EP0971999A1 - Granules detergents - Google Patents

Granules detergents

Info

Publication number
EP0971999A1
EP0971999A1 EP98912430A EP98912430A EP0971999A1 EP 0971999 A1 EP0971999 A1 EP 0971999A1 EP 98912430 A EP98912430 A EP 98912430A EP 98912430 A EP98912430 A EP 98912430A EP 0971999 A1 EP0971999 A1 EP 0971999A1
Authority
EP
European Patent Office
Prior art keywords
weight
detergent
surfactant
alkali
acid
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.)
Withdrawn
Application number
EP98912430A
Other languages
German (de)
English (en)
Inventor
Thomas Holderbaum
Thomas Merz
Edgar Köppelmann
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ecolab GmbH and Co OHG
Original Assignee
Henkel Ecolab GmbH and Co KG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Henkel Ecolab GmbH and Co KG filed Critical Henkel Ecolab GmbH and Co KG
Publication of EP0971999A1 publication Critical patent/EP0971999A1/fr
Withdrawn legal-status Critical Current

Links

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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/08—Silicates
    • 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
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/04—Carboxylic acids or salts thereof
    • 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
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/146—Sulfuric acid esters
    • 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
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
    • 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

Definitions

  • the present invention relates to a commercial detergent and a method for producing particulate detergents for the commercial laundry sector.
  • particulate detergents Probably the simplest method for producing particulate detergents is to mix powdery individual components, for example sodium carbonate, sodium tripolyphosphate and sodium perborate. Since some of these solid inorganic detergent ingredients are sufficiently porous and absorbent, liquid ingredients, which include surfactant substances in particular, can be sprayed onto the mixed product or one or more of the powdery individual components and thus also find their way into the detergent in a simple manner. This approach quickly reaches its limits if, on the one hand, increased demands are placed on the chemical stability of the detergent ingredients, which can be impaired by contact with one another, and on the other hand on the physical stability of the detergent.
  • powdery individual components for example sodium carbonate, sodium tripolyphosphate and sodium perborate. Since some of these solid inorganic detergent ingredients are sufficiently porous and absorbent, liquid ingredients, which include surfactant substances in particular, can be sprayed onto the mixed product or one or more of the powdery individual components and thus also find their way into the detergent in a simple manner. This approach quickly reaches its limits
  • the invention is a process for the production of free-flowing detergents for commercial use by granulating solid and liquid components, which is characterized in that a mixture of, in each case based on the finished detergent, at least 8% by weight of silicate (calculated as anhydrous) and at least 12% by weight of at least partially liquid nonionic surfactant, optionally granulated with further, in particular non-surfactant, detergent ingredients, such as zeolite or sodium carbonate.
  • the invention further relates to a particulate detergent which contains at least 12% by weight, preferably more than 12% by weight, of nonionic surfactant and at least 8% by weight, preferably more than 8% by weight of alkali silicate, preferably alkali metal silicate, and values of over 70% achieved in the trickle test described below.
  • a round funnel made of plastic, e.g. PVC (diameter of the upper funnel opening 80.5 mm, diameter of the lower funnel opening 10 mm, inclination 15 °, straight lower outlet pipe with a length of 30 mm and Diameter 10 mm), which is provided at its upper opening with an open top attachment of the same inner diameter and was attached to a tripod.
  • PVC plastic
  • the lower opening of the outlet pipe is closed and then opened so that the substance to be tested can run out.
  • the time until the test material completely runs out is measured and compared with the time it takes for a dry standard sand to run out under these conditions.
  • a sand whose run-out time is below the specified is usable as standard sand Conditions is 50 seconds ⁇ 10 seconds. Its expiry time is set to 100%. This time is divided by the run-off time of the detergent sample to get the trickle test result of the detergent. Agents according to the invention have a trickle test value of over 70%, preferably of at least 80%.
  • the granulation is carried out in a mixer / granulator or in a plurality of mixers / granulators connected in series, which may have different mixing and granulating speeds.
  • the granulation is carried out in two mixers / granulators connected in series. It is advantageous if a pre-granulate is first created in a high-speed mixer and then - if necessary with the addition of further solid and liquid constituents, in particular with the addition of up to 50% by weight, based on the finished, but still undried, granulate to solid to powdery components - the actual granulation and compaction takes place in a slower running mixer / granulator.
