+

WO1997009411A1 - Procede de preparation de produits granules precurseurs de detergents de faible alcalinite - Google Patents

Procede de preparation de produits granules precurseurs de detergents de faible alcalinite Download PDF

Info

Publication number
WO1997009411A1
WO1997009411A1 PCT/EP1996/003730 EP9603730W WO9709411A1 WO 1997009411 A1 WO1997009411 A1 WO 1997009411A1 EP 9603730 W EP9603730 W EP 9603730W WO 9709411 A1 WO9709411 A1 WO 9709411A1
Authority
WO
WIPO (PCT)
Prior art keywords
salts
weight
carbonate
acid
sodium
Prior art date
Application number
PCT/EP1996/003730
Other languages
German (de)
English (en)
Inventor
Jürgen Härer
Peter Jeschke
Thomas Holderbaum
Frank Wiemer
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
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 Kommanditgesellschaft Auf Aktien filed Critical Henkel Kommanditgesellschaft Auf Aktien
Priority to DE59603641T priority Critical patent/DE59603641D1/de
Priority to EP96930091A priority patent/EP0848750B1/fr
Publication of WO1997009411A1 publication Critical patent/WO1997009411A1/fr

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
    • C11D3/10—Carbonates ; Bicarbonates
    • 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
    • C11D1/825—Mixtures of compounds all of which are non-ionic
    • C11D1/8255—Mixtures of compounds all of which are non-ionic containing a combination of compounds differently alcoxylised or with differently alkylated chains
    • 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
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • C11D17/0091—Dishwashing tablets
    • 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
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2086—Hydroxy carboxylic acids-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
    • C11D1/66—Non-ionic compounds
    • C11D1/662—Carbohydrates or derivatives
    • 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 invention relates to a process for the production of granular preproducts of low-alkaline cleaning agents which are distinguished by improved grain resistance and lower fine-grain fractions and which can be packaged in the customary manner to lower-alkaline cleaners for machine dishwashing.
  • a cleaning agent for use in dishwashers which contains 1 to 30% by weight of a peroxy compound and 10 to 30% by weight. Contains oxo acid salts and / or aminopolycarboxylic acid salts and is phosphate-free.
  • An advantage of this composition is that low pH is combined with the absence of chlorine compounds. None is described in the Japanese application about the production and grain structure of these agents.
  • German patent application DE 42 32 170 AI describes a weakly alkaline agent for machine dishwashing, in which sodium citrate, sodium hydrogen carbonate, a bleach, a bleach activator and enzymes are contained as essential components, and that in 1% by weight aqueous solution has a pH of about 8 to 10.
  • the agents mentioned there are granular. However, detailed information on the production is not included.
  • the European application EP 414 197 claims a machine dishwashing detergent which contains at least 25% by weight of a combination of sodium carbonate and sodium hydrogen carbonate, is free of metasilicates, is free of chlorine bleaching agents and in 1% by weight aqueous solution has a mildly alkaline pH of less than 10.5.
  • a further component can be a Acrylic acid-maleic acid copolymer may be present as the sodium salt. It can only be gathered from the preparation of the compositions that they are formulated in the conventional manner as dry powders or granules.
  • EP 530 635 (Benckiser) it is known to produce a liquid or powdery, phosphate-free automatic dishwashing detergent containing a builder system in which a pH value of 5 to 9 is achieved in a 1% by weight aqueous solution and which contains a builder system from the salt of a hydroxycarboxylic acid, or the mixture of a hydroxycarboxylic acid and the salt of a hydroxycarboxylic acid or the mixture of a hydroxycarboxylic acid and the salt of a hydroxycarboxylic acid and a polymer.
  • This patent application also contains no specific information on the manufacture of the products.
  • German patent application DE-A-4228786 describes a dishwashing detergent with a selected builder system which is said to be solid, lower-alkali, phosphate and chlorine-free and, in addition to an organic water-soluble builder, contains alkali carbonate, oxygen-based bleaching agents, surfactants and other conventional constituents , wherein the builder component contains oxidation products of polyglucosans and / or their soluble salts.
  • a mixing granulation process is disclosed in which the builder component is mixed and granulated in a mixture with at least one further component in the presence of a liquid.
  • Granulation processes are generally used in the production of these products. It has been shown here that it is difficult in technical terms to obtain stable, uniform granules with a small proportion of fines. This applies in particular to products based on the alkali metal salts of carbonic acid and alkali metal salts of polycarbonates. The reason for this is that the alkali metal salts mentioned, especially the sodium salts, such as soda, sodium bicarbonate and sodium nitrate, to name the most important raw materials of this class, are comparatively coarse-crystalline substances that are difficult to bake into a solid grain in a granulation process. Citrate in particular is difficult or cannot be granulated with the other constituents soda and bicarbonate.
