WO2009021867A2 - Agents containing proteases - Google Patents
Agents containing proteases Download PDFInfo
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- WO2009021867A2 WO2009021867A2 PCT/EP2008/060204 EP2008060204W WO2009021867A2 WO 2009021867 A2 WO2009021867 A2 WO 2009021867A2 EP 2008060204 W EP2008060204 W EP 2008060204W WO 2009021867 A2 WO2009021867 A2 WO 2009021867A2
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- protease
- amino acid
- acid sequence
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- proteases
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
- C12N9/00—Enzymes; Proenzymes; Compositions thereof; Processes for preparing, activating, inhibiting, separating or purifying enzymes
- C12N9/14—Hydrolases (3)
- C12N9/48—Hydrolases (3) acting on peptide bonds (3.4)
- C12N9/50—Proteinases, e.g. Endopeptidases (3.4.21-3.4.25)
- C12N9/52—Proteinases, e.g. Endopeptidases (3.4.21-3.4.25) derived from bacteria or Archaea
- C12N9/54—Proteinases, e.g. Endopeptidases (3.4.21-3.4.25) derived from bacteria or Archaea bacteria being Bacillus
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/38—Products with no well-defined composition, e.g. natural products
- C11D3/386—Preparations containing enzymes, e.g. protease or amylase
Definitions
- the invention relates to middle compositions, in particular detergents and cleaners, containing a first protease and a second protease. Furthermore, the invention relates to purification processes in which these agents are used, uses of these agents and purification processes and uses of these proteases.
- proteases of the subtilisin type are particularly important, which are attributed to the serine proteases due to the catalytically active amino acids. They act as nonspecific endopeptidases, that is, they hydrolyze any acid amide linkages that are internal to peptides or proteins. Their pH optimum is usually in the clearly alkaline range.
- Subtilases become natural 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 are, in addition to other enzymes, established active ingredients of detergents and cleaners. They cause the breakdown of protein-containing stains on the items to be cleaned. At best, there are synergies between the enzymes and the remaining components of the funds concerned.
- the detergent and detergent proteases subtilases occupy an outstanding position due to their favorable enzymatic properties such as stability or pH optimum. They are also suitable for a variety of other technical uses, for example as components of cosmetics or in the organic-chemical synthesis.
- subtilisin-type proteases preferably used in detergents and cleaners are the subtilisins BPN 'and Carlsberg, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and those the subtilases, but no longer Enzymes Thermitase, Proteinase K, and Proteases TW3 and TW7, which can be classified as subtilisins in the narrower sense.
- subtilisin BPN ' which is derived from Bacillus amyloliquefaciens, or B. subtilis, is known from the work of Vasantha et al. (1984) in J. Bacteriol., Volume 159, pp. 811-819 and JA Wells et al. (1983) in Nucleic Acids Research, Volume 11, pp. 7911-7925.
- Subtilisin BPN ' is used in particular with regard to the numbering of the positions as reference enzyme of Subtilisins.
- Subtilisin Carlsberg is available in a further developed form under the trade name Alcalase® from Novozymes A / S, Bagsvaerd, Denmark. It is described in the publications of EL Smith et al.
- protease PB92 is naturally derived from the alkaliphilic bacterium Bacillus nov. spec. 92 and was available under the trade name Maxacal® from Gist-Brocades, Delft, The Netherlands. In its original sequence, it is described in the patent application EP 283075 A2.
- the subtilisins 147 and 309 are sold under the trade names Esperase®, and Savinase® by the company Novozymes.
- Bacillus strains which are disclosed in the application GB 1243784 A.
- the protease from Bacillus lentus DSM 5483 (WO 91/02792 A1) is derived from the variants described under the name BLAP®, which are described in particular in WO 92/21760 A1, WO 95/23221 A1, WO 02/088340 A2 and WO 03 / 038082 A2.
- Subtilisin DY is originally from Nedkov et al. Chem., 1985, Biol. Chem. Hoppe-Seyler, Vol. 366, pp. 421-430.
- proteases are, for example, those under the trade names Durazym®, Relase®, Everlase®, Nafizym, Natalase®, Kannase® and Ovozyme® from Novozymes, which are available under the trade names, Purafect®, Purafect® OxP, Purafect® Prime and Properase ® from Genencor, sold under the trade name Protosol® by Advanced Biochemicals Ltd., Thane, India, under the trade name Wuxi® by Wuxi Snyder Bioproducts Ltd., China, under the trade names Proleather® and Protease P From Amano Pharmaceuticals Ltd., Nagoya, Japan, and that available under the name Proteinase K-16 from Kao Corp., Tokyo, Japan.
- proteases used in the compositions according to the invention are either originally derived from microorganisms, for example from microorganisms of the genera Bacillus, Streptomyces, Humicola or Pseudomonas, and / or are produced by biotechnological methods known per se by suitable microorganisms, for example by transgenic expression hosts of the genera Bacillus or by filamentous fungi.
- proteases can be used to improve the washing or cleaning performance together with other enzymes, for example amylases, cellulases, hemicellulases, mannanases, ⁇ -glucosidases, oxidases, oxidoreductases or lipases.
- enzymes for example amylases, cellulases, hemicellulases, mannanases, ⁇ -glucosidases, oxidases, oxidoreductases or lipases.
- proteases in detergents in combination with other active ingredients such as bleaching agents or soil release agents is known in the art.
- corresponding agents in particular washing and cleaning agents, may contain a plurality of proteases.
- agents in particular detergents and cleaners
- the performance of agents is significantly improved with regard to their proteolytic activity, if mixtures of at least two specific proteases with different activity spectrum and / or different sequence are used in these agents.
- different proteases results in a synergistic effect, ie a better performance compared to the individual performances of the respective protease in one-component systems (ie agents that contain only each of these proteases) and also to the sum of Individual performances of the proteases, ie the sum of, for example, two one-component systems.
- the selected combination of particular proteases is another way to improve the performance of agents, especially detergents, with regard to their proteolytic activity. It is therefore an object of the present invention to provide agents which have improved proteolytic activity.
- another object of the present invention is to provide means having improved detergency performance relative to at least one proteinaceous soiling, preferably with respect to multiple proteinaceous soils.
- Another particular object of the present invention is to provide agents which have at least a constant, preferably improved, washing or cleaning performance with respect to at least one proteinaceous soiling, preferably with respect to a plurality of proteinaceous soils, but a reduced content Protease enzyme have.
- the proteases contained develop a synergistic cleaning performance, so that the agents effect a better removal of proteinaceous soils compared to agents containing either only one protease type or compared to the expected cleaning performance of a two-protease agent due to mere addition the jewiligen individual contributions of the contained proteases to the cleaning performance of the agent.
- the selected combination of such proteases constitutes an essential aspect of the invention which has a synergistic effect on the removal of proteinaceous residues or soils in compositions of the invention.
- An object of the invention thus represent means comprising a first protease and a second protease, which are characterized in that the first protease is selected from a) a protease comprising an amino acid sequence corresponding to the amino acid sequence given in SEQ ID NO.1 at least 80% identical; b) a protease comprising an amino acid sequence which is at least 80% identical to the amino acid sequence given in SEQ ID NO. 2; c) a protease which comprises an amino acid sequence which is at least 80% identical to the amino acid sequence given in SEQ ID NO. 2 and additionally has at least one additional amino acid in comparison with SEQ ID NO.
- the second protease comprises an amino acid sequence which is at least 80% identical to the amino acid sequence given in SEQ ID NO.3. It has surprisingly been found that in particular the combination of a protease, as defined above under a) to c) (hereinafter collectively referred to as "BLAP-type protease” or as the first protease) with a protease corresponding to the one described in SEQ ID NO.3 indicated amino acid sequence is at least 80% identical (hereinafter referred to as protease of the type "alkaline protease from Bacillus gibsonii (DSM 14391)" or second protease), in an agent according to the invention leads to a synergistic cleaning performance of the two proteases.
- the synergistic effect of these two types of proteases in an agent according to the invention is based on the fact that the effects of the first and the second protease complement one another in such a way that an overall increased proteolytic effect is achieved.
- This can be made possible, for example, by the fact that the proteolytic cleavage of peptide bonds by the first protease makes substrates for the second protease more accessible and, in turn, further substrates for the first protease become accessible by the proteolytic cleavage of the peptide bonds by the second protease.
- the accessibility of a cleavage site for a protease is often a limiting factor.
- a different spectrum of action of the two proteases therefore shows, for example, in a different substrate specificity.
- a different spectrum of action may be caused by a different proteolytic activity under defined conditions, in particular with regard to temperature, pH, ionic strength, stability towards oxidizing compounds (for example bleaching agents), etc.
- a synergism according to the invention therefore occurs when the first protease differs from the second protease. These differences manifest themselves in the amino acid sequence of the respective proteolytically active enzyme.
- the first protease it is preferably selected from
- a protease which comprises an amino acid sequence which is more preferably at least 82.5%, 85%, 87.5%, 90%, 91%, 92%, 93% to the amino acid sequence given in SEQ ID NO.1, 94%, 95%, 96%, 97%, 98%, 99%, 99.5% and most preferably 100% identical.
- a protease comprising an amino acid sequence which is more preferably at least 82.5%, 85%, 87.5%, 90%, 91%, 92%, 93%, of the amino acid sequence given in SEQ ID NO. 94%, 95%, 96%, 97%, 98%, 99%, 99.5% and most preferably 100% identical.
- a protease comprising an amino acid sequence which is more preferably at least 82.5%, 85%, 87.5%, 90%, 91%, 92%, 93% to the amino acid sequence given in SEQ ID NO. Is 94%, 95%, 96%, 97%, 98%, 99%, 99.5% and most preferably 100% identical and has at least one additional amino acid compared to SEQ ID NO.2.
- the agent is characterized in that the additional amino acid of the first protease is inserted after one of the following positions in the counting manner according to SEQ ID NO.2: 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 95, 96, 97, 98, 99, 100, 101, 102, 103, 125, 126, 127, 126, 129, 130, 131, 132, 153, 154, 155, 156, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 171, 172, 173, 181, 182, 183, 184, 185, 186, 187, 188, 189, 190, 191, 192, 193, 194, 195, 202, 203, 204, 218, 219.
- proteases which are used according to the invention as the first protease in an agent, have a corresponding insertion of at least one amino acid or of a plurality of amino acids, preferably at one or more of said positions on.
- proteases which are described in the European patent application EP 1 032 655. These have, for example, at least one additional amino acid in the counting method according to SEQ ID NO. 2 (that is to say in the counting method of Savinase®, referred to in the named application as BLSAVI), in positions 33 to 43, 95 to 103, 125 to 132 , 153 to 173, 181 to 195, 202 to 204 and / or position 218 to 219.
- proteases which have an insertion of at least one amino acid and can be used according to the invention as the first protease, are derived from the international patent application WO 00/37599 and the international patent application WO 01/44452.
- the agent is characterized in that the second protease comprises an amino acid sequence which is more preferably at least 82.5% to the amino acid sequence given in SEQ ID NO. 85%, 87.5%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, 99.5%, and most preferably 100% identical is.
- a synergistic proteolytic performance of a composition according to the invention is found, in particular, when a first protease of the BLAP type is combined with a second protease of the type "alkaline protease from Bacillus gibsonii (DSM 14391)."
- a first protease of the BLAP type is combined with a second protease of the type "alkaline protease from Bacillus gibsonii (DSM 14391).
- DSM 14391 Bacillus gibsonii
- an enzyme is to be understood as meaning a protein which has a specific biocatalytic function.
- protease is understood as meaning an enzyme which catalyzes the hydrolysis of peptide bonds and is thereby able to cleave peptides or proteins.
- a protein is a largely linear composition composed of the natural amino acids and usually performs one of its functions three-dimensional structure accepting polypeptide.
- a peptide consists of amino acids that are covalently linked to each other via peptide bonds.
- polypeptide clarifies in this regard the fact that this peptide chain usually consists of many amino acids, which are connected to each other via peptide bonds.
- Amino acids may be in an L and a D configuration, with the amino acids that make up proteins in the L configuration. They are called proteinogenic amino acids.
- the proteinogenic, naturally occurring L-amino acids are designated by the internationally used 1- and 3-letter codes.
- pre-proteins ie together with a signal peptide.
- the N-terminal part of the protein the function of which is usually to ensure the discharge of the protein formed from the producing cell into the periplasm or the surrounding medium and / or its correct folding.
- the signal peptide is cleaved under natural conditions by a signal peptidase from the rest of the protein, so that this exerts its actual catalytic activity without the initially present N-terminal amino acids.
- Pro-proteins are inactive precursors of proteins. Their signal sequence precursors are referred to as pre-pro proteins.
- the mature, ie mature, peptides, ie the enzymes processed after their preparation are preferred over the preproteins.
- the SEQ ID NO. 1, SEQ ID NO. 2 and SEQ ID NO. The sequences can therefore be modified from the cells producing them after the production of the polypeptide chain, for example by attachment of sugar molecules, formylations, aminations, etc. Such modifications are referred to as post-translational modifications. These post-translational modifications may or may not have an effect on the function of the protein.
- the enzymatic activity of a considered enzyme can be deduced from the amino acid or nucleotide sequence. This can be qualitatively or quantitatively modified by other regions of the protein that are not involved in the actual reaction. This could, for example, relate to enzyme stability, activity, reaction conditions or substrate specificity.
- Such a comparison is accomplished by associating similar sequences in the nucleotide or amino acid sequences of the proteins of interest. This is called homologization.
- a tabular assignment of the respective positions is referred to as alignment.
- alignments are created using computer programs, such as the algorithms FASTA or BLAST; This procedure is described, for example, by DJ Lipman and WR Pearson (1985) in Science, Vol. 227, pp. 1435-1441.
- sequence comparisons and determinations of homology and / or identity values were performed using the computer program Vector NTI ® Suite 7.0, available from InforMax, Inc., Bethesda, USA with the preset default parameters.
- a summary of all matching positions in the compared sequences is called a consensus sequence.
- Such a comparison also allows a statement about the similarity or homology of the compared sequences to each other. This is represented in percent identity, that is the proportion of identical nucleotides or amino acid residues at the same or in an alignment corresponding positions. A broader concept of homology includes the conserved amino acid substitutions in this value. It then speaks of percent similarity. Such statements can be made about whole proteins or genes or only over individual areas.
- homologous regions of different proteins are defined by matches in amino acid sequence. These can also be identified by identical function. It goes as far as complete identities in the smallest areas, so-called boxes, which contain only a few amino acids and usually perform essential functions for the overall activity.
- the functions of the homologous regions are to be understood as the smallest partial functions of the function carried out by the entire protein, such as, for example, the formation of individual hydrogen bonds for the complexation of a substrate or transition complex.
- Proteases or enzymes in general can be prepared by various methods, e.g. targeted genetic modification by mutagenesis, further developed and optimized for specific uses or specific properties such as catalytic activity, stability, etc.
- Fragments are understood as meaning all proteins or peptides which are smaller than natural proteins and, for example, can be obtained synthetically. Due to their amino acid sequences, they can be assigned to the relevant complete proteins. For example, they may adopt the same structures or perform proteolytic or partial activities, such as the complexation of a substrate. Fragments and deletion variants of starting proteins are in principle similar; while fragments tend to be smaller fragments, the deletion mutants tend to lack only short regions, and thus only individual subfunctions.
- chimeras or hybrid proteins are to be understood as meaning those proteins whose sequence comprises the sequences or partial sequences of at least two starting proteins.
- the source proteins may be derived from different or from the same organism.
- Chimeric or hybrid proteins may be obtained, for example, by recombinant mutagenesis.
- the purpose of such recombination may be to induce or modify a particular enzymatic function using the fused protein portion.
- it is irrelevant whether such a chimeric protein consists of a single polypeptide chain or several subunits on which different functions can be distributed.
- proteins obtained by insertion mutation are meant those variants obtained by inserting a protein fragment into the starting sequences. They are due to their principle similarity to the chimeric proteins. They differ from those only in the size ratio of the unchanged protein part to the size of the entire protein. In such insertionsmut elected proteins, the proportion of foreign protein is lower than in chimeric proteins.
- Inversion mutagenesis ie a partial sequence reversal
- derivatives are understood as meaning those proteins whose pure amino acid chain has been chemically modified. Such derivatizations can be carried out, for example, biologically in connection with protein biosynthesis by the host cell. For this molecular biological methods can be used.
- ком ⁇ онентs can also be carried out chemically, for example by the chemical transformation of a side chain of an amino acid or by covalent binding of another compound to the protein.
- a compound may, for example, also be other proteins which are bound, for example via bifunctional chemical compounds, to proteins according to the invention.
- modifications 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.
- derivatization is understood to mean covalent attachment to a macromolecular carrier, as well as noncovalent inclusion in suitable macromolecular cage structures.
- the agent is thus characterized in that the first protease is present in the agent as fragment, deletion variant, chimeric protein or derivative and / or the second protease is present in the agent as a fragment, deletion variant, chimeric protein or derivative, wherein the first and second proteases are still catalytically active.
- compositions according to the invention include all types of agents, in particular mixtures, formulations, solutions, etc., whose applicability is improved by addition of the proteases described above.
- these may be, for example, solid mixtures, for example powders with freeze-dried or encapsulated proteins, or gel or liquid agents.
- Preferred formulations contain, for example, buffer substances, stabilizers, reaction partners and / or cofactors of the proteases and / or other ingredients synergistic with the proteases. In particular, this appropriation is to be understood as the areas of application set out below. Further fields of application emerge from the prior art and are described, for example, in the manual "Industrial Enzymes and their Applications" by H.
- an agent according to the invention is characterized in that it comprises a detergent, hand washing detergent, dishwashing detergent, hand dishwashing detergent, machine dishwashing detergent, cleaning agent, denture or contact lens care agent, rinse aid, disinfectant, cosmetic agent, pharmaceutical agent or a means for treating filter media, textiles , Furs, paper, skins or leather, especially a laundry detergent or dishwashing detergent.
- This invention includes all conceivable types of detergents or cleaners, both concentrates and undiluted agents to be used on a commercial scale, in the washing machine or in hand washing or cleaning.
- detergents or cleaners include, for example, detergents for textiles, carpets, or natural fibers, for which according to the present invention the term laundry detergent is used.
- laundry detergent includes, 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 such according to the present invention, the term cleaning agent is used.
- An agent according to the invention can be either a means for large consumers or technical users as well as a product for the private consumer, wherein all types of detergents and cleaning agents established in the prior art also constitute embodiments of the present invention.
- the detergents or cleaning agents according to the invention may contain, in addition to the active ingredient used according to the invention - a protease combination according to the invention - in principle all known and conventional ingredients in such agents, wherein at least another ingredient is present in the agent.
- 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, water-miscible organic solvents, enzymes, sequestering agents, electrolytes, pH regulators and other auxiliaries such as optical brighteners, grayness inhibitors, foam regulators and dyes and fragrances and combinations thereof.
- a combination of the protease combination with one or more other ingredients of the compositions proves to be advantageous since such an agent has an improved cleaning performance by resulting synergisms, in particular between a protease or the protease combination and the further ingredient.
- the agent provides improved removal of stains, such as proteinaceous Stains caused in comparison with an agent which either contains only one of the two components, or even compared to the expected cleaning performance of an agent with both components due to the mere addition of the respective individual contributions of these two components to the cleaning performance of the agent.
- Such a synergism is achieved, in particular, by the combination of a protease or protease combination according to the invention with one of the surfactants and / or builders and / or bleaches described below.
- compositions according to the invention may comprise one or more surfactants, in particular anionic surfactants, nonionic surfactants and mixtures thereof, but also cationic, zwitterionic and amphoteric surfactants.
- Suitable nonionic surfactants are in particular alkyl glycosides and ethoxylation and / or propoxylation of alkyl glycosides or linear or branched alcohols each having 12 to 18 carbon atoms in the alkyl moiety and 3 to 20, preferably 4 to 10 alkyl ether groups. Furthermore, corresponding ethoxylation and / or propoxylation of N-alkyl-amines, vicinal diols, fatty acid esters and fatty acid amides, which correspond to said long-chain alcohol derivatives with respect to the alkyl moiety, and of alkylphenols having 5 to 12 carbon atoms in the alkyl radical.
- the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as they are usually present in Oxoalkoholresten.
- EO ethylene oxide
- alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred.
- Preferred ethoxylated alcohols include, for example, Ci 2 - C 4 alcohols containing 3 EO or 4 EO, C 9 -C i-alcohols containing 7 EO, C 3 -C 5 alcohols containing 3 EO, 5 EO, 7 EO or 8 EO, Ci 2 -Ci 8 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of Ci 2 -Ci 4 alcohol with 3 EO and Ci 2 -Ci 8 alcohol with 7 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 of these are (TaIg) fatty alcohols with 14 EO, 16 EO, 20 EO, 25 EO, 30 EO or 40 EO.
- agents for use in mechanical processes usually extremely low-foam compounds are used. These preferably include C 2 -C 8 -Alkylpolyethylenglykol- polypropylene glycol ethers, each containing up to 8 moles of ethylene oxide and propylene oxide units in the molecule.
- low-foam nonionic surfactants such as, for example, C 1 -C 6 -alkylpolyethyleneglycol-polybutylene glycol ethers having up to 8 mol of ethylene oxide and butylene oxide units in the molecule and end-capped alkylpolyalkylene glycol mixed ethers.
- C 1 -C 6 -alkylpolyethyleneglycol-polybutylene glycol ethers having up to 8 mol of ethylene oxide and butylene oxide units in the molecule and end-capped alkylpolyalkylene glycol mixed ethers.
- hydroxyl-containing alkoxylated alcohols as described in European Patent Application EP 0 300 305, so-called hydroxy mixed ethers.
- the nonionic surfactants also include alkyl glycosides of the general formula RO (G) x in which R is a primary straight-chain or methyl-branched, in particular 2-methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G represents a glycose unit having 5 or 6 C atoms, preferably glucose.
