result is a total of a homogeneous melt, which granulates, for example, by spraying on a cooled surface or allowed to solidify by prilling in cooled air.
  • the compounds are comminuted to a particle size between 50 microns and 5 mm. Bulk weights and dissolution rates of these compounds are not disclosed.
  • EP-B-0 554 366 (P & G) describes builder agglomerates which contain (a) 50-75% by weight hydrous aluminosilicate and / or hydrous or anhydrous crystalline layered sodium silicate and (b) polymers as binders, preferably in combination with nonionic surfactants in a weight ratio of at least 1: 1.
  • Preferred polymers are polyethylene glycols having an average molecular weight of between 1,000 and 20,000, in particular between 3,000 and 10,000. Polymers solid at room temperature are melted before being processed.
  • nonionic surfactants C 9 -C 16 -alcohols with 4-8 EO are preferred.
  • the process can be carried out in principle anhydrous; but then obviously high levels of nonionic surfactants liquid at room temperature are required to ensure the granulation ability of the mixture.
  • the nonionic surfactant content is 17% by weight, based on the compound.
  • the average particle size of the agglomerates, which are produced in an intensive mixer with a special energy input, is between 200 and 800 ⁇ m. Information on the bulk density and dissolution rate of the agglomerates are not made.
  • Patent Application WO-A-97/10326 discloses agglomerates which are obtained as intermediates and which are obtained by continuously mixing a surfactant paste containing from 30 to 95% by weight of surfactant, from 0.1 to 50% by weight. of a non-aqueous binder and balance water, with solids in a high speed mixer, followed by granulation and further compression in a moderate post-drying mixer / densifier. Bulk weights of above 650 g / l are achieved. The finished granules can consist of several different ingredients of detergents or cleaners.
  • the content of surfactants introduced by the paste is at most 55 wt .-%, while the introduced solids according to examples not more than each constitute 35 wt .-%.
  • German patent application DE 196 38 599 which has not previously been published, describes the anhydrous preparation of particulate detergents or cleaners, compounds or treated raw materials for this purpose, which have a bulk density above 600 g / l and already have an improved dissolution rate compared with those agents which have been processed of ingredients which are present in aqueous solution, or which are free, ie does not contain bound water in any form.
  • a lubricant with adhesive function at least one ingredient is used, which is at a pressure of 1 bar and temperatures below 45 ° C in solid form, but under the processing conditions as a melt, said melt is used as a polyfunctional, water-soluble binder in the Re-dissolution of the agent in aqueous liquor but disintegrating acts.
  • a treated raw material is understood to mean a relatively fine-particle raw material which is converted into a coarser particle by the process described. As raw materials, very finely divided qualities with dusty proportions can be processed. However, explicit data on particle size distributions are missing.
  • European Patent Application EP 0 299 599 A1 discloses bleach activator bodies, e.g. Extrudates containing 50-97.5% by weight of particulate bleach activator. From 0.5% to 40% by weight of a particulate, water-soluble disintegrant, and from 2-45% by weight of a binder, e.g. Nonionic surfactant or polyethylene glycol, wherein the ingredients are evenly distributed throughout the body, and wherein the bleach activator is a mixture of a relatively surface active bleach activator and a relatively surface inactive bleach activator.
  • a binder e.g. Nonionic surfactant or polyethylene glycol
  • German laid-open specification DE 43 32 373 A1 discloses detergent mixtures which contain certain relatively long-chain and certain shorter-chain alkyl and / or alkenyl sulfates and hydrophobic structure breakers of the formula R 4 O (CH 2 CH 2 O) n H in which R 4 is a linear or branched alkyl and / or alkenyl radical having 12 to 18 carbon atoms and n is 0 or numbers from 1 to 5, wherein the detergent mixtures are anhydrous and the weight ratio between longer and shorter alkyl and / or alkenyl sulfates 90: 10 to 70: 30 is.
  • US Pat. No. 5,431,857 discloses a process for producing detergents having a bulk density of 650 g / l, in which a mixer contains 1-50% by weight of linear alkylbenzenesulfonate as dry particles, 1-50% by weight of C 12-16 Alkyl sulfate as dry particles, 20-50% by weight of builder, and 0.1% by weight to 35% by weight of an agglomeration aid comprising polyethylene glycol, wherein alkylbenzenesulfonate and alkyl sulfate are added in separate feed streams. The resulting agglomerates are then dried to obtain the detergent.
  • the object of the invention was to provide raw materials in relatively coarse-grained form - suitable for the coarse-grained detergent - which not only disintegrate rapidly in an aqueous liquor, but also dissolve quickly. Likewise, washing or cleaning agents should be prepared in relatively coarse-grained form containing these raw materials.
  • the invention accordingly relates, in a first embodiment, to a process for producing a raw material compound from the washing and cleaning agent area, according to claim 1.
  • the melting point is the temperature at which the liquid and the solid phase of a substance are in thermodynamic equilibrium at about 1 bar pressure (or more precisely at 1.013 bar pressure). At the melting point, therefore, a substance passes from the ordered solid to the disordered liquid state (melting). For many substances, such as amorphous substances, but also polymers and mixtures or not 100% pure substances, a wider melting interval is measured.
  • the softening point is the temperature at which these substances begin to collapse due to partially present melts; The softening point can be much lower than the temperature at which the entire substance has completely reached the liquid state.