  • the granule grains therefore disintegrate, especially during long transport and shaking, which leads to individual constituents in the form of fine particles, segregated, collecting on the bottom of the pack and thus, in addition to problems of recipe constancy due to segregation processes, also one which is not desired by the consumer Deliver the appearance of the product.
  • the invention seeks to remedy this; it is based on two findings. On the one hand, it was observed that stable, low-particulate granules can be obtained when the alkali metal salts of polycarboxylic acids are prepared in situ from alkali carbonates under mixing and granulating conditions. Furthermore, the knowledge was gained that alkali carbonates, in particular sodium carbonate, in the presence of water can be converted economically into hydrogen carbonates and salts of polycarboxylic acids if the alkali metal carbonates are mixed with a proportion of the alkali metal salts of the polycarboxylic acids right at the start of the reaction.
  • the invention thus relates to a process for the preparation of granular precursors of low-alkali detergents for automatic dishwashing, consisting of alkali metal salts of carbonic acid and organic polycarboxylic acids, characterized in that a partial amount of the salts of polycarboxylic acids is prepared in a customary manner, then in In the presence of 2 to 12% by weight of water, alkali metal carbonate in the presence of the alkali metal salts of the polycarboxylic acids with the free polycarboxylic acid to give their salts and essentially alkali metal bicarbonate at temperatures below 60 ° C.
  • the invention furthermore relates to a granular precursor of an automatic dishwashing detergent, comprising 20 to 70% by weight of trisodium citrate dihydrate, 20 to 60% by weight of sodium bicarbonate, 0 to 10% by weight of sodium carbonate and 0 to 4% by weight of nonionic An intimate mixture of surfactants, produced by the process according to the invention.
  • alkali metal salts of carbonic acid and of polycarboxylic acids are used.
  • the sodium salts of carbonic acid such as sodium carbonate (soda, anhydrous or in hydrated form) and sodium hydrogen carbonate are preferably used.
  • the sodium salts are also preferred for the salts of the polycarboxylic acids.
  • a particularly preferred polycarboxylic acid is citric acid, a particularly preferred salt is trisodium citrate, in particular trisodium citrate dihydrate.
  • polycarboxylic acids for example malic acid, tartaric acid, nitrogen-containing polycarboxylic acids, such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid or triethylenetetraaminehexaacetic acid, methylglycinediacetic acid and the like, can also be used.
  • the oxidation products of polyglucosans mentioned in DE-A-4228 786 can also be used.
  • copolymers of polymerizable acids if desired copolymerized with esters and sulfonic acids. So especially copolymers based on acrylic acid-maleic anhydride, acrylic acid Maleic anhydride-vinyl acetate (saponified to vinyl alcohol), methacrylic acid-maleic anhydride and the like.
  • the granular precursors have the following composition: 20 to 70% by weight of polycarboxylic acid alkali salt, 20 to 60% by weight of alkali metal bicarbonate, 0 to 10% by weight of alkali metal carbonate, further constituents, such as tensides, for example from 0.1 to 10, but preferably only up to 5 and in particular only up to 4% by weight can be present.
  • the process according to the invention is carried out in such a way that the alkali metal salt of a polycarboxylic acid is prepared in a conventional manner in a first stage.
  • This can be done by reacting the polycarboxylic acid, for example with an alkali metal hydroxide solution, alkali metal bicarbonate or alkali metal carbonate.
  • the alkali metal carbonate for example sodium carbonate
  • the polycarboxylic acid for example citric acid
  • the salt of polycarboxylic acid can be placed in a mixer, granulator or the like, and then the other constituents can be added continuously or in portions in the presence of the amount of water.
  • reaction it may be preferred to carry out the reaction under conditions which are so gentle that a large part of the alkali metal carbonate is converted into hydrogen carbonate and the sodium salt of polycarbonate acid. If one works under drastic conditions, for example under heating or in the presence of only small amounts of polycarboxylic acid salt, alkali carbonate and free CO2 are formed to a substantial extent instead of hydrogen carbonate.
  • the gentle procedure is preferred, this applies in particular if, for the sake of simplicity, the reaction is not carried out in a separate reactor, but rather as a solid reaction in the disperse phase with a high solid content in a mixer with simultaneous granulation.
  • the mixer has the task of allowing the reaction to proceed to completion by intimately mixing the residues and to build up a granular grain, possibly by adding further granulation aids such as surfactants and polycarboxylate solutions. Mixers that are suitable for granulation and in which residence times of 1 to 10 minutes can be set were therefore used.
  • Suitable mixers are e.g. B. Eiri mixers of the R or RV series, manufactured by Maschinenfabrik Gustav Eirich, Hardheim, Germany, the Fukae (R) FS-G mixer, manufactured by Fukal Powtech Kogyo Co., Japan the Lödige (R) FM, KM and CB mixer, manufactured by Lödige Maschinenbau GmbH, Paderborn, Germany or the Drais (R) series T or KT, manufactured by Drais Maschinene GmbH, Mannheim, Germany.
