EP1159392B1 - Produits de lavage et de nettoyage moules contenant une association tensioactif/agent de blanchiment/adjuvant de lavage - Google Patents

Produits de lavage et de nettoyage moules contenant une association tensioactif/agent de blanchiment/adjuvant de lavage Download PDF

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EP1159392B1
EP1159392B1 EP00912538A EP00912538A EP1159392B1 EP 1159392 B1 EP1159392 B1 EP 1159392B1 EP 00912538 A EP00912538 A EP 00912538A EP 00912538 A EP00912538 A EP 00912538A EP 1159392 B1 EP1159392 B1 EP 1159392B1
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Prior art keywords
weight
tablets
acid
surfactant
sodium
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German (de)
English (en)
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EP1159392A1 (fr
EP1159392B2 (fr
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Andreas Lietzmann
Gerhard Blasey
Markus Semrau
Birgit Burg
Hans-Friedrich Kruse
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/06—Phosphates, including polyphosphates
    • 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
    • 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
    • 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
    • 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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3942—Inorganic per-compounds

Definitions

  • the present invention relates to moldings which have washing and cleaning properties have such as detergent tablets, detergent tablets for machine dishwashing, bleach tablets, water softening tablets, etc.
  • the invention relates to detergent tablets for textile laundry in a household washing machine, called detergent tablets for short become.
  • tablette offer special advantages include simple and clean Dosing and the high degree of compaction, which reduces packaging and Transport effort required. It is precisely because of these advantages that detergents and cleaning agents have in tablet form a high level of consumer acceptance. These advantages stand but also disadvantages. So the tablets have to be sufficiently stable to To survive transport and handling, but on the other hand they should be quick disintegrate and be readily soluble in order to quickly release the active substances and residues or to avoid stains on the treated substrates. Ideally, they should Detergent tablets detach into their secondary particles so quickly, that, for example, a dosage via the induction chamber of household washing machines is easily possible.
  • Moldings that are not suitable for this must dosed over the drum where the direct contact of the agent with the laundry too so-called spotting problems.
  • a mitigation of this problem is admittedly through the use of dosing aids or sachets, into which the tablets are added before can be inserted for washing, but on the one hand the problem is not complete solved, on the other hand, this cumbersome procedure leads to significantly reduced Consumer acceptance because of the advantages of easy dosing and the possibility the dosage without skin contact with the agent are thereby nullified.
  • humectants are added to solve this problem Tableting speeds slowed down to prevent air pockets or additives added, which leads to a too high expansion of the molded body after pressing prevent. Microcrystalline cellulose has proven itself here.
  • Detergent tablets which contain phosphates and bleaches are described in the prior art.
  • international patent application WO98 / 42816 discloses detergent tablets which have a density of more than 1040 g / cm 3 and contain 5 to 50% by weight of surfactant and 8 to 30% by weight of bleach.
  • sodium percarbonate or sodium perborate tetrahydrate are used as bleaching agents, which should have been found to be preferred over sodium perborate monohydrate in manual tests. Neither the use of fatty alcohol sulfates nor the problem of capping are mentioned in this document.
  • Detergent tablets with sodium percarbonate and tripolyphosphate are also described in WO98 / 24817 (Unilever).
  • the use of fatty alcohol sulfates is also not described in this document, nor is the problem of capping recognized.
  • the present invention was based on the task of detergent tablets to provide, which have a recipe composition which have the tendency the molded body minimized for capping. On the one hand, this should be independent of the used tableting machine and on the other hand without loss of other quality parameters of the tablets can be reached. In particular, high hardness with short disintegration times and thus the possibility of using the resulting molded article via the induction bowl To be able to dose are further properties that the molded articles according to the invention should have.
  • the present invention relates to laundry detergent and cleaning product tablets compressed, particulate detergent and cleaning agent containing surfactant (s), Bleach, builders and optionally other ingredients of detergents and cleaning agents, characterized in that the moldings fatty alcohol sulfate (s), percarbonate and contain phosphate builders.
  • the moldings according to the invention contain surfactants, phosphate builders and bleaches.
  • the phosphates fulfill builder tasks, while fatty alcohol sulfates act as washing agents Substances are included. Usually the main amount of builder substance made out of the phosphates.
  • phosphates are the alkali metal phosphates with particular preference for pentasodium or pentapotassium triphosphate (Sodium or potassium tripolyphosphate) in the detergent industry greatest importance.
  • pentasodium or pentapotassium triphosphate Sodium or potassium tripolyphosphate
  • Alkali metal phosphates is the general term for the alkali metal (especially sodium and potassium) salts of the various phosphoric acids, in which one can differentiate between metaphosphoric acids (HPO 3 ) n and orthophosphoric acid H 3 PO 4 in addition to higher molecular weight representatives.
  • the phosphates combine several advantages: They act as alkali carriers, prevent limescale deposits on machine parts and lime incrustations in fabrics and also contribute to 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, water-soluble powders that lose water of crystallization when heated and at 200 ° C into the weakly acidic diphosphate (disodium hydrogen diphosphate, Na 2 H 2 P 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 (primary or monobasic potassium phosphate, potassium biphosphate, KDP), KH 2 PO 4 , is a white salt with a density of 2.33 gcm -3 , 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 easily water-soluble crystalline salt. It exists anhydrous and with 2 mol. (Density 2.066 gcm -3 , water loss at 95 °), 7 mol. (Density 1.68 gcm -3 , melting point 48 ° with loss of 5 H 2 O) and 12 mol. Water ( Density 1.52 gcm -3 , melting point 35 ° with loss of 5 H 2 O), becomes anhydrous at 100 ° and changes to diphosphate Na 4 P 2 O 7 when heated more strongly. Disodium hydrogen phosphate is prepared by neutralizing phosphoric acid with soda solution using phenolphthalein as an indicator. Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K 2 HPO 4 , is an amorphous, white salt that is easily soluble in water.
  • Trisodium phosphate, tertiary sodium phosphate, Na 3 PO 4 are colorless crystals which, as dodecahydrate, have a density of 1.62 gcm -3 and a melting point of 73-76 ° C (decomposition), as decahydrate (corresponding to 19-20% P 2 O 5 ) 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 with an alkaline reaction and is produced by evaporating a solution of exactly 1 mol of disodium phosphate and 1 mol of NaOH.
  • Tripotassium phosphate (tertiary or triphase potassium phosphate), K 3 PO 4 , is a white, deliquescent, granular powder with a density of 2.56 gcm -3 , has a melting point of 1340 ° and is easily soluble in water with an alkaline reaction. It arises, for example, when Thomas slag is heated with coal and potassium sulfate. Despite the higher price, the more soluble, therefore highly effective, potassium phosphates are often preferred over corresponding sodium compounds in the cleaning agent industry.
  • Tetrasodium diphosphate (sodium pyrophosphate), Na 4 P 2 O 7 , exists in anhydrous form (density 2.534 gcm -3 , melting point 988 °, also stated 880 °) and as decahydrate (density 1.815-1.836 gcm -3 , melting point 94 ° with loss of water) , Substances are colorless crystals that are soluble in water with an alkaline reaction.
  • Na 4 P 2 O 7 is formed by heating 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 formers 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 value being 1% Solution at 25 ° is 10.4.
  • Sodium and potassium phosphates in which one can differentiate cyclic representatives, the sodium or potassium metaphosphates and chain-like types, the sodium or potassium polyphosphates. A large number of terms are used in particular for the latter: melt or glow phosphates, Graham's salt, Kurrol's 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
  • Approx. 17 g of the salt free from water of crystallization dissolve in 100 g of water at room temperature, approx. 20 g at 60 ° and around 32 g at 100 °; After heating the solution at 100 ° for two hours, hydrolysis produces about 8% orthophosphate and 15% diphosphate.
  • pentasodium triphosphate In the production of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dewatered by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentapotassium triphosphate, K 5 P 3 O 10 (potassium tripolyphosphate), is commercially available, for example, in the form of a 50% strength by weight solution (> 23% P 2 O 5 , 25% K 2 O). The potassium polyphosphates are widely used in the detergent and cleaning agent industry.
