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WO2017211661A1 - Produit de lavage et de nettoyage solide contenant une amylase, une protéase et un adjuvant de détergence soluble - Google Patents

Produit de lavage et de nettoyage solide contenant une amylase, une protéase et un adjuvant de détergence soluble Download PDF

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Publication number
WO2017211661A1
WO2017211661A1 PCT/EP2017/063251 EP2017063251W WO2017211661A1 WO 2017211661 A1 WO2017211661 A1 WO 2017211661A1 EP 2017063251 W EP2017063251 W EP 2017063251W WO 2017211661 A1 WO2017211661 A1 WO 2017211661A1
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Prior art keywords
weight
amino acid
cleaning agent
seq
amylase
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German (de)
English (en)
Inventor
Dilek MADENCI
Brigitte Giesen
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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
    • C11D3/38609—Protease or amylase in solid compositions only

Definitions

  • the invention relates to a solid detergent and cleaning agent containing an amylase in
  • the invention further relates
  • 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.
  • alpha-amylases are among the industrially important enzymes. Their use for detergents and cleaners is established industrially and they are contained in many modern, powerful detergents and cleaners.
  • An alpha-amylase is an enzyme that catalyzes the hydrolysis of the internal a (1-4) glycoside bonds of amylose but not the cleavage of terminal or a (1-6) -glycoside bonds.
  • Alpha-amylases are therefore a group of esterases (E.C. 3.2.1.1.).
  • Alpha-amylases catalyze the cleavage of starch, glycogen, and other oligo- and polysaccharides that have a (1-4) -glycoside linkage. In this respect, alpha-amylases counteract starch residues in the laundry and catalyze their hydrolysis
  • Alpha-amylases with broad substrate spectra are especially there used, where inhomogeneous raw materials or substrate mixtures must be implemented, so for example in detergents and cleaning agents, since contaminants may consist of differently structured starch molecules and oligosaccharides.
  • alpha-amylases used in the washing or cleaning agents known from the prior art are usually of microbial origin and are generally derived from bacteria or fungi, for example the genera Bacillus, Pseudomonas, Acinetobacter, Micrococcus, Humicola, Trichoderma or Trichosporon, in particular Bacillus , Alpha-amylases are usually produced by biotechnological methods known per se by suitable microorganisms, for example by transgenic expression hosts of the genera Bacillus or by filamentous fungi.
  • Combination with a protease according to the invention and a soluble builder system in solid detergents at low pH shows an activity on starch-containing soils, which is markedly improved compared to known agents.
  • starch-containing soils such as rice or corn starch
  • the washability of bleach-sensitive stains is increased.
  • the present invention is therefore in a first aspect containing a solid detergent or cleaning agent
  • Amino acid sequence is at least 89% identical over the entire length and in the count according to SEQ ID NO: 1 at one or more of the positions 180, 181, 182, 183 and 184 deletions;
  • protease comprising an amino acid sequence which is at least 80% identical to that in SEQ ID NO: 2 over its entire length;
  • washing or cleaning agent has a pH of 7.5 to 9.5, preferably 8.0 to 9.0, more preferably about 8.5.
  • the present invention relates to the use of a
  • solid washing or cleaning agent for washing textiles or cleaning hard surfaces, in particular for removing starchy
  • the present invention relates to a method for cleaning textiles or hard surfaces, characterized in that in at least one
  • Numeric ranges specified in the format "from x to y" include the above values. If multiple preferred numeric ranges are specified in this format, it is understood that all ranges resulting from the combination of the various endpoints, also be recorded.
  • At least one refers to 1, 2, 3, 4, 5, 6, 7, 8, 9 or more In the context of components of the compositions described herein, this indication does not refer to the absolute amount Therefore, for example, one or more of the "at least one anionic surfactant” means, for example, one or more
  • anionic surfactants i. one or more different types of anionic surfactants. Together with quantities, the quantities refer to the
  • the pH of an agent is the pH of the washing or cleaning liquor available at 20 ° C with the agent when dissolved in distilled water (1: 100 in weight ratio) unless otherwise specified is specified.
  • 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.
