EP3230429A1 - Agent de lavage et de nettoyage solide comprenant de l'amylase - Google Patents

Agent de lavage et de nettoyage solide comprenant de l'amylase

Info

Publication number
EP3230429A1
EP3230429A1 EP15808163.8A EP15808163A EP3230429A1 EP 3230429 A1 EP3230429 A1 EP 3230429A1 EP 15808163 A EP15808163 A EP 15808163A EP 3230429 A1 EP3230429 A1 EP 3230429A1
Authority
EP
European Patent Office
Prior art keywords
amino acid
seq
amylase
protease
weight
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
EP15808163.8A
Other languages
German (de)
English (en)
Inventor
Nicole BODE
Brigitte Giesen
Annika GÜLDNER
Thorsten Bastigkeit
Timothy O'connell
Dilek MADENCI
Felipe ZILLY CLAUDE
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP3230429A1 publication Critical patent/EP3230429A1/fr
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38609—Protease or amylase in solid compositions only

Definitions

  • the invention relates to a solid detergent and cleaner containing an amylase, preferably in combination with a protease, wherein the amino acid sequences have been changed, in particular with regard to the use in detergents and cleaners.
  • the invention further relates to methods and uses of these solid detergents and cleaners.
  • proteases are among the most technically important enzymes of all. For detergents and cleaners, they are the longest established and contained in virtually all modern, powerful detergents and cleaners enzymes. They cause the degradation of protein-containing stains on the items to be cleaned. Of these, in turn, proteases of the subtilisin type (subtilases, subtilopeptidases, EC 3.4.21 .62) are particularly important, which are serine proteases due to the catalytically active amino acids. They act as nonspecific endopeptidases and hydrolyze any acid amide linkages that are internal to peptides or proteins. Their pH optimum is usually in the clearly alkaline range.
  • Subtilases Subtilisin-like Proteases
  • R. Siezen pages 75-95 in "Subtilisin enzymes", edited by R. Bott and C. Betzel, New York, 1996.
  • Subtilases are naturally occurring formed by microorganisms. Of these, in particular, the subtilisins formed and secreted by Bacillus species are to be mentioned as the most important group within the subtilases.
  • proteases preferably used in detergents and cleaners from
  • Subtilisin type are the subtilisins BPN 'and Carlsberg, the protease PB92, the subtilisins 147 and 309, the protease from Bacillus lentus, in particular from Bacillus lentus DSM 5483,
  • Proteases are selectively or randomly modified by methods known from the prior art and thus optimized, for example, for use in detergents and cleaners. These include point mutagenesis, deletion or insertion mutagenesis or fusion with other proteins or protein parts. Thus, correspondingly optimized variants are known for most proteases known from the prior art.
  • amylases Other enzymes which can be used in detergents and cleaners are amylases.
  • amylases synonymous terms may be used, for example, 1,4-alpha-D-glucan glucanohydrolase or glycogenase.
  • Amylases preferred according to the invention are ⁇ -amylases.
  • Crucial for determining whether an enzyme is an ⁇ -amylase according to the invention is its ability to hydrolyze ⁇ (1-4) -glycoside bonds in the amylose of the starch.
  • amylases and in particular their improved for use in detergents or cleaners further developments are described below.
  • Bacillus licheniformis ⁇ -amylase available as Termamyl® from Novozymes or
  • Purasta DST from the company Danisco / Genencor
  • Duramyl® and Termamy Dultra Novozymes
  • Purasta DOxAm Disco / Genencor
  • Keistase® Diwa Seiko Inc.
  • the a-amylases from Bacillus amyloliquefaciens or from Bacillus stearothermophilus are suitable amylases.
  • the Bacillus amyloliquefaciens ⁇ -amylase is sold by Novozymes under the name BAN®, and variants derived from the Bacillus stearothermophilus ⁇ -amylase under the names BSG® and Novamyl®, also from the company Novozymes.
  • Other known amylases are the ⁇ -amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from Bacillus agaradherens (DSM 9948) and the further developments of the ⁇ -amylase from Aspergillus niger and A. oryzae available under the trade name Fungamyl® from the company Novozymes. Further advantageous commercial products which can be used in detergents and cleaners are
  • amylase-LT® and Stainzyme® or Stainzyme ultra® or Stainzyme plus® the latter also from the company Novozymes.
  • Also available through point mutations variants of these enzymes can be used in detergents and cleaners.
  • Particularly preferred amylases are disclosed in International Published Applications WO 00/60060, WO 03/00271 1, WO 03/054177 and WO07 / 079938, the disclosure of which is therefore expressly referred to, or whose disclosure content is therefore expressly incorporated into the present patent application ,
  • an ⁇ -amylase according to the invention exhibits excellent activity in solid detergents, which is markedly improved in comparison with the known amylases.
  • starch stains are removed more efficiently during washing with solid detergents.
  • the amylase according to the invention has the stability and the performance of a protease in a solid washing and
  • the present invention is therefore a solid detergent or cleaning agent containing 5-70 wt .-% surfactant, 5-55 wt .-% carbonate, 0-10 wt .-% phosphate builder and an ⁇ -amylase, wherein the ⁇ Amylase is characterized by being at least 89% and more preferably at least 90%, 90.5%, 91%, 91, 5%, 92%, 92% of the sequence given in SEQ ID NO.1 over its total length , 5%, 93%, 93.5%, 94%, 94.5%, 95%, 95.5%, 96%, 96.5%, 97%, 97.5%, 98%, 98.5 %, 99%, 99.5% and up to 100% is identical and in the count according to SEQ ID NO.
  • positions 180, 181, 182, 183 and 184 has deletions. Particularly preferred is a deletion of two positions selected from 180 + 181, 181 +182, 182 + 183 and 183 + 184, most preferably deletions at positions 183 + 184 in the count according to SEQ ID NO. 1, more preferably the deletions H183 * + G184 * .
  • the ⁇ -amylase according to the invention in the count according to SEQ ID NO. 1 further includes an amino acid substitution at one or more of 405, 421, 422, and 428.
  • the substitutions are I405L; A421 H, A422P and A428T.
  • the ⁇ -amylase according to the invention in the count according to SEQ ID NO. 1 the deletions H183 * + G184 * and additionally the substitutions I405L, A421 H, A422P and A428T.
  • the solid detergent or cleaner comprises 5-55 wt.%, Preferably 5-35 wt.%, Anionic surfactant, 0-20 wt.%, Preferably 0-10 wt.%, Alkali silicate builder, preferably Sodium silicate builder, and 0-10 wt .-%, preferably 0-5 wt .-%, zeolite builder.