  • sodium potassium tripolyphosphates which can also be used in the context of the present invention. These occur, for example, when hydrolyzing sodium trimetaphosphate with KOH: (NaPO 3 ) 3 + 2 KOH ⁇ Na 3 K 2 P 3 O 10 + H 2 O
  • these are exactly like sodium tripolyphosphate, potassium tripolyphosphate or mixtures of these two can be used; also mixtures of 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 can be used according to the invention.
  • Preferred detergent tablets in the context of the present invention contain as phosphates alkali metal phosphates, preferably pentasodium or Pentapotassium triphosphate (sodium or potassium tripolyphosphate), in quantities of 1 to 60 % By weight, preferably from 5 to 50% by weight, particularly preferably from 10 to 40% by weight and in particular from 15 to 35% by weight, in each case based on the weight of the shaped body.
  • alkali metal phosphates preferably pentasodium or Pentapotassium triphosphate (sodium or potassium tripolyphosphate)
  • pentasodium or Pentapotassium triphosphate sodium or potassium tripolyphosphate
  • the detergent tablets according to the invention can contain other common builders that are both water-soluble and water-insoluble could be.
  • the detergent tablets according to the invention can all builders commonly used in detergents and cleaning agents be included, especially so zeolites, silicates, carbonates and organic Co-builders. These builders can be added to the mixtures to be tabletted, however, they can also be wholly or partly a component of surfactant granules.
  • layered sodium silicates have the general formula NaMSi x O 2x + 1 ⁇ H 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20, preferred values for x are 2, 3 or 4.
  • M sodium or hydrogen
  • x is a number from 1.9 to 4
  • y is a number from 0 to 20
  • preferred values for x are 2, 3 or 4.
  • Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514 .
  • Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3.
  • both ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 O 5 ⁇ yH 2 O are preferred, with ⁇ -sodium disilicate being obtainable for example by the method / described in the international patent application WO-A-91 08,171th
  • Amorphous sodium silicates with a modulus Na 2 O: SiO 2 of 1: 2 to 1: 3.3, preferably 1: 2 to 1: 2.8 and in particular 1: 2 to 1: 2.6, can also be used are delayed in dissolving and have secondary washing properties.
  • the delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying.
  • amorphous is also understood to mean “X-ray amorphous”. This means that the silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle. However, it can very well lead to particularly good builder properties if the silicate particles provide washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred.
  • Such so-called X-ray amorphous silicates which also have a delay in dissolution compared to conventional water glasses, are described, for example, in German patent application DE-A-44 00 024 .
  • Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.
  • the finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P.
  • zeolite P zeolite MAP® (commercial product from Crosfield) is particularly preferred.
  • zeolite X and mixtures of A, X and / or P are also suitable.
  • zeolite X and zeolite A (about 80% by weight of zeolite X)
  • VEGOBOND AX® sold by CONDEA Augusta SpA under the brand name VEGOBOND AX® 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
  • the zeolite can be used both as a builder in a granular compound and can also be used for a kind of "powdering" of the entire mixture to be compressed, usually using both ways of incorporating the zeolite into the premix.
  • Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.
  • Preferred detergent tablets in the context of the present invention additionally contain a zeolite of the faujasite type in amounts of 0.5 to 20% by weight, preferably from 1 to 15% by weight, particularly preferably from 2 to 10% by weight and in particular from 2.5 to 5% by weight, in each case based on the weight of the shaped body, where Zeolite X is preferred.
  • the amount of builder is usually between 10 and 70 wt .-%, preferably between 15 and 60% by weight and in particular between 20 and 50% by weight.
  • the amount of builders used depends on the intended use, so that Bleach tablets can have higher amounts of builders (for example between 20 and 70% by weight, preferably between 25 and 65% by weight and in particular between 30 and 55% by weight), for example detergent tablets (usually 10 to 50% by weight, preferably 12.5 to 45% by weight and in particular between 17.5 and 37.5% by weight).
  • Organic cobuilders that can be used in the detergent tablets according to the invention in particular polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, Aspartic acid, polyacetals, dextrins, other organic cobuilders (see below) and phosphonates are used. These classes of substances are described below.
  • Useful organic builders are, for example, those in the form of their sodium salts usable polycarboxylic acids, such polycarboxylic acids being among polycarboxylic acids can be understood that 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 one such use is not objectionable for ecological reasons, as well as mixtures from these.
  • Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, Succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.
  • the acids themselves can also be used.
  • the acids have a builder effect typically also the property of an acidifying component and serve thus also for setting a lower and milder pH value of washing or Detergents.
  • citric acid succinic acid, glutaric acid, Adipic acid, gluconic acid and any mixtures of these.
  • Polymeric polycarboxylates are also suitable as builders, for example those Alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular mass of 500 to 70,000 g / mol.
  • the molecular weights given for polymeric polycarboxylates are weight-average molecular weights M w of the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used.
  • GPC gel permeation chromatography
  • the measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship to the polymers investigated. This information differs significantly from the molecular weight information for which polystyrene sulfonic acids are used as standard.
  • the molecular weights measured against polystyrene sulfonic acids are generally significantly higher than the molecular weights given in this document.
  • Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of Have 2000 to 20,000 g / mol. Because of their superior solubility, this can Group in turn the short-chain polyacrylates, the poppy seeds from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, preferably his.
  • copolymeric polycarboxylates especially those of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid.
  • the 50 to Contain 90 wt .-% acrylic acid and 50 to 10 wt .-% maleic acid As special copolymers of acrylic acid with maleic acid have proven suitable, the 50 to Contain 90 wt .-% acrylic acid and 50 to 10 wt .-% maleic acid.
  • Your relative molecular mass, based on free acids is generally from 2000 to 70,000 g / mol, preferably 20,000 to 50,000 g / mol and in particular 30,000 to 40,000 g / mol.
  • the (co) polymeric polycarboxylates can either be as a powder or as an aqueous solution be used.
  • the content of (co) polymeric polycarboxylates in the agents is preferably 0.5 to 20% by weight, in particular 3 to 10% by weight.
  • the polymers can also allylsulfonic acids, such as for example, allyloxybenzenesulfonic acid and methallylsulfonic acid, as a monomer.
  • allylsulfonic acids such as for example, allyloxybenzenesulfonic acid and methallylsulfonic acid
  • biodegradable polymers made from more than two different ones Monomer units, for example those which are salts of acrylic acid as monomers and the maleic acid and vinyl alcohol or vinyl alcohol derivatives or as Monomeric salts of acrylic acid and 2-alkylallylsulfonic acid as well as sugar derivatives contain.
  • copolymers are those which are described in German patent applications DE-A-43 03 320 and DE-A-44 17 734 and which preferably contain acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers.
  • polymeric aminodicarboxylic acids their salts or their precursor substances.
  • Particularly preferred are polyaspartic acids or their salts and derivatives, of which it is disclosed in German patent application DE-A-195 40 086 that, in addition to cobuilder properties, they also have a bleach-stabilizing effect.
  • polyacetals which are obtained by reacting dialdehydes with polyol carboxylic acids, which have 5 to 7 carbon atoms and at least 3 hydroxyl groups can be obtained.
  • Preferred polyacetals are made from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from Obtained polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
  • Suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates obtained by partial hydrolysis of starches can be.
  • the hydrolysis can be carried out according to customary methods, for example acid-catalyzed or enzyme-catalyzed Procedures are carried out. They are preferably hydrolysis products with average molecular weights in the range of 400 to 500000 g / mol.
  • DE dextrose equivalent
  • Both maltodextrins with a DE between 3 and 20 and dry glucose syrups can be used with a DE between 20 and 37 as well as so-called yellow dextrins and White dextrins with higher molar masses in the range from 2000 to 30000 g / mol.
  • the 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 capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function.
  • Such oxidized dextrins and processes for their preparation are known, for example, from European patent applications EP-A-0 232 202, EP-A-0 427 349, EP-A-0 472 042 and EP-A-0 542 496 and international patent applications WO 92 / 18542, WO 93/08251, WO 93/16110, WO 94/28030, WO 95/07303, WO 95/12619 and WO 95/20608 .
  • An oxidized oligosaccharide according to German patent application DE-A-196 00 018 is also suitable.
  • a product oxidized at C 6 of the saccharide ring can be
  • oxydisuccinates and other derivatives of disuccinates are other suitable cobuilders.