  • melts present under processing conditions are also understood as meaning partial melts, as present at the softening point and above it.
  • Essential for the invention is that the binder or the binder mixture is present at 45 ° C in the ordered solid form, but at least softened under the process conditions and is present as a partial melt. It is not necessary that the entire binder or the entire binder mixture is present as a complete melt, but this can certainly have advantages.
  • Under a compound is usually a granulate, agglomerate or assembled Understood conglomerate, which consists of at least two components.
  • these two compulsory constituents are the raw material per se or a raw material class and the non-aqueous binder.
  • the compounds according to the invention contain at least 50% by weight, preferably at least 65% by weight and in particular at least 70% by weight, either a single raw material or several raw materials which belong to the same raw material class.
  • Preferred classes of raw materials include anionic surfactants, especially the sulfate and / or sulfonate anionic surfactants, peroxy bleaches, preferably inorganic peroxy bleaches, and bleach activators, preferably organic bleach activators.
  • the compounds may contain, for example, alkyl sulfates and alkylbenzenesulfonates in total in the stated minimum amounts.
  • Another combination of several raw materials of a raw material class would be, for example, the content of the compounds of perborate monohydrate and perborate tetrahydrate or perborate and percarbonate.
  • the specified minimum amounts of the raw materials refer in the context of the present invention - unless otherwise stated - to the anhydrous active substance of the raw materials.
  • Particularly advantageous raw material compounds have at least 80% by weight of the individual raw material or of the raw materials from a raw material class.
  • surfactants of the sulfonate type are preferably C 9 -C 13 alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and Hydroxyalkansulfonaten and disulfonates, such as those from C 12 -C 18 monoolefins having terminal or internal double bond by sulfonation with gaseous Sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation obtained.
  • alkanesulfonates which are obtained from C 12 -C 18 -alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • esters of ⁇ -sulfo fatty acids for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.
  • esters of ⁇ -sulfo fatty acids for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.
  • the alkylbenzenesulfonates are preferred.
  • Alk (en) ylsulfates are the alkali metal salts and, in particular, the sodium salts of the sulfuric monoesters of C 12 -C 18 fatty alcohols, for example of coconut fatty alcohol, tallow fatty alcohol, Lauryl, myristyl, cetyl or stearyl alcohol or C 10 -C 20 oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) ylsulfates of said chain length, which contain a synthetic, produced on a petrochemical basis straight-chain alkyl radical, which have an analogous degradation behavior as the adequate compounds based on oleochemical raw materials.
  • C 12 -C 16 -alkyl sulfates and C 12 -C 15 -alkyl sulfates and C 14 -C 15 -alkyl sulfates and C 14 -C 16 -alkyl sulfates are particularly preferred.
  • 2,3-Alkyl sulfates which are prepared, for example, according to US Pat. Nos. 3,234,258 or 5,075,041 and can be obtained as commercial products of Shell Oil Company under the name DAN (R) , are suitable anionic surfactants.
  • the sodium perborate tetrahydrate and the sodium perborate monohydrate as well as the sodium percarbonate have particular significance.
  • Other useful bleaching agents are, for example, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -forming peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.
  • inorganic peroxy bleaches are particularly preferred, especially the above-mentioned perborates and percarbonates.
  • the preferred organic bleach activators include, in particular, those N-acyl or O-acyl compounds which form organic peracids with H 2 O 2 , preferably polyacylated alkylenediamines, such as N, N'-tetraacylated diamines, acylated glycolurils, in particular tetraacetylglycoluril, N-acyl acylated hydantoins, hydrazides, triazoles, triazines, urazoles, diketopiperazines, sulfuryl amides and cyanurates, as well as carboxylic esters such as p- (alkanoyloxy) benzenesulfonates, especially sodium isononanoyloxybenzenesulfonate, and the p- (alkenoyloxy) benzenesulfonates, further caprolactam derivatives, carboxylic acid anhydrides such as phthalic anhydride and esters of Polyols such as
  • bleach activators are acetylated mixtures of sorbitol and mannitol, as described, for example, in European Patent Application EP-A-0 525 239, and acetylated pentaerythritol.
  • Particularly preferred bleach activators are N, N, N ', N'-tetraacetylethylenediamine (TAED), 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine (DADHT) and acetylated sorbitol-mannitol mixtures (SORMAN),
  • the bleach activator may be coated in a known manner with encapsulating substances or optionally granulated or extruded / pelleted prior to the compounding and enlargement according to the invention using auxiliaries, in particular methylcelluloses and / or carboxymethylcelluloses and, if desired, further additives, for example dye ,
  • auxiliaries in particular methylcelluloses and / or carboxymethylcelluloses and, if desired, further additives, for example dye
  • such raw materials should consist of at least 90% by weight of the bleach activator.
  • a bleach activator is used which forms peracetic acid under washing conditions.
  • the bulk density of the raw material compounds is at least 600 g / l, but preferably at least 700 g / l and in particular at least 750 g / l.
  • Bulk weights of 800 g / l and above are also conceivable without significantly impairing the dissolving behavior of the raw material compounds.
  • a non-aqueous binder is used, which is already present completely at temperatures up to 130 ° C, preferably up to 100 ° C and especially to 90 ° C as a melt.
  • the binder must therefore be selected depending on the process and process conditions or the process conditions, in particular the process temperature must - if a particular binder is desired - be adapted to the binder.
