EP1235896B1 - Procede de production de particules comprimees - Google Patents

Procede de production de particules comprimees Download PDF

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Publication number
EP1235896B1
EP1235896B1 EP00993323A EP00993323A EP1235896B1 EP 1235896 B1 EP1235896 B1 EP 1235896B1 EP 00993323 A EP00993323 A EP 00993323A EP 00993323 A EP00993323 A EP 00993323A EP 1235896 B1 EP1235896 B1 EP 1235896B1
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EP
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Prior art keywords
acid
die
sodium
surfactants
mixture
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German (de)
English (en)
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EP1235896A2 (fr
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Henriette Weber
Wilfried Rähse
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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    • 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

Definitions

  • the present invention relates to a process for the production of compressed Particles which are suitable for incorporation in detergents and cleaners, wherein a Mixture of the solid and liquid starting materials in a pelletizer is pressed.
  • DE 41 00 306 discloses a process for the preparation of ingredients of laundry detergents. and / or detergents contained dry concentrates in the form of free-flowing and storable coarse-grained compacts disclosed, wherein fine-grained ingredients without pronounced adhesive or adhesive properties with fine-grained ingredients with adhesive or adhesive properties as a fine-grained good among such Conditions are largely homogeneously mixed to a loose bulk material, under which no pronounced solidifying adhesive function occurs, the optionally used liquid components mixed in and the bulk material at as far as possible exclusion of shear forces from the main mass below Inclusion of microdispersed air is pressed into compacts.
  • the pressing is done by means of a die press, in particular in a ring die press, wherein the Bulk material on the surface of a rotating, bore-containing die applied and by means of one up or slightly above the die press rotating press tool under compression in the bores einwalzt and by this is extruded through strand-shaped and cut to granules.
  • detergents and cleaners are usually different particulate Contain components, each in predetermined proportions to the finished product be mixed.
  • the individual components come from different sources Production method.
  • the user also pro removed dosing unit always the same ingredients in appropriate Quantities, it is necessary that the particulate washing and cleaning agents consist of individual particles having similar shapes and densities exhibit. Otherwise, shaking during transport, etc. will occur in the course of Time demixing phenomena, so that the withdrawn amount is not the have desired composition.
  • the bleach activators usually contained in detergents and cleaners thermally non-loadable substances, their decomposition by release of vinegar makes noticeable.
  • the granulation in a mixer or granulator leads to Particles with low abrasion stability, resulting in an undesirable fines content in the product generated.
  • the material to be pressed is fed into the press via a screw conveyor, wherein the densification of the material by indirectly via the rotating die driven rollers, which compress the material and into the openings of the pressing around the surrounding die.
  • the material often slips on the inner surface of the circumferential die. This reflux reduces the Compaction of the material and can increase its residence time.
  • the present invention has for its object to provide a process for the preparation of for incorporation into detergents and cleaning agents suitable particles available in which the registered energy is reduced such that also temperature-sensitive particles can be processed.
  • the present invention accordingly provides a process for the preparation of compacted particles suitable for incorporation in detergents and cleaners, wherein a mixture of solid and optionally liquid starting materials of Chamber fed to a provided with a rigid ring die pelleting device is, the mixture by means of a rotatably disposed in the chamber and with Pressing surfaces on the inner shell of the die along running rotor through the Die pressed and on the outer edge of the die in the form of compacted particles is scraped off.
  • the inventive method is particularly for the processing of temperature-sensitive materials, such as bleach activators, enzymes, perfume oils, etc. suitable.
  • the pelletizer In a preferred embodiment of the present invention is in the interior the pelletizer rotatably arranged and with pressing surfaces on the inner surface of the Die along rotor running an impeller.
  • This impeller is special prefers its own drive, i. it does not become mediocre over others powered components in the pelletizer or forward or driven downstream devices.
  • To set the predetermined particle dimension are from the die escaping pellets usually scraped off.
  • In a preferred embodiment are around the outer edge of the die so-called doctor blade in a predetermined Distance away, which rotate around the outer edge.
  • the compacted particles emerging from the petleting device may after the Stripping be further processed in a conventional manner. First they will, if necessary, cooled. As a cooling medium, for example, cooled air can be used become. Additionally or alternatively, the resulting compacted particles may be mixed with very finely divided solids are applied to improve the flowability.
  • a cooling medium for example, cooled air can be used become.
  • the resulting compacted particles may be mixed with very finely divided solids are applied to improve the flowability.
  • the compacted particles produced may be of any shape cylindrical or spherical shapes are particularly preferred.
  • the rounding off can, for example, immediately following the stripping of the particles from Outer jacket of the die are made as long as the particles are still plastically deformable, i.e. has a sufficiently high temperature.
  • the rounding can in from the state The devices known in the art, for example, in a Marumerizer
  • the compacted particles produced according to the invention preferably have Bulk weights of at least 500 g / l on. Particular preference is given to bulk densities in the Range up to 1000 g / l, with bulk weights between 600 and 900 g / l especially are preferred.
  • the bulk weights can each be determined by the given Processing conditions depending on the material properties of the Material mixture are set.
  • the grain size of the particles produced can in a conventional manner to a Range from 0.7 to 3 mm, e.g. through the hole size in the Matrizenpresse and by the distance of the Abstreifmesser.
