EP2386632A1 - Produit de nettoyage ou de lavage avec une amylase spéciale - Google Patents

Produit de nettoyage ou de lavage avec une amylase spéciale Download PDF

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Publication number
EP2386632A1
EP2386632A1 EP11175303A EP11175303A EP2386632A1 EP 2386632 A1 EP2386632 A1 EP 2386632A1 EP 11175303 A EP11175303 A EP 11175303A EP 11175303 A EP11175303 A EP 11175303A EP 2386632 A1 EP2386632 A1 EP 2386632A1
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Prior art keywords
amylase
weight
acid
protease
detergents
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EP11175303A
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German (de)
English (en)
Inventor
Cornelius Bessler
Arnd Kessler
Damien Drillon
Karl-Heinz Maurer
Susanne Wieland
Beatrix Kottwitz
Ingo Hardacker
Christian Nitsch
Johannes Zipfel
Maren Jekel
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Priority claimed from DE200510062984 external-priority patent/DE102005062984A1/de
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP2386632A1 publication Critical patent/EP2386632A1/fr
Withdrawn legal-status Critical Current

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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
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase

Definitions

  • the present invention relates to detergents having a specific ⁇ -amylase characterized by characteristic sequence variations, as well as corresponding washing or cleaning methods and uses.
  • ⁇ -Amylases (E.C. 3.2.1.1) hydrolyze internal ⁇ -1,4-glycosidic bonds of starch and starch-like polymers. Because washing or cleaning agents predominantly have alkaline pH values, ⁇ -amylases which are active in the alkaline medium are used in particular for this purpose. Such are produced and secreted by microorganisms, ie fungi or bacteria, especially those of the genera Aspergillus and Bacillus. Starting from these natural enzymes, there is now an almost unmanageable abundance of variants that have been derived by mutagenesis and have specific advantages depending on the area of application.
  • ⁇ -amylases from Bacillus licheniformis, from B. amyloliquefaciens and from B. stearothermophilus, as well as their further developments improved for use in detergents or cleaners.
  • the enzyme from B. licheniformis is available from Novozymes under the name Termamyl ® and from Genencor under the name Purastar® ® ST.
  • Development products of this ⁇ -amylase are available from Novozymes under the trade names Duramyl ® and Termamyl ® ultra, from Genencor under the name Purastar® ® OxAm and from Daiwa Seiko Inc., Tokyo, Japan, as Keistase ®.
  • amyloliquefaciens is marketed by Novozymes under the name BAN ®, and variants derived from the ⁇ -amylase from B. stearothermophilus under the names BSG ® and Novamyl ®, likewise from Novozymes.
  • ⁇ -amylases from other organisms are further developments available under the trade names Fungamyl.RTM ® by Novozymes of ⁇ -amylase from Aspergillus niger and A. oryzae.
  • Fungamyl.RTM ® Novozymes of ⁇ -amylase from Aspergillus niger and A. oryzae.
  • Another commercial product is, for example, the amylase LT® .
  • An ⁇ -amylase from the alkaliphilic Bacillus sp. KSM-AP1378 (FERM BP-3048) is mentioned in the applications EP 670367 A1 and WO 97/00324 A1 disclosed by the Fa. Kao. It has the characteristic amino acid sequence motif NGTM (M) QYFEW near the N-terminus.
  • EP 985731 A1 go through point mutagenesis obtained variants of this alkaline ⁇ -amylase, which are also described for use in detergents or cleaners.
  • WO 96/23873 A1 The prior art also includes the three patent applications WO 96/23873 A1 .
  • WO 00/60060 A2 and WO 01/66712 A2 which have been registered by the company Novozymes.
  • WO 96/23873 A1 describes in part several different point mutations in a total of more than 30 different positions in four different wild-type amylases and claims those for all amylases with at least 80% identity to one of these four; they are said to have altered enzymatic properties in terms of thermal stability, oxidation stability and calcium dependence.
  • the registration WO 00/60060 A2 also names a variety of possible amino acid changes in 10 different positions on the ⁇ -amylases from two different microorganisms and claims those for all amylases with a homology of at least 96% identity to them.
  • WO 01/66712 A2 denotes 31 different, in part, with the aforementioned identical amino acid positions, in either of the two in the application WO 00/60060 A2 ⁇ -amylases have been mutated.
  • WO 96/23873 A1 For example, there is a concrete possibility to substitute an M in position 9 according to the count of AA560 for an L in the mentioned ⁇ -amylases, in position 202 M versus L and those in positions 182 and 183 (or 183 and 184) To delete amino acids.
  • WO 00/60060 A2 specifically reveals the amino acid variation N195X (that is, in principle against any other amino acid).
  • WO 01/66712 A2 discloses, inter alia, the amino acid variations R118K, G186X (including in particular the not relevant here G186R exchange), N299X (including in particular the not relevant here replacement N299A), R320K, E345R and R458K.
  • This object is achieved by washing or cleaning agents which contain an ⁇ -amylase variant which can be obtained from the ⁇ -amylase AA560 via the following amino acid changes: M9L / G149A / G182T / G186A / M202L / T2571 / Y295F / N299Y / M323T / A339S / E345R.
  • the variant characterizing and preferred according to the invention has an increased stability compared to at least the otherwise same molecule without the variations in these positions, ie, as a rule, with the amino acid residues present in these positions in the wild-type, starting or comparison molecule a destabilizing, in particular oxidizing compound.
  • a destabilizing, in particular oxidizing compound it can be assumed that with the increased stability under otherwise identical conditions, the activity of longer time (storage and / or use) is kept at a higher level.
  • a further advantageous effect of this solution is that an effective combination of a ⁇ -amylase relevant to the invention with a bleaching agent or a bleach system results from several components, the combinability with tetraacetylethylenediamine (TAED) or manganese-containing bleach catalysts being emphasized.
  • TAED tetraacetylethylenediamine
  • a further advantageous effect of this solution is that an effective combination of a relevant ⁇ -amylase results in particular with a coated bleach, the compatibility with a coated tetraacetylethylenediamine (TAED) is particularly noteworthy.
  • TAED coated tetraacetylethylenediamine
  • a further advantageous effect of this solution is that an effective combination of a relevant ⁇ -amylase with a protease, in particular a subtilisin protease results, wherein the combinability is to be emphasized both with wild-type proteases and with protease variants.
  • a further advantageous effect of this solution is that an effective combination of a ⁇ -amylase relevant to the invention is obtained with a glucanase which hydrolyzes plant-modified or modified polysaccharides, the combinability with glycosidases, especially with ⁇ -glucanases or hemicellulases such as mannanases is emphasized.
  • a further advantageous effect of this solution is that, in particular for use in laundry detergents, an effective combination of a ⁇ -amylase relevant to the invention with representatives of a specific class of glycosidases, namely cellulase, can be combined with cellulase mixtures as well as with individual components To emphasize cellulases.
  • a further advantageous effect of this solution is that an effective combination of an ⁇ - ⁇ -amylase relevant to the invention with a complexing agent and / or builders results, wherein the combinability with aluminosilicates, in particular zeolites is particularly noteworthy.
  • Another advantageous effect of this solution is that results in an effective combination of an inventive ⁇ -amylase with an organic-chemical anti-redeposition polymer (in laundry detergents) and / or a rinse aid (in automatic dishwashing), the combinability with both anionic and with To emphasize cationic polymers.
  • a further advantageous effect of this solution is that there is an effective combination of a relevant ⁇ -amylase with a nonionic surfactant, in particular with Hydroxymischethern.
  • ⁇ -amylases are enzymes of the class EC 3.2.1.1 which hydrolyze internal ⁇ -1,4-glycosidic bonds of starch and starch-like polymers to form dextrins and ⁇ -1,6-branched oligosaccharides .
  • the invention is in principle applicable to all known and still to be found ⁇ -amylases, as far as they are compatible with the ⁇ -amylase AA560 from the stored under DSM 12649 microorganism WO 00/60060 A2 homologize. Such a homologation is in FIG. 1 of the present application and allows or makes it easier to find the amino acid positions corresponding to the invention in the other amylases.
  • the invention is applied to those ⁇ -amylases which are already successfully used in technical fields.
  • ⁇ -amylases established in the prior art are given in the introduction and are also described in U.S. Pat FIG. 1 compared to the reference enzyme AA560.
  • WO 02/10356 A2 disclosed ⁇ -amylase from Bacillus sp. A 7-7 (DSM 12368) as an advantageous starting enzyme.
  • ⁇ -Amylase variants are those ⁇ -amylases which have been derived by known genetic engineering modifications from a predecessor molecule. "Variant” is at the level of proteins the term corresponding to "mutant” at the level of the nucleic acids.
  • the precursor or parent molecules may be wild-type enzymes, that is, those obtainable from natural sources. Such have been exemplified by way of example. They may also be enzymes which in themselves already represent variants, that is to say have already been changed with respect to the wild-type molecules. These are, for example, point mutants, those with changes in the amino acid sequence, over several positions or longer contiguous regions, or to understand hybrid molecules composed of complementary sections of various wild-type ⁇ -amylases.
  • nucleic acids coding for them are known, this is done via established mutagenesis methods on the relevant nucleic acids; if they are not known, nucleic acid sequences coding for this purpose can be derived from the amino acid sequence and modified accordingly.
  • amino acid substitutions are meant substitutions of one amino acid against another amino acid. According to the invention, such substitutions are indicated by designation of the positions in which the exchange takes place, if appropriate combined with the relevant amino acids in the internationally used single-letter code.
  • position 320 replacement means that a variant in the position having position 320 in the sequence of a reference protein has a different amino acid.
  • exchanges are performed at the DNA level via mutations of single base pairs (see above).
  • R320K means that the reference enzyme at position 320 has the amino acid arginine, while the variant under consideration has the amino acid lysine at the homologizable position.
  • 320K means that any, that is usually a naturally given, amino acid at a position corresponding to position 320 is replaced with a lysine, which is in this place in the present molecule.
  • R320K, L means that the amino acid arginine at position 320 is replaced with lysine or leucine.
  • R320X means that the amino acid arginine at position 320 is substituted for any other amino acid in principle.
  • amino acid substitutions according to the invention designated by the present application are not limited to being the only substitutions in which the variant in question differs from the wild-type molecule. It is known in the art that the beneficial properties of single point mutations can complement each other.
  • An ⁇ -amylase which has been optimized with regard to certain properties, such as, for example, calcium binding or stability to surfactants, can be further developed according to the invention via the substitutions presented here.
  • embodiments of the present invention include all variants which, in addition to other exchanges with the wild-type molecule, also comprise the exchanges according to the invention.
  • the ⁇ -amylase AA560 from the microorganism deposited under DSM 12649 as reference enzyme with regard to the numbering of the positions is according to the invention WO 00/60060 A2 whose amino acid sequence in the local sequence listing and also in the alignment of the FIG. 1 of the present application is shown.
  • amino acid positions in which the ⁇ -amylases characterizing the agents according to the invention are changed with respect to their starting molecules are in the count according to the ⁇ -amylase AA560 the positions 9, 149, 182, 186, 202, 257, 295, 299, 323, 339 and 345.
  • the positions corresponding thereto in principle to any ⁇ 5-amylase which can be homologated with AA560 can be determined by an alignment as in FIG. 1 be identified.
  • the Vector NTI ® Suite program includes commercial computer programs available from the Informax, Bethesda, USA.
  • an expression vector containing the ⁇ -amylase sequence is suitably mutagenized and transformed according to generally known methods into an expression strain suitable for the expression of the amylase. Since the variant usually has only a few exchanges compared to the starting molecule, one can orient oneself in the choice of the expression system, the cultivation and the work-up procedures on the systems established for the parent molecule.
  • a fiction-relevant ⁇ -amylase surprisingly shows high performance advantages both in laundry detergents and in detergents.
  • the compositions according to the invention can be used not only at higher temperatures but also at lower temperatures with outstanding performance advantages. These advantages are also evident in short cleaning cycles and, above all, when used in short wash programs. It has turned out to be particularly advantageous that these corresponding improved performances are also achieved, and in particular in the presence of denaturing and oxidizing agents.
  • amylases An important application for amylases is as active components in detergents or cleaners for cleaning textiles or solid surfaces such as crockery, floors or implements.
  • the amylolytic activity that is to say that of an ⁇ -amylase relevant to the invention, also serves carbohydrate-containing impurities and especially those based on starch hydrolytically dissolve or detach from the substrate. They can be used alone, in suitable media or in detergents or cleaners for application.
  • the conditions to be chosen for this purpose, such as, for example, temperature, pH, ionic strength, redox ratios or mechanical influences, should be optimized for the respective cleaning problem, that is to say with respect to the soiling and to the carrier material.
  • normal operating temperatures for detergents or cleaners in the range from 10 ° C for manual agents above 30 ° C, 40 ° C and 60 ° C up to 95 ° for mechanical means or in technical applications. Since the temperature is usually infinitely adjustable in modern washing machines and dishwashers, all intermediate stages of the temperature are included. Preferably, the ingredients of the respective agents are coordinated.
  • An ⁇ -amylase variant relevant to the invention can be used both in products for large consumers or technical users and in products for the private consumer, all dosage forms which are established and / or suitable in the prior art also being embodiments of the present invention.
  • the detergents or cleaning agents according to the invention thus all conceivable types of detergents are meant, both concentrates, as well as undiluted applied means; for use on a commercial scale, in the washing machine or in hand washing or cleaning.
  • These include, for example, detergents for textiles, carpets, or natural fibers, for which according to the present invention the term laundry detergent is used.
  • washing or cleaning agent represents an embodiment of the present invention, as far as it is enriched by an amylase according to the invention.
  • Embodiments of the present invention include all of the prior art and / or all suitable dosage forms of the agents according to the invention. These include, for example, solid, powdery, liquid, gelatinous or pasty agents, optionally also of several phases, compressed or uncompressed; further include, for example: extrudates, granules, tablets or pouches or other shaped articles, which may contain solid and / or liquid, soluble to pasty formulations, packed both in bulk containers and in portions.
  • inventive ⁇ -amylases are combined in inventive compositions, for example, with one or more of the following ingredients: nonionic, anionic, cationic or amphoteric surfactants, bleaching agents, bleach activators, bleach catalysts, builders and / or co-builders, solvents, thickeners, sequestering agents, electrolytes, optical brighteners, grayness inhibitors, corrosion inhibitors, in particular silver protectants, soil release agents, color transfer (or transfer) inhibitors, foam inhibitors, abrasives, dyes, fragrances, antimicrobial agents, UV Protectants, enzymes such as proteases, (optionally other) amylases, lipases, cellulases, hemicellulases or oxidases, stabilizers, especially enzyme stabilizers, and other components known in the art.
  • nonionic, anionic, cationic or amphoteric surfactants for example, with one or more of the following ingredients: nonionic, anionic, cationic or amphoteric surfactants, bleaching
  • the preferred ⁇ -amylase variant according to the invention has the following amino acid change compared with ⁇ -amylase AA560: M9L / G149A / G182T / G186A / M202L / T2571 / Y295F / N299Y / M323T / A339S / E345R.
  • compositions are found, if they have, in particular, ⁇ -amylases which, in addition to the exchanges according to the invention, also comprise those which correspond to one or more of the applications WO 96/23873 A1 .
  • ⁇ -amylases which, in addition to the exchanges according to the invention, also comprise those which correspond to one or more of the applications WO 96/23873 A1 .
  • WO 00/60060 A2 and WO 01/66712 A2 can be seen (see below). This is particularly true for the case in which the falling within the description of these applications commercial product Stainzyme ® from. Novozymes improved in further positions, and is additionally provided with at least one inventive exchange.
  • Very particularly preferred ⁇ -amylases are those which, in addition to the replacement, one or more of the applications WO 96/23873 A1 .
  • WO 00/60060 A2 and WO 01/66712 A2 which have the following changes relevant to the invention: M9L / G149A / G182T / G186A / M202L / T2571 / Y295F / N299Y / M323T / A339S / E345R.
  • a particularly preferred embodiments of the present invention are detergents or cleaning agents according to the invention which contain ⁇ -amylase variants in which the ⁇ -amylase variant is replaced by one or more amino acid changes in the following positions relative to a starting compound which can be homologated with the ⁇ -amylase AA560.
  • ⁇ -amylase 118, 183, 184, 195, 320 and 458 (counted according to ⁇ -amylase AA560).
  • Preferred embodiments of the present invention are detergents or cleaners according to the invention, wherein the ⁇ -amylase variant has the following additional amino acid position assignments: 118K, 183- (deletion), 184- (deletion), 195F, 320K and / or 458K (in the count according to US Pat the ⁇ -amylase AA560).
  • the amino acid residues which are introduced in the variants relevant to the invention at the positions to be additionally changed are precisely defined.
  • Preferred embodiments of the present invention are detergents or cleaning agents according to the invention, it being possible for the ⁇ -amylase variant to be derived from the ⁇ -amylase AA560 or a derivative thereof, and preferably derived from it itself.
  • Preferred embodiments of the present invention are detergents or cleaners according to the invention, wherein said ⁇ -amylase variant in the fully-formulated agent has a concentration of the amylase enzyme protein of from 0.000001 to 5% by weight, and more preferably from 0.0000025 to 1 Wt .-%, at 0.000005 to 0.5 wt .-%, at 0.0000075 to 0.1 wt .-% and most preferably at 0.000008 to 0.072 wt .-% is contained, wherein further completely most preferably the concentration for automatic dishwashing agents comprises 0.001 to 0.072% by weight and for textile detergents 0.0009 to 0.04% by weight.
  • a further advantage of the detergents or cleaning agents according to the invention which contain amylases relevant to the invention is that the amylases relevant to the invention can be metered lower than the previously known amylases of the prior art and still the same or even better washing or cleaning performance compared to Detergents or cleaning agents containing conventional amylases can be achieved.
  • 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 may contain linear and methyl-branched radicals in the mixture, as they are usually present in Oxoalkoholresten. They are preferably low-foaming surfactants.
  • alcohol ethoxylates with linear radicals of alcohols of native 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 containing 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C 12-14 alcohol with 3 EO and C12-18 alcohol containing 5 EO.
  • the stated degrees of ethoxylation represent statistical averages, which for a particular product is an integer or a fractional number could be.
  • 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.
  • ethoxylated nonionic surfactants consisting of C 6-20 monohydroxyalkanols or C 6-20 alkylphenols or C 16-20 fatty alcohols and more than 12 mol, preferably more than 15 mol and in particular more than 20 mol of ethylene oxide per mol Alcohol was used.
  • a particularly preferred nonionic surfactant is obtained from a straight-chain fatty alcohol having 16 to 20 carbon atoms (C 16-20 alcohol), preferably a C 18 -alcohol and at least 12 mol, preferably at least 15 mol and especially at least 20 mol of ethylene oxide.
