EP1159392B2 - 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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EP1159392B2
EP1159392B2 EP00912538A EP00912538A EP1159392B2 EP 1159392 B2 EP1159392 B2 EP 1159392B2 EP 00912538 A EP00912538 A EP 00912538A EP 00912538 A EP00912538 A EP 00912538A EP 1159392 B2 EP1159392 B2 EP 1159392B2
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Prior art keywords
weight
tablets
acid
surfactant
sodium
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EP1159392A1 (fr
EP1159392B1 (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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    • 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 molded articles having detergent and cleaning properties such as detergent tablets, automatic dishwashing detergent tablets, bleach tablets, water softening tablets, etc. More particularly, the invention relates to detergent tablets for textile washing in a domestic washing machine, referred to as detergent tablets for short ,
  • tablette The special advantages of the offer form "tablet” include the simple and clean dosing and the high degree of compaction, which requires a reduced packaging and transport costs. Especially because of these advantages, detergents and cleaners in tablet form have a high consumer acceptance. However, these advantages are also faced with disadvantages. Thus, the tablets must be sufficiently stable to survive packaging, shipping and handling, but on the other hand they should disintegrate quickly and be readily soluble in order to quickly release the active ingredients and to avoid residues or stains on the treated substrates. Ideally, the washing and cleaning tablets should disintegrate into their secondary particles so quickly that, for example, metering via the dispensing chamber of household washing machines is possible without problems.
  • Moldings that are not suitable for this purpose must be metered through the drum, where the direct contact of the agent with the laundry can lead to so-called spotting problems.
  • mitigating this problem is possible by the use of dosing or sachets in which the tablets are inserted before adding to the laundry, but on the one hand the problem is not completely solved, on the other hand, this cumbersome approach leads to significantly reduced consumer acceptance, as the Advantages of the easy dosage and the possibility of dosing without skin contact with the agent are thereby nullified.
  • humectants are added to solve this problem, slowing the Tablettier effetives to prevent air inclusions or added adjuvants that prevent too high expansion of the molding after compression.
  • microcrystalline cellulose has proven itself.
  • Detergent tablets containing phosphates and bleaches are described in the prior art.
  • the international patent application discloses WO98 / 42816 (Unilever ) Detergent tablets which have a density of more than 1040 g / cm 3 and contain 5 to 50 wt .-% of surfactant and 8 to 30 wt .-% bleach.
  • bleaching agents sodium perborate or sodium perborate tetrahydrate are used in this document, which in manual tests are said to have been preferred over sodium perborate monohydrate. 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 used in the WO98 / 24817 (Unilever ). Also in this document, the use of fatty alcohol sulfates is not described and the problem of lids not appreciated.
  • phosphate-based and percarbonate-containing detergent tablets can be formulated with outstanding performance properties and significantly reduced lid tilt if they contain fatty alcohol sulfate (s).
  • the present invention provides detergent tablets of compacted, particulate Washing and cleaning compositions containing surfactant (s), bleaching agents, builders and optionally further ingredients of detergents and cleaners, characterized in that the shaped bodies fatty alcohol sulfate (e), from the group of sodium salts of C 12-18 fatty alkylsulfuric acids, percarbonate and phosphate builders contain.
  • surfactant s
  • bleaching agents e
  • builders characterized in that the shaped bodies fatty alcohol sulfate (e), from the group of sodium salts of C 12-18 fatty alkylsulfuric acids, percarbonate and phosphate builders contain.
  • the molded articles according to the invention contain surfactants, phosphate builders and bleaching agents.
  • the phosphate builders perform tasks while the fatty alcohol sulfates are included as detergent-active substances. Usually, this is the major amount of builder substance made up of the phosphates.
  • alkali metal phosphates with a particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), have the greatest importance in the washing and cleaning agent industry.
  • 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 their water of crystallization when heated and at 200 ° C into the weak acid 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), pass.
  • 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 using phenolphthalein as an 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: melting or annealing phosphates, Graham's salt, Kurrolsches and Maddrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates.
  • 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 soda solution or sodium hydroxide solution in a stoichiometric ratio, and the solution is dissolved by spraying dewatered. 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.
  • sodium potassium tripolyphosphates which can also be 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
  • preferred washing and cleaning agent tablets contain, as phosphates, alkali metal phosphates, preferably pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), in amounts of from 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 molding weight.
  • alkali metal phosphates preferably pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate)
  • the detergent tablets according to the invention may contain other customary builders which may be both water-soluble and water-insoluble.
  • all builders commonly used in detergents and cleaning agents may be present, in particular zeolites, silicates, carbonates and organic cobuilders. These builders can be added to the mixtures to be tabletted, but they can also be wholly or partly part of surfactant granules.
  • Crystalline, layered sodium silicates suitable as builders 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 and 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 and preferred values for x are 2, 3 or 4.
  • Such crystalline sheet silicates are described for example in the European Patent Application EP-A-0 164 514 described.
  • Preferred crystalline layered silicates of the formula given are those in which M is sodium and x assumes the values 2 or 3.
  • both ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 O 5 ⁇ yH 2 O are preferred, wherein ⁇ -sodium disilicate can be obtained, for example, by the process described in International Patent Application WO-A-91/08171 is described.
  • the dissolution delay compared with conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction / densification or by overdrying.
  • amorphous is also understood to mean “X-ray amorphous”. This means that the silicates do not yield sharp X-ray reflections typical of crystalline substances in X-ray diffraction experiments, but at most one or more maxima of the scattered X-rays having a width of several degrees of diffraction angle. However, it may well even lead to particularly good builder properties if the silicate particles provide blurred or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline regions of size 10 to a few hundred nm, values of up to max. 50 nm and in particular up to max. 20 nm are preferred.
  • Such so-called X-ray amorphous silicates which likewise have a dissolution delay compared with the conventional water glasses, are described, for example, in US Pat German patent application DE-A-44 00 024 described. Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates.
  • 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 particularly preferred.
  • zeolite X and zeolite A are cocrystal of zeolite X and zeolite A (about 80% by weight of zeolite X) ), which is sold by the company 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 can be described.