  • Compressed particles with Lengths above 3 mm for example, to a predetermined length broken and optionally rounded.
  • the inventive method can for the production of washing and Detergent compacted particles of any ingredients be performed.
  • To carry out the method first the fixed and optionally mixed liquid starting materials.
  • any, usually as solid ingredients in washing and Detergents contained ingredients are processed.
  • Bleach activators are used to improve the bleaching performance of detergents at temperatures below 60 ° C.
  • bleach activators are compounds which, under perhydrolysis conditions, give peroxocarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid.
  • Suitable substances are those which carry O- and / or N-acyl groups of the stated carbon atom number and / or optionally substituted benzoyl groups.
  • polyacylated alkylenediamines in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triaziri (DADHT), acylated glycolurils, in particular 1,3,4,6 -Tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, more particularly n-nonanoyl or isononanoyloxybenzenesulfonate (n - or iso-NOBS), carboxylic anhydrides, more particularly phthalic anhydride, lsatoklareanhydrid and / or succinic anhydride, glycolide , acylated polyhydric alcohols, in particular triacetin
  • bleach activators are sodium 4- (octanoyloxy) benzenesulfonate, undecenoyloxybenzenesulfonate (UDOBS), sodium dodecanoyloxybenzenesulfonate (DOBS), decanoyloxybenzoic acid (DOBA, OBC 10) and / or dodecanoyloxybenzenesulfonate (OBS 12) and N-methylmorpholine-acetonitrile (MMA).
  • Such bleach activators are contained in the compacted particles prepared according to the invention preferably in amounts of from 40 to 90% by weight, particularly preferably from 70 to 90% by weight, based on the finished particle.
  • the components that can also be processed include the enzymes, which include Proteases, amylases, pullulanases, cellulases, cutinases and / or lipases, for example Proteases such as BLAP®, Optimase®, Opticlean®, Maxacal®, Maxapem®, Durazym®, Purafect® OxP, Esperase® and / or Savinase®, amylases such as Termamyl®, Amylase-LT®, Maxamyl®, Duramyl®, Purafect® OxAm.
  • Proteases such as BLAP®, Optimase®, Opticlean®, Maxacal®, Maxapem®, Durazym®, Purafect® OxP, Esperase® and / or Savinase®
  • amylases such as Termamyl®, Amylase-LT®, Maxamyl®, Duramyl®, Purafect® OxAm.
  • Cellulases such as Celluzyme®, Carezyme®, KAC® and / or the international patent applications WO 96/34108 and WO 96/34092 known cellulases and / or lipases such as Lipolase®, Lipomax®, Lumafast® and / or Lipozym®.
  • the enzymes used can be in the form of their aqueous solutions, such as concentrated and purified fennel broths or on Carriers adsorbed and / or be embedded in enveloping substances.
  • dyes and fragrances can be processed in the process of the invention.
  • perfume oils or fragrances individual fragrance compounds, e.g. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and type Hydrocarbons are used. Fragrance compounds of the ester type are e.g.
  • the ethers include, for example, benzyl ethyl ethers, to Aldehydes e.g.
  • the linear alkanals with 8-18 carbon atoms citral, citronellal, Citronellyloxyacetaldehyde, Cyclamenaldehyde, Hydroxycitronellal, Lilial and Bourgeonal
  • the ketones e.g. the Jonone, a-isomethylionone and methylcedryl ketone
  • the hydrocarbons mainly include the terpenes such as limonene and pinas.
  • perfume oils can also contain natural fragrance mixtures, as accessible from plant sources are, e.g. Pine, Citrus, Jasmine, Patchouty, Rose or Ylang-Ylang oil. Also suitable are Muscat, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, Cinnamon oil, lime blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and Labdanum oil and orange blossom oil, neroliol, orange peel oil and sandalwood oil.
  • solid ingredients in the process according to the invention all conventional solid Components are processed. These can also already be compounded in Form, i. exist as prefabricated mixtures.
  • solid ingredients are water-soluble and / or water-insoluble, organic and / or inorganic Builders and cobuilders, bleaches, anionic surfactants, nonionic surfactants and Enzyme compounds.
  • Water-soluble inorganic builder materials are, in particular, polymers Alkaline phosphates, in the form of their alkaline neutral or acidic sodium or Potassium salts may be present, into consideration. Examples are tetrasodium diphosphate, Disodium dihydrogen diphosphate, pentasodium triphosphate, so-called Sodium hexametaphosphate and the corresponding potassium salts or mixtures of sodium and potassium salts.
  • water-insoluble, water-dispersible Inorganic builder materials are especially crystalline or amorphous alkali metal aluminosilicates, in amounts of up to 50 wt .-%, preferably not above 40 wt .-% and in liquid agents, in particular from 1 wt .-% to 5 wt .-%, used.
  • these are the detergent grade crystalline sodium aluminosilicates. in particular zeolite A, P and optionally X, are preferred.
  • Quantities near the mentioned Upper limit are preferably used in solid, particulate agents.
  • suitable aluminosilicates do not convert particles having a particle size 30 microns and preferably consist of at least 80 wt .-% of particles with a Size less than 10 ⁇ m.
  • Their calcium binding capacity which according to the data of the German Patent DE 24 12 837 can be determined, is usually in the range of 100 to 200 mg CaO per gram.