  • the ⁇ -amylase used according to the invention is characterized in that it comprises an amino acid sequence which is at least 89% and increasingly larger than the total amino acid sequence given in SEQ ID NO: 1 over the entire length thereof preferably at least 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%, 99.5% and up to 100% is identical and counted in accordance with SEQ ID NO: 1 one or more of the 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, very particularly preferred are deletions at the positions 183 + 184 in the count according to SEQ ID NO: 1, particularly preferred Deletions H183 * + G184 * .
  • the ⁇ -amylase according to the invention in the counting according to SEQ ID NO: 1 furthermore has an amino acid substitution at one or more of the positions 405, 421, 422 and 428. Particularly preferred are the substitutions I405L, A421H, A422P and A428T.
  • the ⁇ -amylase according to the invention has, in the count according to SEQ ID NO: 1, the deletions H183 * + G184 * and additionally the substitutions I405L, A421H, A422P and A428T.
  • Such amylase preferably has the
  • the protease according to the invention comprises an amino acid sequence which corresponds to the amino acid sequence given in SEQ ID NO: 2 over at least 80% of its total length and increasingly preferably 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.
  • protease which has an amino acid sequence which corresponds to the amino acid sequence given in SEQ ID NO: 2 over at least 80% of its total length and more preferably 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%, Is 95%, 95.5%, 96%, 96.5%, 97%, 97.5%, 98%, 98.5% and 99% identical and in the count according to SEQ ID NO: 2 on at least one of Positions 3, 4 and 199, preferably at two or all three positions, one
  • proteases which have the amino acid threonine (T) at position 3, the amino acid isoleucine (I) at position 4 and the amino acid isoleucine (I) at position 199.
  • T amino acid threonine
  • I amino acid isoleucine
  • I amino acid isoleucine
  • Amino acid positions are determined by an alignment of the amino acid sequence of a
  • amylase or protease of the invention having the amino acid sequence as set forth in SEQ ID NO: X. 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: X.
  • 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.
  • 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.
  • T-Coffee see, for example, Notredame et al (2000): T-Coffee: A novel method for multiple sequence alignments, J. Mol. Biol. 302, 205-217 or programs based on these programs or algorithms.
  • alignment comparisons with the computer program Vector NTI® Suite 10.3 (Invitrogen Corporation, 1600 Faraday Avenue, Carlsbad, California, USA) with the default parameters whose AlignX module for sequence comparisons is based on ClustalW.
  • 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.
  • amino acid position of a numerically designated position in SEQ ID NO: 1 or SEQ ID NO: 2 corresponds to the corresponding position being assigned to the numerically designated position in SEQ ID NO: 1 and SEQ ID NO: 2, respectively, in an alignment as defined above.
  • 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 separated. 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 or protease is characterized in that it consists of an amylase according to the invention or
  • Protease is available as a starting molecule by one or more conservative amino acid substitution.
  • conservative amino acid substitution means the replacement
  • 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, 483, 484 or 485 contiguous amino acids matches the parent molecule.
  • the protease may also be characterized in that it is obtainable from a protease according to the invention as the starting molecule by fragmentation, deletion, insertion or substitution mutagenesis and comprises an amino acid sequence which is over a length of at least 50, 60, 70, 80, 90, 100, 1 10, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 262, 264, 265, 266, 267 or 268, respectively
  • Amino acids coincides with the starting molecule.
  • An enzyme 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 enzyme as described above, which is characterized in that it has at least one chemical modification.
  • An enzyme with such a change is called a derivative, i. the enzyme 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.
  • couplings of low molecular weight compounds such as lipids or oligosaccharides are particularly noteworthy.
  • derivatizations can also be carried out in vitro be carried out by, for example, the chemical transformation of a side chain of an amino acid or by covalent attachment of another compound to the protein.
  • another compound may also be another protein that is bound to a protein of the invention via bifunctional chemical compounds, for example.
  • 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.
  • protease according to the invention in solid detergents and cleaners causes an improved cleaning performance of the solid detergent and cleaner to starchy soils and also to protease-sensitive stains.
