EP1155111B1 - Procede de production de corps moules de produits de lavage et de nettoyage de degradation rapide - Google Patents

Procede de production de corps moules de produits de lavage et de nettoyage de degradation rapide Download PDF

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Publication number
EP1155111B1
EP1155111B1 EP00916837A EP00916837A EP1155111B1 EP 1155111 B1 EP1155111 B1 EP 1155111B1 EP 00916837 A EP00916837 A EP 00916837A EP 00916837 A EP00916837 A EP 00916837A EP 1155111 B1 EP1155111 B1 EP 1155111B1
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Prior art keywords
weight
acid
surfactant
premixture
process according
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German (de)
English (en)
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EP1155111A2 (fr
Inventor
Andreas Lietzmann
Monika Böcker
Gerhard Blasey
Dieter Jung
Markus Semrau
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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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • C11D17/065—High-density particulate detergent compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • 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

Definitions

  • the present invention relates to a process for the production of moldings, the have washing and cleaning properties.
  • the invention relates a process for the preparation of detergent tablets for textile washing in a household washing machine, briefly referred to as detergent tablets become.
  • EP-A-0 466 484 discloses detergent tablets in which the premix to be compressed has particle sizes between 200 and 1200 ⁇ m, the upper and lower limits of the particle sizes differing by not more than 700 ⁇ m. About the surface treatment of individual ingredients nothing is carried out in this document.
  • EP-A-0 522 766 (Unilever) relates to molded articles of a compacted particulate detergent composition containing surfactants, builders and disintegration aids (for example, cellulose-based) wherein at least a portion of the particles are coated with the disintegrating agent containing both binder and binder also shows disintegration effect when dissolving the moldings in water.
  • This document also points to the general difficulty to produce moldings with adequate stability at the same time good solubility.
  • the particle size in the mixture to be compressed should be above 200 microns, with the upper and lower limits of the individual particle sizes should not differ by more than 700 microns.
  • European Patent Application EP 711 828 claims a process for making laundry detergent tablets by compressing a particulate composition containing a binder.
  • the melting point of the binder should be between 35 and 90 ° C and the compression at temperatures below the melting point, but above 28 ° C. So this font combines a "chemical” with a “physical” approach.
  • the present invention was based on the object, a process for the preparation of detergent tablets to enable molding produce, which are free of the disadvantages mentioned. It should be on simple and highly reproducible way washing and cleaning agent moldings are produced can have a high hardness, but still by a fast Decay rate and also on the Ein Titanauersch of Household washing machines can be used. This should the expert the greatest possible Freedom of choice regarding the composition and selection of presses.
  • the invention relates to a process for the preparation of washing and Detergent tablets by shaping pressing in a conventional manner, in the temperature of the premix to be compressed immediately before pressing below 15 ° C.
  • the to be pressed Premix immediately before tableting has a temperature that significantly is below 15 ° C.
  • Process variants according to the invention therefore become so stated that the premix to be compressed immediately before pressing a Temperature below 13 ° C and in particular below 10 ° C.
  • premixing is also possible at temperatures of 14 ° C or 12 ° C or 11 ° C or 9 ° C or 8 ° C or 7 ° C or 6 ° C or 5 ° C or 4 ° C or 3 ° C or 2 ° C or 1 ° C or 0 ° C, according to the invention possible.
  • Premixes with temperatures below freezing are possible according to the invention.
  • Examples are temperatures of -1 ° C, -2 ° C, -3 ° C, -4 ° C, -5 ° C, -6 ° C, -7 ° C, -8 ° C, -9 ° C, -10 ° C, -11 ° C, -12 ° C, -13 ° C, -14 ° C, -15 ° C, -16 ° C, -17 ° C, -18 ° C, -19 ° C or -20 ° C called, wherein the premix can also have lower temperatures.
  • the preparation of surfactant-containing granules can by usual technical granulation processes such as compaction, extrusion, Mixer granulation, pelleting or fluidized bed granulation done. It is there for the later washing and cleaning product molding advantageous when the to be pressed Premix has a bulk density that comes close to the conventional compact detergent.
  • 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 having.
  • the surfactant-containing granules are sufficient in preferred process variants Molchen relienkriterien.
  • 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 microns, more preferably between 400 and 1600 microns and in particular between 600 and 1400 ⁇ m.
  • the surfactant granules preferably also contain excipients, which particularly preferably originate from the group of builders.
  • Particularly advantageous Processes are characterized in that the premix to be compressed containing surfactant-containing granules which anionic and / or nonionic surfactants and Contains builders and the total surfactant content of 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 surfactant granules contain surface-active substances from the group of anionic, nonionic, zwitterionic or cationic Surfactants, where anionic surfactants for economic reasons and because of their Power spectrum are clearly preferred.
  • anionic surfactants for example, those of the sulfonate type and sulfates are used.
  • the surfactants of the sulfonate type are preferably C 9-13 -alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as are obtained, for example, from C 12-18 -monoolefins having terminal or internal double bonds by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation products into consideration.
  • alkanesulfonates which are obtained from C 12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • esters of ⁇ -sulfo fatty acids for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids are suitable.
  • anionic surfactants are sulfated fatty acid glycerol esters.
  • 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.
  • Alk (en) ylsulfates are the alkali metal salts and in particular the sodium salts of the sulfuric monoesters of C 12 -C 18 fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -C 20 oxo alcohols and those half-esters of secondary alcohols of these chain lengths are preferred. Also preferred are alk (en) ylsulfates of said chain length, which contain a synthetic, produced on a petrochemical basis straight-chain alkyl radical, which have an analogous degradation behavior as the adequate compounds based on oleochemical raw materials.