  • Partial substitutes for said alumosilicate are crystalline alkicate silicates which may be present alone or in admixture with amorphous silicates.
  • the alkali metal silicates useful as builders in the compositions according to the invention preferably have a molar ratio of alkali metal oxide to SiO 2 below 0.95, in particular from 1: 1.1 to 1:12, and may be present in amorphous or crystalline form.
  • Preferred alkali metal silicates are the sodium silicates, in particular the amorphous sodium silicates, with a molar ratio of Na 2 O: SiO 2 of 1: 2 to 1: 2.8.
  • the crystalline silicates which may be present alone or in admixture with amorphous silicates, are crystalline layer silicates with the general formula Na 2 Si x O 2x + 1 ⁇ y H are used 2 O, in which x, known as the modulus, an integer from 1 9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4.
  • Preferred crystalline phyllosilicates are those in which x in the abovementioned general formula assumes the values 2 or 3.
  • both ⁇ - and ⁇ -sodium disilicates are preferred, whereby ⁇ -sodium disilicate can be obtained, for example, by the process described in international patent application WO 91/08171.
  • ⁇ -Sodium silicates with a modulus between 1.9 and 3.2 can be prepared according to Japanese patent applications JP 04/238 809 or JP 04/260 610.
  • amorphous alkali metal silicates are also prepared from amorphous alkali metal silicates, practically anhydrous crystalline alkali metal silicates of the abovementioned general formula in which x is a number from 1.9 to 2.1, preparable as in the European patent applications EP 0 548 599, EP 0 502 325 and EP 0 452 428 can be used in agents according to the invention.
  • a crystalline sodium layer silicate with a modulus of 2 to 3 is used, as can be prepared from sand and soda. Crystalline sodium silicates with a modulus in the range from 1.9 to 3.5 are used in a further preferred embodiment of compositions according to the invention.
  • a granular compound of alkali metal silicate and alkali metal carbonate is used, as described, for example, in International Patent Application WO 95/22592 or as it is commercially available, for example, under the name Nabion® 15.
  • alkali metal aluminosilicate, in particular zeolite is also present as an additional builder substance, the weight ratio of aluminosilicate to silicate, based in each case on anhydrous active substances, is preferably 1:10 to 10: 1.
  • the weight ratio of amorphous alkali metal silicate to crystalline alkali metal silicate is preferably 1: 2 to 2: 1 and especially 1: 1 to 2: 1.
  • zeolite for example, fine crystalline, synthetic and bound water containing zeolite, such as zeolite A, zeolite P and mixtures of A and P used become.
  • zeolite P is zeolite MAP®, for example (Commercial product of the company Crosfield) to call.
  • zeolites of To call faujasite type are zeolites of To call faujasite type. Together with the zeolites X and Y belongs the mineral Faujasite to the faujasite types within the zeolite structure group 4, by the Double Six-Ring Subunit D6R is characterized (Compare Donald W. Breck: "Zeolite Molecular Sieves", John Wiley & Sons, New York, London, Sydney, Toronto, 1974, page 92).
  • the zeolite structure group 4 includes besides the mentioned faujasite types the minerals chabazite and gmelinite as well as the synthetic zeolites R (chabazite type), S (gmelinite type), L and ZK-5. The latter two synthetic Zeolites have no mineral analogues.
  • Faujasite-type zeolites are composed of ⁇ -cages which are linked tetrahedrally via D6R subunits, with the ⁇ -cages resembling the carbon atoms in the diamond.
  • the three-dimensional network of the faujasite-type zeolites used in the process according to the invention has pores of 2.2 and 7.4 ⁇ , the unit cell also contains 8 cavities of about 13 ⁇ diameter and can be represented by the formula Na 86 [(AlO 2 ) 86 (SiO 2 ) 106 ]. 264 H 2 O.
  • the network of zeolite X contains a void volume of about 50%, based on the dehydrated crystal, which represents the largest void space of all known zeolites (zeolite Y: about 48% void volume, faujasite: about 47% void volume). (All data from: Donald W. Breck: "Zeolite Molecular Sieves", John Wiley & Sons, New York, London, Sydney, Toronto, 1974, pages 145, 176, 177).
  • the term "faujasite type zeolite” denotes all three zeolites which form the faujasite subgroup of the zeolite structure group 4.
  • zeolite X zeolite Y and faujasite as well as mixtures of these compounds can also be used according to the invention, the pure zeolite X being preferred.
  • Mixtures or cocrystallizates of zeolites of the faujasite type with other zeolites, which need not necessarily belong to the zeolite structure group 4 can be used according to the invention, with the advantages of the process according to the invention becoming particularly clear if at least 50% % By weight of the zeolites zeolites of the faujasite type.
  • the aluminum silicates used in the process according to the invention are commercially available, and the methods for their presentation are in Standard Monographs Described.
  • Examples of commercially available X-type zeolites can be described by the following formulas: Na 86 [(AlO 2 ) 86 (SiO 2 ) 106 ] .xH 2 O, K 86 [(AlO 2 ) 86 (SiO 2 ) 106 ] .xH 2 O, Ca 40 Na 6 [(AlO 2 ) 86 (SiO 2 ) 106 ] xH 2 O, Sr 21 Ba 22 [(AlO 2 ) 86 (SiO 2 ) 106 ] x H 2 O, where x can take values between 0 and 276 and have pore sizes of 8.0 to 8.4 ⁇ .