  • C 16-20 alcohol straight-chain fatty alcohol having 16 to 20 carbon atoms
  • C 18 -alcohol preferably a C 18 -alcohol
  • at least 12 mol preferably at least 15 mol and especially at least 20 mol of ethylene oxide.
  • the so-called “narrow range ethoxylates” are particularly preferred.
  • Nonionic surfactants which have a melting point above room temperature.
  • nonionic surfactants which have melting or softening points in the temperature range mentioned are, for example, low-foaming nonionic surfactants which may be solid or highly viscous at room temperature. If nonionic surfactants are used which are highly viscous at room temperature, it is preferred that they have a viscosity above 20 Pa ⁇ s, preferably above 35 Pa ⁇ s and in particular above 40 Pa ⁇ s. Also, nonionic surfactants having waxy consistency at room temperature are preferable depending on their purpose.
  • Nonionic surfactants from the group of alkoxylated alcohols are also used with particular preference.
  • the nonionic surfactant solid at room temperature preferably has propylene oxide units in the molecule.
  • such PO units make up to 25 wt .-%, more preferably up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic surfactant from.
  • Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols which additionally have polyoxyethylene-polyoxypropylene block copolymer units.
  • the alcohol or alkylphenol content of such nonionic surfactant molecules preferably makes up more than 30% by weight, more preferably more than 50% by weight and in particular more than 70% by weight, of the total molecular weight of such nonionic surfactants.
  • Preferred agents are characterized in that they contain ethoxylated and propoxylated nonionic surfactants in which the propylene oxide units in the molecule up to 25 wt .-%, preferably up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic Make up surfactants.
  • surfactants come from the groups of alkoxylated nonionic surfactants, in particular the ethoxylated primary alcohols and mixtures of these surfactants with structurally complicated surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene ((PO / EO / PO) surfactants).
  • Such (PO / EO / PO) nonionic surfactants are also characterized by good foam control.
  • More particularly preferred nonionic surfactants having melting points above room temperature contain from 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend containing 75% by weight of a reverse block copolymer of polyoxyethylene and polyoxypropylene with 17 moles of ethylene oxide and 44 moles of propylene oxide and 25% by weight. % of a block copolymer of polyoxyethylene and polyoxypropylene initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylolpropane.
  • nonionic surfactants have been low foaming nonionic surfactants which have alternating ethylene oxide and alkylene oxide units.
  • surfactants with EO-AO-EO-AO blocks are preferred, wherein in each case one to ten EO or AO groups are bonded to each other before a block of the other groups follows.
  • R 1 is a straight-chain or branched, saturated or mono- or polyunsaturated C 6-24 alkyl or alkenyl radical; each group R 2 or R 3 is independently selected from -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 -CH 3 , CH (CH 3 ) 2 and the indices w, x, y, z independently of integers from 1 to 6 are available.
  • the preferred nonionic surfactants of the above formula can be prepared by known methods from the corresponding alcohols R 1 -OH and ethylene or alkylene oxide.
  • the radical R 1 in the above formula may vary depending on the origin of the alcohol.
  • the radical R 1 has an even number of carbon atoms and is usually unbranched, the linear radicals being selected from alcohols of natural origin having 12 to 18 C atoms, for example from coconut, palm, tallow fat or oleyl alcohol are preferred.
  • Alcohols which are accessible from synthetic sources are, for example, the Guerbet alcohols or methyl-branched or linear and methyl-branched radicals in the 2-position, as they are usually present in oxo alcohol radicals.
  • nonionic surfactants in which R 1 in the above formula is an alkyl radical having 6 to 24, preferably 8 to 20, particularly preferably 9 to 15 and in particular 9 to 11 Carbon atoms.
  • alkylene oxide unit which is contained in the preferred nonionic surfactants in alternation with the ethylene oxide unit, in particular butylene oxide is considered in addition to propylene oxide.
  • R 2 or R 3 are independently selected from -CH 2 CH 2 -CH 3 or -CH (CH 3 ) 2 are suitable.
  • nonionic surfactants having a C 9-15 alkyl group having 1 to 4 ethylene oxide units followed by 1 to 4 propylene oxide units followed by 1 to 4 ethylene oxide units followed by 1 to 4 propylene oxide units.
  • These surfactants have the required low viscosity in aqueous solution and can be used according to the invention with particular preference.
  • R 1 -CH (OH) CH 2 O- (AO) w - (A'O) x - (A'O) y - (A "'O) x -R 2 in which R 1 and R 2 independently represent a straight-chain or branched, saturated or inclusive polyunsaturated C 2-40 alkyl or alkenyl radical;
  • A, A ', A "and A'” independently represent a radical from the group -CH 2 CH 2 , -CH 2 CH 2 -CH 2 , -CH 2 -CH (CH 3 ), -CH 2 -CH 2 -CH 2 -CH 2 , -CH 2 -CH (CH 3 ) -CH 2 -, -CH 2 -CH (CH 2 -CH 3 ); and
  • w, x, y and z are values between 0.5 and 90, where x, y and / or z can also be 0 are preferred according to the invention.
  • end-capped poly (oxyalkylated) nonionic surfactants which, in accordance with the formula R 1 O [CH 2 CH 2 O] x CH 2 CH (OH) R 2 , in addition to a radical R 1 , which is linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having from 2 to 30 carbon atoms, preferably having from 4 to 22 carbon atoms, furthermore having a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R 2 having from 1 to 30 carbon atoms, where x is from 1 to 30 carbon atoms 90, preferably for values between 30 and 80 and in particular for values between 30 and 60.
  • surfactants of the formula R 1 O [CH 2 CH (CH 3 ) O] x [CH 2 CH 2 O] y CH 2 CH (OH) R 2 , in which R 1 is a linear or branched aliphatic hydrocarbon radical with 4 R 2 is a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x is values between 0.5 and 1.5 and y is a value of at least 15.
  • nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula R 1 O [CH 2 CH (R 3 ) O] x [CH 2 ] k CH (OH) [CH 2 ] j OR 2 in which R 1 and R 2 is a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical having 1 to 30 carbon atoms, R 3 is H or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl or 2-methyl-2-butyl radical, x are values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5.
  • each R 3 in the above formula R 1 O [CH 2 CH (R 3 ) O] x [CH 2 ] k CH (OH) [CH 2 ] j R 2 may be different.
  • R 1 and R 2 are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, with radicals having 8 to 18 carbon atoms being particularly preferred.
  • R 3 H, -CH 3 or -CH 2 CH 3 are particularly preferred.
  • Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.
  • each R 3 in the above formula may be different if x ⁇ 2.
  • the alkylene oxide unit in the square bracket can be varied.
  • the value 3 for x has been selected here by way of example and may well be greater, with the variation width increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa ,
  • R 1 , R 2 and R 3 are as defined above and x is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18.
  • Particularly preferred are surfactants in which the radicals R 1 and R 2 has 9 to 14 C atoms, R 3 is H and x assumes values of 6 to 15.
  • the stated C chain lengths and degrees of ethoxylation or degrees of alkoxylation of the abovementioned nonionic surfactants represent statistical average values which, for a specific product, may be an integer or a fractional number. Due to the production process commercial products of the formulas mentioned are usually not from an individual representative, but from mixtures, which can result in both the C chain lengths and for the degrees of ethoxylation or degrees of alkoxylation averages and resulting broken numbers.
  • nonionic surfactants can be used not only as individual substances, but also as surfactant mixtures of two, three, four or more surfactants.
  • Mixtures of surfactants are not mixtures of nonionic surfactants which fall in their entirety under one of the abovementioned general formulas, but rather mixtures which contain two, three, four or more nonionic surfactants which can be described by different general formulas .
  • anionic surfactants are used as constituents of automatic dishwasher detergents, their content, based on the total weight of the compositions, is preferably less than 4% by weight, preferably less than 2% by weight and very particularly preferably less than 1% by weight.
  • Machine dishwashing detergents which do not contain anionic surfactants are particularly preferred.
  • Detergents in particular automatic dishwashing detergents, which (a) comprise one or more nonionic surfactants having the following general formula: in the R 1 is a C 6-24 alkyl or alkenyl radical, the groups R 2 and R 3 are each for certain hydrocarbon radicals and the indices w, x, y, z each represent integers to 6, or a surfactant system at least one nonionic surfactant F of the general formula: R 1 is -CH (OH) CH 2 O- (AO) w - (A'O) x (A "O) y (A"'O) z -R 2 and at least one nonionic surfactant G of the general formula: R 1 -O- (AO) w (A'O) x - (A "O) y - (A"'O) z -R 2 , in which R 1 is a C 6-24 alkyl or alkenyl radical, R 2 is
  • alkyl glycosides and alkylpolyglycosides are the alkyl glycosides and alkylpolyglycosides (APG) of the general formula RO (G) z , in which R is a linear or branched, in particular 2-methyl-branched, saturated or unsaturated, aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol which represents a glycose unit having 5 or 6 C-atoms, preferably glucose.
  • the degree of glycosylation z is between 1.0 and 10, preferably between 1.0 and 2.0 and in particular between 1.1 and 1.4.
  • 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.
  • 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 proportion of these nonionic surfactants is preferably not higher than that of the ethoxylated fatty alcohols, especially not more than half of them.
  • polyhydroxy fatty acid amides of the formula 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 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
  • 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.
  • [Z] is preferably obtained by reductive amination of a reducing sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • a reducing sugar for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • the N-alkoxy- or N-aryloxy-substituted compounds can be converted into the desired polyhydroxy fatty acid amides, for example, by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
  • anionic surfactants for example, those of the sulfonate type and sulfates are used.
  • Preferred surfactants of the sulfonate type are C 9-13 -alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as those 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 obtained.
  • 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.
  • 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.
  • 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 of 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 are also suitable anionic surfactants.
  • sulfuric acid monoesters of straight-chain or branched C 7-21 alcohols ethoxylated with from 1 to 6 mol of ethylene oxide such as 2-methyl-branched C 9-11 alcohols containing on average 3.5 moles of ethylene oxide (EO) or C 12-18 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 up to 5% by weight, usually 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, soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids.
  • the anionic surfactants 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.
  • Cationic and / or amphoteric surfactants can be used both in detergents and in cleaners.
  • the content of cationic and / or amphoteric surfactants in automatic dishwashing detergents is up to 10% by weight.
  • Advantageous embodiments have less than 6 wt .-%, preferably less than 4 wt .-%, most preferably less than 2 wt .-% and in particular less than 1 wt .-% of cationic and / or amphoteric surfactants.
  • automatic dishwashing detergents need not contain any cationic or amphoteric surfactants.
  • Machine dishwashing detergents which do not contain cationic or amphoteric surfactants are even particularly preferred.
  • the surfactants may be contained in the detergents or detergents according to the invention overall in an amount of preferably from 2% by weight to 50% by weight, in particular from 5% by weight to 30% by weight, based on the finished composition , wherein surfactant contents of at least 8 wt .-%, especially in detergents, are particularly preferred.
  • compositions according to the invention advantageously contain polymers. These include washing or cleaning-active polymers, in particular for automatic dishwashing detergents, for example rinse-aid polymers and / or polymers which act as softeners.
  • washing or cleaning-active polymers in particular for automatic dishwashing detergents, for example rinse-aid polymers and / or polymers which act as softeners.
  • cationic, anionic and amphoteric polymers can be used in detergents or cleaners in addition to nonionic polymers.
  • “Cationic polymers” in the context of the present invention are polymers which carry a positive charge in the polymer molecule. This can be realized, for example, by (alkyl) ammonium groups or other positively charged groups present in the polymer chain.
  • Particularly preferred cationic polymers come from the groups of quaternized cellulose derivatives, the polysiloxanes with quaternary groups, the cationic guar derivatives, the polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid, the copolymers of vinylpyrrolidone with quaternized derivatives of dialkylamino and methacrylates, the vinylpyrrolidone-methoimidazolinium chloride copolymers, the quaternized polyvinyl alcohols or the polymers specified under the INCI names Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27.
  • amphoteric polymers also have, in addition to a positively charged group in the polymer chain, also negatively charged groups or monomer units. These groups may be, for example, carboxylic acids, sulfonic acids or phosphonic acids.
  • particularly preferred cationic or amphoteric polymers contain as monomer unit a compound of the general formula in which R 1 and R 4 are each independently H or a linear or branched hydrocarbon radical having 1 to 6 carbon atoms; R 2 and R 3 are independently an alkyl, hydroxyalkyl, or aminoalkyl group in which the alkyl group is linear or branched and has from 1 to 6 carbon atoms, preferably a methyl group; x and y independently represent integers between 1 and 3.
  • X represents a counterion, preferably a counterion selected from the group consisting of chloride, bromide, iodide, sulfate, hydrogensulfate, methosulfate, laurylsulfate, dodecylbenzenesulfonate, p-toluenesulfonate (tosylate), cumene sulfonate, xylenesulfonate, phosphate, citrate, formate, acetate or mixtures thereof.
  • a counterion selected from the group consisting of chloride, bromide, iodide, sulfate, hydrogensulfate, methosulfate, laurylsulfate, dodecylbenzenesulfonate, p-toluenesulfonate (tosylate), cumene sulfonate, xylenesulfonate, phosphate, citrate, formate, acetate
  • Preferred radicals R 1 and R 4 in the above formula are selected from -CH 3 , -CH 2 -CH 3 , -CH 2 -CH 2 -CH 3 , -CH (CH 3 ) -CH 3 , -CH 2 -OH , -CH 2 -CH 2 -OH, -CH (OH) -CH 3 , -CH 2 -CH 2 -OH, -CH 2 -CH (OH) -CH 3 , -CH (OH) -CH 2 -CH 3 , and - (CH 2 CH 2 -O) n H.
  • R 1 HC CR 2 -C (O) -NH- (CH 2 ) x -N + R 3 R 4 R 5 X - in which R 1 , R 2 , R 3 , R 4 and R 5 independently of one another represent a linear or branched, saturated or unsaturated alkyl or hydroxyalkyl radical having 1 to 6 carbon atoms, preferably a linear or branched alkyl radical selected from -CH 3 , -CH 2 -CH 3 , -CH 2 -CH 2 -CH 3 , -CH (CH 3 ) -CH 3 , -CH 2 -OH, -CH 2 - CH 2 -OH, -CH (OH) -CH 3 , -CH 2 -CH 2 -CH 2 -OH, -CH 2 -CH (OH) -CH 3 , -CH (OH) -CH 3 -CH 3 -CH 3 -CH 3 -CH (OH) -CH 3 -CH 2
  • amphoteric polymers have not only cationic groups but also anionic groups or monomer units.
  • anionic monomer units are derived, for example, from the group of linear or branched, saturated or unsaturated carboxylates, linear or branched, saturated or unsaturated phosphonates, linear or branched, saturated or unsaturated sulfates or linear or branched, saturated or unsaturated sulfonates.
  • Preferred monomer units are acrylic acid, (meth) acrylic acid, (dimethyl) acrylic acid, (ethyl) acrylic acid, cyanoacrylic acid, vinylessingic acid, allylacetic acid, crotonic acid, maleic acid, fumaric acid, cinnamic acid and its derivatives, allylsulfonic acids such as allyloxybenzenesulfonic acid and methallylsulfonic acid or the allylphosphonic acids.
  • Preferred employable amphoteric polymers are selected from the group of the alkylacrylamide / acrylic acid copolymers, the alkylacrylamide / methacrylic acid copolymers, the alkylacrylamide / methylmethacrylic acid copolymers, the alkylacrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / methacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / methylmethacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / alkymethacrylate / alkylaminoethylmethacrylate / alkylmethacrylate copolymers and the copolymers of unsaturated ones Carboxylic acids, cationically derivatized unsaturated carboxylic acids and optionally other ionic or noni
  • Preferred zwitterionic polymers are from the group of acrylamidoalkyltrialkylammonium chloride / acrylic acid copolymers and their alkali metal and ammonium salts, the acrylamidoalkyltrialkylammonium chloride / methacrylic acid copolymers and their alkali metal and ammonium salts and the methacroylethylbetaine / methacrylate copolymers.
  • amphoteric polymers which comprise, in addition to one or more anionic monomers as cationic monomers, methacrylamidoalkyltrialkylammonium chloride and dimethyl (diallyl) ammonium chloride.
  • Particularly preferred amphoteric polymers are selected from the group consisting of the methacrylamidoalkyltrialkylammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers, the methacrylamidoalkyltrialkylammonium chloride / dimethyl (diallyl) ammonium chloride / methacrylic acid copolymers and the methacrylamidoalkyltrialkylammonium chloride / dimethyl (diallyl) ammonium chloride / alkyl (meth) acrylic acid copolymers and their alkali metal and ammonium salts.
  • amphoteric polymers from the group of the methacrylamidopropyltrimethylammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers, the methacrylamidopropyltrimethylammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers and the methacrylamidopropyltrimethylammonium chloride / dimethyl (diallyl) ammonium chloride / alkyl (meth) acrylic acid Copolymers and their alkali metal and ammonium salts.
  • the polymers are present in prefabricated form.
  • the encapsulation of the polymers by means of water-soluble or water-dispersible coating compositions, preferably by means of water-soluble or water-dispersible natural or synthetic polymers; the encapsulation of the polymers by means of water-insoluble, meltable coating compositions, preferably by means of water-insoluble coating agents from the group of waxes or paraffins having a melting point above 30 ° C; the co-granulation of the polymers with inert carrier materials, preferably with carrier materials from the group of washing- or cleaning-active substances, more preferably from the group of builders or cobuilders.
  • Detergents or cleaning agents contain the aforementioned cationic and / or amphoteric polymers preferably in amounts of between 0.01 and 10 wt .-%, each based on the total weight of the detergent or cleaning agent. In the context of the present application, however, preference is given to those detergents or cleaners in which the Weight fraction of the cationic and / or amphoteric polymers between 0.01 and 8 wt .-%, preferably between 0.01 and 6 wt .-%, preferably between 0.01 and 4 wt .-%, particularly preferably between 0.01 and 2 wt .-% and in particular between 0.01 and 1 wt .-%, each based on the total weight of the automatic dishwashing detergent, is.
  • Compositions according to the invention may contain bleaching agents.
  • bleaching agents include sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • Other useful bleaching agents are, for example, peroxopyrophosphates, citrate perhydrates and H 2 O 2 -producing peracidic salts or peracids, such as persulfates or persulfuric acid.
  • peroxopyrophosphates citrate perhydrates and H 2 O 2 -producing peracidic salts or peracids, such as persulfates or persulfuric acid.
  • the urea peroxohydrate percarbamide which can be described by the formula H 2 N-CO-NH 2 .H 2 O 2 .
  • the means for cleaning hard surfaces for example in automatic dishwashing, they may, if desired, also contain bleaching agents from the group of organic bleaches, although their use is also possible in principle for laundry detergents.