  • ⁇ -amylases according to the invention have a performance-improving effect on the protease likewise contained in the washing and cleaning agent and thus, inter alia, by their protease-stabilizing action, enable improved removal of at least one, preferably of several protease-sensitive soils on textiles and / or hard Surfaces, for example dishes.
  • Particularly advantageous cleaning performances show preferred embodiments of washing and cleaning agents according to the invention on blood-containing Stains, for example on the Blood / Milk / Ink stain: Product No. CFT C-05 available from CFT (Center for Test Materials) BV Viaardingen, the Netherlands.
  • amylase, protease, soluble builder and low pH further provides improved cleaning performance on starchy soils, especially improved washability over the same enzyme combinations with less or no soluble builder and higher pH.
  • 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.
  • solid detergents and cleaners having improved cleaning performance are produced specifically with regard to starchy and protease-sensitive soiling.
  • 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 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 the protease.
  • the amylases to be compared are used with the same concentration (based on active protein).
  • the cleaning performance of the enzymes are compared
  • 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. Washing is carried out in a pH range between pH 7.5 and pH 9.5, preferably between pH 8 and pH 9, more preferably at approximately pH 8.5.
  • a preferred powdered detergent for such a washing system is composed as follows (all figures in weight percent): 10-15% linear alkyl benzene sulfonate (sodium salt), 0-1, 5% C12-C18 fatty alcohol sulfate (sodium salt), 2-5% C12-C18 fatty alcohol with 7 EO, 0-2% soaps, 5-15% sodium carbonate, 4-10% amorphous sodium disilicate, 0.5-2% phosphonate (eg HEDP-Na4), 1-4 % Polyacrylate, 1-2% carboxymethylcellulose, balance: sodium sulfate,
  • 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 or about 65g / job.
  • the degree of whiteness i. the brightening of soiling, as a measure of the cleaning performance is preferably determined by optical measuring method, 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)
  • the concentration of protease in the solid detergent or cleaning agent is 0.001-0.5% by weight, preferably 0.01 to 0.1% by weight, based on active protein.
  • the concentration of the amylase in the washing or cleaning agent is 0.0005-0.5 wt .-%, preferably 0.001 to 0.2 wt .-%, based on active protein.
  • the solid detergent also contains a soluble builder system.
  • Soluble or “water soluble,” as used interchangeably in this context, means that the builder, under conditions of use, is at the concentration determined by the amount of the agent containing it at the usual conditions results in completely dissolving in the wash liquor, ie, the residual of the builder remaining as a solid constitutes less than 1% of the total amount of the builder.
  • the water-soluble builder system contains at least one water-soluble, preferably 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, glutamic diacetic acid, nitrilotriacetic acid and ethylenediaminetetraacetic acid and polyaspartic acid, polyphosphonic acids, in particular aminotris (methylenephosphonic acid), ethylenediaminetetrakis (methylenephosphonic acid) and 1-hydroxyethane.
  • polycarboxylic acids in particular citric acid and sugar acids
  • monomeric and polymeric aminopolycarboxylic acids in particular methylglycinediacetic acid, glutamic diacetic acid, nitrilotriacetic acid and ethylenediaminetetraacetic acid and polyaspartic acid
  • polyphosphonic acids in particular aminotris (methylenephosphonic acid),
  • 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 also small amounts of polymerizable substances without carboxylic acid functionality may contain polymerized.
  • the molecular weight of the homopolymers of unsaturated carboxylic acids is generally between 5,000 and 200,000, of the copolymers 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.
  • vinyl ethers such as vinylmethyl ethers, vinyl esters, ethylene, propylene and styrene
  • 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.
  • copolymers are those which have as monomers acrolein and acrylic acid / acrylic acid salts or vinyl acetate. All the acids mentioned can be used in the form of their water-soluble salts, in particular their alkali metal salts. If desired, such organic builder substances may be present in amounts of up to 50% by weight, in particular up to 25% by weight and preferably from 10% by weight to 20% by weight.
  • citric acid and / or citrate is used as the water-soluble, organic builder.