  • C 12 -C 16 alkyl sulfates and C 12 -C 15 alkyl sulfates and C 14 -C 15 alkyl sulfates are preferred.
  • 2,3-alkyl sulfates prepared, for example, according to U.S. Patents 3,234,258 or 5,075,041, which 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 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, soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids.
  • 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.
  • washing and cleaning agent tablets are used preferably, the 5 to 50 wt .-%, preferably 7.5 to 40 wt .-% and in particular 10 to 20 wt .-% anionic surfactant (s), in each case based on the molding body weight.
  • anionic surfactants used in the detergent tablets according to the invention When selecting the anionic surfactants used in the detergent tablets according to the invention are used, the freedom of formulation are none to be observed in the way.
  • Preferred detergent tablets However, they have a soap content of 0.2% by weight, based on the total weight of the molding, exceeds.
  • anionic surfactants are the alkylbenzenesulfonates and fatty alcohol sulfates, with preferred washing and Detergent tablets 2 to 20 wt .-%, preferably 2.5 to 15 wt .-% and in particular From 5 to 10% by weight of fatty alcohol sulphate (e), in each case based on the molding weight, contain.
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten.
  • 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 Japanese Patent Application JP 58/217598 , or which are preferably prepared according to the method described in International Patent Application WO-A-90/13533 .
  • 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 ie 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 can preferably alkylpolyglycosides contained, wherein contents of the moldings to APG over 0.2 wt .-%, based on the entire molding, are preferred.
  • Particularly preferred washing and 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-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamide may be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of ethoxylated fatty alcohols, in particular not more than half of it.
  • polyhydroxy fatty acid amides of the formula (I) wherein RCO is an aliphatic acyl group having 6 to 22 carbon atoms, R 1 is hydrogen, an alkyl or hydroxyalkyl group having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl group having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
  • the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
  • the group of polyhydroxy fatty acid amides also includes compounds of the formula (II) in the R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R 1 is a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R 2 is a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, with C 1-4 alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated Derivatives of this residue.
  • R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
  • R 1 is a linear, branched or cyclic alkyl radical or an aryl radical
  • [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 converted into the desired polyhydroxy fatty acid amides, for example according to the teaching of the international application WO-A-95/07331, by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
  • the nonionic and anionic surfactants can over the different ways in the detergent tablets according to the invention be incorporated.
  • washing and cleaning agent tablets are used preferably containing the surfactants in the form of a surfactant-containing granules, that in amounts of 40 to 95 wt .-%, preferably from 45 to 85 wt .-% and in particular from 55 to 75 wt .-%, each based on the molding weight, in the moldings is included.
  • washing and cleaning agent shaped bodies in which the content of the surfactant granules of anionic surfactants From 5 to 45% by weight, 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 surfactant granules
  • washing and cleaning agent tablets in which the content of surfactant granules of nonionic surfactants From 1 to 30% by weight, preferably from 5 to 25% by weight and in particular from 7.5 to 20% by weight, in each case based on the weight of the surfactant granules, are preferred according to the invention.
  • the surfactant granules So contain builders.
  • Other ingredients of detergents and cleaners, especially so-called small components such as optical brighteners, polymers, Defoamers, phosphonates, dyes and fragrances can form part of the surfactant granules be. These substances are described below.
  • the surfactant granules with further Ingredients of detergents and cleaners to a compressible premix mixed and then tabletted.
  • the production of Detergent tablets preferred so that preferred variants of the method according to the invention characterized in that the proportion of surfactant-containing granules on pressing premix and thus to the washing and cleaning agent moldings 40th to 95 wt .-%, preferably 45 to 85 wt .-% and in particular 55 to 75 wt .-%, respectively based on the weight of the detergent tablets.
  • washing and cleaning agent moldings can all usually in washing and Be used detergents used, in particular zeolites, Silicates, carbonates, organic cobuilders and - where no ecological prejudices against their use - even the phosphates.
  • 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.
  • 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.
  • 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 European Patent Application EP-A-0 164 514 .
  • 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, whereby ⁇ -sodium disilicate can be obtained, for example, by the process described in international patent application WO-A-91/08171 .
  • amorphous sodium silicates with a Na 2 O: SiO 2 modulus of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which Delayed and have secondary washing properties.
  • 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.
  • the term "amorphous” is also understood to mean "X-ray amorphous”.
  • 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 to the conventional water glasses, are described, for example, in German patent application DE-A-44 00 024 .
  • Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates.
  • the amount usually introduced by the surfactant granules may be used of zeolite of the P and / or X type further zeolite incorporated in the premix be added by adding zeolite as a treatment component.
  • the used fine crystalline, synthetic and bound water-containing zeolite is preferred a zeolite of the type A, P, X or Y.
  • zeolite X and mixtures are also suitable from A, X and / or P.
  • Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution, measuring method: Coulter Counter) on and contain preferably 18 to 22 wt .-%, in particular 20 to 22 wt .-% of bound water.