  • soda is used as the alkali carbonate and sodium tricitrate-2-hydrate as the polycarboxylic acid salt.
  • the acid is then worked with citric acid and sodium bicarbonate is obtained in an intimate mixture with sodium tricitrate dihydrate and, if desired, small amounts of soda.
  • the amount by weight of polycarboxylic acid sodium salts which is quasi introduced into the reaction as a buffer can be freely determined by the person skilled in the art, based on the amount of soda it is 10 to 500% by weight, preferably 50 to 150% by weight, based on alkali carbonate .
  • the process according to the invention is controlled so that the residual alkali carbonate content is less than 20% by weight, preferably less than 10% by weight and in particular less than 5% by weight.
  • Low alkali carbonate contents with a high amount of hydrogen carbonate can be achieved by specifying 50 to 150% by weight, based on alkali carbonate, of polycarboxylic acid salts and working under mild temperature conditions.
  • Higher levels of alkali carbonate, with less hydrogen carbonate can be achieved either by working at higher temperatures or by starting with lower amounts of the salts of the polycarboxylic acids.
  • alkali carbonate from alkali metal bicarbonate in a post-drying step in the process according to the invention. This happens in particular when the temperature is raised to or above the decomposition point of the sodium hydrogen carbonate.
  • the amount of alkali carbonate can be increased at the expense of the amount of alkali hydrogen carbonate, for example at temperatures from 50 to 150 ° C., particularly 100 ° C. to 150 ° C.
  • Surfactants can also be used as further constituents in the process according to the invention.
  • the total surfactant content of the compositions is generally between 0.5% by weight and 8% by weight and can preferably be 0.8 to 5% by weight.
  • Usual surfactants for cleaning agents belong to the groups of anionic, nonionic and / or zwitterionic surfactants, the use of anionic and / or nonionic surfactants being preferred.
  • Particularly suitable anionic surfactants are sulfonates and sulfates and soaps made from preferably natural fatty acids or fatty acid mixtures.
  • Cg_i3_alkylbenzosulfonates, olefin sulfonates, esters and alpha sulfo fatty acids or alpha sulfo fatty acid disalts are used, for example, as surfactants of the sulfonate type.
  • Suitable surfactants of the sulfate type are the sulfuric acid monoesters from primary alcohols of natural or synthetic origin, ie from C - ⁇ - l ⁇ 'fatty alcohols ° or from C ⁇ o-20 ⁇ 0x ° alcohols, and those secondary alcohols of this chain length.
  • the sulfuric acid monoesters of the alcohols reacted with 1 to 6 mol of ethylene oxide (EO) are also suitable.
  • Addition products of preferably 2 to 20 moles of EO with 1 mole of an aliphatic compound with essentially 10 to 20 carbon atoms from the group of alcohols, carboxylic acids, fatty amines, carboxamides and alkanesulfonamides are of particular interest as nonionic surfactants.
  • nonionic surfactants polyglycol ethers with 2 to 7 ethylene glycol ether residues in the molecule, which are not completely water-soluble, are also important, especially when they are used together with water-soluble nonionic or anionic surfactants.
  • nonionic surfactants made from alkyl polyglycosides of the general formula R-0- (G) x can be used, in which R denotes a primary, straight-chain or branched aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms, G stands for a glycose unit with 5 or 6 carbon atoms and the degree of oligomerization x is between 1 and 10.
  • the dishwashing detergents of the invention contain no more than 10% by weight of water-soluble organic complexing agents or co-builders from the group of synthetic polymeric polycarboxylates, which are taken to mean the salts of polymerization products of unsaturated carboxylic acids and which include, for example, polyacrylates, polymethacrylates, polymaleinates or copolymers of acrylic acid with maleic acid or maleic anhydride. Such substances are preferably completely absent from the agents according to the invention.
  • the solid dishwashing detergents produced by the process according to the invention can also contain up to 10% by weight of further alkalizing agents. These include in particular the alkali silicates.
  • Preferred alkali silicates are the sodium silicates, in particular the amorphous sodium silicates with a molar ratio Na2 ⁇ : Si ⁇ 2 of 1: 1.5 to 1: 2.5.
  • amorphous alkali silicates are commercially available, for example, under the trade name Porti1 (R).
  • Compounds of alkali silicates and soda, as are commercially available, can also be used.
  • the process products of the process according to the invention are in particular as granular precursors for the production of cleaning agents for. machine dishwashing. As a rule, they do not contain any oxidizing agents, nor do they contain the components, some of which are sensitive in terms of quantity, that are present in machine dishwashing detergents. In order to produce automatic dishwashing detergents from the products, they can be mixed or granulated with these remaining constituents to give the end products. These remaining ingredients include primarily bleach and bleach activators.
  • the sodium perborate tetrahydrate and the sodium perborate monohydrate are of particular importance.