  • the zeolite can be used both as a builder in a granular compound, as well as to a kind of "powdering" of the entire mixture to be pressed, usually both ways of incorporating the zeolite into the premix can be used.
  • Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution, measuring method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.
  • preferred washing and cleaning agent tablets additionally comprise a faujasite-type zeolite in amounts of from 0.5 to 20% by weight, preferably from 1 to 15% by weight, more preferably from 2 to 10% by weight. % and in particular from 2.5 to 5 wt .-%, each based on the molding weight, with zeolite X is preferred.
  • the amount of builder is usually between 10 and 70 wt .-%, preferably between 15 and 60 wt .-% and in particular between 20 and 50 wt .-%.
  • the amount of builders used depends on the intended use, so that bleach tablets may 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 wt .-%, preferably 12.5 to 45 wt .-% us in particular between 17.5 and 37.5 wt .-%).
  • organic cobuilders it is possible in particular to use polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, further organic cobuilders (see below) and phosphonates in the detergent tablets according to the invention. These classes of substances are described below.
  • Useful organic builder substances are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. These are, for example, 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 is not objectionable for ecological reasons, and 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 thereof.
  • the acids themselves can also be used.
  • the acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH of detergents or cleaners.
  • citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.
  • polymeric polycarboxylates for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those having a relative molecular mass of from 500 to 70,000 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 preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have poppy weights of 2,000 to 10,000 g / mol, and more preferably of 3,000 to 5,000 g / mol, may again be preferred from this group.
  • copolymeric polycarboxylates in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid.
  • Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable.
  • Their relative molecular weight, based on free acids is generally from 2000 to 70000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular from 30,000 to 40,000 g / mol.
  • the (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution.
  • the content of (co) polymeric polycarboxylates in the compositions is preferably 0.5 to 20% by weight, in particular 3 to 10% by weight.
  • the polymers may also contain allylsulfonic acids such as allyloxybenzenesulfonic acid and methallylsulfonic acid as a monomer.
  • biodegradable polymers of more than two different monomer units for example those which contain as monomers salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or as monomers salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives ,
  • copolymers are those described in the German patent applications DE-A-43 03 320 and DE-A-44 17 734 be described and as monomers preferably acrolein and acrylic acid / acrylic acid salts or Acrolein and vinyl acetate.
  • polymeric aminodicarboxylic acids their salts or their precursors.
  • polyaspartic acids or their salts and derivatives of which in the German patent application DE-A-195 40 086 is disclosed that they also have a bleach-stabilizing effect in addition to Cobuilder properties.
  • polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 C atoms and at least 3 hydroxyl groups.
  • Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
  • dextrins for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches.
  • the hydrolysis can be carried out by customary, for example acid or enzyme catalyzed processes.
  • it is hydrolysis products having average molecular weights in the range of 400 to 500,000 g / mol.
  • a polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30 is preferred, DE being a common measure of the reducing action of a polysaccharide compared to dextrose, which has a DE of 100 , is.
  • DE dextrose equivalent
  • 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 methods of their preparation are 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 as well as the 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 known. Also suitable is an oxidized oligosaccharide according to German patent application DE-A-196 00 018 , A product oxidized to C 6 of the saccharide
  • Oxydisuccinates and other derivatives of disuccinates are other suitable co-builders.
  • ethylenediamine-N, N'disuccinate (EDDS) is 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 in zeolithissen and / or silicate-containing formulations at 3 to 15 wt .-%.
  • organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally also be present 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 co-builders are described, for example, in the international patent application WO 95/20029 described.
  • phosphonates are, in particular, hydroxyalkane or aminoalkanephosphonates.
  • hydroxyalkane phosphonates 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a co-builder.
  • HEDP 1-hydroxyethane-1,1-diphosphonate
  • Preferred aminoalkanephosphonates are ethylenediamine tetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. They are preferably in the form of neutral sodium salts, eg. B.
  • the builder used here is preferably HEDP from the class of phosphonates.
  • the aminoalkanephosphonates also have a pronounced heavy metal binding capacity. Accordingly, in particular if the agents also contain bleach, it may be preferable to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.
  • the shaped articles according to the invention contain surfactants for unfolding the washing or cleaning performance.
  • surfactants for unfolding the washing or cleaning performance.
  • fatty alcohol sulfates from the group of the sodium salts of C 12-18 fatty alkyl sulfuric acids are contained in the moldings, while other surfactants can optionally additionally be used.
  • Fatty alcohol sulfates the alkali metal salts, in particular sodium salts, of the sulfuric monoesters of relatively long-chain alcohols are industrially available from fatty alcohols which are reacted with sulfuric acid, chlorosulfonic acid, sulfamic acid or sulfur trioxide to give the corresponding alkyl sulfuric acids and subsequently neutralized.
  • the fatty alcohols are thereby obtained from the relevant fatty acids or fatty acid mixtures by high-pressure hydrogenation of fatty acid methyl esters.
  • the quantitatively most important industrial process for the preparation of fatty alkylsulfuric acids is the sulfation of the alcohols with SO 3 / air mixtures in special cascade, falling film or tube bundle reactors.
  • the fatty acids whose methyl esters are high pressure hydrogenated to the fatty alcohols, become technical mostly from native fats and oils obtained by hydrolysis. While the alkaline saponification already carried out in the past century led directly to the alkali salts (soaps), today only large amounts of water are used for cleavage, which cleaves the fats into glycerol and the free fatty acids. Alternatively, the cleavage can be performed with methanol to directly recover the methyl esters and glycerol. Examples of industrially applied processes are the autoclave cleavage or continuous high pressure cleavage.
  • hexanoic acid caproic acid
  • heptanoic acid capnonic acid
  • octanoic acid caprylic acid
  • nonanoic acid pelargonic acid
  • decanoic acid capric acid
  • undecanoic acid etc.
