EP3353274B1 - Utilisation d'enzymes sous forme de granulés à concentration élevée pour augmenter la stabilité au stockage d'enzymes - Google Patents

Utilisation d'enzymes sous forme de granulés à concentration élevée pour augmenter la stabilité au stockage d'enzymes Download PDF

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EP3353274B1
EP3353274B1 EP16760749.8A EP16760749A EP3353274B1 EP 3353274 B1 EP3353274 B1 EP 3353274B1 EP 16760749 A EP16760749 A EP 16760749A EP 3353274 B1 EP3353274 B1 EP 3353274B1
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weight
enzyme
acid
cleaning
agents
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EP3353274A1 (fr
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Inga Kerstin Vockenroth
Thomas Weber
Noelle Wrubbel
Silke Menke
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38672—Granulated or coated enzymes
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets

Definitions

  • the invention relates to the use of highly concentrated enzyme granules in enzyme-containing detergents or cleaning agents to increase the stability of enzymes and an enzyme-containing washing or cleaning agent, in particular a liquid washing or cleaning agent with improved enzyme stability.
  • Common washing or cleaning agents on the market contain surfactants to remove dirt and stains.
  • surfactants to remove dirt and stains.
  • combinations of several surfactants in particular from the group of anionic, nonionic, cationic and amphoteric surfactants, are used here.
  • These surfactants alone are often not able to sufficiently remove dirt and stains, so that further auxiliaries are used in modern detergents or cleaning agents.
  • additional auxiliaries include enzymes of various types such as proteases, amylases, cellulases, mannanases, pectate lyases. Further enzyme classes are known to the person skilled in the art.
  • hydrolytic enzymes such as proteases, amylases or lipases are part of numerous textile and dishwashing detergents because of their direct cleaning effect.
  • the cleaning effect of the enzymes used in detergents or cleaning agents is determined not only by the enzyme structure but also to a significant extent by the way these enzymes are packaged and how they are stabilized against environmental influences. Washing or cleaning enzymes are packaged in both solid and liquid form.
  • the group of solid enzyme preparations includes, in particular, the enzyme granules consisting of several ingredients, which for their part are preferably incorporated into solid washing or cleaning agents.
  • liquid or gel-form washing or cleaning agents often contain liquid enzyme preparations, which, unlike enzyme granules, are far less protected against external influences.
  • a second group of known stabilizers is formed by borax, boric acids, boronic acids or their salts or esters. These include, in particular, derivatives with aromatic groups, for example ortho-, meta- or para-substituted phenylboronic acids, in particular 4-formylphenylboronic acid (4-FPBA) or the salts or esters of the compounds mentioned.
  • the latter compounds as enzyme stabilizers are disclosed, for example, in the international patent application WO 96/41859 A1 (Novo Nordisk ).
  • boric acids and boric acid derivatives for example, often have the disadvantage that they form undesirable by-products with other ingredients of a composition, in particular detergent ingredients, so that these are no longer available in the relevant agents for the desired cleaning purpose or even as contamination remain on the laundry.
  • Boric acids and borates are also considered to be disadvantageous from an environmental point of view.
  • the present invention is therefore based on the object of providing a stabilization route for enzymes which as far as possible avoids the disadvantages of the prior art.
  • the present invention therefore relates to the use of highly concentrated enzyme granules in enzyme-containing detergents or cleaning agents to increase the stability of proteases, whereby highly concentrated enzyme granules are understood to mean those enzyme granules which contain proteases in amounts of 0.1% by weight to 20% by weight , particularly preferably from 6% by weight to 19% by weight.
  • the washing or cleaning agent is preferably a solid washing or cleaning agent, preferably a solid, tablet-shaped machine dishwashing agent.
  • the enzyme is a protease, especially a subtilisin.
  • proteases are meant according to the invention.
  • an enzyme granulate is understood to mean any solid form of enzyme, for example PrNIs, granulates, extrudates or particles obtainable by dropping, in each case in uncoated or single or multiple coated form.
  • protease characterized as protease 4 according to SEQ ID NO.3.
  • the highly concentrated enzyme granules are preferably used in amounts of 0.05% by weight to 9% by weight, in particular in amounts of 0.1% by weight to 4.0% by weight, particularly preferably in amounts of 3.0 Wt .-% to 4.0 wt .-% used. Quantities of 0.5% by weight to 9% by weight, particularly preferably quantities of 3.0% by weight to 4.0% by weight, are used in cleaning agents in particular.
  • Another object of the present invention is an enzyme-containing washing or cleaning agent which is characterized in that it contains enzymes stabilized by highly concentrated enzyme granules.
  • An agent according to the invention contains at least one protease, particularly preferably at least one protease and at least one amylase.
  • proteases of the prior art are suitable as proteases.
  • those of the subtilisin type are preferred.
  • the subtilisins BPN 'and Carlsberg as well as their further developed forms, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus (BLAP), subtilisin DY and those which can be assigned to the subtilases, but no longer to the subtilisins in the narrower sense
  • the protease is a BLAP-type subtilisin.
  • subtilisin BPN ' which originates from Bacillus amyloliquefaciens or B. subtilis, is from the work by Vasantha et al. (1984) in J. Bacteriol., Volume 159, pp. 811-819 and by JA Wells et al. (1983) in Nucleic Acids Research, Volume 11, pp. 7911-7925 known.
  • Subtilisin BPN ' serves as a reference enzyme for the subtilisins, in particular with regard to the numbering of the positions.
  • Subtilisin Carlsberg is available in a further developed form under the trade name Alcalase® from Novozymes A / S, Bagsv ⁇ rd, Denmark.
  • subtilisins 147 and 309 are sold by the Novozymes company under the trade names Esperase® and Savinase®, respectively. They originally come from Bacillus strains with the application GB 1243784 A to be revealed. From the protease from Bacillus lentus DSM 5483 ( WO 91/02792 A1 ) are derived from the variants listed under the name BLAP®, which are in particular in WO 92/21760 A1 , WO 95/23221 A1 , WO 02/088340 A2 and WO 03/038082 A2 to be discribed. Subtilisin DY is native by Nedkov et al. 1985 in Biol.
  • proteases that can be used are, for example, those under the trade names Durazym®, Relase®, Ever-Iase®, Nafizym, Natalase®, Kannase® and Ovozyme® from Novozymes, which are sold under the trade names, Purafect®, Purafect® OxP, Purafect® Prime and Properase® from Genencor, sold under the trade name Protosol® from Advanced Biochemicals Ltd., Thane, India, sold under the trade name Wuxi® from Wuxi Snyder Bioproducts Ltd., China, sold under the trade names Proleather® and Protease P® from Amano Pharmaceuticals Ltd., Nagoya, Japan, and the enzyme available under the name Proteinase K-16 from Kao Corp., Tokyo, Japan.