  • Further bleaching agents that can be used are, for example, peroxycarbonate (Na2CO3. 1.5 H2O2) or persic acid salts of organic acids, such as perbenzoates or salts of diperdodecanedioic acid.
  • Suitable bleach activators for these oxidizing agents are, in particular, the N-acyl or O-acyl compounds which form organic peracids with H2O2, preferably N, N'-tetraacylated diamines such as N, N, N ', N'-tetraacetylethylene diamine.
  • the preliminary products are usually mixed with the bleaching agents and other constituents in amounts of about 7: 3 to 9: 1.
  • the oxygenated oxidizing agent content of the ready-made dishwashing detergent is preferably about 5% by weight to 15% by weight, in particular in combination with 1% by weight to 10% by weight, in particular 2% by weight. up to 5% by weight of a bleach activator.
  • other active ingredients which are usually only present in small amounts can be added to the precursors according to the invention. These substances are preferably used in amounts of 5 to 10% by weight, based on the finally produced cleaning agent.
  • the enzymes can be adsorbed on carriers in a conventional manner and / or embedded in Hü11 substances and are preferably used in amounts not exceeding 5% by weight, in particular 2 to 4% by weight.
  • Suitable non-surfactant-like and preferably used foam inhibitors are organopolysiloxanes and their mixtures with microfine, optionally silanized silica.
  • the foam-inhibiting use of long-chain soaps is also possible.
  • Mixtures of different foam inhibitors can also be suitable, for example those composed of silicones and paraffins or waxes. These foam inhibitors are preferably bound to a granular, water-soluble or dispersible carrier substance.
  • inorganic transition metal salts e.g. B. manganese salts such as manganese sulfate, potassium hexafluorotianate and the like, inorganic transition metal complexes, nitrogen-containing heterocycles such as benzotriazole or isocyanuric acid, natural amino acids such as cystine, histidine, methionine, reversible organic redox systems such as quinone / hydroquinone and / or reversible inorganic + redox systems Fe3 + .
  • inorganic transition metal salts e.g. B.
  • manganese salts such as manganese sulfate, potassium hexafluorotianate and the like
  • inorganic transition metal complexes nitrogen-containing heterocycles such as benzotriazole or isocyanuric acid
  • natural amino acids such as cystine, histidine, methionine
  • reversible organic redox systems such as quinone / hydroquinone and / or
  • the preliminary products produced by the process according to the invention can further be processed into tablets.
  • the preliminary products are mixed with the other constituents mentioned in a mixer and as a mixture using conventional tablet presses, for example eccentric presses or rotary presses, with pressures in the range of 200. 10 5 Pa to 1 500. IO 5 Pa pressed.
  • tablets are obtained which are unbreakable but nevertheless dissolve sufficiently quickly under conditions of use and have bending strengths of normally above 150 N.
  • a tablet produced in this way preferably has a weight of 15 g to 40 g, in particular 20 g to 30 g, with a diameter of 35 mm to 40 mm.
  • the granular detergent precursors produced by the process according to the invention are stable granules, they show a low proportion of fine matter and can be built up in a favorable manner, in particular with the other constituents mentioned. Granulate to homogeneous, non-segregating cleaning agents.
  • a particular advantage of the process according to the invention is that only very small amounts of carbon dioxide are produced in the neutralization and granulation step. It is shown, for example, by the surprisingly high bulk weights (bulk weights over 900 g / l can be generated), which in turn shows that the process products are not inflated by CO2.
  • THC Trisodium citrate 2 H20
  • Citric acid 1 H2O (Z5-H3) 1.87 1.87 1.87
  • Example No. 3 differs from Example 1 only in that bicarbonate was initially introduced. According to the two possible parallel reactions, a favored formation of CO 2 is to be expected:
  • the granules thus obtained were dried in a fluidized bed dryer.
  • the following amounts of CO2 were generated during the granulation:
  • the percentages are based on the batch amount and surprisingly low despite the high amounts of bicarbonate present in Example 3 in the neutralization step.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Afin de contrecarrer la tendance à se dissocier d'un détergent de faible alcalinité pour lave-vaisselle, on met en oeuvre un procédé de préparation de produits granulés précurseurs de ces détergents qui contiennent des sels de métaux alcalins de l'acide carboxylique et des acides polycarboxyliques organiques. A cet effet, on produit une partie des sels des acides polycarboxyliques de la manière usuelle, puis on fait réagir le carbonate alcalin avec les acides polycarboxyliques libres et leurs sels, ainsi que l'hydrocarbonate alcalin, en présence de 2 à 12 % en poids d'eau et des sels de métaux alcalins des acides polycarboxyliques à des températures inférieures à 60 °C.
PCT/EP1996/003730 1995-09-01 1996-08-23 Procede de preparation de produits granules precurseurs de detergents de faible alcalinite WO1997009411A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
DE59603641T DE59603641D1 (de) 1995-09-01 1996-08-23 Verfahren zur herstellung granularer vorprodukte niederalkalischer reinigungsmittel
EP96930091A EP0848750B1 (fr) 1995-09-01 1996-08-23 Procede de preparation de produits granules precurseurs de detergents de faible alcalinite