  • fatty alcohol sulfates the use of fatty acids such as dodecanoic acid (lauric acid), tetradecanoic acid (myristic acid), hexadecanoic acid (palmitic acid), octadecanoic acid (stearic acid), eicosanoic acid (arachidic acid), docosanoic acid (behenic acid), tetracosanic acid (lignoceric acid), hexacosanoic acid (cerotic acid), triacotanoic acid (melissic acid) and Unsaturated Sezies 9c-hexadecenoic acid (palmitoleic acid), 6c-octadecenoic acid (petroselinic acid), 6t-octadecenoic acid (petroselaidinic acid), 9c-octadecenoic acid (oleic acid), 9t-octadecenoic acid (oleic acid), 9t-oct
  • Such mixtures are for example coconut oil (about 6 wt .-% C 8 , 6 wt .-% C 10 , 48 wt .-% C 12 , 18 wt .-% C 14 , 10 wt .-% C 16 , 2 wt % C 18 , 8% by weight C 18 , 1% by weight C 18 " ), palm kernel oil fatty acid (about 4% by weight C 8 , 5% by weight C 10 , 50% by weight C 12 , 15 wt .-% C 14 , 7 wt .-% C 16 , 2 wt .-% C 18 , 15 wt .-% C 18 ' , 1 wt .-% 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
  • % C 18 , 1% by weight C 18 ' soybean oil fatty acid (about 2% by weight C 14 , 15 wt .-% C 16 , 5 wt .-% C 18 , 25 wt .-% C 18 ' , 45 wt .-% C 18'' , 7 wt .-% C 18''' ).
  • the alkyl sulfates used are the sodium salts of the sulfuric monoesters of C 12 -C 18 fatty alcohols, for example of coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol.
  • alk (en) ylsulfates of the aforementioned chain length which contain a synthetic, petrochemical-based, straight-chain alkyl radical which has an analogous decomposition behavior to the adequate compounds based on oleochemical raw materials.
  • alk (en) ylsulfates of the aforementioned chain length which contain a synthetic, petrochemical-based, straight-chain alkyl radical which has an analogous decomposition behavior to the adequate compounds based on oleochemical raw materials.
  • the C 12 -C 16 alkyl sulfates and C 12 -C 15 alkyl sulfates and C 14 -C 15 alkyl sulfates are preferred.
  • Detergent tablets claimed in the present invention contain sodium salts of C 12-18 fatty alkylsulfuric acids.
  • detergent tablets which contain the sodium salts of C 12-18 fatty alkylsulfuric acids in amounts of from 0.5 to 30% by weight, particularly preferably from 1 to 20% by weight in particular from 2 to 10% by weight, in each case based on the molding weight.
  • surfactants which may be used in addition to the fatty alcohol sulfates may be derived from the groups of anionic, nonionic, cationic or amphoteric surfactants. Due to their performance spectrum and their availability, anionic and nonionic surfactants are preferred.
  • anionic surfactants used are those of the sulfonate and sulfates type.
  • suitable surfactants of the sulfonate type are alkylbenzenesulfonates (ABS), olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as those obtained from C 12-18 monoolefins having terminal or internal double bonds by sulfonating with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation obtained.
  • ABS alkylbenzenesulfonates
  • olefinsulfonates ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates
  • 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 ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids are suitable.
  • sulfated fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and mixtures thereof, as obtained in the preparation by esterification of a monoglycerol with 1 to 3 moles of fatty acid or 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 acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
  • 2,3-alkyl sulfates which, for example, according to the U.S. Patents 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.
  • 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 are particularly soaps into consideration.
  • Suitable are 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 of natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.
  • the anionic surfactants including the soaps may 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 present in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
  • detergent tablets are preferred whose total content of anionic surfactants is above 5% by weight, preferably above 7.5% by weight and in particular above 10% by weight, in each case based on the tablet weight , lies.
  • the formulation freedom does not stand in the way of any conditions to be observed.
  • preferred washing and cleaning agent tablets have a soap content which exceeds 0.2% by weight, based on the total weight of the tablet.
  • nonionic surfactants are preferably used alkoxylated, preferably ethoxylated, especially primary alcohols having 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 linear or preferably methyl branched in the 2-position may be or 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 or 4 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 5 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 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 having from 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl esters as they are for example in the Japanese Patent Application JP 58/217598 are described or preferably according to the in the international patent application WO 90/13533 be prepared described methods.
  • alkyl polyglycosides Another class of nonionic surfactants that can be used to advantage are the alkyl polyglycosides (APG).
  • APG alkyl polyglycosides
  • Usable Alkypolyglycoside meet the general formula RO (G) z , in which R is a linear or branched, especially in the 2-position methyl branched, saturated or unsaturated, aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the Is a symbol which represents a glycose unit having 5 or 6 C atoms, preferably 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 that is to say alkyl polyglycosides 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 may preferably contain alkylpolyglycosides, with contents of the tablets of APG being more than 0.2% by weight, based on the total tablet, being preferred.
  • Particularly preferred detergent tablets contain APG in amounts of from 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-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.
  • polyhydroxy fatty acid amides of the formula (II) 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 (III) 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
  • [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 be used, for example, according to the teaching of the international application WO-A-95/07331 be converted by reaction with fatty acid methyl esters in the presence of an alkoxide as a catalyst in the desired polyhydroxy fatty acid amides.
  • detergent tablets which additionally contain nonionic surfactant (s) and in which the content of nonionic surfactants in the tablets is above 2% by weight, preferably above 5% by weight and in particular above 7.5% by weight, in each case based on the molding weight.
  • nonionic surfactants from all the groups mentioned above can be used. Irrespective of the chemical nature of the nonionic surfactants used, preference is given to washing and cleaning agent tablets which additionally contain nonionic surfactants having a melting point below 40 ° C., preferably below 30 ° C. and in particular below 25 ° C., in amounts of from 0.5 to 20% by weight. -%, preferably from 1 to 10 wt .-% and in particular from 1.5 to 5 wt .-%, each based on the molding body weight, contain.
  • the detergent tablets of the present invention contain sodium percarbonate.
  • sodium percarbonate is a non-specific term used for sodium carbonate peroxohydrates, which strictly speaking are not “percarbonates” (ie salts of percarbonate) but hydrogen peroxide adducts of sodium carbonate.