  • Particularly preferred is the use of 5 wt .-% to 25 wt .-%, preferably 7.5 to 12.5 wt .-% citric acid and / or 5 wt .-% to 25 wt .-%,
  • citrate preferably alkali citrate, more preferably
  • Citric acid / citrate can each be used in the form of their hydrates, for example, citric acid in the form of monohydrate, citrate in the form of
  • Trisodium citrate dihydrate are used.
  • the agents of the invention may further contain inorganic water-soluble builders.
  • Suitable water-soluble inorganic builder materials are, in particular, alkali metal silicates. Suitable examples are crystalline alkali metal silicates, which may be present alone or in a mixture with amorphous silicates.
  • the alkali metal silicates useful as builders in the compositions according to the invention preferably have a molar ratio of alkali metal oxide to SiO 2 below 0.95, in particular from 1: 1, 1 to 1: 12, and may be present in amorphous or crystalline form.
  • Preferred alkali metal silicates are
  • Sodium silicates in particular the amorphous sodium silicates, with a molar ratio Na20: SiO 2 of 1: 1, 8 to 1: 2.8.
  • Crystalline silicates which may be present alone or in a mixture with amorphous silicates are preferably crystalline phyllosilicates of the general formula Na.sub.2SixO.sub.2.sup.x + H.sub.2O.sub.2, in which x, the so-called modulus, is a number from 1.9 to 4 and y is a number from 0 is up to 20 and preferred values for x are 2, 3 or 4.
  • Preferred crystalline phyllosilicates of the general formula Na.sub.2SixO.sub.2.sup.x + H.sub.2O.sub.2, in which x, the so-called modulus, is a number from 1.9 to 4 and y is a number from 0 is up to 20 and preferred values for x are 2, 3 or 4.
  • Phyllosilicates are those in which x in the abovementioned general formula assumes the values 2 or 3.
  • both beta- and delta-sodium disilicates Na 2 Si 2 O y H 2 O
  • x is a number from 1, 9 to 2.1
  • inventive compositions can be used in inventive compositions.
  • Embodiment of the invention means a crystalline sodium layer silicate is used with a modulus of 2 to 3, as it can be prepared from sand and soda. Crystalline sodium silicates with a modulus in the range of 1.9 to 3.5 are used in a further preferred embodiment of compositions according to the invention.
  • the weight ratio of amorphous alkali metal silicate to crystalline alkali metal silicate is preferably 1: 2 to 2: 1 and especially 1: 1 to 2: 1.
  • the carbonates (and hyo-hydrogencarbonates), in particular sodium carbonate, and the phosphonic acids / phosphonates are also important as water-soluble inorganic builder substances. Under phosphonic acids are also optionally substituted
  • Understood alkylphosphonic which also have several phosphonic acid groups could (so-called polyphosphonic acids). They are preferably selected from the hydroxy and / or aminoalkylphosphonic acids and / or their alkali metal salts, for example dimethylaminomethanediphosphonic acid, 3-aminopropane-1-hydroxy-1,1-diphosphonic acid, 1-amino-1-phenylmethanediphosphonic acid, 1 Hydroxyethane-1, 1-diphosphonic acid (HEDP), amino tris (methylenephosphonic acid), N, N, N ', N'-ethylenediamine tetrakis (methylenephosphonic acid),
  • DTPMP Diethylentriaminpenta (methylenephosphonic acid) (DTPMP) and acylated derivatives of phosphorous acid, which can also be used in any mixtures.
  • the builder system is preferably composed of the components, based in each case on the total mass of the composition:
  • Alkali phosphonate especially HEDP and / or DTPMP
  • 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 agents of the invention are preferably free of phosphate builder, i. contain less than 1 wt .-% preferably no deliberately added phosphate builder.
  • the agents may also contain water-insoluble builders.
  • the aluminosilicates and in this case preferably the zeolites are of importance.
  • 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 hard surface cleaners As metal, glass, porcelain, ceramics, tiles, stone, painted surfaces, plastics, wood or leather, for which the term detergent is used, so in addition to manual and automatic dishwashing detergents, for example, scouring agents, glass cleaner, toilet scenters, etc. Zu den solid detergents and cleaning agents in the context of the invention also include washing aids which are metered into the actual detergent during manual or automatic textile washing in order 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 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.