- the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is an arbitrary number - which, as a variable to be determined analytically, may also assume fractional values - between 1 and 10; preferably x is 1, 2 to 1, 4.
- polyhydroxy fatty acid amides of the formula (III) in which R 1 CO is an aliphatic acyl radical having 6 to 22 carbon atoms, R 2 is hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups:
- the polyhydroxy fatty acid amides are preferably derived from reducing sugars having 5 or 6 carbon atoms, in particular from glucose.
- the group of polyhydroxy fatty acid amides also includes compounds of the formula (IV)
- R 3 is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
- R 4 is a linear, branched or cyclic alkylene radical or an arylene radical having 2 to 8 carbon atoms
- R 5 is a linear, branched or cyclic alkyl radical or a Aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, wherein dC 4 alkyl or phenyl radicals are preferred
- [Z] is a linear polyhydroxyalkyl radical whose alkyl chain is substituted with at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives this rest stands.
- [Z] is also here preferably by reductive amination of a sugar such as glucose, fructose, maltose, lactose, galactose, mannose or Get xylose.
- a sugar such as glucose, fructose, maltose, lactose, galactose, mannose or Get xylose.
- the N-alkoxy- or N-aryloxy-substituted compounds can then be converted into the desired polyhydroxy fatty acid amides, for example by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
- nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants, in particular together with alkoxylated fatty alcohols and / or alkyl glycosides, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably from 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl ester.
- Nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable.
- nonionic surfactants are so-called gemini surfactants. These are generally understood as meaning those compounds which have two hydrophilic groups per molecule. These groups are usually separated by a so-called "spacer". This spacer is typically a carbon chain that should be long enough for the hydrophilic groups to be spaced sufficiently apart for them to act independently of each other. Such surfactants are generally characterized by an unusually low critical micelle concentration and the ability to greatly reduce the surface tension of the water. In exceptional cases, the term gemini surfactants not only such "dimer”, but also corresponding to "trimeric” surfactants understood.
- Suitable gemini surfactants are, for example, sulfated hydroxy mixed ethers or dimer alcohol bis and trimer alcohol tris sulfates and ether sulfates.
- End-capped dimeric and trimeric mixed ethers are characterized in particular by their bi- and multi-functionality.
- the end-capped surfactants mentioned have good wetting properties and are low foaming, so that they are particularly suitable for use in machine washing or cleaning processes.
- gemini-polyhydroxy fatty acid amides or poly-polyhydroxy fatty acid amides it is also possible to use gemini-polyhydroxy fatty acid amides or poly-polyhydroxy fatty acid amides.
- Schwefelkladoester the ethoxylated with 1 to 6 moles of ethylene oxide, linear or branched C 7 -C 2 i-alcohols such as 2-methyl-branched C 9 -CN alcohols containing on average 3.5 mol ethylene oxide (EO) or C 2 - Ci 8 fatty alcohols with 1 to 4 EO.
- the preferred anionic surfactants also include the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters, and the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols.
- alcohols preferably fatty alcohols and in particular ethoxylated fatty alcohols.
- Preferred sulfosuccinates contain C 8 - to C 18 - fatty alcohol residues or mixtures of these.
- Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols, which by themselves are nonionic surfactants.
- Sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are particularly important prefers.
- alk (en) ylsuccinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
- Suitable further anionic surfactants are fatty acid derivatives of amino acids, for example N-methyltaurine (Tauride) and / or N-methylglycine (sarcosides).
- sarcosides or the sarcosinates and here especially sarcosinates of higher and optionally monounsaturated or polyunsaturated fatty acids such as oleyl sarcosinate.
- anionic surfactants are particularly soaps into consideration.
- Particularly 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. Together with these soaps or as a substitute for soaps, it is also possible to use the known alkenylsuccinic acid salts.
- the anionic surfactants may be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine.
- the anionic surfactants are preferably present in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
- Surfactants are present in inventive compositions in proportions of preferably 5 wt .-% to 50 wt .-%, in particular from 8 wt .-% to 30 wt .-%.
- An agent according to the invention preferably contains at least one water-soluble and / or water-insoluble, organic and / or inorganic builder.
- the water-soluble organic builder substances include polycarboxylic acids, in particular citric acid and sugar acids, monomeric and polymeric aminopolycarboxylic acids, in particular methylglycine diacetic 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 the accessible by oxidation of polysaccharides or dextrins polycarboxylates, polymeric acrylic acids, methacrylic acids, maleic acids and copolymers thereof, which also small amounts of polymerizable substances without carboxylic acid functionality
- the molecular weight of the homopolymers of unsaturated carboxylic acids is generally between 3,000 and 200,000, of the copolymers between 2,000 and 200,000, preferably 30,000 to 120,000, each based on the free acid.
- a particularly preferred acrylic acid-maleic acid copolymer has a molecular weight of from 30,000 to 100,000.
- Commercially available products are, for example, Sokalan® CP 5, CP 10 and PA 30 from BASF.
- Suitable, although less preferred compounds of this class are copolymers of the Acrylic acid or methacrylic acid with vinyl ethers, such as vinylmethyl ethers, vinyl esters, ethylene, propylene and styrene, in which the proportion of the acid is at least 50% by weight.
- the first acidic monomer or its salt is derived from a monoethylenically unsaturated C 3 -C 8 -carboxylic acid and preferably from a C 3 -C 4 -monocarboxylic acid, in particular from (meth) -acrylic acid.
- the second acidic monomer or its salt may be a derivative of a C 4 -C 8 -dicarboxylic acid, with maleic acid being particularly preferred, and / or a derivative of an allylsulfonic acid substituted in the 2-position with an alkyl or aryl radical.
- Such polymers generally have a molecular weight between 1,000 and 200,000.
- Further preferred copolymers are those which preferably 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 paste-form or liquid, in particular water-containing, agents according to the invention.
- Suitable water-soluble inorganic builder materials are, in particular, alkali metal silicates, alkali metal carbonates and alkali metal phosphates, which may be in the form of their alkaline, neutral or acidic sodium or potassium salts.
- alkali metal silicates alkali metal carbonates and alkali metal phosphates, which may be in the form of their alkaline, neutral or acidic sodium or potassium salts.
- examples of these are trisodium phosphate, tetra sodium diphosphate, disodium dihydrogen diphosphate, pentasodium triphosphate, so-called sodium hexametaphosphate, oligomeric trisodium phosphate with degrees of oligomerization of from 5 to 1000, in particular from 5 to 50, and the corresponding potassium salts or mixtures of sodium and potassium salts.
- Crystalline or amorphous alkali metal aluminosilicates in amounts of up to 50% by weight, preferably not more than 40% by weight, and in liquid agents, in particular from 1% by weight to 5% by weight, are particularly suitable as water-insoluble, water-dispersible inorganic builder materials.
- suitable aluminosilicates have no particles with a particle size greater than 30 .mu.m and preferably consist of at least 80% by weight of particles having a size of less than 10 .mu.m.
- Your calcium binding capacity which can be determined according to the specifications of German Patent DE 24 12 837, is generally in the range of 100 to 200 mg CaO per gram.
- Suitable substitutes or partial substitutes for the said aluminosilicate are crystalline alkali 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 of less than 0.95, in particular of 1: 1, 1 to 1: 12, and may be amorphous or crystalline.
- Preferred alkali metal silicates are the sodium silicates, in particular the amorphous sodium silicates, with a molar ratio of Na 2 O: SiO 2 of 1: 2 to 1: 2.8.
- the crystalline silicates which may be present alone or in admixture with amorphous silicates, are crystalline layer silicates with the general formula Na 2 Si x O y are used 2x + 1 H 2 O, in which x, known as the modulus, an integer of 1, 9 to 22, in particular 1, 9 to 4 and y is a number from 0 to 33 and preferred values for x are 2, 3 or 4.
- Preferred crystalline phyllosilicates are those in which x in the abovementioned general formula assumes the values 2 or 3. In particular, both ⁇ - and ⁇ -sodium disilicates (Na 2 Si 2 O 5 y H 2 O) are preferred.
- amorphous alkali silicates practically anhydrous crystalline alkali silicates of the abovementioned general formula in which x is a number from 1, 9 to 2.1, can be used in inventive compositions.
- a crystalline sodium layer silicate with a modulus of 2 to 3 is used, as 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.
- Crystalline layer-form silicates of formula (I) given above are sold by Clariant GmbH under the trade name Na-SKS, eg Na-SKS-1 (Na 2 Si 22 O 45 XH 2 O, Kenyaite), Na-SKS-2 (Na 2 Si 14 O 29 XH 2 O, magadiite), Na-SKS-3 (Na 2 Si 8 O 17 XH 2 O) or Na-SKS-4 (Na 2 Si 4 O 9 XH 2 O, makatite).
- Na-SKS eg Na-SKS-1 (Na 2 Si 22 O 45 XH 2 O, Kenyaite)
- Na-SKS-2 Na 2 Si 14 O 29 XH 2 O, magadiite
- Na-SKS-3 Na 2 Si 8 O 17 XH 2 O
- Na-SKS-4 Na 2 Si 4 O 9 XH 2 O, makatite
- Na-SKS-5 OC-Na 2 Si 2 O 5
- Na-SKS-7 ⁇ -Na 2 Si 2 0 5 , natrosilite
- Na-SKS-9 NaHSi 2 O 5 3H 2 O
- Na-SKS-10 NaHSi 2 O 5 3H 2 O, kanemite
- Na-SKS-11 t-Na 2 Si 2 0 5
- Na-SKS-13 NaHSi 2 O 5
- Na-SKS-6 5-Na 2 Si 2 O 5 .
- composition according to the invention a granular compound of crystalline phyllosilicate and citrate, of crystalline phyllosilicate and of the above-mentioned (co-) polymeric polycarboxylic acid, or of alkali silicate and alkali metal carbonate, such as, for example, commercially available under the name Nabion® 15, is used ,
- Builder substances are preferably present in the compositions according to the invention in amounts of up to 75% by weight, in particular 5% by weight to 50.
- Suitable peroxygen compounds for use in compositions according to the invention are, in particular, organic peracids or persistent salts of organic acids, such as phthalimidopercaproic acid, perbenzoic acid or salts of diperdodecanedioic acid, hydrogen peroxide and under the washing conditions hydrogen peroxide-releasing inorganic salts, which include perborate, percarbonate, persilicate and / or persulfate such as caroate into consideration.
- organic peracids or persistent salts of organic acids such as phthalimidopercaproic acid, perbenzoic acid or salts of diperdodecanedioic acid, hydrogen peroxide and under the washing conditions hydrogen peroxide-releasing inorganic salts, which include perborate, percarbonate, persilicate and / or persulfate such as caroate into consideration.
- solid peroxygen compounds are to be used, they can be used in the form of powders or granules, which can also be
- 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.
- bleach activators it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid.
- Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups.
- polyacylated alkylenediamines in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate, 2,5-diacetoxy- 2,5-dihydrofuran and enol esters
- TAED
- hydrophilic substituted acyl acetals and the acyl lactams are also preferably used.
- Combinations of conventional bleach activators can also be used.
- 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.
- organic solvents which can be used in addition to water include alcohols having 1 to 4 C atoms, in particular methanol, ethanol, isopropanol and tert-butanol, diols having 2 to 4 C -Ato- men, in particular ethylene glycol and propylene glycol, and mixtures thereof and derived from the said classes of compounds ethers.
- water-miscible solvents are preferably present in the compositions according to the invention in amounts of not more than 30% by weight, in particular from 6% by weight to 20% by weight.
- the compositions according to the invention may contain system and environmentally acceptable acids, in particular citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid and / or adipic acid, but also mineral acids, in particular sulfuric acid, or bases, in particular ammonium or alkali metal hydroxides.
- Such pH regulators are present in the compositions according to the invention in amounts of preferably not more than 20% by weight, in particular from 1.2% by weight to 17% by weight.
- Graying inhibitors have the task of keeping suspended from the textile fiber dirt suspended in the fleet.
- Water-soluble colloids of mostly organic nature are suitable for this purpose, for example starch, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or of cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
- water-soluble polyamides containing acidic groups are suitable for this purpose.
- starch derivatives can be used, for example aldehyde starches.
- cellulose ethers such as carboxymethylcellulose (Na salt), methylcellulose, hydroxyalkylcellulose and mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof, for example in amounts of from 0.1 to 5% by weight, based on the compositions ,
- Detergents according to the invention may contain, for example, derivatives of diaminostilbenedisulfonic acid or their alkali metal salts as optical brighteners, although they are preferably free of optical brighteners for use as color detergents.
- optical brighteners for use as color detergents.
- salts of 4,4'-bis (2-anilino-4-morpholino-1, 3,5-triazinyl-6-amino) stilbene-2,2'-disulphonic acid or compounds of similar construction which are used instead of the morpholino Group carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group.
- brighteners of the substituted diphenylstyrene type may be present, for example, the alkali salts of 4,4'-bis (2-sulfostyryl) -diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) -diphenyl, or 4 - (4-chlorostyryl) -4 '- (2-sulfostyryl).
- Mixtures of the aforementioned optical brightener can be used.
- foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of C 18 -C 24 fatty acids.
- Suitable non-surfactant foam inhibitors are, for example, organopolysiloxanes and mixtures thereof with microfine, optionally silanized silica and paraffins, waxes, microcrystalline waxes and mixtures thereof with silanated silicic acid or bis-fatty acid alkylenediamides. It is also advantageous to use mixtures of various foam inhibitors, for example those of silicones, paraffins or waxes.
- the foam inhibitors in particular silicone and / or paraffin-containing foam inhibitors, are bound to a granular, water-soluble or dispersible carrier substance.
- mixtures of paraffins and bistearylethylenediamide are preferred.
- the proteases are combined, for example, with one or more of the following ingredients: nonionic, anionic and / or cationic surfactants, (optionally further) bleaches, bleach activators, bleach catalysts, builders and / or cobuilders, Acids, alkaline substances, hydrotropes, solvents, thickeners, sequestering agents, electrolytes, optical brighteners, grayness inhibitors, corrosion inhibitors, in particular silver protectants (silver corrosion inhibitors), disintegration aids, soil release agents, color transfer (or transfer) inhibitors, foam inhibitors, abrasives, Dyes, fragrances, perfumes, antimicrobial agents, UV protectants or absorbents, antistatic agents, pearlescers and skin protection agents, enzymes such as protease, amylase, cellulase, hemicellulase, mannanase, tannase, xylanase, xanthine
- nonionic, anionic and / or cationic surfactants
- an agent according to the invention is therefore characterized in that it contains at least one further component selected from the group consisting of surfactants, builders, acids, alkaline substances, hydrotropes, solvents, thickeners, bleaching agents, dyes, perfumes, corrosion inhibitors , Sequestering agents, electrolytes, optical brighteners, grayness inhibitors, silver corrosion inhibitors, color transfer inhibitors, foam inhibitors, disintegration aids, abrasives, UV absorbers, solvents, antistatic agents, pearlescers and skin protection agents.
- the ingredients to be selected as well as the conditions under which the agent is used, such as temperature, pH, ionic strength, redox ratios or mechanical influences, should be optimized for the particular cleaning problem. So are usual Temperatures for detergents and cleaning agents in areas of 1O 0 C for manual compositions over 4O 0 C and 6O 0 C to 95 ° for machine agents or industrial applications. Since the temperature is usually infinitely adjustable in modern washing machines and dishwashers, all intermediate stages of the temperature are included.
- the ingredients of the respective agents are coordinated. Synergies in terms of cleaning performance are preferred. Particularly preferred in this regard are synergies resulting from the interaction of the two proteases in the composition according to the invention with at least one or more further ingredients. In a further preferred embodiment, these synergies are present in a temperature range between 2O 0 C and 6O 0 C, as well as the proteases contained in the inventive compositions are catalytically active in this temperature range.
- an agent according to the invention in particular 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.
- inventive compositions having an increased bulk density in particular in the range from 650 g / l to 950 g / l, a process comprising an extrusion step is preferred.
- compositions according to the invention in tablet form, which may be monophasic or multiphase, monochromatic or multicolor and in particular consist of one or more layers, in particular two layers
- the procedure is preferably such that all constituents - if appropriate one per layer - in one Mixer mixed together and the Mixture by means of conventional tablet presses, such as eccentric or rotary presses, pressed with compressive forces in the range of about 50 to 100 kN, preferably at 60 to 70 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.
- the size of rectangular or cuboid-shaped tablets, which are introduced predominantly via the metering device, for example the dishwasher, is dependent on the geometry and the volume of this metering device.
- Exemplary preferred embodiments have a base area of (20 to 30 mm) x (34 to 40 mm), in particular of 26x36 mm or 24x38 mm.
- Liquid or pasty compositions according to the invention in the form of customary solvent-containing solutions are generally prepared by simply mixing the ingredients, which can be added in bulk or as a solution in an automatic mixer.
- Embodiments of the present invention thus comprise all such 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. Of course, means according to the invention may also consist of several phases.
- the washing or cleaning agent is therefore characterized in that it is divided into several components.
- the solid dosage forms according to the invention also include extrudates, granules, tablets or pouches, which may be present both in large packages 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.
- the agent in particular the washing or cleaning agent, is in liquid, gel or pasty form, in particular in the form of a non-aqueous liquid detergent or a non-aqueous paste or in the form of an aqueous liquid detergent or a water-containing paste.
- the agent according to the invention in particular washing or cleaning agent, can be packaged in a container, preferably an air-permeable container, from which it is released shortly before use or during the washing process.
- a container preferably an air-permeable container, from which it is released shortly before use or during the washing process.
- at least one, preferably both, of the proteases contained in the agent and / or further ingredients of the agent may be coated with a substance impermeable to the enzyme (s) at room temperature or in the absence of water, which under application conditions of the agent is permeable to the enzyme / the enzymes becomes.
- Such an embodiment of the invention is therefore characterized in that at least one protease is coated with a substance that is impermeable to the protease at room temperature or in the absence of water.
- an agent according to the invention is characterized in that it contains the proteases in an amount of from 0.1 ⁇ g to 100 mg, preferably from 1 ⁇ g to 50 mg, more preferably from 10 ⁇ g to 50 mg, particularly preferably from 25 ⁇ g to 25 mg and most preferably from 50 ⁇ g to 20 mg per g of the agent.
- the agent contains the proteases in an amount of 0.00001 weight percent to 10 weight percent, preferably 0.0001 weight percent to 5 weight percent, more preferably 0.001 weight percent to 5 weight percent, most preferably 0.00025 weight percent to 2.5 Percent by weight and most preferably from 0.005% to 2% by weight.
- the quantities shown contain the first protease and the second protease.
- compositions according to the invention may contain exclusively the two proteases described above. Alternatively, they may also contain other proteases or other enzymes in a concentration effective for the effectiveness of the agent.
- a further subject of the invention thus represents agents which further comprise one or more further enzymes, wherein in principle all enzymes established in the prior art for these purposes can be used.
- enzymes preferably used are all enzymes that can develop a catalytic activity in the agent of the invention, in particular proteases, amylases, cellulases, hemicellulases, mannanases, tannases, xylanases, xanthanases, ß-glucosidases, carrageenases, oxidases, oxidoreductases, pectin-degrading Enzymes (pectinases) or lipases, and preferably mixtures thereof.
- proteases amylases, cellulases, hemicellulases, mannanases, tannases, xylanases, xanthanases, ß-glucosidases, carrageenases, oxidases, oxidoreductases, pectin-degrading Enzymes (pectinases) or lipases, and preferably mixtures thereof.
- pectinases pec
- compositions according to the invention preferably contain enzymes in total amounts of 1 ⁇ 10 -8 to 5 percent by weight, based on active protein.
- the enzymes are from 0.00001 to 5 Wt .-%, more preferably from 0.0001 to 2.5 wt .-%, even more preferably from 0.0001 to 1 wt .-% and particularly preferably from 0.0001 to 0.072 wt .-% in inventive compositions , Wherein each enzyme contained can be present in the stated proportions.
- 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 further enzymes particularly preferably support the effect of the agent, for example the cleaning performance of a washing or cleaning agent, with regard to certain stains or stains. Most preferably, the enzymes exhibit synergistic effects on their action against certain soils or stains, i. the enzymes contained in the middle composition mutually support each other in their cleaning performance.
- the agent according to the invention is therefore characterized in that it contains at least one further enzyme which comprises a protease, amylase, cellulase, hemicellulase, mannanase, tannase, xylanase, xanthanase, ⁇ -glucosidase, carrageenase, oxidase, oxidoreductase , Pectin degrading enzyme or lipase.
- at least one further enzyme which comprises a protease, amylase, cellulase, hemicellulase, mannanase, tannase, xylanase, xanthanase, ⁇ -glucosidase, carrageenase, oxidase, oxidoreductase , Pectin degrading enzyme or lipase.
- protease activity in such agents can be determined by the method described in Tenside, Vol. 7 (1970), pp. 125-132. It is given in PE (protease units) accordingly.
- the enzymes used in the compositions according to the invention are either originally derived from microorganisms, for example the genera Bacillus, Streptomyces, Humicola or Pseudomonas, and / or are prepared by suitable biotechnological processes Microorganisms produced, for example, by transgenic expression hosts of the genera Bacillus or by filamentous fungi.
- a separate subject of the invention is the use of an above-described agent according to the invention for the removal of protease-sensitive stains on textiles or hard surfaces, i. for cleaning textiles or hard surfaces.
- agents according to the invention can be used, in particular in accordance with the properties described above, to remove proteinaceous impurities from textiles or from hard surfaces.
- Embodiments include, for example, hand washing, manual removal of stains from fabrics or hard surfaces, or use in conjunction with a machine process.
- the relevant agents according to the invention preferably detergents or cleaning agents, are provided according to one of the above-described embodiments.
- a further subject of the invention are processes for the cleaning of textiles or of hard surfaces, in which an agent according to the invention is used at least in one of the process steps.
- the process for the cleaning of textiles or hard surfaces is accordingly characterized in that an agent according to the invention is used in at least one process step.