  • the residence time in the high-speed mixer is usually less than 1 minute, in particular significantly less than 1 minute, while the residence times in the preferably continuously operating slower granulators can be up to several minutes, for example between 1 and 10 minutes.
  • a process control is preferred which, according to the teaching of international patent application WO 93/23523, also uses two consecutive mixers / granulators, but first the slower-running mixer / granulator and then the high-speed mixer are used.
  • the solid and liquid components can be added in any order.
  • the solid constituents are initially introduced and then the liquid components, with the mixing tools running, to which, in the context of this invention, also those at the respective processing temperature, which are normally between 30 ° C. and 70 ° C. is in particular between 40 ° C and 60 ° C, belong to pumpable components, added.
  • Nonionic surfactants are preferably used as liquid constituents used which are completely liquid at room temperature or flowable at the respective processing temperature.
  • nonionic surfactants water and, for example, also anionic surfactant acids, anionic surfactant pastes, aqueous alkali metal hydroxide solutions, in particular sodium hydroxide solution, polycarboxylate solutions and / or phosphonate solutions can be used as liquid constituents or pumpable at the respective processing temperature. If desired, silicones and paraffins can also be used in minor amounts. However, it is particularly preferred that aqueous solutions and or aqueous dispersions are used in this process step, with surfactant-containing solutions and / or dispersions also being suitable at this point in the process.
  • the granulation is continued until the desired particle size distribution, that is to say the desired granule structure, has been reached.
  • the total mixing and granulating time is preferably between 1 and 10 minutes, in particular between 2 and 8 minutes, with mixing and granulating times between 3 and 5 minutes being particularly advantageous. Mixing times that are too long may result in undesirably high coarse grain fractions.
  • Granules produced according to the invention preferably have an average particle size in the range from 0.2 mm to 1.2 mm, in particular from 0.4 mm to 1.0 mm. It is preferably free of particles larger than 2 mm in size.
  • the granules can be treated with an aqueous solution or an aqueous dispersion of one or more non-surfactant ingredients of detergents or cleaning agents before or during drying.
  • an aqueous solution or an aqueous dispersion of one or more non-surfactant ingredients of detergents or cleaning agents before or during drying.
  • the aftertreatment it is also possible for the aftertreatment to be carried out with several solutions and / or dispersions, but this is generally not preferred. This treatment must take place in such a way that the surface of the granules is covered, but further granulation in the sense of progressive build-up granulation is largely avoided.
  • Water-soluble inorganic salts, such as amorphous silicates, carbonates are preferred as non-surfactant ingredients of detergents.
  • Sulfates, and / or organic salts such as phosphonates, polycarboxylates, especially citrate, and polymeric polycarboxylates are used.
  • aqueous solutions of sodium silicates and / or polymeric polycarboxylates contain the non-surfactant detergent ingredient (s) preferably in concentrations of 25 to 50% by weight and in particular in amounts of 30 to 40% by weight.
  • the aqueous solution or dispersion or the aqueous solutions or dispersions are preferably used in amounts of 1 to 15% by weight and in particular in amounts of 2 to 8% by weight, based on the untreated granules.
  • any drying process that follows the granulation can be carried out in all conventional drying devices. However, drying in the fluidized bed is preferred. If desired, a finely divided powder with an average particle size of less than 40 ⁇ m, preferably of at most 10 ⁇ m, can be added during or after the drying step, preferably during the drying in the fluidized bed.
  • Such finely divided powders are, for example, hydrophobic or hydrophilic silicas, calcium or magnesium stearates, calcium or magnesium carbonates, aluminum silicates, in particular zeolite A and / or zeolite P, and titanium dioxide. Mixtures of finely divided powders can also be used. As is known, this measure allows the bulk density of the granules to be increased.
  • the process according to the invention can be carried out continuously, both batchwise and advantageously. Free-flowing and storage-stable granules are obtained which have bulk densities of preferably above 700 g / 1, in particular in the range from 850 g / 1 to 1000 g / 1. The content of the finished, finally dried granules of nonionic surfactants is over 12% by weight.
  • All known detergent ingredients can advantageously be used in the commercial laundry in the process according to the invention.
  • Such agents are preferably highly alkaline detergents which, in aqueous solution, have a pH in the range from 10 to 13, in particular from 10 to 12, at a concentration of 1% by weight.
  • the solid ingredients can preferably be introduced into the process as powder, but if desired also as prefabricated granules.
  • the agent produced according to the invention contains larger amounts of alkalizing agents, which include, in particular, alkali metal silicates and alkali carbonates, but also the alkali metal hydroxides.