  • a co-crystallizate of zeolite X and zeolite A (about 80% by weight of zeolite X) available commercially from CONDEA Augusta SpA under the trade name VEGO-BOND is also commercially available and preferably usable in the process according to the invention
  • AX® is distributed and by the formula nNa 2 O • (1-n) K 2 O • Al 2 O 3 • (2 - 2.5) SiO 2 • (3.5-5.5) H 2 O can be described.
  • Y-type zeolites are also commercially available and can be obtained, for example, by the formulas Na 56 [(AlO 2 ) 56 (SiO 2 ) 136 ] xH 2 O, K 56 [(AlO 2 ) 56 (SiO 2 ) 136 ] xH 2 O, where x is numbers between 0 and 276 and has pore sizes of 8.0 ⁇ .
  • the particle sizes of the zeolites used in the process of the invention Fauja-sit type is in the range of 0.1 to 100 microns, preferably between 0.5 and 50 ⁇ m, and more preferably between 1 and 30 ⁇ m, each with standard particle size determination methods measured.
  • Alkali metal phosphates is the summary term for the alkali metal (especially sodium and potassium) salts of various phosphoric acids, in which one can distinguish metaphosphoric acids (HPO 3 ) n and orthophosphoric H 3 PO 4 in addition to higher molecular weight representatives.
  • the phosphates combine several advantages: they act as alkali carriers, prevent lime deposits on machine parts or lime incrustations in fabrics and also contribute to the cleaning performance.
  • Sodium dihydrogen phosphate, NaH 2 PO 4 exists as a dihydrate (density 1.91 gcm -3 , melting point 60 °) and as a monohydrate (density 2.04 gcm -3 ). Both salts are white powders which are very soluble in water and which lose the water of crystallization when heated and at 200 ° C into the weak acid diphosphate (disodium hydrogen diphosphate, Na 2 HP 2 O 7 ), at higher temperature in sodium trimetaphosphate (Na 3 P 3 O 9 ) and Maddrell's salt (see below).
  • NaH 2 PO 4 is acidic; It arises when phosphoric acid is adjusted to a pH of 4.5 with sodium hydroxide solution and the mash is sprayed.
  • Potassium dihydrogen phosphate potassium phosphate primary or monobasic potassium phosphate, KDP
  • KH 2 PO 4 is a white salt of 2.33 gcm -3 density, has a melting point of 253 ° [decomposition to form potassium polyphosphate (KPO 3 ) x ] and is light soluble in water.
  • Disodium hydrogen phosphate (secondary sodium phosphate), Na 2 HPO 4 , is a colorless, very slightly water-soluble crystalline salt. It exists anhydrous and with 2 moles (density 2.066 gcm -3 , loss of water at 95 °), 7 moles (density 1.68 gcm -3 , melting point 48 ° with loss of 5 H 2 O) and 12 moles water ( Density 1.52 gcm -3 , melting point 35 ° with loss of 5 H 2 O) becomes anhydrous at 100 ° C and, upon increased heating, passes into the diphosphate Na 4 P 2 O 7 .
  • Disodium hydrogen phosphate is prepared by neutralization of. Phosphoric acid with soda solution prepared using phenolphthalein as indicator.
  • Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K 2 HPO 4 , is an amorphous, white salt that is readily soluble in water.
  • Trisodium phosphate, tertiary sodium phosphate, Na 3 PO 4 are colorless crystals which have a density of 1.62 gcm -3 as dodecahydrate and a melting point of 73-76 ° C (decomposition), as decahydrate (corresponding to 19-20% P 2 O 5 ) have a melting point of 100 ° C and in anhydrous form (corresponding to 39-40% P 2 O 5 ) have a density of 2.536 gcm -3 .
  • Trisodium phosphate is readily soluble in water under alkaline reaction and is prepared by evaporating a solution of exactly 1 mole of disodium phosphate and 1 mole of NaOH.
  • Tripotassium phosphate (tertiary or tribasic potassium phosphate), K 3 PO 4 , is a white, deliquescent, granular powder of density 2.56 gcm -3 , has a melting point of 1340 ° and is readily soluble in water with an alkaline reaction. It arises, for example, when heating Thomasschlacke with coal and potassium sulfate. Despite the higher price, the more soluble, therefore highly effective, potassium phosphates are often preferred over the corresponding sodium compounds in the detergent industry.
  • Tetrasodium diphosphate (sodium pyrophosphate), Na 4 P 2 O 7 , exists in anhydrous form (density 2.534 gcm -3 , melting point 988 °, also indicated 880 °) and as decahydrate (density 1.815-1.836 gcm -3 , melting point 94 ° with loss of water) , For substances are colorless, in water with alkaline reaction soluble crystals.
  • Na 4 P 2 O 7 is formed on heating of disodium phosphate to> 200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and dewatering the solution by spraying.
  • the decahydrate complexes heavy metal salts and hardness agents and therefore reduces the hardness of the water.
  • Potassium diphosphate (potassium pyrophosphate), K 4 P 2 O 7 , exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33 gcm -3 , which is soluble in water, the pH being 1% Solution at 25 ° 10.4.