  • phosphates as builders possible, unless such use is avoided for environmental reasons should be.
  • Particularly suitable are the sodium salts of orthophosphates, pyrophosphates and in particular the tripolyphosphates.
  • organic cobuilders can 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, wherein among polycarboxylic acids such carboxylic acids 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 environmental 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 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.
  • Further suitable builders are 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 mass of 2000 to 20,000 g / mol. Because of their superior solubility, this can be Group again the short-chain polyacrylates, the molar masses from 2000 to 10000 g / mol, and more preferably from 3000 to 5000 g / mol, are preferred be.
  • copolymeric polycarboxylates in particular those of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid.
  • copolymeric polycarboxylates in particular those of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid.
  • Your molecular weight, based on free acids, is generally from 2000 to 70000 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 be used either as a powder or as an aqueous solution be used.
  • the content of the (co) polymeric polycarboxylates is preferably 0.5 to 20 wt .-%, in particular 3 to 10 wt .-%.
  • the polymers may also be allyl sulfonic acids, such as For example, allyloxybenzenesulfonic acid and methallylsulfonic acid, as a monomer.
  • biodegradable polymers of more than two different Monomer units for example those containing as monomers salts of acrylic acid and the maleic acid and vinyl alcohol or vinyl alcohol derivatives or as Monomeric salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives contain.
  • copolymers are those which are described in the German patent applications DE-A-43 03 320 and DE-A-44 17 734 and preferably have as monomers 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 German Patent Application DE-A-195 40 086 discloses that they also have a bleach-stabilizing effect in addition to cobuilder properties.
  • polyacetals which are prepared by reaction of dialdehydes with polyol carboxylic acids having 5 to 7 C 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 Polyolcarboxylic acids such as gluconic acid and / or glucoheptonic acid.
  • dextrins for example oligomers or polymers of carbohydrates obtained by partial hydrolysis of starches can be.
  • the hydrolysis can be carried out by conventional, for example acid or enzyme catalyzed Procedures are performed.
  • they are hydrolysis products with average molecular weights in the range of 400 to 500,000 g / mol.
  • This is a polysaccharide with a dextrose equivalent (DE) in the range of 0.5 to 40, in particular from 2 to 30, where DE is a common measure of the reducing effect of a polysaccharide compared to dextrose which has a DE of 100.
  • DE dextrose equivalent
  • Useful are both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and White dextrins with higher molecular weights in the range from 2000 to 30,000 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 described, for example, in 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 the German patent application DE-A-196 00 018.
  • a product oxidized to C 6 of the saccharide ring may be particularly advantageous
  • oxydisuccinates and other derivatives of disuccinates are other suitable cobuilders.
  • This is ethylenediamine-N, N'-disuccinate (EDDS) preferably used in the form of its sodium or magnesium salts.
  • EDDS ethylenediamine-N, N'-disuccinate
  • glycerol disuccinates and glycerol trisuccinates are also preferred. Suitable amounts are 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 International Patent Application WO 95/20029 .
  • phosphonates are in particular hydroxyalkane or aminoalkanephosphonates.
  • HEDP 1-hydroxyethane-1,1-diphosphonate
  • It is preferably used as the sodium salt, wherein the disodium salt neutral and the tetrasodium salt alkaline (pH 9).
  • Aminoalkane phosphonates are preferably ethylenediamine tetramethylene phosphonate (EDTMP), Diethylentriaminpentamethylenphosphonat (DTPMP) and their higher homologues in question. They are preferably in the form of neutral sodium salts, z.
  • the builder used here is preferably HEDP from the class of phosphonates.
  • the aminoalkanephosphonates also have a pronounced heavy metal binding capacity. Accordingly, especially if the agents also contain bleach, be preferred to use Aminoalkanphosphonate, in particular DTPMP, or Use mixtures of the above phosphonates.
  • the surfactant-containing granules not by spray drying, but by a granulation process will be produced.
  • a granulation process which are carried out in a wide variety of mixed granulators and mixed agglomerators can be used, for example, also Preßagglomerationsvon be used.
  • Method in which the surfactant-containing granules by granulation, agglomeration, press agglomeration or a combination of these methods are therefore preferred.
  • the granulation can be used in a variety of in the detergent industry usually used apparatus are carried out. For example, it is possible to use the common in pharmacy Verrunder. In such turntable apparatus 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 be both high-intensity mixer (“high-shear mixer”) and normal Mixer can be used with lower rotational speeds.
  • high-shear mixer high-intensity mixer
  • normal Mixer normal Mixer can be used with lower rotational speeds.
  • Suitable mixers For example, Eirich® mixers of the R or RV series (trademarks of Maschinenfabrik Gustav Eirich, Hardheim), the Schugi® Flexomix, the Fukae® FS-G mixers (trademark 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 residence times The granules in the mixers are in the range of less than 60 seconds, with the Dwell also depends on the rotational speed of the mixer. Shorten it The residence times corresponding to, the faster the mixer is running.
  • the amount Residence times of the granules in the mixer / rounder under one minute preferably below 15 seconds.
  • slow speed mixers e.g. a Lödige KM
  • residence times set up to 20 minutes, with retention times under 10 minutes due to the Process economics are preferred.
  • the surfactant-containing granules under pressure and compacted under the action of shear forces and thereby homogenized and then shaping out of the apparatus.
  • the most technically significant pressing agglomeration processes are extrusion, roll compacting, pelleting and tableting.
  • preference is given to the preparation of the surfactant-containing Granules used Preßagglomerations vide are the extrusion, the roll compaction and pelleting.
  • excipients are understood to mean excipients which are suitable for rapid disintegration of tablets in water or gastric juice and for the release of the drugs in resorbable form.