  • Such alkalizing agents are present in the agents according to the invention preferably in amounts of 20% by weight to 85% by weight, in particular 30% by weight to 50% by weight, mixtures of anhydrous alkali metasilicate, in particular sodium metasilicate, and alkali carbonate, especially sodium carbonate, from 8: 1 to 1: 2 are preferred.
  • An agent produced according to the invention also contains nonionic surfactant, in particular in an amount in the range from 12% by weight to 25% by weight. preferably from 15% to 22% by weight.
  • the nonionic surfactants in question include the alkoxylates, in particular the ethoxylates and / or propoxylates of saturated or mono- to polyunsaturated linear or branched chain alcohols having 10 to 22 carbon atoms, preferably 12 to 18 carbon atoms.
  • the degree of alkoxylation of the alcohols is generally in the range from 1 to 20, preferably from 3 and 14. They can be prepared in a known manner by reacting the corresponding alcohols with the corresponding alkylene oxides.
  • the derivatives of fatty alcohols are particularly suitable, although their branched chain isomers, in particular so-called oxo alcohols, can also be used to prepare alkoxylates which can be used.
  • the alkoxylates in particular the ethoxylates, of primary alcohols with linear, in particular dodecyl, tetra-decyl, hexadecyl or octadecyl radicals, and mixtures thereof, can be used.
  • 1 to 20 times, in particular 3 to 10 times, alkoxylation products of alkylamines, vicinal diols and carboxamides, which correspond to the alcohols mentioned with regard to the alkyl part, can be used.
  • ethylene oxide and / or propylene oxide insertion products of fatty acid alkyl esters as can be prepared in accordance with the process specified in international patent application WO 90/13533
  • fatty acid polyhydroxyamides as are, for example, in accordance with the processes of the US patent specifications US 1 985 424, US 2 016 962 and US 2 703 798 and international patent application WO 92/06984 can be considered.
  • alkyl polyglycosides suitable for incorporation into the agents according to the invention are compounds of general formula (G) p -OR, in which R is an alkyl or alkenyl radical having 8 to 22 carbon atoms, G is a glycose unit and p is a number between 1 and 10.
  • R is an alkyl or alkenyl radical having 8 to 22 carbon atoms
  • G is a glycose unit
  • p is a number between 1 and 10.
  • Such compounds and their preparation are described, for example, in European patent applications EP 92 355, EP 301 298, EP 357 969 and EP 362 671 or US Pat. No. 3,547,828.
  • the glycoside component (G) p is oligomers or polymers from naturally occurring aldose or ketose monomers, in particular glucose, mannose, fructose, galactose, talose, gulose, altrose, allose, idose, ribose, arabinose, Xylose and Lyxose belong to.
  • the oligomers consisting of such glycosidically linked monomers are characterized not only by the type of sugar they contain, but also by their number, the so-called degree of oligomerization.
  • the degree of oligomerization p generally takes fractional numerical values as the quantity to be determined analytically; it is between 1 and 10, for the glycosides preferably used below 1.5, in particular between 1.2 and 1.4.
  • the preferred monomer building block is glucose because of its good availability.
  • the alkyl or alkenyl part R of the glycosides preferably also originates from easily accessible derivatives of renewable raw materials, in particular from fatty alcohols, although their branched-chain isomers, in particular so-called oxo alcohols, can also be used to produce usable glycosides. Accordingly, the primary alcohols with linear octyl, decyl, dodecyl, tetradecyl, hexadecyl or octadecyl radicals and mixtures thereof are particularly useful.
  • Agents according to the invention or produced by the method according to the invention can additionally contain further surfactants, in particular synthetic anionic surfactants of the sulfate or sulfonate type, in amounts of preferably not more than 10% by weight, in particular from 0.1% by weight to 5% by weight, in each case based on the total mean.
  • Synthetic anionic surfactants which are particularly suitable for use in such compositions are the alkyl and / or alkenyl sulfates having 8 to 22 carbon atoms and carrying an alkali metal, ammonium or alkyl or hydroxyalkyl-substituted ammonium ion as countercation.
  • the derivatives of fatty alcohols having in particular 12 to 18 carbon atoms are preferred and their branched chain analogs, the so-called oxo alcohols.
  • the alkyl and alkenyl sulfates can be prepared in a known manner by reacting the corresponding alcohol component with a conventional sulfating reagent, in particular sulfur trioxide or chlorosulfonic acid, and then neutralizing with alkali, ammonium or alkyl or hydroxyalkyl-substituted ammonium bases.
  • suitable anionic surfactants of the sulfonate type include the .alpha.-sulfoesters obtainable by reacting fatty acid esters with sulfur trioxide and subsequent neutralization, in particular those derived from fatty acids having 8 to 22 carbon atoms, preferably 12 to 18 carbon atoms, and linear Alcohols with 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, derived sulfonation products, as well as the sulfofatty acids resulting from these by formal saponification.