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19532304.1 1995-09-01
DE19532304A DE19532304A1 (de) 1995-09-01 1995-09-01 Verfahren zur Herstellung granularer Vorprodukte niederalkalischer Reinigungsmittel

Publications (1)

Publication Number Publication Date
WO1997009411A1 true WO1997009411A1 (fr) 1997-03-13

Family

ID=7771024

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1996/003730 WO1997009411A1 (fr) 1995-09-01 1996-08-23 Procede de preparation de produits granules precurseurs de detergents de faible alcalinite

Country Status (4)

Country Link
EP (1) EP0848750B1 (fr)
DE (2) DE19532304A1 (fr)
ES (1) ES2140894T3 (fr)
WO (1) WO1997009411A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998014548A3 (fr) * 1996-10-02 2000-08-24 Herbert Schmitz Procede de production d'un produit de nettoyage, notamment sous forme de poudre pour lave-vaisselle

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6124253A (en) * 1997-09-16 2000-09-26 Church & Dwight Co., Inc. Aqueous composition for low-temperature metal-cleaning and method of use
DE102008028229A1 (de) * 2008-06-16 2009-12-17 Fit Gmbh Zusammensetzung zur Herstellung von Reinigungsmitteln, Tablettiermischung, Polymerkombination, Reinigunsmittel-Formkörper und Verfahren zur deren Herstellung

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0504091A1 (fr) * 1991-03-15 1992-09-16 Cleantabs A/S Composition pour le lavage machinal de la vaisselle sans phosphate
WO1993017089A1 (fr) * 1992-02-20 1993-09-02 Henkel Kommanditgesellschaft Auf Aktien Procede de fabrication de produits de rinçage pour lave-vaisselle faiblement alcalins, exempts de chlore actif, de silicate et de phosphates, sous forme de granules lourds
US5256327A (en) * 1991-08-01 1993-10-26 Shaklee Corporation Method of preparing a sequestering agent for a non-phosphate cleaning composition
DE4232170A1 (de) * 1992-09-25 1994-03-31 Henkel Kgaa Schwachalkalische Geschirreinigungsmittel
WO1995012654A1 (fr) * 1993-11-03 1995-05-11 The Procter & Gamble Company Limitation de la precipitation de carbonate de calcium dans les lave-vaisselle