  • ethylenediamine-N, N'disuccinate (EDDS) preferably used in the form of its sodium or magnesium salts.
  • Glycerol disuccinates and glycerol trisuccinates are also preferred in this context. Suitable amounts are those containing zeolite and / or silicate Formulations at 3 to 15% by weight.
  • organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may also be in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups.
  • Such cobuilders are described, for example, in international patent application WO 95/20029 .
  • HEDP 1-hydroxyethane-1,1-diphosphonate
  • HEDP 1-hydroxyethane-1,1-diphosphonate
  • Aminoalkane phosphonates preferably come from ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologues in question. They are preferably in the form of neutral sodium salts, z. B.
  • HEDP is preferably used as the builder from the class of the phosphonates.
  • the aminoalkanephosphonates also have a pronounced ability to bind heavy metals. Accordingly, especially if the agents also contain bleach, be preferred to use aminoalkanephosphonates, in particular DTPMP, or To use mixtures of the phosphonates mentioned.
  • the moldings according to the invention contain to develop the washing or cleaning performance Surfactants.
  • Surfactants According to the invention, fatty alcohol sulfates are in the moldings included, while other surfactants can optionally be used in addition.
  • Fatty alcohol sulfates the alkali metal, in particular sodium salts of the sulfuric acid half-esters of longer-chain alcohols, are commercially available from fatty alcohols which are reacted with sulfuric acid, chlorosulfonic acid, amidosulfonic acid or sulfur trioxide to give the alkyl sulfuric acids concerned and are subsequently neutralized.
  • the fatty alcohols are obtained from the fatty acids or fatty acid mixtures concerned by high-pressure hydrogenation of the fatty acid methyl esters.
  • the most important industrial process for the production of fatty alkyl sulfuric acids is the sulfonation of the alcohols with SO 3 / air mixtures in special cascade, falling film or tube bundle reactors.
  • the fatty acids are technically largely obtained from native fats and oils by hydrolysis. While the alkaline saponification that was carried out in the past century led directly to the alkali salts (soaps), today only water is used on an industrial scale that splits the fats into glycerol and the free fatty acids.
  • the cleavage can be carried out with methanol, the methyl esters and glycerol being obtained directly. Large-scale processes are, for example, cleavage in an autoclave or continuous high pressure cleavage.
  • Carboxylic acids which can be used as the basis for the fatty alcohol sulfates in the context of the present invention are, for example, hexanoic acid (caproic acid), heptanoic acid (enanthic acid), octanoic acid (caprylic acid), nonanoic acid (pelargonic acid), decanoic acid (capric acid), undecanoic acid, etc.
  • fatty acids such as dodecanoic acid (lauric acid), tetradecanoic acid (myristic acid), hexadecanoic acid (palmitic acid), octadecanoic acid (stearic acid), eicosanoic acid (arachic acid), docosanoic acid (behenic acid), tetracosanoic acid (lignoceric acid), triacotonic acid (melotonic acid), triacotonic acid (cerotonic acid) of the unsaturated species 9c-hexadecenoic acid (palmitoleic acid), 6c-octadecenoic acid (petroselinic acid), 6t-octadecenoic acid (petroselaidic acid), 9c-octadecenoic acid (oleic acid), 9t-octadecenoic acid ((elaidinic acid), 9c, 12c-linadoleic acid
  • Such mixtures are for example, coconut oil fatty acid (about 6 wt .-% C 8, 6 wt .-% C 10 48 wt .-% C 12 18 wt .-% C14, 10 wt .-% C 16, 2 wt .-% C18, 8 wt .-% C 18: 1 wt .-% C 18 ''), palm kernel oil fatty acid (about 4 wt .-% C 8, 5 wt .-% C 10, 50 wt .-% C 12 , 15% by weight C 14 , 7% by weight C 16 , 2% by weight C 18 , 15% by weight C 18 ' , 1% by weight C 18'' ), tallow fatty acid (approx 3 wt% C 14 , 26 wt% C 16 , 2 wt% C 16 ' , 2 wt% C 17 , 17 wt% C 18 , 44 wt% C 18' , 3 wt%
  • the alk (en) yl sulfates are preferably the alkali and in particular the sodium salts of the sulfuric acid half esters of C 12 -C 18 fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -C 20 - Oxo alcohols and those half esters of secondary alcohols of this chain length are preferred.
  • alk (en) yl sulfates of the chain length mentioned which contain a synthetic, petrochemical-based straight-chain alkyl radical which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials.
  • the C 12 -C 16 alkyl sulfates and C 12 -C 15 alkyl sulfates as well as C 14 -C 15 alkyl sulfates are preferred from the point of view of washing technology.
  • Preferred detergent tablets in the context of the present invention contain the alkali metal, preferably sodium, salts of C 8-22 , preferably C 10-20 and in particular C 12-18 fatty alkyl sulfuric acids.
  • detergent tablets which contain the alkali metal, preferably sodium salts of C 8-22 , preferably C 10-20 , and in particular C 12-18 fatty alkyl sulfuric acids, preferably in amounts of 0. 5 to 30 wt .-%, particularly preferably from 1 to 20 wt .-% and in particular from 2 to 10 wt .-%, each based on the weight of the moldings.
  • alkali metal preferably sodium salts of C 8-22 , preferably C 10-20 , and in particular C 12-18 fatty alkyl sulfuric acids, preferably in amounts of 0. 5 to 30 wt .-%, particularly preferably from 1 to 20 wt .-% and in particular from 2 to 10 wt .-%, each based on the weight of the moldings.
  • surfactants that can be used in addition to the fatty alcohol sulfates can from the groups of anionic, nonionic, cationic or amphoteric surfactants come. Due to their range of services and their availability, are here anionic and nonionic surfactants preferred.
  • anionic surfactants used are those of the sulfonate and sulfate type.
  • the surfactants of the sulfonate type include, for example, alkylbenzenesulfonates (ABS), olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates such as are obtained, for example, from C 12-18 monoolefins with an end or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent ones receives alkaline or acidic hydrolysis of the sulfonation products.
  • ABS alkylbenzenesulfonates
  • olefin sulfonates ie mixtures of alkene and hydroxyalkanesulfonates
  • disulfonates such as are obtained, for example, from C 12-18 monoolefins with an end or internal double bond by sulfonation with gaseous sulfur trioxide
  • alkanesulfonates obtained from C 12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • the esters of ⁇ -sulfofatty acids for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.
  • Suitable anionic surfactants are sulfonated fatty acid glycerol esters.
  • fatty acid glycerol esters the mono-, di- and triesters and their mixtures are to be understood as they are the production by esterification of a monoglycerin with 1 to 3 moles of fatty acid or obtained in the transesterification of triglycerides with 0.3 to 2 mol of glycerol.
  • preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids with 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, Myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
  • 2,3-Alkyl sulfates which are produced, for example, according to US Pat . Nos . 3,234,258 or 5,075,041 and can be obtained as commercial products from the Shell Oil Company under the name DAN®, are also suitable anionic surfactants.
  • the sulfuric acid monoesters of the straight-chain or branched C 7-21 alcohols ethoxylated with 1 to 6 mol of ethylene oxide such as 2-methyl-branched C 9-11 alcohols with an average of 3.5 mol of ethylene oxide (EO) or C 12-18 - Fatty alcohols with 1 to 4 EO are suitable. Because of their high foaming behavior, they are used in cleaning agents only in relatively small amounts, for example in amounts of 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 which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols.
  • alcohols preferably fatty alcohols and especially ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain C 8-18 fatty alcohol residues or mixtures thereof.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue, which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below).
  • sulfosuccinates the fatty alcohol residues of which are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are particularly preferred. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
  • Soaps are particularly suitable as further anionic surfactants.
  • saturated 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 or tallow fatty acids, derived soap mixtures.
  • the anionic surfactants including the soaps can be in the form of their sodium, potassium or Ammonium salts and as soluble salts of organic bases, such as mono-, di- or Triethanolamine.
  • the anionic surfactants are preferably in the form of their Sodium or potassium salts, especially in the form of the sodium salts.
  • detergent tablets are shaped preferred, the total content of anionic surfactants above 5 wt .-%, preferably above 7.5% by weight and in particular above 10% by weight, in each case based on the weight of the molded body.