  • the lipases which are obtainable or further developed from Humicola lanuginosa (Thermomyces lanuginosus), in particular those having one or more of the following amino acid substitutions starting from said lipase in positions D96L, T213R and / or N233R, particularly preferably T213R and N233R.
  • the cutinases can be used, which were originally isolated from Fusarium solani pisi and Humicola insolens. It is also possible to use lipases, or cutinases, whose initial enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii.
  • 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, particularly preferably aromatic, compounds which interact with the enzymes in order to enhance the activity of the relevant oxidoreductases (enhancers) or in the case of strong different redox potentials between the oxidizing enzymes and the soiling to ensure the flow of electrons (mediators).
  • compositions contain 5-70% by weight of 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.
  • the agent may preferably contain other anionic surfactants, in particular alkyl ether sulfates, and
  • nonionic surfactants especially fatty alcohol alkoxylates. These can then make up the rest of the surfactants.
  • 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.
  • Further preferred Alk (en) ylsulfates of said chain length which contain a synthetic, petrochemical-based straight-chain alkyl radical having an analogous degradation behavior as the adequate compounds based on oleochemical raw materials.
  • sulfuric monoesters of ethoxylated with 1 to 6 moles of ethylene oxide straight-chain or branched C7-21 alcohols such as 2-methyl-branched C9-1 1 alcohols having an average of 3.5 moles of ethylene oxide (EO) or C12-18 fatty alcohols 1 to 4 EO, are suitable.
  • EO ethylene oxide
  • C12-18 fatty alcohols 1 to 4 EO are suitable.
  • 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
  • detergents additionally contain soap (s).
  • Preferred detergents are therefore characterized as containing soap (s).
  • Suitable are saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular of natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.
  • the 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.
  • alkyl polyglycosides Another class of nonionic surfactants that can be used to advantage are the alkyl polyglycosides (APG).
  • 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.
  • Preferably used are linear alkylpolyglycosides, ie alkyl polyglycosides in which the polyglycosyl is a glucose residue and the alkyl radical is an n-alkyl radical.
  • 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.
  • Suitable amphoteric surfactants are, for example, betaines of the formula (R 1, XR 1) XR 3 NTC 3 COO- in which R i is an alkyl radical optionally interrupted by hetero atoms or heteroatom groups having 8 to 25, preferably 10 to 21 carbon atoms and R iv and R v are identical or different Alkyl radicals having 1 to 3 carbon atoms, in particular Cio-Cis-alkyl dimethylcarboxymethylbetain and Cn-Ci7-alkylamidopropyl-dimethylcarboxymethylbetain.
  • Suitable cationic surfactants are i.a. the quaternary ammonium compounds of the formula
  • R VI (R VI ) (R vii ) (R viii ) (R ix ) N + X "
  • R vi to R ix for four identical or different, in particular two long and two short-chain, alkyl radicals and X " for an anion , in particular a halide ion, for example, didecyldimethylammonium chloride, Alkylbenzyldidecylammoniumchlorid and mixtures thereof.
  • Suitable cationic surfactants are the quaternary surface-active compounds, in particular with a sulfonium, phosphonium, iodonium or
  • Arsonium group which are also known as antimicrobial agents.
  • the agent can be designed with an antimicrobial effect or its possibly existing antimicrobial effect due to other ingredients can be improved.
  • compositions according to the invention may in principle comprise all known ingredients customary in such agents.
  • these include, but are not limited to, bleaching agents based on organic and / or inorganic peroxygen compounds, bleach activators, bleach catalysts, water-miscible organic solvents, sequestering agents, electrolytes, pH regulators, and other adjuvants such as optical brighteners, grayness inhibitors, foam regulators, and colorants Perfumes and combinations thereof.
  • solid detergents or cleaners according to the invention can be provided in the form of dressings known to the person skilled in the art.
  • 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.
  • 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 packaged.
  • the agent is as free-flowing Powder, in particular having 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.
  • 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 solid detergents or cleaners according to the invention preferably have less than 10% by weight, preferably less than 5% by weight, of water, based on their total weight.