- Methods for cleaning textiles are generally distinguished by the fact that various cleaning-active substances are applied to the items to be cleaned in a plurality of process steps and washed off after the action time, or that the items to be cleaned are otherwise treated with a detergent or a solution of this agent.
- a single substep of such a process may be for cleaning, in particular for machine cleaning, textiles or hard surfaces therein
- an enzyme mixture according to the invention is applied as sole cleaning-active component. This represents a particularly simplified embodiment of the present invention.
- Another object of the invention are methods for the purification of textiles or hard surfaces, which are characterized in that in at least one method step, a first protease and a second protease are proteolytically active, wherein the first protease is selected from a) a protease, the an amino acid sequence which is at least 80% identical to the amino acid sequence given in SEQ ID NO.1; b) a protease comprising an amino acid sequence which is at least 80% identical to the amino acid sequence given in SEQ ID NO. 2; c) a protease which comprises an amino acid sequence which is at least 80% identical to the amino acid sequence given in SEQ ID NO. 2 and additionally has at least one additional amino acid in comparison with SEQ ID NO. 2; and the second protease comprises an amino acid sequence which is at least 80% identical to the amino acid sequence given in SEQ ID NO.3.
- the first protease is selected from a) a protease, the an amino acid sequence which is at least 80%
- the first protease is selected from a) a protease which comprises an amino acid sequence which is increasingly preferably at least 82.5%, 85%, 87.5% to the amino acid sequence given in SEQ ID NO. 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, 99.5%, and most preferably 100% identical.
- a protease comprising an amino acid sequence which is more preferably at least 82.5%, 85%, 87.5%, 90%, 91%, 92%, 93%, of the amino acid sequence given in SEQ ID NO. 94%, 95%, 96%, 97%, 98%, 99%, 99.5% and most preferably 100% identical.
- a protease comprising an amino acid sequence which is more preferably at least 82.5%, 85%, 87.5%, 90%, 91%, 92%, 93% to the amino acid sequence given in SEQ ID NO. Is 94%, 95%, 96%, 97%, 98%, 99%, 99.5% and most preferably 100% identical and has at least one additional amino acid compared to SEQ ID NO.2.
- the method is characterized in that the additional amino acid of the first protease is inserted in one of the following positions in the counting manner according to SEQ ID NO.
- proteases which are used according to the invention as the first protease in a corresponding method, have a corresponding insertion of at least one amino acid or of a plurality of amino acids, preferably at one or more of said positions on.
- agents according to the invention - for example for proteases, which are described in the European patent application EP 1 032 655.
- These have, for example, at least one additional amino acid in the counting method according to SEQ ID NO.
- proteases which have an insertion of at least one amino acid and can be used according to the invention as the first protease, are derived from the international patent application WO 00/37599 and the international patent application WO 01/44452.
- the method is characterized in that the second protease comprises an amino acid sequence which is increasingly preferably at least 82.5% to the amino acid sequence given in SEQ ID NO. 85%, 87.5%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, 99.5%, and most preferably 100% identical is.
- the proteases are preferably used in an amount of from 40 ⁇ g to 4 g, preferably from 50 ⁇ g to 3 g, particularly preferably from 100 ⁇ g to 2 g and very particularly preferably from 200 ⁇ g to 1 g per application.
- the quantities shown contain the first protease and the second protease.
- methods for textile raw materials, fibers or textiles with natural components are preferred, and especially for those with wool or silk.
- These may be, for example, processes in which materials for processing in textiles are prepared, for example for anti-fungal finishing, or, for example, for processes which enrich the cleaning of worn textiles with a nourishing component.
- they are processes for the treatment of textile raw materials, fibers or textiles with natural constituents, in particular with wool or silk.
- a further inventive subject matter is the use of a first protease and a second protease for the purification of textiles or hard surfaces, characterized in that the first protease is selected from a) a protease comprising an amino acid sequence corresponding to the amino acid sequence shown in SEQ ID NO. 1 amino acid sequence is at least 80% identical; b) a protease comprising an amino acid sequence which is at least 80% identical to the amino acid sequence given in SEQ ID NO. 2; c) a protease which comprises an amino acid sequence which is at least 80% identical to the amino acid sequence given in SEQ ID NO. 2 and additionally has at least one additional amino acid in comparison with SEQ ID NO. 2; and the second protease comprises an amino acid sequence which is at least 80% identical to the amino acid sequence given in SEQ ID NO.3.
- combinations of proteases according to the invention can be used, in particular because of the properties described above, to eliminate proteinaceous impurities from textiles or from hard surfaces.
- Embodiments include, for example, hand washing, manual removal of stains from fabrics or hard surfaces, or use in conjunction with a machine process.
- the subject combinations of proteases of this invention are provided according to any of the above recipes.
- the first protease is selected from a) a protease which comprises an amino acid sequence which is more preferably at least 82.5%, 85%, 87.5% to the amino acid sequence given in SEQ ID NO. 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, 99.5%, and most preferably 100% identical.
- a protease comprising an amino acid sequence which is more preferably at least 82.5%, 85%, 87.5%, 90%, 91%, 92%, 93% to the amino acid sequence given in SEQ ID NO. Is 94%, 95%, 96%, 97%, 98%, 99%, 99.5% and most preferably 100% identical and has at least one additional amino acid compared to SEQ ID NO.2.
- the use is characterized in that the additional amino acid of the first protease is inserted in one of the following positions in the counting manner according to SEQ ID NO.2: 33, 34, 35, 36, 37, 38, 39, 40 , 41, 42, 43, 95, 96, 97, 98, 99, 100, 101, 102, 103, 125, 126, 127, 126, 129, 130, 131, 132, 153, 154, 155, 156, 157 , 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 171, 172, 173, 181, 182, 183, 184, 185, 186, 187, 188, 189 , 190, 191, 192, 193, 194, 195, 202, 203, 204, 218, 219.
- proteases which are useful according to the invention as the first protease, have a corresponding insertion of at least one amino acid.
- examples of such enzymes which have a corresponding insertion are already discussed above in the present application for the agents according to the invention and the methods according to the invention.
- the use is characterized in that the second protease comprises an amino acid sequence which is increasingly preferably at least 82.5% to the amino acid sequence given in SEQ ID NO. , 85%, 87.5%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, 99.5% and most preferably 100% is identical.
- a preferred use of a combination of proteases according to the invention is characterized in that the proteases are present in an amount of from 40 ⁇ g to 4 g, preferably from 50 ⁇ g to 3 g, more preferably from 100 ⁇ g to 2 g and most preferably from 200 ⁇ g to 1 g per application are used.
- the quantities shown contain the first protease and the second protease.
- Example 1 Synergistic Performance of the Protease Variant S99SD + S99A According to WO 01/44452 and the Alkaline Protease from Bacillus Gibsonii (DSM 14391)
- the pure enzyme granules and mixtures of the protease disclosed as Subtilase 309 (also referred to as Subtilisin 309 or Savinase®) variant S99SD + S99A are disclosed in international patent application WO 01/44452 (see especially Examples 1 and 2 of WO 01/44452) as a representative of the first protease and the alkaline protease from Bacillus gibsonii (DSM 14391) as a representative of the second protease.
- the mixture was calculated in proportion to the insertions of the single enzymes.
- the granules of the alkaline protease from Bacillus gibsonii (DSM 14391) were prepared according to WO 97/40128 A1 and coated according to WO 98/26037 A2.
- Table 1 Results of the performance comparison of a mixture of proteases compared to the pure proteases in a machine dishwashing detergent.
- the pure enzyme granules and mixtures of the alkaline protease from Bacillus lentus F49 were incorporated as a representative of the first protease and the alkaline protease from Bacillus gibsonii (DSM 14391) as a representative of the second protease.
- the mixture was calculated in proportion to the insertions of the single enzymes.
- the granules of the alkaline protease from Bacillus gibsonii (DSM 14391) were prepared according to WO 97/40128 A1 and coated according to WO 98/26037 A2.
- Table 2 Results of the performance comparison of higher concentrated granules with low concentrated granules in a machine dishwashing detergent.
- Amylase 0 - 0.072 pure protein
- formulations of solid detergents with this framework formulation were produced within the scope of the invention:
- Amylase 0 - 0.072 pure protein
- Pectinase 0 - 0.072 pure protein
- Linear alkylbenzene sulfonic acid 0-20%
- Amylase 0 - 0.072 pure protein
- Pectinase 0 - 0.072 pure protein
- Amylase 0 - 0.072 pure protein
- Pectinase 0 - 0.072 (pure protein) Balance water, optical brightener, salts
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Abstract
The invention relates to agent compositions, particularly detergents and cleaning agents, comprising a first protease of the “BLAP” type and a second protease of the “alkaline protease from Bacillus gibsonii (DSM 14391)” type. The invention further relates to cleaning methods, in which said agents are used, to the use of said agents, and to cleaning methods and the use of said proteases.
Description
Mittel enthaltend Proteasen Agents containing proteases
Die Erfindung betrifft Mittelzusammensetzungen, insbesondere Wasch- und Reinigungsmittel, die eine erste Protease und eine zweite Protease enthalten. Weiterhin betrifft die Erfindung Reinigungsverfahren, in denen diese Mittel eingesetzt sind, Verwendungen dieser Mittel sowie Reinigungsverfahren und Verwendungen dieser Proteasen.The invention relates to middle compositions, in particular detergents and cleaners, containing a first protease and a second protease. Furthermore, the invention relates to purification processes in which these agents are used, uses of these agents and purification processes and uses of these proteases.
Proteasen gehören zu den technisch bedeutendsten Enzymen überhaupt. Hierunter sind wiederum Proteasen vom Subtilisin-Typ (Subtilasen, Subtilopeptidasen, EC 3.4.21.62) besonders wichtig, welche aufgrund der katalytisch wirksamen Aminosäuren den Serin-Proteasen zugerechnet werden. Sie wirken als unspezifische Endopeptidasen, das heißt, sie hydrolysieren beliebige Säureamidbindungen, die im Inneren von Peptiden oder Proteinen liegen. Ihr pH-Optimum liegt meist im deutlich alkalischen Bereich. Einen Überblick über diese Familie bietet beispielsweise der Artikel „Subtilases: Subtilisin-like Proteases" von R. Siezen, Seite 75-95 in „Subtilisin enzymes", herausgegegeben von R. Bott und C. Betzel, New York, 1996. Subtilasen werden natürlicherweise von Mikroorganismen gebildet; hierunter sind insbesondere die von Bacillus-Spezies gebildeten und sekretierten Subtilisine als bedeutendste Gruppe innerhalb der Subtilasen zu erwähnen.Proteases are among the most technically important enzymes of all. Of these, in turn, proteases of the subtilisin type (subtilases, subtilopeptidases, EC 3.4.21.62) are particularly important, which are attributed to the serine proteases due to the catalytically active amino acids. They act as nonspecific endopeptidases, that is, they hydrolyze any acid amide linkages that are internal to peptides or proteins. Their pH optimum is usually in the clearly alkaline range. For an overview of this family, see for example the article "Subtilases: Subtilisin-like Proteases" by R. Siezen, pages 75-95 in "Subtilisin enzymes", edited by R. Bott and C. Betzel, New York, 1996. Subtilases become natural 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.
Proteasen sind neben anderen Enzymen etablierte aktive Inhaltsstoffe von Wasch- und Reinigungsmitteln. Sie bewirken dabei den Abbau proteinhaltiger Anschmutzungen auf dem Reinigungsgut. Günstigenfalls ergeben sich Synergieeffekte zwischen den Enzymen und den übrigen Bestandteilen der betreffenden Mittel. Unter den Wasch- und Reinigungsmittelproteasen nehmen Subtilasen aufgrund ihrer günstigen enzymatischen Eigenschaften wie Stabilität oder pH- Optimum eine herausragende Stellung ein. Sie eignen sich daneben noch für eine Vielzahl weiterer technischer Verwendungsmöglichkeiten, beispielsweise als Bestandteile von Kosmetika oder in der organisch-chemischen Synthese.Proteases are, in addition to other enzymes, established active ingredients of detergents and cleaners. They cause the breakdown of protein-containing stains on the items to be cleaned. At best, there are synergies between the enzymes and the remaining components of the funds concerned. Among the detergent and detergent proteases subtilases occupy an outstanding position due to their favorable enzymatic properties such as stability or pH optimum. They are also suitable for a variety of other technical uses, for example as components of cosmetics or in the organic-chemical synthesis.
Beispiele für die in Wasch- und Reinigungsmitteln bevorzugt eingesetzten Proteasen vom Subtilisin-Typ sind die Subtilisine BPN' und Carlsberg, die Protease PB92, die Subtilisine 147 und 309, die Alkalische Protease aus Bacillus lentus, Subtilisin DY und die den Subtilasen, nicht mehr jedoch den Subtilisinen im engeren Sinne zuzuordnenden Enzyme Thermitase, Proteinase K und die Proteasen TW3 und TW7.Examples of the subtilisin-type proteases preferably used in detergents and cleaners are the subtilisins BPN 'and Carlsberg, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and those the subtilases, but no longer Enzymes Thermitase, Proteinase K, and Proteases TW3 and TW7, which can be classified as subtilisins in the narrower sense.
Das Subtilisin BPN', welches aus Bacillus amyloliquefaciens, beziehungsweise B. subtilis stammt, ist aus den Arbeiten von Vasantha et al. (1984) in J. Bacteriol., Volume 159, S. 811-819 und von J. A. Wells et al. (1983) in Nucleic Acids Research, Volume 11 , S. 7911-7925 bekannt. Subtilisin BPN' dient insbesondere hinsichtlich der Numerierung der Positionen als Referenzenzym der
Subtilisine. Subtilisin Carlsberg ist in weiterentwickelter Form unter dem Handelsnamen Alcalase® von der Firma Novozymes A/S, Bagsvaerd, Dänemark, erhältlich. Sie wird in den Publikationen von E. L. Smith et al. (1968) in J. Biol. Chem., Volume 243, S. 2184-2191 , und von Jacobs et al. (1985) in Nucl. Acids Res., Band 13, S. 8913-8926 beschrieben und wird natürlicherweise von Bacillus licheniformis gebildet. Die Protease PB92 wird natürlicherweise von dem alkaliphilen Bakterium Bacillus nov. spec. 92 produziert und war unter dem Handelsnamen Maxacal® von der Fa. Gist- Brocades, Delft, Niederlande, erhältlich. In ihrer ursprüglichen Sequenz wird sie in der Patentanmeldung EP 283075 A2 beschrieben. Die Subtilisine 147 und 309 werden unter den Handelsnamen Esperase®, beziehungsweise Savinase® von der Firma Novozymes vertrieben. Sie stammen ursprünglich aus Bacillus-Stämmen, die mit der Anmeldung GB 1243784 A offenbart werden. Von der Protease aus Bacillus lentus DSM 5483 (WO 91/02792 A1 ) leiten sich die unter der Bezeichnung BLAP® geführten Varianten ab, die insbesondere in WO 92/21760 A1 , WO 95/23221 A1 , WO 02/088340 A2 und WO 03/038082 A2 beschrieben werden. Subtilisin DY ist ursprünglich von Nedkov et al. 1985 in Biol. Chem Hoppe-Seyler, Band 366, S. 421-430 beschrieben. Weitere verwendbare Proteasen sind beispielsweise die unter den Handelsnamen Durazym®, Relase®, Everlase®, Nafizym, Natalase®, Kannase® und Ovozyme® von der Firma Novozymes, die unter den Handelsnamen, Purafect®, Purafect® OxP, Purafect® Prime und Properase® von der Firma Genencor, das unter dem Handelsnamen Protosol® von der Firma Advanced Biochemicals Ltd., Thane, Indien, das unter dem Handelsnamen Wuxi® von der Firma Wuxi Snyder Bioproducts Ltd., China, die unter den Handelsnamen Proleather® und Protease P® von der Firma Amano Pharmaceuticals Ltd., Nagoya, Japan, und das unter der Bezeichnung Proteinase K-16 von der Firma Kao Corp., Tokyo, Japan, erhältlichen Enzyme.The subtilisin BPN ', which is derived from Bacillus amyloliquefaciens, or B. subtilis, is known from the work of Vasantha et al. (1984) in J. Bacteriol., Volume 159, pp. 811-819 and JA Wells et al. (1983) in Nucleic Acids Research, Volume 11, pp. 7911-7925. Subtilisin BPN 'is used in particular with regard to the numbering of the positions as reference enzyme of Subtilisins. Subtilisin Carlsberg is available in a further developed form under the trade name Alcalase® from Novozymes A / S, Bagsvaerd, Denmark. It is described in the publications of EL Smith et al. (1968) in J. Biol. Chem., Volume 243, pp. 2184-2191, and Jacobs et al. (1985) in Nucl. Acids Res., Vol. 13, pp. 8913-8926 and is naturally produced by Bacillus licheniformis. The protease PB92 is naturally derived from the alkaliphilic bacterium Bacillus nov. spec. 92 and was available under the trade name Maxacal® from Gist-Brocades, Delft, The Netherlands. In its original sequence, it is described in the patent application EP 283075 A2. The subtilisins 147 and 309 are sold under the trade names Esperase®, and Savinase® by the company Novozymes. They are originally from Bacillus strains, which are disclosed in the application GB 1243784 A. The protease from Bacillus lentus DSM 5483 (WO 91/02792 A1) is derived from the variants described under the name BLAP®, which are described in particular in WO 92/21760 A1, WO 95/23221 A1, WO 02/088340 A2 and WO 03 / 038082 A2. Subtilisin DY is originally from Nedkov et al. Chem., 1985, Biol. Chem. Hoppe-Seyler, Vol. 366, pp. 421-430. Further useful proteases are, for example, those under the trade names Durazym®, Relase®, Everlase®, Nafizym, Natalase®, Kannase® and Ovozyme® from Novozymes, which are available under the trade names, Purafect®, Purafect® OxP, Purafect® Prime and Properase ® from Genencor, sold under the trade name Protosol® by Advanced Biochemicals Ltd., Thane, India, under the trade name Wuxi® by Wuxi Snyder Bioproducts Ltd., China, under the trade names Proleather® and Protease P From Amano Pharmaceuticals Ltd., Nagoya, Japan, and that available under the name Proteinase K-16 from Kao Corp., Tokyo, Japan.
Die in erfindungsgemäßen Mitteln eingesetzten Proteasen stammen entweder ursprünglich aus Mikroorganismen, beispielsweise aus Mikroorganismen der Gattungen Bacillus, Streptomyces, Humicola, oder Pseudomonas, und/oder werden nach an sich bekannten biotechnologischen Verfahren durch geeignete Mikroorganismen produziert, beispielsweise durch transgene Expressionswirte der Gattungen Bacillus oder durch filamentöse Fungi.The proteases used in the compositions according to the invention are either originally derived from microorganisms, for example from microorganisms of the genera Bacillus, Streptomyces, Humicola or Pseudomonas, and / or are produced by biotechnological methods known per se by suitable microorganisms, for example by transgenic expression hosts of the genera Bacillus or by filamentous fungi.
Komplexe Protein-Anschmutzungen bzw. -Rückstände stellen hohe Anforderungen an die in dem jeweiligen Mittel enthaltene Protease. Beispielsweise werden Anschmutzungen durch eine in dem Mittel enthaltene Protease nicht vollständig bzw. zufrieden stellend entfernt. Auch können weitere Inhaltsstoffe der Anschmutzung die Leistung einer Protease herabsetzen. Um die Leistungsfähigkeit von Mitteln, insbesondere Wasch- und Reinigungsmitteln, hinsichtlich ihrer proteolytischen Aktivität zu verbessern, wird beispielsweise versucht, neue Proteasen mit vorteilhaften Eigenschaften zu gewinnen, indem beispielsweise Mikroorganismen-haltige Proben aus natürlichen Habitaten entnommen werden und unter den als geeignet angesehenen Bedingungen
- zum Beispiel in alkalischem Milieu - zu kultivieren. Auch ist es möglich, Proteasen über an sich bekannte Mutagenese-Verfahren für den Einsatz in den jeweiligen Mitteln, insbesondere Wasch- und Reinigungsmitteln, zu optimieren. Dazu gehören Punktmutagenese, Deletion, Insertion oder Fusion mit anderen Proteinen oder Proteinteilen oder über sonstige, insbesondere chemische Modifikationen. Beispielsweise werden hierdurch die Oberflächenladungen und/oder den isoelektrischen Punkt der Moleküle und darüber ihre Wechselwirkungen mit dem Substrat verändert oder die Stabilität der betreffenden Proteasen und damit ihre Wirksamkeit erhöht. Jedoch weisen die hier beispielhaft dargestellten Weiterentwicklungsmöglichkeiten der in entsprechenden Mitteln einsetzbaren Proteasen den Nachteil auf, dass sie komplex und zeitaufwändig sind.Complex protein soiling or residues make high demands on the protease contained in the respective agent. For example, soils are not completely or satisfactorily removed by a protease contained in the agent. Also, other contaminant ingredients may decrease the performance of a protease. In order to improve the performance of agents, in particular detergents and cleaners, with regard to their proteolytic activity, it is for example attempted to obtain novel proteases having advantageous properties, for example by removing microorganism-containing samples from natural habitats and under the conditions regarded as suitable - for example, in an alkaline medium - to cultivate. It is also possible to optimize proteases by mutagenesis methods known per se for use in the respective compositions, in particular detergents and cleaners. These include point mutagenesis, deletion, insertion or fusion with other proteins or protein parts or other, in particular chemical modifications. For example, this changes the surface charges and / or the isoelectric point of the molecules and above their interactions with the substrate or increases the stability of the proteases in question and thus their effectiveness. However, the further development possibilities of the proteases which can be used in corresponding agents have the disadvantage that they are complex and time-consuming.