  • Binders to be used according to the invention which can be used alone or in admixture with other binders, are polyethylene glycols and 1,2-polypropylene glycols.
  • modified polyethylene glycols and polypropylene glycols include, in particular, the sulfates and / or the disulfates of polyethylene glycols or polypropylene glycols having a molecular weight between 600 and 12000 and in particular between 1000 and 4000.
  • Another group consists of mono- and / or disuccinates of the polyalkylene glycols, which in turn are molecular weights between 600 and 6000, preferably between 1000 and 4000.
  • modified polyalkylene glycol ethers For a more detailed description of the modified polyalkylene glycol ethers, reference is made to the disclosure of International Patent Application WO-A-93/02176.
  • polyethylene glycols are included such polymers, in addition to ethylene glycol also C 3 -C 5 glycols and glycerol and mixtures thereof are used as starting molecules in their production.
  • ethoxylated derivatives such as trimethylolpropane having 5 to 30 EO.
  • the polyethylene glycols preferably used may have a linear or branched structure, with particular preference being given to linear polyethylene glycols.
  • Particularly preferred polyethylene glycols include those having molecular weights between 2,000 and 12,000, advantageously about 4,000, wherein polyethylene glycols having molecular weights below 3500 and above 5000, especially in combination with polyethylene glycols having a molecular weight of 4000, can be used and advantageously such combinations are more than 50 wt .-%, based on the total amount of polyethylene glycols, polyethylene glycols having a molecular weight between 3500 and 5000 have.
  • polyethylene glycols which are present in liquid form at room temperature and a pressure of 1 bar can also be used as binders; Here is mainly of polyethylene glycol with a molecular weight of 200, 400 and 600 the speech.
  • these per se liquid polyethylene glycols should be used only in a mixture with at least one other binder, said mixture must meet the requirements of the invention again, ie must have a melting point or softening point of at least above 45 ° C.
  • the optionally usable modified polyethylene glycols also include one or more end-capped polyethylene glycols, the end groups preferably being C 1 -C 12 alkyl chains, which may be linear or branched.
  • the end groups on the alkyl chains between C 1 and C 6 especially between C 1 and C 4 , wherein also represent isopropyl and isobutyl or tert-butyl quite possible alternatives.
  • additional binders are low molecular weight polyvinylpyrrolidones and derivatives of these having molecular weights of up to a maximum of 30,000. Preferred here are molecular weight ranges between 3,000 and 30,000, for example 10,000. Polyvinylpyrrolidones are preferably used in combination with polyethylene glycols.
  • Suitable other optional, additional binders have proven to be substances which already have wash or cleaning-active properties, for example nonionic surfactants with melting points of at least 45 ° C. or mixtures of nonionic surfactants and other binders.
  • the preferred nonionic surfactants include alkoxylated fatty or oxo alcohols, in particular C 12 -C 18 -alcohols.
  • degrees of alkoxylation, in particular degrees of ethoxylation averaging 18 to 100 AO, in particular EO per mole of alcohol and mixtures thereof have proved to be particularly advantageous.
  • Especially fatty alcohols with an average of 18 to 35 EO, in particular with an average of 20 to 25 EO show advantageous binding properties in the sense of the present invention.
  • ethoxylated alcohols having an average of less EO units per mole of alcohol may also be present in binder mixtures, for example tallow fatty alcohol with 14 EO.
  • binder mixtures for example tallow fatty alcohol with 14 EO.
  • the content of the binder in these relatively low ethoxylated alcohols is less than 50% by weight, in particular less than 40% by weight, based on the total amount of binder used.
  • nonionic surfactants usually used in detergents or cleaning agents, such as C 12 -C 18 -alcohols having an average of 3 to 7 EO, which are liquid at temperatures up to 30 ° C.
  • nonionic surfactants are preferably present, if at all the binder mixtures are present only in amounts such that 0 to at most 10 wt .-%, in particular 0 to 5 wt .-% of these nonionic surfactants are contained in the raw material compounds.
  • liquid nonionic surfactants are therefore not a constituent of the binder mixture, since these not only the softening point reduce the mixture, but also contribute to the stickiness of the final product and also often do not meet the requirement of rapid dissolution of the binder / the partition in the final product by their tendency to lead on contact with water to gels to the desired extent.
  • anionic surfactants used in detergents or cleaning agents or their precursors, the anionic surfactant acids, are contained in the binder mixture, since they usually do not have a sufficient binding effect.
  • anionic surfactants can be part of the raw material compound itself.
  • nonionic surfactants which are useful as optional, additional binders are the non-gelative fatty acid methyl ester ethoxylates, especially those having an average of 10 to 25 EO (for a more detailed description of this group of substances, see below). Particularly preferred representatives of this substance group are predominantly methyl esters based on C 16 -C 18 -fatty acids, for example hardened beef tallow methyl ester with an average of 12 EO or with an average of 20 EO.
  • ethoxylated fatty acids having 2 to 100 EO, whose "fatty acid” radicals may be linear or branched in the context of this invention.
  • fatty acid radicals
  • such ethoxylates are preferred which have a narrowed homolog distribution (NRE) and / or a melting point above 50 ° C.
  • NRE narrowed homolog distribution
  • Such fatty acid ethoxylates may be used in combination with the binders of the invention, while the non-ethoxylated sodium and potassium soaps are less preferred.