  • the commodity has the average composition 2 Na 2 CO 3 .3H 2 O 2 and is therefore no peroxycarbonate.
  • Sodium percarbonate forms a white, water-soluble powder with a density of 2.14 gcm -3 , which readily decomposes into sodium carbonate and bleaching or oxidizing oxygen.
  • the industrial production of sodium percarbonate is predominantly produced by precipitation from aqueous solution (so-called wet process).
  • aqueous solutions of sodium carbonate and hydrogen peroxide are combined and the sodium by salting-out agent (mainly sodium chloride), Kristallisierangesstoff (for example, polyphosphates, polyacrylates) and stabilizers (for example, Mg 2+ ions) like.
  • the precipitated salt which still contains 5 to 12 wt .-% mother liquor, is then removed by centrifugation and dried in fluid bed dryers at 90 ° C.
  • the bulk density of the finished product may 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 used in varying amounts in the detergent tablets according to the invention, depending on the desired product. Usual contents are between 5 and 50 wt .-%, preferably between 10 and 40 wt .-% and in particular between 15 and 35 wt .-%, each based on the total molding.
  • the content of the shaped bodies on this substance depends on the intended use of the shaped bodies.
  • conventional universal detergents in tablet form contain between 5 and 30% by weight, preferably between 7.5 and 25% by weight and in particular between 12.5 and 22.5% by weight of sodium percarbonate
  • the levels are bleach or bleach booster tablets between 15 and 50% by weight, preferably between 22.5 and 45% by weight, in particular between 30 and 40% by weight.
  • a preferred embodiment of the present invention provides laundry detergent tablets for laundering textiles in a home-washing machine.
  • These preferred detergent tablets are characterized in that they contain as sole bleaching agent sodium percarbonate in amounts of from 1 to 40% by weight, preferably from 2.5 to 35% by weight, more preferably from 5 to 30% by weight and in particular from 7.5 to 25% by weight, in each case based on the molding weight.
  • the detergent tablets according to the invention may contain bleach activator (s), which is preferred in the context of the present invention.
  • Bleach activators are incorporated into detergents to achieve improved bleaching performance when washed at temperatures of 60 ° C and below.
  • As bleach activators it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic 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 C 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-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2,5-diacetoxy- 2,5-dihydrofuran.
  • TAED tetraacet
  • bleach catalysts can be incorporated into the moldings.
  • These substances are bleach-enhancing transition metal salts or transition metal complexes such as Mn, Fe, Co, Ru or Mo saline complexes or carbonyl complexes.
  • Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru ammine complexes can also be used as bleach catalysts.
  • the shaped articles according to the invention contain, based in each case on the entire shaped article, 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 molded body produced, these quantities may vary. Thus, in typical universal detergent tablets bleach activator levels between 0.5 and 10 wt .-%, preferably between 2 and 8 wt .-% and in particular between 4 and 6 wt .-% usual, while bleach tablets quite higher levels, for example between 5 and 30 wt .-%, preferably between 7.5 and 25 wt .-% and in particular between 10 and 20 wt .-% may have.
  • the expert is in its formulation freedom is not limited and can thus produce stronger or weaker bleaching detergent tablets, detergent tablets or bleach tablets by varying the levels of bleach activator and bleach.
  • a particularly preferred bleach activator is N, N, N ', N'-tetraacetylethylenediamine, which is widely used in detergents and cleaners. Accordingly, preferred detergent tablets are characterized in that the bleach activator is tetraacetylethylenediamine in the abovementioned amounts.
  • Phosphate (s) and fatty alcohol sulfate (s) can be introduced in any desired manner into the detergent tablets according to the invention. It has proved to be advantageous if the premix to be pressed into moldings contains phosphate (s) and fatty alcohol sulfate (s) in the form of a surfactant granulate. For this purpose, a surfactant granules is first prepared, which preferably contains the total amount of the phosphates and fatty alcohol sulfates contained in the moldings, and subsequently mixed with further treatment components, after which the premix is a tabletting is supplied.
  • the above-mentioned surfactant granules contain the total amount of the nonionic surfactants contained in the moldings, preferably even the total amount of the total surfactants contained in the moldings.
  • detergent tablets and detergent tablets are therefore preferred, which are characterized in that they contain a total amount of phosphates in the form of a surfactant granules, preferably. also contains the total amount of the surfactants contained in the moldings.
  • inventively preferred surfactant granules have higher phosphate contents than the overall shaped article.
  • detergent tablets are preferred in which the surfactant granules contain from 5 to 70% by weight, preferably from 10 to 65% by weight, particularly preferably from 20 to 60% by weight and in particular from 25 to 50% by weight of phosphate, in each case based on the weight of the surfactant granules.
  • ingredients of detergents and cleaners especially so-called small components such as optical brighteners, polymers, defoamers, phosphonates, dyes and fragrances, may be part of the surfactant granules. These substances are described below.
  • the premix to be compressed may further contain one or more of bleaches, bleach activators, disintegration aids, etc.
  • the said substances, which are described below, may also be part of the surfactant granules in specific embodiments of the present invention.
  • Another object of the present invention is a process for the preparation of detergent tablets by blending a surfactant-containing granules with pulverulent preparation components and subsequent shaping compression, wherein the premix to be tabletted fatty alcohol sulfate (e), from the group of sodium salts of C 12- 18 fatty alkyl sulfuric acids percarbonate and phosphate builder contains.
  • fatty alcohol sulfate e
  • the premix to be tabletted contains surfactant-containing granules (e) and further preparation components, phosphate (s) and preferably the surfactants being part of the granules.
  • the preparation of the surfactant-containing granules can be carried out by conventional industrial granulation processes such as compaction, extrusion, mixer granulation, pelleting or fluidized bed granulation. It is advantageous for the later detergent tablets if the premix to be compressed has a bulk density which approximates the conventional compact detergent. In particular, it is preferred that the premix to be compressed has 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 granules satisfies certain particle size criteria in preferred process variants.