  • proteases used in agents according to the invention originate either originally from microorganisms, for example from microorganisms of the genera Bacillus, Streptomyces, Humicola, or Pseudomonas, and / or are produced according to known biotechnological processes by suitable microorganisms, for example by transgenic expression hosts of the genera Bacillus or by filamentous fungi.
  • Amylases which can be packaged according to the invention are preferably ⁇ -amylases.
  • the decisive factor for whether an enzyme is an ⁇ -amylase within the meaning of the invention is its ability to hydrolyze ⁇ (1-4) -glycoside bonds in the amylose of starch.
  • Amylases that can be packaged according to the invention are, for example, the ⁇ -amylases from Bacillus licheniformis, from Bacillus amyloliquefaciens or from Bacillus stearothermophilus and, in particular, their improved further developments for use in detergents or cleaning agents.
  • the enzyme from Bacillus licheniformis is available from the Novozymes company under the name Termamyl® and from the Danisco / Genencor company under the name Purastar® ST. Further development products of this ⁇ -amylase are available from Novozymes under the trade names Duramyl® and Termamyl® ultra, from Danisco / Genencor under the name Purastar® OxAm and from Daiwa Seiko Inc., Tokyo, Japan, as Keistase®.
  • the ⁇ -amylase from Bacillus amyloliquefaciens is marketed by the Novozymes company under the name BAN®, and variants derived from the ⁇ -amylase from Bacillus stearothermophilus under the names BSG® and Novamyl®, also by the Novozymes company. Furthermore, the ⁇ -amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from Bacillus agaradherens (DSM 9948) should be emphasized. Fusion products of all mentioned molecules can also be used.
  • amylases are disclosed in the international laid-open specifications WO 00/60060 , WO 03/002711 , WO 03/054177 and WO 07/079938 , to the disclosure of which is therefore expressly referred to, or whose related disclosure content is therefore expressly included in the present patent application.
  • washing or cleaning agents contain, based on their total weight, between 0.002 and 9.0 wt .-%, preferably between 0.02 and 6.0 wt .-% and in particular between 0.1 and 5.0 wt .-% % Protease preparations. Washing or cleaning agents which, based on their total weight, contain between 0.1 and 4.0% by weight of protease preparations are particularly preferred.
  • Washing or cleaning agents preferred according to the invention contain, based on their total weight, between 0.001 and 5.0% by weight, preferably between 0.01 and 4.0% by weight and in particular between 0.05 and 3.0% by weight % Amylase preparations. Washing or cleaning agents which, based on their total weight, contain between 0.07 and 2.0% by weight of amylase preparations are particularly preferred.
  • the enzyme-containing washing or cleaning agent according to the invention is a washing agent in tablet form, in another preferred embodiment a washing-up agent in tablet form for cleaning hard surfaces, in particular dishes.
  • an enzyme is to be understood as a protein which performs a specific biocatalytic function.
  • a protease is understood to mean an enzyme which catalyzes the hydrolysis of peptide bonds and is thus able to cleave peptides or proteins.
  • a protein is a largely linearly constructed polypeptide composed of natural amino acids and usually assuming a three-dimensional structure in order to perform its function.
  • a peptide consists of amino acids that are covalently linked to one another via peptide bonds.
  • polypeptide clarifies the fact that this peptide chain usually consists of many amino acids that are connected to one another via peptide bonds.
  • Amino acids can be in an L and a D configuration, with the amino acids that make up proteins being in the L configuration. They are called proteinogenic amino acids.
  • proteinogenic amino acids In the present application the proteinogenic, naturally occurring L-amino acids are referred to with the internationally used 1- and 3-letter codes.
  • Numerous proteins are formed as so-called preproteins, i.e. together with a signal peptide. This is then to be understood as the N-terminal part of the protein, the function of which is mostly to ensure that the protein formed is released from the producing cell into the periplasm or the surrounding medium and / or its correct folding.
  • the signal peptide is then split off from the rest of the protein under natural conditions by a signal peptidase, so that the latter exerts its actual catalytic activity without the N-terminal amino acids initially present.
  • Pro-proteins are inactive precursors of proteins. Their precursors with signal sequence are called pre-pro-proteins. For technical applications, due to their enzymatic activity, mature, ie mature peptides, ie the enzymes processed after their production, are preferred over preproteins.
  • the proteins can be modified by the cells producing them after the production of the polypeptide chain, for example by attaching sugar molecules, formylations, aminations, etc. Such modifications are referred to as post-translational modifications. These post-translational modifications can, but need not, have an influence on the function of the protein.
  • Proteases or enzymes in general can be produced by various methods, e.g. targeted genetic modification through mutagenesis processes, further developed and optimized for specific purposes or with regard to special properties, for example catalytic activity, stability, etc.
  • Fragments are understood to mean all proteins or peptides that are smaller than natural proteins and can also be obtained synthetically, for example. Based on their amino acid sequences, they can be assigned to the relevant complete proteins. For example, they can assume the same structures or exert proteolytic activities or partial activities, such as complexing a substrate. Fragments and deletion variants of starting proteins are in principle similar; while fragments tend to represent smaller fragments, the deletion mutants tend to lack only short areas and thus only individual partial functions.
  • chimeric or hybrid proteins are to be understood as meaning those proteins whose sequence comprises the sequences or partial sequences of at least two starting proteins.
  • the starting proteins can come from different or from the same organism.
  • Chimeric or hybrid proteins can be obtained, for example, by recombination mutagenesis. The purpose of such a recombination can be, for example, to bring about or modify a certain enzymatic function with the aid of the fused protein part.
  • it is immaterial whether such a chimeric protein consists of a single polypeptide chain or several subunits on which different functions can be distributed.
  • Proteins obtained by insertion mutation are to be understood as meaning those variants which have been obtained by inserting a protein fragment into the starting sequences. Because of their similarity in principle, they can be assigned to the chimeric proteins. They differ from those only in the size ratio of the unchanged protein part to the size of the entire protein. The proportion of foreign protein in such insertion-mutated proteins is lower than in chimeric proteins.
  • Inversion mutagenesis i.e. a partial sequence reversal
  • inversion mutagenesis can be viewed as a special form of both deletion and insertion. The same applies to a regrouping of different parts of the molecule that deviates from the original amino acid sequence. It can be viewed both as a deletion variant, as an insertion variant, and as a shuffling variant of the original protein.
  • derivatives are understood to mean proteins whose pure amino acid chain has been chemically modified. Such derivatizations can take place, for example, biologically in connection with protein biosynthesis by the host cell. Molecular biological methods can be used for this.
  • the enzyme-containing agent is thus characterized in that the enzyme, preferably the protease, is present in the agent as a fragment, deletion variant, chimeric protein or derivative, the protease still being catalytically active.
  • Agents according to the invention include all types of enzyme-containing agents, in particular mixtures, formulations, solutions, etc., the enzyme stability of which is improved by adding the above-described highly concentrated enzyme granules.