  • hydroxy mixed ethers which can be obtained by ring-opening epoxides of unsaturated fatty acid esters according to the teaching of European Patent Application EP-A-0 754 667 (BASF) as optional, additional binders, in particular in combination with polyethylene glycols, the aforementioned fatty acid methyl ester or the fatty acid ethoxylates, suitable.
  • the binder used is a mixture containing C 12 -C 18 fatty alcohol based on coconut or tallow with an average of 20 EO and polyethylene glycol having a relative molecular weight of 400 to 4000.
  • a mixture is used as the binder, which predominantly based on C 16 -C 18 fatty acid methyl esters with an average of 10 to 25 EO, in particular hydrogenated beef tallow with an average of 12 EO or 20 EO average, a C 12 -C 18 fatty alcohol based on coconut or tallow with an average of 20 EO and polyethylene glycol having a molecular weight of 400 to 4000 contains.
  • binders have proven, either alone on polyethylene glycols having a molecular weight around 4000 or on a mixture of C 12 -C 18 fatty alcohol based coconut or tallow with an average of 20 EO, one of the above-described fatty acid methyl ester and a polyethylene glycol, in particular with a molecular weight around 4000, are based.
  • raw materials such as trimethylolpropylenes (commercial products from BASF, Federal Republic of Germany) may optionally be contained in binder mixtures, especially in admixture with polyethylene glycols.
  • alkyl glycosides of the general formula RO (G) x can also be used as further binders in combination with the binders according to the invention, in which R is a primary straight-chain or methyl-branched, in particular in the 2-position methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol which represents a glycose unit having 5 or 6 C atoms, preferably glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1.2 to 1.4.
  • those alkyl glycosides are suitable which have a degree of softening above 80 ° C and a melting point above 140 ° C.
  • highly concentrated compounds with contents of at least 70 wt .-% alkyl glycosides, preferably at least 80 wt .-% alkyl glycosides.
  • the melt agglomeration and in particular the melt extrusion with such highly concentrated compounds can already be carried out at temperatures which are above the softening point but still below the melting temperature.
  • Particular preference is given to mixtures of polyethylene glycols and alkyl glycosides, advantageously in weight ratios of from 25: 1 to 1: 5, with particular preference from 10: 1 to 2: 1.
  • Polyhydroxy fatty acid amides of the formula (I) in which R 2 CO is an aliphatic acyl radical having 6 to 22 carbon atoms, R 1 is hydrogen, an alkyl or hydroxyalkyl radical having 1 , are also suitable as optional, additional binders, in particular in combination with polyethylene glycols and alkyl glycosides to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
  • the polyhydroxy fatty acid amides are derived from reducing sugars with 5 or 6 carbon atoms, in particular from the glucose.
  • the group of polyhydroxy fatty acid amides also includes compounds of the formula (II)
  • 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 having 2 to 8 carbon atoms
  • R 5 is a linear, branched or cyclic alkyl radical or a Aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, wherein C 1 -C 4 alkyl or phenyl radicals are preferred
  • [Z] is a linear polyhydroxyalkyl radical whose alkyl chain is substituted with at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this group.
  • [Z] is also obtained here preferably 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 be converted into the desired polyhydroxy fatty acid amides, for example according to the teaching of international patent application WO-A-95/07331, by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
  • Particularly preferred glucamides melt even at 95 to 105 ° C. But here too - as in the case of the alkyl glycosides - working temperatures of the invention which are above the softening temperature but below the melting temperature are normally sufficient.
  • the content of binder or binders in the raw material compound is preferably at least 2% by weight, but less than 20% by weight, in particular less than 15% by weight, with particular preference being given to amounts in the range of 3% by weight. to 10% by weight.
  • binder for the sake of simplicity, only one or the binder will be discussed. However, it should be made clear that the use of several different binders and mixtures of different binders is always possible.
  • the raw material compounds may contain in minor amounts more at temperatures below 30 ° C (1 bar) solid ingredients. It is particularly desirable if, as further components, those are selected which have already been mentioned above as the preferred raw materials and raw material classes.
  • a bleach activator granule containing more than 60% by weight of TAED could additionally contain anionic surfactant or anionic surfactants, for example, alkyl sulfates and / or alkylbenzenesulfonates. Since it is considered advantageous in the context of the invention to provide the highest possible concentration of only one raw material in the compound, it is preferred that the second solid raw material is contained in the compounds in amounts of up to a maximum of 30% by weight.
  • the proportions of such compounds in the compound of the invention are preferably less than 25 wt .-% and in particular less than 20 wt .-%.
  • further constituents such as finely divided aluminosilicates, for example zeolite A, X and / or P, amorphous or crystalline silicates, carbonates, optionally also sulfates in minor amounts, which are usually not above 5 wt .-%, based on the compound of the invention, lie, be contained.
  • the finely divided aluminosilicates can serve tofastpudem the raw material compounds of the invention.
  • liquid ingredients are - with the exception of the above-mentioned maximum of 10 wt .-% of nonionic surfactants - in the raw material compounds of the invention not included.
  • the raw material compounds according to the invention contain substantially no free water, ie no water, which is not bound to the solids in any chemical or physical form. This is achieved by the substantially anhydrous preparation of the raw material compounds (see below), whereby water is introduced only in the amounts as it is contained in the solid materials used as it were "impurity".