  • preferred processes according to the invention are those in which the surfactant-containing granules have particle sizes between 100 and 2000 ⁇ m, 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 excipients, which more preferably originate from the group of builders.
  • the premix to be compressed contains a surfactant-containing granulate which contains anionic and / or nonionic surfactants and builders and whose total surfactant content is 5 to 60% by weight, preferably 10 to 50% by weight and in particular 15 to 40 wt .-%, each based on the Tensidgranulat is.
  • the premix contains a surfactant-containing granules, the Surfactant contents of 5 to 60 wt .-%, preferably from 10 to 50 wt .-% and in particular from 15 to 40 wt .-%, each based on the weight of the surfactant granules having (see above).
  • detergent tablets in which the content of surfactant granules of anionic surfactants is 5 to 45% by weight, preferably 10 to 40% by weight and in particular 15 to 35% by weight, based in each case on the weight of the surfactant granules and detergent tablets in which the content of surfactant granules of nonionic surfactants is from 1 to 30% by weight, preferably from 5 to 25% by weight and in particular from 7.5 to 20% by weight, based in each case on the weight of the surfactant granules , is, are preferred according to the invention.
  • Particularly preferred variants of the method according to the invention are characterized in that the proportion of surfactant-containing granules to be pressed premix and thus to the detergent tablets 40 to 95 wt .-%, preferably 45 to 85 wt .-% and in particular 55 to 75 wt .-%, in each case based on the weight of the detergent tablets.
  • the surfactant-containing granules are produced not by spray-drying but by a granulation process.
  • a granulation process which can be carried out in a wide variety of mixed granulators and mixing agglomerators, for example, also Preßagglomerationsvon be used. Processes in which the surfactant-containing granules are prepared by granulation, agglomeration, press agglomeration or a combination of these processes are therefore preferred.
  • the granulation can be carried out in a variety of apparatuses commonly used in the washing and cleaning industry. Thus, it is possible, for example, to use the usual in pharmacy Verrunder. In such turntable apparatus, the residence time of the granules is usually less than 20 seconds.
  • Conventional mixers and mixed granulators are also suitable for granulation. Both high-intensity mixers (“high-shear mixers”) and normal mixers with lower speeds of rotation can be used as mixers.
  • Suitable mixers are, for example, Eirich® mixers of the R or RV series (trademarks of the Maschinenfabrik Gustav Eirich, Hardheim), the Schugi® Flexomix, the Fukae® FS-G mixers (trademarks of Fukae Powtech, Kogyo Co., Japan), the Lödige® FM, KM and CB mixers (trademark of Lödige Maschinenbau GmbH, Paderborn) or the Drais® series T or KT (trademark of Drais-Werke GmbH, Mannheim).
  • the residence times of the granules in the mixers are in the range of less than 60 seconds, wherein the Verwei time also depends on the rotational speed of the mixer. In this case, the residence times are shortened accordingly, the faster the mixer runs.
  • the residence times of the granules in the mixer / rounder are less than one minute, preferably less than 15 seconds.
  • residence times of up to 20 minutes are set, with residence times below 10 minutes being preferred because of the process economy.
  • the surfactant-containing granules are compacted under pressure and under the action of shear forces and thereby homogenized and then discharged by molding from the apparatus.
  • the most technically significant press agglomeration processes are extrusion, roll compacting, pelletizing and tableting.
  • Preßagglomerationsvon used in the present invention for the preparation of the surfactant-containing granules are the extrusion, the Walzenkompakt réelle and pelleting.
  • disintegration aids so-called tablet disintegrating agents
  • disintegration aids so-called tablet disintegrating agents
  • Excipients which ensure the rapid disintegration of tablets in water or gastric juice and for the release of the pharmaceuticals in resorbable form.
  • Preferred detergent tablets contain from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6% by weight, of one or more disintegration aids, in each case based on the weight of the tablet.
  • Preferred disintegrating agents in the context of the present invention are disintegrating agents used on cellulose base, so that preferred detergent tablets contain such cellulose-based disintegrating agent in amounts of 0.5 to 10 wt .-%, preferably 3 to 7 wt .-% and in particular 4 to 6 wt .-%.
  • Pure cellulose has the formal gross composition (C 6 H 10 O 5 ) n and is formally a ⁇ -1,4-polyacetal of cellobiose, which in turn is composed of two molecules of glucose.
  • Suitable celluloses consist of about 500 to 5000 glucose units and therefore have average molecular weights of 50,000 to 500,000.
  • Cellulose-based disintegrating agents which can be used in the context of the present invention are also cellulose derivatives obtainable by polymer-analogous reactions of cellulose.
  • Such chemically modified celluloses include, for example, products of esterifications or etherifications in which hydroxy hydrogen atoms have been substituted.
  • Celluloses in which the hydroxy 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 metal celluloses, carboxymethylcellulose (CMC), cellulose esters and ethers, and aminocelluloses.
  • the cellulose derivatives mentioned are preferably not used alone as disintegrating agents based on cellulose, but used in admixture with cellulose.
  • the content of these mixtures of cellulose derivatives is preferably below 50% by weight, particularly preferably below 20% by weight, based on the cellulose-based disintegrating agent. It is particularly preferred to use cellulose-based disintegrating agent which is free of cellulose
  • the cellulose used as a disintegration aid is preferably not used in finely divided form, but converted into a coarser form, for example granulated or compacted, before it is added to the premixes to be tabletted.
  • Detergents and cleaning product tablets containing disintegrators in granular or optionally cogranulated form are incorporated into the German patent applications DE 197 09 991 (Stefan Herzog ) and DE 197 10 254 (Henkel ) as well as the international patent application WO98 / 40463 (Henkel ). Further details of the production of granulated, compacted or cogranulated cellulose explosives can be found in these publications.
  • the particle sizes of such disintegrating agents are usually above 200 .mu.m, preferably at least 90 wt .-% between 300 and 1600 .mu.m and in particular at least 90 wt .-% between 400 and 1200 microns.
  • the above-mentioned coarser disintegration aids based on cellulose 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 can be used as a further disintegrating agent based on cellulose or as a component of this component.