  • detergent tablets When selecting the anionic surfactants in the detergent tablets according to the invention are used, there is no freedom of formulation in the way.
  • Preferred detergent tablets however, have a soap content of 0.2% by weight, based on the total weight of the molded body.
  • the optionally used nonionic surfactants are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols with preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical has a linear or preferably 2-methyl branching may be or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
  • EO ethylene oxide
  • alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow fat or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred.
  • the preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 3 EO or 4 EO, C 9-11 alcohol 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 thereof, such as mixtures of C 12-14 alcohol with 3 EO and C 12-18 alcohol with 5 EO.
  • the degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • nonionic surfactants which are used either as the sole nonionic surfactant or in combination with other nonionic 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 esters, such as them are described, for example, in Japanese patent application JP 58/217598 or which are preferably produced by the process described in international patent application WO-A-90/13533 .
  • alkyl polyglycosides Another class of nonionic surfactants that can be used advantageously are the alkyl polyglycosides (APG).
  • Alkypolyglycosides that can be used satisfy the general formula RO (G) z , in which R denotes a linear or branched, in particular methyl-branched, saturated or unsaturated, aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms and G is the Is symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
  • the degree of glycosidation z is between 1.0 and 4.0, preferably between 1.0 and 2.0 and in particular between 1.1 and 1.4.
  • Linear alkyl polyglucosides ie alkyl polyglycosides, are preferably used in which the polyglycosyl radical is a glucose radical and the alkyl radical is an n-alkyl radical.
  • the detergent tablets according to the invention can preferably alkyl polyglycosides included, with APG contents of the molded articles being above 0.2% by weight on the entire molded body, are preferred.
  • Particularly preferred washing and Detergent tablets contain APG in amounts of 0.2 to 10% by weight, preferably 0.2 to 5 wt .-% and in particular from 0.5 to 3 wt .-%.
  • nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half of it.
  • Suitable surfactants are polyhydroxy fatty acid amides of the formula (II), in which RCO stands for an aliphatic acyl radical with 6 to 22 carbon atoms, R 1 for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
  • 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 (III) in which R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R 1 represents a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R 2 represents a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, 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 remainder.
  • R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
  • R 1 represents a linear, branched or cyclic alkyl radical or an aryl radical
  • [Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • a reduced sugar for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • the N-alkoxy- or N-aryloxy-substituted compounds can then, for example according to the teaching of international application WO-A-95/ 07331, be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
  • detergent tablets are shaped preferred, which additionally contain nonionic surfactant (s) and in which the content of Shaped bodies of nonionic surfactants above 2% by weight, preferably above of 5% by weight and in particular above 7.5% by weight, in each case based on the weight of the shaped body, lies.
  • nonionic surfactants from all of the above mentioned groups are used. Regardless of the chemical nature of the nonionic surfactants used are preferred detergent tablets, the additional nonionic surfactants with a melting point below 40 ° C, preferably below 30 ° C and especially below 25 ° C, in amounts of 0.5 to 20 wt .-%, preferably from 1 to 10% by weight and in particular from 1.5 to 5% by weight, in each case based on the molded body weight.
  • the detergent tablets of the present invention contain sodium percarbonate to develop the desired bleaching performance.
  • Sodium percarbonate is a non-specific term for sodium carbonate peroxohydrates which, strictly speaking, are not “percarbonates” (that is, salts of percarbonic acid) but hydrogen peroxide adducts with sodium carbonate.
  • the merchandise has the average composition 2 Na 2 CO 3 .3 H 2 O 2 and is therefore not peroxycarbonate.
  • Sodium percarbonate forms a white, water-soluble powder with a density of 2.14 gcm -3 , which easily breaks down into sodium carbonate and bleaching or oxidizing oxygen.
  • the industrial production of sodium percarbonate is predominantly produced by precipitation from an aqueous solution (so-called wet process).
  • aqueous solutions of sodium carbonate and hydrogen peroxide are combined and the sodium percarbonate is precipitated by salting-out agents (predominantly sodium chloride), crystallization aids (for example polyphosphates, polyacrylates) and stabilizers (for example Mg 2+ ions).
  • the precipitated salt which still contains 5 to 12% by weight of mother liquor, is then centrifuged off and dried in fluidized bed dryers at 90.degree.
  • the bulk density of the finished product can vary between 800 and 1200 g / l depending on the manufacturing process.
  • the percarbonate is stabilized by an additional coating.
  • the sodium percarbonate bleach is in depending on the desired product varying amounts in the detergent tablets according to the invention used. Usual contents are between 5 and 50% by weight, preferably between 10 and 40 wt .-% and in particular between 15 and 35 wt .-%, each based on the entire molded body.
  • the content of the shaped bodies in this substance is also of the intended use the shaped body depends. While common universal detergent in tablet form between 5 and 30% by weight, preferably between 7.5 and 25% by weight and in particular contain between 12.5 and 22.5 wt .-% sodium percarbonate, the contents are for bleach or bleach booster tablets between 15 and 50 wt .-%, preferably between 22.5 and 45% by weight and in particular between 30 and 40% by weight.
  • a preferred embodiment of the present invention provides detergent tablets ready for washing textiles in a household washing machine.
  • These preferred Detergent tablets are characterized in that they are the only ones Bleaching agent sodium percarbonate in amounts of 1 to 40% by weight, preferably of 2.5 to 35% by weight, particularly preferably from 5 to 30% by weight and in particular from 7.5 up to 25 wt .-%, each based on the weight of the molded body.
  • the detergent tablets according to the invention can Bleach activator (s) contain what is within the scope of the present Invention is preferred. Bleach activators are incorporated into detergents and cleaning agents, to improve when washing at temperatures of 60 ° C and below To achieve bleaching effect.
  • bleach activators can be compounds that are under perhydrolysis conditions aliphatic peroxocarboxylic acids with preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or optionally substituted perbenzoic acid result, are used. Substances containing O- and / or N-acyl groups are suitable the number of carbon atoms mentioned and / or optionally substituted benzoyl groups wear.
  • Multi-acylated alkylenediamines are preferred (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, especially tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated Phenol sulfonates, especially n-nonanoyl or isononanoyloxybenzene sulfonate (n- or iso-NOBS), carboxylic anhydrides, especially phthalic anhydride, acylated polyvalent Alcohols, especially triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran.
  • TAED acylated triazine derivatives
  • bleaching catalysts can be incorporated into the moldings.
  • these fabrics are bleach-enhancing transition metal salts or transition metal complexes such as Mn, Fe, Co, Ru or Mo salt complexes or Carbonyl complexes.
  • Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing ones Tripod ligands as well as Co, Fe, Cu and Ru amine complexes are used as bleaching catalysts usable.
  • the moldings according to the invention contain, based in each case on the entire moldings, between 0.5 and 30% by weight, preferably between 1 and 20% by weight and in particular between 2 and 15% by weight of one or more bleach activators or bleach catalysts. Depending on the intended use of the moldings produced, these amounts can vary.
  • bleach activator contents in typical universal detergent tablets between 0.5 and 10% by weight, preferably between 2 and 8% by weight and in particular between 4 and 6% by weight usual, while bleach tablets definitely have higher contents, for example between 5 and 30% by weight, preferably between 7.5 and 25% by weight and in particular can have between 10 and 20% by weight.
  • the specialist is there not restricted in its freedom of formulation and can be stronger or weaker bleaching detergent tablets, detergent tablets or bleach tablets by varying the bleach activator and bleach content.
  • a particularly preferred bleach activator is N, N, N ', N'-tetraacetylethylenediamine, which is widely used in detergents and cleaning agents. Accordingly, preferred detergent tablets are characterized in that that as a bleach activator tetraacetylethylenediamine in the above Amounts are used.
  • Phosphate (s) and fatty alcohol sulfate (s) can be used in any way in the invention Detergent tablets are introduced. It has proven to be beneficial proven when the premix to be molded to form phosphate (s) and Contains fatty alcohol sulfate (s) in the form of a surfactant granulate. First of all, a surfactant granulate prepared, which preferably the total amount contained in the moldings Contains phosphates and fatty alcohol sulfates, and subsequently with other processing components mixed, after which the premix is fed to a tableting becomes.