  • the solid washing or cleaning agent comprises 5-55% by weight, preferably 5-35% by weight, anionic surfactant, 0-20% by weight, preferably 0-10% by weight,
  • the solid detergent or cleaner according to the invention comprises 10 to 30% by weight of anionic surfactant, 0 to 5% by weight of phosphate builder, 5 to 30% by weight of sodium carbonate, 0 to 10% by weight, preferably 1 to 10 wt .-% sodium silicate builder, 0 to 10 wt .-%, preferably 1 to 3 wt .-% polyacrylate, 0 to 5 wt .-%, preferably 0 to 1 wt .-% zeolite builder, 0.005 to 10 Wt .-%, preferably 0.5 to 2 wt .-% phosphonate, preferably HEDP on.
  • the protease according to the invention comprises an amino acid sequence which corresponds to the amino acid sequence shown in SEQ ID NO. 2 and / or to the amino acid sequence given in SEQ ID NO.3 over the entire length thereof to at least 80% and increasingly preferably to at least 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 90.5%, 91%, 91, 5%, 92%, 92.5%, 93%, 93.5%, 94%, 94.5%, 95%, 95.5% , 96%, 96.5%, 97%, 97.5%, 98%, 98.5%, 99%, or 100% identical.
  • E amino acid glutamic acid
  • a protease having an amino acid sequence corresponding to that shown in SEQ ID NO. At least 80% and more preferably at least 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 90.5%, of the total amino acid sequence 91%, 91, 5%, 92%, 92.5%, 93%, 93.5%, 94%, 94.5%, 95%, 95.5%, 96%, 96.5%, 97% , 97.5%, 98%, 98.5% and 99% is identical and in the count according to SEQ ID NO. 2 at position 3 the amino acid glutamic acid (T), at position 4 the amino acid isoleucine (I) and at position 199 the amino acid isoleucine (I).
  • the solid detergent or cleaning agent comprises 0-15% by weight, preferably 0-10% by weight, of nonionic surfactant and / or 0-25% by weight, preferably 0-15% by weight of a peroxygen compound and / or a protease according to SEQ ID NO.4.
  • the solid detergent or cleaning agent has 0-15% by weight, preferably 0-10% by weight, of nonionic surfactant.
  • the solid detergent or cleaner comprises amylase in an amount of 0.001-0.15 weight percent, preferably 0.005-0.012 weight percent, based on the total weight of the detergent or cleaning agent.
  • the present invention relates to the use of a
  • solid detergent or cleaner for washing textiles or cleaning hard surfaces.
  • the present invention relates to the use of a
  • solid detergent or cleaner according to the invention for the removal of starch-containing stains on textiles or hard surfaces.
  • the present invention relates to a method for cleaning textiles or hard surfaces, characterized in that in at least one
  • Amino acid positions which are given in the context of the present invention with the formulation "counting according to SEQ ID NO. 1" are as follows: The further amino acid positions are determined by an alignment of the amino acid sequence of a
  • Amylase or protease according to the invention with the amino acid sequence as shown in SEQ ID NO. 1 is defined. Furthermore, the assignment of positions depends on the mature (matures) protein. This assignment is also to be used in particular if the amino acid sequence of a protein according to the invention comprises a higher number of amino acid residues than the amylase or protease in SEQ ID NO. 1.
  • Positions in the amino acid sequence are the change positions in one
  • amylase or protease according to the invention those which are just assigned to these positions in an alignment.
  • the inventive combination of an ⁇ -amylase according to the invention with a protease in solid detergents and cleaners effects an improved cleaning performance of the solid detergent and cleaner on at least one protease-sensitive soiling.
  • A-amylases according to the invention have a performance-improving effect on the protease likewise contained in the washing and cleaning agent and consequently, inter alia, by their protease-stabilizing action, enable improved removal of at least one, preferably of several protease-sensitive stains on textiles and / or hard surfaces For example, dishes.
  • Particularly advantageous cleaning performance is shown by preferred embodiments of detergents and cleaners according to the invention on blood-containing soils, for example on the Blood / Milk / Ink soiling: Product No. CFT C-05 available from CFT (Center For Testmaterials) B.V. Viaardingen, Netherlands.
  • solid detergents and cleaners with improved cleaning performance are produced specifically with regard to protease-sensitive soiling.
  • amylase and protease combinations achieve such advantageous cleaning performance even at low temperatures, especially in the temperature ranges between 10 ° C and 60 ° C, preferably between 15 ° C and 50 ° C and more preferably between 20 ° C and 40 ° C. , Further preferred
  • Embodiments of the invention amylase and protease combinations achieve such advantageous cleaning performance in a wide temperature range, for example between 15 ° C and 90 ° C, preferably between 20 ° C and 60 ° C.
  • cleaning performance is understood to mean the whitening performance of one or more stains, in particular laundry or dishes.
  • both the washing or cleaning agent which comprises the combination of amylase and protease or the washing or cleaning liquor formed by this agent, as well as the protease and amylase itself have a respective cleaning performance.
  • the cleaning performance of the enzymes thus contributes to the cleaning performance of the agent
  • Cleaning performance is preferably determined as indicated below.
  • the purification performance of the protease is primarily illuminated, wherein the synergistic effect of the ⁇ -amylase according to the invention is shown indirectly by the improved purification performance of the protease on protease-containing soils.
  • a protease has a proteolytic activity, that is, it is for the hydrolysis of
  • a protease is therefore an enzyme which catalyzes the hydrolysis of peptide bonds and thereby is able to cleave peptides or proteins.
  • Amylases and proteases of the invention are preferably the mature amylase / protease, i. to the catalytically active molecule without signal and / or propeptide (s). Unless otherwise stated, the sequences given refer to each mature enzyme.
  • sequence comparison is based on the BLAST algorithm established and commonly used in the prior art (see, for example, Altschul, SF, Gish, W., Miller, W., Myers, EW & Lipman, DJ. (1990) "Basic local alignment search Biol. 215: 403-410; and Altschul, Stephan F., Thomas L. Madden, Alejandro A. Schaffer, Jinghui Zhang, Hheng Zhang, Webb Miller, and David J.
  • Lipman (1997): "Gapped BLAST and PSI-BLAST: a new generation of protein database search programs"; Nucleic Acids Res., 25, pp.3389-3402) and is in principle accomplished by similar sequences of nucleotides or amino acids in the nucleic acid or amino acid sequences of each other be assigned. A tabular assignment of the respective positions is referred to as alignment.
  • Another algorithm available in the prior art is the FASTA algorithm. Sequence comparisons (alignments), in particular multiple sequence comparisons, are created with computer programs.