  • a raw material compound contains 55 to 85 wt .-% bleach activator, 0 to 25 wt .-%, preferably 5 to 22 wt .-% of anionic surfactants such as alkylbenzenesulfonates and / or alkyl sulfates, optionally in pre-compounded form, 5 to 12 wt .-% of a non-aqueous binder, preferably polyethylene glycol having a molecular weight above 3500, in particular by 4000, or a swollen polymer.
  • the raw material compound additionally contains 1 to 7.5 wt .-%, preferably 2 to 6 wt .-% of a liquid at temperatures below 35 ° C (1 bar) nonionic surfactant, such as a C 12th C 18 fatty alcohol with 3 to 7 EO.
  • the raw material compound additionally contains 0.5 to 5 wt .-% of a finely divided, in particular water-insoluble ingredient, such as an aluminosilicate as indicated above.
  • a finely divided, in particular water-insoluble ingredient such as an aluminosilicate as indicated above.
  • Such ingredients generally serve as a powdering agent and can also be applied later in the context of this invention to the raw material compound.
  • the raw material compound contains 60 to 85% by weight of one or more inorganic builder substances, 3 to 10% by weight of a binder used according to the invention and up to 20% by weight of anionic and / or nonionic surfactants ,
  • builder compounds are preferred which contain 50 to 65% by weight of zeolite A, X, Y and / or P and 15 to 30% by weight of an amorphous one Alkali silicate have.
  • the raw material compounds according to the invention have surprisingly good release properties.
  • R-test serves the determination of the residue behavior (R-test), wherein in a 2-1 beaker 8 g of the test agent with stirring (800 rev / min centered with laboratory stirrer / propeller stirring 1.5 cm from the beaker bottom) sprinkled in 1 liter of water and stirred for 1.5 minutes at 30 ° C. The test is carried out with water of a hardness of 16 ° d. The wash solution is then poured off through a sieve (80 ⁇ m). The beaker is rinsed with very little cold water over the sieve. There is a 2-fold determination.
  • crystalline tetraacetylethylenediamine has a residue of about 60%, granular TAED containing about 95% by weight of TAED, 3.5% by weight of carboxymethylcellulose and 1.5% by weight of water still 54%.
  • extruded TAED which can be obtained, for example, from Rettenmaier, with residues of about 30%, is significantly above the value desired for use in detergents or cleaners.
  • TAED By grinding of TAED to a particle size distribution below 100 microns, although the residue behavior can be improved to 22%;
  • Residue values below 10% are usually obtained when the raw material used has been ground before compounding to particle sizes of less than 500 ⁇ m, for example less than 200 ⁇ m and possibly even less than 100 ⁇ m.
  • the compound has a particle size distribution that is significantly coarser compared to the particle size distribution of the raw material used Values is shifted. So it is particularly preferred that the d90 value (particle size of at least 90 wt .-% of the substance under consideration) of the raw material compound is at least 200 microns greater than the d90 value of at least 50 wt .-% of raw material used. This means that with a d90 value of the raw material of at most 400 .mu.m, the d90 value of the raw material compound is at least 600 .mu.m, but with a d90 value of the raw material of at most 1 mm, the d90 value of the raw material compound is included at least 1.2 mm.
  • the d90 value of the raw material compound is not less than 400 .mu.m, even if the d90 value of the raw material should be below 150 .mu.m, since the raw material compounds should be dust-free according to the invention.
  • the compounding of the ingredients of the raw material compounds with simultaneous or subsequent shaping can be carried out by conventional methods in which compression forces such as granulation, compacting, for example roll compacting or extrusion, or tabletting, optionally with the addition of small amounts of conventional disintegrants, and pelletizing done.
  • compression forces such as granulation, compacting, for example roll compacting or extrusion, or tabletting
  • spray-dried granules can be used as prefabricated compounds in the premix, but the invention is by no means limited thereto. Rather, the process according to the invention lends itself to use no spray-dried granules, since even very finely divided raw materials with dust-like proportions can be easily processed according to the invention, without previously precompounded, for example, spray-dried.
  • the actual granulation, compaction, tabletting, pelleting or extrusion process takes place according to the invention at processing temperatures which, at least in the densification step, correspond at least to the temperature of the softening point, if not even the temperature of the melting point of the binder.
  • the process temperature is significantly above the melting point or above the temperature at which the binder is present as a melt.
  • the process temperature in the compression step is not more than 20 ° C above the melting temperature or the upper limit of the melting range of the binder.
  • the possibility of precise temperature control of the binder in particular in the decisive step of the compression, ie between the mixing / homogenization of the premix and the shaping, allows an energetically very favorable and extremely gentle for the temperature-sensitive components of the premix process, since the premix for a short time the is exposed to higher temperatures.
  • the duration of the action of temperature is between 10 seconds and a maximum of 5 minutes, in particular, it is a maximum of 3 minutes.
  • the substantially anhydrous process allows not only that peroxy bleach can be processed without loss of activity, it is thereby also possible to process peroxy bleach and bleach activators together, without having to fear serious loss of activity.
  • the process according to the invention is carried out by means of an extrusion, as described, for example, in European Patent EP-B-0 486 592 or International Patent Applications WO-A-93/02176 and WO-A-94/09111 ,
  • a solid premix is extruded under pressure extruded and cut the strand after exiting the hole shape by means of a cutting device to the predeterminable granule dimension.