Hinsichtlich der Anwendung von Proteasen in Wasch- und Reinigungsmitteln ist bekannt, dass Proteasen zur Verbesserung der Wasch- beziehungsweise Reinigungsleistung zusammen mit weiteren Enzymen, beispielsweise Amylasen, Cellulasen, Hemicellulasen, Mannanasen, ß- Glucosidasen, Oxidasen, Oxidoreduktasen oder Lipasen eingesetzt werden können. Ebenso ist der Einsatz von Proteasen in Waschmitteln in Kombination mit anderen Wirkstoffen wie etwa Bleichmitteln oder Soil-Release-Wirkstoffen dem Fachmann bekannt. Aus dem Stand der Technik ist ferner bekannt, dass entsprechende Mittel, insbesondere Wasch- und Reinigungsmittel, mehrere Proteasen enthalten können. So offenbart die internationale Patentanmeldung WO 03/054185 A1 , dass die Alkalische Protease aus Bacillus gibsonii (DSM 14391 ) in einem entsprechenden Mittel zusammen mit weiteren Proteasen eingesetzt werden kann. Allerdings enthält diese Anmeldung wie auch der weitere Stand der Technik keinen Hinweis darauf, mit welchen spezifischen Proteasen dieses Enzym vorteilhafterweise zu kombinieren ist, um ein synergistisches Zusammenwirken der Proteasen in einem entsprechenden Mittel zu erzielen.With regard to the use of proteases in detergents and cleaning agents it is known that proteases can be used to improve the washing or cleaning performance together with other enzymes, for example amylases, cellulases, hemicellulases, mannanases, β-glucosidases, oxidases, oxidoreductases or lipases. Likewise, the use of proteases in detergents in combination with other active ingredients such as bleaching agents or soil release agents is known in the art. It is further known from the prior art that corresponding agents, in particular washing and cleaning agents, may contain a plurality of proteases. For example, International Patent Application WO 03/054185 A1 discloses that the Bacillus gibsonii alkaline protease (DSM 14391) can be used in an appropriate composition together with further proteases. However, this application as well as the further prior art contains no indication as to which specific proteases this enzyme is advantageously to be combined in order to achieve a synergistic interaction of the proteases in a corresponding agent.
Überraschenderweise wurde gefunden, dass die Leistungsfähigkeit von Mitteln, insbesondere Wasch- und Reinigungsmitteln, hinsichtlich ihrer proteolytischen Aktivität signifikant verbessert wird, wenn in diesen Mitteln Mischungen von mindestens zwei bestimmten Proteasen mit unterschiedlichem Wirkspektrum und/oder unterschiedlicher Sequenz eingesetzt sind. Hinsichtlich des Zusammenwirkens von diesen bestimmten, unterschiedlichen Proteasen ergibt sich eine synergistische Wirkung, d.h. eine bessere Leistung im Vergleich mit den Einzelleistungen der jeweiligen Protease in Ein-Komponenten-Systemen (d.h. Mitteln, die nur jeweils diese Proteasen enthalten) und auch gegenüber der Summe der Einzelleistungen der Proteasen, d.h. der Summe von beispielsweise zwei Ein-Komponenten-Systemen. Somit stellt die ausgewählte Kombination von bestimmten Proteasen eine weitere Möglichkeit dar, um die Leistungsfähigkeit von Mitteln, insbesondere Wasch- und Reinigungsmitteln, hinsichtlich ihrer proteolytischen Aktivität zu verbessern.
Der vorliegenden Erfindung liegt daher die Aufgabe zugrunde, Mittel bereitzustellen, die eine verbesserte proteolytische Aktivität aufweisen.Surprisingly, it has been found that the performance of agents, in particular detergents and cleaners, is significantly improved with regard to their proteolytic activity, if mixtures of at least two specific proteases with different activity spectrum and / or different sequence are used in these agents. With regard to the interaction of these particular, different proteases results in a synergistic effect, ie a better performance compared to the individual performances of the respective protease in one-component systems (ie agents that contain only each of these proteases) and also to the sum of Individual performances of the proteases, ie the sum of, for example, two one-component systems. Thus, the selected combination of particular proteases is another way to improve the performance of agents, especially detergents, with regard to their proteolytic activity. It is therefore an object of the present invention to provide agents which have improved proteolytic activity.
Hiermit verbunden ist eine weitere Aufgabe der vorliegenden Erfindung, Mittel bereitzustellen, die eine verbesserte Wasch- bzw. Reinigungsleistung in Bezug auf zumindest eine proteinhaltige Anschmutzung, vorzugsweise in Bezug auf mehrere proteinhaltige Anschmutzungen, aufweisen.Relatedly, another object of the present invention is to provide means having improved detergency performance relative to at least one proteinaceous soiling, preferably with respect to multiple proteinaceous soils.
Eine weitere besondere Aufgabe der vorliegenden Erfindung ist es, Mittel bereitzustellen, die eine mindestens gleich bleibende, vorzugsweise eine verbesserte Wasch- bzw. Reinigungsleistung in Bezug auf zumindest eine proteinhaltige Anschmutzung, vorzugsweise in Bezug auf mehrere proteinhaltige Anschmutzungen, aufweisen, aber eine reduzierten Gehalt an Proteaseenzym aufweisen.Another particular object of the present invention is to provide agents which have at least a constant, preferably improved, washing or cleaning performance with respect to at least one proteinaceous soiling, preferably with respect to a plurality of proteinaceous soils, but a reduced content Protease enzyme have.
Diese Aufgabe wird erfindungsgemäß gelöst gemäß der Lehre des Anspruchs 1 durch die Bereitstellung von Mitteln, die Mischungen von Proteasen mit unterschiedlichen Wirkspektren bzw. unterschiedlicher Sequenz enthalten. In diesen erfindungsgemäßen Mitteln entfalten die enthaltenen Proteasen eine synergistische Reinigungsleistung, so dass die Mittel eine bessere Entfernung proteinhaltiger Anschmutzungen bewirken im Vergleich zu Mitteln, die entweder nur einen Proteasetyp enthalten, oder im Vergleich zur erwarteten Reinigungsleistung eines Mittels mit zwei Proteasen auf Grund der bloßen Addition der jewiligen Einzelbeiträge der enthaltenen Proteasen zur Reinigungsleistung des Mittels. Somit stellt die ausgewählte Kombination von solchen Proteasen einen wesentlichen Aspekt der Erfindung dar, die in erfindungsgemäßen Mitteln eine synergistische Wirkung hinsichlich der Entfernung von proteinhaltigen Rückständen oder Anschmutzungen aufweisen.This object is achieved according to the teaching of claim 1 by the provision of agents containing mixtures of proteases with different activity spectra or different sequence. In these compositions according to the invention, the proteases contained develop a synergistic cleaning performance, so that the agents effect a better removal of proteinaceous soils compared to agents containing either only one protease type or compared to the expected cleaning performance of a two-protease agent due to mere addition the jewiligen individual contributions of the contained proteases to the cleaning performance of the agent. Thus, the selected combination of such proteases constitutes an essential aspect of the invention which has a synergistic effect on the removal of proteinaceous residues or soils in compositions of the invention.
Einen Gegenstand der Erfindung stellen somit Mittel dar enthaltend eine erste Protease und eine zweite Protease, die dadurch gekennzeichnet sind, dass die erste Protease ausgewählt ist aus a) einer Protease, die eine Aminosäuresequenz umfasst, die zu der in SEQ ID NO.1 angegebenen Aminosäuresequenz mindestens zu 80% identisch ist; b) einer Protease, die eine Aminosäuresequenz umfasst, die zu der in SEQ ID NO.2 angegebenen Aminosäuresequenz mindestens zu 80% identisch ist; c) einer Protease, die eine Aminosäuresequenz umfasst, die zu der in SEQ ID NO.2 angegebenen Aminosäuresequenz mindestens zu 80% identisch ist und zusätzlich mindestens eine zusätzliche Aminosäure im Vergleich mit SEQ ID NO.2 aufweist; und die zweite Protease eine Aminosäuresequenz umfasst, die zu der in SEQ ID NO.3 angegebenen Aminosäuresequenz mindestens zu 80% identisch ist.
Es hat sich überraschenderweise herausgestellt, dass insbesondere die Kombination einer Protease, wie sie vorstehend unter a) bis c) definiert ist (nachfolgend zusammenfassend als Protease vom „BLAP-Typ" bzw. als erste Protease bezeichnet) mit einer Protease, die zu der in SEQ ID NO.3 angegebenen Aminosäuresequenz mindestens zu 80% identisch ist (nachfolgend als Protease vom Typ „Alkalische Protease aus Bacillus gibsonii (DSM 14391 )" bzw. zweite Protease bezeichnet), in einem erfindungsgemäßen Mittel zu einer synergistischen Reinigungsleistung der beiden Proteasen führt. Die synergistische Wirkung dieser beiden Typen von Proteasen in einem erfindungsgemäßen Mittel beruht darauf, dass sich die Wirkungen der ersten und der zweiten Protease so ergänzen, dass in der Gesamtheit eine gesteigerte proteolytischen Wirkung erreicht wird. Dies kann beispielsweise dadurch ermöglicht werden, dass durch die proteolytische Spaltung von Peptidbindungen durch die erste Protease Substrate für die zweite Protease verbessert zugänglich werden und durch die proteolytische Spaltung der Peptidbindungen durch die zweite Protease wiederum weitere Substrate für die erste Protease zugänglich werden. Gerade bei komplexen proteinhaltigen Substraten ist die Zugänglichkeit einer Spaltstelle für eine Protease häufig ein limitierender Faktor. Ein unterschiedliches Wirkspektrum der beiden Proteasen zeigt sich daher beispielsweise in einer unterschiedlichen Substratspezifität. Ebenso kann ein unterschiedliches Wirkspektrum hervorgerufen sein durch eine unterschiedliche proteolytische Aktivität unter definierten Bedingungen, insbesondere hinsichtlich Temperatur, pH-Wert, lonenstärke, Stabilität gegenüber oxidierenden Verbindungen (beispielsweise Bleichmitteln), usw.An object of the invention thus represent means comprising a first protease and a second protease, which are characterized in that the first protease is selected from a) a protease comprising an amino acid sequence corresponding to the amino acid sequence given in SEQ ID NO.1 at least 80% identical; b) a protease comprising an amino acid sequence which is at least 80% identical to the amino acid sequence given in SEQ ID NO. 2; c) a protease which comprises an amino acid sequence which is at least 80% identical to the amino acid sequence given in SEQ ID NO. 2 and additionally has at least one additional amino acid in comparison with SEQ ID NO. 2; and the second protease comprises an amino acid sequence which is at least 80% identical to the amino acid sequence given in SEQ ID NO.3. It has surprisingly been found that in particular the combination of a protease, as defined above under a) to c) (hereinafter collectively referred to as "BLAP-type protease" or as the first protease) with a protease corresponding to the one described in SEQ ID NO.3 indicated amino acid sequence is at least 80% identical (hereinafter referred to as protease of the type "alkaline protease from Bacillus gibsonii (DSM 14391)" or second protease), in an agent according to the invention leads to a synergistic cleaning performance of the two proteases. The synergistic effect of these two types of proteases in an agent according to the invention is based on the fact that the effects of the first and the second protease complement one another in such a way that an overall increased proteolytic effect is achieved. This can be made possible, for example, by the fact that the proteolytic cleavage of peptide bonds by the first protease makes substrates for the second protease more accessible and, in turn, further substrates for the first protease become accessible by the proteolytic cleavage of the peptide bonds by the second protease. Especially with complex protein-containing substrates, the accessibility of a cleavage site for a protease is often a limiting factor. A different spectrum of action of the two proteases therefore shows, for example, in a different substrate specificity. Likewise, a different spectrum of action may be caused by a different proteolytic activity under defined conditions, in particular with regard to temperature, pH, ionic strength, stability towards oxidizing compounds (for example bleaching agents), etc.
Ein erfindungsgemäßer Synergismus tritt demnach dann auf, wenn sich die erste Protease von der zweiten Protease unterscheidet. Diese Unterschiede manifestieren sich in der Aminosäuresequenz des jeweils proteolytisch aktiven Enzyms. Betreffend die erste Protease ist diese bevorzugt ausgewählt ausA synergism according to the invention therefore occurs when the first protease differs from the second protease. These differences manifest themselves in the amino acid sequence of the respective proteolytically active enzyme. As for the first protease, it is preferably selected from
a) einer Protease, die eine Aminosäuresequenz umfasst, die zu der in SEQ ID NO.1 angegebenen Aminosäuresequenz zunehmend bevorzugt zu mindestens 82,5%, 85%, 87,5%, 90%, 91 %, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, 99,5% und ganz besonders bevorzugt zu 100% identisch ist. b) einer Protease, die eine Aminosäuresequenz umfasst, die zu der in SEQ ID NO.2 angegebenen Aminosäuresequenz zunehmend bevorzugt zu mindestens 82,5%, 85%, 87,5%, 90%, 91 %, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, 99,5% und ganz besonders bevorzugt zu 100% identisch ist. c) einer Protease, die eine Aminosäuresequenz umfasst, die zu der in SEQ ID NO.2 angegebenen Aminosäuresequenz zunehmend bevorzugt zu mindestens 82,5%, 85%, 87,5%, 90%, 91 %, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, 99,5% und ganz besonders bevorzugt zu 100% identisch ist und mindestens eine zusätzliche Aminosäure im Vergleich mit SEQ ID NO.2 aufweist.
In einer weiteren bevorzugten Ausführungsformder Erfindung ist das Mittel dadurch gekennzeichnet, dass die zusätzliche Aminosäure der ersten Protease nach einer der folgenden Positionen in der Zählweise gemäß SEQ ID NO.2 eingefügt ist: 33, 34, 35, 36, 37, 38, 39, 40, 41 , 42, 43, 95, 96, 97, 98, 99, 100, 101 , 102, 103, 125, 126, 127, 126, 129, 130, 131 , 132, 153, 154, 155, 156, 157, 158, 159, 160, 161 , 162, 163, 164, 165, 166, 167, 168, 169, 170, 171 , 172, 173, 181 , 182, 183, 184, 185, 186, 187, 188, 189, 190, 191 , 192, 193, 194, 195, 202, 203, 204, 218, 219. Denn verschiedene Proteasen, die erfindungsgemäß als erste Protease in einem Mittel einsetzbar sind, weisen eine entsprechende Insertion von zumindest einer Aminosäure oder auch von mehreren Aminosäuren, bevorzugt an einer oder mehreren der genannten Positionen, auf. Dies gilt beispielsweise für Proteasen, die in der europäischen Patentanmeldung EP 1 032 655 beschrieben sind. Diese weisen beispielsweise mindestens eine zusätzliche Aminosäure auf in der Zählweise gemäß SEQ ID NO.2 (das heißt in der Zählweise der Savinase®, in der genannten Anmeldung bezeichnet als BLSAVI), in den Positionen 33 bis 43, 95 bis 103, 125 bis 132, 153 bis 173, 181 bis 195, 202 bis 204 und/oder Position 218 bis 219. Weitere Proteasen, die eine Insertion von mindestens einer Aminosäure aufweisen und erfindungsgemäß als erste Protease einsetzbar sind, gehen aus der internationalen Patentanmeldung WO 00/37599 und der internationalen Patentanmeldung WO 01/44452 hervor.a) a protease which comprises an amino acid sequence which is more preferably at least 82.5%, 85%, 87.5%, 90%, 91%, 92%, 93% to the amino acid sequence given in SEQ ID NO.1, 94%, 95%, 96%, 97%, 98%, 99%, 99.5% and most preferably 100% identical. b) a protease comprising an amino acid sequence which is more preferably at least 82.5%, 85%, 87.5%, 90%, 91%, 92%, 93%, of the amino acid sequence given in SEQ ID NO. 94%, 95%, 96%, 97%, 98%, 99%, 99.5% and most preferably 100% identical. c) a protease comprising an amino acid sequence which is more preferably at least 82.5%, 85%, 87.5%, 90%, 91%, 92%, 93% to the amino acid sequence given in SEQ ID NO. Is 94%, 95%, 96%, 97%, 98%, 99%, 99.5% and most preferably 100% identical and has at least one additional amino acid compared to SEQ ID NO.2. In a further preferred embodiment of the invention, the agent is characterized in that the additional amino acid of the first protease is inserted after one of the following positions in the counting manner according to SEQ ID NO.2: 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 95, 96, 97, 98, 99, 100, 101, 102, 103, 125, 126, 127, 126, 129, 130, 131, 132, 153, 154, 155, 156, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 171, 172, 173, 181, 182, 183, 184, 185, 186, 187, 188, 189, 190, 191, 192, 193, 194, 195, 202, 203, 204, 218, 219. For different proteases, which are used according to the invention as the first protease in an agent, have a corresponding insertion of at least one amino acid or of a plurality of amino acids, preferably at one or more of said positions on. This applies, for example, proteases, which are described in the European patent application EP 1 032 655. These have, for example, at least one additional amino acid in the counting method according to SEQ ID NO. 2 (that is to say in the counting method of Savinase®, referred to in the named application as BLSAVI), in positions 33 to 43, 95 to 103, 125 to 132 , 153 to 173, 181 to 195, 202 to 204 and / or position 218 to 219. Further proteases which have an insertion of at least one amino acid and can be used according to the invention as the first protease, are derived from the international patent application WO 00/37599 and the international patent application WO 01/44452.
Hinsichtlich der zweiten Protease, die in erfindungsgemäßen Mitteln mit der ersten Protease kombiniert wird, ist das Mittel dadurch gekennzeichnet, dass die zweite Protease eine Aminosäuresequenz umfasst, die zu der in SEQ ID NO.3 angegebenen Aminosäuresequenz zunehmend bevorzugt zu mindestens 82,5%, 85%, 87,5%, 90%, 91 %, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, 99,5% und ganz besonders bevorzugt zu 100% identisch ist. Wie vorstehend bereits erwähnt wird eine synergistische proteolytische Leistung eines erfindungsgemäßen Mittels insbesondere dann festgestellt, wenn eine erste Protease von BLAP-Typ mit einer zweiten Protease vom Typ „Alkalische Protease aus Bacillus gibsonii (DSM 14391 )" kombiniert wird. Eine solche Protease wurde aus Bacillus gibsonii (DSM 14391 ) erhalten und ist in der internationalen Offenlegungsschrift WO 03/054185 A1 beschrieben, deren Offenbarungsgehalt ausdrücklich in die vorliegende Patentanmeldung einbezogen wird.With regard to the second protease, which is combined in means according to the invention with the first protease, the agent is characterized in that the second protease comprises an amino acid sequence which is more preferably at least 82.5% to the amino acid sequence given in SEQ ID NO. 85%, 87.5%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, 99.5%, and most preferably 100% identical is. As already mentioned above, a synergistic proteolytic performance of a composition according to the invention is found, in particular, when a first protease of the BLAP type is combined with a second protease of the type "alkaline protease from Bacillus gibsonii (DSM 14391)." One such protease was obtained from Bacillus gibsonii (DSM 14391) and is described in International Publication WO 03/054185 A1, the disclosure content of which is expressly incorporated into the present patent application.
Unter einem Enzym ist im Sinne der vorliegenden Anmeldung ein Protein zu verstehen, das eine bestimmte biokatalytische Funktion ausübt. Unter Protease im Sinne der vorliegenden Anmeldung wird ein Enzym verstanden, welches die Hydrolyse von Peptidbindungen katalysiert und dadurch in der Lage ist, Peptide oder Proteine zu spalten.For the purposes of the present application, an enzyme is to be understood as meaning a protein which has a specific biocatalytic function. For the purposes of the present application, protease is understood as meaning an enzyme which catalyzes the hydrolysis of peptide bonds and is thereby able to cleave peptides or proteins.
Ein Protein ist im Sinne der vorliegenden Anmeldung ein aus den natürlichen Aminosäuren zusammengesetztes, weitgehend linear aufgebautes, zur Ausübung seiner Funktion zumeist eine
dreidimensionale Struktur annehmendes Polypeptid. Ein Peptid besteht aus Aminosäuren, die über Peptidbindungen miteinander kovalent verbunden sind. Die Bezeichnung Polypeptid verdeutlicht diesbezüglich den Sachverhalt, dass diese Peptidkette in der Regel aus vielen Aminosäuren besteht, die über Peptidbindungen miteinander verbunden sind. Aminosäuren können in einer L- und einer D-Konfiguration vorliegen, wobei die Aminosäuren, aus denen Proteine bestehen, in der L-Konfiguration vorliegen. Sie werden als proteinogene Aminosäuren bezeichnet. In der vorliegenden Anmeldung werden die proteinogenen, natürlich vorkommenden L-Aminosäuren mit den international gebräuchlichen 1- und 3-Buchstaben-Codes bezeichnet. Zahlreiche Proteine werden als sogenannte Präproteine, also zusammen mit einem Signalpeptid gebildet. Darunter ist dann der N-terminale Teil des Proteins zu verstehen, dessen Funktion zumeist darin besteht, die Ausschleusung des gebildeten Proteins aus der produzierenden Zelle in das Periplasma oder das umgebende Medium und/oder dessen korrekte Faltung zu gewährleisten. Anschließend wird das Signalpeptid unter natürlichen Bedigungen durch eine Signalpeptidase vom übrigen Protein abgespalten, so dass dieses seine eigentliche katalytische Aktivität ohne die zunächst vorhandenen N-terminalen Aminosäuren ausübt. Pro-Proteine sind inaktive Vorstufen von Proteinen. Deren Vorläufer mit Signalsequenz werden als Prä-Pro-Proteine bezeichnet. Für technische Anwendungen sind aufgrund ihrer enzymatischen Aktivität die maturen, d.h. reifen Peptide, d.h. die nach ihrer Herstellung prozessierten Enzyme gegenüber den Präproteinen bevorzugt. Die unter SEQ ID NO. 1 , SEQ ID NO. 2 und SEQ ID NO. 3 angegeben Sequenzen stellen daher jeweils die reife (mature) Protease dar. Die Proteine können von den sie produzierenden Zellen nach der Herstellung der Polypeptidkette modifiziert werden, beispielsweise durch Anknüpfung von Zuckermolekülen, Formylierungen, Aminierungen, usw. Solche Modifikationen werden als posttranslationale Modifikationen bezeichnet. Diese posttranslationalen Modifizierungen können, müssen jedoch nicht einen Einfluss auf die Funktion des Proteins ausüben.For the purposes of the present application, a protein is a largely linear composition composed of the natural amino acids and usually performs one of its functions three-dimensional structure accepting polypeptide. A peptide consists of amino acids that are covalently linked to each other via peptide bonds. The term polypeptide clarifies in this regard the fact that this peptide chain usually consists of many amino acids, which are connected to each other via peptide bonds. Amino acids may be in an L and a D configuration, with the amino acids that make up proteins in the L configuration. They are called proteinogenic amino acids. In the present application, the proteinogenic, naturally occurring L-amino acids are designated by the internationally used 1- and 3-letter codes. Numerous proteins are formed as so-called pre-proteins, ie together with a signal peptide. By this is meant the N-terminal part of the protein, the function of which is usually to ensure the discharge of the protein formed from the producing cell into the periplasm or the surrounding medium and / or its correct folding. Subsequently, the signal peptide is cleaved under natural conditions by a signal peptidase from the rest of the protein, so that this exerts its actual catalytic activity without the initially present N-terminal amino acids. Pro-proteins are inactive precursors of proteins. Their signal sequence precursors are referred to as pre-pro proteins. For technical applications, due to their enzymatic activity, the mature, ie mature, peptides, ie the enzymes processed after their preparation, are preferred over the preproteins. The SEQ ID NO. 1, SEQ ID NO. 2 and SEQ ID NO. The sequences can therefore be modified from the cells producing them after the production of the polypeptide chain, for example by attachment of sugar molecules, formylations, aminations, etc. Such modifications are referred to as post-translational modifications. These post-translational modifications may or may not have an effect on the function of the protein.