  • 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 the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy- ⁇ -naphthoic acid and magnesium monoperphthalate, the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ⁇ -phthalimidoperoxycaproic acid (phthalimidoperoxyhexanoic acid, PAP), o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinates, and aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperoxysebacic acid, diperoxybrassic acid, the diperoxyphthalic acids, 2-decyldiperoxybutane-1,4-d
  • perborate monohydrate or percarbonate preferably sodium percarbonate.
  • chlorine or bromine releasing substances can be used.
  • suitable chlorine or bromine releasing materials are, for example, heterocyclic N-bromo- and N-chloroamides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium.
  • DICA dichloroisocyanuric acid
  • Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydantoin are also suitable.
  • the content of the bleach agent may be 1 to 40% by weight, preferably 2.5 to 30% by weight, more preferably 3.5 to 25% by weight and most preferably 5 to 20% by weight.
  • the active oxygen content of the washing or cleaning agents, in particular the automatic dishwashing agents is in each case based on the total weight of the composition, preferably between 0.3 and 15 wt .-%, particularly preferably between 0.5 and 10 wt .-% and in particular between 0.6 and 8 wt .-%, for example, 5 wt .-%.
  • Particularly preferred compositions have an active oxygen content above 0.7% by weight, more preferably above 0.8% by weight and in particular above 1.0% by weight.
  • the means may also contain bleach activators.
  • 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 1,3,4,6 Tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), acylated hydroxycarboxylic acids, such as triethyl-O-acetylcitrate (TEOC), Carboxylic acid anhydrides, in particular phthalic anhydride, isatoic anhydride and / or succinic
  • Hydrophilic substituted acyl acetals and acyl lactams are also preferably used. Combinations of conventional bleach activators can also be used. Likewise, nitrile derivatives such as cyanopyridines, nitrile quats, for example N-alkylammonium acetonitriles, and / or cyanamide derivatives can be used.
  • Preferred bleach activators are sodium 4- (octanoyloxy) benzenesulfonate, n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), undecenoyloxybenzenesulfonate (UDOBS), sodium dodecanoyloxybenzenesulfonate (DOBS), decanoyloxybenzoic acid (DOBA, OBC 10) and / or dodecanoyloxybenzenesulfonate (OBS 12), as well as N-methylmorpholine-acetonitrile (MMA).
  • n-nonanoyl or isononanoyloxybenzenesulfonate n- or isononanoyloxybenzenesulfonate
  • UOBS undecenoyloxybenzenesulfonate
  • DOBS dodecanoyloxybenzenesulfonate
  • Such bleach activators can be used in the customary amount range of from 0.01 to 20% by weight, preferably in amounts of from 0.1 to 15% by weight, in particular from 1% to 10% by weight, based on the total composition, be included.
  • Further bleach activators preferably used in the context of the present application are compounds from the group of cationic nitriles, in particular cationic nitriles of the formula in the R 1 is -H , -CH 3 , a C 2-24 alkyl or alkenyl radical, a substituted C 2-24 alkyl or alkenyl radical having at least one substituent from the group -Cl, -Br, - OH, -NH 2 , -CN, an alkyl or alkenylaryl radical having a C 1-24 -alkyl group, or represents a substituted alkyl or alkenylaryl radical having a C 1-24 -alkyl group and at least one further substituent on the aromatic ring, R 2 and R 3 are independently selected from -CH 2 -CN, -CH 3 , -CH 2 -CH 3 , -CH 2 -CH 2 -CH 3 , -CH (CH 3 ) -CH 3 , -CH 2
  • bleach catalysts may also be included. These substances are bleach-enhancing transition metal salts or transition metal complexes such as Mn, Fe, Co, Ru or Mo-salene 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 amine complexes are also suitable as bleach catalysts.
  • complexes of manganese in the oxidation state II, III, IV or IV which preferably contain one or more macrocyclic ligands with the donor functions N, NR, PR, O and / or S.
  • ligands are used which have nitrogen donor functions.
  • bleach catalyst (s) in the compositions of the invention, which as macromolecular ligands 1,4,7-trimethyl-1,4,7-triazacyclononan (Me-TACN), 1,4,7-triazacyclononane (TACN ), 1,5,9-trimethyl-1,5,9-triazacyclododecane (Me-TACD), 2-methyl-1,4,7-trimethyl-1,4,7-triazacyclononane (Me / Me-TACN) and or 2-methyl-1,4,7-triazacyclononane (Me / TACN).
  • Me-TACN 1,4,7-trimethyl-1,4,7-triazacyclononan
  • TACN 1,4,7-triazacyclononane
  • TACD 1,5,9-trimethyl-1,5,9-triazacyclododecane
  • Me-TACD 2-methyl-1,4,7-trimethyl-1,4,7-triazacyclononane
  • 2-methyl-1,4,7-triazacyclononane
  • Bleach catalysts may be used in conventional amounts, preferably in an amount up to 5 wt .-%, in particular from 0.0025 wt .-% to 1 wt .-% and particularly preferably from 0.01 wt .-% to 0.25 wt. %, in each case based on the total weight of the bleach activator-containing agents. In special cases, however, more bleach catalyst can be used.
  • compositions according to the invention contain one or more builders, in particular zeolites, silicates, carbonates, organic cobuilders or else the phosphates.
  • builders in particular zeolites, silicates, carbonates, organic cobuilders or else the phosphates.
  • the latter are particularly preferred builders to be used in automatic dishwashing detergents.
  • Preferred crystalline layered silicates of the formula given are those in which M is sodium and x assumes the values 2 or 3.
  • the crystalline layer-form silicates of the formula NaMSi x O 2x + 1 .yH 2 O are sold, for example, by the company Clariant GmbH (Germany) under the trade name Na-SKS.
  • Examples of these silicates are Na-SKS-1 (Na 2 Si 22 O 45 .xH 2 O, Kenyaite), Na-SKS-2 (Na 2 Si 14 O 29 .xH 2 O, magadiite), Na-SKS -3 (Na 2 Si 8 O 17 .xH 2 O) or Na-SKS-4 (Na 2 Si 4 O 9 .xH 2 O, Makatite).
  • both ⁇ - and ⁇ -sodium disilicates are Na 2 Si 2 O 5 .yH 2 O and furthermore, above all, Na-SKS-5 ( ⁇ -Na 2 Si 2 O 5 ), Na-SKS-7 ( ⁇ -Na 2 Si 2 O 5, natrosilite), Na-SKS-9 (NaHSi 2 O 5 ⁇ H 2 O), Na-SKS-10 (NaHSi 2 O 5.
  • Na-SKS-11 t-Na 2 Si 2 O 5
  • Na-SKS-13 NaHSi 2 O5
  • Na-SKS-6 ⁇ -Na 2 Si 2 O 5
  • Detergents or cleaning agents preferably contain a weight fraction of the crystalline layered silicate of the formula NaMSi x O 2x + 1 .yH 2 O of from 0.1 to 20% by weight, preferably from 0.2 to 15% by weight and in particular of 0.4 to 10 wt .-%, each based on the total weight of these agents.
  • the alkalinity of the phyllosilicates can be suitably influenced.
  • Phyllosilicates doped with phosphate or with carbonate have, in comparison to the ⁇ -sodium di silicate, altered crystal morphologies, dissolve more rapidly and show an increased calcium binding capacity in comparison to ⁇ -sodium di silicate.
  • phyllosilicates of the general empirical formula x Na 2 O • y SiO 2 • zP 2 O 5 , in which the ratio x to y is a number 0.35 to 0.6, the ratio x to z a number of 1.75 to 1200 and the ratio y to z correspond to a number from 4 to 2800.
  • the solubility of the phyllosilicates can also be increased by using particularly finely divided phyllosilicates.
  • compounds from the crystalline phyllosilicates with other ingredients can be used.
  • compounds with cellulose derivatives which have advantages in the disintegrating effect and are used in particular in detergent tablets, and compounds with polycarboxylates, for example citric acid, or polymeric polycarboxylates, for example copolymers of acrylic acid, may be mentioned.
  • 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. In the context of this invention is under the term "amorphous” also understood as "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. Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates.
  • An optionally usable, finely crystalline, synthetic and bound water-containing zeolite is preferably zeolite A and / or P.
  • zeolite P zeolite MAP ® commercial product from Crosfield
  • 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 n Na 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.
  • phosphates As builders, the alkali metal phosphates, with particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), are of greatest importance in the washing or 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).
  • 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 is produced, for example, by heating Thomasschlacke with coal and potassium sulfate. Despite the higher price, in the detergent industry the more easily soluble, therefore highly effective, potassium phosphates over corresponding sodium compounds many times preferred.
  • 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) , Both substances are colorless crystals which are soluble in water with an alkaline reaction.
  • Na 4 P 2 O 7 is formed on heating of disodium phosphate to> 200 ° C 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.
  • Condensation of the NaH 2 PO 4 or of the KH 2 PO 4 gives rise to relatively high molecular weight sodium and potassium phosphates, in which cyclic representatives, the sodium or potassium metaphosphates and chain-type, the sodium or potassium polyphosphates, can be distinguished.
  • cyclic representatives, the sodium or potassium metaphosphates and chain-type, the sodium or potassium polyphosphates can be distinguished.
  • hot or cold phosphates Graham's salt, Kurrolsches and Maddrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates.
  • pentasodium triphosphate Na 5 P 3 O 10 (sodium tripolyphosphate)
  • sodium tripolyphosphate sodium tripolyphosphate
  • n 3
  • 100 g of water dissolve at room temperature about 17 g, at 60 ° about 20 g, at 100 ° around 32 g of the salt water-free salt; after two hours of heating the solution to 100 ° caused by hydrolysis about 8% orthophosphate and 15% diphosphate.
  • pentasodium triphosphate In the preparation of pentasodium triphosphate, phosphoric acid is reacted with soda solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dehydrated by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentakaliumtriphosphat, K 5 P 3 O 10 (potassium tripolyphosphate), for example, in the form of a 50 wt .-% solution (> 23% P 2 O 5 , 25% K 2 O) in the trade. The potassium polyphosphates are widely used in the washing or cleaning industry. There are also 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
  • phosphates are used as detergents or cleaning agents in the context of the present application
  • preferred agents comprise this phosphate (s), preferably alkali metal phosphate (s), particularly preferably pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), in amounts of 5 to 80 wt .-%, preferably from 15 to 75 wt .-% and in particular from 20 to 70 wt .-%, each based on the weight of the detergent or cleaning agent.
  • alkali carriers can also serve as builders. Suitable alkali carriers are, for example, alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogencarbonates, alkali metal sesquicarbonates, the cited alkali metal silicates, alkali metal silicates and mixtures of the abovementioned substances, preference being given to using alkali metal carbonates, in particular sodium carbonate, sodium bicarbonate or sodium sesquicarbonate for the purposes of this invention.
  • a builder system comprising a mixture of tripolyphosphate and sodium carbonate is particularly preferred.
  • a builder system comprising a mixture of tripolyphosphate and sodium carbonate and sodium disilicate.
  • Further preferred builder systems which are used in particular in laundry detergents, include zeolites and carbonates as well as optional additional organic builders.
  • Other advantageous builder systems contain neither phosphates nor zeolites, but may contain various carbonates, optionally in combination with silicates, in particular also in combination with the above-described crystalline layered silicates and in a further advantageous embodiment also in combination with organic builders.
  • the alkali metal hydroxides are preferably only in small amounts, preferably in amounts below 10 wt .-%, preferably below 6 wt .-%, more preferably below 4 % By weight and in particular below 2% by weight, in each case based on the total weight of the washing or cleaning agent.
  • Particularly preferred are agents which, based on their total weight, contain less than 0.5% by weight and in particular no alkali metal hydroxides.
  • compositions which, based on the weight of the washing or cleaning agent, contain less than 20% by weight, preferably less than 17% by weight, preferably less than 13% by weight and in particular less than 9% by weight of carbonate ( e) and / or bicarbonate (s), preferably alkali metal carbonate (s), particularly preferably sodium carbonate.
  • organic cobuilders it is possible in particular to use in the detergents or cleaners according to the invention polycarboxylates or polycarboxylic acids, polymeric polycarboxylates, polyaspartic acid, polyacetals, optionally oxidized dextrins, further organic cobuilders and also phosphonates. 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 can not be avoided 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. In addition to their builder effect, they also typically have the property of an acidifying component and thus also serve to set a lower and milder pH of detergents or cleaners, unless the pH resulting from the mixture of the other components is desired.
  • environmentally friendly acids such as citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures of these are to be mentioned here.
  • mineral acids, in particular sulfuric acid or bases, in particular ammonium or alkali hydroxides can serve as pH regulators.
  • Such regulators are contained in the agents according to the invention in amounts of preferably not more than 20% by weight, in particular from 1.2% by weight to 17% by weight.
  • polymeric polycarboxylates for example the alkali metal salts of polyacrylic acid or of polymethacrylic acid, for example those having a relative molecular weight of 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 from 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molecular weights of from 2,000 to 10,000 g / mol, and particularly preferably from 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 2,000 to 70,000 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 the (co) polymeric polycarboxylates may be from 0.5 to 20% by weight, in particular from 1 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.
  • Further preferred copolymers are those which have as monomers preferably acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.
  • softening effective polymers for example, the sulfonic acid-containing polymers, which are used with particular preference.
  • sulfonic acid-containing polymers are copolymers of unsaturated carboxylic acids, sulfonic acid-containing monomers and optionally other ionic or nonionic monomers.
  • R 1 (R 2 ) C C (R 3 ) COOH in which R 1 to R 3, independently of one another, denote -H, -CH 3 , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, NH 2 , -OH or -COOH substituted alkyl or alkenyl radicals or -COOH or -COOR 4 , wherein R 4 is a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.
  • Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3 Methacrylamido-2-hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propene-1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate , Sulfomethacrylamide, sulfomethylmethacrylamide and water-soluble salts of said acids.
  • Particularly suitable other ionic or nonionic monomers are ethylenically unsaturated compounds.
  • the content of the polymers used in these other ionic or nonionic monomers is preferably less than 20% by weight, based on the polymer.
  • the copolymers may contain the monomers from groups i) and ii) and, if appropriate, iii) in varying amounts, it being possible for all representatives from group i) to be combined with all representatives from group ii) and all representatives from group iii).
  • Particularly preferred polymers have certain structural units, which are described below.
  • copolymers which are structural units of the formula are preferred - [CH 2 -CHCOOH] m - [CH 2 -CHC (O) -Y-SO 3 H] p - in which m and p are each an integer between 1 and 2,000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or substituted aromatic hydrocarbon radicals having 1 to 24 carbon atoms, wherein spacer groups in which Y.
  • These polymers are prepared by copolymerization of acrylic acid with a sulfonic acid-containing acrylic acid derivative.
  • acrylic acid derivative containing sulfonic acid groups is copolymerized with methacrylic acid, another polymer is obtained whose use is likewise preferred.
  • the corresponding copolymers contain the structural units of the formula - [CH 2 -C (CH 3 ) COOH] m - [CH 2 -CHC (O) -Y-SO 3 H] p -,
  • Acrylic acid and / or methacrylic acid can also be copolymerized completely analogously with methacrylic acid derivatives containing sulfonic acid groups, as a result of which the structural units in the molecule are changed.
  • copolymers which are structural units of the formula - [CH 2 -CHCOOH] m - [CH 2 -C (CH 3 ) C (O) -Y-SO 3 H] p -
  • m and p are each an integer between 1 and 2,000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or substituted aromatic hydrocarbon radicals having 1 to 24 carbon atoms, wherein spacer groups in which Y.
  • maleic acid can also be used as a particularly preferred monomer from group i).
  • copolymers which contain structural units of the formula - [HOOCCH-CHCOOH] m - [CH 2 -C (CH 3 ) C (O) OY-SO 3 H] p - in which m and p are each an integer between 1 and 2,000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or substituted aromatic hydrocarbon radicals having 1 to 24 carbon atoms, wherein spacer groups in which Y.
  • the sulfonic acid groups may be wholly or partly in neutralized form, that is, that the acidic acid of the sulfonic acid group in some or all sulfonic acid groups may be exchanged for metal ions, preferably alkali metal ions and especially sodium ions.
  • metal ions preferably alkali metal ions and especially sodium ions.
  • the monomer distribution of the copolymers preferably used according to the invention in the case of copolymers containing only monomers from groups i) and ii) is preferably from 5 to 95% by weight of i) or ii), particularly preferably from 50 to 90% by weight of monomer the group i) and 10 to 50 wt .-% of monomer from the group ii), each based on the polymer.
  • terpolymers particular preference is given to those containing from 20 to 85% by weight of monomer from group i), from 10 to 60% by weight of monomer from group ii) and from 5 to 30% by weight of monomer from group iii) ,
  • the molar mass of the sulfo copolymers preferably used according to the invention can be varied in order to adapt the properties of the polymers to the desired end use.
  • Preferred detergents or cleaners are characterized in that the copolymers have molar masses of from 2000 to 200,000 mol -1 , preferably from 4000 to 25,000 mol mol -1 and in particular from 5000 to 15,000 mol mol -1 .
  • polymeric aminodicarboxylic acids their salts or their precursors.
  • polyaspartic acids or their salts and derivatives are particularly preferred.
  • 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 with 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 customary measure of the reducing action of a polysaccharide in comparison to dextrose, which is a DE of 100 has.
  • DE dextrose equivalent
  • Both maltodextrins with a DE of between 3 and 20 and dry glucose syrups with a DE of between 20 and 37 and also yellow dextrins and white dextrins with relatively high molecular weights in the range from 2 000 to 30 000 g / mol are useful.
  • oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function.
  • oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function.
  • Particularly preferred organic builders for agents according to the invention are oxidized starches or their known derivatives.
  • 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 quantities are in zeolithissen and / or silicate-containing formulations between 3 and 15 wt .-%.
  • the automatic dishwashing agents according to the invention contain methylglycinediacetic acid or a salt of methylglycinediacetic acid, wherein the proportion by weight of methylglycinediacetic acid or of the salt of methylglycinediacetic acid is preferably between 0.5 and 15% by weight, preferably between 0.5 and 10% by weight and in particular between 0.5 and 6 wt .-% is.
  • 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.
  • phosphonates are, in particular, hydroxyalkane or aminoalkane phosphonates.
  • hydroxyalkane phosphonates 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance. It is preferably used as the sodium salt, the disodium salt neutral and the tetrasodium salt alkaline (pH 9).
  • Ethylenediamine tetramethylene phosphonate (EDTMP), diethylene triamine pentamethylene phosphonate (DTPMP) and their higher homologs are preferably used as aminoalkane phosphonates Question.
  • 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.
  • Builder substances may optionally be present in the compositions according to the invention in amounts of up to 90% by weight. They are preferably contained in amounts of up to 75% by weight. Detergents according to the invention have builder contents of, in particular, from 5% by weight to 50% by weight. In agents according to the invention for the cleaning of hard surfaces, in particular for the automated cleaning of dishes, the content of builder substances is in particular from 5% by weight to 88% by weight, wherein preferably no water-insoluble builder materials are used in such agents.