  • the homogeneous and solid premix contains a plasticizer and / or lubricant which causes the premix to be plastically softened and extrudable under the pressure of specific work.
  • Preferred plasticizers and / or lubricants are surfactants and / or polymers which, however, in the context of the present invention, with the exception of the abovementioned nonionic surfactants, are not introduced into the premix in liquid form and in particular not in aqueous form but in solid form.
  • the premix is preferably fed continuously to a planetary roller extruder or a 2-screw extruder with co-rotating or counter-rotating screw guide, whose housing and its extruder granulating head can be heated to the predetermined extrusion temperature.
  • the premix under pressure which is preferably at least 25 bar, at extremely high throughputs depending on the apparatus used but also may be below, compacted, plasticized, extruded in the form of fine strands through the hole die plate in the extruder head and finally
  • the extrudate is reduced by means of a rotating doctor blade to approximately spherical to cylindrical granules.
  • the hole diameter of the hole nozzle plate and the strand cut length are matched to the selected granule dimension.
  • the production of granules of a substantially uniformly predictable particle size succeeds, wherein in detail the absolute particle sizes can be adapted to the intended use.
  • particle diameters of at most 0.8 cm are preferred.
  • Important embodiments provide for the production of uniform granules in the millimeter range, for example in the range of 0.5 to 5 mm and in particular in the range of about 0.8 to 3 mm.
  • the length / diameter ratio of the chopped primary granules in one important embodiment is in the range of about 1: 1 to about 3: 1.
  • zeolite powder such as zeolite NaA powder
  • This shaping can be done in commercially available Rondiertechnikn. It is important to ensure that only small amounts of Feinkomanteil arise in this stage.
  • a drying which is described in the above-mentioned prior art documents as a preferred embodiment, but is unnecessary in the context of the present invention, since the method according to the invention is essentially anhydrous, ie without the addition of free, unbound water.
  • extrusion / compression can also be carried out in low-pressure extruders, in the Kahl press or in the Bextruder.
  • the invention now provides that the temperature control in the transition region of the screw, the predistributor and the nozzle plate is designed such that the melting temperature of the binder or the upper limit of the melting range of the binder at least achieved, but preferably exceeded.
  • the duration of the action of temperature in the compression region of the extrusion is preferably less than 2 minutes and in particular in a range between 30 seconds and 1 minute.
  • the binder used has a melting temperature or a melting range up to 75 ° C .; Process temperatures, which is a maximum of 10 ° C and in particular a maximum of 5 ° C above the melting temperature or the upper temperature limit of the melting range of the binder, have then proved to be particularly favorable.
  • the binder also exerts the function of a lubricant in addition to the previously mentioned modes of action and at least prevents or reduces the formation of adhesions on apparatus walls and compaction tools. This applies not only to the processing in the extruder, but equally also to processing, for example, in continuous mixers / granulators or rollers.
  • the compacted material preferably has temperatures not exceeding 80 ° C. directly after leaving the production apparatus, temperatures between 35 and 75 ° C. being particularly preferred. It has been found that exit temperatures - especially in the extrusion process - from 40 to 70 ° C, for example up to 60 ° C, are particularly advantageous.
  • the particle size distribution of the premix is applied substantially wider than that of the end product according to the invention and produced according to the invention.
  • the premix may contain much larger fine grain fractions, even dust fractions, and possibly also coarse-grained fractions, but it is preferred that a premix with relatively broad particle size distribution and relatively high levels of fine grain in a final product with relatively narrow particle size distribution and relatively low levels of fine grain is transferred.
  • the process according to the invention is essentially anhydrous - i.
  • impurities water contents
  • anhydrous - is not only the risk of gelling the surfactant raw materials already minimized in the manufacturing process to exclude, in addition, an environmentally valuable process is also provided, as by waiving a subsequent drying step not only energy is saved, but also emissions, as they occur predominantly in conventional types of drying, can be avoided.
  • a further subject of the invention is a particulate detergent or cleaning agent containing at least one raw material compound resulting from the process according to the invention.
  • the subject matter of the invention is also a particulate agent, in particular for textile prewashing, which contains at least one raw material compound, especially with more than 50% by weight of peroxy bleach or bleach activator, resulting from the process according to the invention.
  • Means M1 to M3 were prepared by the following procedure:
  • a solid premix was prepared from the solid ingredients, including the binder, which in this case was added in solid form. Thereafter, the mixture was homogenized for a further 2 minutes and then fed to a 2-screw extruder, the granulating head to temperatures between 50 and 65 ° C, preferably to 62 ° C, preheated. The addition of the optionally present at temperatures below 45 ° C and a pressure of 1 bar liquid nonionic surfactants was carried out in the powder stream by spraying through nozzles.
  • the premix was plasticized and then extruded at a pressure between 50 and 100 bar, preferably around 78 bar, through the extruder head hole die plate into fine strands with a diameter of 1.4 mm, which after the nozzle exit by means of a doctor blade were crushed to approximately spherical granules (length / diameter ratio about 1, hot break).
  • the resulting warm granules were rounded for one minute in a marketable spheronizer type Marumerizer ® and optionally coated with a finely divided powder.
  • the bulk density of the extrudates produced was above 600 g / l.
  • % Polyethylene glycol prepared as a 4000 molecular weight binder.