  • Preferred washing and cleaning agent tablets contain from 0.5 to 10% by weight, preferably 3 to 7 wt .-% and in particular 4 to 6 wt .-% of one or more disintegration aids, in each case based on the molding body weight.
  • Preferred disintegrating agents in the context of the present invention are cellulose-based disintegrating agents, so that preferred washing and cleaning agent tablets contain such cellulose-based disintegrating agents in amounts of from 0.5 to 10% by weight, preferably from 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 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 bonded via 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
  • 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 agent tablets containing disintegrators in granular or optionally 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 WO 98/40463 (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. This microcrystalline cellulose is obtained by partial hydrolysis of celluloses under conditions which only attack the amorphous areas (about 30% of the total cellulose mass) of the celluloses and completely dissolve, leaving the crystalline areas (about 70%) undamaged. A subsequent deaggregation of the microfine celluloses resulting from the hydrolysis provides the microcrystalline celluloses having primary particle sizes of about 5 microns and, for example, compactable into granules with an average particle size of 200 microns are.
  • the pressing premix additionally a disintegration aid, preferably a Cellulosic disintegration aids, preferably granular, co-granulated or compacted form, in amounts of from 0.5 to 10% by weight, preferably from 3 to 7 Wt .-% and in particular from 4 to 6 wt .-%, each based on the weight of the premix, contains.
  • a disintegration aid preferably a Cellulosic disintegration aids, preferably granular, co-granulated or compacted form, in amounts of from 0.5 to 10% by weight, preferably from 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 bleaching agents, bleach activators, enzymes, pH adjusters, fragrances, Perfume carriers, fluorescers, dyes, foam inhibitors, silicone oils, anti redeposition agents, optical brighteners, grayness inhibitors, color transfer inhibitors and corrosion inhibitors. These substances are described below.
  • sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • Other useful bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid. Even when using the bleaching agents, it is possible to dispense with the use of surfactants and / or builders, so that pure bleach tablets can be produced.
  • bleach tablets are to be used for textile washing, a combination of sodium percarbonate with sodium sesquicarbonate is preferred, regardless of which other ingredients are contained in the tablets.
  • bleaching agents from the group of organic bleaching agents.
  • Typical organic bleaches are the diacyl peroxides such as dibenzoyl peroxide.
  • Other typical organic bleaches are the peroxyacids, examples of which include the alkyl peroxyacids and the aryl peroxyacids.
  • Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy- ⁇ -naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ⁇ -phthalimidoperoxycaproic acid [Phthaloiminoperoxyhexanoic acid (PAP )], o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperoxysebacic acid, diperoxybrassic acid, the diperoxyphthalic acids, 2-decy
  • Bromine releasing substances are used.
  • suitable chlorine or bromine releasing materials include, for example, heterocyclic N-bromo- and N-chloroamides, for example, trichloroisocyanuric acid, tribromoisocyanuric acid, Dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or salts thereof with Cations such as potassium and sodium into consideration.
  • Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydanthoin are also suitable.
  • bleach activators can be incorporated into the premix become.
  • compounds which are under perhydrolysis conditions aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 carbon atoms, and / or optionally substituted perbenzoic acid, be used.
  • Suitable substances are the O- and / or N-acyl groups of the mentioned C atom number and / or optionally substituted benzoyl groups.
  • TAED te
  • bleach catalysts are incorporated into the moldings.
  • 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 as well as Co, Fe, Cu and Ru ammine complexes are used as bleach catalysts usable.
  • Enzymes are those from the class of proteases, lipases, amylases, cellulases or mixtures thereof in question. Particularly suitable are from bacterial strains or Fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus enzymatic agents. Preferably, subtilisin-type proteases and in particular Proteases derived from Bacillus lentus.
  • enzyme mixtures for example from protease and amylase or protease and lipase or Protease and cellulase or cellulase and lipase or protease, amylase and lipase or protease, lipase and cellulase, but especially cellulase-containing mixtures of special interest. Peroxidases or oxidases have also been found in some Cases proved to be suitable.
  • the enzymes can be adsorbed to carriers and / or embedded in encapsulants to protect against premature decomposition.
  • Proportion of enzymes enzyme mixtures or enzyme granules in the inventive Moldings may, for example, about 0.1 to 5 wt .-%, preferably 0.1 to about 2 Wt .-% amount.
  • the detergent tablets may also contain components which have a positive effect on the oil and grease wash-out properties of textiles (so-called soil repellents). This effect is particularly evident when a textile is dirty is already several times before with a detergent according to the invention, this oil and fat dissolving component, was washed.
  • nonionic cellulose ethers such as methyl cellulose and methylhydroxypropylcellulose with a proportion of methoxyl groups of 15 to 30 wt .-% and of hydroxypropoxyl groups from 1 to 15 wt .-%, each based to the nonionic cellulose ether, as well as those 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 of these. Especially preferred of these are the sulfonated derivatives of phthalic and terephthalic acid polymers.
  • the moldings can be used as optical brighteners derivatives of Diaminostilbendisulfonklare 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, are a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group.
  • brighteners of the substituted diphenylstyrene type may be present, e.g.
  • Dyes and fragrances are the washing and starsmittelformkörpem invention added to improve the aesthetic appeal of the products and to the consumer in addition to the washing and cleaning performance a visual and sensory "typical and unmistakable "product as perfume oils or fragrances
  • individual perfume compounds e.g. the synthetic products of the type Esters, ethers, aldehydes, ketones, alcohols and hydrocarbons are used. Fragrance compounds of the ester type are known e.g.