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0504091A1 (fr) * 1991-03-15 1992-09-16 Cleantabs A/S Composition pour le lavage machinal de la vaisselle sans phosphate
US5256327A (en) * 1991-08-01 1993-10-26 Shaklee Corporation Method of preparing a sequestering agent for a non-phosphate cleaning composition
WO1993017089A1 (fr) * 1992-02-20 1993-09-02 Henkel Kommanditgesellschaft Auf Aktien Procede de fabrication de produits de rinçage pour lave-vaisselle faiblement alcalins, exempts de chlore actif, de silicate et de phosphates, sous forme de granules lourds
DE4232170A1 (de) * 1992-09-25 1994-03-31 Henkel Kgaa Schwachalkalische Geschirreinigungsmittel
WO1995012654A1 (fr) * 1993-11-03 1995-05-11 The Procter & Gamble Company Limitation de la precipitation de carbonate de calcium dans les lave-vaisselle

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998014548A3 (fr) * 1996-10-02 2000-08-24 Herbert Schmitz Procede de production d'un produit de nettoyage, notamment sous forme de poudre pour lave-vaisselle

Also Published As

Publication number Publication date
DE19532304A1 (de) 1997-03-06
ES2140894T3 (es) 2000-03-01
EP0848750A1 (fr) 1998-06-24
DE59603641D1 (de) 1999-12-16
EP0848750B1 (fr) 1999-11-10

Similar Documents

Publication Publication Date Title
EP0579659B1 (fr) Procede de production de pastilles de detergent pour machines a laver la vaisselle
EP0743978B1 (fr) Comprime de blanchiment contenant des adjuvants
EP0777721B1 (fr) Procede de production de produits de lavage et de nettoyage en comprimes
EP0523099B1 (fr) Procede pour la fabrication d'agents de lavage et de nettoyage
DE4228786A1 (de) Geschirrspülmittel mit ausgewähltem Builder-System
EP0738237A1 (fr) Adjuvants silicates et utilisation dans les produits de lavage ou de nettoyage et melanges complexes destines a etre utilises dans ce secteur
DE19709411A1 (de) Waschmittelformkörper
EP0720644B1 (fr) Melanges detergents et produits de lavage ou de nettoyage a proprietes ameliorees de dissolution
EP0985728B1 (fr) Activateur de blanchiment en forme granulaire
EP0699231B1 (fr) Produit blanchissant et desinfectant
EP3138895B1 (fr) Particules, leur utilisation comme detergent pour lave-vaisselle et leur fabrication
EP0888449B1 (fr) Detergent et nettoyant solide a masse volumique apparente elevee contenant des tensioactifs et des adjuvants, et compose approprie
EP0814152A2 (fr) Procédé de préparation des détergents solides
EP0848750B1 (fr) Procede de preparation de produits granules precurseurs de detergents de faible alcalinite
EP0703969B1 (fr) Detergents pour lave-vaisselle formant peu de depot
DE10123621B4 (de) Verfahren zur Herstellung einer Wasserenthärtertablette
WO1997031096A1 (fr) Procede de fabrication de pastilles d'agent detergent pour lave-vaisselle
EP0612347A1 (fr) Procede de fabrication de produits pour machine lave-vaisselle faiblement alcalins, exempts de chlore actif et de phosphate, sous forme de granules lourds
DE19601841A1 (de) Niotensidreiche Granulate und Verfahren zu ihrer Herstellung
EP0705328A1 (fr) Agents de lavage a proprietes inhibitrices de la decoloration
EP0814149A2 (fr) Procédé de préparation des détergents solides
DE19752601C1 (de) Verfahren zur Herstellung von Geschirrspülmitteltabletten
DE19545726A1 (de) Dextrinhaltige Reinigungsmittel für harte Oberflächen
EP1489160B1 (fr) Corps moules a action detergente ou nettoyante a usage menager
DE19644591A1 (de) Verfahren zur Herstellung enzym- und bleichmittelhaltiger Wasch- und Reinigungsmittel

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): CA JP US

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FI FR GB GR IE IT LU MC NL PT SE

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 1996930091

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: 1996930091

Country of ref document: EP

NENP Non-entry into the national phase

Ref country code: CA

WWG Wipo information: grant in national office

Ref document number: 1996930091

Country of ref document: EP

点击 这是indexloc提供的php浏览器服务，不要输入任何密码和下载