Durch Vergleich mit bekannten Enzymen, die beispielsweise in allgemein zugänglichen Datenbanken hinterlegt sind, lässt sich aus der Aminosäure- oder Nukleotid-Sequenz die enzymatische Aktivität eines betrachteten Enzyms folgern. Diese kann durch andere Bereiche des Proteins, die nicht an der eigentlichen Reaktion beteiligt sind, qualitativ oder quantitativ modifiziert werden. Dies könnte beispielsweise die Enzymstabilität, die Aktivität, die Reaktionsbedingungen oder die Substratspezifität betreffen.By comparison with known enzymes, which are deposited for example in generally accessible databases, the enzymatic activity of a considered enzyme can be deduced from the amino acid or nucleotide sequence. This can be qualitatively or quantitatively modified by other regions of the protein that are not involved in the actual reaction. This could, for example, relate to enzyme stability, activity, reaction conditions or substrate specificity.
Solch ein Vergleich geschieht dadurch, dass ähnliche Abfolgen in den Nukleotid- oder Aminosäuresequenzen der betrachteten Proteine einander zugeordnet werden. Dies nennt man Homologisierung. Eine tabellarische Zuordnung der betreffenden Positionen wird als Alignment bezeichnet. Bei der Analyse von Nukleotidsequenzen sind wiederum beide komplementären Stränge und jeweils allen drei möglichen Leserastern zu berücksichtigen; ebenso die Degeneriertheit des genetischen Codes und die organismenspezifische Verwendung der Codons
(Codon-Usage). Inzwischen werden Alignments über Computerprogramme erstellt, wie beispielsweise durch die Algorithmen FASTA oder BLAST; dieses Vorgehen wird beispielsweise von D. J. Lipman und W. R. Pearson (1985) in Science, Band 227, S. 1435-1441 beschrieben.Such a comparison is accomplished by associating similar sequences in the nucleotide or amino acid sequences of the proteins of interest. This is called homologization. A tabular assignment of the respective positions is referred to as alignment. In the analysis of nucleotide sequences, in turn, both complementary strands and all three possible reading frames are to be taken into account; as well the degeneracy of the genetic code and the organism specific use of the codons (Codon usage). Meanwhile, alignments are created using computer programs, such as the algorithms FASTA or BLAST; This procedure is described, for example, by DJ Lipman and WR Pearson (1985) in Science, Vol. 227, pp. 1435-1441.
Alle in der vorliegenden Patentanmeldung durchgeführten Sequenzvergleiche und Bestimmungen von Homologie- und/oder Identitätswerten wurden mit dem Computer-Programm Vector NTI® Suite 7.0, erhältlich von der Firma InforMax, Inc., Bethesda, USA, mit den vorgegebenen Default- Parametern durchgeführt.All carried out in the present application sequence comparisons and determinations of homology and / or identity values were performed using the computer program Vector NTI ® Suite 7.0, available from InforMax, Inc., Bethesda, USA with the preset default parameters.
Eine Zusammenstellung aller in den verglichenen Sequenzen übereinstimmenden Positionen wird als Konsensus-Sequenz bezeichnet.A summary of all matching positions in the compared sequences is called a consensus sequence.
Solch ein Vergleich erlaubt auch eine Aussage über die Ähnlichkeit oder Homologie der verglichenen Sequenzen zueinander. Diese wird in Prozent Identität, das heißt dem Anteil der identischen Nukleotide oder Aminosäurereste an denselben bzw. in einem Alignment einander entsprechenden Positionen wiedergegeben. Ein weiter gefaßter Homologiebegriff bezieht die konservierten Aminosäure-Austausche in diesen Wert mit ein. Es ist dann von Prozent Ähnlichkeit die Rede. Solche Aussagen können über ganze Proteine oder Gene oder nur über einzelne Bereiche getroffen werden.Such a comparison also allows a statement about the similarity or homology of the compared sequences to each other. This is represented in percent identity, that is the proportion of identical nucleotides or amino acid residues at the same or in an alignment corresponding positions. A broader concept of homology includes the conserved amino acid substitutions in this value. It then speaks of percent similarity. Such statements can be made about whole proteins or genes or only over individual areas.
Homologe Bereiche von verschiedenen Proteinen sind durch Übereinstimmungen in der Aminosäuresequenz definiert. Diese können auch durch identische Funktion gekennzeichnet sein. Sie geht bis zu völligen Identitäten in kleinsten Bereichen, sogenannten Boxen, die nur wenige Aminosäuren umfassen und meist für die Gesamtaktivität essentielle Funktionen ausüben. Unter den Funktionen der homologen Bereiche sind kleinste Teilfunktionen der vom gesamten Protein ausgeübten Funktion zu verstehen, wie beispielsweise die Ausbildung einzelner Wasserstoffbrückenbindungen zur Komplexierung eines Substrats oder Übergangskomplexes.Homologous regions of different proteins are defined by matches in amino acid sequence. These can also be identified by identical function. It goes as far as complete identities in the smallest areas, so-called boxes, which contain only a few amino acids and usually perform essential functions for the overall activity. The functions of the homologous regions are to be understood as the smallest partial functions of the function carried out by the entire protein, such as, for example, the formation of individual hydrogen bonds for the complexation of a substrate or transition complex.
Proteasen bzw. Enzyme im allgemeinen können durch verschiedene Verfahren, z.B. gezielte genetische Veränderung durch Mutageneseverfahren, weiterentwickelt und für bestimmte Einsatzzwecke oder hinsichtlich spezieller Eigenschaften, beispielsweise katalytische Aktivität, Stabilität, usw., optimiert werden.Proteases or enzymes in general can be prepared by various methods, e.g. targeted genetic modification by mutagenesis, further developed and optimized for specific uses or specific properties such as catalytic activity, stability, etc.
Es ist aus dem Stand der Technik weiterhin allgemein bekannt, dass sich vorteilhafte Eigenschaften einzelner Mutationen, z.B. einzelner Punktmutationen, ergänzen können. Eine hinsichtlich bestimmter Eigenschaften bereits optimierte Protease, zum Beispiel hinsichtlich ihrer
Stabilität gegenüber Tensiden oder anderen Komponenten, kann erfindungsgemäß zusätzlich weiterentwickelt werden.It is furthermore generally known from the prior art that advantageous properties of individual mutations, for example individual point mutations, can complement one another. A protease already optimized with regard to certain properties, for example with regard to its properties Stability to surfactants or other components can be further developed according to the invention.
Unter Fragmenten werden alle Proteine oder Peptide verstanden, die kleiner sind als natürliche Proteine und beispielsweise auch synthetisch erhalten werden können. Aufgrund ihrer Aminosäuresequenzen können sie den betreffenden vollständigen Proteinen zugeordnet werden. Sie können beispielsweise gleiche Strukturen annehmen oder proteolytische Aktivitäten oder Teilaktivitäten ausüben, wie beispielsweise die Komplexierung eines Substrats. Fragmente und Deletionsvarianten von Ausgangsproteinen sind prinzipiell gleichartig; während Fragmente eher kleinere Bruchstücke darstellen, fehlen den Deletionsmutanten eher nur kurze Bereiche, und damit nur einzelne Teilfunktionen.Fragments are understood as meaning all proteins or peptides which are smaller than natural proteins and, for example, can be obtained synthetically. Due to their amino acid sequences, they can be assigned to the relevant complete proteins. For example, they may adopt the same structures or perform proteolytic or partial activities, such as the complexation of a substrate. Fragments and deletion variants of starting proteins are in principle similar; while fragments tend to be smaller fragments, the deletion mutants tend to lack only short regions, and thus only individual subfunctions.
Unter Chimären oder hybriden Proteinen sind im Sinne der vorliegenden Anmeldung solche Proteine zu verstehen, deren Sequenz die Sequenzen oder Teilsequenzen von mindestens zwei Ausgangsproteinen umfasst. Die Ausgangsproteine können diesbezüglich aus verschiedenen oder aus demselben Organismus stammen. Chimäre oder hybride Proteine können beispielsweise durch Rekombinationsmutagenese erhalten werden. Der Sinn einer solchen Rekombination kann beispielsweise darin bestehen, mithilfe des heranfusionierten Proteinteils eine bestimmte enzymatische Funktion herbeizuführen oder zu modifizieren. Es ist dabei im Sinne der vorliegenden Erfindung unwesentlich, ob solch ein chimäres Protein aus einer einzelnen Polypeptidkette oder mehreren Untereinheiten besteht, auf weiche sich unterschiedliche Funktionen verteilen können.For the purposes of the present application, chimeras or hybrid proteins are to be understood as meaning those proteins whose sequence comprises the sequences or partial sequences of at least two starting proteins. The source proteins may be derived from different or from the same organism. Chimeric or hybrid proteins may be obtained, for example, by recombinant mutagenesis. For example, the purpose of such recombination may be to induce or modify a particular enzymatic function using the fused protein portion. For the purposes of the present invention, it is irrelevant whether such a chimeric protein consists of a single polypeptide chain or several subunits on which different functions can be distributed.
Unter durch Insertionsmutation erhaltene Proteine sind solche Varianten zu verstehen, die durch Einfügen eines Proteinfragments in die Ausgangssequenzen erhalten worden sind. Sie sind ihrer prinzipiellen Gleichartigkeit wegen den Chimären Proteinen zuzuordnen. Sie unterscheiden sich von jenen lediglich im Größenverhältnis des unveränderten Proteinteils zur Größe des gesamten Proteins. In solchen insertionsmutierten Proteinen ist der Anteil an Fremdprotein geringer als in Chimären Proteinen.By proteins obtained by insertion mutation are meant those variants obtained by inserting a protein fragment into the starting sequences. They are due to their principle similarity to the chimeric proteins. They differ from those only in the size ratio of the unchanged protein part to the size of the entire protein. In such insertionsmutierten proteins, the proportion of foreign protein is lower than in chimeric proteins.
Inversionsmutagenese, also eine partielle Sequenzumkehrung, kann als Sonderform sowohl der Deletion, als auch der Insertion angesehen werden. Dasselbe gilt für eine von der ursprünglichen Aminosäureabfolge abweichende Neugruppierung verschiedener Molekülteile. Sie kann sowohl als Deletionsvariante, als Insertionsvariante, als auch als Shuffling-Variante des ursprünglichen Proteins angesehen werden.
Unter Derivaten werden im Sinne der vorliegenden Anmeldung solche Proteine verstanden, deren reine Aminosäurekette chemisch modifiziert worden ist. Solche Derivatisierungen können beispielsweise biologisch im Zusammenhang mit der Proteinbiosynthese durch die Wirtszelle erfolgen. Hierfür können molekularbiologische Methoden eingesetzt werden. Sie können aber auch chemisch durchgeführt werden, etwa durch die chemische Umwandlung einer Seitenkette einer Aminosäure oder durch kovalente Bindung einer anderen Verbindung an das Protein. Bei solch einer Verbindung kann es sich beispielsweise auch um andere Proteine handeln, die beispielsweise über bifunktionelle chemische Verbindungen an erfindungsgemäße Proteine gebunden werden. Derartige Modifizierungen können beispielsweise die Substratspezifität oder die Bindungsstärke an das Substrat beeinflussen oder eine vorübergehende Blockierung der enzymatischen Aktivität herbeiführen, wenn es sich bei der angekoppelten Substanz um einen Inhibitor handelt. Dies kann beispielsweise für den Zeitraum der Lagerung sinnvoll sein. Ebenso ist unter Derivatisierung die kovalente Bindung an einen makromolekularen Träger zu verstehen, genauso wie auch ein nichtkovalenter Einschluss in geeignete makromolekulare Käfigstrukturen.Inversion mutagenesis, ie a partial sequence reversal, can be regarded as a special form of both the deletion and the insertion. The same applies to a new grouping of different parts of the molecule which deviates from the original amino acid sequence. It can be regarded as a deletion variant, as an insertion variant, as well as a shuffling variant of the original protein. For the purposes of the present application, derivatives are understood as meaning those proteins whose pure amino acid chain has been chemically modified. Such derivatizations can be carried out, for example, biologically in connection with protein biosynthesis by the host cell. For this molecular biological methods can be used. However, they can also be carried out chemically, for example by the chemical transformation of a side chain of an amino acid or by covalent binding of another compound to the protein. Such a compound may, for example, also be other proteins which are bound, for example via bifunctional chemical compounds, to proteins according to the invention. Such modifications 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. Also, derivatization is understood to mean covalent attachment to a macromolecular carrier, as well as noncovalent inclusion in suitable macromolecular cage structures.
In einer weiteren Ausführungsform der Erfindung ist das Mittel somit dadurch gekennzeichnet, dass die erste Protease in dem Mittel als Fragment, Deletionsvariante, chimäres Protein oder Derivat vorliegt und/oder die zweite Protease in dem Mittel als Fragment, Deletionsvariante, chimäres Protein oder Derivat vorliegt, wobei die erste und die zweite Protease weiterhin katalytisch aktiv sind.In a further embodiment of the invention, the agent is thus characterized in that the first protease is present in the agent as fragment, deletion variant, chimeric protein or derivative and / or the second protease is present in the agent as a fragment, deletion variant, chimeric protein or derivative, wherein the first and second proteases are still catalytically active.
Im Sinne der vorliegenden Erfindung werden alle Enzyme, Proteine, Fragmente, chimäre Proteine und Derivate, sofern sie nicht explizit als solche angesprochen zu werden brauchen, unter dem Oberbegriff Proteine zusammengefaßt.For the purposes of the present invention, all enzymes, proteins, fragments, chimeric proteins and derivatives, unless they need to be addressed explicitly as such, are summarized under the generic term proteins.
Erfindungsgemäße Mittel umfassen alle Arten von Mitteln, insbesondere Gemische, Rezepturen, Lösungen etc., deren Einsetzbarkeit durch Zugabe der oben beschriebenen Proteasen verbessert wird. Es kann sich dabei je nach Einsatzgebiet beispielsweise um feste Gemische, beispielsweise Pulver mit gefriergetrockeneten oder verkapselten Proteinen, oder um gelförmige oder flüssige Mittel handeln. Bevorzugte Rezepturen enthalten beispielsweise Puffersubstanzen, Stabilisatoren, Reaktionspartner und/oder Cofaktoren der Proteasen und/oder andere mit den Proteasen synergistische Inhaltsstoffe. Insbesondere sind darunter Mittel für die weiter unten ausgeführten Einsatzgebiete zu verstehen. Weitere Einsatzgebiete gehen aus dem Stand der Technik hervor und werden beispielsweise in dem Handbuch „Industrial enyzmes and their applications" von H. Uhlig, Wiley-Verlag, New York, 1998 dargestellt.
In bevorzugten Ausführungsformen der Erfindung ist ein erfindungsgemäßes Mittel dadurch gekennzeichnet, dass es ein Waschmittel, Handwaschmittel, Spülmittel, Handgeschirrspülmittel, Maschinengeschirrspülmittel, Reinigungsmittel, Zahnprothesen- oder Kontaktlinsenpflegemittel, Nachspülmittel, Desinfektionsmittel, kosmetisches Mittel, pharmazeutisches Mittel oder ein Mittel zur Behandlung von Filtermedien, Textilien, Pelzen, Papier, Fellen oder Leder, ist, insbesondere ein Wäschewaschmittel oder ein Geschirrspülmittel.Compositions according to the invention include all types of agents, in particular mixtures, formulations, solutions, etc., whose applicability is improved by addition of the proteases described above. Depending on the field of application, these may be, for example, solid mixtures, for example powders with freeze-dried or encapsulated proteins, or gel or liquid agents. Preferred formulations contain, for example, buffer substances, stabilizers, reaction partners and / or cofactors of the proteases and / or other ingredients synergistic with the proteases. In particular, this appropriation is to be understood as the areas of application set out below. Further fields of application emerge from the prior art and are described, for example, in the manual "Industrial Enzymes and their Applications" by H. Uhlig, Wiley-Verlag, New York, 1998. In preferred embodiments of the invention, an agent according to the invention is characterized in that it comprises a detergent, hand washing detergent, dishwashing detergent, hand dishwashing detergent, machine dishwashing detergent, cleaning agent, denture or contact lens care agent, rinse aid, disinfectant, cosmetic agent, pharmaceutical agent or a means for treating filter media, textiles , Furs, paper, skins or leather, especially a laundry detergent or dishwashing detergent.
Zu diesem Erfindungsgegenstand zählen alle denkbaren Wasch- bzw. Reinigungsmittelarten, sowohl Konzentrate als auch unverdünnt anzuwendende Mittel, zum Einsatz im kommerziellen Maßstab, in der Waschmaschine oder bei der Hand-Wäsche beziehungsweise -Reinigung. Dazu gehören beispielsweise Waschmittel für Textilien, Teppiche, oder Naturfasern, für die nach der vorliegenden Erfindung die Bezeichnung Waschmittel verwendet wird. Dazu gehören beispiels weise auch Geschirrspülmittel für Geschirrspülmaschinen oder manuelle Geschirrspülmittel oder Reiniger für harte Oberflächen wie Metall, Glas, Porzellan, Keramik, Kacheln, Stein, lackierte Oberflächen, Kunststoffe, Holz oder Leder; für solche wird nach der vorliegenden Erfindung die Bezeichnung Reinigungsmittel verwendet.This invention includes all conceivable types of detergents or cleaners, both concentrates and undiluted agents to be used on a commercial scale, in the washing machine or in hand washing or cleaning. These include, for example, detergents for textiles, carpets, or natural fibers, for which according to the present invention the term laundry detergent is used. 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 such according to the present invention, the term cleaning agent is used.
Ein erfindungsgemäßes Mittel kann sowohl ein Mittel für Großverbraucher oder technische Anwender als auch ein Produkt für den Privatverbraucher sein, wobei alle im Stand der Technik etablierten Wasch- und Reinigungsmittelarten ebenfalls Ausführungsformen der vorliegenden Erfindung darstellen.An agent according to the invention can be either a means for large consumers or technical users as well as a product for the private consumer, wherein all types of detergents and cleaning agents established in the prior art also constitute embodiments of the present invention.
Die erfindungsgemäßen Wasch- oder Reinigungsmittel, die als insbesondere pulverförmige Feststoffe, in nachverdichteter Teilchenform, als homogene Lösungen oder Suspensionen vorliegen können, können außer dem erfindungsgemäß eingesetzten Wirkstoff - einer erfindungsgemäßen Proteasekombination - im Prinzip alle bekannten und in derartigen Mitteln üblichen Inhaltsstoffe enthalten, wobei mindestens ein weiterer Inhaltsstoff in dem Mittel vorhanden ist. Die erfindungsgemäßen Mittel können insbesondere Buildersubstanzen, oberflächenaktive Tenside, Bleichmittel auf Basis organischer und/oder anorganischer Persauerstoffverbindungen, Bleichaktivatoren, wassermischbare organische Lösungsmittel, Enzyme, Sequestrierungsmittel, Elektrolyte, pH-Regulatoren und weitere Hilfsstoffe wie optische Aufheller, Vergrauungsinhibitoren, Schaumregulatoren sowie Färb- und Duftstoffe sowie Kombinationen hiervon enthalten.The detergents or cleaning agents according to the invention, which may be in the form of homogeneous solutions or suspensions, especially in powdered solids, may contain, in addition to the active ingredient used according to the invention - a protease combination according to the invention - in principle all known and conventional ingredients in such agents, wherein at least another ingredient is present in the agent. 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, water-miscible organic solvents, enzymes, sequestering agents, electrolytes, pH regulators and other auxiliaries such as optical brighteners, grayness inhibitors, foam regulators and dyes and fragrances and combinations thereof.