  • they can be, for example, solid mixtures, for example powder with freeze-dried or encapsulated proteins, or preferably gel-like or liquid agents.
  • these are to be understood as means for the areas of application set out below. Further areas of application emerge from the prior art and are, for example, in the Handbook "Industrial enyzmes and their applications" by H. Uhlig, Wiley-Verlag, New York, 1998 shown.
  • an agent according to the invention is characterized in that it is a detergent, hand washing agent, dishwashing detergent, hand dishwashing detergent, machine dishwashing detergent, cleaning agent, denture or contact lens care agent, rinsing agent, disinfectant and in particular a laundry detergent or dishwashing detergent.
  • This subject matter of the invention includes all conceivable types of detergents or cleaning agents, both concentrates and agents to be used undiluted, for use on a commercial scale, in the washing machine or for hand washing or cleaning.
  • detergents or cleaning agents include, for example, detergents for textiles, carpets or natural fibers, for which the term detergent is used according to the present invention.
  • An agent according to the invention can be both an agent for bulk consumers or technical users and a product for private consumers, with all types of detergents and cleaning agents established in the prior art likewise representing embodiments of the present invention.
  • the washing or cleaning agents according to the invention can in principle contain all known ingredients that are customary in such agents, at least one further ingredient being present in the agent.
  • the agents according to the invention can in particular builder substances, surface-active surfactants, bleaching agents based on organic and / or inorganic peroxygen compounds, bleach activators, water-miscible organic solvents, enzymes, sequestering agents, electrolytes, pH regulators and other auxiliaries such as optical brighteners, graying inhibitors, foam regulators and dyes and fragrances as well as combinations thereof.
  • the agents according to the invention can contain one or more surfactants, in particular anionic surfactants, nonionic surfactants and their mixtures, but also cationic, zwitterionic and amphoteric surfactants.
  • Suitable nonionic surfactants are, in particular, alkyl glycosides and ethoxylation and / or propoxylation products of alkyl glycosides or linear or branched alcohols each having 12 to 18 carbon atoms in the alkyl part and 3 to 20, preferably 4 to 10, alkyl ether groups.
  • alkyl glycosides and ethoxylation and / or propoxylation products of N-alkylamines, vicinal diols, fatty acid esters and fatty acid amides which correspond to the long-chain alcohol derivatives mentioned in terms of the alkyl moiety, and of alkylphenols with 5 to 12 carbon atoms in the alkyl radical, can also be used.
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols with preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical 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 oxo alcohol radicals.
  • EO ethylene oxide
  • alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow 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 -C 14 alcohols with 3 EO or 4 EO, C 9 -C 11 alcohols with 7 EO, C 13 -C 15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12 -C 18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 12 -C 14 alcohol with 3 EO and C 12 -C 18 alcohol with 7 EO.
  • the stated degrees of ethoxylation represent statistical mean values which, for a specific product, can be an integer or a fraction.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples of this are (tallow) fatty alcohols with 14 EO, 16 EO, 20 EO, 25 EO, 30 EO or 40 EO.
  • Extremely low-foam compounds are usually used in machine processes. These include preferably C 12 -C 18 -alkyl polyethylene glycol-polypropylene glycol ethers, each with up to 8 moles of ethylene oxide and propylene oxide units in the molecule.
  • low-foam nonionic surfactants can also be used, such as, for example, C 12 -C 18 -alkyl polyethylene glycol polybutylene glycol ethers with up to 8 moles of ethylene oxide and butylene oxide units in the molecule, and end-capped alkyl polyalkylene glycol mixed ethers.
  • the alkoxylated alcohols containing hydroxyl groups as described in the European patent application, are also particularly preferred EP 0 300 305 are described, so-called hydroxy mixed ethers.
  • the nonionic surfactants also include alkyl glycosides of the general formula RO (G) x , in which R is a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical with 8 to 22, preferably 12 to 18, carbon atoms and G stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
  • R is a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical with 8 to 22, preferably 12 to 18, carbon atoms and G stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number - which as a variable to be determined analytically can also assume fractional values - between 1 and 10; preferably x is 1.2 to 1.4.
  • polyhydroxy fatty acid amides of the formula (III) in which R 1 is CO for an aliphatic acyl radical having 6 to 22 carbon atoms, R 2 is hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups:
  • the polyhydroxy fatty acid amides are preferably derived from reducing sugars having 5 or 6 carbon atoms, in particular from glucose.
  • the group of polyhydroxy fatty acid amides also includes compounds of the formula (IV), in which R 3 stands for a linear or branched alkyl or alkenyl radical with 7 to 12 carbon atoms, R 4 for a linear, branched or cyclic alkylene radical or an arylene radical with 2 to 8 carbon atoms and R 5 for a linear, branched or cyclic alkyl radical or a Aryl radical or an oxy-alkyl radical with 1 to 8 carbon atoms, C 1 -C 4 -alkyl or phenyl radicals being preferred, and [Z] represents a linear polyhydroxyalkyl radical whose alkyl chain is substituted with at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this radical.
  • [Z] is preferably obtained by reductive amination of a sugar such as glucose, fructose, maltose, lactose, galactose, mannose or xylose receive.
  • a sugar such as glucose, fructose, maltose, lactose, galactose, mannose or xylose receive.
  • the N-alkoxy- or N-aryloxy-substituted compounds can then 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.
  • nonionic surfactants which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, in particular together with alkoxylated fatty alcohols and / or alkyl glycosides, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl ester.
  • 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 can also be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half that.
  • So-called gemini surfactants can be used as further surfactants. These are generally understood to mean those compounds which have two hydrophilic groups per molecule. These groups are usually separated from one another by a so-called "spacer".
  • This spacer is usually a carbon chain that should be long enough that the hydrophilic groups are sufficiently spaced so that they can act independently of one another.
  • Such surfactants are generally characterized by an unusually low critical micelle concentration and the ability to greatly reduce the surface tension of the water.
  • the term gemini surfactants is understood to mean not only such "dimeric” surfactants, but also correspondingly "trimeric” surfactants.
  • Suitable gemini surfactants are, for example, sulfated hydroxy mixed ethers or dimer alcohol bis- and trimer alcohol tris sulfates and ether sulfates. End-capped dimeric and trimeric mixed ethers are distinguished in particular by their bi- and multifunctionality.
  • end-capped surfactants mentioned have good wetting properties and are low-foaming, so that they are particularly suitable for use in machine washing or cleaning processes.
  • Gemini-polyhydroxy fatty acid amides or poly-polyhydroxy fatty acid amides can also be used.
  • sulfuric acid monoesters of the straight-chain or branched C 7 -C 21 alcohols ethoxylated with 1 to 6 mol of ethylene oxide such as 2-methyl-branched C 9 -C 11 alcohols with an average of 3.5 mol of ethylene oxide (EO) or C 12 - C 18 fatty alcohols with 1 to 4 EO.