  • the ethers include Benzyl ethyl ether, to the aldehydes e.g.
  • the linear alkanals with 8-18 carbon atoms citral, Citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and Bourgeonal, to the ketones e.g. the ionone, ⁇ -isomethylionone and methyl cedryl ketone, to the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons mainly include the terpenes such as limonene and pinas. However, preference is given to using mixtures of different fragrances, which together create an appealing scent.
  • perfume oils can also contain natural fragrance mixtures, as available from plant sources, e.g. Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil.
  • the content of the detergent tablets according to the invention is Dyes below 0.01 wt .-%, while perfumes up to 2 wt .-% of the total Formulation can make.
  • the fragrances can be incorporated directly into the compositions according to the invention but it may also be advantageous to apply the fragrances on carriers, which the adhesion of the Enhance perfumes on the lingerie and through a slower fragrance release for long-lasting Fragrance of the textiles provide.
  • carrier materials for example Cyclodextrins proven, the cyclodextrin-perfume complexes additionally with other excipients can be coated.
  • the detergent tablets according to the invention can be colored with suitable dyes.
  • suitable dyes preferred Dyes, the selection of which the expert has no difficulty, own a high storage stability and insensitivity to the other ingredients of the Medium and against light and no pronounced substantivity to textile fibers, um do not stain them.
  • the premix may contain finely divided surface treatment agents be "powdered". This may be for the texture and physical properties both the premix (storage, compression) and the finished detergent tablets be beneficial.
  • Fine particulate powdering agents are in the state of Technique well known, with mostly zeolites, silicates or other inorganic salts used become.
  • the premix is preferred with finely divided zeolite "powdered", wherein faujasite-type zeolites are preferred.
  • the term "faujasite-type zeolite” denotes all three zeolites form the faujasite subgroup of zeolite structure group 4 (cf. Donald W.
  • the or one of the admixed conditioning components a faujasite-type zeolite with particle sizes below 100 ⁇ m, preferably below 10 ⁇ m and especially below 5 ⁇ m and at least 0.2 Wt .-%, preferably at least 0.5 wt .-% and in particular more than 1 wt .-% of to be compressed premix makes up.
  • the production of the shaped body according to the invention is initially carried out by the dry Mixing the ingredients, which may be pre-granulated in whole or in part, and subsequent Informing, in particular compression to tablets, wherein conventional Method can be used.
  • Shaped body is the premix in a so-called template between two punches condensed into a fixed comprimat. This process, hereinafter briefly referred to as tableting is divided into four sections: dosage, 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 molded body by the position of the lower Stamp and the shape of the press tool can be determined.
  • the constant dosage even at high molding throughputs is preferably a volumetric Dosing of the premix achieved.
  • the premix will also crush a portion of the premix particles and at even higher pressures sintering of the premix occurs. at increasing press speed, so high throughputs, the phase of the elastic Deformation further and further shortened, so that the resulting moldings more or may have less large cavities.
  • the finished moldings pushed out through the lower die from the die and through subsequent transport facilities carried away. At this time, only the Weight of the molded article finally determined because the compacts due to physical Processes (re-stretching, crystallographic effects, cooling, etc.) their shape and size can still change.
  • the tabletting is carried out in commercially available tablet presses, which are in principle or double stamping. In the latter case, not only the upper punch used for pressure build-up, also the lower punch moves during the Pressing on the upper punch, while the upper punch presses down.
  • the one or more stamps are attached to an eccentric disc, which in turn to a Axis is mounted at a certain rotational speed.
  • the movement of this Preßstempel is similar to the operation of a conventional four-stroke engine.
  • the compression can be done with a top and bottom stamp, but it can also be several Stamp be attached to an eccentric disc, the number of die holes is extended accordingly.
  • the throughputs of eccentric presses vary according to type from a few hundred to a maximum of 3000 tablets per hour.
  • rotary tablet presses where on a so-called Matrizentisch a larger number of matrices is arranged in a circle.
  • the Number of matrices varies depending on the model between 6 and 55, with larger matrices are commercially available.
  • Each die on the die table is a top and bottom stamp assigned, in turn, the pressing pressure active only by the upper or lower punch, but can also be built by both stamps.
  • the die table and the Stamps move around a common perpendicular axis, with the stamp by means of rail-like cam tracks during circulation in the positions for filling, Compression, plastic deformation and ejection are brought.
  • these curved paths are supplemented by Low pressure pieces, Nierderzugschienen and Aushebebahnen supported.
  • the filling the die is made via a rigidly arranged supply device, the so-called Fill shoe connected to a pre-mix reservoir.
  • the pressing pressure the pre-mix can be individually adjusted via the pressing paths for upper and lower punches, wherein the pressure build-up by the rolling forward of the punch shaft heads on adjustable Pressure rollers happens.
  • Concentric presses can also be equipped with two filling shoes to increase throughput be, with the preparation of a tablet only a semicircle are passed through got to.
  • several filling shoes are used arranged one behind the other without the slightly pressed first layer before further filling is ejected.
  • suitable process control are in this way also shell and point tablets produced, which have a onion-bowl-like 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.
  • Rotary tablet presses are also available 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.
  • Even rotating stamps have proven to be beneficial proven, where possible upper and lower punch be made rotatable should. With rotating punches can be dispensed with a plastic insert usually become. Here, the stamp surfaces should be electropolished.