  • means for the particular automatic cleaning of dishes are 20 wt .-% to 40 wt .-% of water-soluble organic builder, in particular alkali, 5 wt .-% to 15 wt .-% alkali carbonate and 20 wt .-% bis 40 wt .-% Alkalidisilikat included.
  • An agent of the invention may further comprise a dye transfer inhibitor, which in a preferred embodiment of the invention is a polymer of vinylpyrrolidone, vinylimidazole, vinylpyridine-N-oxide or a copolymer thereof.
  • a dye transfer inhibitor which in a preferred embodiment of the invention is a polymer of vinylpyrrolidone, vinylimidazole, vinylpyridine-N-oxide or a copolymer thereof.
  • enzymatic systems comprising a peroxidase and hydrogen peroxide or a substance which produces hydrogen peroxide in water.
  • a mediator compound for the peroxidase for example an acetosyringone, a phenol derivative or a phenotiazine or phenoxazine, is preferred in this case, whereby also above-mentioned polymeric Farbübertragungsinhibitorwirkstoffe can be used.
  • Polyvinylpyrrolidone preferably has an average molecular weight in the range for use in agents according to the invention from 10 000 to 60 000, in particular in the range of 25 000 to 50 000.
  • copolymers those of vinylpyrrolidone and vinylimidazole in a molar ratio of 5: 1 to 1: 1 having an average molecular weight in the range of 5,000 to 50,000, especially 10,000 to 20,000 are preferred.
  • dye transfer inhibiting agents are included in the compositions in amounts of from 0.1% to 2%, more preferably from 0.2% to 1%, by weight.
  • Solvents that can be used in the liquid to gelatinous or pasty compositions of detergents or cleaning agents including, for example, in liquid or gel-like textile detergents, liquid or gelatinous automatic dishwashing detergents, liquid or gelatinous manual dishwashing detergents, for example, come from the group or polyhydric alcohols, alkanolamines or glycol ethers, provided that they are miscible with water in the specified concentration range.
  • the solvents are preferably selected from ethanol, n- or i-propanol, butanols, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol methyl, ethyl or propyl ether, dipropylene glycol monomethyl, or ethyl ether, diisopropylene glycol monomethyl or ethyl ether, methoxy, ethoxy or butoxy triglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene glycol t-butyl ether. Mixtures of these solvents are possible.
  • Solvents may be used in the liquid to gelled detergents or cleaners according to the invention in amounts of between 0.1 and 20% by weight, but preferably below 15% by weight and in particular below 10% by weight.
  • compositions according to the invention may be admixed with one or more thickeners or thickening systems.
  • These high-molecular substances which are also called swelling agents, usually absorb the liquids and swell up to finally pass into viscous true or colloidal solutions.
  • Suitable thickeners are inorganic or polymeric organic compounds.
  • the inorganic thickeners include, for example, polysilicic acids, clay minerals such as montmorillonites, zeolites, silicas and bentonites.
  • the organic thickeners are derived from the groups of natural polymers, modified natural polymers and fully synthetic polymers.
  • Such naturally derived polymers include, for example, agar-agar, carrageenan, tragacanth, gum arabic, alginates, pectins, polyoses, guar gum, locust bean gum, starch, dextrins, gelatin and casein.
  • Modified natural products, which are used as thickeners come mainly from the group of modified starches and celluloses. Exemplary here are carboxymethyl cellulose and other cellulose ethers,
  • Fully synthetic thickeners are polymers such as polyacrylic and polymethacrylic compounds, vinyl polymers, polycarboxylic acids, polyethers, polyimines, polyamides and polyurethanes.
  • the thickeners may be present in an amount of up to 5% by weight, preferably from 0.05 to 2% by weight, and more preferably from 0.1 to 1.5% by weight, based on the finished composition ,
  • washing or cleaning agent according to the invention may contain sequestering agents, electrolytes and other auxiliaries as further customary ingredients.
  • Detergents according to the invention may contain, as optical brighteners, derivatives of diaminostilbenedisulfonic acid or their alkali metal salts.
  • Suitable salts are, for example, salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulphonic acid or compounds of similar construction which are used in place of the morpholino Group carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group.
  • brighteners of the substituted diphenylstyrene type may be present, for example, the alkali salts of 4,4'-bis (2-sulfostyryl) -diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) -diphenyl, or 4 - (4-chlorostyryl) -4 '- (2-sulfostyryl).
  • Mixtures of the aforementioned optical brightener can be used.
  • Graying inhibitors have the task of keeping the soil detached from the textile fiber suspended in the liquor.
  • Water-soluble colloids of mostly organic nature are suitable for this purpose, for example starch, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or of cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
  • water-soluble polyamides containing acidic groups are suitable for this purpose.
  • starch derivatives can be used, for example aldehyde starches.
  • cellulose ethers such as carboxymethylcellulose (Na salt), methylcellulose, hydroxyalkylcellulose and mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof, for example in amounts of from 0.1 to 5% by weight, based on the compositions.
  • silver corrosion inhibitors can be used in dishwashing detergents according to the invention.
  • dishwashing detergents Such are known in the art, for example benzotriazoles, ferric chloride or CoSO 4 .
  • suitable silver corrosion inhibitors are manganese, titanium, zirconium, hafnium, vanadium, cobalt or cerium salts and / or complexes in which the Metals in one of the oxidation states II, III, IV, V or VI are present.
  • Examples of such compounds are MnSO 4 , V 2 O 5 , V 2 O 4 , VO 2 , TiOSO 4 , K 2 TiF 6 , K 2 ZrF 6 , Co (NO 3 ) 2 , Co (NO 3 ) 3 , and the like mixtures.
  • Soil release agents or soil repellents are mostly polymers which, when used in a laundry detergent detergent, impart soil repellency and / or aid the soil release properties of the other detergent ingredients. A similar effect can also be observed in their use in hard surface cleaners.
  • Particularly effective and long-known soil release agents are copolyesters with dicarboxylic acid, alkylene glycol and polyalkylene glycol units.
  • these are copolymers or copolymers of polyethylene terephthalate and polyoxyethylene glycol and acidic agents which contain inter alia a copolymer of a dibasic carboxylic acid and an alkylene or cycloalkylene polyglycol.
  • Polymers of ethylene terephthalate and polyethylene oxide terephthalate are also advantageously used, and copolyesters of ethylene glycol, polyethylene glycol, aromatic dicarboxylic acid and sulfonated aromatic dicarboxylic acid in certain molar ratios.
  • polyesters having ethylene and / or propylene terephthalate and polyethylene oxide terephthalate units and detergents containing such soil release polymer and polyesters which also substituted for oxyethylene groups and terephthalic acid units Contain ethylene units and glycerol units.
  • polyesters which contain, in addition to oxyethylene groups and terephthalic acid units, 1,2-propylene, 1,2-butylene and / or 3-methoxy-1,2-propylene groups and also glycerol units and with C 1 - to C 4 -alkyl groups end-capped, and at least partially by C 1-4 alkyl or acyl radicals end-capped polyesters with poly-propylene terephthalate and polyoxyethylene terephthalate units.
  • sulfoethylene end-capped terephthalate-containing soil release polyesters and soil release polyesters prepared by sulfonation of unsaturated end groups with terephthalate, alkylene glycol and poly C 2-4 glycol units are also known.
  • a first entity which may be cationic, for example, is capable of adsorption to the cotton surface by electrostatic interaction, and a second Unit that is hydrophobic is responsible for the retention of the drug at the water / cotton interface.
  • color transfer inhibitors include in particular polyvinylpyrrolidones, polyvinylimidazoles, polymeric N-oxides such as poly (vinylpyridine N-oxide) and copolymers of vinylpyrrolidone with vinylimidazole.
  • the layered silicates may contain hydrogen, alkali, alkaline earth metal ions, in particular Na + and Ca ++ .
  • the amount of water of hydration is usually in the range of 8 to 20 wt .-% and is dependent on the swelling state or on the type of processing.
  • phyllosilicates are used, which are largely free of calcium ions and strong coloring iron ions due to an alkali treatment.
  • foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of C 18 -C 24 fatty acids.
  • Suitable non-surfactant foam inhibitors are, for example, organopolysiloxanes and mixtures thereof with microfine, optionally silanized silica and paraffins, waxes, microcrystalline waxes and mixtures thereof with silanated silica or bistearylethylenediamide. It is also advantageous to use mixtures of various foam inhibitors, for example those of silicones, paraffins or waxes.
  • foam inhibitors in particular silicone- and / or paraffin-containing foam inhibitors, are preferably bound to a granular, water-soluble or dispersible carrier substance.
  • a granular, water-soluble or dispersible carrier substance In particular, mixtures of paraffins and bistearylethylenediamides are preferred.
  • detergents in particular automatic dishwashing detergents, which comprise a copolymer of (i) unsaturated carboxylic acids, (ii) monomers containing sulfonic acid groups and (iii) optionally further ionic or nonionogenic monomers, ⁇ -amylase variants which are relevant to the invention, in particular if they are not only relevant to the invention Exchanging those having one or more of the applications WO 96/23873 A1 . WO 00/60060 A2 and WO 01/66712 A2 can be seen. This is particularly true for the case where the falling under these applications, commercial product Stainzyme ® from. Novozymes improved in further positions, and is additionally provided with at least one inventive Aurier. In principle, an additive effect of the various modifications must be assumed.
  • a hard surface cleaning agent according to the invention may contain abrasive constituents, in particular from the group comprising quartz flours, wood flours, plastic flours, chalks and glass microspheres and mixtures thereof.
  • Abrasive substances are preferably not more than 20% by weight, in particular from 5% by weight to 15% by weight, in the cleaning agents according to the invention.
  • Dyes and fragrances are added to detergents or cleaners in order to improve the aesthetic appearance of the products and to provide the consumer with a visually and sensory "typical and unmistakable" product in addition to the washing or cleaning performance.
  • a fragrance In order to be perceptible, a fragrance must be volatile, whereby besides the nature of the functional groups and the structure of the chemical compound, the molecular weight also plays an important role. For example, most odorants have molecular weights up to about 200 daltons, while molecular weights of 300 daltons and above are more of an exception. Due to the different volatility of fragrances, the smell of a perfume or fragrance composed of several fragrances changes during evaporation, whereby the odor impressions in "top note”, “middle note” or “middle note” and " Base note “(end note or dry out).
  • the top note of a perfume or fragrance is not only from volatile compounds, while the base note for the most part consists of less volatile, that is adherent fragrances.
  • the base note for the most part consists of less volatile, that is adherent fragrances.
  • more volatile fragrances can be bound to certain fixatives, preventing them from evaporating too quickly.
  • the subsequent classification of the fragrances in "more volatile” or “adherent” fragrances so nothing is said about the olfactory impression and whether the corresponding fragrance is perceived as the head or middle note.
  • perfume oils or fragrances individual perfume compounds, for example the synthetic products of the ester type, ethers, aldehydes, ketones, alcohols and hydrocarbons can be used. Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethylmethylphenyl glycinate, allylcyclohexyl propionate, styrallyl propionate and benzyl salicylate.
  • the ethers include, for example, benzyl ethyl ether, to the aldehydes, for example, the linear alkanals having 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilial and bourgeonal, to the ketones, for example, the ionones, ⁇ -
  • the hydrocarbons include mainly the terpenes such as limonene and pinene.
  • terpenes such as limonene and pinene.
  • fragrances are used, which together produce an attractive fragrance.
  • perfume oils may also contain natural fragrance mixtures such as are available from vegetable sources, for example, pine, citrus, jasmine, patchouly, rose or ylang-ylang oil.
  • content of detergents or cleaners to dyes is below 0.01 wt .-%, while fragrances can account for up to 2 wt .-% of the total formulation.
  • the fragrances can be incorporated directly into the detergents or cleaners, but it can also be advantageous to apply the fragrances to carriers, which enhance the adhesion of the perfume to the items to be cleaned and provide a slower release of fragrance for long-lasting fragrance, especially of treated textiles.
  • carrier materials for example, cyclodextrins have been proven, the cyclodextrin-perfume complexes can be additionally coated with other excipients.
  • a further preferred carrier for fragrances is the described zeolite X, which can also absorb fragrances instead of or in mixture with surfactants. Preference is therefore given to washing or cleaning agents containing the described zeolite X and fragrances which are preferably at least partially absorbed on the zeolite.
  • 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 colorant When choosing the colorant, it must be taken into account that the colorants have a high storage stability and insensitivity to light. At the same time, it should also be taken into account when choosing suitable colorants that colorants have different stabilities to oxidation. In general, water-insoluble colorants are more stable to oxidation than water-soluble colorants. Depending on the solubility and thus also on the sensitivity to oxidation, the concentration of the colorant in the detergents or cleaners varies. In the case of readily water-soluble colorants, colorant concentrations in the range of a few 10 -2 to 10 -3 % by weight are typically selected. In the due to their brilliance particularly preferred, but less readily water-soluble pigment dyes the appropriate concentration of the colorant in detergents, however, typically at some 10 -3 to 10 -4 wt .-%.
  • Dyeing agents which can be oxidatively destroyed in the washing process and mixtures thereof with suitable blue dyes, so-called blue toners, are preferred. It has proven to be advantageous to use colorants which are soluble in water or at room temperature in liquid organic substances. Suitable examples are anionic colorants, for example anionic nitrosofarbstoffe.
  • Detergents or cleaners may contain antimicrobial agents to combat microorganisms. Depending on the antimicrobial spectrum and mechanism of action, a distinction is made between bacteriostatic agents and bactericides, fungistatics and fungicides, etc. Important substances from these groups are, for example, benzalkonium chlorides, alkylarylsulfonates, halophenols and phenolmercuric acetate. The terms antimicrobial action and antimicrobial agent have the usual meaning within the scope of the teaching according to the invention.
  • Suitable antimicrobial agents are preferably selected from the groups of alcohols, amines, aldehydes, antimicrobial acids or their salts, carboxylic esters, acid amides, phenols, phenol derivatives, diphenyls, diphenylalkanes, urea derivatives, oxygen, nitrogen acetals and formals, benzamidines, isothiazolines, Phthalimide derivatives, pyridine derivatives, antimicrobial surface active compounds, guanidines, antimicrobial amphoteric compounds, quinolines, 1,2-dibromo-2,4-dicyanobutane, iodo-2-propyl-butyl-carbamate, iodine, iodophores, peroxo compounds, halogen compounds and any mixtures of the foregoing ,
  • the antimicrobial agent may be selected from ethanol, n-propanol, i-propanol, 1,3-butanediol, phenoxyethanol, 1,2-propylene glycol, glycerol, undecylenic acid, benzoic acid, salicylic acid, dihydracetic acid, o-phenylphenol, N-methylmorpholine.
  • acetonitrile MMA
  • 2-benzyl-4-chlorophenol 2,2'-methylenebis (6-bromo-4-chlorophenol), 4,4'-dichloro-2'-hydroxydiphenyl ether (dichlosan), 2,4 , 4'-trichloro-2'-hydroxydiphenylether (trichlosan), chlorhexidine, N- (4-chlorophenyl) -N- (3,4-dichlorophenyl) -urea, N, N '- (1,10-decanediyldi- 1-pyridinyl-4-ylidene) bis- (1-octanamine) dihydrochloride, N, N'-bis (4-chlorophenyl) -3,12-diimino-2,4,11,13-tetraaza-tetradecane diimidamide, Glucoprotamines, antimicrobial quaternary surface active compounds, guanidines including the bi- and polyguanidine
  • halogenated xylene and cresol derivatives such as p-chlorometacresol or p-chloro-meta-xylene, and natural antimicrobial agents of plant origin (for example, from spices or herbs), animal and microbial origin.
  • antimicrobial surface-active quaternary compounds a natural antimicrobial agent of plant origin and / or a natural antimicrobial agent of animal origin, most preferably at least one natural antimicrobial agent of plant origin from the group comprising caffeine, theobromine and theophylline and essential oils such as eugenol, thymol and geraniol, and / or at least one natural antimicrobial agent of animal origin from the group, comprising enzymes such as protein from milk, lysozyme and lactoperoxidase, and / or at least one antimicrobial surface-active quaternary compound with an ammonium, sulfonium, phosphonium, iodonium - or Arsonium distr, peroxo compounds and chlorine compounds are used. Also substances of microbial origin, so-called bacteriocins, can be used.
  • the quaternary ammonium compounds (QAV) suitable as antimicrobial agents have the general formula (R 1 ) (R 2 ) (R 3 ) (R 4 ) N + X - , in which R 1 to R 4 are the same or different C 1 -C 22- alkyl radicals, C 7 -C 28 -aralkyl radicals or heterocyclic radicals, where two or, in the case of an aromatic incorporation such as in pyridine, even three radicals together with the nitrogen atom form the heterocycle, for example a pyridinium or imidazolinium compound, and X - halide ions, sulfate ions, Hydroxide ions or similar anions are.
  • at least one of the radicals has a chain length of 8 to 18, in particular 12 to 16, carbon atoms.
  • QACs can be prepared by reacting tertiary amines with alkylating agents, such as, for example, methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide, but also ethylene oxide.
  • alkylating agents such as, for example, methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide, but also ethylene oxide.
  • alkylating agents such as, for example, methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide, but also ethylene oxide.
  • alkylating agents such as, for example, methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide, but also ethylene oxide.
  • alkylating agents such as, for example, methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide, but also
  • Suitable QACs are, for example, benzalkonium chloride (N-alkyl-N, N-dimethylbenzyl-ammonium chloride, CAS No. 8001-54-5), benzalkone B (m, p-dichlorobenzyl-dimethyl-C 12 -alkyl-ammonium chloride, CAS no. 58390-78-6), benzoxonium chloride (benzyldodecyl-bis (2-hydroxyethyl) ammonium chloride), cetrimonium bromide (N-hexadecyl-N, N-trimethylammonium bromide, CAS No.
  • benzalkonium chloride N-alkyl-N, N-dimethylbenzyl-ammonium chloride, CAS No.
  • benzalkone B m, p-dichlorobenzyl-dimethyl-C 12 -alkyl-ammonium chloride, CAS no. 58390-78-6
  • Benzetonium chloride N, N-dimethyl-N- [2- [2- [p- (1,1,3,3-tetramethylbutyl) phenoxy] ethoxy] ethyl] benzyl ammonium chloride, CAS No. 121-54
  • Dialkyldimethylammonium chlorides such as di-n-decyldimethylammonium chloride (CAS No. 7173-51-5-5), didecyldimethylammonium bromide (CAS No. 2390-68-3), dioctyldimethylammoniumchloric, 1-cetylpyridiniumchloride ( CAS No.
  • QACs are the benzalkonium chlorides having C 8 -C 18 -alkyl radicals, in particular C 12 -C 14 -alkyl-benzyl-dimethyl-ammonium chloride.