  • Identity and / or homology information can be made about whole polypeptides or genes or only over individual regions. Homologous or identical regions of different nucleic acid or amino acid sequences are therefore defined by matches in the sequences. Such areas often have identical functions. They can be small and comprise only a few nucleotides or amino acids. Often, such small regions exert essential functions for the overall activity of the protein. It may therefore be useful to relate sequence matches only to individual, possibly small areas. Unless otherwise indicated, identity or homology information in the present application, however, refers to the total length of the particular nucleic acid or amino acid sequence indicated.
  • the cleaning performance is determined in a washing system containing a detergent in a dosage between 3.5 and 6.5 grams per liter of wash liquor as well as the amylase and preferably the protease.
  • the amylases to be compared are used with the same concentration (based on active protein).
  • the cleaning performance of the protease is determined against blood staining by measuring the whiteness of the laundered fabrics. The washing is carried out for 70 minutes at a temperature of 40 ° C, the water has a water hardness between 13.5 and 16.5 ° (German hardness).
  • the concentration of the protease in the detergent intended for this washing system is from 0.001 to 0.1% by weight, preferably from 0.01 to 0.06% by weight, based on active protein.
  • the concentration of the amylase in the detergent intended for this washing system is from 0.001-0, 15% by weight, preferably from 0.005 to 0.012% by weight, based on active protein.
  • the dosage of the solid detergent is between 3.5 and 6.0 grams per liter of wash liquor, for example, 4.7, 4.9 or 5.9 grams per liter of wash liquor. Preference is given to washing in a pH range between pH 8 and pH 10.5, preferably between pH 8 and pH 9.
  • a preferred powdered detergent for such a washing system is composed as follows (all figures in weight percent): 10% linear alkylbenzenesulfonate (sodium salt), 1.5% C12-C18 fatty alcohol sulfate (sodium salt), 2.0% C12-C18 fatty alcohol with 7 EO, 20% sodium carbonate, 6.5% sodium bicarbonate, 4.0% amorphous sodium disilicate, 17% sodium carbonate peroxohydrate, 4.0% TAED, 3.0% polyacrylate, 1.0% Carboxymethylcellulose, 1, 0% phosphonate, 27% sodium sulfate, balance: foam inhibitors, optical brightener, fragrances.
  • the dosage of the powdered detergent is between 4.5 and 7.0 grams per liter of wash liquor, for example, and more preferably 4.7 grams per liter of wash liquor, or 5.5, 5.9 or 6.7 grams per liter of wash liquor. Preference is given to washing in a pH range between pH 9 and pH 11.
  • the degree of whiteness i. the brightening of the stains, as a measure of the cleaning performance is preferably determined by optical measurement methods, preferably photometrically.
  • a suitable device for this purpose is for example the spectrometer Minolta CM508d.
  • the devices used for the measurement are previously calibrated with a white standard, preferably a supplied white standard.
  • 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 (AG Gornall, CS Bardawill and MM David, J. Biol. Chem., 177 (1948), pp. 751-766).
  • the determination of the active protein concentration in this regard can be carried out by titration of the active sites using a suitable irreversible inhibitor (for proteases, for example phenylmethylsulfonyl fluoride (PMSF)) and determination of the residual activity (see M. Bender et al., J. Am. Chem. Soc 24 (1966), pp. 5890-5913).
  • a suitable irreversible inhibitor for proteases, for example phenylmethylsulfonyl fluoride (PMSF)
  • amylases and proteases of the invention may have other amino acid changes, especially amino acid substitutions, insertions or deletions.
  • Such amylases and proteases are, for example, by targeted genetic modification, i. by mutagenesis, further developed and optimized for specific applications or specific properties (for example, in terms of catalytic activity, stability, etc.).
  • nucleic acids according to the invention can be introduced into recombination mixtures and thus used for
  • the goal is to introduce into the known molecules targeted mutations such as substitutions, insertions or deletions, for example, to improve the cleaning performance of enzymes of the invention.
  • targeted mutations such as substitutions, insertions or deletions, for example, to improve the cleaning performance of enzymes of the invention.
  • the surface charges and / or the isoelectric point of the molecules and thereby their interactions with the substrate can be changed.
  • the net charge of the enzymes can be changed in order to influence the substrate binding, in particular for use in detergents and cleaners.
  • the stability of the amylase or protease can be increased by one or more corresponding mutations, thereby improving its purification performance.
  • amino acid exchanges the following convention is used: first, the naturally occurring amino acid in the form of the international one-letter code is called, then follows the associated sequence position and finally the inserted amino acid. Several exchanges within the same polypeptide chain are separated by slashes. For insertions, additional amino acids are named after the sequence position. For deletions, the missing amino acid is replaced by a symbol, such as a star or a dash. For example, A95G describes the substitution of alanine at position 95 by glycine, A95AG the insertion of glycine after the amino acid alanine at position 95 and A95 * the deletion of alanine at position 95. This nomenclature is known to those skilled in the art of enzyme technology.
  • Another object of the present invention is therefore a washing and cleaning agent containing a combination of an ⁇ -amylase and a protease, wherein the ⁇ -amylase is characterized in that it can be obtained from an amylase according to the invention as starting molecule by one or more conservative amino acid substitution is.
  • conservative amino acid substitution means the substitution of one amino acid residue for another amino acid residue, which substitution does not result in a change in polarity or charge at the position of the exchanged amino acid, e.g. Example, the replacement of a nonpolar amino acid residue against another nonpolar amino acid residue.
  • Another object of the present invention is therefore a washing and cleaning agent containing a combination of an ⁇ -amylase and a protease, wherein the ⁇ -amylase is characterized in that it is obtainable from an amylase according to the invention as the starting molecule by fragmentation, deletion, Insertion or substitution mutagenesis and an amino acid sequence over a length of at least 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300, 310, 320, 330, 340, 350, 360, 370, 380, 390, 400, 410, 420, 430, 440, 450, 460, 470, 475, 480, 482, 484 or 485 contiguous amino acids matches the parent molecule.
  • the enzymes retain their proteolytic activity even after mutagenesis, ie their proteolytic activity is at least equal to that of the starting enzyme. Substitutions can also show beneficial effects. Both single and multiple contiguous amino acids can be substituted for other amino acids.
  • An amylase according to the invention may additionally be stabilized, in particular by one or more mutations, for example substitutions, or by coupling to a polymer.
  • mutations for example substitutions
  • coupling to a polymer.
  • amino acid (s) involved in the calcium binding with one or more negatively charged amino acids and / or by introducing sequence changes in at least one of the sequences of the two amino acids arginine / glycine;
  • Preferred embodiments are those in which the enzyme is stabilized in several ways, as several stabilizing mutations act additive or synergistic.