  • Soaps can be considered as further optional surfactant ingredients, whereby saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid or stearic acid, as well as soaps derived from natural fatty acid mixtures, for example coconut, palm kernel or tallow fatty acids, are suitable.
  • Soap mixtures are particularly preferred which are composed of 50% by weight to 100% by weight of saturated C 12 -C 18 fatty acid soaps and up to 50% by weight of oleic acid soap. Soap is preferably contained in amounts of up to 15% by weight, in particular from 2% by weight to 8% by weight.
  • An agent according to the invention or produced by the method according to the invention can be water-soluble and / or water-insoluble builders, in particular selected from alkali alumosilicate, alkali tripolyphosphate, crystalline alkali silicate with a modulus above 1, monomeric polycarboxylate, polymeric polycarboxylate and mixtures thereof, preferably in amounts in the range from 10% by weight. % to 50 wt .-%, in particular from 15 wt .-% to 40 wt .-%, contain.
  • organic builders are suitable from the class of the aminopolycarboxylic acids and polyphosphonic acids.
  • the aminopolycarboxylic acids include nitrilotriacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid and their higher homologues, preference being given to using N, N-bis (carboxymethyl) aspartic acid becomes.
  • Suitable polyphosphonic acids are l-hydroxyethane-l, l-diphosphonic acid.
  • the water-soluble organic builder substances from the class of the polymeric polycarboxylic acids include, in particular, the polycarboxylates of the international patent application WO 93/16110 which are accessible by oxidation of polysaccharides, and polymeric acrylic acids, methacrylic acids, maleic acids and mixed polymers from these, which also contain small amounts of polymerizable substances may contain copolymerized without carboxylic acid functionality.
  • the relative molecular weight of the homopolymers of unsaturated carboxylic acids is generally between 5000 and 200000, that of the copolymers between 2000 and 200000, preferably 50,000 to 120,000, based on free acid.
  • a particularly preferred acrylic acid-maleic acid copolymer has a relative molecular weight of 50,000 to 100,000.
  • Suitable, albeit less preferred, compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinyl methyl ether, vinyl esters, ethylene, propylene and styrene, in which the proportion of acid is at least 50% by weight.
  • vinyl ethers such as vinyl methyl ether, vinyl esters, ethylene, propylene and styrene
  • the proportion of acid is at least 50% by weight.
  • Terpolymers which contain two unsaturated acids and / or their salts as monomers and vinyl alcohol and / or a vinyl alcohol derivative or a carbohydrate as the third monomer can also be used as water-soluble organic builder substances. The use of the third monomer presumably creates predetermined breaking points in the polymer, which are responsible for the good biodegradability of the polymer.
  • terpolymers can be produced in particular by processes which are described in German patent specification DE 42 21 381 and German patent application DE 43 00 772 and generally have a relative molecular mass between 1000 and 200000, preferably between 200 and 50,000 and in particular between 3000 and 10,000. They can be used in the form of aqueous solutions, preferably in the form of 30 to 50 percent by weight aqueous solutions. All of the polycarboxylic acids mentioned are generally used in the form of their water-soluble salts, in particular their alkali metal salts.
  • crystalline or amorphous alkali alumosilicates in amounts of up to 50% by weight, are provided as water-insoluble, water-dispersible inorganic builder materials. preferably not more than 40% by weight.
  • the crystalline aluminosilicates in detergent quality in particular zeolite A, zeolite P and optionally zeolite X, alone or in mixtures, are preferred.
  • Suitable aluminosilicates in particular have no particles with a grain size above 30 ⁇ m and preferably consist of at least 80% by weight of particles with a size below 10 ⁇ m.
  • Suitable substitutes or partial substitutes for the aluminosilicate mentioned are certain crystalline or amorphous alkali silicates, which can be present alone or in a mixture with one another.
  • the alkali silicates which can be used as builders in the agents according to the invention have a molar ratio of alkali oxide to SiO 2 below 0.95, in particular from 1: 1.1 to 1:12.
  • Alkali silicates preferred as builder substances are the sodium silicates, in particular the amorphous sodium silicates, with a Na 2 O: SiO 2 molar ratio of 1: 2 to 1: 2.8, as can be prepared, for example, by the process of European patent application EP 0 425 427 .
  • Silicates which can be used as builders are also described, for example, in European patent application EP 0 164 514.
  • inorganic builder mentioned and the alkalizing agent further water-soluble or water-insoluble inorganic solid substances can be used in the agents produced according to the invention.
  • the alkali chlorides, alkali hydrogen carbonates and alkali sulfates and mixtures thereof are suitable.
  • additional inorganic filler material can be present in amounts up to 40% by weight, but is preferably absent entirely.
  • the agents can contain further constituents customary in washing and cleaning agents.
  • These optional components include in particular enzymes, so-called soil release polymers, for example copolyesters, the dicarboxylic acid units.