  • the preferred anionic surfactants also include 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 to C 18 fatty alcohol residues or mixtures of these.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols which, considered in isolation, represent nonionic surfactants.
  • Sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution are particularly preferred. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof. Fatty acid derivatives are further anionic surfactants of amino acids, for example of N-methyltaurine (tauride) and / or of N-methylglycine (sarcosides).
  • Soaps are suitable as further anionic surfactants.
  • saturated fatty acid soaps such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid and, in particular, soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids.
  • the known alkenylsuccinic acid salts can also be used together with these soaps or as a substitute for soaps.
  • the anionic surfactants can be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine.
  • the anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
  • the detergents according to the invention contain surfactants in proportions of preferably 5% by weight to 50% by weight, in particular 8% by weight to 30% by weight.
  • builders such as silicates, aluminum silicates (especially zeolites), salts of organic di- and polycarboxylic acids and mixtures of these substances, preferably water-soluble builders, can be advantageous.
  • the use of phosphates is largely or completely dispensed with.
  • the agent contains preferably less than 5% by weight, particularly preferably less than 3% by weight, in particular less than 1% by weight of phosphate (s).
  • the agent is particularly preferably completely phosphate-free, i.e. the agents contain less than 0.1% by weight of phosphate (s).
  • the builders include, in particular, carbonates, citrates, phosphonates, organic builders and silicates.
  • the proportion by weight of the total builders in the total weight of the compositions according to the invention is preferably 15 to 80% by weight and in particular 20 to 70% by weight.
  • Organic builders suitable according to the invention are, for example, the polycarboxylic acids (polycarboxylates) which can be used in the form of their sodium salts, polycarboxylic acids being understood as meaning those carboxylic acids which have more than one, in particular two to eight acid functions, preferably two to six, in particular two, three, four or five acid functions carry throughout the molecule.
  • Preferred polycarboxylic acids are dicarboxylic acids, tricarboxylic acids, tetracarboxylic acids and pentacarboxylic acids, in particular di-, tri- and tetracarboxylic acids.
  • the polycarboxylic acids can also carry further functional groups, such as hydroxyl or amino groups.
  • these are citric acid, adipic acid, succinic acid, Glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids (preferably aldaric acids, for example galactaric acid and glucaric acid), aminocarboxylic acids, especially aminodicarboxylic acids, aminotricarboxylic acids, aminotetracarboxylic acids such as nitrilotriacetic acid (NTA), glutamine, N-, N-di-acetic acid (also as nitrilotriacetic acid) Bis (carboxymethyl) -L-glutamic acid or GLDA), methylglycinediacetic acid (MGDA)) and their derivatives and mixtures of these.
  • Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, GLDA, MGDA and mixtures of these.
  • polymeric polycarboxylates organic polymers with a large number of (in particular more than ten) carboxylate functions in the macromolecule
  • polyaspartates organic polymers with a large number of (in particular more than ten) carboxylate functions in the macromolecule
  • polyacetals polyacetals and dextrins.
  • the free acids typically also have the property of an acidifying component and can thus, if desired, also serve to set a lower pH value.
  • Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures of these should be mentioned in particular.
  • dishwashing detergents preferably automatic dishwashing detergents
  • these are preferably in a proportion of 2 to 40% by weight, in particular 5 to 30% by weight, especially 7 to 28% by weight, particularly preferably 10 to 25% by weight, very particularly preferably 15 to Contain 20 wt .-%, each based on the total weight of the agent.
  • dishwashing detergents preferably automatic dishwashing agents
  • dishwashing detergents are characterized in that they contain at least two builders from the group of silicates, phosphonates, carbonates, aminocarboxylic acids and citrates, the proportion by weight of these builders, based on the total weight of the cleaning agent according to the invention, is preferably 5 to 70% by weight, preferably 15 to 60% by weight and in particular 20 to 50% by weight.
  • the combination of two or more builders from the group mentioned above has proven to be advantageous for the cleaning and rinsing performance of cleaning agents according to the invention, in particular dishwashing detergents, preferably automatic dishwashing detergents.
  • one or more other builders can also be included.
  • Preferred cleaning agents in particular dishwashing detergents, preferably machine dishwashing detergents, are characterized by a builder combination of citrate and carbonate and / or hydrogen carbonate.
  • a mixture of carbonate and citrate is used, the amount of carbonate preferably being from 5 to 40% by weight, in particular from 10 to 35% by weight, very particularly preferably from 15 to 30% by weight and the amount of citrate is preferably from 5 to 35% by weight, in particular 10 to 25% by weight, very particularly preferably 15 to 20% by weight, in each case based on the total amount of the cleaning agent, the total amount of these two Builders is preferably 20 to 65% by weight, in particular 25 to 60% by weight, preferably 30 to 50% by weight. In addition, one or more other builders can also be included.
  • the cleaning agents according to the invention can in particular contain phosphonates as a further builder.
  • a hydroxyalkane and / or aminoalkane phosphonate is preferably used as the phosphonate compound.
  • HEDP 1-hydroxyethane-1,1-diphosphonate
  • Ethylenediamine tetramethylene phosphonate (EDTMP), diethylenetriamine pentamethylene phosphonate (DTPMP) and their higher homologues are preferred as aminoalkanephosphonates.
  • Phosphonates are preferably used in agents according to the invention in amounts from 0.1 to 10% by weight, in particular in amounts from 0.5 to 8% by weight, very particularly preferably from 2.5 to 7.5% by weight, in each case based on the total weight of the agent.
  • citrate, (hydrogen) carbonate and phosphonate are particularly preferred. These can be used in the abovementioned amounts. In particular, amounts of, based on the total weight of the agent, 10 to 25% by weight of citrate, 10 to 30% by weight of carbonate (or hydrogen carbonate), and 2.5 to 7.5% by weight Phosphonate used.
  • dishwashing detergents preferably automatic dishwashing detergents
  • they contain at least one further phosphorus-free builder.
  • this is selected from the aminocarboxylic acids, the further phosphorus-free builder being preferably selected from methylglycinediacetic acid (MGDA), glutamic acid diacetate (GLDA), aspartic acid diacetate (ASDA), hydroxyethyliminodiacetate (HEIDA), iminodisuccinate (IDSDS) and ethylenediamine disuccinate (preferably from MGDA or GLDA.
  • MGDA methylglycinediacetic acid
  • GLDA glutamic acid diacetate
  • ASDA aspartic acid diacetate
  • HEIDA hydroxyethyliminodiacetate
  • IDSDS iminodisuccinate
  • ethylenediamine disuccinate preferably from MGDA or GLDA.
  • a particularly preferred combination is, for example, citrate, (hydrogen) carbonate and MGDA and optionally phosphonate.