  • Sodium and potassium phosphates in which one can distinguish cyclic representatives, the sodium or Kaliummetaphosphate and chain types, the sodium or potassium polyphosphates. In particular, for the latter are a variety of names in use: hot or cold phosphates, Graham's salt, Kurrolsches and Maddrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates.
  • pentasodium triphosphate Na 5 P 3 O 10 (sodium tripolyphosphate)
  • sodium tripolyphosphate sodium tripolyphosphate
  • n 3
  • 100 g of water dissolve at room temperature about 17 g, at 60 ° about 20 g, at 100 ° around 32 g of the salt water-free salt; after two hours of heating the solution to 100 ° caused by hydrolysis about 8% orthophosphate and 15% diphosphate.
  • pentasodium triphosphate In the preparation of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dehydrated by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentakaliumtriphosphat, K 5 P 3 O 10 (potassium tripolyphosphate), for example, in the form of a 50 wt .-% solution (> 23% P 2 O 5 , 25% K 2 O) in the trade. The potassium polyphosphates are widely used in the washing and cleaning industry.
  • Nafiumkaliumtripolyphosphate also exist, which are also used in the context of the present invention. These arise, for example, when hydrolyzed sodium trimetaphosphate with KOH: (NaPO 3 ) 3 + 2 KOH ⁇ Na 3 K 2 P 3 O 10 + H 2 O
  • sodium tripolyphosphate, potassium tripolyphosphate or mixtures of these two can be used; also mixtures from Sodium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of Potassium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of Sodium tripolyphosphate and potassium tripolyphosphate and sodium potassium tripolyphosphate are used according to the invention.
  • organic cobuilders in the washing and especiallysmittelformkörpem particular polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, other organic Cobuilder (see below) and phosphonates are used. These substance classes are described below.
  • Useful organic builders are, for example, in the form of their Sodium salts usable polycarboxylic acids, among polycarboxylic acids such Carboxylic acids are understood to carry more than one acid function.
  • these are citric acid, adipic acid, succinic acid, glutaric acid, Malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, Nitrilotriacetic acid (NTA), if such use for ecological reasons not is objectionable, as well as mixtures of these.
  • Preferred salts are the salts of Polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, Tartaric acid, sugar acids and mixtures of these.
  • the acids themselves can also be used.
  • the acids are next to theirs Builder effect also typically the property of an acidifying component and thus also serve to set a lower and milder pH of Detergents or cleaners.
  • here are citric acid, Succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures to call this.
  • polymeric polycarboxylates are suitable, these are for example the Alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a molecular weight of 500 to 70000 g / mol.
  • the molecular weights stated for polymeric polycarboxylates are weight-average molar masses M w of the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the polymers investigated. These data differ significantly from the molecular weight data, in which polystyrene sulfonic acids are used as standard. The molar masses measured against polystyrenesulfonic acids are generally significantly higher than the molecular weights specified in this document.
  • Suitable polymers are, in particular, polyacrylates, which are preferably of molecular weight from 2000 to 20,000 g / mol. Because of their superior solubility can be this group in turn the short-chain polyacrylates, the molecular weights of 2000 to 10000 g / mol, and more preferably from 3000 to 5000 g / mol, are preferred be.
  • copolymeric polycarboxylates in particular those of Acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid.
  • copolymers of acrylic acid with maleic acid proven, the 50 to 90 wt .-% acrylic acid and 50 to 10 wt .-% maleic acid contain.
  • Their molecular weight relative to free acids is generally 2000 to 70000 g / mol, preferably 20,000 to 50,000 g / mol and in particular 30,000 up to 40,000 g / mol.
  • the (co) polymeric polycarboxylates can be used either as a powder or as an aqueous Solution can be used.
  • the content of (co-) Potymeren polycarboxylates is preferably 0.5 to 20 wt .-%, in particular 3 to 10 wt .-%.
  • the polymers may also be allyl sulfonic acids, such as allyloxybenzenesulfonic acid and methallylsulfonic acid, as a monomer contain.
  • allyl sulfonic acids such as allyloxybenzenesulfonic acid and methallylsulfonic acid
  • biodegradable polymers of more than two various monomer units for example those which are salts of the monomers Acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or the as monomers, salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives contain.
  • copolymers are those which are preferably acrolein monomers and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.
  • polymeric aminodicarboxylic acids are polymeric aminodicarboxylic acids, to mention their salts or their precursors.
  • polyacetals which are obtained by reaction of Dialdehydes with Polyolcarbonklaren, which 5 to 7 C-atoms and at least 3 Hydroxyl groups can be obtained.
  • Preferred polyacetals are from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
  • Suitable organic builders are dextrins, for example Oligomers or polymers of carbohydrates obtained by partial hydrolysis of starches can be obtained.
  • the hydrolysis can by customary, for example acid or enzyme-catalyzed process can be performed.
  • it is Hydrolysis products with average molecular weights in the range of 400 to 500,000 g / mol.
  • a polysaccharide with a dextrose equivalent (DE) in the range of 0.5 to 40, in particular from 2 to 30, where DE is a customary measure for the reducing effect of a polysaccharide compared to dextrose, which is a DE of 100 is.
  • oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function.
  • oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function.
  • an oxidized oligosaccharide wherein a product oxidized to C 6 of the saccharide ring may be particularly advantageous.
  • oxydisuccinates and other derivatives of disuccinates preferably Ethylenediamine disuccinate are other suitable cobuilders.