  • Another subject 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 used and the use of a solid detergent or cleaning agent according to the invention for washing textiles or cleaning hard surfaces, in particular For removing starchy soiling on textiles or hard surfaces.
  • Methods for cleaning textiles are generally distinguished by the fact that various cleaning-active substances are applied to the items to be cleaned and washed off after the contact time, or that the items to be cleaned are otherwise treated with a detergent or a solution or dilution of this product. The same applies to processes for cleaning all other materials than textiles, especially hard surfaces. All conceivable washing or cleaning methods can be enriched in at least one of the method steps to the application of a washing or cleaning agent according to the invention and then provide
  • Table 1 shows a powder detergent B according to the invention with a soluble builder (builder mixture) in comparison with the reference powder detergent A.
  • Table 2 The values given (Table 2) are mean values of 6 determinations. The soiled textiles were bought. The remission values in Table A and the differences between the remission values for the standard detergent and the errors in the 6-fold determination (HSD) in Table 3 are shown.
  • SEQ ID NO: 3 The use of the combination of the amylase according to the invention (SEQ ID NO: 3) with the protease according to the invention (SEQ ID NO: 4) and a lower pH soluble builder system in Detergent Formulation B shows an improvement in leachability on starch stains as compared to Detergent Formulation A with the same amylase.

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Abstract

L'invention concerne un produit de lavage et de nettoyage solide contenant une amylase en association avec une protéase, ainsi qu'un système d'adjuvant de détergence soluble, ce produit présentant une efficacité de nettoyage améliorée sur les salissures contenant de l'amidon. L'invention concerne en outre des procédés de nettoyage de textiles et des utilisations de produits de lavage et de nettoyage solides de ce type.
PCT/EP2017/063251 2016-06-09 2017-06-01 Produit de lavage et de nettoyage solide contenant une amylase, une protéase et un adjuvant de détergence soluble Ceased WO2017211661A1 (fr)

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DE102016210174.9A DE102016210174A1 (de) 2016-06-09 2016-06-09 Festes Wasch- und Reinigungsmittel mit Amylase, Protease und löslichem Builder
DE102016210174.9 2016-06-09

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009149130A2 (fr) * 2008-06-06 2009-12-10 Danisco Us Inc. Variants d'alpha-amylase (amys) de geobacillus stearothermophilus présentant des propriétés améliorées
WO2010090915A1 (fr) * 2009-02-09 2010-08-12 The Procter & Gamble Company Composition détergente
WO2014183920A1 (fr) * 2013-05-17 2014-11-20 Novozymes A/S Polypeptides présentant une activité alpha-amylase
WO2016092009A1 (fr) * 2014-12-10 2016-06-16 Henkel Ag & Co. Kgaa Agent de lavage et de nettoyage solide comprenant de l'amylase

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009149130A2 (fr) * 2008-06-06 2009-12-10 Danisco Us Inc. Variants d'alpha-amylase (amys) de geobacillus stearothermophilus présentant des propriétés améliorées
WO2010090915A1 (fr) * 2009-02-09 2010-08-12 The Procter & Gamble Company Composition détergente
WO2014183920A1 (fr) * 2013-05-17 2014-11-20 Novozymes A/S Polypeptides présentant une activité alpha-amylase
WO2016092009A1 (fr) * 2014-12-10 2016-06-16 Henkel Ag & Co. Kgaa Agent de lavage et de nettoyage solide comprenant de l'amylase

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ALTSCHUL, S.F.; GISH, W.; MILLER, W.; MYERS, E.W.; LIPMAN, D.J.: "Basic local alignment search tool", J. MOL. BIOL, vol. 215, 1990, pages 403 - 410
ALTSCHUL, STEPHAN F.; THOMAS L. MADDEN; ALEJANDRO A. SCHAFFER; JINGHUI ZHANG; HHENG ZHANG; WEBB MILLER; DAVID J. LIPMAN: "Gapped BLAST and PSI-BLAST: a new generation of protein database search programs", NUCLEIC ACIDS RES., vol. 25, 1997, pages 3389 - 3402
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