  • the premix was then extruded and subsequently powdered with 2% by weight of finely divided zeolite A.
  • the extrudate had such a particle size distribution that the d90 value was above 0.8 mm.
  • the R-test (description see above) gave a value of 0.1%.
  • the granules M2 were prepared in the same way as M1. However, its composition was: 71.1% by weight untreated TAED, 15% by weight of alkylbenzenesulfonate, 9.8% by weight of polyethylene glycol having a molecular weight of 4000, 2.1% by weight of C 12 -C 18 . Fatty alcohol with an average of 7 EO and 2 wt .-% zeolite A. The bulk density was 640 g / l, the d90 value was again significantly greater than 0.8 mm. The R value was 10%.
  • the granulate M3 was composed like M2 and was prepared as M2, except that grinded TAED was used for particle sizes smaller than 100 ⁇ m.
  • the bulk density was 660 g / l; the d90 value was also significantly above 0.8 mm. However, the R value was only 0.7%.
  • the R value of crystalline TAED (d90 value at 0.2 mm, bulk density 560 g / l) was 60% that of a TAED granulate (95% by weight TAED, 3.5% by weight). Carboxymethylcellulose and 1.5% by weight of water; d90 at 0.4 mm; bulk density 550 g / l) at 54%, of an extruded TAED commercial product from Rettenmaier (90% by weight TAED; d90 value at 0 , 8 mm, bulk density 580 g / l) of 30% and that measured to particle sizes of less than 100 microns TAED measured to 22%.
  • Spray-dried granules 26.30% by weight C 9 -C 13 alkylbenzenesulfonate 1.10% by weight Tallow fatty alcohol with an average of 5 EO 1.40% by weight C 12 -C 18
  • Sodium fatty acid soap 9.40% by weight sodium 4.00% by weight Copolymer sodium salt of acrylic acid and maleic acid 39.50% by weight Zeolite A, based on anhydrous active substance 2.80% by weight amorphous sodium disilicate 13.60% by weight water rest Salts of solutions
  • This premix was then metered into a co-rotating twin-screw extruder with a capacity of 10 kg / h.
  • the extruder was preheated to 45 ° C by means of hot water.
  • the mixture was heated to about 55 ° C and plasticized by the resulting melt of fatty alcohol ethoxylate and polyethylene glycol.
  • the thus plasticized premix was transported into the extruder head and extruded through the nozzle holes of the nozzle plate installed there under pressure.
  • a pair of blades rotated, which cut the emerging strands to a length-diameter ratio of about 1: 1.
  • the diameter was about 1mm.
  • the cylindrical to spherical particles were free-flowing, had a bulk density of 750 g / l and excellent water solubility.
  • the R-test showed less than 1%, so it could be increased again compared to the starting material Perkasil. A degradation of the active oxygen could not be detected.
  • Texapon Z ® sodium lauryl sulfate; d90 value 200 microns; bulk density 100 g / l; R-value of 2%) and 1.5 kg of polyethylene glycol with a relative molecular mass of 4000 for approximately 60 seconds premixed and then one to 45 to 50 ° C preheated twin-screw extruder with a capacity of 8 kg / h added.
  • the premix was homogenized, plasticized and fed at temperatures of 50 to 55 ° C under pressure to the nozzle plate.
  • the dislocated product was cut by the rotating knives on approximately 1.4 mm long strands (length / diameter ratio of about 1: 1).
  • the product had a bulk density of 620 to 650 g / l and had an R-value of less than 2%.
  • This premix was extruded as described in Example 5 and then powdered in a muller (Marumerizer ® ) with 1 wt .-% zeolite A and rounded.
  • the product thus obtained had a bulk density of 773 g / l and an R value of 0.4%.

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Claims (10)

  1. Procédé pour la préparation d'un composite de matières premières dans le domaine des agents de lavage et de nettoyage, qui contient au moins un liant non aqueux, caractérisé en ce qu'on prépare d'abord un prémélange solide qui contient la matière première solide ou les matières premières solides d'une classe de matières premières, qui est, respectivement sont présentes sous la forme d'une substance solide à la température ambiante et sous une pression de 1 bar et qui présente, respectivement présentent un point de fusion, respectivement un point de ramollissement qui n'est pas inférieur à 45 °C, dans des quantités d'au moins 50 % en poids, et on transforme le prémélange en un granulé en mettant en oeuvre des forces de densification à des températures d'au moins 45 °C, et on le soumet ensuite, le cas échéant, à un traitement ultérieur ou à une préparation, avec les mesures que
    - le prémélange est essentiellement anhydre et
    - dans le prémélange, est présent au moins un liant non aqueux, qui n'est pas un agent tensioactif anionique et qui est présent sous forme solide sous une pression de 1 bar et à des températures inférieures à 45 °C, mais qui est présent sous la forme d'une masse fondue dans les conditions de traitement, cette masse fondue faisant office de liant polyfonctionnel soluble dans l'eau, qui exerce, lors de la fabrication des agents, aussi bien la fonction d'un agent de glissement qu'une fonction d'adhésif pour les matières premières solides, tout en ayant par contre un effet de désagrégation lors de la redissolution de l'agent dans le bain aqueux,
    ledit ou lesdits liant(s) faisant partie du groupe des polyéthylèneglycols, des 1,2-polypropylèneglycols,
    ce ou ces liant(s) étant contenu(s) dans le composite dans des quantités de 2 à moins de 20 % en poids, de préférence jusqu'à concurrence de moins de 15 % en poids;
    et on met le cas échéant en oeuvre des agents tensioactifs anioniques
    - et on règle une masse volumique apparente d'au moins 600 g/l.