  • This is ethylenediamine-N, N'-disuccinate (EDDS) preferably in the form of its sodium or magnesium salts used.
  • EDDS ethylenediamine-N, N'-disuccinate
  • Glycerol disuccinates and glycerol trisuccinates are also preferred in this context. Suitable quantities are in zeolite-containing and / or silicate-containing formulations at 3 to 15 wt .-%.
  • organic cobuilders are, for example, acetylated Hydroxycarboxylic acids or their salts, which may also be in lactone form and which at least 4 carbon atoms and at least one Hydroxy group and a maximum of two acid groups.
  • phosphonates are in particular hydroxyalkane or aminoalkanephosphonates.
  • hydroxyalkane phosphonates is 1-hydroxyethane-1,1-diphosphonate (HEDP) of particular importance as a co-builder.
  • HEDP 1-hydroxyethane-1,1-diphosphonate
  • the disodium salt is neutral and the tetrasodium salt is alkaline (pH 9). responding.
  • Ethylenediamine tetramethylene phosphonates are preferably used as aminoalkane phosphonates (EDTMP), diethylene triamine pentamethylene phosphonate (DTPMP) and their higher homoengine in question. They are preferably in the form of neutral sodium salts, e.g.
  • a builder is doing from the Class of phosphonates preferably used HEDP.
  • the aminoalkane phosphonates also have a pronounced Schwermetallbindeabmögen. Accordingly, can it may be preferred, in particular if the agents also contain bleach, Aminoalkanphosphonate, in particular DTPMP, use, or mixtures of the to use said phosphonates.
  • anionic surfactants for example, those of the sulfonate type and sulfates are used.
  • the surfactants of the sulfonate type are preferably C 9-13 -alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as are obtained, for example, from C 12-18 -monoolefins having terminal or internal double bonds by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation products into consideration.
  • alkanesulfonates which are obtained from C 12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • esters of ⁇ -sulfo fatty acids for example the x-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.
  • 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 coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -C 20 oxo alcohols and those half-esters of secondary alcohols of these chain lengths 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 having 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 are 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 the Shell Oil Company under the name DAN®, are suitable anionic surfactants.
  • sulfated fatty acid glycerol esters are sulfated fatty acid glycerol esters.
  • fatty acid glycerine esters are the mono-, di- and triesters and their mixtures to understand how they in the preparation by esterification of a monoglycerol with 1 to 3 moles of fatty acid or obtained in the transesterification of triglycerides with 0.3 to 2 moles of glycerol.
  • Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated Fatty acids having 6 to 22 carbon atoms, for example caproic acid, Caprylic, capric, myristic, lauric, palmitic, stearic or Behenic acid.
  • EO ethylene oxide
  • Fatty alcohols with 1 to 4 EO are suitable. Due to their high foaming behavior, they are only used in detergents in relatively small amounts, for example in amounts of from 1 to 5% by weight.
  • Suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • alcohols preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain C 8-18 fatty alcohol residues or mixtures of these.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols, which in themselves constitute nonionic surfactants (see description below).
  • Sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are again particularly preferred.
  • alk (en) ylsuccinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
  • anionic surfactants also include soaps. Suitable are saturated and unsaturated fatty acid soaps, such as the salts of lauric acid, myristic acid, Palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid and in particular from natural fatty acids, e.g. Coconut, palm kernel, olive oil or tallow fatty acids, derived soap mixtures.
  • saturated and unsaturated fatty acid soaps such as the salts of lauric acid, myristic acid, Palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid and in particular from natural fatty acids, e.g. Coconut, palm kernel, olive oil or tallow fatty acids, derived soap mixtures.
  • the other anionic surfactants may be in the form of theirs Sodium, potassium or ammonium salts and as soluble salts of organic bases, such as Mono-, di- or triethanolamine present.
  • the anionic surfactants are in the form of their sodium or potassium salts, especially in the form of the sodium salts.
  • sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • Other useful bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid. Even when using the bleaching agents, it is possible to dispense with the use of surfactants and / or builders, so that pure bleach tablets can be produced.
  • bleach tablets are to be used for textile washing, a combination of sodium percarbonate with sodium sesquicarbonate is preferred, regardless of which other ingredients are contained in the tablets.
  • bleaching agents from the group of organic bleaching agents.
  • Typical organic bleaches are the diacyl peroxides such as dibenzoyl peroxide.
  • Other typical organic bleaches are the peroxyacids, examples of which include the alkyl peroxyacids and the aryl peroxyacids.
  • Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy-a-naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ⁇ -phthalimidoperoxycaproic acid [Phthaloiminoperoxyhexanoic acid (PAP )], o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperoxysebacic acid, diperoxybrassic acid, the diperoxyphthalic acids, 2-decy
  • chlorine or bromine releasing substances In compacted particles incorporated in automatic dishwashing compositions can be used, chlorine or bromine releasing substances.
  • suitable chlorine or bromine releasing materials are, for example heterocyclic N-bromo- and N-chloroamides, for example trichloroisocyanuric acid, Tribromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium into consideration.
  • DICA dichloroisocyanuric acid
  • Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydantoin are also suitable.
  • solid nonionic surfactants are alkyl glycosides, alkoxylated fatty acid alkyl esters, amine oxides, polyhydroxy fatty acid amides or their any mixtures.