  • the percentage by weight of the further phosphorus-free builder, in particular of MGDA and / or GLDA, is preferably 0 to 40% by weight, in particular 5 to 30% by weight, especially 7 to 25% by weight.
  • the use of MGDA or GLDA, in particular MGDA, as granules is particularly preferred. MGDA granulates which contain as little water as possible and / or have a lower hygroscopicity (water absorption at 25 ° C., normal pressure) compared to the non-granulated powder are advantageous.
  • Polymeric polycarboxylates are also suitable as organic builders, for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 500 to 70,000 g / mol.
  • Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of 2000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates from this group, which have molecular weights from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, can be preferred.
  • the (homo) polymeric polycarboxylate content of the cleaning agents according to the invention is preferably 0.5 to 20% by weight, more preferably 2 to 15% by weight and in particular 4 to 10% by weight.
  • Suitable, albeit less preferred, compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinyl methyl ethers, vinyl esters, ethylene, propylene and styrene, in which the acid makes up at least 50% by weight.
  • vinyl ethers such as vinyl methyl ethers, vinyl esters, ethylene, propylene and styrene
  • the acid makes up at least 50% by weight.
  • Terpolymers which contain two unsaturated acids and / or their salts as monomers and vinyl alcohol and / or an esterified vinyl alcohol or a carbohydrate as a third monomer can also be used as water-soluble organic builder substances.
  • the first acidic monomer or its salt is derived from a monoethylenically unsaturated C 3 -C 8 carboxylic acid and preferably from a C 3 -C 4 monocarboxylic acid, in particular from (meth) acrylic acid.
  • the second acidic monomer or its salt can be a derivative of a C 4 -C 8 dicarboxylic acid, maleic acid being particularly preferred, and / or a derivative of an allylsulphonic acid which is substituted in the 2-position by an alkyl or aryl radical.
  • Such polymers generally have a relative molecular weight between 1,000 and 200,000.
  • Further preferred copolymers are those which preferably have acrolein and acrylic acid / acrylic acid salts or vinyl acetate as monomers.
  • Cleaning agents according to the invention in particular dishwashing agents, preferably automatic dishwashing agents, can furthermore contain crystalline layered silicates of the general formula NaMSixO2x + 1 ⁇ y H2O, where M is sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4, with particularly preferred values for x being 2, 3 or 4, and y being a number from 0 to 33, preferably from 0 to 20.
  • Amorphous sodium silicates with a Na2O: SiO2 modulus of 1: 2 to 1: 3.3, preferably 1: 2 to 1: 2.8 and in particular 1: 2 to 1: 2.6, which are preferably delayed in dissolution, can also be used and have secondary washing properties.
  • the silicate content based on the total weight of the detergent, is limited to amounts below 10% by weight, preferably below 5% by weight and in particular below 2% by weight .
  • the water-insoluble, water-dispersible inorganic builder materials used are in particular crystalline or amorphous alkali metal aluminosilicates, in amounts of up to 50% by weight, preferably not more than 40% by weight and, in liquid agents, in particular from 1% by weight to 5% by weight, used.
  • the crystalline sodium aluminosilicates in detergent quality, in particular zeolite A, P and optionally X, alone or in mixtures, for example in the form of a co-crystallizate from the zeolites A and X (Vegobond® AX, a commercial product from Condea Augusta SpA), are preferred .
  • Quantities close to the upper limit mentioned are preferably used in solid, particulate compositions.
  • Suitable aluminosilicates in particular have no particles with a particle size greater than 30 ⁇ m and preferably consist of at least 80% by weight of particles with a size less than 10 ⁇ m.
  • Your calcium binding capacity, according to the information in the German patent DE 24 12 837 can be determined is usually in the range of 100 to 200 mg CaO per gram.
  • Suitable substitutes or partial substitutes for said aluminosilicate are crystalline alkali metal silicates, which can be present alone or in a mixture with amorphous silicates.
  • the alkali silicates which can be used as builders in the agents according to the invention preferably have a molar ratio of alkali oxide to SiO 2 below 0.95, in particular from 1: 1.1 to 1:12, and can be amorphous or crystalline.
  • Preferred alkali silicates are the sodium silicates, in particular the amorphous sodium silicates, with a molar ratio Na 2 O: SiO 2 of 1: 2 to 1: 2.8.
  • the crystalline silicates used alone or in a mixture with amorphous silicates are preferably crystalline sheet silicates of the general formula Na 2 Si x O 2x + 1 y H 2 O, in which x, the so-called module, is a number of 1, 9 to 22, in particular 1.9 to 4 and y is a number from 0 to 33 and preferred values for x are 2, 3 or 4.
  • Preferred crystalline sheet silicates are those in which x assumes the values 2 or 3 in the general formula mentioned. In particular, both ß- and ⁇ -sodium disitics (Na 2 Si 2 O 5 ⁇ y H 2 O) are preferred.
  • 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
  • Na-SKS-4 Na 2 Si 4 O 9 ⁇ xH 2 O , Makatite
  • Na-SKS-5 ( ⁇ -Na 2 Si 2 O 5 ), Na-SKS-7 (ß-Na 2 Si 2 O 5 , Natrosilit), Na-SKS-9 (NaHSi 2 O 5 ⁇ 3H 2 O), Na-SKS-10 (NaHSi 2 O 5 ⁇ 3H 2 O, Kanemite), Na-SKS-11 (t-Na 2 Si 2 O 5 ) and Na-SKS-13 (NaHSi 2 O 5 ), but especially Na-SKS-6 ( ⁇ -Na 2 Si 2 O 5 ).
  • a granular compound of crystalline sheet silicate and citrate, of crystalline sheet silicate and the above-mentioned (co) polymeric polycarboxylic acid, or of alkali silicate and alkali carbonate, as is commercially available, for example, under the name Nabion® 15, is used .
  • the builder substances are contained in the agents according to the invention, in particular in detergents, preferably in amounts of up to 75% by weight, in particular 5% to 50% by weight.
  • the washing or cleaning agents according to the invention can also contain alkali metal hydroxides.
  • alkali carriers are used in the detergents or cleaning agents and in particular in the second phases preferably only in small amounts, preferably in amounts below 10% by weight, preferably below 6% by weight, preferably below 5% by weight, particularly preferably between 0.1 and 5% by weight and in particular between 0.5 and 5% by weight, each based on the total weight of the detergent or cleaning agent, are used.
  • Alternative cleaning agents according to the invention are free from alkali metal hydroxides.
  • Peroxygen compounds suitable for use in agents according to the invention are, in particular, organic peracids or peracid salts of organic acids, such as phthalimidopercaproic acid, perbenzoic acid or salts of diperdodecanedioic acid, hydrogen peroxide and inorganic salts which release hydrogen peroxide under the washing conditions, to which perborate, percarbonate, persilicate and / or persulfate such as Caroat are considered. If solid peroxygen compounds are to be used, these can be used in the form of powders or granules, which can also be coated in a manner known in principle.