Insbesondere eine Kombination der Proteasekombination mit einem oder mehreren weiteren lnhaltsstoff(en) der Mittel erweist sich als vorteilhaft, da ein solches Mittel eine verbesserte Reinigungsleistung durch sich ergebende Synergismen, insbesondere zwischen einer Protease bzw. der Proteasekombination und dem weiteren Inhaltsstoff, aufweist. Dies bedeutet, dass das Mittel eine verbesserte Entfernung von Anschmutzungen, beispielsweise proteinhaltigen
Anschmutzungen, bewirkt im Vergleich mit einem Mittel, welches entweder nur eine der beiden Komponenten beinhaltet, oder auch im Vergleich zur erwarteten Reinigungsleistung eines Mittels mit beiden Komponenten auf Grund der bloßen Addition der jeweiligen Einzelbeiträge dieser beiden Komponenten zur Reinigungsleistung des Mittels. Insbesondere durch die Kombination einer erfindungsgemäßen Protease bzw. Proteasekombination mit einem der nachfolgend beschriebenen Tenside und/oder Buildersubstanzen und/oder Bleichmittel wird ein solcher Synergismus erreicht.In particular, a combination of the protease combination with one or more other ingredients of the compositions proves to be advantageous since such an agent has an improved cleaning performance by resulting synergisms, in particular between a protease or the protease combination and the further ingredient. This means that the agent provides improved removal of stains, such as proteinaceous Stains caused in comparison with an agent which either contains only one of the two components, or even compared to the expected cleaning performance of an agent with both components due to the mere addition of the respective individual contributions of these two components to the cleaning performance of the agent. Such a synergism is achieved, in particular, by the combination of a protease or protease combination according to the invention with one of the surfactants and / or builders and / or bleaches described below.
Die erfindungsgemäßen Mittel können ein Tensid oder mehrere Tenside enthalten, wobei insbesondere anionische Tenside, nichtionische Tenside und deren Gemische, aber auch kationische, zwitterionische und amphotere Tenside in Frage kommen.The compositions according to the invention may comprise one or more surfactants, in particular anionic surfactants, nonionic surfactants and mixtures thereof, but also cationic, zwitterionic and amphoteric surfactants.
Geeignete nichtionische Tenside sind insbesondere Alkylglykoside und Ethoxylierungs- und/oder Propoxylierungsprodukte von Alkylglykosiden oder linearen oder verzweigten Alkoholen mit jeweils 12 bis 18 C-Atomen im Alkylteil und 3 bis 20, vorzugsweise 4 bis 10 Alkylethergruppen. Weiterhin sind entsprechende Ethoxylierungs- und/oder Propoxylierungsprodukte von N-Alkyl-aminen, vicinalen Diolen, Fettsäureestern und Fettsäureamiden, die hinsichtlich des Alkylteils den genannten langkettigen Alkoholderivaten entsprechen, sowie von Alkylphenolen mit 5 bis 12 C- Atomen im Alkylrest brauchbar.Suitable nonionic surfactants are in particular alkyl glycosides and ethoxylation and / or propoxylation of alkyl glycosides or linear or branched alcohols each having 12 to 18 carbon atoms in the alkyl moiety and 3 to 20, preferably 4 to 10 alkyl ether groups. Furthermore, corresponding ethoxylation and / or propoxylation of N-alkyl-amines, vicinal diols, fatty acid esters and fatty acid amides, which correspond to said long-chain alcohol derivatives with respect to the alkyl moiety, and of alkylphenols having 5 to 12 carbon atoms in the alkyl radical.
Als nichtionische Tenside werden vorzugsweise alkoxylierte, vorteilhafterweise ethoxylierte, insbesondere primäre Alkohole mit vorzugsweise 8 bis 18 C-Atomen und durchschnittlich 1 bis 12 Mol Ethylenoxid (EO) pro Mol Alkohol eingesetzt, in denen der Alkoholrest linear oder bevorzugt in 2-Stellung methylverzweigt sein kann beziehungsweise lineare und methylverzweigte Reste im Gemisch enthalten kann, so wie sie üblicherweise in Oxoalkoholresten vorliegen. Insbesondere sind jedoch Alkoholethoxylate mit linearen Resten aus Alkoholen nativen Ursprungs mit 12 bis 18 C-Atomen, z.B. aus Kokos-, Palm-, Taigfett- oder Oleylalkohol, und durchschnittlich 2 bis 8 EO pro Mol Alkohol bevorzugt. Zu den bevorzugten ethoxylierten Alkoholen gehören beispielsweise Ci2- Ci4-Alkohole mit 3 EO oder 4 EO, C9-Ci i-Alkohole mit 7 EO, Ci3-Ci5-Alkohole mit 3 EO, 5 EO, 7 EO oder 8 EO, Ci2-Ci8-Alkohole mit 3 EO, 5 EO oder 7 EO und Mischungen aus diesen, wie Mischungen aus Ci2-Ci4-Alkohol mit 3 EO und Ci2-Ci8-Alkohol mit 7 EO. Die angegebenen Ethoxylierungsgrade stellen statistische Mittelwerte dar, die für ein spezielles Produkt eine ganze oder eine gebrochene Zahl sein können. Bevorzugte Alkoholethoxylate weisen eine eingeengte Homologenverteilung auf (narrow ränge ethoxylates, NRE). Zusätzlich zu diesen nichtionischen Tensiden können auch Fettalkohole mit mehr als 12 EO eingesetzt werden. Beispiele hierfür sind (TaIg-) Fettalkohole mit 14 EO, 16 EO, 20 EO, 25 EO, 30 EO oder 40 EO. Insbesondere in Mitteln für den Einsatz in maschinellen Verfahren werden üblicherweise extrem schaumarme Verbindungen eingesetzt. Hierzu zählen vorzugsweise Ci2-Ci8-Alkylpolyethylenglykol-
polypropylenglykolether mit jeweils bei zu 8 Mol Ethylenoxid- und Propylenoxideinheiten im Molekül. Man kann aber auch andere bekannt schaumarme nichtionische Tenside verwenden, wie zum Beispiel C^-C-is-Alkylpolyethylenglykol-polybutylenglykolether mit jeweils bis zu 8 Mol Ethylenoxid- und Butylenoxideinheiten im Molekül sowie endgruppenverschlossene Alkylpolyalkylenglykol- mischether. Besonders bevorzugt sind auch die hydroxylgruppenhaltigen alkoxylierten Alkohole, wie sie in der europäischen Patentanmeldung EP 0 300 305 beschrieben sind, sogenannte Hydroxymischether. Zu den nichtionischen Tensiden zählen auch Alkylglykoside der allgemeinen Formel RO(G)x eingesetzt werden, in der R einen primären geradkettigen oder methylverzweigten, insbesondere in 2-Stellung methylverzweigten aliphatischen Rest mit 8 bis 22, vorzugsweise 12 bis 18 C-Atomen bedeutet und G für eine Glykoseeinheit mit 5 oder 6 C-Atomen, vorzugsweise für Glucose, steht. Der Oligomerisierungsgrad x, der die Verteilung von Monoglykosiden und Oligoglykosiden angibt, ist eine beliebige Zahl - die als analytisch zu bestimmende Größe auch gebrochene Werte annehmen kann - zwischen 1 und 10; vorzugsweise liegt x bei 1 ,2 bis 1 ,4. Ebenfalls geeignet sind Polyhydroxyfettsäureamide der Formel (III), in der R1CO für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen, R2 für Wasserstoff, einen Alkyl- oder Hydroxyalkylrest mit 1 bis 4 Kohlenstoffatomen und [Z] für einen linearen oder verzweigten Polyhydroxyalkylrest mit 3 bis 10 Kohlenstoffatomen und 3 bis 10 Hydroxylgruppen steht:The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as they are usually present in Oxoalkoholresten. In particular, however, alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred. Preferred ethoxylated alcohols include, for example, Ci 2 - C 4 alcohols containing 3 EO or 4 EO, C 9 -C i-alcohols containing 7 EO, C 3 -C 5 alcohols containing 3 EO, 5 EO, 7 EO or 8 EO, Ci 2 -Ci 8 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of Ci 2 -Ci 4 alcohol with 3 EO and Ci 2 -Ci 8 alcohol with 7 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). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples of these are (TaIg) fatty alcohols with 14 EO, 16 EO, 20 EO, 25 EO, 30 EO or 40 EO. In particular, agents for use in mechanical processes usually extremely low-foam compounds are used. These preferably include C 2 -C 8 -Alkylpolyethylenglykol- polypropylene glycol ethers, each containing up to 8 moles of ethylene oxide and propylene oxide units in the molecule. However, it is also possible to use other known low-foam nonionic surfactants, such as, for example, C 1 -C 6 -alkylpolyethyleneglycol-polybutylene glycol ethers having up to 8 mol of ethylene oxide and butylene oxide units in the molecule and end-capped alkylpolyalkylene glycol mixed ethers. Also particularly preferred are the hydroxyl-containing alkoxylated alcohols, as described in European Patent Application EP 0 300 305, so-called hydroxy mixed ethers. The nonionic surfactants also include alkyl glycosides of the general formula RO (G) x in which R is a primary straight-chain or methyl-branched, in particular 2-methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G represents a glycose unit having 5 or 6 C atoms, preferably glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is an arbitrary number - which, as a variable to be determined analytically, may also assume fractional values - between 1 and 10; preferably x is 1, 2 to 1, 4. Also suitable are polyhydroxy fatty acid amides of the formula (III) in which R 1 CO is an aliphatic acyl radical having 6 to 22 carbon atoms, R 2 is hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups:
R2 R 2
R1-CO-N-[Z] (III)R 1 -CO-N- [Z] (III)
Vorzugsweise leiten sich die Polyhydroxyfettsäureamide von reduzierenden Zuckern mit 5 oder 6 Kohlenstoffatomen, insbesondere von der Glucose ab. Zur Gruppe der Polyhydroxyfettsäureamide gehören auch Verbindungen der Formel (IV),The polyhydroxy fatty acid amides are preferably derived from reducing sugars having 5 or 6 carbon atoms, in particular from glucose. The group of polyhydroxy fatty acid amides also includes compounds of the formula (IV)
R4-O-R5 I (IV)R 4 -OR 5 I (IV)
R3-CO-N-[Z]R 3 -CO-N- [Z]
in der R3 für einen linearen oder verzweigten Alkyl- oder Alkenylrest mit 7 bis 12 Kohlenstoffatomen, R4 für einen linearen, verzweigten oder cyclischen Alkylenrest oder einen Arylenrest mit 2 bis 8 Kohlenstoffatomen und R5 für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest oder einen Oxy-Alkylrest mit 1 bis 8 Kohlenstoffatomen steht, wobei d-C4-Alkyl- oder Phenylreste bevorzugt sind, und [Z] für einen linearen Polyhydroxyalkylrest, dessen Alkylkette mit mindestens zwei Hydroxylgruppen substituiert ist, oder alkoxylierte, vorzugsweise ethoxylierte oder propoxylierte Derivate dieses Restes steht. [Z] wird auch hier vorzugsweise durch reduktive Aminierung eines Zuckers wie Glucose, Fructose, Maltose, Lactose, Galactose, Mannose oder
Xylose erhalten. Die N-Alkoxy- oder N-Aryloxy-substituierten Verbindungen können dann beispielsweise durch Umsetzung mit Fettsäuremethylestern in Gegenwart eines Alkoxids als Katalysator in die gewünschten Polyhydroxyfettsäureamide überführt werden. Eine weitere Klasse bevorzugt eingesetzter nichtionischer Tenside, die entweder als alleiniges nichtionisches Tensid oder in Kombination mit anderen nichtionischen Tensiden, insbesondere zusammen mit alkoxylierten Fettalkoholen und/oder Alkylglykosiden, eingesetzt werden, sind alkoxylierte, vorzugsweise ethoxylierte oder ethoxylierte und propoxylierte Fettsäurealkylester, vorzugsweise mit 1 bis 4 Kohlenstoffatomen in der Alkylkette, insbesondere Fettsäuremethylester. Auch nichtionische Tenside vom Typ der Aminoxide, beispielsweise N-Kokosalkyl-N,N-dimethylaminoxid und N-Talgalkyl-N,N-dihydroxyethylaminoxid, und der Fettsäurealkanolamide können geeignet sein. Die Menge dieser nichtionischen Tenside beträgt vorzugsweise nicht mehr als die der ethoxylierten Fettalkohole, insbesondere nicht mehr als die Hälfte davon. Als weitere Tenside kommen sogenannte Gemini-Tenside in Betracht. Hierunter werden im Allgemeinen solche Verbindungen verstanden, die zwei hydrophile Gruppen pro Molekül besitzen. Diese Gruppen sind in der Regel durch einen sogenannten "Spacer" voneinander getrennt. Dieser Spacer ist in der Regel eine Kohlenstoffkette, die lang genug sein sollte, dass die hydrophilen Gruppen einen ausreichenden Abstand haben, damit sie unabhängig voneinander agieren können. Derartige Tenside zeichnen sich im Allgemeinen durch eine ungewöhnlich geringe kritische Micell- konzentration und die Fähigkeit, die Oberflächenspannung des Wassers stark zu reduzieren, aus. In Ausnahmefällen werden unter dem Ausdruck Gemini-Tenside nicht nur derartig "dimere", sondern auch entsprechend "trimere" Tenside verstanden. Geeignete Gemini-Tenside sind beispielsweise sulfatierte Hydroxymischether oder Dimeralkohol-bis- und Trimeralkohol-tris-sulfate und -ethersulfate. Endgruppenverschlossene dimere und trimere Mischether zeichnen sich insbesondere durch ihre Bi- und Multifunktionalität aus. So besitzen die genannten endgruppenverschlossenen Tenside gute Netzeigenschaften und sind dabei schaumarm, so dass sie sich insbesondere für den Einsatz in maschinellen Wasch- oder Reinigungsverfahren eignen. Eingesetzt werden können aber auch Gemini-Polyhydroxyfettsäureamide oder Poly-Polyhydroxy- fettsäureamide. Geeignet sind auch die Schwefelsäuremonoester der mit 1 bis 6 Mol Ethylenoxid ethoxylierten geradkettigen oder verzweigten C7-C2i-Alkohole, wie 2-Methylverzweigte C9-Cn- Alkohole mit im Durchschnitt 3,5 Mol Ethylenoxid (EO) oder Ci2-Ci8-Fettalkohole mit 1 bis 4 EO. Zu den bevorzugten Aniontensiden gehören auch die Salze der Alkylsulfobernsteinsäure, die auch als Sulfosuccinate oder als Sulfobernsteinsäureester bezeichnet werden, und die Monoester und/oder Diester der Sulfobernsteinsäure mit Alkoholen, vorzugsweise Fettalkoholen und insbesondere ethoxylierten Fettalkoholen darstellen. Bevorzugte Sulfosuccinate enthalten C8- bis C18- Fettalkoholreste oder Mischungen aus diesen. Insbesondere bevorzugte Sulfosuccinate enthalten einen Fettalkoholrest, der sich von ethoxylierten Fettalkoholen ableitet, die für sich betrachtet nichtionische Tenside darstellen. Dabei sind wiederum Sulfosuccinate, deren Fettalkohol-Reste sich von ethoxylierten Fettalkoholen mit eingeengter Homologenverteilung ableiten, besonders
bevorzugt. Ebenso ist es auch möglich, Alk(en)ylbernsteinsäure mit vorzugsweise 8 bis 18 Kohlenstoffatomen in der Alk(en)ylkette oder deren Salze einzusetzen. Als weitere anionische Tenside kommen Fettsäure-Derivate von Aminosäuren, beispielsweise von N-Methyltaurin (Tauride) und/oder von N-Methylglycin (Sarkoside) in Betracht. Insbesondere bevorzugt sind dabei die Sarkoside beziehungsweise die Sarkosinate und hier vor allem Sarkosinate von höheren und gegebenenfalls einfach oder mehrfach ungesättigten Fettsäuren wie Oleylsarkosinat. Als weitere anionische Tenside kommen insbesondere Seifen in Betracht. Geeignet sind insbesondere gesättigte Fettsäureseifen, wie die Salze der Laurinsäure, Myristinsäure, Palmitinsäure, Stearinsäure, hydrierten Erucasäure und Behensäure sowie insbesondere aus natürlichen Fettsäuren, zum Beispiel Kokos-, Palmkern- oder Taigfettsäuren, abgeleitete Seifengemische. Zusammen mit diesen Seifen oder als Ersatzmittel für Seifen können auch die bekannten Alkenylbernsteinsäuresalze eingesetzt werden.in the R 3 is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R 4 is a linear, branched or cyclic alkylene radical or an arylene radical having 2 to 8 carbon atoms and R 5 is a linear, branched or cyclic alkyl radical or a Aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, wherein dC 4 alkyl or phenyl radicals are preferred, and [Z] is a linear polyhydroxyalkyl radical whose alkyl chain is substituted with at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives this rest stands. [Z] is also here preferably by reductive amination of a sugar such as glucose, fructose, maltose, lactose, galactose, mannose or Get xylose. The N-alkoxy- or N-aryloxy-substituted compounds can then be converted into the desired polyhydroxy fatty acid amides, for example by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst. Another class of preferred nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants, in particular together with alkoxylated fatty alcohols and / or alkyl glycosides, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably from 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl ester. Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides 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. Other suitable surfactants are so-called gemini surfactants. These are generally understood as meaning those compounds which have two hydrophilic groups per molecule. These groups are usually separated by a so-called "spacer". This spacer is typically a carbon chain that should be long enough for the hydrophilic groups to be spaced sufficiently apart for them to act independently of each other. Such surfactants are generally characterized by an unusually low critical micelle concentration and the ability to greatly reduce the surface tension of the water. In exceptional cases, the term gemini surfactants not only such "dimer", but also corresponding to "trimeric" surfactants understood. Suitable gemini surfactants are, for example, sulfated hydroxy mixed ethers or dimer alcohol bis and trimer alcohol tris sulfates and ether sulfates. End-capped dimeric and trimeric mixed ethers are characterized in particular by their bi- and multi-functionality. Thus, the end-capped surfactants mentioned have good wetting properties and are low foaming, so that they are particularly suitable for use in machine washing or cleaning processes. However, it is also possible to use gemini-polyhydroxy fatty acid amides or poly-polyhydroxy fatty acid amides. Also suitable are the Schwefelsäuremonoester the ethoxylated with 1 to 6 moles of ethylene oxide, linear or branched C 7 -C 2 i-alcohols such as 2-methyl-branched C 9 -CN alcohols containing on average 3.5 mol ethylene oxide (EO) or C 2 - Ci 8 fatty alcohols with 1 to 4 EO. The preferred anionic surfactants also include the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters, and the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain C 8 - to C 18 - fatty alcohol residues or mixtures of these. Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols, which by themselves are nonionic surfactants. Sulfosuccinates, whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are particularly important prefers. Likewise, it is also possible to use alk (en) ylsuccinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof. Suitable further anionic surfactants are fatty acid derivatives of amino acids, for example N-methyltaurine (Tauride) and / or N-methylglycine (sarcosides). Particularly preferred are the sarcosides or the sarcosinates and here especially sarcosinates of higher and optionally monounsaturated or polyunsaturated fatty acids such as oleyl sarcosinate. As further anionic surfactants are particularly soaps into consideration. Particularly 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. Together with these soaps or as a substitute for soaps, it is also possible to use the known alkenylsuccinic acid salts.
Die anionischen Tenside, einschließlich der Seifen, können in Form ihrer Natrium-, Kalium- oder Ammoniumsalze sowie als lösliche Salze organischer Basen, wie Mono-, Di- oder Triethanolamin, vorliegen. Vorzugsweise liegen die anionischen Tenside in Form ihrer Natrium- oder Kaliumsalze, insbesondere in Form der Natriumsalze vor.The anionic surfactants, including soaps, may be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine. The anionic surfactants are preferably present in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
Tenside sind in erfindungsgemäßen Mitteln in Mengenanteilen von vorzugsweise 5 Gew.-% bis 50 Gew.-%, insbesondere von 8 Gew.-% bis 30 Gew.-%, enthalten.Surfactants are present in inventive compositions in proportions of preferably 5 wt .-% to 50 wt .-%, in particular from 8 wt .-% to 30 wt .-%.