  • Alkyl glycosides have the general formula RO (G) x , in which R is a primary straight-chain or methyl-branched, in particular 2-methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol for a glycose unit with 5 or 6 C atoms, preferably for 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.
  • nonionic surfactants used either as sole nonionic surfactant or in combination with other nonionic surfactants
  • Surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 Carbon atoms in the alkyl chain, in particular fatty acid methyl ester.
  • amine oxides are N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide to call.
  • the amount of amine oxides and the Fatty acid alcohol amides is preferably not more than that of the ethoxylated Fatty alcohols, especially not more than half of them.
  • Polyhydroxy fatty acid amides have the formula I, wherein RCO is an aliphatic acyl group having 6 to 22 carbon atoms, R 1 is hydrogen, an alkyl or hydroxyalkyl group having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl group having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
  • the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
  • the group of polyhydroxy fatty acid amides also includes compounds of the formula II, in the R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R 1 is a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R 2 is a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, with C 1-4 alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated Derivatives of this residue.
  • R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
  • R 1 is a linear, branched or cyclic alkyl radical or an aryl radical having 2
  • [Z] is preferably obtained by reductive amination of a sugar, for example Glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • a sugar for example Glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • the N-alkoxy or N-aryloxy-substituted compounds may then be exemplified by Reaction with fatty acid methyl esters in the presence of an alkoxide as a catalyst in the desired polyhydroxy fatty acid amides are converted.
  • liquid starting materials are usually present in liquid form nonionic surfactants used.
  • granulating aids can also be added such as paraffins, polyethylene glycols, polyoxyethylene glycols and aqueous Solutions of organic builders, such as aqueous solutions of acrylic acid-maleic anhydride copolymers.
  • organic builders such as aqueous solutions of acrylic acid-maleic anhydride copolymers.
  • Fragrance oils or aqueous enzyme solutions are used. Liquid in the sense of The present invention means that these substances are liquid at the processing temperature are.
  • the liquid components are usually in the process according to the invention in an amount of 2 to 10 wt .-%, preferably from 2 to 8 wt .-%, based on the finished particles, used.
  • liquid surfactants are the alkoxylated alcohols.
  • alkoxylated, advantageously ethoxylated, in particular primary alcohols are preferably those having 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol used in which the alcohol radical may be linear or methyl branched preferably in the 2-position or may contain linear and methyl-branched radicals in the mixture, as they are usually present in Oxoalkoholresten.
  • EO ethylene oxide
  • alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred.
  • the preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 3 EO, 4 EO or 7 EO, C 9-11 alcohols with 7 EO, C 13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12-18 -alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 12-14 -alcohol with 3 EO and C 12-18 -alcohol with 7 EO.
  • the degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • Nonionic surfactants containing EO and PO groups together in the molecule can also be used according to the invention.
  • block copolymers with EO-PO block units or PO-EO block units can be used, but also EO-PO-EO copolymers or PO-EO-PO copolymers.
  • the components listed in Table 1 were mixed in a Lodige mixer and homogenized and then fed via a solids metering in a die press with a rotatably arranged in the chamber and with pressing surfaces on the inner shell of the die running rotor and a rigid ring die.
  • the emerging product was broken to the desired length and in a roundabout for about 1 min. rounded.
  • Example 1 [% by weight] Example 2 [% by weight] Example 3 [% by weight] tower powder 79.5 - - FAS compound 9.1 20.0 10.0 trisodium citrate 4.5 - - TAED - 71.0 81.0 PEG 4000 2.3 7.0 7.0 C 12/18 fatty alcohol x 7 EO 4.6 1.5 1.5 PEG 400 - 0.5 0.5 Residue test /% 17 18 17 Abrasion stability /% 5 4 5 tower powder component Amount [wt%] Zeolite A 46,25 Sokalan CP 5 3 8.75 phosphonate 0.5 C 9-13 alkyl benzene sulphonate 31.25 Soap 2.5 water 10.75 Surfactant granules component Amount [wt%] C 12/18 alkyl benzene sulphonate 28.29 C 12/18 alkyl sulfate 7.75 Texapon Z 65 1.93 C 12/18 fatty alcohol x 7 EO 9.48 Tallow alcohol x 5 EO 1.43 Na stearate
  • the abrasion was determined by placing a tablet on a sieve of the Mesh size 1.6 mm was gelgt. This sieve was then placed in a Retsch analytical sieve machine used. The tablet was added by sieving for 2 minutes mechanically stressed at an amplitude of 2 mm. By forging the tablet in front and after the wear, the abrasion can be determined directly and is in the table in % specified.

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
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Claims (9)

  1. Procédé pour préparer des particules compactées convenant à l'incorporation dans des agents de lavage et de nettoyage, dans lequel un mélange constitué de matière de départ solide et éventuellement liquide, est introduit dans la chambre d'un dispositif granulateur muni d'une matrice annulaire rigide, le mélange est pressé à travers la matrice au moyen d'un rotor, disposé à rotation dans la chambre et tournant à contresens le long de l'enveloppe intérieure de la matrice avec des surfaces de pressage, et raclé sur le bord externe de la matrice sous forme de particules compactées.