  • an agent according to the invention contains peroxygen compounds, these are present in amounts of preferably up to 50% by weight, in particular from 5% by weight to 30% by weight.
  • bleach stabilizers such as phosphonates, borates or metaborates and metasilicates and magnesium salts such as magnesium sulfate can be useful.
  • Bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or optionally substituted perbenzoic acid. Substances which carry O- and / or N-acyl groups with the number of carbon atoms mentioned and / or optionally substituted benzoyl groups are suitable.
  • Polyacylated alkylenediamines especially tetraacetylethylenediamine (TAED), acylated triazine derivatives, especially 1,5-diacetyl-2,4-dioxohexa-hydro-1,3,5-triazine (DADHT), acylated glycolurils, especially tetraacetylglycoluril (TAGU), are preferred, N-acylimides, in particular N-nonanoyl succinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin 2.5 Diacetoxy-2,5-dihydrofuran and enol esters as well as acetylated sorbitol and manni
  • hydrophilically substituted acyl acetals and the acyl lactams are also used with preference.
  • Combinations of conventional bleach activators can also be used.
  • Such bleach activators can, in particular in the presence of the abovementioned bleaching agents providing hydrogen peroxide, in the usual quantity range, preferably in quantities of 0.5% by weight to 10% by weight, in particular 1% by weight to 8% by weight, based on However, if percarboxylic acid is used as the sole bleaching agent, it is preferably completely absent.
  • bleach catalysts In addition to the conventional bleach activators or instead of them, sulfonimines and / or bleach-enhancing transition metal salts or transition metal complexes can also be present as so-called bleach catalysts.
  • the organic solvents which can be used in addition to water in the agents according to the invention, especially if they are in liquid or paste form, include alcohols with 1 to 4 carbon atoms, in particular methanol, ethanol, isopropanol and tert-butanol, diols with 2 to 4 C. Atoms, in particular ethylene glycol and propylene glycol, as well as their mixtures and the ethers which can be derived from the cited classes of compounds.
  • Such water-miscible solvents are preferably present in the agents according to the invention in amounts not exceeding 30% by weight, in particular from 6% by weight to 20% by weight.
  • the agents according to the invention can contain acids that are compatible with the system and the environment, in particular citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid and / or adipic acid, but also contain mineral acids, especially sulfuric acid, or bases, especially ammonium or alkali hydroxides.
  • acids that are compatible with the system and the environment, in particular citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid and / or adipic acid, but also contain mineral acids, especially sulfuric acid, or bases, especially ammonium or alkali hydroxides.
  • Such pH 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.
  • the task of graying inhibitors is to keep the dirt detached from the textile fiber suspended in the liquor.
  • Water-soluble colloids of mostly organic nature are suitable for this, for example starch, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
  • Water-soluble polyamides containing acidic groups are also suitable for this purpose. It is also possible to use starch derivatives other than those mentioned above, for example aldehyde starches.
  • Cellulose ethers such as carboxymethyl cellulose (Na salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as methyl hydroxyethyl cellulose, methyl hydroxy propyl cellulose, methyl carboxymethyl cellulose and their mixtures, for example in amounts of 0.1 to 5% by weight, based on the agent, are preferably used .
  • Textile detergents according to the invention can contain, for example, derivatives of diaminostilbene disulfonic acid or their alkali metal salts as optical brighteners, although they are preferably free from optical brighteners for use as color detergents.
  • optical brighteners for use as color detergents.
  • salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or similarly structured compounds which, instead of morpholino -Group carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group.
  • brighteners of the substituted diphenylstyryl type can be present, for example the alkali metal salts of 4,4'-bis (2-sulfostyryl) -diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) -diphenyl, or 4 - (4-chlorostyryl) -4 '- (2-sulfostyryl) -diphenyls.
  • Mixtures of the aforementioned optical brighteners can also be used.
  • foam inhibitors In particular when used in machine processes, it can be advantageous to add customary foam inhibitors to the agents.
  • Soaps of natural or synthetic origin which have a high proportion of C 18 -C 24 fatty acids are suitable as foam inhibitors.
  • Suitable non-surfactant foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silicic acid, and paraffins, waxes, microcrystalline waxes and their mixtures with silanized silicic acid or bisfatty acid alkylenediamides.
  • Mixtures of different foam inhibitors are also advantageously used, for example those made from silicones, paraffins or waxes.
  • the foam inhibitors, in particular silicone- and / or paraffin-containing foam inhibitors are preferably granular, water-soluble or dispersible carrier substance bound. Mixtures of paraffins and bistearylethylene diamide are particularly preferred.
  • the enzymes to be stabilized preferably proteases, and the highly concentrated enzyme granulates are combined, for example, with one or more of the following ingredients: nonionic, anionic and / or cationic surfactants, (optionally further) bleaching agents, Bleach activators, bleach catalysts, builders and / or co-builders, acids, alkaline substances, hydrotropes, solvents, thickeners, sequestering agents, electrolytes, optical brighteners, graying inhibitors, corrosion inhibitors, in particular silver protectants (silver corrosion inhibitors), disintegration transfer aids, soil release agents or -, Transfer) inhibitors, foam inhibitors, abrasives, dyes, fragrances, perfumes, antimicrobial agents, UV protection agents or absorbents, antistatic agents, pearlescent agents and skin protection agents, other enzymes such as, for example ice protease, amylase, cellulase, hemicellulase,
  • an agent according to the invention is thus characterized in that it contains at least one further component selected from the group consisting of surfactants, builders, acids, alkaline substances, hydrotropes, solvents, thickeners, bleaches, dyes, perfumes, corrosion inhibitors , Sequestering agents, electrolytes, optical brighteners, graying inhibitors, silver corrosion inhibitors, color transfer inhibitors, foam inhibitors, disintegration aids, abrasives, UV absorbents, solvents, antistatic agents, pearlescent agents and skin protection agents.
  • the ingredients to be selected and the conditions under which the agent is used should be optimized for the respective cleaning problem.
  • the usual temperatures for detergents and cleaning agents are in the range of 10 ° C for manual agents, over 40 ° C and 60 ° C up to 95 ° for mechanical agents or for technical applications. Since the temperature in modern washing machines and dishwashers is usually infinitely adjustable, all intermediate temperature levels are also included.
  • the ingredients of the agents in question are preferably matched to one another.
  • the agent can further comprise optical brighteners, preferably from 0.01 to 5% by weight.
  • dishwashing detergents preferably automatic dishwashing detergents: Wt% Preferred% by weight Citrate, sodium salt 10-25 15-20 Phosphonate (e.g. HEDP) 0-10 2.5-7.5 MGDA, sodium salt 0-40 0-25 Disilicate, sodium salt 0-40 5-35 soda 10-30 10-25 Percarbonate, sodium salt 5.0-20.0 10-15 Bleach catalyst (preferably Mn-based) 0.0-0.8 0.02-0.5 Bleach activator (e.g.