  • the above-mentioned surfactant granules have the total amount of the nonionic surfactants contained in the moldings, preferably even those Total amount of surfactants contained in the moldings.
  • Summarized detergent tablets are preferred, which are characterized by are that they total amount of phosphates in the form of a surfactant granulate included that preferably. also the total amount contained in the moldings Contains surfactants.
  • Such preferred surfactant granules naturally have higher phosphate contents than the overall molded body.
  • Detergent and cleaning product tablets are in accordance with the invention preferred, in which the surfactant granules 5 to 70 wt .-%, preferably 10 to 65% by weight, particularly preferably 20 to 60% by weight and in particular 25 to 50 % By weight of phosphate, based in each case on the weight of the surfactant granules.
  • ingredients of detergents and cleaning agents especially so-called Small components such as optical brighteners, polymers, defoamers, phosphonates, color and Fragrances can be part of the surfactant granulate. These substances continue to grow described below.
  • the premix to be pressed can also be one or more Substances from the groups of bleaching agents, bleach activators, disintegration aids etc. included.
  • the substances mentioned, which are described below, can be specified in special Embodiments of the present invention also form part of the surfactant granules his.
  • Another object of the present invention is a method for producing Detergent tablets by mixing granules containing surfactants with pulverulent preparation components and subsequent shaping pressing, the premix to be pressed containing fatty alcohol sulfate (s), percarbonate and Contains phosphate builder.
  • s fatty alcohol sulfate
  • Preferred methods are therefore characterized, for example, in that the surfactant-containing granules contain the total amount contains the phosphate contained in the moldings, with granules, which additionally the total amount of nonionic surfactants, preferably the total amount of all surfactants, included, are preferred.
  • the premix to be pressed contains Granulate (s) containing surfactant as well as further processing components, whereby Phosphate (s) and preferably the surfactants are part of the granules.
  • the production the surfactant-containing granules can be produced using customary industrial granulation processes such as compacting, extrusion, mixer granulation, pelleting or fluidized bed granulation respectively. It is for the later detergent tablets of advantage if the premix to be compressed has a bulk density which corresponds to the usual compact detergent comes close.
  • the material to be pressed Premix a bulk density of at least 500 g / l, preferably at least 600 g / l and in particular at least 700 g / l.
  • the surfactant-containing granulate satisfies certain particle size criteria.
  • Methods according to the invention are preferred in which the surfactant-containing Granules particle sizes between 100 and 2000 microns, preferably between 200 and 1800 ⁇ m, particularly preferably between 400 and 1600 ⁇ m and in particular between 600 and 1400 ⁇ m.
  • the surfactant granules preferably also contain carriers, which particularly preferably come from the group of builders.
  • the premix to be compressed is a Contains surfactant-containing granules which contain anionic and / or nonionic surfactants as well Contains builders and their total surfactant content 5 to 60 wt .-%, preferably 10 up to 50% by weight and in particular 15 to 40% by weight, in each case based on the surfactant granules, is.
  • the premix contains a surfactant-containing granulate, the surfactant contents of 5 to 60 wt .-%, preferably from 10 to 50% by weight and in particular from 15 to 40% by weight, in each case based on the Weight of the surfactant granules, has (see above).
  • detergent tablets in which the content of the surfactant granules of anionic surfactants 5 to 45% by weight, preferably 10 to 40% by weight and in particular 15 to 35% by weight, in each case based on the weight of the surfactant granules
  • detergent tablets in which the content of the surfactant granules of nonionic surfactants 1 to 30% by weight, preferably 5 to 25% by weight and in particular 7.5 to 20% by weight, each based on the weight of the surfactant granules are preferred according to the invention.
  • the surfactant-containing granules not by spray drying, but by a granulation process will be produced.
  • a granulation process carried out in a wide variety of mixing granulators and mixing agglomerators press agglomeration processes can also be used, for example. Method, in which the surfactant-containing granules by granulation, agglomeration, press agglomeration or a combination of these methods is preferred.
  • Granulation can be found in a wide variety of industries in the laundry and home care industries usually used apparatus are carried out. For example, it is possible to use the rounders commonly used in pharmacy. In such turntable devices the residence time of the granules is usually less than 20 seconds. Also conventional mixers and mixing granulators are suitable for granulation. As a mixer can both high-intensity mixers (“high-shear mixer”) and normal Mixers with lower circulation speeds can be used.
  • high-shear mixer high-intensity mixers
  • normal Mixers with lower circulation speeds can be used.
  • Suitable mixers are, for example, Eirich® mixers of the R or RV series (trademark of the machine factory Gustav Eirich, Hardheim), the Schugi® Flexomix, the Fukae® FS-G mixer (trademark the Fukae Powtech, Kogyo Co., Japan), the Lödige® FM, KM and CB mixers (Trademark of Lödige Maschinenbau GmbH, Paderborn) or the Drais® series T or K-T (trademark of Drais-Werke GmbH, Mannheim).
  • the dwell times the granules in the mixers are in the range of less than 60 seconds, the Dwell time also depends on the speed of rotation of the mixer. Shorten here the faster the mixer runs, the dwell times accordingly.
  • Residence times of the granules in the mixer / rounder are less than one minute, preferably less than 15 seconds.
  • dwell times of up to 20 minutes, with dwell times of less than 10 minutes due to the Process economics are preferred.
  • the surfactant-containing granules are under pressure and compressed under the influence of shear forces and homogenized and then discharged form-giving from the apparatus.
  • the most technically significant press agglomeration processes are extrusion, roller compaction, pelleting and tableting.
  • Press agglomeration processes used in granules are extrusion, roller compaction and pelleting.
  • disintegration aids so-called tablet disintegrants
  • tablet disintegrants or disintegration accelerators are understood as auxiliary substances which are necessary for the rapid disintegration of Tablets in water or gastric juice and ensure the release of the pharmaceuticals in an absorbable form.
  • Swelling enlarge their volume when water enters, whereby on the one hand the volume increases (Swelling), on the other hand, a pressure can be generated via the release of gases which can break the tablet into smaller particles.
  • disintegration tools are, for example, carbonate / citric acid systems, with other organic ones Acids can be used.
  • Swelling disintegration aids are, for example synthetic polymers such as polyvinylpyrrolidone (PVP) or natural polymers or modified Natural substances such as cellulose and starch and their derivatives, alginates or casein derivatives.
  • Preferred detergent tablets contain 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular 4 to 6% by weight of one or more disintegration aids, each based on the weight of the molded article.
  • Disintegrants based on cellulose are used as preferred disintegrants in the context of the present invention, so that preferred detergent tablets have such a disintegrant based on cellulose in amounts of 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular 4 contain up to 6 wt .-%.
  • Pure cellulose has the formal gross composition (C 6 H 10 O 5 ) n and, viewed formally, is a ⁇ -1,4-polyacetal of cellobiose, which in turn is made up of two molecules of glucose.
  • Suitable celluloses consist of approximately 500 to 5000 glucose units and consequently have average molecular weights of 50,000 to 500,000.
  • Cellulose-based disintegrants which can be used in the context of the present invention are also cellulose derivatives which can be obtained from cellulose by polymer-analogous reactions.
  • Such chemically modified celluloses include, for example, products from esterifications or etherifications in which hydroxy hydrogen atoms have been substituted.
  • celluloses in which the hydroxyl groups have been replaced by functional groups which are not bound by an oxygen atom can also be used as cellulose derivatives.
  • the group of cellulose derivatives includes, for example, alkali celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers and aminocelluloses.
  • the cellulose derivatives mentioned are preferably not used alone as a cellulose-based disintegrant, but are used in a mixture with cellulose.
  • the content of cellulose derivatives in these mixtures is preferably below 50% by weight, particularly preferably below 20% by weight, based on the cellulose-based disintegrant. Pure cellulose which is free of cellulose derivatives is particularly preferably used as the cellulose-based disintegrant.
  • the cellulose used as disintegration aid is preferably not used in finely divided form, but is converted into a coarser form, for example granulated or compacted, before being added to the premixes to be pressed.
  • Detergent tablets which contain disintegrants in granular or, if appropriate, cogranulated form are described in German patent applications DE 197 09 991 (Stefan Herzog) and DE 197 10 254 (Henkel) and in international patent application WO98 / 40463 (Henkel). These documents can also be found in more detail on the production of granulated, compacted or cogranulated cellulose disintegrants.