  • This microcrystalline cellulose is obtained by partial hydrolysis of celluloses under conditions which attack and completely dissolve only the amorphous regions (about 30% of the total cellulose mass) of the celluloses, leaving the crystalline regions (about 70%) intact.
  • Subsequent deaggregation of the microfine celluloses produced by the hydrolysis yields the microcrystalline celluloses which have primary particle sizes of about 5 ⁇ m and can be compacted, for example, into granules having an average particle size of 200 ⁇ m.
  • the premix to be compressed additionally contains a disintegration assistant, preferably a disintegration aid based on cellulose, preferably in granular, cogranulated or compacted form, in amounts of from 0.5 to 10% by weight, preferably 3 to 7 wt .-% and in particular from 4 to 6 wt .-%, each based on the weight of the premix contains.
  • a disintegration assistant preferably a disintegration aid based on cellulose, preferably in granular, cogranulated or compacted form, in amounts of from 0.5 to 10% by weight, preferably 3 to 7 wt .-% and in particular from 4 to 6 wt .-%, each 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 adjusters, fragrances, perfume carriers, fluorescers, dyes, foam inhibitors, silicone oils, antiredeposition agents, optical brighteners, grayness inhibitors, dye transfer inhibitors and corrosion inhibitors.
  • these substances are described below. The most important representatives from the groups of builders and bleach activators have been described above. Below are details of the other ingredients.
  • Suitable enzymes are those from the class of proteases, lipases, amylases, cellulases or mixtures thereof. Particularly suitable are bacterial strains or fungi, such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus derived enzymatic agents.
  • subtilisin-type proteases and in particular proteases derived from Bacillus lentus are used.
  • Enzyme mixtures for example from protease and amylase or protease and lipase or protease and cellulase or from cellulase and lipase or from protease, amylase and lipase or protease, lipase and cellulase, but in particular cellulase-containing mixtures are of particular interest.
  • Peroxidases or oxidases have also proved suitable in some cases.
  • the enzymes may be adsorbed to carriers and / or embedded in encapsulants to protect against premature degradation.
  • the proportion of enzymes, enzyme mixtures or enzyme granules in the moldings 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 may also contain components which positively influence the oil and grease washability from textiles (so-called soil repellents). This effect is particularly evident when a textile is soiled, which previously several times with a detergent according to the invention, containing this oil and fat dissolving component was washed.
  • the preferred oil and fat dissolving components include, for example, nonionic cellulose ethers such as methylcellulose and methylhydroxypropylcellulose with a proportion of methoxyl groups of 15 to 30 wt .-% and hydroxypropoxyl groups of 1 to 15 wt .-%, each based on the nonionic Cellulose ethers, as well as known from the prior art polymers of phthalic acid and / or terephthalic acid or derivatives thereof, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionic and / or nonionic modified derivatives thereof. Particularly preferred of these are the sulfonated derivatives of phthalic and terephthalic acid polymers.
  • the shaped bodies may contain, as optical brighteners, derivatives of diaminostilbenedisulfonic acid or its 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, a diethanolamino group , a methylamino group, an anilino group or a 2-methoxyethylamino group. Furthermore, brighteners of the substituted diphenylstyrene type may be present, e.g.
  • Dyes and fragrances are added to the detergent tablets according to the invention in order to improve the aesthetic impression of the products and to provide the consumer, in addition to the washing or cleaning performance, with a visually and sensory "typical and unmistakable" product.
  • perfume oils or fragrances individual fragrance compounds, e.g. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type are used. Fragrance compounds of the ester type are known e.g.
  • the ethers include, for example, benzyl ethyl ether, to the aldehydes e.g.
  • the linear alkanals having 8-18 C atoms citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilial and bourgeonal
  • the ketones e.g. the ionones, ⁇ -isomethylionone and methyl cedryl ketone
  • the alcohols anethole, citronellol, eugenol, geraniol, linalcol, phenylethyl alcohol and terpineol
  • the hydrocarbons mainly include the terpenes such as limonene and pinene.
  • mixtures of different fragrances are used, which together produce an attractive fragrance.
  • perfume oils may also contain natural fragrance mixtures such as are available from vegetable sources, e.g. Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage, chamomile, clove, lemon balm, mint, cinnamon, lime, juniper, vetiver, olibanum, galbanum and labdanum, and orange blossom, neroliol, orange peel and sandalwood.
  • the content of the detergent tablets according to the invention is usually less than 0.01% by weight of dyes, while fragrances may account for up to 2% by weight of the total formulation.
  • the fragrances can be incorporated directly into the compositions of the invention, but it may also be advantageous to apply the fragrances on carriers, which enhance the adhesion of the perfume on the laundry and provide by a slower release of fragrance for long-lasting fragrance of the textiles.
  • carrier materials for example, cyclodextrins have been proven, the cyclodextrin-perfume complexes can be additionally coated with other excipients.
  • the detergent tablets can be dyed with suitable dyes.
  • Preferred dyes the selection of which presents no difficulty to the skilled person, have a high storage stability and insensitivity to the other ingredients of the agents and to light and no pronounced substantivity to textile fibers so as not to stain them.
  • the premix Before the particulate premix is compressed into detergent tablets, the premix can be "powdered” with finely divided surface treatment agents. This may be advantageous for the nature and physical properties of both the premix (storage, compression) and the finished detergent tablets. Fine particulate powdering agents are well known in the art, with mostly zeolites, silicates or other inorganic salts are used. Preferably, however, the premix is "powdered” with finely divided zeolite, with faujasite-type zeolites being preferred. In the context of the present invention, the term “faujasite-type zeolite” denotes all three zeolites which form the faujasite subgroup of the zeolite structure group 4 (cf. Donald W.
  • the one or more admixed preparation components is a faujasite-type zeolite having particle sizes below 100 ⁇ m, preferably below 10 ⁇ m and in particular below 5 ⁇ m, and at least 0.2% by weight .-%, preferably at least 0.5 wt .-% and in particular more than 1 wt .-% of the to be pressed Make up premix.