  • Tableting machines suitable for the purposes of the present invention are, for example available from Apparatebau Holzwarth GbR, Asperg, Wilhelm Fette GmbH, Schwarzenbek, Hofer GmbH, Weil, KILIAN, Cologne, KOMAGE, Kell am See, KORSCH Pressen GmbH, Berlin, Mapag Maschinenbau AG, Berne (CH) and Courtoy N.V., Halle (BE / LU).
  • the hydraulic double pressure press HPF is particularly suitable 630 of the company LAEIS, D.
  • the moldings can be made in a predetermined spatial form and predetermined size become.
  • a form of space come practically all useful manageable configurations considered, for example, the training as a blackboard, the bar or bar form, Cube, cuboid and corresponding room elements with flat side surfaces as well in particular cylindrical configurations with a circular or oval cross-section.
  • This last embodiment detects the presentation form of the tablet to compact cylinder pieces with a ratio of height to diameter above 1.
  • the portioned compacts can each as separate individual elements be formed, the predetermined dosage of the detergent and / or detergent equivalent. However, it is also possible to form compacts, a plurality connect such mass units in a compact, in particular by predetermined Predetermined breaking points the easy separability of portioned smaller units provided is.
  • the formation of the portioned compacts as Tablets to be useful in cylindrical or cuboidal shape, with a diameter / height ratio in the range of about 0.5: 2 to 2: 0.5 is preferred.
  • Commercial hydraulic presses, Eccentric or rotary presses are suitable devices in particular for producing such compacts.
  • the spatial form of another embodiment of the moldings is in their dimensions the Ein Honeycomb adapted from commercial household washing machines, so that the Moldings can be metered without dosing directly into the dispenser, where it dissolves during the flushing process.
  • the detergent molding via a dosing easily possible and in the context of present invention.
  • Another preferred molded article which can be produced has a plate or panel-like structure with alternately thick long and thin short segments, so that individual segments of this "bar" at the predetermined breaking points, which are the short thin ones Segments, aborted and entered into the machine.
  • This Principle of the "bar-shaped" molding detergent can also be used in other geometric Shapes, such as vertical triangles, only on one side alongside each other, be realized.
  • the various components are not uniform Tablet are pressed, but that moldings are obtained, the several layers, So at least two layers. It is also possible that these different Layers have different dissolution rates. From this you can advantageous performance properties of the molded articles result. For example Components contained in the moldings are mutually negative it is possible to influence the one component in the faster soluble layer integrate and 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 either in a stack, wherein a solution process the inner layer (s) already takes place at the edges of the shaped body, if the outer layers are not yet completely dissolved, but it can also be a complete encasement of the inner layer (s) by the further outer layer (s) Layer (s) are achieved, resulting in a prevention of premature solution of components the inner layer (s) leads.
  • a shaped body is made at least three layers, so two outer and at least one inner layer, wherein at least one of the inner layers contains a peroxy bleach while in the stack-shaped molded body, the two outer layers and the shell-shaped Shaped body, however, the outermost layers are free from peroxy bleach.
  • peroxy bleach and any bleach activators present and / or to spatially separate enzymes in a molding are also possible.
  • Such multilayer molded bodies have the advantage that they not only have a Ein Titanauersch or via a metering device, which is added to the wash liquor, can be used; Rather, it is also possible in such skins, the molding in the to give direct contact to the textiles in the machine, without any stains Bleaching agents and the like would be feared.
  • the bodies to be coated can be used, for example aqueous solutions or emulsions, or via the process of Schmelzbesehichtung receive a coating.
  • the detergent tablets After pressing, the detergent tablets have a high stability.
  • ⁇ stands for the diametrical fracture stress (DFS) in Pa
  • P is the force in N that leads to the pressure exerted on the molding that breaks it
  • D is the shape diameter in meters
  • t is the height of the molding Moldings.
  • Another object of the present invention is the use of cooled Premixes with temperatures below 15 ° C for the production of detergents and cleaners supply medium molded bodies.
  • This use according to the invention of the cooled premixes leads to moldings with advantageous properties, such as the examples below demonstrate.
  • preferred embodiments of the use according to the invention (lower temperatures, composition of the premix, etc.) is analogous to the above What has been said for the method according to the invention.
  • the surfactant granules were then treated with further components to form a compressible premix, the composition of which is given in Table 2.
  • the compressible premix was cut in half and each half packed airtight.
  • the two subsets of the premix were stored for 18 h at different temperatures (according to the invention: 9 ° C, Comparative Example: room temperature, 22 ° C) and then unpacked and in a Korsch eccentric press to tablets (diameter: 44 mm, height: 22 mm, weight : 37.5 g) pressed.
  • the measured values of the tablet hardness and decay times are in each case the mean values of a double determination, the individual values for each type of molded article varying by a maximum of 2 N or 2 s.
  • Table 2 which shows the composition of the premixes, also indicates the temperature of the respective premix immediately before the pressing operation.
  • Composition of the surfactant granules [% by weight] C 9-13 alkyl benzene sulphonate 19.4 C 12-18 fatty alcohol sulfate 5.2 C 12-18 fatty alcohol with 7 EO 4.8 Soap 1.6 C 12-16 fatty alcohol 1,4-glucoside 1.0 sodium 17.0 Zeolite A 28.5 sodium silicate 5.6 Na-hydroxyethane-1,1-diphosphonate 0.8 Acrylic acid-maleic acid copolymer 5.6 optical brightener 0.3 Water, salts rest Composition of premixes [% by weight]: e V Surfactant granules (Table 1) 62.9 62.9 sodium 17.0 17.0 TAED 7.3 7.3 foam inhibitor 3.5 3.5 enzymes 1.7 1.7 Repel-O-Tex® SRP 4 1.1 1.1 Perfume 0.5 0.5 Wessalith® P (zeolite A) 1.0
  • the hardness of the tablets was after preparation by deformation of the tablet until measured to break, with the force acting on the side surfaces of the tablet and the maximum strength that withstood the tablet was detected.
  • Table 3 shows that the disintegration times of detergent tablets by the procedure according to the invention can be significantly reduced, which is especially true in higher hardness results in significant improvements.