  • Another object of the invention is an amylase as described above, which is characterized in that it has at least one chemical modification.
  • An amylase with such a change is called a derivative, i. the amylase is derivatized.
  • derivatives are understood as meaning those proteins whose pure amino acid chain has been chemically modified.
  • Derivatizations can be made, for example, in vivo by the host cell expressing the protein. In this regard, couplings of low molecular weight compounds such as lipids or Particular emphasis should be given to oligosaccharides. However, derivatizations can also be carried out in vitro, for example by the chemical transformation of a side chain of an amino acid or by covalent binding of another compound to the protein. For example, the coupling of amines to carboxyl groups of an enzyme to alter the isoelectric point is possible. Such another compound may also be another protein that is bound to a protein of the invention via bifunctional chemical compounds, for example. Similarly, derivatization is the covalent bond to a
  • Derivatizations may, for example, affect the substrate specificity or binding strength to the substrate or cause a temporary blockage of the enzymatic activity when the coupled substance is an inhibitor. This can be useful, for example, for the period of storage. Such modifications may further affect stability or enzymatic activity. They can also serve to reduce the allergenicity and / or immunogenicity of the protein and thus, for example, increase its skin compatibility. For example, couplings with macromolecular compounds, for example, polyethylene glycol, can improve the protein in terms of stability and / or skin tolerance.
  • a protein may be associated with various other substances, for example from the culture of the producing microorganisms.
  • a protein may also have been deliberately added to other substances, for example to increase its storage stability.
  • the subject matter of the invention includes all conceivable solid types of washing or cleaning agents, both concentrates and undiluted agents, for use on a commercial scale, in the washing machine or in hand washing or cleaning. These include detergents for textiles, carpets, or natural fibers for which the
  • Label detergent is used. These include, for example, dishwashing detergents for dishwashers or manual dishwashing detergents or cleaners for hard surfaces such as metal, glass, porcelain, ceramics, tiles, stone, painted surfaces, plastics, wood or leather, for which the term detergent is used, ie in addition to manual and machine Dishwashing agents, for example, scouring agents, glass cleaner, toilet scenters, etc.
  • the solid detergents and cleaning agents in the invention also include Detergents that are added to the actual detergent in the manual or machine textile laundry, to achieve a further effect.
  • laundry detergents and cleaners in the context of the invention also include textile pre-treatment and post-treatment agents, ie those agents with which the laundry item is brought into contact before the actual laundry, for example to dissolve stubborn soiling, and also agents which are in one of the actual Textile laundry downstream step to give the laundry further desirable properties such as comfortable grip, crease resistance or low static charge.
  • textile pre-treatment and post-treatment agents ie those agents with which the laundry item is brought into contact before the actual laundry, for example to dissolve stubborn soiling
  • agents which are in one of the actual Textile laundry downstream step to give the laundry further desirable properties such as comfortable grip, crease resistance or low static charge.
  • the fabric softeners are calculated.
  • the solid detergents or cleaners according to the invention may contain, in addition to the amylase, in particular in addition to the amylase and the protease, further enzymes.
  • lipases or cutinases can be used as further enzymes, in particular because of their triglyceride-splitting activities, but also in order to generate peracids in situ from suitable precursors. These include, for example, those originally from Humicola lanuginosa
  • Thermomyces lanuginosus available, or further developed lipases, especially those with the amino acid exchange D96L. These include, for example, the lipases originally obtainable from Humicola lanuginosa (Thermomyces lanuginosus) or further developed, in particular those having one or more of the following
  • the cutinases can be used, which were originally isolated from Fusarium solani pisi and Humicola insolens. Also usable are lipases, or cutinases, whose
  • Oxidoreductases for example oxidases, oxygenases, catalases, peroxidases, such as halo, chloro, bromo, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases) can be used according to the invention to increase the bleaching effect.
  • oxidases oxygenases, catalases, peroxidases, such as halo, chloro, bromo, lignin, glucose or manganese peroxidases, dioxygenases or laccases
  • organic, more preferably aromatic, enzyme-interacting compounds to enhance the activity of the respective oxidoreductases (enhancers) or to react at greatly varying redox potentials between the oxidizing enzymes and the
  • the solid detergents or cleaners may contain cleaning-active substances in addition to the ingredients described above, substances from the group of surfactants,
  • Perfume carriers are preferred. These preferred ingredients will be described in more detail below.
  • At least one anionic surfactant based on the total amount of anionic surfactants contained in the composition.
  • the present invention relates to the use of the detergents or cleaners defined herein as detergents or cleansers.
  • the present invention relates to the use of the detergents or cleaners defined herein as laundry detergents, hand wash detergents, travel detergents, dishwashing detergents, especially dishwashing detergents, more preferably hand dishwashing detergents or toilet cleaners.
  • the composition of the invention in a sink produces excellent foam in the cleaning liquor when the liquor carries dirt.
  • At least one refers to 1 or more, for example 1, 2, 3, 4, 5, 6, 7, 8, 9 or more In the context of components of those described herein
  • At least one anionic surfactant means one or more different anionic surfactants, ie, one or more different types of anionic surfactants the quantities given to the total amount of the corresponding designated type of ingredient, as already defined above.
  • compositions contain 5-70% by weight of surfactant, by which is meant one or more surfactants.
  • surfactant by which is meant one or more surfactants.
  • the agents comprise 5-55% by weight, more preferably 5-35% by weight of surfactant.
  • anionic surfactants, nonionic surfactants and mixtures thereof are suitable, but it is also possible for cationic, zwitterionic and / or amphoteric surfactants to be present.
  • anionic surfactants for example, those of the sulfonate type and sulfates are used.
  • surfactants of the sulfonate type preferably come C9-13-Alkylbenzolsul- fonate, Olefinsulfonate, i. Mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as obtained for example from C12-18 monoolefins with terminal or internal double bond by sulfonating with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation, into consideration.
  • alkanesulfonates which are obtained from C12-18-alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • esters of ⁇ -sulfo fatty acids e.g. the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids suitable.
  • the agent comprises 5-55% by weight, preferably 5-35% by weight, of anionic surfactant.
  • the agent comprises 5-35% by weight of alkylbenzenesulfonate.
  • Suitable alkylbenzenesulfonates are preferably selected from linear or branched alkylbenzenesulfonates of the formula
  • a particularly preferred representative is sodium dodecylbenzylsulfonate.
  • Alk (en) ylsulfates are the alkali metal and in particular the sodium salts of
  • Sulfuric acid half esters of C12-C18 fatty alcohols for example from coconut fatty alcohol,
  • Tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C10-C20 oxo alcohols and those half-esters of secondary alcohols of these chain lengths are preferred.