  • TAED 1.0-4.0 1-3
  • Non-surfactant for example fatty alcohol alkoxylate, preferably 20-40 EO, optionally endcapped 1.5-15.0 2.5-10
  • Polycarboxylate 0.5 -15 4-10
  • Cationic copolymer 0.0 -1.0 0-0.75
  • Disintegrant - e.g. Crosslinked PVP
  • Protease preparation tq
  • tq 1.0-7 1.5-5
  • Amylase preparation 0.2-6 0.5-3
  • Silver protection (benzotriazole) 0.0 - 1.0 0-0.5 Perfume 0.0-0.5 0.05-0.25
  • Dye solution 0.0 - 1.5 0.0-1 Zn salt (e.g.
  • solid agents according to the invention does not present any difficulties and can be carried out in a known manner, for example by spray drying or granulation, enzymes and any other thermally sensitive ingredients such as bleaching agents being added later if necessary.
  • agents according to the invention with increased Bulk weight in particular in the range from 650 g / l to 950 g / l, a method having an extrusion step is preferred.
  • the procedure is preferably such that all constituents - optionally one layer each - are in one Mixers are mixed with one another and the mixture is pressed by means of conventional tablet presses, for example eccentric presses or rotary presses, with pressing forces in the range from about 50 to 100 kN, preferably at 60 to 70 kN.
  • a tablet produced in this way preferably has a weight of 10 g to 50 g, in particular 15 g up to 40 g.
  • the three-dimensional shape of the tablets is arbitrary and can be round, oval or angular, with intermediate shapes also being possible. Corners and edges are advantageously rounded.
  • Round tablets preferably have a diameter of 30 mm to 40 mm.
  • the size of angular or cuboid tablets, which are introduced predominantly via the dosing device, for example the dishwasher depends on the geometry and the volume of this dosing device.
  • Exemplary preferred embodiments have a base area of (20 to 30 mm) ⁇ (34 to 40 mm), in particular of 26 ⁇ 36 mm or of 24 ⁇ 38 mm.
  • Liquid or pasty agents according to the invention in the form of solutions containing customary solvents are generally produced by simply mixing the ingredients, which can be added to an automatic mixer in substance or as a solution.
  • Embodiments of the present invention thus include all such solid, powdery, liquid, gel-like or pasty dosage forms of the agents, which can optionally also consist of several phases and can be in compressed or uncompressed form.
  • Agents which are characterized in that they are present as a one-component system therefore represent a further embodiment of the invention. Such means preferably consist of one phase.
  • agents according to the invention can also consist of several phases.
  • the detergent or cleaning agent is therefore characterized in that it is divided into several components.
  • the solid dosage forms according to the invention also include extrudates, granules, tablets or pouches, which can be present both in large containers and in portions.
  • the agent is in the form of a free-flowing powder, in particular with a bulk density of 300 g / l to 1200 g / l, in particular 500 g / l to 900 g / l or 600 g / l to 850 g / l.
  • the agent according to the invention in particular washing or cleaning agent, can be packaged in a container, preferably an air-permeable container, from which it is released shortly before use or during the washing process.
  • Agents according to the invention can also contain further proteases or other enzymes in a concentration appropriate for the effectiveness of the agent.
  • the invention thus also provides agents which further comprise one or more further enzymes, in principle all of the enzymes established in the prior art for these purposes being usable.
  • enzymes that can preferably be used are all enzymes which can develop a catalytic activity in the agent according to the invention, in particular proteases, amylases, cellulases, hemicellulases, mannanases, tannases, xylanases, xanthanases, ⁇ -glucosidases, carrageenases, oxidases, oxidoreductases, pectin-degrading ones Enzymes (pectinases) or lipases, and preferably mixtures thereof.
  • proteases amylases
  • cellulases hemicellulases
  • mannanases tannases
  • xylanases xanthanases
  • ⁇ -glucosidases carrageenases
  • oxidases oxidoreductases
  • pectin-degrading ones Enzymes (pectinases) or lipases, and preferably mixtures thereof.
  • 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 enzymes are preferably from 0.00001 to 5% by weight, more preferably from 0.0001 to 2.5% by weight, even more preferably from 0.0001 to 1% by weight and particularly preferably from 0.0001 up to 0.072% by weight in agents according to the invention, each enzyme contained may be present in the stated proportions.
  • the protein concentration can be determined using known methods, for example the BCA method (bicinchoninic acid; 2,2'-bichinolyl-4,4'-dicarboxylic acid) or the biuret method ( AG Gornall, CS Bardawill and MM David, J. Biol. Chem., 177 (1948), pp. 751-766 ) can be determined.
  • the further enzymes particularly preferably support the action of the agent, for example the cleaning performance of a washing or cleaning agent, with regard to certain soiling or stains.
  • the enzymes particularly preferably show synergistic effects with regard to their effect on certain soiling or stains, ie the enzymes contained in the agent composition mutually support one another in their cleaning performance.
  • the agent according to the invention is thus characterized in that it contains at least one further enzyme which is a protease, amylase, cellulase, hemicellulase, mannanase, tannase, xylanase, xanthanase, ⁇ -glucosidase, carrageenase, oxidase, oxidoreductase , Pectin-degrading enzyme or a lipase.
  • at least one further enzyme which is a protease, amylase, cellulase, hemicellulase, mannanase, tannase, xylanase, xanthanase, ⁇ -glucosidase, carrageenase, oxidase, oxidoreductase , Pectin-degrading enzyme or a lipase.
  • the protease activity in such agents can be determined according to the in Tenside, Vol. 7 (1970), pp. 125-132 described method can be determined. It is given accordingly in PU (protease units).
  • the protease activity can be determined via the release of the chromophore para-nitroaniline (pNA) from the substrate suc-L-Ala-L-Ala-L-Pro-L-Phe-p-nitroanilide (AAPF).
  • the protease cleaves the substrate and releases pNA.
  • the release of the pNA causes an increase in the extinction at 410 nm, the course of which over time is a measure of the enzymatic activity.
  • the measurement takes place at a temperature of 25 ° C., at pH 8.6, and a wavelength of 410 nm.
  • the measurement time is 5 minutes and the measurement interval is 20s to 60s.
  • the enzymes used in the agents according to the invention either originally come from microorganisms, such as the genera Bacillus, Streptomyces, Humicola, or Pseudomonas, and / or are produced by suitable microorganisms according to known biotechnological processes, for example by transgenic expression hosts of the genera Bacillus or by filamentous fungi .
  • Another subject of the invention of its own is a method for cleaning textiles or hard surfaces, in which an enzyme-containing washing or cleaning agent according to the invention is active in at least one method step.