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Claims (11)

  1. Procédé de production de corps moulés de produits de lavage et de nettoyage par pressage pour leur donner une forme, de façon connue, caractérisé en ce que le prémélange à presser présente immédiatement avant le pressage une température inférieure à 15 °C.
  2. Procédé selon la revendication 1, caractérisé en ce que le prémélange à presser présente immédiatement avant le pressage une température inférieure à 13 °C et en particulier inférieure à 10 °C.
  3. Procédé selon l'une des revendications 1 ou 2, caractérisé en ce que le prémélange à presser contient un ou plusieurs granulés incluant un ou des agents tensioactifs ainsi que d'autres composants de préparation.
  4. Procédé selon la revendication 3, caractérisé en ce que le prémélange à presser contient un granulé incluant un ou des agents tensioactifs, qui contient des agents tensioactifs anioniques et/ou non ioniques ainsi que des builders et dont la teneur totale en agent tensioactif est de 5 à 60 % en poids, de préférence de 10 à 50 % en poids et en particulier de 15 à 40 % en poids, toujours par rapport au granulé tensioactif.
  5. Procédé selon l'une des revendications 3 ou 4, caractérisé en ce que le granulé incluant un ou des agents tensioactifs présente des tailles particulaires comprises entre 100 et 2000 µm, de préférence entre 200 et 1800 µm, de façon particulièrement préférée entre 400 et 1600 µm et en particulier entre 600 et 1400 µm.
  6. Procédé selon l'une des revendications 3 à 5, caractérisé en ce que la proportion du granulé incluant un ou des agents tensioactifs par rapport aux 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, toujours par rapport au poids des corps moulés de produits de lavage et de nettoyage.
  7. Procédé selon l'une des revendications 1 à 6, caractérisé en ce que le prémélange à presser présente une densité apparente d'au moins 500 g/l, de préférence d'au moins 600 g/l et en particulier supérieure à 700 g/l.
  8. Procédé selon l'une des revendications 1 à 7, caractérisé en ce que le prémélange à presser contient en outre un adjuvant de désintégration, de préférence un adjuvant de désintégration à base de cellulose, de préférence sous une forme granulaire, cogranulée 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, toujours par rapport au poids du prémélange.
  9. Procédé selon l'une des revendications 3 à 8, caractérisé en ce que le ou l'un des composant(s) de préparation ajouté(s) au mélange est une zéolithe de type faujasite avec des tailles particulaires inférieures à 100 µm, de préférence inférieures à 10 µm et en particulier inférieures à 5 µm et représente au moins 0,2 % en poids, de préférence au moins 0,5 % en poids et en particulier plus de 1 % en poids du prémélange à presser.
  10. Procédé selon l'une des revendications 1 à 9, caractérisé en ce que le prémélange à presser contient en outre une ou plusieurs substances du groupe des produits de blanchiment, des activateurs de blanchiment, des enzymes, des régulateurs de pH, des parfums, des supports de parfums, des agents de fluorescence, des colorants, des antimousses, des huiles de silicones, des agents antiredépôt, des azurants optiques, des inhibiteurs de grisaillement, des inhibiteurs de transfert de colorants et des inhibiteurs de corrosion.
  11. Utilisation de prémélanges refroidis présentant des températures inférieures à 15 °C pour la production de corps moulés de produits de lavage et de nettoyage.
EP00916837A 1999-02-25 2000-02-16 Procede de production de corps moules de produits de lavage et de nettoyage de degradation rapide Expired - Lifetime EP1155111B1 (fr)