  • the production of the shaped bodies according to the invention takes place firstly by the dry mixing of the constituents, which may be completely or partially pre-granulated, and subsequent informing, in particular pressing into tablets, wherein conventional methods can be used.
  • the premix is compacted in a so-called matrix between two punches to form a solid compressed product. This process, hereinafter referred to as tabletting, is divided into four sections: dosing, compaction (elastic deformation), plastic deformation and ejection.
  • the premix is introduced into the die, wherein the filling amount and thus the weight and the shape of the resulting shaped body are determined by the position of the lower punch and the shape of the pressing tool.
  • the constant dosage even at high molding throughputs is preferably achieved via a volumetric metering of the premix.
  • the upper punch contacts the pre-mix and continues to descend toward the lower punch.
  • the particles of the premix are pressed closer to each other, with the void volume within the filling between the punches decreasing continuously. From a certain position of the upper punch (and thus from a certain pressure on the premix) begins the plastic deformation, in which the particles flow together and it comes to the formation of the molding.
  • the premix particles are also crushed, and even higher pressures cause sintering of the premix.
  • the phase of the elastic deformation is shortened more and more, so that the resulting moldings may have more or less large cavities.
  • the finished molded body is pushed out of the die by the lower punch and carried away by subsequent transport means. At this time, only the weight of the shaped body is finally determined because the compacts due to physical processes (re-expansion, crystallographic effects, cooling, etc.) can change their shape and size.
  • the tableting is carried out in commercial tablet presses, which can be equipped in principle with single or double punches. In the latter case, not only the upper punch is used to build up pressure, and the lower punch moves during the pressing on the upper punch, while the upper punch presses down.
  • eccentric tablet presses are preferably used in which the die or punches are attached to an eccentric disc, which in turn is mounted on an axis at a certain rotational speed. The movement of these punches is comparable to the operation of a conventional four-stroke engine.
  • the compression can be done with a respective upper and lower punch, but it can also be attached more stamp on an eccentric disc, the number of Matrizenbohritch is extended accordingly.
  • the throughputs of eccentric presses vary depending on the type of a few hundred to a maximum of 3000 tablets per hour.
  • rotary tablet presses are selected in which a larger number of dies are arranged in a circle on a so-called die table.
  • the number of matrices varies between 6 and 55 depending on the model, although larger matrices are commercially available.
  • Each die on the die table is assigned an upper and lower punch, in turn, the pressing pressure can be actively built only by the upper or lower punch, but also by both stamp.
  • the die table and the punches move about a common vertical axis, the punches are brought by means of rail-like cam tracks during the circulation in the positions for filling, compression, plastic deformation and ejection.
  • these curved paths are supported by additional low-pressure pieces, Nierderzugschienen and lifting tracks.
  • the filling of the die via a rigidly arranged supply device, the so-called filling shoe, which is connected to a reservoir for the premix.
  • the pressing pressure on the premix is individually adjustable via the compression paths for upper and lower punches, wherein the pressure build-up is done by the Vorbeirollen the stamp shank heads on adjustable pressure rollers.
  • Concentric presses can be provided with two Drik to increase the throughput, with the production of a tablet only a semicircle must be traversed.
  • several filling shoes are arranged one after the other without the slightly pressed-on first layer being ejected before further filling.
  • suitable process control coat and point tablets can be produced in this way, which have a zwiebelschalenartigen structure, wherein in the case of the point tablets, the top of the core or the core layers is not covered and thus remains visible.
  • Even rotary tablet presses can be equipped with single or multiple tools, so that, for example, an outer circle with 50 and an inner circle with 35 holes are used simultaneously for pressing.
  • the throughputs of modern rotary tablet presses amount to over one million moldings per hour.
  • Plastic coatings, plastic inserts or plastic stamps are particularly advantageous.
  • Rotary punches have also proved to be advantageous, wherein, if possible, upper and lower punches should be rotatable. With rotating punches can be dispensed with a plastic insert usually. Here, the stamp surfaces should be electropolished.
  • Tableting machines which are suitable for the purposes of the present invention are obtainable, for example, 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 NV, Halle (BE / LU).
  • the hydraulic double pressure press HPF 630 from LAEIS, D. is particularly suitable.
  • the moldings can be made in a predetermined spatial form and predetermined size.
  • a form of space practically all useful manageable configurations come into consideration, for example, the training as a blackboard, the bar or bar shape, cubes, cuboids and corresponding space elements with flat side surfaces and in particular cylindrical configurations with circular or oval cross-section.
  • This last embodiment covers the presentation form of the tablet up to compact cylinder pieces with a ratio of height to diameter above 1.
  • the portioned compacts can be designed in each case as separate individual elements, which corresponds to the predetermined dosage amount of the washing and / or cleaning agent.
  • the formation of the portioned compacts as tablets, in cylindrical or cuboidal form may be appropriate, with a diameter / height ratio in the range of about 0.5: 2 to 2: 0.5 is preferred.
  • Commercially available hydraulic presses, eccentric presses or rotary presses are suitable devices, in particular for producing such compacts.
  • the spatial form of another embodiment of the moldings is adapted in their dimensions of the dispenser of commercial household washing machines, so that the moldings can be metered without dosing directly into the dispenser, where it dissolves during the dispensing process.
  • a use of the detergent tablets via a dosing is easily possible and preferred in the context of the present invention.
  • Another preferred shaped article that can be made has a plate-like or tabular structure with alternating thick long and thin short segments so that individual segments of this "bar" are broken at the predetermined breaking points that constitute the short thin segments and into the machine can be entered.
  • This principle of the "bar-shaped" shaped body wash can also be realized in other geometric shapes, for example vertical triangles, which are joined together only on one side thereof.
  • the various components are not pressed into a single tablet, but that moldings are obtained which have multiple layers, ie at least two layers. It is also possible that these different layers have different dissolution rates. This can result in advantageous performance properties of the molded body. If, for example, components are contained in the moldings which interact negatively, it is possible to integrate one component in the faster soluble layer and to incorporate the other component into a slower soluble layer, so that the first component has already reacted, when the second goes into solution.