  • Benzalkonium halides and / or substituted benzalkonium halides are for example commercially available as Barquat ® ex Lonza, Marquat® ® ex Mason, Variquat ® ex Witco / Sherex and Hyamine ® ex Lonza and as Bardac ® ex Lonza.
  • antimicrobial agents are N- (3-chloroallyl) hexaminium chloride such as Dowicide and Dowicil ® ® ex Dow, benzethonium chloride such as Hyamine ® 1622 ex Rohm & Haas, methylbenzethonium as Hyamine ® 10X ex Rohm & Haas, cetylpyridinium chloride such as Cepacol ex Merrell Labs ,
  • the antimicrobial agents are used in amounts of 0.0001 wt .-% to 1 wt .-%, preferably from 0.001 wt .-% to 0.8 wt .-%, particularly preferably from 0.005 wt .-% to 0.3 wt .-% and in particular from 0.01 to 0.2 wt .-% used.
  • the agents may contain UV absorbers (UV absorbers), which are applied to the treated textiles and improve the light resistance of the fibers and / or the light resistance of other formulation ingredients.
  • UV absorber are organic substances (sunscreen) to understand, which are able to absorb ultraviolet rays and the absorbed energy in the form of longer-wave radiation, for example, to give off heat.
  • Compounds having these desired properties include, for example, the non-radiative deactivating compounds and derivatives of benzophenone having substituents in the 2- and / or 4-position. Also suitable are substituted benzotriazoles, in the 3-position phenyl-substituted acrylates (cinnamic acid derivatives, optionally with cyano groups in the 2-position), salicylates, organic Ni complexes and natural substances such as umbelliferone and the body's own urocanic acid.
  • the biphenyl and especially stilbene derivatives such as those available commercially as Tinosorb ® FD or Tinosorb ® FR are available ex Ciba.
  • UV-B absorbers may be mentioned: 3-Benzylidencampher or 3-Benzylidennorcampher and its derivatives, for example 3- (4-methylbenzylidene) camphor; 4-aminobenzoic acid derivatives, preferably 2-ethylhexyl 4- (dimethylamino) benzoate, 2-octyl 4- (dimethylamino) benzoate and 4- (dimethylamino) benzoic acid ester; Esters of cinnamic acid, preferably 4-methoxycinnamic acid 2-ethylhexyl ester, 4-methoxycinnamic acid propyl ester, 4-methoxycinnamic acid isoamyl ester, 2-cyano-3,3-phenylcinnamic acid 2-ethylhexyl ester (octocrylene); Esters of salicylic acid, preferably 2-ethylhexyl salicylate, 4-isopropylbenzyl salicy
  • 2-phenylbenzimidazole-5-sulfonic acid and its alkali metal, alkaline earth metal, ammonium, alkylammonium, alkanolammonium and glucammonium salts Sulfonic acid derivatives of benzophenones, preferably 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its salts
  • Sulfonic acid derivatives of 3-Benzylidencamphers such as 4- (2-oxo-3-bionylidenemethyl) benzenesulfonic acid and 2-methyl-5- (2-oxo-3-bomylidene) sulfonic acid and salts thereof.
  • UV-A filter in particular derivatives of benzoylmethane are suitable, such as 1- (4'-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-1,3-dione, 4-tert-butyl 4'-methoxydibenzoylmethane (Parsol 1789), 1-phenyl-3- (4'-isopropylphenyl) -propane-1,3-dione and enamine compounds (BASF).
  • the UV-A and UV-B filters can also be used in mixtures.
  • insoluble sunscreen pigments namely finely dispersed, preferably nano-metal oxides or salts in question.
  • suitable metal oxides are in particular zinc oxide and titanium dioxide and, in addition, oxides of iron, zirconium, silicon, manganese, aluminum and cerium and mixtures thereof.
  • silicates (talc) barium sulfate or zinc stearate can be used.
  • the oxides and salts are already used in the form of the pigments for skin-care and skin-protecting emulsions and decorative cosmetics.
  • the particles should have an average diameter of less than 100 nm, preferably between 5 and 50 nm and in particular between 15 and 30 nm. They may have a spherical shape, but it is also possible to use those particles which have an ellipsoidal or otherwise deviating shape from the spherical shape.
  • the pigments may also be surface-treated, that is to say hydrophilized or hydrophobicized.
  • Typical examples are coated titanium dioxides, such as, for example, titanium dioxide T 805 (Degussa) or Eusolex® T2000 (Merck), silicones and particularly preferably trialkoxyoctylsilanes or simethicones are preferred for this purpose, preferably micronized zinc oxide is used as the hydrophobic coating agent.
  • the UV absorbents are usually used in amounts of from 0.01% by weight to 5% by weight, preferably from 0.03% by weight to 1% by weight.
  • Agents according to the invention may comprise further enzymes in addition to the ⁇ -amylase variants according to the invention for increasing the washing or cleaning performance, it being possible in principle to use all enzymes established for this purpose in the prior art.
  • These include in particular proteases, other amylases, lipases, hemicellulases, cellulases or oxidoreductases such as peroxidases and / or perhydrolases, and preferably mixtures thereof.
  • These enzymes are basically of natural origin; Starting from the natural molecules, improved variants are available for use in detergents or cleaning agents, which are preferably used accordingly.
  • Agents according to the invention preferably contain enzymes in total amounts of 1 ⁇ 10 -8 to 5 percent by weight, based on active protein.
  • the protein concentration can be determined by known methods, for example the BCA method (bicinchoninic acid, 2,2'-biquinolyl-4,4'-dicarboxylic acid) or the biuret method ( Gornall AG, CS Bardawill and MM David, J. Biol. Chem., 177 (1948), pp. 751-766 ).
  • BCA method bicinchoninic acid, 2,2'-biquinolyl-4,4'-dicarboxylic acid
  • the biuret method Gornall AG, CS Bardawill and MM David, J. Biol. Chem., 177 (1948), pp. 751-766 .
  • subtilisin type examples thereof are the subtilisins BPN 'and Carlsberg, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the enzymes thermitase, proteinase K and the subtilases, but not the subtilisins in the narrower sense Proteases TW3 and TW7.
  • subtilisin Carlsberg in a developed form under the trade names Alcalase ® from Novozymes A / S, Bagsvaerd, Denmark.
  • Subtilisins 147 and 309 will be sold under the trade names Esperase ® , and Savinase ® by the company Novozymes. From the protease from Bacillus lentus DSM 5483 ( WO 91/02792 A1 ) derive from the name under the name BLAP ® variants, which in particular in WO 92/21760 A1 . WO 95/23221 A1 . WO 02/088340 A2 and WO 03/038082 A2 to be discribed. Other useful proteases from various Bacillus sp. and B. gibsonii go out of the patent applications WO 03/054185 A1 . WO 03/056017 A2 . WO 03/055974 A2 and WO 03/054184 A1 out.
  • proteases are, for example, under the trade names Durazym ®, relase ®, Everlase® ®, Nafizym, Natalase ®, Kannase® ® and Ovozymes ® from Novozymes, under the trade names Purafect ®, Purafect ® OxP and Properase.RTM ® by the company Genencor, that under the trade name Protosol® ® from Advanced Biochemicals Ltd., Thane, India, under the trade name Wuxi ® from Wuxi Snyder Bioproducts Ltd., China, under the trade names Proleather® ® and protease P ® by the company Amano Pharmaceuticals Ltd., Nagoya, Japan, and the enzyme available under the name Proteinase K-16 from Kao Corp., Tokyo, Japan.
  • amylases which can be used according to the invention are the ⁇ -amylases from Bacillus licheniformis, B. amyloliquefaciens or B. stearothermophilus and also their further developments improved for use in detergents or cleaners.
  • the enzyme from B. licheniformis is available from Novozymes under the name Termamyl ® and from Genencor under the name Purastar® ® ST. Development products of this ⁇ -amylase are available from Novozymes under the trade names Duramyl ® and Termamyl ® ultra, from Genencor under the name Purastar® ® OxAm and from Daiwa Seiko Inc., Tokyo, Japan, as Keistase ®.
  • the ⁇ -amylase from B. amyloliquefaciens is marketed by Novozymes under the name BAN ®, and variants derived from the ⁇ -amylase from B. stearothermophilus under the names BSG ® and Novamyl ®, likewise from Novozymes.
  • ⁇ -amylase from Bacillus sp. A 7-7 (DSM 12368) and in the application WO 02/44350 A2 described cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948).
  • CGTase cyclodextrin glucanotransferase
  • DSM 9948 cyclodextrin glucanotransferase
  • amylolytic enzymes belonging to the sequence space of ⁇ -amylases can be used, which in the application WO 03/002711 A2 is defined, and the ones in the application WO 03/054177 A2 to be discribed.
  • fusion products of said molecules can be used, for example those from the application DE 10138753 A1 or point mutations of it.
  • compositions according to the invention may contain lipases or cutinases, in particular because of their triglyceride-cleaving activities, but also in order to generate in situ peracids from suitable precursors.
  • lipases or cutinases include, for example, the lipases originally obtainable from Humicola lanuginosa (Thermomyces lanuginosus) or further developed, in particular those with the amino acid exchange D96L. They are sold, for example, by Novozymes under the trade names Lipolase ®, Lipolase Ultra ®, LipoPrime® ®, Lipozyme® ® and Lipex ®.
  • the cutinases can be used, which were originally isolated from Fusarium solani pisi and Humicola insolens.
  • lipases are available from Amano under the designations Lipase CE ®, Lipase P ®, Lipase B ®, or lipase CES ®, Lipase AKG ®, Bacillis sp. Lipase® , Lipase AP® , Lipase M- AP® and Lipase AML® are available. From the company Genencor, for example, the lipases, or cutinases can be used, the initial enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii.
  • Detergents according to the invention may contain cellulases, depending on the purpose, as pure enzymes, as enzyme preparations or in the form of mixtures in which the individual components advantageously supplement each other in terms of their various performance aspects.
  • These performance aspects include, in particular, contributions to the primary washing performance, the secondary washing performance of the composition (anti-redeposition effect or graying inhibition) and softening (fabric effect), up to the exercise of a "stone-washed" effect.
  • EG endoglucanase
  • Novozymes A useful fungal, endoglucanase (EG) -rich cellulase preparation, or its further developments are offered by Novozymes under the trade name Celluzyme ®.
  • Further commercial products of this company are Cellusoft® ® and Renozyme ®. The latter is based on the application WO 96/29397 A1 , Performance-enhanced cellulase variants For example, go from the application WO 98/12307 A1 out.
  • WO 97/14804 A1 disclosed cellulases used; For example, it revealed 20 kD EG Melanocarpus, available from AB Enzymes, Finland, under the trade names Ecostone® ® and Biotouch ®. Further commercial products from AB Enzymes are Econase® ® and ECOPULP ®. Other suitable cellulases from Bacillus sp. CBS 670.93 and CBS 669.93 are in WO 96/34092 A2 disclosed, the Bacillus sp. CBS 670.93 from the company Genencor under the trade name Puradax ® is available. Further commercial products of the company Genencor are "Genencor detergent cellulase L" and IndiAge ® Neutra.
  • compositions according to the invention may contain, in particular for the removal of certain problem soiling, further enzymes which are combined under the term hemicellulases.
  • further enzymes which are combined under the term hemicellulases.
  • Suitable mannanases for example, under the name Gamanase ® and Pektinex AR ® from Novozymes, under the name Rohapec ® B1 L from AB Enzymes, under the name Pyrolase® ® from Diversa Corp., San Diego, CA, USA, and under the name Purabrite ® from Genencor Int., Inc., Palo Alto, CA, USA.
  • a suitable ⁇ -glucanase from a B. alcalophilus for example, from the application WO 99/06573 A1 out.
  • the obtained from B. subtilis ⁇ -glucanase is available under the name Cereflo ® from Novozymes.
  • detergents or cleaners according to the invention may be oxidoreductases, for example oxidases, oxygenases, catalases, peroxidases, such as halo-, chloro-, bromo-, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases) contain.
  • oxidases oxygenases, catalases
  • peroxidases such as halo-, chloro-, bromo-, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases) contain.
  • Suitable commercial products Denilite® ® 1 and 2 from Novozymes should be mentioned.
  • advantageous systems for an enzymatic perhydrolysis can be applied to the application WO 98/45398 A1 directed.
  • choline oxidases useful for such a system are disclosed WO 2004/058955 A2
  • Modified proteases with pronounced, at this point also advantageously usable perhydrolase activity, in particular for achieving a mild bleaching in laundry detergents go from the application WO 2004/058961 A1 out.
  • a combined enzymatic bleaching system comprising an oxidase and a perhydrolase describes the application PCT / EP2005 / 006178 , Further perhydrolases which can be used according to the invention are also disclosed WO 2005/056782 A2 , Advantageously, it is additionally preferred to add organic, particularly preferably aromatic, compounds which interact with the enzymes, in order to enhance the activity of the relevant oxidoreductases (enhancers) or at greatly varying redox potentials to ensure the flow of electrons between the oxidizing enzymes and the stains (mediators).
  • organic, particularly preferably aromatic, compounds which interact with the enzymes, in order to enhance the activity of the relevant oxidoreductases (enhancers) or at greatly varying redox potentials to ensure the flow of electrons between the oxidizing enzymes and the stains (mediators).
  • the enzymes used in agents of the invention are either originally from microorganisms, such as the genera Bacillus, Streptomyces, Humicola, or Pseudomonas, and / or are produced by biotechnological methods known per se by suitable microorganisms, such as transgenic expression hosts of the genera Bacillus or by filamentous fungi ,
  • the purification of the relevant enzymes is conveniently carried out by conventional methods, for example by precipitation, sedimentation, concentration, filtration of the liquid phases, microfiltration, ultrafiltration, exposure to chemicals, deodorization or suitable combinations of these steps.
  • the agents of the invention may be added to the enzymes in any form known in the art. These include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, especially in the case of liquid or gel-form detergents, solutions of the enzymes, advantageously as concentrated as possible, sparing in water and / or added with stabilizers.
  • the enzymes may be encapsulated for both the solid and liquid dosage forms, for example by spray-drying or extruding the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are entrapped as in a solidified gel are or in those of the core-shell type, in which an enzyme-containing core is coated with a water, air and / or chemical impermeable protective layer.
  • further active ingredients for example stabilizers, emulsifiers, pigments, bleaches or dyes, may additionally be applied.
  • Such capsules are applied by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes.
  • such granules for example by applying polymeric film-forming agent, low in dust and storage stable due to the coating.
  • a protein and / or enzyme contained in an agent according to the invention can be protected against damage, for example inactivation, denaturation or decomposition, for example by physical influences, oxidation or proteolytic cleavage, in particular during storage.
  • damage for example inactivation, denaturation or decomposition, for example by physical influences, oxidation or proteolytic cleavage, in particular during storage.
  • inhibition of proteolysis is particularly preferred, especially if the agents also contain proteases.
  • Preferred agents according to the invention contain stabilizers for this purpose.
  • One group of stabilizers are reversible protease inhibitors.
  • Benzamidine hydrochloride, borax, boric acids, boronic acids or their salts or esters are frequently used for this purpose, including, in particular, derivatives with aromatic groups, for example ortho, meta or para-substituted phenylboronic acids, in particular 4-formylphenylboronic acid, or the salts or Esters of the compounds mentioned.
  • peptide aldehydes that is oligopeptides with a reduced C-terminus, especially those of 2 to 50 monomers are used for this purpose.
  • the peptidic reversible protease inhibitors include ovomucoid and leupeptin.
  • specific, reversible peptide inhibitors for the protease subtilisin and fusion proteins from proteases and specific peptide inhibitors are suitable.
  • enzyme stabilizers are amino alcohols such as mono-, di-, triethanol- and -propanolamine and mixtures thereof, aliphatic carboxylic acids up to C 12 , such as succinic acid, other dicarboxylic acids or salts of said acids. End-capped fatty acid amide alkoxylates are also suitable for this purpose. Certain organic acids used as builders are capable of, as in WO 97/18287 discloses additionally stabilizing a contained enzyme.
  • Lower aliphatic alcohols but especially polyols such as glycerol, ethylene glycol, propylene glycol or sorbitol are other frequently used enzyme stabilizers.
  • Di-glycerol phosphate also protects against denaturation due to physical influences.
  • Polyamide oligomers or polymeric compounds such as lignin, water-soluble vinyl copolymers or cellulose ethers, acrylic polymers and / or polyamides stabilize the enzyme preparation, inter alia, against physical influences or pH fluctuations.
  • Polyamine N-oxide containing polymers act simultaneously as enzyme stabilizers and as dye transfer inhibitors.
  • Other polymeric stabilizers are linear C 8 -C 18 polyoxyalkylenes.
  • alkylpolyglycosides can stabilize the enzymatic components of the agent according to the invention and, preferably, are capable of additionally increasing their performance.
  • Crosslinked N-containing compounds preferably perform a dual function as soil release agents and as enzyme stabilizers. Hydrophobic, nonionic polymer stabilizes in particular an optionally contained cellulase.
  • Reducing agents and antioxidants increase the stability of the enzymes to oxidative degradation;
  • sulfur-containing reducing agents are familiar.
  • Other examples are sodium sulfite and reducing sugars.
  • peptide-aldehyde stabilizers for example of polyols, boric acid and / or borax, the combination of boric acid or borate, reducing salts and succinic acid or other dicarboxylic acids or the combination of boric acid or borate with polyols or polyamino compounds and with reducing salts.
  • the effect of peptide-aldehyde stabilizers is favorably enhanced by the combination with boric acid and / or boric acid derivatives and polyols, and still further by the additional action of divalent cations, such as calcium ions.
  • Agents according to the invention are characterized in a preferred embodiment in that they consist of more than one phase, for example in order to release the active substances contained in time or space separately from each other. These can be phases in different but also phases in the same physical states.
  • compositions according to the invention which are composed of more than one solid component, can be prepared in a simple manner by mixing together various solid components, in particular powders, granules or extrudates with different ingredients and / or different release behavior in total loose form.
  • the preparation of solid agents according to the invention from one or more phases can be carried out in a known manner, for example by spray-drying or granulation, the enzymes and any other thermally sensitive ingredients such as, for example, bleaching agents optionally added separately later.
  • various prior art production processes are known. By way of example, these are processes which comprise at least one granulation step and / or at least one extrusion step.
  • Proteins can be used for solid agents, for example in dried, granulated, encapsulated or encapsulated and additionally dried form. They may be added separately, ie as a separate phase, or with other ingredients together in the same phase, with or without compaction. If microencapsulated enzymes are to be processed in solid form, the water can be removed by methods known from the prior art from the aqueous solutions resulting from the workup, such as spray drying, centrifuging or by solubilization. The particles obtained in this way usually have a particle size between 50 and 200 microns.
  • the encapsulated form lends itself to protecting the enzymes from other ingredients, such as bleaches, or to allow for controlled release. Depending on the size of these capsules, a distinction is made according to milli, micro and nano capsules, with microcapsules for enzymes being particularly preferred.