  • Alkylene glycol units and polyalkylene glycol units contain complexing agents for heavy metals, for example aminopolycarboxylic acids, aminohydroxypolycarboxylic acids, polyphosphonic acids, hydroxypolyphosphonic acids and / or aminopolyphosphonic acids.
  • Organopolysiloxanes or paraffins, and optical brighteners for example stilbene disulfonic acid derivatives.
  • optical brighteners in particular compounds from the class of the substituted 4,4'-bis- (2nd , 4,6-triamino-s-triazinyl) -stilbene-2,2'-disulfonic acids, up to 5% by weight, in particular 0.1% by weight to 2% by weight, of complexing agents for heavy metals, in particular hydroxyalkylenephosphonic acids and their salts, and up to 2% by weight, in particular 0.05% by weight to 1% by weight, of foam inhibitors, the proportions by weight referred to in each case based on the total agent.
  • Any enzyme present are preferably selected from the group comprising protease, amylase, lipase, cellulase, hemicellulase, oxidase, peroxidase or mixtures of these.
  • Protease obtained from microorganisms, such as bacteria or fungi is primarily suitable. It can be obtained in a known manner by fermentation processes from suitable microorganisms, which are described, for example, in German Offenlegungsschriften DE 19 40 488, DE 20 44 161, DE 21 01 803 and DE 21 21 397, and US Pat. Nos. 3,623 957 and US 4,264,738, European patent application EP 006 638 and international patent application WO 91/02792.
  • Proteases are commercially available, for example, under the names BLAP®, Savinase®, Esperase®, Maxatase®, Optimase®, Alcalase®, Durazym® or Maxapem®.
  • the lipase which can be used can be obtained from Humicola lanuginosa, as described, for example, in European patent applications EP 258 068, EP 305 216 and EP 341 947, from Bacillus species, as described, for example, in international patent application WO 91/16422 or European patent application EP 384 717 , from Pseudomonas species, for example in European patent applications EP 468 102, EP 385 401, EP 375 102, EP 334462, EP 331 376, EP 330 641, EP 214 761, EP 218 272 or EP 204 284 or the international patent application WO 90/10695 described, from Fusarium species, as described for example in European patent application EP 130 064, from Rhizopus species, as
  • Suitable lipases are commercially available, for example, under the names Lipolase®, Lipozym®, Lipomax®, Amano® lipase, Toyo-Jozo® lipase, Meito® lipase and Diosynth® lipase.
  • Suitable amylases are commercially available, for example, under the names Maxamyl®, Termamyl® and Duramyl®.
  • the cellulase which can be used can be an enzyme which can be obtained from bacteria or fungi and which has a pH optimum, preferably in the weakly acidic to weakly alkaline range from 6 to 9.5.
  • Such cellulases are known, for example, from German published applications DE 31 17 250, DE 32 07 825, DE 32 07 847, DE 33 22 950 or European patent applications EP 265 832, EP 269 977, EP 270 974, EP 273 125 and EP 339 550 known.
  • Suitable foam inhibitors include phosphoric acid mono- and difatty alkyl esters, long-chain soaps, in particular beef soap, fatty acid amides, paraffins, waxes, microcrystalline waxes, organopolysiloxanes and mixtures thereof, which may additionally contain microfine, optionally silanized or otherwise hydrophobized silica.
  • foam inhibitors are preferably bound to granular, water-soluble carrier substances, as described, for example, in German Offenlegungsschrift DE 34 36 194, European patent applications EP 262 588, EP 301 414, EP 309 931 or European patent EP 150 386.
  • an agent according to the invention or manufactured according to the method according to the invention contains up to 6% by weight, in particular 2% by weight to 5% by weight, of synthetic anionic surfactant from the group comprising alkylbenzenesulfonate and alkylsulfate, up to 10% by weight .-%, in particular 3 wt .-% to 8 wt .-% soap, 12 wt .-% to 25 wt .-%, in particular 15 wt .-% to 22 wt .-% nonionic surfactant in the form of alkoxylated fatty alcohols, in particular an approximately 2: 1 to 1: 1 mixture of low ethoxylated fatty alcohol, for example 3-fold ethoxylated C 12.18 fatty alcohol, with higher ethoxylated fatty alcohol, for example 7-fold ethoxylated C 16/18 fatty alcohol, 10% by weight % to 50% by weight of alkali metal silicate, 4% by weight to
  • a detergent produced according to the invention can be metered into a commercial washing machine with ease using a conventional, controlled powder metering device, such as is known, for example, from European Patent EP 0 297 371.
  • a conventional, controlled powder metering device such as is known, for example, from European Patent EP 0 297 371.
  • more than 1000 g of a detergent according to the invention can be metered within 30 seconds using such a powder metering device.
  • a comparative product VI which contained the same ingredients as Ml according to Example 1, was obtained by simply mixing the components in a Forberg mixer, in which the zeolite and the polycarboxylate were combined in the form of a spray-dried powder and this was applied to the other components.
  • the agent obtained in this way could not be metered using the powder metering device known from European Patent EP 0 297 371.
  • the trickle test gave a value of 0%, which means that due to the formation of bridges, no powder ran out of the funnel opening.