  • the layer structure of the moldings can be carried out both in a staggered manner, wherein a dissolution process of the inner layer (s) takes place at the edges of the molded body already when the outer layers are not completely dissolved, but it can also be a complete coating of the inner layer (s ) through each further outward lying layer (s) are achieved, which leads to a prevention of premature dissolution of components of the inner layer (s).
  • a shaped body consists of at least three layers, ie two outer and at least one inner layer, at least in one of the inner layers containing a peroxy bleach, while the stacked shaped body, the two outer layers and the envelope-shaped body
  • outermost layers are free of peroxy bleach.
  • peroxy bleach and optionally present bleach activators and / or enzymes spatially in a molding from each other.
  • Such multilayer moldings have the advantage that they can be used not only via a dispensing compartment or via a metering device, which is placed in the wash liquor; Rather, it is also possible in such cases, to give the molding in direct contact with the textiles in the machine without stains caused by bleach and the like to be feared.
  • the detergent tablets After pressing, the detergent tablets have a high stability.
  • the breaking strength of cylindrical shaped bodies can be detected by the measurand of the diametric breaking load. This is determinable
  • ⁇ is the diametrical fracture stress (DFS) in Pa
  • P is the force in N which results in the pressure applied to the molded article causing the breakage of the molded article
  • D is the molded article diameter in meters and t the height of the moldings.
  • the surfactant granules were then treated with other components to form compressible premixes whose composition is given in Table 2.
  • the premix E according to the invention contained sodium percarbonate, while the premixes of comparative examples V1 and V2 contained sodium perborate.
  • the premixes were compressed in a Korsch eccentric press into tablets (diameter: 44 mm, height: 22 mm, weight: 37.5 g).
  • the measured values of the tablet hardnesses are in each case the mean values of a double determination, wherein the individual values per form-body type varied by a maximum of 2 N.
  • Table 1 Composition of the surfactant granules [% by weight] granules C 9-13 alkyl benzene sulphonate 11.0 C 12-18 fatty alcohol sulfate 8.0 C 12-18 fatty alcohol with 7 EO 4.0 Soap 1.5 Zeolite X 7.0 sodium tripolyphosphate 48.0 Na-hydroxyethane-1,1-diphosphonate 1.2 Acrylic acid-maleic acid copolymer 3.1 NaOH 0.2 Water, salts rest Composition of premixes [% by weight]: e V1 V2 Surfactant granules (Table 1) 66.0 66.0 66.0 sodium 17.0 - - Sodium perborate tetrahydrate - 17.0 - Sodium perborate monohydrate - - 17.0 TAED 5.0 5.0 5.0 foam inhibitor 2.0 2.0 2.0 enzymes 2.0 2.0 2.0 Repel-O-Tex® SRP 4 * 1.0 1.0 1.0 Perfume 0.5 0.5 0.5 0.5 0.5 Wessalith® P (ze
  • the hardness of the tablets was measured after two days of storage by deformation of the tablet until fracture, with the force acting on the side surfaces of the tablet and determining the maximum force that could withstand the tablet.
  • Table 3 Detergent tablets [physical data] tablet E1 V1 V2 Tablet hardness [N] 39 37 42 lids No No Yes Tablet hardness [N] 52 47 54 lids No Yes Yes Tablet hardness [N] 58 59 65 lids No Yes Yes
  • Table 3 shows that the moldings V1 and V2 tend to lid already at tablet hardness above 40N, while the moldings E according to the invention can be pressed without problems even to hardness of 60 N, without a layered tearing of the moldings occurs.

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Claims (15)

  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 issus des sels sodiques d'acides sulfuriques d'alkyle gras en C12 à C18, 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 du corps moulé.
  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 acides sulfuriques d'alkyle gras en C12 à C18, 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 du corps moulé.
  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 du 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 du corps moulés, la 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 du 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 des sulfates d'alcools gras issu du groupe des sels sodiques d'acides sulfuriques d'alkyle gras en C12 à C18, du 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 contient 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.
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)

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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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EP1159392B2 true 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.

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5002682A (en) † 1983-04-29 1991-03-26 The Procter & Gamble Company Bleach compositions, their manufacture and use in bleach and laundry compositions
GB2276345A (en) † 1993-03-24 1994-09-28 Unilever Plc Process for making shaped articles
EP0711828A2 (fr) † 1994-11-14 1996-05-15 Unilever Plc Compositions détergentes
GB2334528A (en) † 1998-02-21 1999-08-25 Procter & Gamble Hydrogen peroxide releasing detergent composition
EP0975734A1 (fr) † 1997-04-15 2000-02-02 Unilever Plc Compositions detergentes
EP1054946B1 (fr) † 1998-02-10 2004-01-28 Unilever Plc Compositions detergentes sous forme de pastilles

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JPS5070286A (fr) * 1973-10-25 1975-06-11
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
DE19749749A1 (de) * 1997-11-11 1999-05-12 Henkel Kgaa Verfahren zur Herstellung stabiler und schnell zerfallender Waschmittelformkörper
DE19808758A1 (de) * 1998-03-02 1999-09-09 Henkel Kgaa Verfahren zur Herstellung von Wasch- und Reinigungsmittelformkörpern

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5002682A (en) † 1983-04-29 1991-03-26 The Procter & Gamble Company Bleach compositions, their manufacture and use in bleach and laundry compositions
GB2276345A (en) † 1993-03-24 1994-09-28 Unilever Plc Process for making shaped articles
EP0711828A2 (fr) † 1994-11-14 1996-05-15 Unilever Plc Compositions détergentes
EP0975734A1 (fr) † 1997-04-15 2000-02-02 Unilever Plc Compositions detergentes
EP1054946B1 (fr) † 1998-02-10 2004-01-28 Unilever Plc Compositions detergentes sous forme de pastilles
GB2334528A (en) † 1998-02-21 1999-08-25 Procter & Gamble Hydrogen peroxide releasing detergent composition

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EP1159392A1 (fr) 2001-12-05
EP1159392B1 (fr) 2004-06-16
WO2000053717A1 (fr) 2000-09-14
DE19910819A1 (de) 2000-09-14
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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