  • Another possible encapsulation method is that the enzymes suitable for use in detergents or cleaning agents, starting from a mixture of the enzyme solution with a solution or suspension of starch or a starch derivative, are encapsulated in starch or the starch derivative.
  • compositions according to the invention in tablet form which may be single-phase or multiphase, monochromatic or multicolored and / or consist of a plurality of layers, preferably all constituents - optionally one layer at a time - are mixed together in a mixer and the mixture is mixed by means of conventional tablet presses, For example, eccentric or rotary presses, pressed with compressive forces in the range of about 50 to 100 kN / cm 2 , preferably at 60 to 70 kN / cm 2 . Particularly in the case of multilayer tablets, it may be advantageous if at least one layer is pre-compressed. This is preferably carried out at pressing forces between 5 and 20 kN / cm 2 , in particular at 10 to 15 kN / cm 2 .
  • a tablet prepared in this way has a weight of 10 g to 50 g, in particular from 15 g to 40 g.
  • the spatial form of the tablets is arbitrary and can be round, oval or angular, with intermediate forms are also possible.
  • in multiphase means at least one of the phases contains an amylase-sensitive material, in particular starch, or is at least partially surrounded or coated by it.
  • this phase is mechanically stabilized and / or protected against external influences and simultaneously attacked by an effective in the wash liquor amylase, so that the release of the ingredients is facilitated.
  • agents according to the invention are characterized in that they are in total liquid, gelatinous or pasty.
  • the proteins contained, preferably a protein of the invention are preferably based on a carried out in the prior art protein recovery and preparation in concentrated aqueous or nonaqueous solution, for example in liquid form, such as solution, suspension or emulsion, but also in gel form or encapsulated or added as a dried powder.
  • Such detergents or cleaners according to the invention in the form of solutions in customary solvents are generally prepared by simple mixing of the ingredients which can be added in bulk or as a solution in an automatic mixer.
  • One embodiment of the present invention is those liquid, gelatinous or pasty compositions to which a protein essential to the invention and / or one of the other proteins contained and / or one of the other ingredients contained has been encapsulated, preferably added in the form of microcapsules.
  • Particularly preferred are those with capsules of amylase sensitive material.
  • Such co-use of amylase-sensitive materials and the essential amylolytic enzyme of the present invention in a detergent may exhibit synergistic effects, such that the starch-cleaving enzyme aids cleavage of the microcapsules and thus controls the release process of the encapsulated ingredients so that their release does not occur storage and / or not at the beginning of the cleaning process, but only at a certain time takes place.
  • complex detergent or cleaner systems can be based on a wide variety of ingredients and various types of capsules, which are particularly preferred embodiments of the present invention.
  • a comparable effect is given when the ingredients of the detergent or cleaner are distributed over at least two different phases, for example two or more solid, interconnected phases of a tablet detergent or detergent, or different granules within the same powdered agent.
  • Two or more phase cleaners are suitable for use in both automatic dishwashers and in detergents state of the art.
  • the activity of an amylolytic enzyme in an earlier activated phase is a prerequisite for the activation of a later phase when it is surrounded by an amylase-sensitive envelope or coating or the amylase-sensitive material is an integral part of the solid phase, in its partial or complete Hydrolysis disintegrates the relevant phase.
  • the use of the enzyme essential to the invention for this purpose thus represents a preferred embodiment of the present invention.
  • a particularly preferred embodiment of the invention provides that the means have at least two solid phases.
  • a further preferred embodiment of the invention provides that the means have at least two liquid to gel phases.
  • a further preferred embodiment of the invention provides that the means have at least one solid and one liquid to gel phase.
  • ⁇ -amylase variants of the invention may serve to activate one's own or other phases when they are provided alone or together with at least one other detergent-active or cleaning-active ingredient in a washing or cleaning agent consisting of more than one phase. Similarly, they may also serve to release ingredients from capsules when provided in encapsulated form in a detergent or cleaning agent.
  • Machine dishwashing detergents in particular advantageously contain glass corrosion inhibitors. These prevent the occurrence of turbidity, streaks and scratches but also iridescence of the glass surface of machine-cleaned glasses.
  • Preferred glass corrosion inhibitors come from the group of magnesium and zinc salts and magnesium and zinc complexes.
  • the spectrum of the invention preferred zinc salts, preferably organic acids, particularly preferably organic carboxylic acids, ranging from salts which are difficult or insoluble in water, ie a solubility below 100 mg / l, preferably below 10 mg / l, in particular below 0.01 have mg / l, to those salts which have a solubility in water above 100 mg / l, preferably above 500 mg / l, more preferably above 1 g / l and in particular above 5 g / l (all solubilities at 20 ° C. water temperature).
  • the first group of zinc salts includes, for example, zinc citrate, zinc oleate and zinc stearate
  • the group of soluble zinc salts includes, for example, zinc formate, zinc acetate, zinc lactate and zinc gluconate.
  • the glass corrosion inhibitor at least one zinc salt of an organic carboxylic acid, particularly preferably a zinc salt from the group zinc stearate, zinc oleate, zinc gluconate, zinc acetate, zinc lactate and zinc citrate.
  • Zinc ricinoleate, zinc abietate and zinc oxalate are also preferred.
  • the content of zinc salt in detergents or cleaners is preferably between 0.1 and 5% by weight, preferably between 0.2 and 4% by weight and in particular between 0.4 and 3% by weight.
  • the content of zinc in oxidized form (calculated as Zn 2+ ) between 0.01 to 1 wt .-%, preferably between 0.02 to 0.5 wt .-% and in particular between 0.04 to 0.2 Wt .-%, each based on the total weight of the glass corrosion inhibitor-containing agent.
  • Compositions according to the invention may contain corrosion inhibitors which serve to protect the ware or the machine, with particular silver protectants being of particular importance in the field of automatic dishwashing. It is possible to use the known substances of the prior art. In general, silver protectants from the group of the triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes can be used in particular. Particularly preferred to use are benzotriazole and / or alkylaminotriazole.
  • 3-amino-5-alkyl-1,2,4-triazoles or their physiologically tolerated salts preference is given to using 3-amino-5-alkyl-1,2,4-triazoles or their physiologically tolerated salts, these substances being particularly preferably used in a concentration of 0.001 to 10% by weight, preferably 0.0025 to 2% by weight .-%, particularly preferably 0.01 to 0.04 wt .-% are used.
  • Preferred acids for salt formation are hydrochloric acid, sulfuric acid, phosphoric acid, carbonic acid, sulphurous acid, organic carboxylic acids such as acetic, glycolic, citric and succinic acid.
  • cleaner formulations often contain active chlorine-containing agents which can markedly reduce the corrosion of the silver surface.
  • active chlorine-containing agents such as di- and trihydric phenols, for example hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol, pyrogallol or derivatives of these classes of compounds are used.
  • salt and complex inorganic compounds such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce are often used.
  • transition metal salts which are selected from the group of the manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (ammin) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) - complex the chlorides of cobalt or manganese and manganese sulfate.
  • zinc compounds can be used to prevent corrosion on the items to be washed.
  • redox-active substances can be used. These substances are preferably inorganic redox-active substances from the group of manganese, titanium, zirconium, hafnium, vanadium, cobalt and cerium salts and / or complexes, wherein the metals preferably in one of the oxidation states II, III, IV, V or VI are present.
  • the metal salts or metal complexes used should be at least partially soluble in water.
  • the counterions suitable for salt formation comprise all conventional mono-, di-, or tri-negatively charged inorganic anions, for example, oxide, sulfate, nitrate, fluoride, but also organic anions such as stearate.
  • metal salts and / or metal complexes are selected from the group MnSO 4 , Mn (II) citrate, Mn (II) stearate, Mn (II) acetylacetonate, Mn (II) - [1-hydroxyethane-1,1- diphosphonate], V 2 O 5 , V 2 O 4 , VO 2 , TiOSO 4 , K 2 TiF 6 , K 2 ZrF 6 , CoSO 4 , Co (NO 3 ) 2 , Ce (NO 3 ) 3 , and mixtures thereof, such that the metal salts and / or metal complexes are selected from the group MnSO 4 , Mn (II) citrate, Mn (II) stearate, Mn (II) acetylacetonate, Mn (II) - [1-hydroxyethane-1,1- diphosphonate], V 2 O 5 , V 2 O 4 , VO 2 , TiOSO 4 ,
  • the inorganic redox-active substances are preferably coated, that is to say completely coated with a water-tight material which is readily soluble in the cleaning temperatures, in order to prevent their premature decomposition or oxidation during storage.
  • Preferred coating materials which are applied by known methods, such as Sandwik from the food industry, are paraffins, microwaxes, waxes of natural origin such as carnauba wax, candellila wax, beeswax, higher melting alcohols such as hexadecanol, soaps or fatty acids.
  • the metal salts and / or metal complexes mentioned are contained in cleaning agents, preferably in an amount of 0.05 to 6 wt .-%, preferably 0.2 to 2.5 wt .-%, each based on the total agent.
  • agents according to the invention are packaged in shaped bodies, for example tablets, it is possible, in order to facilitate the disintegration of these tablets, to incorporate disintegration aids, so-called tablet disintegrants, into these compositions. this shortens the disintegration times.
  • tablet disintegrants or disintegrants are meant excipients which ensure the rapid disintegration of tablets in water or other media and for the rapid release of the active ingredients.
  • Swelling disintegration aids are, for example, carbonate / citric acid systems, although other organic acids can also be used.
  • Swelling disintegration aids are, for example, synthetic polymers such as polyvinylpyrrolidone (PVP) or natural polymers or modified natural substances such as cellulose and starch and their derivatives, alginates or casein derivatives.
  • Disintegration aids are preferably used in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6% by weight, based in each case on the total weight of the disintegration assistant-containing agent.
  • Preferred disintegrating agents are cellulosic disintegrating agents, so that preferred washing or cleaning agents comprise such cellulose-based disintegrants in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6% by weight. % contain.
  • Pure cellulose has the formal gross composition (C 6 H 10 O 5 ), and formally represents 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.
  • CMC carboxymethylcellulose
  • 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 derivatives.
  • 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.
  • 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.
  • microcrystalline cellulose As a further disintegrating agent based on cellulose or as a component of this component microcrystalline cellulose can be used.
  • This microcrystalline cellulose is obtained by partial hydrolysis of celluloses under conditions 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, for example, can be compacted into granules having an average particle size of 200 ⁇ m.
  • Preferred disintegration aids preferably cellulose-based disintegration aids, preferably in granular, cogranulated or compacted form, are present in the disintegrating agent-containing agents in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6 Wt .-%, each based on the total weight of the disintegrating agent-containing agent.
  • gas-evolving effervescent systems can furthermore be used as tablet disintegration auxiliaries.
  • the gas-evolving effervescent system may consist of a single substance that releases a gas upon contact with water.
  • the gas-releasing effervescent system in turn consists of at least two constituents which react with one another to form gas.
  • the bubble system used in the detergents or cleaners can be selected both on the basis of economic and ecological considerations.
  • Preferred effervescent systems consist of alkali metal carbonate and / or bicarbonate and an acidifying agent which is suitable for liberating carbon dioxide from the alkali metal salts in aqueous solution.
  • Aciditysmittel which release carbon dioxide from the alkali metal salts in aqueous solution
  • boric acid and alkali metal hydrogen sulfates, alkali metal dihydrogen phosphates and other inorganic salts can be used.
  • organic Acidifier wherein the citric acid is a particularly preferred Acidiser.
  • acidifying agents in the effervescent system from the group of organic di-, tri- and oligocarboxylic acids or mixtures thereof.
  • agents according to the invention which contain antiredeposition agents have particularly advantageous properties.
  • agents according to the invention are therefore detergents or cleaning agents according to the invention which also contain antiredeposition agents in addition to the amylases according to the invention.
  • the anti-redeposition agents suitable in the context of the present invention have already been described in detail above.
  • Preferred embodiments of the present invention are laundry detergents, wherein the anti-redeposition agent is a cellulose or a cellulose derivative obtainable by substitution and / or alkylation of hydroxyl groups, preferably cellulose ethers, such as carboxymethyl cellulose (Na salt), methyl cellulose, Hydroxyalkylcellulose and mixed ethers, such as methylhydroxyethyl-cellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof.
  • cellulose ethers such as carboxymethyl cellulose (Na salt), methyl cellulose, Hydroxyalkylcellulose and mixed ethers, such as methylhydroxyethyl-cellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof.
  • These preferred laundry detergents may be in solid or liquid form. Particularly advantageous effects are achieved in powdered or granular, or tablet-shaped textile detergents.
  • the bulk densities of the powdery to granular textile detergents can vary within a broad range, for example from 300 to 900 g / l.
  • Particularly preferred solid laundry detergents according to the invention contain antiredeposition agents and in particular CMC in amounts of from 0.2 to 5% by weight, in particular from 0.2 to 3% by weight.
  • a preferred embodiment of the present invention therefore relates to detergents or cleaners according to the invention, which additionally contain a bleach or a bleach system composed of several components.
  • compositions according to the invention which comprise a combination of ⁇ -amylases relevant to the invention and bleach or a bleach system have significant performance advantages over bleach-containing agents with other conventional ⁇ -amylases.
  • Preferred embodiments of this aspect of the invention are detergents or cleaners according to the invention, wherein the bleach or a component of the bleach system is an organic or inorganic per compound and / or an oxidative enzyme.
  • Preferred embodiments of this aspect of the invention are detergents or cleaners according to the invention, wherein the bleach or the component of the bleach system is percarbonate, perborate, phthalimidoperoxyhexanoic acid (PAP) and / or an oxidase, in which case a substrate of this oxidase is preferably additionally present ,
  • the agents comprise percarbonate, in particular a combination of percarbonate and the bleach activator TAED.
  • the agents contain phthalimidoperoxyhexanoic acid (PAP), optionally in combination with TAED.
  • PAP phthalimidoperoxyhexanoic acid
  • these agents are solid, powdery to granular, optionally compacted, extruded or tabletted or else liquid to gel-like laundry detergents. Particularly surprising was the increase in performance of the liquid to gel detergent laundry detergents according to the invention.
  • these are solid, powdery to granular, optionally compacted, extruded or tabletted or liquid to gelatin machine dishwashing detergents, which also show surprising performance advantages.
  • agents which consist of several phases for example of at least one liquid phase and at least one solid phase, it is particularly preferred that the bleach is housed in the solid phase (s). Also, separation of bleach and amylases is possible but not required to the extent that is the case with conventional combinations of amylases and bleach.
  • the bleach-containing detergents according to the invention are solid or liquid to gel-like pretreatment agents which, in the context of the present invention, are always counted among the detergents and in particular the laundry detergents.
  • Textile aftertreatment agents which contain the amylases relevant to the invention, irrespective of whether they additionally contain bleach or not, are included within the scope of the present invention as detergents and, in particular, to laundry detergents.
  • Preferred embodiments of the invention are agents which oxidases, optionally in combination with one of the abovementioned bleaching agents mentioned below, bleach activators or bleach catalysts.
  • the particular substrates for the potential oxidases will be apparent to those skilled in the art in light of the reactions naturally catalyzed by these enzymes. With regard to the perhydrolase activities, reference should also be made to the published prior art.
  • Preferred embodiments of this aspect of the invention are detergents or cleaners according to the invention, wherein additionally organic or inorganic bleach activators and / or organic or inorganic bleach catalysts are contained. Some preferred embodiments have already been mentioned above.
  • Preferred embodiments of this aspect of the invention are detergents or cleaners according to the invention, wherein the bleach activators and / or bleach catalysts are one or more of the following compounds: tetraacetylethylenediamine (TAED), nonanoyloxybenzylsulfonate (NOBS), lauryloxybenzylsulfonate (LOBS), iso-lauryloxybenzylsulfonate (i -LOBS), pentaacetylglucose, a manganese-containing bleach catalyst, in particular 5,12-diethyl-1,5,8,12-tetraazabicyclo [6,6,2] hexadecane manganese dichloride (Mn-TACN), cobalt pentamine complexes, nitrile quats, Benzoyl caprolactam (BzCL), 4-nitrobenzoyl caprolactam, 3-chlorobenzoyl caprolactam, benzoyloxybenzyl sulfonate
  • Preferred embodiments of this aspect of the invention are detergents or cleaners according to the invention wherein the bleach or at least one component of the bleach system is provided in coated form.
  • bleaching agents such as perborate, percarbonate or PAP as well as bleach activators such as TAED are preferably used coated.
  • TAED bleach activators
  • Another preferred object of the present invention is a washing or cleaning agent which additionally contains at least one further enzyme.
  • these are detergents or cleaning agents containing a protease, preferably a subtilisin protease.
  • proteases look at and hydrolyze other enzymes as well as fiction-relevant ⁇ -amylases as substrates, this result was all the more surprising.
  • Preferred embodiments of this aspect of the invention are detergents according to the invention wherein the protease in the fully-formulated agent is in a concentration of the protease enzyme protein of from 0.000001 to 5% by weight, and more preferably from 0.0000025 to 1% by weight, to 0.000005 to 0.5% by weight, to 0.0000075 to 0.15% by weight, and most preferably to 0.00001 to 0.13 wt .-%, wherein still more particularly preferably the concentration for automatic dishwashing comprises 0.003 to 0.13 wt .-%.
  • a protease preferably subtilisin protease
  • subtilisin protease can also be used with comparatively low concentration.
  • Preferred embodiments of this aspect of the invention are detergents or cleaners according to the invention, wherein the subtilisin protease is a wild-type protease or a protease variant.
  • wild-type proteases in particular when they are produced by a cultivatable strain, can be produced comparatively easily, namely by directly taking this wild-type strain into culture.
  • Protease variants on the other hand, which are described in detail in the prior art, have performance differences or special compatibilities or incompatibilities with other ingredients, so that depending on the purposed cleaning purpose, the most diverse, each optimal proteases can be used.
  • Particularly advantageous embodiments are those which contain proteases lying in the respective regions of homology as explained above with the ⁇ -amylases described here as being particularly relevant to the invention and not only show advantageous performance properties of the agents per se, but also these improved performances on particularly advantageous interactions between the different enzymes are attributed.
  • the enzymes disclosed there in each case can also serve as starting points for the generation of protease variants which show even better interactions with the ⁇ -amylases described here in particular as being relevant to the invention (see below).
  • Preferred embodiments of this aspect of the invention are detergents or cleaners according to the invention, wherein the protease variant is an amino acid change relative to a starting protease homologizable with the Bacillus lentus alkaline protease in one or more of the following positions: 3, 4, 36, 42, 43, 47, 56, 61, 69, 87, 96, 99, 101, 102, 104, 114, 118, 120, 130, 139, 141, 142, 154, 157, 188, 193, 199, 205, 211, 224, 229, 236, 237, 242, 243, 250, 253, 255 and 268, in the count of the alkaline protease from Bacillus lentus.