  • the method for cleaning textiles or hard surfaces is accordingly characterized in that an agent according to the invention is used in at least one method step.
  • Processes for cleaning textiles are generally characterized in that, in several process steps, various active cleaning substances are applied to the items to be cleaned and washed off after the exposure time, or that the items to be cleaned are otherwise Way is treated with a detergent or a solution of this agent.
  • processes for cleaning all materials other than textiles which are summarized under the term hard surfaces. All conceivable washing or cleaning processes can be enriched with an agent according to the invention in at least one of the process steps, and then represent embodiments of the present invention.
  • the enzymes are preferably used in an amount of from 40 ⁇ g to 4 g, preferably from 50 ⁇ g to 3 g, particularly preferably from 100 ⁇ g to 2 g and very particularly preferably from 200 ⁇ g to 1 g per application.
  • Another subject of the invention of its own is a method for treating raw textile materials or for textile care, in which an enzyme-containing detergent or cleaning agent according to the invention is active in at least one method step.
  • This can be, for example, a process in which materials are prepared for processing in textiles, for example for anti-felting, or processes which enrich the cleaning of worn textiles with a care component.
  • preferred embodiments are processes for treating raw textile materials, fibers or textiles with natural components, in particular with wool or silk.
  • a commercially available automatic dishwashing detergent in the form of a dishwashing detergent tablet was used which contained 15% by weight of sodium percarbonate as the hydrogen peroxide source (bleach), 0.03% by weight of bleach catalyst and 2.2% by weight of TAED as the bleach activator.
  • the tablet weight was 20 g.
  • protease 4 characterized as protease 4 according to SEQ ID NO.3.
  • the granules are available from Novozymes under the name Blaze Evity 100T and Blaze Evity 125T.
  • the cleaning performance describes the ability of a dishwashing agent, in particular an automatic dishwashing agent, to partially or completely remove existing soiling.
  • the cleaning performance was determined after the agent containing the protease granules had been stored for 8 weeks at 30 ° C. and 80% atmospheric humidity.
  • the dishwashing process was carried out in the Miele GSL dishwasher (program: 50 ° C, program duration 57 min, water hardness 21 ° German hardness).
  • the dishwashing detergent tablet was placed in the dosing device before the start of the cleaning program.
  • the activity of the samples was determined by means of a test method in which the enzyme-containing Sample is incubated under standardized conditions with the substrate N, N-dimethylcasein. Proteolysis in sodium sulfite solution at 50 ° C creates primary amino groups which react with 2,4,6-trinitrobenzenesulfonic acid to form a stable, yellow dye. The detection then takes place at 420 nm in the flow, as in AFSA HABEEB, Determination of Amino Groups in Proteins by Trinitrobenzenesulfonic Acid, Analy. Biochemestry 14, 328-336 (1966 ) described.
  • CPE enzyme activity units
  • the cleaning performance should have been the same when using 0.8 times the amount of Blaze 125T compared to Blaze 100T.
  • the activity of the two enzyme samples was measured and it was found that Blaze 125T had a lower activity than expected. Therefore, the same active content was not used in the cleaning performance test, but a smaller amount of Blaze 125T (Table 3, right column).

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Claims (10)

  1. Utilisation d'enzymes sous forme de granulés à concentration élevée dans des produits de lavage ou de nettoyage contenant des enzymes, pour augmenter la stabilité des protéases, les enzymes sous forme de granulés à concentration élevée contenant des protéases dans des quantités de 0,1 % en poids à 20 % en poids, de manière particulièrement préférée de 6 % en poids à 19 % en poids.
  2. Utilisation selon la revendication 1, caractérisée en ce que l'enzyme est la protéase caractérisée en tant que protéase 4 selon SEQ ID N°3 dans la demande WO 2012/171980 A1.
  3. Utilisation selon l'une des revendications précédentes, caractérisée en ce que le produit de lavage ou de nettoyage est un produit de lavage ou de nettoyage solide, de préférence un détergent pour lave-vaisselle solide sous forme de pastilles.
  4. Utilisation selon l'une des revendications précédentes, caractérisée en ce que les enzymes sous forme de granulés à concentration élevée sont utilisées dans des quantités de 0,05 % en poids à 9 % en poids, en particulier dans des quantités de 0,1 % en poids à 4,0 % en poids, de manière particulièrement préférée dans des quantités de 3,0 % en poids à 4,0 % en poids.
  5. Produit de lavage ou de nettoyage contenant des enzymes, caractérisé en ce qu'il contient des protéases stabilisées par des enzymes sous forme de granulés à concentration élevée, les enzymes sous forme de granulés à concentration élevée contenant des protéases dans des quantités de 0,1 % en poids à 20 % en poids, de manière particulièrement préférée de 6 % en poids à 19 % en poids.
  6. Produit de lavage ou de nettoyage contenant des enzymes selon la revendication 5, caractérisé en ce que l'enzyme est la protéase caractérisée en tant que protéase 4 selon SEQ ID N°3 dans la demande WO 2012/171980 A1.
  7. Produit de lavage ou de nettoyage contenant des enzymes selon la revendication 5 ou 6, caractérisé en ce qu'il s'agit d'un produit de lavage sous forme de pastilles.
  8. Produit de lavage ou de nettoyage contenant des enzymes selon la revendication 5 ou 6, caractérisé en ce qu'il s'agit d'un détergent sous forme de pastilles pour nettoyer les surfaces dures, en particulier la vaisselle.
  9. Produit de lavage ou de nettoyage contenant des enzymes selon l'une des revendications 5 à 8, caractérisé en ce que des enzymes sous forme de granulés à concentration élevée sont utilisées dans des quantités de 0,05 % en poids à 9 % en poids, en particulier dans des quantités de 0,1 % en poids à 4,0 % en poids, de manière particulièrement préférée dans des quantités de 3,0 % en poids à 4,0 % en poids.
  10. Procédé de nettoyage de textiles ou de surfaces dures, caractérisé en ce qu'un produit de lavage ou de nettoyage contenant des enzymes selon l'une des revendications 5 à 9 est actif dans au moins une étape du procédé.
EP16760749.8A 2015-09-17 2016-09-07 Utilisation d'enzymes sous forme de granulés à concentration élevée pour augmenter la stabilité au stockage d'enzymes Active EP3353274B1 (fr)

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DE102015217816.1A DE102015217816A1 (de) 2015-09-17 2015-09-17 Verwendung hochkonzentrierter Enzymgranulate zur Erhöhung der Lagerstabilität von Enzymen
PCT/EP2016/071023 WO2017045979A1 (fr) 2015-09-17 2016-09-07 Utilisation d'enzymes sous forme de granulés à concentration élevée pour augmenter la stabilité au stockage d'enzymes

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WO2017045979A1 (fr) 2017-03-23
ES2837049T3 (es) 2021-06-29

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