  • the particle sizes of such disintegrants are usually above 200 ⁇ m, preferably at least 90% by weight between 300 and 1600 ⁇ m and in particular at least 90% by weight between 400 and 1200 ⁇ m.
  • the above-mentioned coarser disintegration aids based on cellulose and described in more detail in the cited documents are preferably to be used as disintegration aids in the context of the present invention and are commercially available, for example, under the name Arbocel® TF-30-HG from Rettenmaier.
  • microcrystalline cellulose As another disintegrant based on cellulose or as a component of this component microcrystalline cellulose can be used.
  • This microcrystalline cellulose is obtained by partial hydrolysis of celluloses under conditions that only attack the amorphous areas (approx. 30% of the total cellulose mass) of the celluloses and dissolve completely, but leave the crystalline areas (approx. 70%) undamaged.
  • a subsequent disaggregation of the microfine celluloses resulting from the hydrolysis delivers the microcrystalline celluloses, which have primary particle sizes of approx. 5 ⁇ m and compactible, for example, into granules with an average particle size of 200 ⁇ m are.
  • a disintegration aid preferably a Disintegration aid based on cellulose, preferably in granular, cogranulated or compacted form, in amounts of 0.5 to 10 wt .-%, preferably from 3 to 7 % By weight and in particular from 4 to 6% by weight, in each case based on the weight of the premix, contains.
  • the premix additionally contains one or more substances from the group of builders, bleach activators, enzymes, pH regulators, fragrances, perfume carriers, fluorescent agents, dyes, foam inhibitors, silicone oils, anti-redeposition agents, optical brighteners, graying inhibitors, color transfer inhibitors and corrosion inhibitors.
  • Suitable enzymes are those from the class of proteases, lipases, amylases, cellulases or mixtures thereof. Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus are particularly suitable.
  • proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used.
  • Enzyme mixtures for example of protease and amylase or protease and lipase or protease and cellulase or of cellulase and lipase or of protease, amylase and lipase or protease, lipase and cellulase, but in particular mixtures containing cellulase, are of particular interest.
  • Peroxidases or oxidases have also proven to be suitable in some cases.
  • the enzymes can be adsorbed on carriers and / or embedded in coating substances in order to protect them against premature decomposition.
  • the proportion of enzymes, enzyme mixtures or enzyme granules in the shaped bodies according to the invention can be, for example, about 0.1 to 5% by weight, preferably 0.1 to about 2% by weight.
  • the detergent tablets can also contain components which positively influence the oil and fat washability from textiles (so-called soil repellents). This effect is particularly evident when a textile is dirty is already several times with a detergent according to the invention, this contains oil and fat-dissolving component, was washed.
  • nonionic cellulose ethers such as methyl cellulose and methylhydroxypropyl cellulose containing methoxyl groups of 15 to 30 wt .-% and of hydroxypropoxyl groups of 1 to 15 wt .-%, each based on the nonionic cellulose ether, as well as those known from the prior art Polymers of phthalic acid and / or terephthalic acid or their derivatives, in particular Polymers made from ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives of these. Particularly preferred of these are the sulfonated derivatives of phthalic acid and terephthalic acid polymers.
  • the moldings can, as optical brighteners, derivatives of diaminostilbenedisulfonic acid or their alkali metal salts. Suitable are e.g. Salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or similarly constructed Compounds which, instead of the morpholino group, have a diethanolamino group, a methylamino group, carry an anilino group or a 2-methoxyethylamino group.
  • Farther brighteners of the substituted diphenylstyryl type may be present, e.g.
  • Dyes and fragrances are the detergent tablets according to the invention added to improve the aesthetic impression of the products and the consumer in addition to the washing or cleaning performance, a visually and sensory "typical and distinctive "product.
  • perfume oils or fragrances individual fragrance compounds, e.g. synthetic products of the type Esters, ethers, aldehydes, ketones, alcohols and hydrocarbons can be used. Fragrance compounds of the ester type are e.g.
  • the ethers include, for example Benzyl ethyl ether, to the aldehydes e.g.
  • the linear alkanals with 8-18 C atoms citral, Citronellal, Citronellyloxyacetaldehyde, Cyclamenaldehyde, Hydroxycitronellal, Lilial and Bourgeonal
  • the ketones e.g. the Jonone, ⁇ -isomethyl ionone and methyl cedryl ketone
  • the hydrocarbons mainly include terpenes such as limonene and pinene.
  • mixtures of different fragrances are preferably used, which together create an appealing fragrance.
  • perfume oils can also contain natural fragrance mixtures as they are accessible from plant sources, e.g. Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil.
  • plant sources e.g. Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil.
  • the content of the detergent tablets according to the invention is usually in the range of dyes below 0.01% by weight, while fragrances up to 2% by weight of the total Can make up wording.
  • the fragrances can be incorporated directly into the agents according to the invention but it can also be advantageous to apply the fragrances to the carrier, which the liability of the Reinforcing perfumes on the laundry and by a slower fragrance release for long-lasting Ensure the fragrance of the textiles.
  • Such carrier materials have, for example Cyclodextrins have proven themselves, with the cyclodextrin-perfume complexes additionally other auxiliaries can be coated.
  • the detergent tablets according to the invention can be colored with suitable dyes.
  • suitable dyes preferred Dyes, the selection of which is not difficult for the person skilled in the art a high storage stability and insensitivity to the other ingredients of the Medium and against light and no pronounced substantivity towards textile fibers in order not to stain them.
  • the premix with finely divided surface treatment agents be "powdered". This can affect the nature and physical properties of the premix (storage, pressing) as well as the finished detergent tablets be an advantage.
  • Finely divided powdering agents are known in the art Well-known technology, mostly using zeolites, silicates or other inorganic salts become.
  • the premix is preferred with finely divided zeolite "powdered", with zeolites of the faujasite type being preferred.
  • zeolites of the faujasite type As part of the present Invention characterizes the term "faujasite type zeolite” all three zeolites that form the faujasite subgroup of zeolite structure group 4 (compare Donald W.
  • a zeolite of the faujasite type with particle sizes below 100 ⁇ m is preferably below 10 ⁇ m and in particular below 5 ⁇ m and at least 0.2 % By weight, preferably at least 0.5% by weight and in particular more than 1% by weight of the pre-mix to be compressed.
  • the moldings according to the invention are first produced by dry Mixing the components, which can be partially or completely pre-granulated, and then Inform, in particular pressing into tablets, whereby conventional Procedure can be used.
  • the premix is molded in a so-called die between two stamps compacted into a solid compressed. This process, hereinafter briefly referred to as tableting is divided into four sections: dosage, compression (elastic Deformation), plastic deformation and ejection.
  • the premix is introduced into the die, the filling quantity and thus the weight and shape of the resulting molded body by the position of the lower one Stamp and the shape of the press tool can be determined.
  • the constant dosage even with high throughputs of shaped bodies, a volumetric flow rate is preferably used Dosage of the premix reached.
  • the Upper stamp the premix and continues to lower towards the lower stamp. at this compression, the particles of the premix are pressed closer together, whereby the void volume within the filling between the punches is continuous decreases. From a certain position of the upper stamp (and thus from a certain Pressure on the premix) begins the plastic deformation at which the particles flow together and the molded body is formed.
  • the phase of elastic Deformation is shortened further and further, so that the resulting shaped body more or may have smaller cavities.
  • the Finished moldings are pressed out of the die by the lower punch and through subsequent transport devices transported away. At this point, it's just that Weight of the molded body finally determined, because the compacts due to physical Processes (stretching, crystallographic effects, cooling etc.) their shape and size can still change.
  • Tableting takes place in commercially available tablet presses, which are basically single or Double stamps can be equipped. In the latter case, it is not only the upper stamp used to build up pressure, also the lower stamp moves during the Pressing process towards the upper punch, while the upper punch presses down.
  • eccentric tablet presses which the stamp or stamps are attached to an eccentric disc, which in turn on one Axis is mounted with a certain rotational speed. The movement of this Press ram is comparable to the way a conventional four-stroke engine works.
  • the pressing can be done with one upper and one lower stamp, but several can also be used Stamp be attached to an eccentric disc, the number of die holes is expanded accordingly.