  • Preferred embodiments herein are detergents or cleaners according to the invention, wherein the protease variant is one having an amino acid change relative to the starting molecule in one or more of the following positions: 3, 4, 43, 61, 188, 193, 199, 211 , 224, 250 and 253.
  • detergents or cleaning agents which are one or more of the amino acid substitutions S3T, V4I, I43V, G61A, A188P, V193M, V199I, L211D, L211E, L211G, L211N or L211Q, A224V, S250G and S253N ,
  • Variants with amino acid substitutions in these positions are exemplified by the applications WO 92/21760 A1 . WO 95/23221 A1 . WO 03/038082 A2 . WO 02/088340 A2 , and WO 2005/118793 disclosed.
  • variant F49 which has given a surprisingly positive result in conjunction with the particularly relevant to the invention ⁇ -amylase variants.
  • Other proteases covered by this aspect of the invention can be prepared on the basis of the information given in the respective applications.
  • Preferred embodiments of this aspect of the invention are detergents or cleaning agents according to the invention, wherein the starting molecule is the alkaline protease from Bacillus lentus, preferably from Bacillus lentus DSM 5483, or a variant thereof.
  • This enzyme can be easily prepared starting from the deposited strain and from the aforementioned applications.
  • a protease F49 as described above can according to WO 95/23221 A1 exactly derived from this protease.
  • Further preferred embodiments of the present invention are therefore detergents or cleaners containing a glucanase which hydrolyzes plant polysaccharides, in particular a hemicellulase.
  • plant polysaccharides in particular hemicelluloses, form common problem soiling on textiles and on hard surfaces.
  • enzymes of this class with the ⁇ -amylase relevant to the invention, a surprising washing or cleaning performance of corresponding agents results in complex stains attributable, inter alia, to vegetable polysaccharides.
  • Preferred embodiments of this aspect of the invention are detergents or cleaners according to the invention wherein the glucanase in the fully-formulated agent has a concentration of the glucanase enzyme protein of from 0.000001 to 5% by weight, and more preferably from 0.0000025 to 1% by weight 0.000005 to 0.5 wt .-%, to 0.0000075 to 0.1 wt .-% and most preferably to 0.00001 to 0.075 wt .-% is contained, wherein furthermore very particularly preferably the concentration for mechanical Dishwashing agent is not more than 0.01 wt .-%, in particular 0.001 to 0.0072 wt .-%, and for textile detergent not more than 0.05 wt .-%, in particular 0.0009 to 0.04 wt .-% is.
  • a preferred embodiment of this aspect of the invention comprises detergents or cleaning agents, wherein the glucanase or hemicellulase is a ⁇ -glucanase.
  • WO 99/06573 A1 WO 99/06515 A1 and WO 99/06516 A1 that is, those from Bacillus alkalophilus DSM 9956 and that from B. amyloliquefaciens available from Novozymes under the tradename Cereflo.
  • a likewise preferred embodiment of this aspect of the invention comprises detergents or cleaners, wherein the glucanase or hemicellulase is a mannanase.
  • a likewise preferred embodiment of this aspect of the invention comprises detergents or cleaning agents, wherein the glucanase or hemicellulase is a pullulanase.
  • a further preferred embodiment of the invention therefore relates to detergents or cleaners which contain a cellulase.
  • Cellulases have long been established as cleaning enzymes, especially as enzymes for laundry detergents. This is partly because they are able to hydrolyze soils based on cellulose. On the other hand, they act as anti redeposition agents and as enzymes which react with the textile surface and in this way, for example, can provide a finishing and / or a color refreshing effect. Their graying-inhibiting effect is also described. Especially in the case of grayness inhibition and color refreshment even positive interactions could be observed. These were particularly evident when starchy stains were present on the laundry and / or in the wash liquor.
  • all cellulase-mediated effects of detergents or cleaners can be improved in interaction with an ⁇ -amylase relevant to the invention, or an improvement in the effect of the ⁇ -amylase can be observed.
  • the scope of the present application thus also includes the use of a cellulase and a ⁇ -amylase relevant for the invention for cleaning textiles or hard surfaces, as well as for anti-redeposition, color refreshment and grayness inhibition in the washing of textiles. This applies in particular within the framework of appropriately designed washing or cleaning agents.
  • Preferred embodiments of this aspect of the invention are detergents or cleaners according to the invention wherein the cellulase in the fully-formulated agent is in a concentration of the cellulase enzyme protein of from 0.000001 to 5% by weight and more preferably from 0.0000025 to 1% by weight 0.000005 to 0.5 wt%, to 0.0000075 to 0.1 wt%, and more particularly preferably to 0.00001 to 0.072 wt .-% is contained, wherein still more particularly preferably the concentration for textile detergent comprises 0.0007 to 0.005 wt .-%.
  • Both embodiments are directed to the respective cleaning aspects that are pursued with these alternatives, which are described in the prior art.
  • WO 96/34092 A2 show how two cellulases or cellulase mixtures with different activity spectra are able to complement each other in corresponding laundry detergents.
  • an aggressive single-component cellulase can be combined with an ⁇ -amylase in accordance with the invention.
  • the washing or cleaning agents contain, apart from the ⁇ -amylases relevant to the invention, at least two further enzymes, advantageously at least one protease and one cellulase or at least one protease and one glucanase, in particular a mannanase, or at least one protease, a cellulase and a glucanase.
  • a further preferred embodiment of the invention consists in a washing or cleaning agent, which in addition to the ⁇ -amylases relevant to the invention at least one further enzyme and at least one bleach or a bleach system as described above, advantageously containing percarbonate and / or PAP and optionally TAED and / or a Manganese or cobalt bleach catalyst.
  • Preferred embodiments of the present invention are detergents or cleaners containing builders.
  • washing or cleaning agents according to the invention contain at least zeolite as builder.
  • detergents or cleaners according to the invention also contain at least one builder substance in addition to the ⁇ -amylases relevant to the invention, this at least one builder substance being in particular a zeolite, as is customarily used in laundry detergents, and at least one further enzyme.
  • washing or cleaning agents according to the invention also comprise at least one builder substance in addition to the ⁇ -amylases relevant to the invention, this at least one builder substance being in particular a zeolite, as is customarily used in laundry detergents, and at least one bleaching agent or bleach system, wherein percarbonate and / or PAP optionally in combination with TAED and / or a manganese or cobalt bleach catalyst is particularly preferred.
  • a washing or cleaning agent according to the invention which, in addition to the ⁇ -amylases relevant to the invention, also comprises at least one builder, at least one further enzyme and at least one bleach or bleach system.
  • Preferred embodiments of the present invention are detergents containing an organic chemical polymer.
  • Further preferred embodiments of the present invention are detergents or cleaners according to the invention, wherein the organic-chemical polymer is an anionic or cationic polymer.
  • Suitable examples thereof are sulfopolymers and polyacrylates, such as those obtainable, for example, under the trade name Mirapol from Rhodia.
  • Preferred embodiments of the present invention are detergents containing a nonionic surfactant.
  • Preferred embodiments of this aspect of the invention are detergents or cleaners according to the invention, wherein the nonionic surfactant is a hydroxy mixed ether.
  • Preferred embodiments of the present invention are detergents containing at least one optical brightener.
  • This class of ingredients especially for textile detergents, leads to a perceived positive impression of the cleaned laundry.
  • ⁇ -amylases relevant to the invention therefore, particularly positive results with regard to the visual perceived degree of whiteness of the textiles have been shown.
  • Preferred embodiments of this aspect of the invention are detergents or cleaners, wherein the optical brighteners are, in particular, derivatives of diaminostilbenedisulfonic acid or its alkali metal salts.
  • Suitable salts are, for example, salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulphonic acid or compounds of similar construction which, instead of the morpholino Group carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group.
  • brighteners of the substituted diphenylstyrene type may be present, for example, the alkali salts of 4,4'-bis (2-sulfostyryl) -diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) -diphenyl, or 4 - (4-chlorostyryl) -4 '- (2-sulfostyryl).
  • Mixtures of the aforementioned brightener can be used.
  • Particularly suitable are mixtures of optical brighteners of a distyryl-biphenyl derivative and a stilbentriazine derivative. These brightener types can be used in any desired mixing ratios.
  • Such brighteners are available, for example, under the trade name Tinopal from Ciba.
  • textile pretreatment agents containing invention-relevant amylases represent a preferred embodiment of the invention.
  • such textile pretreatment agents are suitable, which also contain at least one bleaching agent or a bleach system of the type described above in addition to the invention relevant amylases.
  • Very particularly advantageous textile pretreatment agents also contain fat-dissolving substances, for example nonionic surfactants, apart from the amylases relevant to the invention.
  • textile pretreatment compositions which contain, apart from the amylases relevant to the invention, at least two additives from the group of bleaching agents and bleach systems, enzymes and fat-dissolving substances.
  • Anti-redeposition agents for example CMC, may also be included in the fabric pretreatment compositions.
  • the washing or cleaning agents according to the invention cause a reduced formation of odor on the washed or cleaned material.
  • the amylases relevant to the invention are able to support such an effect, in particular if they are contained in the agents according to the invention in combination with one or more of the group of the following ingredients.
  • This group includes bleaching agents and bleach activators, complexing agents, phosphonates, polycarboxylates such as citrates and polymeric polycarboxylates, but also dispersants and strong salts. Most of these ingredients have already been described in detail above. This description will be referred to again at this point.
  • the dispersants which can be used according to the invention include dye transfer inhibitors, polycarboxylates and polymeric polycarboxylates, soil release polymers, all of which have also been described in detail above, but also and in particular polyethyleneimines and also cyclodextrins and cyclodextrin derivatives.
  • the strong salts in the context of the present invention include phosphates, carbonates, bicarbonates and sesquicarbonates, sulfates and chlorides, especially in the form of the sodium, potassium and / or calcium salts.
  • these salts are in the form of the sodium salts, with mixtures of sodium salts and calcium salts being particularly preferred.
  • calcium salts are only present in relatively small amounts in the compositions.
  • Preferred washing or cleaning agents contain strong salts as calcium salts in amounts of 0.001 to 5 wt .-%, preferably in amounts not above 3 wt .-%.
  • the laundry detergents according to the invention contain not only the amylases relevant to the invention but also fabric softening ingredients, especially sheet silicates of the smectite or bentonite type. It has been found that combinations of the invention-relevant amylases with conventional textile-softening phyllosilicates cause a special softness effect of the laundered textiles.
  • the washing or cleaning agents according to the invention can be present in solid form, that is to say in pulverulent or granular, in compacted or tableted form, as extrudate, as pellet or as shaped article or as constituent. It is also possible that they are present as a constituent of a shaped body, for example, represent the content of a water-soluble or water-insoluble bag.
  • Solid compositions according to the invention may also comprise a plurality of solid phases, each of these solid phases being pulverulent, granular, may be extruded or tableted.
  • agents according to the invention may have at least one powdery, granulated or extruded phase and at least one tablet-like phase.
  • compositions according to the invention can also have multiple phases of at least one solid and at least one liquid to gelatinous or even pasty phase.
  • water content of the agents or solid phases containing enzymes has always been a critical parameter, since it has been known that water was able to destabilize conventional enzymes by hydrolysis. It is irrelevant whether the water is present in bound form or as free water in the agents. For this reason, many enzymes must be elaborately encased and protected from water.
  • solid detergents or cleaners according to the invention or at least detergents or cleaners having at least one solid phase which optionally contains the amylases relevant to the invention in coated form may have a significantly higher water content without adverse effect on the amylase than has hitherto been used known, optionally also coated amylases.
  • washing or cleaning agents which are solid or at least have a solid phase which contain the amylases relevant to the invention in optionally coated form, the water content of the solid or solid phase being from 1 to 20% by weight, preferably from 3 to 18 wt .-% and in particular a maximum of 15 wt .-% is.
  • particularly preferred water contents of the compositions according to the invention in solid form or the solid phase which contains the amylase relevant to the invention are 5% by weight, 10% by weight, 12% by weight or 15% by weight, all of them also Intermediate values are possible.
  • the agents according to the invention can also be present in liquid, gelatinous or pasty form. It is likewise possible to provide agents which contain the amylases relevant to the invention in a liquid, gelatinous or pasty phase, this phase optionally being present separately from at least one other phase, which may be solid or liquid. In the context of the present invention, from this point liquid is also understood to mean gelatinous or pasty. Accordingly, preferred liquid agents or phases thereof which contain invention-relevant amylases have a water content of 50 to 99 wt .-%.
  • washing or cleaning agents or phases according to the invention which comprise the amylases relevant to the invention, which have a viscosity of from 50 mPas to 20,000 mPas, preferably from 50 mPas to 10,000 mPas and in particular at least 100 mPas or at most 8,000 mPas.
  • the viscosity of the agents can be measured by conventional standard methods (for example Brookfield LVT-II viscosimeter at 20 rpm and 20 ° C., spindle 3).
  • washing or cleaning agents which are liquid or contain at least one liquid phase which contains an amylase relevant to the invention also contain at least one bleaching agent or a bleach system.
  • liquid detergents or cleaners which have at least 2 liquid phases. These liquid phases can be spatially separated from each other. Suitable embodiments are so-called two-chamber or multi-chamber bag, which are particularly always preferred when the funds are offered in single portions. However, another preferred form of supply also represent two-chamber or multi-chamber systems, from which the funds can be dosed.
  • a further preferred embodiment of the invention relates to washing or cleaning agents, in particular automatic dishwashing detergents, which are characterized in that the washing or cleaning agent further contains phthalimidoperoxyhexanoic acid (PAP) and the ⁇ -amylase variant and the phthalimidoperoxyhexanoic acid separated from one another in different phases of the wash cycle. or detergent.
  • PAP phthalimidoperoxyhexanoic acid
  • the multiphase detergents or cleaners according to the invention can be present in solid or liquid form, but also as combination products of solid and liquid preparations. They can be made up in the form of prefabricated dosing units for individual washing or cleaning operations or in the form of large containers containing detergents or cleaners for more than one wash or cleaning cycle. Prefabricated metering units preferably have a weight between 12 and 28 g, preferably between 13 and 24 g and in particular between 14 and 20 g and are adapted in their spatial form any dosing aids such as the dispensing chambers of washing machines or dishwashers.
  • the washing or cleaning agents according to the invention are in the form of prefabricated compressed metering units.
  • the compressed washing or cleaning agents according to the invention advantageously have three, preferably four, preferably five and in particular six phases.
  • the preparation of these metering units is preferably carried out by tableting, extrusion or roll compaction.
  • the tabletting is preferably carried out in a manner known to those skilled in the art by compressing particulate starting substances. To prepare the tablets, the premix is compressed in a so-called matrix between two punches to form a solid compressed product. This process, which is referred to below as tabletting, is divided into four sections: metering, compaction (elastic deformation), plastic deformation and ejection.
  • the tabletting is preferably carried out on so-called rotary presses.
  • preferred methods are characterized in that the pressing takes place at pressing pressures of 0.01 to 50 kNcm-2, preferably from 0.1 to 40 kNcm-2 and in particular from 1 to 25 kNcm-2.
  • the individual phases of the two- or more-phase tablet are preferably arranged in layers.
  • the tablet may have two, three, four or more layers.
  • At least one of the layers has a cavity.
  • the term "cavity" in the present invention troughs, which are located for example in the bottom and / or roof surface of the molding.
  • the shape of the trough can be chosen freely, wherein tablets are preferred in which one trough has a round opening area.
  • the bottom surface of the trough can be flat or inclined.
  • the trough is preferably filled with a further washing or cleaning agent phase. This phase may also be a compressed, preferably tableted molded article. Alternatively, cast bodies, solidifying melts, gels or powders can also be filled.
  • the volume of the well is preferably between 0.1 and 20 ml, preferably between 0.2 and 15 ml, more preferably between 1 and 10 ml and in particular between 2 and 7 ml.
  • the structure of the tablet is onion-like.
  • at least one inner layer is completely surrounded by at least one outer layer.
  • the weight ratio of the phase with the lowest weight fraction of the tablet is preferably at least 5 wt .-%, preferably at least 10 wt .-% and in particular at least 20 wt .-%.
  • the proportion by weight of the phase with the highest proportion by weight of the tablet in the case of biphasic tablets is preferably not more than 90% by weight, preferably not more than 80% by weight and in particular between 55 and 70% by weight.
  • the proportion by weight of the phase with the highest proportion by weight of the tablet is preferably not more than 80% by weight, preferably not more than 70% by weight and in particular between 40 and 60% by weight.
  • washing or cleaning agents are characterized in that the washing or cleaning agent is in the form of a compressed, preferably in the form of a tableted shaped body.
  • the compressed washing or cleaning agents according to the invention advantageously have three, preferably four, preferably five and in particular six phases.
  • the three, four, five, six or more phases are preferably configured in the form of layers of the same base area and arranged one above the other.
  • the phase containing the ⁇ -amylase variant and the phase containing the phthalimidoperoxyhexanoic acid do not form a common phase boundary.
  • the washing or cleaning agent tablet according to the invention comprises a two-layer main body having a first layer, a second layer with a depression and a core inserted into this depression.
  • the preferred distribution of some of the washing or cleaning active ingredients contained in these tablets is given in the following table: 1st shift 2 layer core PAP nonionic surfactant ⁇ -amylase variant PAP bleach ⁇ -amylase variant PAP Silver protectants ⁇ -amylase variant ⁇ -amylase variant nonionic surfactant PAP ⁇ -amylase variant bleach PAP ⁇ -amylase variant Silver protectants PAP PAP ⁇ -amylase variant nonionic surfactant PAP ⁇ -amylase variant bleach PAP ⁇ -amylase variant Silver protectants ⁇ -amylase variant PAP nonionic surfactant ⁇ -amylase variant PAP bleach ⁇ -amylase variant PAP Silver protectants ⁇ -amylase variant PAP nonionic surfactant ⁇ -amylase variant PAP bleach ⁇ -amylase variant
  • the washing or cleaning agent tablet according to the invention comprises a three-layered base body having a first layer, a second layer, a third layer with a depression and a core inserted into this depression.
  • the preferred distribution of some of the washing or cleaning active ingredients contained in these tablets is given in the following table: 1st shift 2 layer 3 layer core PAP bleach Silver protectants ⁇ -amylase variant PAP Silver protectants bleach ⁇ -amylase variant bleach PAP Silver protectants ⁇ -amylase variant Silver protectants PAP bleach ⁇ -amylase variant bleach Silver protectants PAP ⁇ -amylase variant bleach Silver protectants PAP ⁇ -amylase variant Silver protectants bleach PAP ⁇ -amylase variant PAP bleach Silver protectants ⁇ -amylase variant PAP nonionic surfactant bleach ⁇ -amylase variant bleach PAP nonionic surfactant ⁇ -amylase variant nonionic surfactant PAP bleach ⁇ -amylase variant bleach nonionic surfactant PAP ⁇ -amylase variant nonionic surfact
  • these metering units are preferably packed with a water-soluble packaging material.