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Wood Science & Technology (AREA)
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  • Detergent Compositions (AREA)

Abstract

L'invention vise à mettre au point un procédé aussi simple et économique que possible pour produire des détergents coulants pour le domaine commercial, qui soient aisés à manipuler tout en présentant une bonne stabilité au stockage. A cet effet, on soumet à une opération de granulation un mélange comprenant, dans chaque cas par rapport au détergent fini, au moins 8 % en poids de silicate et au moins 12 % en poids de tensioactif non ionique proportionnellement fluide avec éventuellement d'autres ingrédients détergents habituels en particulier non tensioactifs, tels que par exemple du zéolithe ou du carbonate de sodium.
EP98912430A 1997-03-12 1998-03-03 Granules detergents Withdrawn EP0971999A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE1997110156 DE19710156A1 (de) 1997-03-12 1997-03-12 Granuliertes Waschmittel
DE19710156 1997-03-12
PCT/EP1998/001175 WO1998040454A1 (fr) 1997-03-12 1998-03-03 Granules detergents

Publications (1)

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EP0971999A1 true EP0971999A1 (fr) 2000-01-19

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EP98912430A Withdrawn EP0971999A1 (fr) 1997-03-12 1998-03-03 Granules detergents

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EP (1) EP0971999A1 (fr)
DE (1) DE19710156A1 (fr)
WO (1) WO1998040454A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19855381A1 (de) * 1998-12-01 2000-06-08 Henkel Kgaa Tensidmischung in fester Form zum Einsatz als Wasch- und Reinigungsmittel
DE102004011087A1 (de) * 2004-03-06 2005-09-22 Henkel Kgaa Partikel umfassend diskrete, feinpartikuläre Tensidpartikel

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1993021292A1 (fr) * 1992-04-16 1993-10-28 Church & Dwight Company, Inc. Composition detergente particulaire a ecoulement libre contenant un tensioactif non ionique, et procede et appareil de production de celle-ci
DE19529908A1 (de) * 1995-08-15 1997-02-20 Henkel Kgaa Verfahren zur Herstellung eines amorphen Alkalisilikats mit Imprägnierung
DE19533790A1 (de) * 1995-09-13 1997-03-20 Henkel Kgaa Verfahren zur Herstellung eines amorphen Alkalisilikats mit Imprägnierung

Non-Patent Citations (1)

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Title
See references of WO9840454A1 *

Also Published As

Publication number Publication date
DE19710156A1 (de) 1998-09-17
WO1998040454A1 (fr) 1998-09-17

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