  • the throughputs of eccentric presses vary depending on the type from a few hundred to a maximum of 3000 tablets per hour.
  • Matrix table For larger throughputs, rotary tablet presses are selected, on which a so-called Matrix table a larger number of matrices is arranged in a circle.
  • the number of matrices varies between 6 and 55, depending on the model, with larger matrices also are commercially available.
  • Each die on the die table is an upper and lower stamp assigned, with the pressure again being active only through the upper or lower stamp, but can also be built using both stamps.
  • the matrix table and the Stamps move around a common vertical axis, the stamp with the help of rail-like cam tracks during the circulation in the positions for filling, Compression, plastic deformation and discharge are brought.
  • Rotary presses can also be equipped with two filling shoes to increase the throughput be, whereby only a semicircle is run through to produce a tablet got to.
  • Several filling shoes are used to produce two- and multi-layer molded articles arranged one behind the other without the slightly pressed first layer in front of the further filling is ejected.
  • By appropriate process control are in this way also coated and dot tablets can be produced, which have an onion-shell-like structure, where in the case of the point tablets the top of the core or core layers is not covered and therefore remains visible.
  • Rotary tablet presses are also included Single or multiple tools can be equipped so that, for example, an outer circle with 50 and an inner circle with 35 holes can be used simultaneously for pressing.
  • the throughputs of modern rotary tablet presses are over a million tablets per hour.
  • Tableting machines suitable for the purposes of the present invention are, for example available from the companies Apparatebau Holzwarth GbR, Asperg, Wilhelm Fette GmbH, Schwarzenbek, Hofer GmbH, Weil, KILIAN, Cologne, KOMAGE, Kell am See, KORSCH Pressen GmbH, Berlin, Mapag Maschinenbau AG, Bern (CH) and Courtoy N.V., Halle (BE / LU).
  • the hydraulic double-pressure press HPF for example, is particularly suitable 630 from LAEIS, D.
  • the moldings can be made in a predetermined spatial shape and size become. Practically all useful configurations come as a spatial form into consideration, for example the formation as a board, the shape of bars or bars, Cubes, cuboids and corresponding room elements with flat side surfaces as well in particular cylindrical configurations with a circular or oval cross section. This last embodiment covers the form of presentation from the tablet to to compact cylinder pieces with a ratio of height to diameter above 1.
  • the portioned compacts can each be separate individual elements be formed, the predetermined dosage of detergents and / or cleaning agents equivalent. However, it is also possible to form compacts that have a plurality connect such mass units in a compact, in particular by predetermined The easy separation of portioned smaller units is provided for predetermined breaking points is.
  • the formation of the portioned compacts as Tablets, in the shape of a cylinder or cuboid, are appropriate, with a diameter / height ratio in the range of about 0.5: 2 to 2: 0.5 is preferred.
  • Commercial hydraulic presses, Eccentric presses or rotary presses are suitable devices in particular for the production of such compacts.
  • the spatial shape of another embodiment of the shaped body is in its dimensions the induction chamber of commercial household washing machines adapted so that the Shaped bodies can be metered directly into the induction chamber without a metering aid, where it dissolves during the induction process.
  • a metering aid where it dissolves during the induction process.
  • the detergent tablets are easily possible via a dosing aid and within the present invention preferred.
  • Another preferred molded body that can be produced has a plate or panel-like structure with alternating thick long and thin short segments, so that individual segments of this "bar" at the predetermined breaking points, the short thin Display segments, can be canceled and entered into the machine.
  • This The principle of the "bar-shaped" shaped body detergent can also be used in other geometric Shapes, for example vertical triangles, only on one of their sides are connected alongside each other, can be realized.
  • the layer structure of the moldings can be done in a stack-like manner, with one dissolution process the inner layer (s) on the edges of the molded body already takes place, if the outer layers are not yet completely detached, it can also be one complete covering of the inner layer (s) by the outer layer (s) Layer (s) can be achieved, which prevents the premature dissolution of components the inner layer (s).
  • a molded body consists of at least three layers, ie two outer and at least one inner layer, wherein at least one of the inner layers contains a peroxy bleach, while in the case of the stacked shaped body, the two outer layers and in the case of the shell-shaped one Moldings, the outermost layers, however, are free of peroxy bleach.
  • peroxy bleaching agents and any bleach activators present and / or spatially separate enzymes from each other in a molded body.
  • Such multilayer Shaped bodies have the advantage that they do not have only one induction chamber or via a metering device which is added to the wash liquor can; rather, in such cases it is also possible to direct the molded body To give contact to the textiles in the machine without staining Bleach and the like would be feared.
  • the bodies to be coated can be coated with, for example aqueous solutions or emulsions are sprayed, or via the process of Get a coating on the melt coating.
  • ⁇ stands for diametral fracture stress (DFS) in Pa
  • P is the force in N which leads to the pressure exerted on the molded body, which is the Breakage of the molded body causes
  • D is the molded body diameter in meters
  • t is the Height of the molded body.
  • the present invention can also be used in low-phosphate detergent tablets Realizing approach so that the use of particulate premixes, which contain fatty alcohol sulfate (s) and percarbonate for the production of hardness and Disintegration time-improved detergent tablets with reduced Cover inclination is another object of the present invention. Leave here too preferred quantities etc. can be found in the above text.
  • premixes were then processed with further components to form compressible premixes, the composition of which is given in Table 2.
  • Premix E according to the invention contained sodium percarbonate, while the premixes of comparative examples V1 and V2 contained sodium perborate.
  • the premixes were pressed into tablets in a Korsch eccentric press (diameter: 44 mm, height: 22 mm, weight: 37.5 g).
  • the measured values of the tablet hardness are in each case the mean values of a double determination, the individual values varying by a maximum of 2 N for each molded body type.
  • the hardness of the tablets became after two days of storage by deforming the tablet measured to break, the force acting on the side surfaces of the tablet and the maximum force that the tablet withstood was determined.
  • Table 3 shows that the moldings V1 and V2 already at tablet hardness above 40N tend to cover, while the moldings E according to the invention also without problems can be pressed to a hardness of 60 N without tearing the layers in layers Shaped body occurs.

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Claims (16)

  1. Corps moulés de produits de nettoyage et de lavage, constitués de produits de lavage et de nettoyage comprimés, sous forme de particules, contenant un ou des tensio-actifs, des agents de blanchiment, des adjuvants de lavage, ainsi que d'autres ingrédients en option des produits de lavage et de nettoyage, caractérisés en ce que les corps moulés contiennent un ou des sulfates d'alcool gras, un percarbonate et un builder au phosphate.
  2. Corps moulés de produits de lavage et de nettoyage selon la revendication 1, caractérisés en ce qu'ils contiennent en tant que phosphates, des phosphates de métal alcalin, de préférence le triphosphate pentasodique ou pentapotassique (tripolyphosphate de sodium ou de potassium), en des quantités de 1 à 60% en poids, de préférence de 5 à 50% en poids, de manière particulièrement préférée de 10 à 40% en poids, et en particulier de 15 à 35% en poids, à chaque fois par rapport au poids des corps moulés.
  3. Corps moulés de produits de lavage et de nettoyage selon l'une quelconque des revendications 1 ou 2, caractérisés en ce qu'ils contiennent les sels de métal alcalin, de préférence de sodium, et d'acides sulfuriques d'alkyle gras en C8 à C22, de préférence en C10 à C20, et en particulier en C12 à C18, de préférence en des quantités de 0,5 à 30% en poids, de manière particulièrement préférée de 1 à 20% en poids, et en particulier de 2 à 10% en poids, à chaque fois par rapport au poids des corps moulés.
  4. Corps moulés de produits de lavage et de nettoyage selon l'une quelconque des revendications 1 à 3, caractérisés en ce qu'ils contiennent en tant qu'agent de blanchiment unique, du percarbonate de sodium en des quantités de 1 à 40% en poids, de préférence de 2,5 à 35% en poids, de manière particulièrement préférée de 5 à 30% en poids, et en particulier de 7,5 à 25% en poids, à chaque fois par rapport au poids des corps moulés.