  • 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.
  • Alkyl ether sulfates are, for example, compounds of the formula
  • R 1 is a linear or branched, substituted or unsubstituted alkyl radical, preferably a linear, unsubstituted alkyl radical, particularly preferably a fatty alcohol radical.
  • Preferred radicals R 1 are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl radicals and mixtures thereof, where the representatives with even number of C atoms are preferred.
  • radicals R 1 are derived from C 12 -C 18 -fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or from C 10 -C 20 oxo alcohols.
  • AO represents an ethylene oxide (EO) or propylene oxide (PO) moiety, preferably an ethylene oxide moiety.
  • EO ethylene oxide
  • PO propylene oxide
  • n stands for an integer from 1 to 50, preferably from 1 to 20 and especially from 2 to 10. Most preferably, n stands for the numbers 2, 3, 4, 5, 6, 7 or 8.
  • X stands for a monovalent cation or the nth part of an n-valent cation, the alkali metal ions are preferred, and Na + or K + including Na, with Na + being extremely preferred. Further cations X + can be selected from NH4 +, ⁇ +, Ca2 +, 1 ⁇ Mn2 +, and mixtures thereof.
  • the alkyl ether sulfate may be selected from
  • Degree of ethoxylation represents a statistical average that may be an integer or a fractional number for a particular product.
  • the indicated degrees of alkoxylation represent statistical averages, which may be an integer or a fractional number for a particular product.
  • Preferred alkoxylates / ethoxylates have a narrow homolog distribution (narrow rank ethoxylates, NRE).
  • anionic surfactants also means soaps. Accordingly, soaps come as additional ingredients of detergents or cleaning agents 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.
  • anionic surfactants as well as soaps may be present 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 and soaps are in the form of their sodium, potassium or magnesium salts, especially in the form of the sodium salts.
  • anionic surfactants are the freedom from formulation no conditions to be observed in the way.
  • Preferred anionic surfactants to be used are the alkylbenzenesulfonates and fatty alcohol sulfates, in particular the alkylbenzenesulfonates.
  • the agent comprises 0-15% by weight, preferably 0-10% by weight, even more preferably 5-10% by weight of nonionic surfactant.
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten.
  • alcohol ethoxylates having linear radicals of alcohols of native origin having 12 to 18 carbon atoms, e.g. from coconut, palm, tallow or oleyl alcohol, and on average from 2 to 8 EO per mole of alcohol.
  • the preferred ethoxylated alcohols include, for example, C12-14 alcohols with 3 EO or 4 EO, C9-1 1 alcohol with 7 EO, C13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C12-18 Alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C12-14 alcohol with 3 EO and C12-18 alcohol with 5 EO.
  • the degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow rank 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 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters.
  • APG alkyl polyglycosides
  • Usable alkylpolyglycosides satisfy the general formula RO (G) z, in which R is a linear or branched, in particular in the 2-position methyl-branched, saturated or unsaturated, aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the Is a symbol which represents a glycose unit having 5 or 6 C atoms, preferably glucose.
  • the glycosidation degree z is between 1, 0 and 4.0, preferably between 1, 0 and 2.0 and in particular between 1, 1 and 1, 4.
  • Nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.
  • carbonate means in the context of the present invention, alkali metal carbonate and
  • Alkali hydrogen carbonate Preferably, it is sodium carbonate and
  • the agent comprises 5-55 wt.%, Preferably 5-40 wt.%, More preferably 5-35 wt.%, Even more preferably 5-25 wt.% Of carbonate. In various embodiments, the agent comprises 5-55 wt.%, Preferably 5-40 wt.%, More preferably 5-35 wt.%, Even more preferably 5-25 wt.% Of alkali carbonate. In preferred
  • the agent comprises 5-55 wt%, preferably 5-40 wt%, more preferably 5-35 wt%, still more preferably 5-25 wt% sodium carbonate.
  • a washing or cleaning agent preferably contains at least one water-soluble and / or water-insoluble organic builder.
  • the water-soluble organic builder substances include polycarboxylic acids, in particular citric acid and sugar acids, monomeric and polymeric aminopolycarboxylic acids, in particular methylglycinediacetic acid, nitrilotriacetic acid and ethylenediaminetetraacetic acid and polyaspartic acid, polyphosphonic acids, in particular aminotris (methylenephosphonic acid), ethylenediaminetetrakis (methylenephosphonic acid) and 1-hydroxyethane-1, 1 diphosphonic acid, polymeric hydroxy compounds such as dextrin and polymeric (poly) carboxylic acids, in particular by oxidation of polysaccharides or dextrins accessible polycarboxylates, and / or polymeric acrylic acids, methacrylic acids, maleic acids and copolymers thereof, which may also contain polymerized small amounts of polymerizable substances without carboxylic acid functionality.
  • the molecular weight of the homopolymers of unsaturated carboxylic acids is generally between 5,000 and 200,000, that of the copolymer between 2,000 and 200,000, preferably 50,000 to 120,000, each based on the free acid.
  • a particularly preferred acrylic acid-maleic acid copolymer has a molecular weight of 50,000 to 100,000.
  • Suitable, although less preferred, compounds of this class are copolymers of acrylic or methacrylic acid with vinyl ethers, such as vinylmethyl ethers, vinyl esters, ethylene, propylene and styrene, in which the acid content is at least 50% by weight.
  • Terpolymers which contain two unsaturated acids and / or their salts as monomers and also vinyl alcohol and / or an esterified vinyl alcohol or a carbohydrate as the third monomer may also be used as water-soluble organic builder substances.
  • the first acidic monomer or its salt is derived from a monoethylenically unsaturated C3-Cs-carboxylic acid and preferably from a C3-C4-monocarboxylic acid, in particular from (meth) -acrylic acid.
  • the second acidic monomer or its salt may be a derivative of a C4-Cs-dicarboxylic acid, with maleic acid being particularly preferred, and / or a derivative of an allylsulfonic acid which is substituted in the 2-position by an alkyl or aryl radical.
  • Such polymers generally have a molecular weight between 1,000 and 200,000.
  • Further preferred copolymers are those which have as monomers acrolein and acrylic acid / acrylic acid salts or vinyl acetate.
  • the organic builder substances can be used, in particular for the preparation of liquid agents, in the form of aqueous solutions, preferably in the form of 30 to 50 percent by weight aqueous solutions. All of the acids mentioned are generally used in the form of their water-soluble salts, in particular their alkali metal salts.
  • organic builder substances may be present in amounts of up to 40% by weight, in particular up to 25% by weight and preferably from 1% by weight to 8% by weight. Quantities close to the stated upper limit are preferably used in pasty or liquid, in particular water-containing agents.