  • the water-soluble packaging material preferably comprises a water-soluble polymer.
  • Some particularly preferred water-soluble polymers which are suitable for processing as packaging materials are polyvinyl alcohols, acetalated polyvinyl alcohols, polyvinylpyrrolidones, polyethylene oxides, celluloses and gelatin.
  • Polyvinyl alcohols (abbreviated PVAL, occasionally PVOH) is the name for polymers of the general structure in small proportions (about 2%) also structural units of the type contain.
  • polyvinyl alcohols which are available as white-yellowish powders or granules with degrees of polymerization in the range of about 100 to 2500 (molar masses of about 4000 to 100,000 g / mol), have degrees of hydrolysis of 98-99 or 87-89 mol%. , so still contain a residual content of acetyl groups.
  • the polyvinyl alcohols are characterized by the manufacturer by indicating the degree of polymerization of the starting polymer, the degree of hydrolysis, the saponification number or the solution viscosity.
  • polyvinyl alcohols are soluble in water and a few highly polar organic solvents (formamide, dimethylformamide, dimethyl sulfoxide); They are not attacked by (chlorinated) hydrocarbons, esters, fats and oils.
  • Polyvinyl alcohols are classified as toxicologically safe and are biologically at least partially degradable.
  • the water solubility can be reduced by aftertreatment with aldehydes (acetalization), by complexation with Ni or Cu salts or by treatment with dichromates, boric acid or borax.
  • the polyvinyl alcohol coatings are largely impermeable to gases such as oxygen, nitrogen, helium, hydrogen, carbon dioxide, but allow water vapor to pass through.
  • the packaging material at least partially comprises a polyvinyl alcohol whose degree of hydrolysis is 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol% % is.
  • the packaging material comprises at least 20% by weight, more preferably at least 40% by weight, most preferably at least 60% by weight and in particular at least 80% by weight, of a polyvinyl alcohol whose Hydrolysis degree 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol%.
  • Polyvinyl alcohols of a certain molecular weight range are preferably used as materials for the packaging, it being preferred according to the invention that the packaging material comprises a polyvinyl alcohol whose molecular weight is in the range of 10,000 to 100,000 gmol-1, preferably 11,000 to 90,000 gmol-1, particularly preferably 12,000 to 80,000 gmol-1 and in particular from 13,000 to 70,000 gmol-1.
  • the degree of polymerization of such preferred polyvinyl alcohols is between about 200 to about 2100, preferably between about 220 to about 1890, more preferably between about 240 to about 1680, and most preferably between about 260 to about 1500.
  • polyvinyl alcohols described above are widely available commercially, for example under the trademark Mowiol® (Clariant).
  • Polyvinyl alcohols which are particularly suitable for the purposes of the present invention are, for example, Mowiol® 3-83, Mowiol® 4-88, Mowiol® 5-88 and Mowiol® 8-88.
  • polyvinyl alcohols suitable as packaging material are ELVANOL® 51-05, 52-22, 50-42, 85-82, 75-15, T-25, T-66, 90-50 (trademark of Du Pont), ALCOTEX® 72.5, 78, B72, F80 / 40, F88 / 4, F88 / 26, F88 / 40, F88 / 47 (trademark of Harlow Chemical Co.), Gohsenol® NK-05, A-300, AH-22, C-500, GH-20, GL-03, GM-14L, KA-20, KA-500, KH-20, KP-06, N-300, NH-26, NM11Q, KZ-06 (Trademark of Nippon Gohsei KK).
  • the water solubility of PVAL can be altered by post-treatment with aldehydes (acetalization) or ketones (ketalization).
  • Polyvinyl alcohols which are acetalated or ketalized with the aldehyde or keto groups of saccharides or polysaccharides or mixtures thereof have proven to be particularly advantageous and particularly advantageous on account of their pronounced cold water solubility.
  • To use extremely advantageous are the reaction products of PVAL and starch.
  • the water solubility can be changed by complexing with Ni or Cu salts or by treatment with dichromates, boric acid, borax and thus set specifically to desired values.
  • Films made of PVAL are largely impermeable to gases such as oxygen, nitrogen, helium, hydrogen, carbon dioxide, but allow water vapor to pass through.
  • PVAL films examples include the PVAL films available under the name "SOLUBLON®” from Syntana bottlesgesellschaft E. Harke GmbH & Co. Their solubility in water can be adjusted to the exact degree, and films of this product series are available which are soluble in aqueous phase in all temperature ranges relevant for the application.
  • PVP Polyvinylpyrrolidones
  • PVP are prepared by radical polymerization of 1-vinylpyrrolidone.
  • Commercially available PVP have molecular weights in the range of about 2,500 to 750,000 g / mol and are available as white, hygroscopic powders or as aqueous solutions.
  • Polyethylene oxides are polyalkylene glycols of the general formula H- [O-CH 2 -CH 2] n -OH, which are prepared industrially by base-catalyzed polyaddition of ethylene oxide (oxirane) in systems containing mostly small amounts of water with ethylene glycol as starting molecule. They have molar masses in the range of about 200 to 5,000,000 g / mol, corresponding to degrees of polymerization n of about 5 to> 100,000. Polyethylene oxides have an extremely low concentration of reactive hydroxy end groups and show only weak glycol properties.
  • Gelatin is a polypeptide (molecular weight: about 15,000 to> 250,000 g / mol), which is obtained primarily by hydrolysis of the collagen contained in the skin and bones of animals under acidic or alkaline conditions.
  • the amino acid composition of gelatin is broadly similar to that of the collagen from which it was obtained and varies depending on its provenance.
  • the use of gelatin as a water-soluble packaging material is extremely widespread, especially in pharmacy in the form of hard or soft gelatin capsules. In the form of films, gelatin has little use because of its high price compared to the polymers mentioned above.
  • packaging materials which comprise a polymer from the group starch and starch derivatives, cellulose and cellulose derivatives, in particular methyl cellulose, and mixtures thereof.
  • Starch is a homoglycan, wherein the glucose units are linked ⁇ -glycosidically.
  • Starch is composed of two components of different molecular weight: from about 20 to 30% straight chain amylose (MW about 50,000 to 150,000) and 70 to 80% branched chain amylopectin (MW about 300,000 to 2,000,000).
  • small amounts of lipids, phosphoric acid and cations are still included. While the amylose forms long, helical, entangled chains with about 300 to 1,200 glucose molecules as a result of the binding in the 1,4-position, the chain branches in amylopectin after an average of 25 glucose building blocks by 1,6-binding to a branch-like structure with about 1,500 to 12,000 molecules of glucose.
  • starch-derivatives which are obtainable from starch by polymer-analogous reactions are also suitable for the preparation of water-soluble coatings of the detergent, detergent and cleaner portions in the context of the present invention.
  • Such chemically modified starches include, for example, products of esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. But even starches in which the hydroxy groups have been replaced by functional groups that are not bound by an oxygen atom, can be used as starch derivatives.
  • the group of starch derivatives includes, for example, alkali starches, carboxymethyl starch (CMS), starch esters and ethers, and amino starches.
  • Pure cellulose has the formal gross composition (C6H10O5) n and formally represents a ⁇ -1,4-polyacetal of cellobiose, which in turn is composed of two molecules of glucose.
  • Suitable celluloses consist of about 500 to 5,000 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.
  • Preferred packaging materials are transparent or translucent.
  • the material used as packaging material is preferably transparent.
  • transparency means that the transmittance within the visible spectrum of the light (410 to 800 nm) is greater than 20%, preferably greater than 30%, more preferably greater than 40% and in particular greater than 50%.
  • a wavelength of the visible spectrum of the light has a transmittance greater than 20%, it is to be regarded as transparent within the meaning of the invention.
  • Stabilizing agents are materials which protect the ingredients contained in the dosing unit from decomposition or deactivation by light irradiation. Antioxidants, UV absorbers and fluorescent dyes have proven to be particularly suitable here.
  • Detergents or cleaning agents which are preferred according to the invention are characterized in that the washing or cleaning agent is in the form of a water-soluble metering unit comprising the washing or cleaning agent and a water-soluble packaging material.
  • the water-soluble packaging material can be shaped by the methods known to those skilled in the art.
  • the water-soluble polymer has been at least partially formed by an injection molding process or a deep-drawing process.
  • Detergents or cleaning agents which are preferred according to the invention are characterized in that the water-soluble metering unit has two, preferably three, preferably four and in particular five phases.
  • the separation of the individual phases in the water-soluble dosing units is realized by intermediate walls made of water-soluble packaging material and training by means of these intermediate walls of separate receiving chambers.
  • the washing or cleaning agent dosing unit comprises a water-soluble container with two separate receiving chambers.
  • the preferred distribution of some of the washing or cleaning active ingredients contained in these containers is given in the following table: 1st chamber 2nd chamber PAP ⁇ -amylase variant PAP ⁇ -amylase variant + bleach activator PAP ⁇ -amylase variant + silver protectant
  • the washing or cleaning agent dosing unit comprises a water-soluble container with three separate receiving chambers.
  • the preferred distribution of some of the washing or cleaning active ingredients contained in these containers is given in the following table: 1st chamber 2nd chamber 3rd chamber PAP nonionic surfactant ⁇ -amylase variant PAP bleach ⁇ -amylase variant PAP Silver protectants ⁇ -amylase variant
  • the washing or cleaning agent preparations present separately from one another in the chambers of the water-soluble container may be in solid or liquid form.
  • water-insoluble containers which contain one liquid in the two chambers or one solid each in one of the chambers or one liquid in one of the chambers and a solid in the other chamber are conceivable.
  • Particularly preferred according to the invention are water-soluble containers with three receiving chambers, of which two chambers are filled with a solid and the third chamber is filled with a liquid.
  • washing or cleaning agents in water-soluble containers, characterized in that the washing or cleaning agent comprises at least two solid and at least one liquid phase, wherein the ⁇ -amylase variant and the phthalimidoperoxyhexanoic acid are present separately in the solid phases, while the liquid Phase contains a nonionic surfactant.
  • these containers with three or more receiving chambers are injection-molded containers.
  • water-insoluble packaging materials it is of course also possible to use water-insoluble packaging materials.
  • the abovementioned detergents or cleaners are packaged in water-insoluble containers which have at least two separate chambers. These water-insoluble containers can contain prefabricated two- or multi-phase dosing units, but are used with particular preference for the packaging of large containers.
  • the ⁇ -amylase variant and the phthalimidoperoxyhexanoic acid are separated from one another, it being possible for the individual washing or cleaning agent preparations to be in solid or liquid form, as in the case of the water-soluble packaging materials.
  • water-insoluble containers which contain one liquid in the two chambers or one solid each in one of the chambers or one liquid in one of the chambers and a solid in the other chamber are conceivable.
  • Detergents or cleaning agents which are preferred according to the invention are characterized in that the washing or cleaning agent comprises at least one solid and at least one liquid phase, the ⁇ -amylase variant being present with particular preference in the solid phase.
  • the phthalimidoperoxyhexanoic acid is preferably used in the compositions according to the invention in powder form or in the form of a suspension.
  • particulate phthalimido peroxyhexanoic acid powder is preferably used in granulated and / or coated form.
  • the granulation and / or the coating not only improves the thermal stability but also ensures safe handling during processing, transport and storage.
  • Preferred granulation aids are sulfate, phosphates or fatty acids. Furthermore, stabilizers such as borax or EDTMP can be processed. The addition of surface-active compounds promotes the dissolution rate at low washing temperatures.
  • the granule core or, preferably, the particulate phthalimidoperoxyhexanoic acid is preferably coated with a film-forming substance such as polyacrylic acid or copolymers of allylaminomethylenephosphonic acid and acrylic acid. Through this coating, interactions between the peracid and oxidation-sensitive detergent ingredients are largely suppressed.
  • the active content of preferred PAP granules is between 65 and 85% by weight.
  • the PAP granules used have at least 50% by weight, preferably at least 80% by weight, more preferably at least 90% by weight and in particular at least 95% by weight, a particle size between 10 and 500 ⁇ m, preferably between 100 and 300 ⁇ m and in particular between 200 and 300 ⁇ m.
  • the mean particle size of the PAP granules used is preferably between 100 and 400 ⁇ m, preferably between 150 and 350 ⁇ m and in particular between 200 and 300 ⁇ m.
  • liquid formulations are also suitable as a field of application for powdered PAP.
  • the low solubility of the PAP allows peracid levels up to 15% by weight.
  • the suspension aids used are preferably nonionic surfactants or polymeric thickeners.
  • the Phtalimidoperoxyhexanklare can be used in phosphate-containing and phosphate-free detergents or cleaners.
  • the proportion by weight of phtalimidoperoxyhexanoic acid in the total weight of these detergents or cleaners is preferably between 0.1 and 20% by weight, preferably between 0.2 and 15% by weight and in particular between 0.5 and 10% by weight.
  • amylases relevant to the invention leads to detergents or cleaners according to the invention which give excellent washing results even after a relatively short time.
  • washing or cleaning agents and in particular textile detergents are preferred, which are used in so-called short-wash programs or cleaning programs and lead in such methods to excellent performance compared to conventionally assembled detergents or laundry detergents.
  • detergents or cleaning agents according to the invention already at lower temperatures lead to results, for example, in the whiteness of the laundered textiles or in the purity of the rinsed dishes, which in the application of conventional agents with conventional amylases only at higher temperatures or even can not be reached. Therefore, those detergents which are already used in machine washing processes at 40 ° C. or less, particularly preferably at 30 ° C. or less and very particularly preferably 20 ° C. or less, are particularly preferred. Likewise preferred in particular are those automatic dishwashing agents which are already used in automatic rinsing processes at 50 ° C. or less, preferably at 40 ° C. or less and very particularly preferably at 30 ° C. or less.
  • a further subject of the invention is washing or cleaning processes in which an ⁇ -amylase variant comes into action, which can be obtained from the ⁇ -amylase AA560 via the following amino acid changes: M9L / G149A / G182T / G186A / M202L / T2571 / Y295F / N299Y / M323T / A339S / E345R.
  • the present application thus relates to washing or cleaning processes in which washing or cleaning agents according to the invention are used.
  • a further subject of the invention is the use of an ⁇ -amylase variant for washing or cleaning, which can be obtained from the ⁇ -amylase AA560 via the following amino acid changes: M9L / G149A / G182T / G186A / M202L / T257I / Y295F / N299Y / M323T / A339S / E345R.
  • a further subject of the invention is the use of an ⁇ -amylase relevant to the invention and / or an ingredient combination according to the invention for the preparation of a washing or cleaning agent.
  • the washing-up agent used was a commercially available formulation for a bleached automatic dishwashing detergent for the respective test series with the ⁇ -amylases Duramyl to be compared, the ⁇ -amylase according to SEQ ID NO. 2 of WO 2005/108540 A1 and WO 2005/108537 A1 (WO) and an essential for the invention ⁇ -amylase (Erf.).
  • the weight of additional amylase was 0.009% by weight in the case of Duramyl and 0.006% by weight in the other two cases.
  • the bleached automatic dishwashing detergent of the invention provided significantly better performance than a similarly composed automatic dishwashing detergent containing conventional amylases.
  • This test material in 3.5 kg of clean ballast washing (also cotton), various detergent formulations in a commercial washing machine (Miele Novotronic ® W 308; 1,200 rpm) tested for washing performance. For this purpose, it was washed in a liquor of 17 l, with the short course program at 40 ° C. and about 40 min of washing time.
  • the dosage was 100 g of the respective agent + 0.1 wt .-% silicone oil.
  • the water hardness was 16 ° German hardness.
  • the control detergent used was a detergent base formulation of the following composition (all figures in percent by weight): 4% linear alkylbenzenesulfonate (sodium salt), 4% C 12 -C 18 fatty alcohol sulfate (sodium salt), 5.5 % C 12 -C 18 fatty alcohol with 7 EO, 1% sodium soap, 11% sodium carbonate, 2.5% amorphous sodium disilicate, 20% sodium perborate tetrahydrate, 5.5% TAED, 25% zeolite A, 4.5% polymeric polycarboxylate (Sokalan CP5 ®), 0.5% phosphonate, 2.5% granular foam inhibitor, 5% sodium sulfate, rest: water, optical brighteners, salts.
  • composition all figures in percent by weight: 4% linear alkylbenzenesulfonate (sodium salt), 4% C 12 -C 18 fatty alcohol sulfate (sodium salt), 5.5 % C 12 -C 18 fatty alcohol with 7 EO,
  • ⁇ -amylases termamyl and again the ⁇ -amylase according to SEQ ID NO. 2 of WO 2005/108540 A1 and WO 2005/108537 A1 (WO) and an invention-relevant ⁇ -amylase (Erf.) Tested.
  • the bleach detergent according to the invention gave a significantly better result than the comparative detergents. This was all the more surprising, since even after the short washing time of 40 minutes, a clear superiority of the inventive composition over the comparison means was achieved.
  • Example 3 Washing process at 30 ° C
  • Example 2 was repeated under otherwise identical conditions and with the same formulations, the formulations were selected, the Termamyl or the invention relevant amylase (Erf.) Contained. The only variation was that in Example 3 30 ° C was selected as the washing temperature.
  • the detergent according to the invention with the amylase relevant to the invention provided a significantly better washing result than the detergent containing Termamyl.
  • the detergent according to the invention achieved a higher washing performance at 30 ° C. than at 40 ° C.
  • Example 1 was repeated with significantly lower amylase concentrations and at different temperatures but under otherwise identical conditions.
  • Example 1 recipes with 0.0048 wt .-% of ⁇ -amylases according to SEQ ID NO. 2 of WO 2005/108540 A1 and WO 2005/108537 A1 (WO) or the invention-relevant ⁇ -amylase of the present application (Erf.) Made.
  • These formulations showed at the two tested cleaning temperatures of 40 ° C and 55 ° C the results shown in Table 3 below: Table 3: Cleaning procedure with bleached automatic dishwashing detergents at temperatures of 40 ° C and 55 ° C. Basic detergent with Removal in% at 40 ° C Removal in% at 55 ° C Where 56.2 64.2 Req. 75.9 99.9
  • compositions of the invention showed at both temperatures tested, surprisingly even at a low temperature of 40 ° C, a significantly better cleaning performance than the comparison means.

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EP11175303A 2005-12-28 2006-12-20 Produit de nettoyage ou de lavage avec une amylase spéciale Withdrawn EP2386632A1 (fr)

Applications Claiming Priority (3)

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DE200510062984 DE102005062984A1 (de) 2005-12-28 2005-12-28 Wasch- oder Reinigungsmittel mit spezieller Amylase
DE200610038448 DE102006038448A1 (de) 2005-12-28 2006-08-16 Enzym-haltiges Reinigungsmittel
EP06829764A EP1974027A2 (fr) 2005-12-28 2006-12-20 Détergents contenant une amylase spéciale

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