Ein erfindungsgemäßes Mittel enthält vorzugsweise mindestens einen wasserlöslichen und/oder wasserunlöslichen, organischen und/oder anorganischen Builder. Zu den wasserlöslichen organischen Buildersubstanzen gehören Polycarbonsäuren, insbesondere Citronensäure und Zuckersäuren, monomere und polymere Aminopolycarbonsäuren, insbesondere Methylglycin- diessigsäure, Nitrilotriessigsäure und Ethylendiamintetraessigsäure sowie Polyasparaginsäure, Polyphosphonsäuren, insbesondere Aminotris(methylenphosphonsäure), Ethylendiamintetra- kis(methylenphosphonsäure) und 1-Hydroxyethan-1 ,1-diphosphonsäure, polymere Hydroxy- verbindungen wie Dextrin sowie polymere (Poly-)carbonsäuren, insbesondere die durch Oxidation von Polysacchariden beziehungsweise Dextrinen zugänglichen Polycarboxylate, polymere Acryl- säuren, Methacrylsäuren, Maleinsäuren und Mischpolymere aus diesen, die auch geringe Anteile polymerisierbarer Substanzen ohne Carbonsäurefunktionalität einpolymerisiert enthalten können. Die relative Molekülmasse der Homopolymeren ungesättiger Carbonsäuren liegt im allgemeinen zwischen 3 000 und 200 000, die der Copolymeren zwischen 2 000 und 200 000, vorzugsweise 30 000 bis 120 000, jeweils bezogen auf freie Säure. Ein besonders bevorzugtes Acrylsäure- Maleinsäure-Copolymer weist eine relative Molekülmasse von 30 000 bis 100 000 auf. Handelsübliche Produkte sind zum Beispiel Sokalan® CP 5, CP 10 und PA 30 der Firma BASF. Geeignete, wenn auch weniger bevorzugte Verbindungen dieser Klasse sind Copolymere der
Acrylsäure oder Methacrylsäure mit Vinylethern, wie Vinylmethylethern, Vinylester, Ethylen, Propy- len und Styrol, in denen der Anteil der Säure mindestens 50 Gew.-% beträgt. Als wasserlösliche organische Buildersubstanzen können auch Terpolymere eingesetzt werden, die als Monomere zwei ungesättigte Säuren und/oder deren Salze sowie als drittes Monomer Vinylalkohol und/oder einem veresterten Vinylalkohol oder ein Kohlenhydrat enthalten. Das erste saure Monomer beziehungsweise dessen Salz leitet sich von einer monoethylenisch ungesättigten C3-C8-Carbonsäure und vorzugsweise von einer C3-C4-Monocarbonsäure, insbesondere von (Meth)-acrylsäure ab. Das zweite saure Monomer beziehungsweise dessen Salz kann ein Derivat einer C4-C8-Dicarbonsäure, wobei Maleinsäure besonders bevorzugt ist, und/oder ein Derivat einer Allylsulfonsäure, die in 2- Stellung mit einem Alkyl- oder Arylrest substituiert ist, sein. Derartige Polymere weisen im Allgemeinen eine relative Molekülmasse zwischen 1 000 und 200 000 auf. Weitere bevorzugte Copolymere sind solche, die als Monomere vorzugsweise Acrolein und Acrylsäure/Acrylsäuresalze beziehungsweise Vinylacetat aufweisen. Die organischen Buildersubstanzen können, insbesondere zur Herstellung flüssiger Mittel, in Form wäßriger Lösungen, vorzugsweise in Form 30- bis 50- gewichtsprozentiger wäßriger Lösungen eingesetzt werden. Alle genannten Säuren werden in der Regel in Form ihrer wasserlöslichen Salze, insbesondere ihre Alkalisalze, eingesetzt.An agent according to the invention preferably contains at least one water-soluble and / or water-insoluble, organic and / or inorganic builder. The water-soluble organic builder substances include polycarboxylic acids, in particular citric acid and sugar acids, monomeric and polymeric aminopolycarboxylic acids, in particular methylglycine diacetic 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 the accessible by oxidation of polysaccharides or dextrins polycarboxylates, 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 3,000 and 200,000, of the copolymers between 2,000 and 200,000, preferably 30,000 to 120,000, each based on the free acid. A particularly preferred acrylic acid-maleic acid copolymer has a molecular weight of from 30,000 to 100,000. Commercially available products are, for example, Sokalan® CP 5, CP 10 and PA 30 from BASF. Suitable, although less preferred compounds of this class are copolymers of the Acrylic acid or methacrylic acid with vinyl ethers, such as vinylmethyl ethers, vinyl esters, ethylene, propylene and styrene, in which the proportion of the acid is at least 50% by weight. It is also possible to use terpolymers which contain two unsaturated acids and / or salts thereof as monomers and also vinyl alcohol and / or an esterified vinyl alcohol or a carbohydrate as the third monomer as water-soluble organic builder substances. The first acidic monomer or its salt is derived from a monoethylenically unsaturated C 3 -C 8 -carboxylic acid and preferably from a C 3 -C 4 -monocarboxylic acid, in particular from (meth) -acrylic acid. The second acidic monomer or its salt may be a derivative of a C 4 -C 8 -dicarboxylic acid, with maleic acid being particularly preferred, and / or a derivative of an allylsulfonic acid substituted in the 2-position with an alkyl or aryl radical. Such polymers generally have a molecular weight between 1,000 and 200,000. Further preferred copolymers are those which preferably 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.
Derartige organische Buildersubstanzen können gewünschtenfalls in Mengen bis zu 40 Gew.-%, insbesondere bis zu 25 Gew.-% und vorzugsweise von 1 Gew.-% bis 8 Gew.-% enthalten sein. Mengen nahe der genannten Obergrenze werden vorzugsweise in pastenförmigen oder flüssigen, insbesondere wasserhaltigen, erfindungsgemäßen Mitteln eingesetzt.If desired, such 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 paste-form or liquid, in particular water-containing, agents according to the invention.
Als wasserlösliche anorganische Buildermaterialien kommen insbesondere Alkalisilikate, Alkalicarbonate und Alkaliphosphate, die in Form ihrer alkalischen, neutralen oder sauren Natriumoder Kaliumsalze vorliegen können, in Betracht. Beispiele hierfür sind Trinatriumphosphat, Tetra- natriumdiphosphat, Dinatriumdihydrogendiphosphat, Pentanatriumtriphosphat, sogenanntes Natriumhexametaphosphat, oligomeres Trinatriumphosphat mit Oligomerisierungsgraden von 5 bis 1000, insbesondere 5 bis 50, sowie die entsprechenden Kaliumsalze beziehungsweise Gemische aus Natrium- und Kaliumsalzen. Als wasserunlösliche, wasserdispergierbare anorganische Buildermaterialien werden insbesondere kristalline oder amorphe Alkalialumosilikate, in Mengen von bis zu 50 Gew.-%, vorzugsweise nicht über 40 Gew.-% und in flüssigen Mitteln insbesondere von 1 Gew.-% bis 5 Gew.-%, eingesetzt. Unter diesen sind die kristallinen Natriumalumosilikate in Waschmittelqualität, insbesondere Zeolith A, P und gegebenenfalls X, allein oder in Mischungen, beispielsweise in Form eines Co-Kristallisats aus den Zeolithen A und X (Vegobond® AX, ein Handelsprodukt der Condea Augusta S.p.A.), bevorzugt. Mengen nahe der genannten Obergrenze werden vorzugsweise in festen, teilchenförmigen Mitteln eingesetzt. Geeignete Alumosilikate weisen insbesondere keine Teilchen mit einer Korngröße über 30 μm auf und bestehen vorzugsweise zu wenigstens 80 Gew.-% aus Teilchen mit einer Größe unter 10 μm. Ihr Calcium-
bindevermögen, das nach den Angaben der deutschen Patentschrift DE 24 12 837 bestimmt werden kann, liegt in der Regel im Bereich von 100 bis 200 mg CaO pro Gramm.Suitable water-soluble inorganic builder materials are, in particular, alkali metal silicates, alkali metal carbonates and alkali metal phosphates, which may be in the form of their alkaline, neutral or acidic sodium or potassium salts. Examples of these are trisodium phosphate, tetra sodium diphosphate, disodium dihydrogen diphosphate, pentasodium triphosphate, so-called sodium hexametaphosphate, oligomeric trisodium phosphate with degrees of oligomerization of from 5 to 1000, in particular from 5 to 50, and the corresponding potassium salts or mixtures of sodium and potassium salts. Crystalline or amorphous alkali metal aluminosilicates, in amounts of up to 50% by weight, preferably not more than 40% by weight, and in liquid agents, in particular from 1% by weight to 5% by weight, are particularly suitable as water-insoluble, water-dispersible inorganic builder materials. used. Among these, preferred are the detergent grade crystalline sodium aluminosilicates, particularly zeolite A, P and optionally X, alone or in mixtures, for example in the form of a cocrystal of zeolites A and X (Vegobond® AX, a commercial product of Condea Augusta SpA) , Amounts near the above upper limit are preferably used in solid, particulate agents. In particular, suitable aluminosilicates have no particles with a particle size greater than 30 .mu.m and preferably consist of at least 80% by weight of particles having a size of less than 10 .mu.m. Your calcium binding capacity, which can be determined according to the specifications of German Patent DE 24 12 837, is generally in the range of 100 to 200 mg CaO per gram.
Geeignete Substitute beziehungsweise Teilsubstitute für das genannte Alumosilikat sind kristalline Alkalisilikate, die allein oder im Gemisch mit amorphen Silikaten vorliegen können. Die in den erfindungsgemäßen Mitteln als Gerüststoffe brauchbaren Alkalisilikate weisen vorzugsweise ein molares Verhältnis von Alkalioxid zu SiO2 unter 0,95, insbesondere von 1 :1 ,1 bis 1 :12 auf und können amorph oder kristallin vorliegen. Bevorzugte Alkalisilikate sind die Natriumsilikate, insbesondere die amorphen Natriumsilikate, mit einem molaren Verhältnis Na2O:SiO2 von 1 :2 bis 1 :2,8. Als kristalline Silikate, die allein oder im Gemisch mit amorphen Silikaten vorliegen können, werden vorzugsweise kristalline Schichtsilikate der allgemeinen Formel Na2SixO2x+1 y H2O eingesetzt, in der x, das sogenannte Modul, eine Zahl von 1 ,9 bis 22, insbesondere 1 ,9 bis 4 und y eine Zahl von 0 bis 33 ist und bevorzugte Werte für x 2, 3 oder 4 sind. Bevorzugte kristalline Schichtsilikate sind solche, bei denen x in der genannten allgemeinen Formel die Werte 2 oder 3 annimmt. Insbesondere sind sowohl ß- als auch δ-Natriumdisilikate (Na2Si2O5 y H2O) bevorzugt. Auch aus amorphen Alkalisilikaten hergestellte, praktisch wasserfreie kristalline Alkalisilikate der obengenannten allgemeinen Formel, in der x eine Zahl von 1 ,9 bis 2,1 bedeutet, können in erfindungsgemäßen Mitteln eingesetzt werden. In einer weiteren bevorzugten Ausführungsform erfindungsgemäßer Mittel wird ein kristallines Natriumschichtsilikat mit einem Modul von 2 bis 3 eingesetzt, wie es aus Sand und Soda hergestellt werden kann. Kristalline Natriumsilikate mit einem Modul im Bereich von 1 ,9 bis 3,5 werden in einer weiteren bevorzugten Ausführungsform erfindungsgemäßer Mittel eingesetzt. Kristalline schichtförmige Silikate der oben angegebenen Formel (I) werden von der Fa. Clariant GmbH unter dem Handelsnamen Na-SKS vertrieben, z.B. Na-SKS-1 (Na2Si22O45XH2O, Kenyait), Na-SKS-2 (Na2Si14O29XH2O, Magadiit), Na-SKS-3 (Na2Si8O17XH2O) oder Na-SKS-4 (Na2Si4O9XH2O, Makatit). Von diesen eignen sich vor allem Na- SKS-5 (OC-Na2Si2O5), Na-SKS-7 (ß-Na2Si205, Natrosilit), Na-SKS-9 (NaHSi2O53H2O), Na-SKS-10 (NaHSi2O53H2O, Kanemit), Na-SKS-11 (t-Na2Si205) und Na-SKS-13 (NaHSi2O5), insbesondere aber Na-SKS-6 (5-Na2Si2O5). In einer bevorzugten Ausgestaltung erfindungsgemäßer Mittel setzt man ein granuläres Compound aus kristallinem Schichtsilikat und Citrat, aus kristallinem Schichtsilikat und oben genannter (co-)polymerer Polycarbonsäure, oder aus Alkalisilikat und Alkalicarbonat ein, wie es beispielsweise unter dem Namen Nabion® 15 im Handel erhältlich ist.Suitable substitutes or partial substitutes for the said aluminosilicate are crystalline alkali 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 of less than 0.95, in particular of 1: 1, 1 to 1: 12, and may be amorphous or crystalline. Preferred alkali metal silicates are the sodium silicates, in particular the amorphous sodium silicates, with a molar ratio of Na 2 O: SiO 2 of 1: 2 to 1: 2.8. The crystalline silicates which may be present alone or in admixture with amorphous silicates, are crystalline layer silicates with the general formula Na 2 Si x O y are used 2x + 1 H 2 O, in which x, known as the modulus, an integer of 1, 9 to 22, in particular 1, 9 to 4 and y is a number from 0 to 33 and preferred values for x are 2, 3 or 4. Preferred crystalline phyllosilicates are those in which x in the abovementioned general formula assumes the values 2 or 3. In particular, both β- and δ-sodium disilicates (Na 2 Si 2 O 5 y H 2 O) are preferred. Also prepared from amorphous alkali silicates, practically anhydrous crystalline alkali silicates of the abovementioned general formula in which x is a number from 1, 9 to 2.1, can be used in inventive compositions. In a further preferred embodiment of the composition according to the invention, a crystalline sodium layer silicate with a modulus of 2 to 3 is used, as 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. Crystalline layer-form silicates of formula (I) given above are sold by Clariant GmbH under the trade name Na-SKS, eg Na-SKS-1 (Na 2 Si 22 O 45 XH 2 O, Kenyaite), Na-SKS-2 (Na 2 Si 14 O 29 XH 2 O, magadiite), Na-SKS-3 (Na 2 Si 8 O 17 XH 2 O) or Na-SKS-4 (Na 2 Si 4 O 9 XH 2 O, makatite). Of these, especially Na-SKS-5 (OC-Na 2 Si 2 O 5 ), Na-SKS-7 (β-Na 2 Si 2 0 5 , natrosilite), Na-SKS-9 (NaHSi 2 O 5 3H 2 O), Na-SKS-10 (NaHSi 2 O 5 3H 2 O, kanemite), Na-SKS-11 (t-Na 2 Si 2 0 5) and Na-SKS-13 (NaHSi 2 O 5), but especially Na-SKS-6 (5-Na 2 Si 2 O 5 ). In a preferred embodiment of the composition according to the invention, a granular compound of crystalline phyllosilicate and citrate, of crystalline phyllosilicate and of the above-mentioned (co-) polymeric polycarboxylic acid, or of alkali silicate and alkali metal carbonate, such as, for example, commercially available under the name Nabion® 15, is used ,
Buildersubstanzen sind in den erfindungsgemäßen Mitteln vorzugsweise in Mengen bis zu 75 Gew.-%, insbesondere 5 Gew.-% bis 50 enthalten.Builder substances are preferably present in the compositions according to the invention in amounts of up to 75% by weight, in particular 5% by weight to 50.
Als für den Einsatz in erfindungsgemäßen Mitteln geeignete Persauerstoffverbindungen kommen insbesondere organische Persäuren beziehungsweise persaure Salze organischer Säuren, wie Phthalimidopercapronsäure, Perbenzoesäure oder Salze der Diperdodecandisäure, Wasserstoff-
peroxid und unter den Waschbedingungen Wasserstoffperoxid abgebende anorganische Salze, zu denen Perborat, Percarbonat, Persilikat und/oder Persulfat wie Caroat gehören, in Betracht. Sofern feste Persauerstoffverbindungen eingesetzt werden sollen, können diese in Form von Pulvern oder Granulaten verwendet werden, die auch in im Prinzip bekannter Weise umhüllt sein können. Falls ein erfindungsgemäßes Mittel Persauerstoffverbindungen enthält, sind diese in Mengen von vorzugsweise bis zu 50 Gew.-%, insbesondere von 5 Gew.-% bis 30 Gew.-%, vorhanden. Der Zusatz geringer Mengen bekannter Bleichmittelstabilisatoren wie beispielsweise von Phosphonaten, Boraten beziehungsweise Metaboraten und Metasilikaten sowie Magnesiumsalzen wie Magnesiumsulfat kann zweckdienlich sein.Suitable peroxygen compounds for use in compositions according to the invention are, in particular, organic peracids or persistent salts of organic acids, such as phthalimidopercaproic acid, perbenzoic acid or salts of diperdodecanedioic acid, hydrogen peroxide and under the washing conditions hydrogen peroxide-releasing inorganic salts, which include perborate, percarbonate, persilicate and / or persulfate such as caroate into consideration. If solid peroxygen compounds are to be used, they can be used in the form of powders or granules, which can also be enveloped in a manner known in principle. If 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. The addition of small amounts of known bleach stabilizers such as phosphonates, borates or metaborates and metasilicates and magnesium salts such as magnesium sulfate may be useful.
Als Bleichaktivatoren können Verbindungen, die unter Perhydrolysebedingungen aliphatische Peroxocarbonsäuren mit vorzugsweise 1 bis 10 C-Atomen, insbesondere 2 bis 4 C-Atomen, und/oder gegebenenfalls substituierte Perbenzoesäure ergeben, eingesetzt werden. Geeignet sind Substanzen, die O- und/oder N-Acylgruppen der genannten C-Atomzahl und/oder gegebenenfalls substituierte Benzoylgruppen tragen. Bevorzugt sind mehrfach acylierte Alkylendiamine, insbesondere Tetraacetylethylendiamin (TAED), acylierte Triazinderivate, insbesondere 1 ,5- Diacetyl-2,4-dioxohexahydro-1 ,3,5-triazin (DADHT), acylierte Glykolurile, insbesondere Tetraacetylglykoluril (TAGU), N-Acylimide, insbesondere N-Nonanoylsuccinimid (NOSI), acylierte Phenolsulfonate, insbesondere n-Nonanoyl- oder Isononanoyloxybenzolsulfonat (n- bzw. iso- NOBS), Carbonsäureanhydride, insbesondere Phthalsäureanhydrid, acylierte mehrwertige Alkohole, insbesondere Triacetin, Ethylenglykoldiacetat, 2,5-Diacetoxy-2,5-dihydrofuran und Enolester sowie acetyliertes Sorbitol und Mannitol beziehungsweise deren beschriebene Mischungen (SORMAN), acylierte Zuckerderivate, insbesondere Pentaacetylglukose (PAG), Pentaacetylfruktose, Tetraacetylxylose und Octaacetyllactose sowie acetyliertes, gegebenenfalls N-alkyliertes Glucamin und Gluconolacton, und/oder N-acylierte Lactame, beispielsweise N- Benzoylcaprolactam. Die hydrophil substituierten Acylacetale und die Acyllactame werden ebenfalls bevorzugt eingesetzt. Auch Kombinationen konventioneller Bleichaktivatoren können eingesetzt werden. Derartige Bleichaktivatoren können, insbesondere bei Anwesenheit obengenannter Wasserstoffperoxid-Iiefernder Bleichmittel, im üblichen Mengenbereich, vorzugsweise in Mengen von 0,5 Gew.-% bis 10 Gew.-%, insbesondere 1 Gew.-% bis 8 Gew.-%, bezogen auf gesamtes Mittel, enthalten sein, fehlen bei Einsatz von Percarbonsäure als alleinigem Bleichmittel jedoch vorzugsweise ganz.As bleach activators, it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups. Preference is given to 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 isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate, 2,5-diacetoxy- 2,5-dihydrofuran and enol esters and also acetylated sorbitol and mannitol or mixtures thereof (SORMAN), 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-benzoyl-caprolactam. The hydrophilic substituted acyl acetals and the acyl lactams are also preferably used. Combinations of conventional bleach activators can also be used. 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.
Zusätzlich zu den konventionellen Bleichaktivatoren oder an deren Stelle können auch Sulfonimine und/oder bleichverstärkende Übergangsmetallsalze beziehungsweise Übergangsmetallkomplexe als sogenannte Bleichkatalysatoren enthalten sein.
Zu den in den erfindungsgemäßen Mitteln, insbesondere wenn sie in flüssiger oder pastöser Form vorliegen, neben Wasser verwendbaren organischen Lösungsmitteln gehören Alkohole mit 1 bis 4 C-Atomen, insbesondere Methanol, Ethanol, Isopropanol und tert.-Butanol, Diole mit 2 bis 4 C-Ato- men, insbesondere Ethylenglykol und Propylenglykol, sowie deren Gemische und die aus den genannten Verbindungsklassen ableitbaren Ether. Derartige wassermischbare Lösungsmittel sind in den erfindungsgemäßen Mitteln vorzugsweise in Mengen nicht über 30 Gew.-%, insbesondere von 6 Gew.-% bis 20 Gew.-%, vorhanden.In addition to the conventional bleach activators or in their place, sulfone imines and / or bleach-enhancing transition metal salts or transition metal complexes may also be present as so-called bleach catalysts. Among the solvents according to the invention, in particular when they are in liquid or pasty form, organic solvents which can be used in addition to water include alcohols having 1 to 4 C atoms, in particular methanol, ethanol, isopropanol and tert-butanol, diols having 2 to 4 C -Ato- men, in particular ethylene glycol and propylene glycol, and mixtures thereof and derived from the said classes of compounds ethers. Such water-miscible solvents are preferably present in the compositions according to the invention in amounts of not more than 30% by weight, in particular from 6% by weight to 20% by weight.
Zur Einstellung eines gewünschten, sich durch die Mischung der übrigen Komponenten nicht von selbst ergebenden pH-Werts können die erfindungsgemäßen Mittel System- und umweltverträgliche Säuren, insbesondere Citronensäure, Essigsäure, Weinsäure, Äpfelsäure, Milchsäure, Glykolsäure, Bernsteinsäure, Glutarsäure und/oder Adipinsäure, aber auch Mineralsäuren, insbesondere Schwefelsäure, oder Basen, insbesondere Ammonium- oder Alkalihydroxide, enthalten. Derartige pH-Regulatoren sind in den erfindungsgemäßen Mitteln in Mengen von vorzugsweise nicht über 20 Gew.-%, insbesondere von 1 ,2 Gew.-% bis 17 Gew.-%, enthalten.In order to establish a desired pH, which does not naturally result from the mixture of the other components, the compositions according to the invention may contain system and environmentally acceptable acids, in particular citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid and / or adipic acid, but also mineral acids, in particular sulfuric acid, or bases, in particular ammonium or alkali metal hydroxides. Such pH regulators are present in the compositions according to the invention in amounts of preferably not more than 20% by weight, in particular from 1.2% by weight to 17% by weight.