  5. Corps moulés de produits de lavage et de nettoyage selon l'une quelconque des revendications 1 à 4, caractérisés en ce qu'ils contiennent en outre, une zéolithe du type faujasite en des quantités de 0,5 à 20% en poids, de préférence de 1 à 15% en poids, de manière particulièrement préférée de 2 à 10% en poids, et en particulier de 2,5 à 5% en poids, à chaque fois par rapport au poids des corps moulés, !a zéolithe X étant préférée.
  6. Corps moulés de produits de lavage et de nettoyage selon l'une quelconque des revendications 1 à 5, caractérisés en ce qu'ils contiennent en outre, des tensio-actifs non ioniques ayant un point de fusion inférieur à 40°C, de préférence inférieur à 30°C et en particulier inférieur à 25°C, en des quantités de 0,5 à 20% en poids, de préférence de 1 à 10% en poids et en particulier de 1,5 à 5% en poids, à chaque fois par rapport au poids des corps moulés.
  7. Corps moulés de produits de lavage et de nettoyage selon l'une quelconque des revendications 1 à 6, caractérisés en ce qu'ils contiennent la quantité totale de phosphates sous forme d'un granulé de tensio-actifs, qui contient également de préférence la quantité totale des tensio-actifs contenus dans les corps moulés.
  8. Corps moulés de produits de lavage et de nettoyage selon la revendication 7, caractérisés en ce que le granulé de tensio-actifs contient de 5 à 70% en poids, de préférence de 10 à 65% en poids, de manière particulièrement préférée de 20 à 60% en poids, et en particulier de 25 à 50% en poids de phosphate, à chaque fois par rapport au poids du granulé de tensio-actifs.
  9. Procédé de préparation de corps moulés de produits de lavage et de nettoyage par mélange d'un granulé contenant des tensio-actifs avec des composants de traitement sous forme de poudre, suivi par une compression moulante, caractérisé en ce que le prémélange à comprimer contient un ou des sulfates d'alcool gras, un percarbonate et un builder au phosphate.
  10. Procédé selon la revendication 9, caractérisé en ce que le granulé contenant des tensio-actifs contient la quantité totale du phosphate contenu dans les corps moulés, les granulés qui contiennent en outre la quantité totale des tensio-actifs non ioniques, de préférence la quantité totale de tous les tensio-actifs, étant préférés.
  11. Procédé selon l'une quelconque des revendications 9 ou 10, caractérisé en ce que le granulé contenant des tensio-actifs, contient des tensio-actifs anioniques et/ou non ioniques ainsi que des adjuvants et présente une teneur totale en tensio-actifs de 5 à 60% en poids, de préférence de 10 à 50% en poids, et en particulier de 15 à 40% en poids, à chaque fois par rapport au granulé de tensio-actifs.
  12. Procédé selon l'une quelconque des revendications 9 à 11, caractérisé en ce que le granulé contenant les tensio-actifs présente des tailles de particule comprises entre 100 et 2 000 µm, de préférence entre 200 et 1 800 µm, de manière particulièrement préférée entre 400 et 1 600 µm, et en particulier entre 600 et 1 400 µm.
  13. Procédé selon l'une quelconque des revendications 9 à 12, caractérisé en ce que la proportion du granulé contenant des tensio-actifs dans les corps moulés de produits de lavage et de nettoyage, est de 40 à 95% en poids, de préférence de 45 à 85% en poids, et en particulier de 55 à 75% en poids, à chaque fois par rapport au poids des corps moulés de produits de lavage et de nettoyage.
  14. Procédé selon l'une quelconque des revendications 9 à 13, caractérisé en ce que le prémélange à comprimer contient en outre, un adjuvant de délitement, de préférence un adjuvant de délitement à base de cellulose, de préférence sous une forme granulaire, co-granulée, ou compactée, en des quantités de 0,5 à 10% en poids, de préférence de 3 à 7% en poids, et en particulier de 4 à 6% en poids, à chaque fois par rapport au poids du prémélange.
  15. Procédé selon l'une quelconque des revendications 9 à 14, caractérisé en ce que, le prémélange à comprimer content de plus une ou plusieurs substances du groupe des adjuvants de lavage, des activateurs de blanchiment, des enzymes, des ajusteurs de pH, des parfums, des supports de parfums, des agents fluorescents, des colorants, des inhibiteurs de mousse, des huiles siliconées, des agents anti-redéposition, des azurants optiques, des inhibiteurs de grisage, des inhibiteurs de transfert de couleurs, et des agents anti-corrosion.
  16. Utilisation de prémélanges sous forme de particules, lesquels contiennent un ou des phosphates, un ou des sulfates d'alcool gras et un percarbonate, pour préparer des corps moulés de produits de lavage et de nettoyage ayant une dureté et une durée de décomposition améliorées avec une tendance réduite au clivage.
EP00912538A 1999-03-11 2000-03-02 Produits de lavage et de nettoyage moules contenant une association tensioactif/agent de blanchiment/adjuvant de lavage Expired - Lifetime EP1159392B2 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19910819 1999-03-11
DE19910819A DE19910819A1 (de) 1999-03-11 1999-03-11 Wasch- und Reinigungsmittelformkörper mit Tensid-Bleichmittel-Builderkombination
PCT/EP2000/001812 WO2000053717A1 (fr) 1999-03-11 2000-03-02 Produits de lavage et de nettoyage moules contenant une association tensioactif/agent de blanchiment/adjuvant de lavage

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EP1159392A1 EP1159392A1 (fr) 2001-12-05
EP1159392B1 true EP1159392B1 (fr) 2004-06-16
EP1159392B2 EP1159392B2 (fr) 2007-12-12

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EP (1) EP1159392B2 (fr)
AT (1) ATE269395T1 (fr)
AU (1) AU3426600A (fr)
CA (1) CA2300616A1 (fr)
DE (2) DE19910819A1 (fr)
ES (1) ES2223479T5 (fr)
WO (1) WO2000053717A1 (fr)

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DE19932569A1 (de) * 1999-07-13 2001-01-18 Henkel Kgaa Wasch- und Reinigungsmittelformkörper, insbesondere für das maschinelle Geschirrspülen
US6541441B2 (en) * 1999-12-01 2003-04-01 Jose Alejandro Mumoli Single-dose soap unit and method
BR0114336B1 (pt) * 2000-09-29 2010-07-27 processo para produzir tira de aço fundido preparada por esse processo.

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Publication number Priority date Publication date Assignee Title
JPS5070286A (fr) * 1973-10-25 1975-06-11
GB8311865D0 (en) † 1983-04-29 1983-06-02 Procter & Gamble Ltd Bleach compositions
GB2276345A (en) † 1993-03-24 1994-09-28 Unilever Plc Process for making shaped articles
GB9422925D0 (en) † 1994-11-14 1995-01-04 Unilever Plc Detergent compositions
DE19601840A1 (de) * 1996-01-19 1997-07-24 Henkel Kgaa Verfahren zur Herstellung von Wasch- oder Reinigungsmittelformkörpern
DE19709411A1 (de) * 1997-03-07 1998-09-10 Henkel Kgaa Waschmittelformkörper
GB9706083D0 (en) * 1997-03-24 1997-05-14 Unilever Plc Detergent compositions
GB9707582D0 (en) † 1997-04-15 1997-06-04 Unilever Plc Detergent compositions
DE19749749A1 (de) * 1997-11-11 1999-05-12 Henkel Kgaa Verfahren zur Herstellung stabiler und schnell zerfallender Waschmittelformkörper
CZ20002935A3 (cs) † 1998-02-10 2001-10-17 Unilever N. V. Způsob výroby pracího prostředku
GB2334528A (en) † 1998-02-21 1999-08-25 Procter & Gamble Hydrogen peroxide releasing detergent composition
DE19808758A1 (de) * 1998-03-02 1999-09-09 Henkel Kgaa Verfahren zur Herstellung von Wasch- und Reinigungsmittelformkörpern

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EP1159392A1 (fr) 2001-12-05
WO2000053717A1 (fr) 2000-09-14
DE19910819A1 (de) 2000-09-14
EP1159392B2 (fr) 2007-12-12
ES2223479T5 (es) 2008-05-16
CA2300616A1 (fr) 2000-09-11
ATE269395T1 (de) 2004-07-15
AU3426600A (en) 2000-09-28
DE50006819D1 (de) 2004-07-22
ES2223479T3 (es) 2005-03-01

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