  • the agent comprises a water-soluble builder block.
  • builder block it is intended to express that the agents contain no further builder substances than those which are water-soluble, ie all builder substances contained in the agent are present in the "block” thus characterized.
  • Impurities or stabilizing additives may be present in small amounts in the remaining ingredients of the products commercially.
  • water-soluble is to be understood as meaning that the builder block dissolves without leaving a residue at the concentration which results from the use of the agent containing it under the usual conditions, preferably at least 15% by weight and up to 55% by weight %, in particular 25 wt .-% to 50 wt .-% of water-soluble builder block contained in the agents.
  • This is preferably composed of the components a) 5% by weight to 35% by weight of citric acid, alkali citrate and / or alkali metal carbonate, which may also be replaced at least proportionally by alkali metal bicarbonate,
  • the water-soluble builder block contains at least 2 of components b), c), d), e) and f) in amounts greater than 10% by weight.
  • component a in a preferred embodiment, 15% by weight to 25% by weight of alkali carbonate, which may be replaced at least proportionally by alkali metal bicarbonate, and up to 5% by weight, in particular 0.5% by weight, bis 2.5% by weight of citric acid and / or alkali citrate.
  • Alkalihydrogencarbonat preferably in the weight ratio of 10: 1 to 1: 1.
  • component b in a preferred embodiment, 1% by weight to 5% by weight of alkali metal silicate with a modulus in the range from 1.8 to 2.5 are contained.
  • phosphonic acid and / or alkali metal phosphonate in a preferred embodiment, from 0.05% by weight to 1% by weight of phosphonic acid and / or alkali metal phosphonate is contained.
  • Phosphonic acids are also understood as meaning optionally substituted alkylphosphonic acids, which may also have a plurality of phosphonic acid groups (so-called polyphosphonic acids).
  • They are preferably selected from the hydroxy and / or aminoalkylphosphonic acids and / or their alkali salts, for example dimethylaminomethane diphosphonic acid, 3-aminopropane-1-hydroxy-1, 1-diphosphonic acid, 1-amino-1-phenylmethane diphosphonic acid, 1-hydroxyethane -1, 1-diphosphonic acid, amino-tris (methylenephosphonic acid), N, N, N ', N'-ethylenediaminetrakis (methylenephosphonic acid) and acylated derivatives of phosphorous acid, which can also be used in any mixtures.
  • dimethylaminomethane diphosphonic acid 3-aminopropane-1-hydroxy-1, 1-diphosphonic acid, 1-amino-1-phenylmethane diphosphonic acid, 1-hydroxyethane -1, 1-diphosphonic acid, amino-tris (methylenephosphonic acid), N, N, N ', N'-ethylenediaminetrakis (methylenephosphonic acid
  • component d reference is made to the definition of the phosphate builder.
  • the alkali metal salts of polyacrylic acid or polymethacrylic acid for example, those having a molecular weight of 500 to 70,000 g / mol are suitable. This class of substances has already been described in detail above.
  • the (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution.
  • the content of (co) polymeric polycarboxylates in the compositions is preferably 0.5 to 20% by weight, in particular 3 to 10% by weight.
  • zeolite builder is understood to mean not only zeolite in the strict sense, both crystalline and amorphous alkali metal aluminosilicate.
  • Zeolite is present in the composition in amounts of 0 to 10% by weight, preferably not more than 5% by weight.
  • preferred are the detergent grade crystalline sodium aluminosilicates, especially zeolite A, P and optionally X. Amounts near the above upper limit are preferably used in solid, particulate agents.
  • Suitable aluminosilicates have, in particular, no particles with a particle size greater than 30 ⁇ m, and preferably consist of at least 80% by weight of particles having a size of less than 10 ⁇ m.
  • Their calcium binding capacity which can be determined according to the specifications of the German patent DE 24 12 837, is generally in the range of 100 to 200 mg CaO per gram.
  • the agent preferably has 0-10% by weight, preferably 0-5% by weight, zeolite builder.
  • alkali metal silicate refers to crystalline and amorphous alkali silicates.
  • Crystalline alkali metal silicates comprise layered sodium silicates of the general formula NaMSix Ctex + ryl-bO, where M is sodium or hydrogen, x is a number from 1 to 9 and 4 is a number from 0 to 20 and preferred values for x are 2, 3 or 4 , They are suitable for the substitution of zeolites or phosphates.
  • Such crystalline layered silicates are described, for example, in European Patent Application EP-A-0 164 514.
  • Preferred crystalline layered silicates of the formula given are those in which M is sodium and x assumes the values 2 or 3.
  • both ⁇ - and ⁇ -sodium disilicates Na2Si205'yH20 are preferred.
  • Preferred amorphous alkali metal silicates are amorphous sodium silicates having a modulus Na 2 O: SiO 2 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 are delay-delayed and secondary wash properties.
  • the dissolution delay compared to conventional amorphous sodium silicates can in various ways, for example by surface treatment, compounding, compaction / compaction or by
  • amorphous is also understood to mean “X-ray amorphous”. This means that the silicates are present
  • X-ray diffraction experiments do not give sharp X-ray reflections, as they are typical for crystalline substances, but at best one or more maxima of the scattered X-rays having a width of several degrees of the diffraction angle. However, it may well even lead to particularly good builder properties if the silicate particles are washed out or even frayed in electron diffraction experiments
  • diffraction maxima This is to be interpreted as meaning that the products have microcrystalline regions of size 10 to a few hundred nm, with values of up to max. 50 nm and in particular up to max. 20 nm are preferred.
  • Such so-called X-ray amorphous silicates which also have a dissolution delay compared to the conventional water glasses are
  • compacted / compacted amorphous silicates particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates, wherein in particular the overdried silicates preferably also occur as carriers in the granules according to the invention or are used as carriers in the process according to the invention.
  • the agent preferably has 0-20% by weight, preferably 0-15% by weight, more preferably 0-10% by weight of alkali silicate builder, preferably sodium silicate builder.
  • compositions according to the invention have 0-10% by weight, preferably 0-5% by weight, more preferably 0-1% by weight of phosphate builder.
  • the alkali metal phosphates are of greatest importance for the agents according to the invention.
  • preferred agents contain this phosphate (s), preferably pentakalium triphosphate, wherein the
  • wt .-% preferably 0 to 10 wt .-%, preferably 0 to 5 wt .-% and in particular 0 to 1 wt .-% is.
  • solid detergents or cleaners according to the invention can be used in the preparation forms known to the person skilled in the art, ie, for example, as powders, granules, extrudates or
  • Kompaktate in particular tablets are provided.