  2. Procédé selon la revendication 1, caractérisé en ce que la teneur du composite en agents tensioactifs non ioniques liquides jusqu'à une température de 30 °C (sous une pression de 1 bar) se situe entre 0 et 10 % en poids, de préférence entre 0 et 5 % en poids.
  3. Procédé selon la revendication 1 ou 2, caractérisé en ce que, sont contenus, à titre de liants, des polyéthylèneglycols possédant une masse moléculaire relative entre 2000 et 12.000, en particulier d'environ 4000.
  4. Procédé selon l'une quelconque des revendications 1 à 3, caractérisé en ce qu'on met en oeuvre une ou plusieurs matières premières faisant partie des classes de matières premières des agents de blanchiment peroxydés, de préférence des agents de blanchiment peroxydés inorganiques, et des activateurs de blanchiment organiques, ainsi que des agents tensioactifs anioniques sulfatés, respectivement sulfonatés.
  5. Procédé selon l'une quelconque des revendications 1 à 4, caractérisé en ce que la teneur du composite en une matière première individuelle ou en une classe de matières premières s'élève à au moins 65 % en poids, de préférence à au moins 70 % en poids et en particulier à au moins 80 % en poids.
  6. Procédé selon l'une quelconque des revendications 1 à 3 ou 5, caractérisé en ce qu'il contient, à concurrence de 60 à 85 % en poids, une ou plusieurs substances inorganiques faisant office de builder, à concurrence de 3 à 10 % en poids, le liant, et jusqu'à concurrence de 20 % en poids, des agents tensioactifs anioniques et/ou non ioniques.
  7. Procédé selon la revendication 6, caractérisé en ce qu'il présente de la zéolithe A, X, Y et/ou P à concurrence de 50 à 65 % en poids et un silicate alcalin amorphe à concurrence de 15 à 30 % en poids.
  8. Procédé selon l'une quelconque des revendications 1 à 7, caractérisé en ce que la matière première mise en oeuvre à concurrence d'au moins 50 % en poids subit un grossissement granulométrique de telle sorte que la valeur d90 du composite de matières premières manifeste une augmentation à concurrence d'au moins 200 µm par rapport à la valeur d90 du composite.
  9. Agent de lavage ou de nettoyage particulaire, contenant au moins un composite de matières premières résultant d'un procédé selon l'une quelconque des revendications 1 à 8.
  10. Agent particulaire pour le prélavage des textiles, contenant au moins un composite de matières premières, de préférence comprenant des agents de blanchiment peroxydés ou des activateurs de blanchiment à concurrence de plus de 50 % en poids, résultant d'un procédé selon l'une quelconque des revendications 1 à 9.
EP98963490A 1997-12-02 1998-11-20 Procede de production de melanges de matieres premieres de masse volumique apparente elevee Expired - Lifetime EP1036158B1 (fr)

Applications Claiming Priority (3)

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DE19753310A DE19753310A1 (de) 1997-12-02 1997-12-02 Rohstoff-Compounds mit hohem Schüttgewicht
DE19753310 1997-12-02
PCT/EP1998/007497 WO1999028433A1 (fr) 1997-12-02 1998-11-20 Melanges de matieres premieres a masse volumique apparente elevee

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EP1036158B1 true EP1036158B1 (fr) 2007-03-07

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JP (1) JP2001525454A (fr)
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ID30054A (id) * 1999-01-18 2001-11-01 Kao Corp Komposisi deterjen densitas-tinggi
DE19923627A1 (de) * 1999-05-22 2000-11-23 Henkel Kgaa Verfahren zur Herstellung von Tensidgranulaten
DE19953793A1 (de) * 1999-11-09 2001-05-17 Cognis Deutschland Gmbh Tensidgranulate mit verbesserter Auflösegeschwindigkeit
DE10212169A1 (de) * 2002-03-19 2003-10-02 Sued Chemie Ag Waschmittelzusatz mit hohem Gehalt an nichtionischen Tensiden und schnellem Auflösevermögen

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Publication number Priority date Publication date Assignee Title
GB8711153D0 (en) * 1987-05-12 1987-06-17 Warwick International Ltd Bleach activator compositions
DE4024759A1 (de) * 1990-08-03 1992-02-06 Henkel Kgaa Bleichaktivatoren in granulatform
US5574005A (en) * 1995-03-07 1996-11-12 The Procter & Gamble Company Process for producing detergent agglomerates from high active surfactant pastes having non-linear viscoelastic properties
MX9708236A (es) * 1995-04-27 1997-12-31 Procter & Gamble Procedimiento para producir componentes o composiciones detergentes granulados.
DE19638599A1 (de) * 1996-09-20 1998-03-26 Henkel Kgaa Verfahren zur Herstellung eines teilchenförmigen Wasch- oder Reinigungsmittels

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ES2283083T3 (es) 2007-10-16
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DE59813941D1 (de) 2007-04-19
WO1999028433A1 (fr) 1999-06-10
ATE356194T1 (de) 2007-03-15

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