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DE19908025A DE19908025A1 (de) 1999-02-25 1999-02-25 Verfahren zur Herstellung schnell zerfallender Wasch- und Reinigungsmittelformkörper
DE19908025 1999-02-25
PCT/EP2000/001241 WO2000050548A2 (fr) 1999-02-25 2000-02-16 Procede de production de corps moules de produits de lavage et de nettoyage de degradation rapide

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EP1155111B1 true EP1155111B1 (fr) 2005-10-05

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EP00916837A Expired - Lifetime EP1155111B1 (fr) 1999-02-25 2000-02-16 Procede de production de corps moules de produits de lavage et de nettoyage de degradation rapide

Country Status (7)

Country Link
EP (1) EP1155111B1 (fr)
AT (1) ATE305963T1 (fr)
AU (1) AU3804400A (fr)
CA (1) CA2300017A1 (fr)
DE (2) DE19908025A1 (fr)
ES (1) ES2249255T3 (fr)
WO (1) WO2000050548A2 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2177212T3 (es) † 1999-03-05 2002-12-01 Procter & Gamble Procedimiento de produccion para comprimidos de detergente.
CN107177429A (zh) * 2016-03-11 2017-09-19 华北制药秦皇岛有限公司 一种便于携带、使用方便的洗衣片及其制备工艺

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19709411A1 (de) * 1997-03-07 1998-09-10 Henkel Kgaa Waschmittelformkörper
GB9707614D0 (en) * 1997-04-15 1997-06-04 Unilever Plc Detergent compositions

Also Published As

Publication number Publication date
ATE305963T1 (de) 2005-10-15
ES2249255T3 (es) 2006-04-01
WO2000050548A2 (fr) 2000-08-31
AU3804400A (en) 2000-09-14
CA2300017A1 (fr) 2000-08-25
EP1155111A2 (fr) 2001-11-21
WO2000050548A3 (fr) 2000-12-21
DE19908025A1 (de) 2000-08-31
DE50011294D1 (de) 2006-02-16

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