  • a fabric e.g. a composition or agent, as defined by the invention, is solid when in the solid state at 25 ° C and 1013 mbar.
  • a substance for example a composition or an agent, according to the definition of the invention, is liquid when it is in the liquid state of aggregation at 25 ° C. and 1013 mbar.
  • liquid also includes gel.
  • the agents according to the invention may in particular be builders, surface-active surfactants, bleaches based on organic and / or inorganic peroxygen compounds, bleach activators, bleach catalysts, water-miscible organic solvents, enzymes, sequestering agents, electrolytes, pH regulators and other auxiliaries such as optical brighteners, scorch inhibitors, foam regulators and Dyes and fragrances and combinations thereof.
  • a washing or cleaning agent further comprises
  • grayness inhibitor 0.01 to 5% by weight of grayness inhibitor and / or
  • the agent may further comprise optical brighteners, preferably from 0.01% to 5% by weight.
  • compositions according to the invention presents no difficulties and can be carried out in a known manner, for example by spray-drying or granulation, enzymes and possibly other thermally sensitive ingredients such as, for example, bleaching agents optionally being added separately later.
  • a process comprising an extrusion step is preferred.
  • the procedure is preferably such that all constituents, if appropriate one layer, are added mixed with a mixer and the mixture by means of conventional tablet presses, such as eccentric or rotary presses, with pressing forces in the range of about 50 to 100 kN, preferably compressed at 60 to 70 kN.
  • conventional tablet presses such as eccentric or rotary presses
  • pressing forces in the range of about 50 to 100 kN, preferably compressed at 60 to 70 kN.
  • at least one layer is pre-compressed. This is preferably carried out at pressing forces between 5 and 20 kN, in particular at 10 to 15 kN.
  • a tablet produced in this way has a weight of 10 g to 50 g, in particular 15 g up to 40 g.
  • the spatial form of the tablets is arbitrary and can be round, oval or angular, with intermediate forms are also possible. Corners and edges are advantageously rounded. Round tablets preferably have a diameter of 30 mm to 40 mm. In particular, the size of square or cuboid shaped tablets, which predominantly over the
  • Dosing device for example, the washing machine are introduced, is dependent on the geometry and the volume of this metering device.
  • Embodiments have a footprint of (20 to 30 mm) x (34 to 40 mm), in particular 26 x 36 mm or 24 x 38 mm.
  • the agent comprises 0-25% by weight, more preferably 0-15% by weight of one
  • Peroxygen compounds suitable for use in solid compositions according to the invention are, in particular, organic peracids or persalts 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, including perborate, percarbonate, persilicate and / or persulfate like Caroat belong.
  • organic peracids or persalts 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, including perborate, percarbonate, persilicate and / or persulfate like Caroat belong.
  • solid peroxygen compounds are to be used, they can be used in the form of powders or granules, which can also be enveloped in
  • an agent according to the invention contains peroxygen compounds, they 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 may be useful.
  • Perhydrolysis aliphatic peroxycarboxylic acids having preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or optionally substituted perbenzoic acid, are used. Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups.
  • polyacylated alkylenediamines in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or Isononanoyloxybenzolsulfonat (n- or iso-NOBS), carboxylic acid anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate, 2,5-diacetoxy-2,5-dihydrofuran and enol esters, acyl
  • acylated sugar derivatives in particular pentaacetylglucose (PAG), pentaacetylfruktose, tetraacetylxylose and octaacetyllactose as well as acetylated, optionally N-alkylated glucamine and gluconolactone, and / or N-acylated lactams, for example N-benzoylcaprolactam.
  • PAG pentaacetylglucose
  • pentaacetylfruktose pentaacetylfruktose
  • tetraacetylxylose tetraacetylxylose
  • octaacetyllactose acetylated
  • lactams for example N-benzoylcaprolactam.
  • the hydrophilic substituted acyl acetals and the acyl lactams are also
  • Such bleach activators can, in particular in the presence of the abovementioned hydrogen peroxide-supplied bleach, in the usual amount range, preferably in amounts of from 0.5 wt .-% to 10 wt .-%, in particular 1 wt .-% to 8 wt .-%, based on However, total agent, be included, missing when using percarboxylic acid as the sole bleach, preferably completely.
  • sulfonimines and / or bleach-enhancing transition metal salts may also be used in solid compositions
  • Transition metal complexes may be included as so-called bleach catalysts.
  • the solid dosage forms according to the invention include extrudates, granules, tablets or pouches containing solid agents, which may be present both in bulk and in portions.
  • the agent is present as 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.
  • Embodiments of the present invention include all solid, powdered, liquid, gelatinous or paste-like administration forms of the agents, which if appropriate can also consist of several phases and can be present in compressed or uncompressed form.
  • a further embodiment of the invention therefore represents agents which are characterized in that they are present as a one-component system. Such means preferably consist of one phase.
  • agents according to the invention may also consist of several phases, for example two liquid, two solid or one liquid and one solid phase.
  • the washing or cleaning agent is therefore characterized in that it is divided into several components.
  • the solid detergents or cleaners according to the invention preferably have less than 10% by weight, preferably between 1 and 10% by weight, and in particular between 1 and 5% by weight, based on their total weight of water.
  • Another object of the invention is a process for the cleaning of textiles or hard surfaces, which is characterized in that in at least one process step, an inventive agent is applied.
  • Processes for the purification of textiles are generally distinguished by the fact that various cleaning-active substances are applied to the fabric in several process steps
  • the material to be cleaned is applied and washed off after the action time, or the material to be cleaned is treated in any other way with a detergent or a solution or dilution of this agent.
  • a detergent or a solution or dilution of this agent is applied in any other way with a detergent or a solution or dilution of this agent.
  • All conceivable washing or cleaning processes can be enriched in at least one of the process steps by the use of a washing or cleaning agent according to the invention or an amylase according to the invention, preferably in combination with the protease, and then provide
  • Embodiments described for amylase of the invention preferably in combination with protease, and agents containing them are also applicable to this subject of the invention. Therefore, reference is made at this point expressly to the disclosure in the appropriate place with the statement that this disclosure also for the above
  • a protease of the invention is active.
  • methods for textile raw materials, fibers or textiles with natural components are preferred, and especially for those with wool or silk.
  • a further subject of the invention is the use of an agent according to the invention for cleaning textiles or hard surfaces, in particular such that the combination of amylase and protease in an amount of 4C ⁇ g to 4g, preferably from 5C ⁇ g to 3g, more preferably from 10C ⁇ g to 2g and most preferably from 20C ⁇ g to 1g is used.