  2. Procédé selon la revendication 1, caractérisé en ce que le rotor est une roue à aubes.
  3. Procédé selon la revendication 1 ou 2, caractérisé en ce que le raclage des particules compactées sortant de la matrice se réalise au moyen d'un couteau racloir rotatif.
  4. Procédé selon l'une quelconque des revendications 1 à 3, caractérisé en ce que les granulés sortant de la matrice sont arrondis dans un appareil arrondisseur.
  5. Procédé de préparation selon l'une quelconque des revendications 1 à 4, caractérisé en ce que les matières de départ solides sont choisies parmi les builders, les agents de blanchiment, les activateurs de blanchiment, les tensio-actifs et les compounds tensio-actifs, les enzymes et les compounds enzymatiques.
  6. Procédé selon l'une quelconque des revendications 1 à 5, caractérisé en ce que les matières de départ liquides sont choisies parmi les tensio-actifs non ioniques, les paraffines, les polyéthylèneglycols, les polyoxyéthylèneglycols, les solutions aqueuses de substances builder organiques, les huiles de parfums, ou les concentrés d'huiles de parfums, ainsi que les solutions enzymatiques aqueuses.
  7. Procédé selon l'une quelconque des revendications 1 à 6, caractérisé en ce que la densité apparente est dans la plage comprise entre 500 et 1000 g/l, en particulier dans la plage de 600 à 900 g/l.
  8. Procédé selon l'une quelconque des revendications 1 à 7, caractérisé en ce que les particules compactées préparées présentent une forme cylindrique ou sphérique, et possèdent une longueur de particule, respectivement un diamètre de particule moyen, dans la plage de 0,7 à 3 mm, de préférence de 1 à 2 mm.
  9. Procédé selon l'une quelconque des revendications 1 à 8, caractérisé en ce que les particules compactées contiennent de 50 à 98% en poids d'activateurs de blanchiment, et de 2 à 50% en poids de liants, choisis parmi les tensio-actifs non ioniques, les tensio-actifs anioniques, les builders et les polymères filmogènes.
EP00993323A 1999-12-08 2000-11-29 Procede de production de particules comprimees Expired - Lifetime EP1235896B1 (fr)

Applications Claiming Priority (3)

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DE19959002 1999-12-08
DE19959002A DE19959002C2 (de) 1999-12-08 1999-12-08 Verfahren zur Herstellung von verdichteten Teilchen
PCT/EP2000/011963 WO2001042407A2 (fr) 1999-12-08 2000-11-29 Procede de production de particules comprimees

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JP5489996B2 (ja) * 2008-06-02 2014-05-14 ライオン株式会社 脂肪酸アルキルエステルスルホナート金属塩フレーク及びその製造方法
CN106422974B (zh) * 2016-09-11 2019-11-12 张元才 组合式破碎造粒干燥机
US20220380706A1 (en) * 2021-05-24 2022-12-01 Church & Dwight Co., Inc. Laundry detergent article

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JPS5988088A (ja) * 1982-11-12 1984-05-21 Nagase Seikagaku Kogyo Kk 酵素含有顆粒剤の製造方法
DE3624336A1 (de) * 1986-07-18 1988-01-28 Henkel Kgaa Verfahren zur herstellung von rieselfaehigen alkalischen reinigungsmitteln durch kompaktierende granulation
JPS63134045A (ja) * 1986-11-27 1988-06-06 Katsumi Takao 造粒装置
US5318733A (en) * 1989-08-09 1994-06-07 Henkel Kommanditgesellschaft Auf Aktien Production of compacted granules for detergents
DE4024759A1 (de) * 1990-08-03 1992-02-06 Henkel Kgaa Bleichaktivatoren in granulatform
DE4100306A1 (de) * 1991-01-08 1992-07-09 Henkel Kgaa Kornfoermige, leicht loesliche trockenkonzentrate von inhaltsstoffen aus wasch- und/oder reinigungsmitteln und verfahren zu ihrer herstellung
DE4143016A1 (de) * 1991-12-24 1993-07-01 Henkel Kgaa Bleichaktivatoren in granulatform (ii)
ATE182484T1 (de) * 1992-11-14 1999-08-15 Degussa Verfahren zur herstellung kugelförmiger granulate aus pulverförmigen feststoffen
DE4336548C2 (de) * 1992-11-14 1994-11-17 Degussa Verfahren zur Herstellung kugelförmiger Granulate aus pulverförmigen Feststoffen
JPH0889782A (ja) * 1994-09-21 1996-04-09 Taiheiyo Tokushu Chuzo Kk 造粒装置
DE19649119A1 (de) * 1996-11-27 1998-05-28 Huels Chemische Werke Ag Verfahren zur Granulierung von schmutzlösenden, amphiphilen Polymeren durch Preßagglomeration
DE19939806A1 (de) * 1999-08-21 2001-02-22 Cognis Deutschland Gmbh Schaumkontrollierte feste Waschmittel

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EP1235896A2 (fr) 2002-09-04
CA2328047A1 (fr) 2001-06-08
ATE302840T1 (de) 2005-09-15
DE19959002C2 (de) 2002-12-05
ES2246933T3 (es) 2006-03-01
JP2003516467A (ja) 2003-05-13
DE50011037D1 (de) 2005-09-29
WO2001042407A3 (fr) 2001-12-06
WO2001042407A2 (fr) 2001-06-14

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