  • Standardized soiled textiles are used. The following stain is used:
  • the solid detergents or cleaners according to the invention containing the amylase according to the invention show an improved cleaning behavior in comparison with corresponding agents containing the amylase Stainzyme®.
  • the advantage is particularly clear when the amylases are combined with protease.
  • the synergistic effect of the ⁇ -amylase according to the invention with the protease in solid phosphate-poor and carbonate-rich detergents was demonstrated by the improved cleaning performance on starch-containing soils.
  • the amylase according to the invention surprisingly works particularly well in so-called soluble-builder formulations, i. in formulations containing only small amounts of zeolite and phosphate builders.
  • the improvement of the leachability branches especially in starch spots and foods with starch such as chocolate cream.
  • powdered detergent containing 10% linear alkylbenzenesulfonate (sodium salt), 1, 5% C12-C18 fatty alcohol sulfate (sodium salt), 2.0% C12-C18 fatty alcohol with 7 EO, 20% sodium carbonate, 6.5 % Natnumhydrogencarbonat, 4.0% amorphous sodium disilicate, 17% sodium carbonate peroxohydrate, 4.0% TAED, 3.0% polyacrylate, 1, 0% carboxymethylcellulose, 1, 0% phosphonate, 27% sodium sulfate, balance: foam inhibitors, optical brightener Given fragrances.
  • the dosage of the powdered detergent is between 4.5 and 7.0 grams per liter of wash liquor. It is washed in a pH of 8.5 at 30 ° C, water hardness 16 ° dH, in a Miele W 1935, with a total washing time of 70 min.
  • Table 1 shows an inventive powder detergent B compared with not
  • Thermamyl® (as%) 0.0308 - -
  • Amylase * (as%) - 0.01470 0.01470
  • Protease * (protease having an amino acid sequence which, in the counting according to SEQ ID NO 2, has the following amino acid substitution S3T, V4I, V199I, and otherwise the amino acid sequence given in SEQ ID NO: 2)
  • Amylase * Amylase according to the invention
  • Table 2 The values given (Table 2) are mean values of 6 determinations. The soiled textiles were bought. The mean values of the remission values in column A (for composition A) and B (for composition B) are shown. Table 3 gives the differences of the remission values to the standard detergent and the errors in the 6-fold determination (HSD) in Table 3.
  • HSD 6-fold determination
  • composition B according to the invention significantly removes starch-containing stains.
  • composition B according to the invention significantly removes starch-containing stains.

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Abstract

La présente invention concerne des agents de lavage et de nettoyage solides contenant de l'amylase dont la séquence d'acides aminés a été modifiée notamment par rapport à une utilisation dans des agents de lavage et de nettoyage. L'invention concerne également des procédés et des utilisations de ces agents de lavage et de nettoyage.
EP15808163.8A 2014-12-10 2015-12-10 Agent de lavage et de nettoyage solide comprenant de l'amylase Ceased EP3230429A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102014018149.9A DE102014018149A1 (de) 2014-12-10 2014-12-10 Festes Wasch- und Reinigungsmittel mit Amylase
PCT/EP2015/079232 WO2016092009A1 (fr) 2014-12-10 2015-12-10 Agent de lavage et de nettoyage solide comprenant de l'amylase

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DE102016210174A1 (de) * 2016-06-09 2017-12-14 Henkel Ag & Co. Kgaa Festes Wasch- und Reinigungsmittel mit Amylase, Protease und löslichem Builder
DE102016221850B4 (de) * 2016-11-08 2025-12-24 Henkel Ag & Co. Kgaa Festes Wasch- oder Reinigungsmittel mit Amylase und löslichem Builder
BR112021006317A2 (pt) 2018-10-05 2021-07-06 Basf Se preparação de enzima, processo para preparar uma preparação de enzima estável, métodos para reduzir perda da atividade amiolítica, de preparação de uma formulação detergente, para remover manchas sensíveis à amilase e para aumentar a estabilidade no armazenamento de uma formulação detergente líquida, usos de um composto e da preparação de enzima, e, formulação detergente
EP3677676A1 (fr) 2019-01-03 2020-07-08 Basf Se Composés de stabilisation d'amylases dans des liquides
WO2020229480A1 (fr) 2019-05-14 2020-11-19 Basf Se Composés stabilisant des hydrolases dans des liquides
US20240132808A1 (en) 2019-10-18 2024-04-25 Basf Se Storage-Stable Hydrolase Containing Liquids
BR112021021050A2 (pt) 2019-11-29 2022-09-13 Basf Se Composição, uso de uma composição, polímero, processo para preparar polímeros, e, método para melhorar o desempenho de limpeza de uma composição líquida de detergente
WO2021115912A1 (fr) 2019-12-09 2021-06-17 Basf Se Formulations comprenant une polyéthylèneimine modifiée de manière hydrophobe et une ou plusieurs enzymes
WO2022008732A1 (fr) 2020-07-10 2022-01-13 Basf Se Amélioration de l'activité de conservateurs antimicrobiens
WO2022063699A1 (fr) 2020-09-22 2022-03-31 Basf Se Combinaison améliorée d'inhibiteur de protéase et inhibiteur de protéase ayant une enzyme secondaire
EP4217367A1 (fr) 2020-09-22 2023-08-02 Basf Se Composition liquide comprenant un aldéhyde peptidique
EP4015629A1 (fr) 2020-12-18 2022-06-22 Basf Se Mélanges de polymères pour augmenter la stabilité et la performance des détergents contenant de l'hydrolase
EP4294917A1 (fr) 2021-02-22 2023-12-27 Basf Se Variants d'amylase
EP4047088A1 (fr) 2021-02-22 2022-08-24 Basf Se Variants d'amylase
WO2023118015A1 (fr) 2021-12-21 2023-06-29 Basf Se Attributs environnementaux pour des ingrédients de composition de soins
EP4555061A1 (fr) 2022-07-15 2025-05-21 Basf Se Formiates d'alcanolamine pour la stabilisation d'enzymes dans des formulations liquides
US20260055347A1 (en) 2022-08-11 2026-02-26 Basf Se Amylase variants
WO2024033135A2 (fr) 2022-08-11 2024-02-15 Basf Se Variants d'amylase
CN120153068A (zh) 2022-11-04 2025-06-13 巴斯夫欧洲公司 用于在洗涤剂组合物中使用的具有蛋白酶活性的多肽
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WO2025132258A1 (fr) 2023-12-20 2025-06-26 Basf Se Composition enzymatique stabilisée comprenant une protéase
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EP4624572A1 (fr) 2024-03-27 2025-10-01 Basf Se Polypeptides ayant une activité protéase destinés à être utilisés dans des compositions détergentes
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