Vergrauungsinhibitoren haben die Aufgabe, den von der Textilfaser abgelösten Schmutz in der Flotte suspendiert zu halten. Hierzu sind wasserlösliche Kolloide meist organischer Natur geeignet, beispielsweise Stärke, Leim, Gelatine, Salze von Ethercarbonsäuren oder Ethersulfonsäuren der Stärke oder der Cellulose oder Salze von sauren Schwefelsäureestern der Cellulose oder der Stärke. Auch wasserlösliche, saure Gruppen enthaltende Polyamide sind für diesen Zweck geeignet. Weiterhin lassen sich andere als die obengenannten Stärkederivate verwenden, zum Beispiel Aldehydstärken. Bevorzugt werden Celluloseether, wie Carboxymethylcellulose (Na-SaIz), Methylcellulose, Hydroxyalkylcellulose und Mischether, wie Methylhydroxyethylcellulose, Methyl- hydroxypropylcellulose, Methylcarboxymethylcellulose und deren Gemische, beispielsweise in Mengen von 0,1 bis 5 Gew.-%, bezogen auf die Mittel, eingesetzt.Graying inhibitors have the task of keeping suspended from the textile fiber dirt suspended in the fleet. Water-soluble colloids of mostly organic nature are suitable for this purpose, for example starch, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or of cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Also, water-soluble polyamides containing acidic groups are suitable for this purpose. Furthermore, other than the above-mentioned starch derivatives can be used, for example aldehyde starches. Preference is given to using cellulose ethers, such as carboxymethylcellulose (Na salt), methylcellulose, hydroxyalkylcellulose and mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof, for example in amounts of from 0.1 to 5% by weight, based on the compositions ,
Erfindungsgemäße Textilwaschmittel können als optische Aufheller beispielsweise Derivate der Diaminostilbendisulfonsäure beziehungsweise deren Alkalimetallsalze enthalten, obgleich sie für den Einsatz als Colorwaschmittel vorzugsweise frei von optischen Aufhellern sind. Geeignet sind zum Beispiel Salze der 4,4'-Bis(2-anilino-4-morpholino-1 ,3,5-triazinyl-6-amino)stilben-2,2'- disulfonsäure oder gleichartig aufgebaute Verbindungen, die anstelle der Morpholino-Gruppe eine Diethanolaminogruppe, eine Methylaminogruppe, eine Anilinogruppe oder eine 2- Methoxyethylaminogruppe tragen. Weiterhin können Aufheller vom Typ der substituierten Diphenylstyryle anwesend sein, zum Beispiel die Alkalisalze des 4,4'-Bis(2-sulfostyryl)-diphenyls, 4,4'-Bis(4-chlor-3-sulfostyryl)-diphenyls, oder 4-(4-Chlorstyryl)-4'-(2-sulfostyryl)-diphenyls. Auch Gemische der vorgenannten optischen Aufheller können verwendet werden.
Insbesondere beim Einsatz in maschinellen Verfahren kann es von Vorteil sein, den Mitteln übliche Schauminhibitoren zuzusetzen. Als Schauminhibitoren eignen sich beispielsweise Seifen natürlicher oder synthetischer Herkunft, die einen hohen Anteil an C18-C24-Fettsäuren aufweisen. Geeignete nichttensidartige Schauminhibitoren sind beispielsweise Organopolysiloxane und deren Gemische mit mikrofeiner, gegebenenfalls silanierter Kieselsäure sowie Paraffine, Wachse, Mikrokristallinwachse und deren Gemische mit silanierter Kieselsäure oder Bisfettsäurealkylendiamiden. Mit Vorteilen werden auch Gemische aus verschiedenen Schauminhibitoren verwendet, zum Beispiel solche aus Silikonen, Paraffinen oder Wachsen. Vorzugsweise sind die Schauminhibitoren, insbesondere Silikon- und/oder Paraffin-haltige Schauminhibitoren, an eine granuläre, in Wasser lösliche beziehungsweise dispergierbare Trägersubstanz gebunden. Insbesondere sind dabei Mischungen aus Paraffinen und Bistearylethylendiamid bevorzugt.Detergents according to the invention may contain, for example, derivatives of diaminostilbenedisulfonic acid or their alkali metal salts as optical brighteners, although they are preferably free of optical brighteners for use as color detergents. For example, salts of 4,4'-bis (2-anilino-4-morpholino-1, 3,5-triazinyl-6-amino) stilbene-2,2'-disulphonic acid or compounds of similar construction which are used instead of the morpholino Group carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group. Further, brighteners of the substituted diphenylstyrene type may be present, for example, the alkali salts of 4,4'-bis (2-sulfostyryl) -diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) -diphenyl, or 4 - (4-chlorostyryl) -4 '- (2-sulfostyryl). Mixtures of the aforementioned optical brightener can be used. In particular, when used in mechanical processes, it may be advantageous to add conventional foam inhibitors to the compositions. As foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of C 18 -C 24 fatty acids. Suitable non-surfactant foam inhibitors are, for example, organopolysiloxanes and mixtures thereof with microfine, optionally silanized silica and paraffins, waxes, microcrystalline waxes and mixtures thereof with silanated silicic acid or bis-fatty acid alkylenediamides. It is also advantageous to use mixtures of various foam inhibitors, for example those of silicones, paraffins or waxes. Preferably, the foam inhibitors, in particular silicone and / or paraffin-containing foam inhibitors, are bound to a granular, water-soluble or dispersible carrier substance. In particular, mixtures of paraffins and bistearylethylenediamide are preferred.
In weiteren Ausführungsformen erfindungsgemäßer Mittel, insbesondere Wasch- oder Reinigungsmittel, werden die Proteasen beispielsweise mit einzelnen oder mehreren der folgenden Inhaltsstoffe kombiniert: nichtionische, anionische und/oder kationische Tenside, (gegebenenfalls weitere) Bleichmittel, Bleichaktivatoren, Bleichkatalysatoren, Builder und/oder Cobuilder, Säuren, alkalische Substanzen, Hydrotropen, Lösungsmittel, Verdicker, Sequestrierungsmittel, Elektrolyt^, optische Aufheller, Vergrauungsinhibitoren, Korrosionsinhibitoren, insbesondere Silberschutzmittel (Silberkorrosionsinhibitoren), Desintegrationshilfsmittel, Soil-Release-Wirkstoffe, Farbtransfer (oder -Übertragungs) -Inhibitoren, Schauminhibitoren, Abrasivstoffe, Farbstoffe, Duftstoffe, Parfüms, antimikrobielle Wirkstoffe, UV-Schutzmittel bzw. -Absorbenzien, Antistatika, Perlglanzmitteln und Hautschutzmitteln, Enzyme wie beispielsweise Protease, Amylase, Cellulase, Hemicellulase, Mannanase, Tannase, Xylanase, Xanthanase, ß-Glucosidase, Carrageenase, Oxidase, Oxidoreduktase, Pektin-abbauendes Enzym oder eine Lipase, Stabilisatoren, insbesondere Enzymstabilisatoren, und andere Komponenten, die aus dem Stand der Technik bekannt sind. In einer weiteren Ausführungsform der Erfindung ist ein erfindungsgemäßes Mittel somit dadurch gekennzeichnet, dass es mindestens eine weitere Komponente enthält, ausgewählt aus der Gruppe bestehend aus Tensiden, Buildern, Säuren, alkalischen Substanzen, Hydrotropen, Lösungsmitteln, Verdickungsmitteln, Bleichmitteln, Farbstoffen, Parfüms, Korrosionsinhibitoren, Sequestriermitteln, Elektrolyten, optischen Aufhellern, Vergrauungsinhibitoren, Silberkorrosionsinhibitoren, Farbübertragungsinhibitoren, Schauminhibitoren, Desintegrationshilfsmittel, Abrasivstoffen, UV-Absorbenzien, Lösungsmitteln, Antistatika, Perlglanzmitteln und Hautschutzmitteln.In further embodiments of agents according to the invention, in particular detergents or cleaners, the proteases are combined, for example, with one or more of the following ingredients: nonionic, anionic and / or cationic surfactants, (optionally further) bleaches, bleach activators, bleach catalysts, builders and / or cobuilders, Acids, alkaline substances, hydrotropes, solvents, thickeners, sequestering agents, electrolytes, optical brighteners, grayness inhibitors, corrosion inhibitors, in particular silver protectants (silver corrosion inhibitors), disintegration aids, soil release agents, color transfer (or transfer) inhibitors, foam inhibitors, abrasives, Dyes, fragrances, perfumes, antimicrobial agents, UV protectants or absorbents, antistatic agents, pearlescers and skin protection agents, enzymes such as protease, amylase, cellulase, hemicellulase, mannanase, tannase, xylanase, xanthine anase, β-glucosidase, carrageenase, oxidase, oxidoreductase, pectin degrading enzyme or a lipase, stabilizers, especially enzyme stabilizers, and other components known in the art. In a further embodiment of the invention, an agent according to the invention is therefore characterized in that it contains at least one further component selected from the group consisting of surfactants, builders, acids, alkaline substances, hydrotropes, solvents, thickeners, bleaching agents, dyes, perfumes, corrosion inhibitors , Sequestering agents, electrolytes, optical brighteners, grayness inhibitors, silver corrosion inhibitors, color transfer inhibitors, foam inhibitors, disintegration aids, abrasives, UV absorbers, solvents, antistatic agents, pearlescers and skin protection agents.
Die zu wählenden Inhaltsstoffe wie auch die Bedingungen, unter denen das Mittel eingesetzt wird, wie beispielsweise Temperatur, pH-Wert, lonenstärke, Redox-Verhältnisse oder mechanische Einflüsse, sollten für das jeweilige Reinigungsproblem optimiert sein. So liegen übliche
Temperaturen für Wasch- und Reinigungsmittel in Bereichen von 1O0C bei manuellen Mitteln über 4O0C und 6O0C bis hin zu 95° bei maschinellen Mitteln oder bei technischen Anwendungen. Da bei modernen Wasch- und Spülmaschinen die Temperatur meist stufenlos einstellbar ist, sind auch alle Zwischenstufen der Temperatur eingeschlossen. Vorzugsweise werden die Inhaltsstoffe der betreffenden Mittel aufeinander abgestimmt. Bevorzugt sind Synergien hinsichtlich der Reinigungsleistung. Besonders bevorzugt diesbezüglich sind Synergien, die sich aus dem Zusammenwirken der beiden Proteasen in dem erfindungsgemäßen Mittel mit mindestens einem oder mehreren weiteren Inhaltsstoff ergeben. In einer weiteren bevorzugten Ausführungsform sind diese Synergien in einem Temperaturbereich zwischen 2O0C und 6O0C vorhanden, da auch die in den erfindungsgemäßen Mitteln enthaltenen Proteasen in diesem Temperaturbereich katalytisch aktiv sind.The ingredients to be selected as well as the conditions under which the agent is used, such as temperature, pH, ionic strength, redox ratios or mechanical influences, should be optimized for the particular cleaning problem. So are usual Temperatures for detergents and cleaning agents in areas of 1O 0 C for manual compositions over 4O 0 C and 6O 0 C to 95 ° for machine agents or industrial applications. Since the temperature is usually infinitely adjustable in modern washing machines and dishwashers, all intermediate stages of the temperature are included. Preferably, the ingredients of the respective agents are coordinated. Synergies in terms of cleaning performance are preferred. Particularly preferred in this regard are synergies resulting from the interaction of the two proteases in the composition according to the invention with at least one or more further ingredients. In a further preferred embodiment, these synergies are present in a temperature range between 2O 0 C and 6O 0 C, as well as the proteases contained in the inventive compositions are catalytically active in this temperature range.
In einer weiteren Ausführungsform umfasst ein erfindungsgemäßes Mittel, insbesondere ein Wasch- oder Reinigungsmittel, fernerIn a further embodiment, an agent according to the invention, in particular a washing or cleaning agent, further comprises
- 5 Gew.-% bis 70 Gew.-%, insbesondere 5 Gew.-% bis 30 Gew.-% Tenside und/oder- 5 wt .-% to 70 wt .-%, in particular 5 wt .-% to 30 wt .-% of surfactants and / or
- 10 Gew.-% bis 65 Gew.-%, insbesondere 12 Gew.-% bis 60 Gew. -% wasserlösliches oder wasserdispergierbares anorganisches Buildermaterial und/oderFrom 10% by weight to 65% by weight, in particular from 12% by weight to 60% by weight, of water-soluble or water-dispersible inorganic builder material and / or
- 0,5 Gew.-% bis 10 Gew.-%, insbesondere 1 Gew.-% bis 8 Gew.-%, wasserlösliche organische Buildersubstanzen und/oderFrom 0.5% by weight to 10% by weight, in particular from 1% by weight to 8% by weight, of water-soluble organic builders and / or
- 0,01 bis 15 Gew.-% feste anorganische und/oder organische Säuren beziehungsweise saure Salze und/oder0.01 to 15% by weight of solid inorganic and / or organic acids or acid salts and / or
- 0,01 bis 5 Gew.-% Komplexbildner für Schwermetalle und/oder0.01 to 5% by weight complexing agent for heavy metals and / or
- 0,01 bis 5 Gew.-% Vergrauungsinhibitor und/oder0.01 to 5% by weight of grayness inhibitor and / or
- 0,01 bis 5 Gew. -% Farbübertragungsinhibitor und/oder0.01 to 5% by weight of color transfer inhibitor and / or
- 0,01 bis 5 Gew.-% Schauminhibitor.- 0.01 to 5 wt .-% foam inhibitor.
Optional kann das Mittel ferner optische Aufheller umfassen, bevorzugt von 0,01 bis 5 Gew-%.Optionally, the agent may further comprise optical brighteners, preferably from 0.01% to 5% by weight.
Die Herstellung erfindungsgemäßer fester Mittel bietet keine Schwierigkeiten und kann auf bekannte Weise, zum Beispiel durch Sprühtrocknen oder Granulation, erfolgen, wobei Enzyme und eventuelle weitere thermisch empfindliche Inhaltsstoffe wie zum Beispiel Bleichmittel gegebenenfalls später separat zugesetzt werden. Zur Herstellung erfindungsgemäßer Mittel mit erhöhtem Schüttgewicht, insbesondere im Bereich von 650 g/l bis 950 g/l, ist ein einen Extrusionschritt aufweisendes Verfahren bevorzugt.The preparation of solid 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. For the preparation of inventive compositions having an increased bulk density, in particular in the range from 650 g / l to 950 g / l, a process comprising an extrusion step is preferred.
Zur Herstellung von erfindungsgemäßen Mitteln in Tablettenform, die einphasig oder mehrphasig, einfarbig oder mehrfarbig und insbesondere aus einer Schicht oder aus mehreren, insbesondere aus zwei Schichten bestehen können, geht man vorzugsweise derart vor, dass man alle Bestandteile - gegebenenfalls je einer Schicht - in einem Mischer miteinander vermischt und das
Gemisch mittels herkömmlicher Tablettenpressen, beispielsweise Exzenterpressen oder Rundläuferpressen, mit Preßkräften im Bereich von etwa 50 bis 100 kN, vorzugsweise bei 60 bis 70 kN verpreßt. Insbesondere bei mehrschichtigen Tabletten kann es von Vorteil sein, wenn mindestens eine Schicht vorverpreßt wird. Dies wird vorzugsweise bei Preßkräften zwischen 5 und 20 kN, insbesondere bei 10 bis 15 kN durchgeführt. Man erhält so problemlos bruchfeste und dennoch unter Anwendungsbedingungen ausreichend schnell lösliche Tabletten mit Bruch- und Biegefestigkeiten von normalerweise 100 bis 200 N, bevorzugt jedoch über 150 N. Vorzugsweise weist eine derart hergestellte Tablette ein Gewicht von 10 g bis 50 g, insbesondere von 15 g bis 40 g auf. Die Raumform der Tabletten ist beliebig und kann rund, oval oder eckig sein, wobei auch Zwischenformen möglich sind. Ecken und Kanten sind vorteilhafterweise abgerundet. Runde Tabletten weisen vorzugsweise einen Durchmesser von 30 mm bis 40 mm auf. Insbesondere die Größe von eckig oder quaderförmig gestalteten Tabletten, welche überwiegend über die Dosiervorrichtung beispielsweise der Geschirrspülmaschine eingebracht werden, ist abhängig von der Geometrie und dem Volumen dieser Dosiervorrichtung. Beispielhaft bevorzugte Ausführungsformen weisen eine Grundfläche von (20 bis 30 mm) x (34 bis 40 mm), insbesondere von 26x36 mm oder von 24x38 mm auf.For the preparation of compositions according to the invention in tablet form, which may be monophasic or multiphase, monochromatic or multicolor and in particular consist of one or more layers, in particular two layers, the procedure is preferably such that all constituents - if appropriate one per layer - in one Mixer mixed together and the Mixture by means of conventional tablet presses, such as eccentric or rotary presses, pressed with compressive forces in the range of about 50 to 100 kN, preferably at 60 to 70 kN. Particularly in the case of multilayer tablets, it may be advantageous if at least one layer is pre-compressed. This is preferably carried out at pressing forces between 5 and 20 kN, in particular at 10 to 15 kN. This gives fracture-resistant, yet sufficiently rapidly soluble tablets under application conditions with fracture and flexural strengths of normally 100 to 200 N, but preferably above 150 N. Preferably, 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 rectangular or cuboid-shaped tablets, which are introduced predominantly via the metering device, for example the dishwasher, is dependent on the geometry and the volume of this metering device. Exemplary preferred embodiments have a base area of (20 to 30 mm) x (34 to 40 mm), in particular of 26x36 mm or 24x38 mm.
Flüssige beziehungsweise pastöse erfindungsgemäße Mittel in Form von übliche Lösungsmittel enthaltenden Lösungen werden in der Regel durch einfaches Mischen der Inhaltsstoffe, die in Substanz oder als Lösung in einen automatischen Mischer gegeben werden können, hergestellt.Liquid or pasty compositions according to the invention in the form of customary solvent-containing solutions are generally prepared by simply mixing the ingredients, which can be added in bulk or as a solution in an automatic mixer.
Ausführungsformen der vorliegenden Erfindung umfassen somit alle derartigen festen, pulverförmigen, flüssigen, gelförmigen oder pastösen Darreichungsformen der Mittel, die gegebenenfalls auch aus mehreren Phasen bestehen können sowie in komprimierter oder nicht komprimierter Form vorliegen können. Eine weitere Ausführungsform der Erfindung stellen daher Mittel dar, die dadurch gekennzeichnet sind, dass sie als Einkomponentensystem vorliegen. Solche Mittel bestehen bevorzugt aus einer Phase. Selbstverständlich können erfindungsgemäße Mittel aber auch aus mehreren Phasen bestehen. In einer weiteren Ausführungsform der Erfindung ist das Wasch- oder Reinigungsmittel daher dadurch gekennzeichnet sind, dass es in mehrere Komponenten aufgeteilt ist.Embodiments of the present invention thus comprise all such 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. Of course, means according to the invention may also consist of several phases. In a further embodiment of the invention, the washing or cleaning agent is therefore characterized in that it is divided into several components.
Zu den erfindungsgemäßen festen Darreichungsformen zählen ferner Extrudate, Granulate, Tabletten oder Pouches, die sowohl in Großgebinden als auch portionsweise abgepackt vorliegen können. Alternativ liegt das Mittel als rieselfähiges Pulver vor, insbesondere mit einem Schüttgewicht von 300 g/l bis 1200 g/l, insbesondere 500 g/l bis 900 g/l oder 600 g/l bis 850 g/l.The solid dosage forms according to the invention also include extrudates, granules, tablets or pouches, which may be present both in large packages and in portions. Alternatively, 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.
In einer weiteren Ausführungsform der Erfindung liegt das Mittel, insbesondere das Wasch- oder Reinigungsmittel, in flüssiger, gelförmiger oder pastöser Form vor, insbesondere in Form eines
nicht-wäßrigen Flüssigwaschmittels oder einer nicht-wäßrigen Paste oder in Form eines wäßrigen Flüssigwaschmittels oder einer wasserhaltigen Paste.In a further embodiment of the invention, the agent, in particular the washing or cleaning agent, is in liquid, gel or pasty form, in particular in the form of a non-aqueous liquid detergent or a non-aqueous paste or in the form of an aqueous liquid detergent or a water-containing paste.
Das erfindungsgemäße Mittel, insbesondere Wasch- oder Reinigungsmittel, kann in einem Behältnis, vorzugsweise einem luftdurchlässigen Behältnis, verpackt sein, aus dem es kurz vor Gebrauch oder während des Waschvorgangs freigesetzt wird. Insbesondere kann ferner mindestens eine, bevorzugt beide der in dem Mittel enthaltenen Proteasen und/oder weitere Inhaltsstoffe des Mittels mit einer bei Raumtemperatur oder bei Abwesenheit von Wasser für das Enzym/die Enzyme undurchlässigen Substanz umhüllt sein, welche unter Anwendungsbedingungen des Mittels durchlässig für das Enzym/die Enzyme wird. Eine solche Ausführungsform der Erfindung ist somit dadurch gekennzeichnet, dass mindestens eine Protease mit einer bei Raumtemperatur oder bei Abwesenheit von Wasser für die Protease undurchlässigen Substanz umhüllt ist.The agent according to the invention, in particular washing or cleaning agent, can be packaged in a container, preferably an air-permeable container, from which it is released shortly before use or during the washing process. In particular, at least one, preferably both, of the proteases contained in the agent and / or further ingredients of the agent may be coated with a substance impermeable to the enzyme (s) at room temperature or in the absence of water, which under application conditions of the agent is permeable to the enzyme / the enzymes becomes. Such an embodiment of the invention is therefore characterized in that at least one protease is coated with a substance that is impermeable to the protease at room temperature or in the absence of water.
Bevorzugt ist ein erfindungsgemäßes Mittel dadurch gekennzeichnet, dass es die Proteasen in einer Menge von 0,1 μg bis 100 mg, vorzugsweise von 1 μg bis 50 mg, weiter bevorzugt von 10 μg bis 50 mg, besonders bevorzugt von 25 μg bis 25 mg und ganz besonders bevorzugt von 50 μg bis 20 mg pro g des Mittels enthält. Angegeben in Gewichtsprozent enthält das Mittel daher die Proteasen in einer Menge von 0,00001 Gewichtsprozent bis 10 Gewichtsprozent, vorzugsweise 0,0001 Gewichtsprozent bis 5 Gewichtsprozent, weiter bevorzugt von 0,001 Gewichtsprozent bis 5 Gewichtsprozent, besonders bevorzugt von 0,00025 Gewichtsprozent bis 2,5 Gewichtsprozent und ganz besonders bevorzugt von 0,005 Gewichtsprozent bis 2 Gewichtsprozent. In den dargestellten Mengenangaben sind die erste Protease und die zweite Protease enthalten.Preferably, an agent according to the invention is characterized in that it contains the proteases in an amount of from 0.1 μg to 100 mg, preferably from 1 μg to 50 mg, more preferably from 10 μg to 50 mg, particularly preferably from 25 μg to 25 mg and most preferably from 50 μg to 20 mg per g of the agent. Thus, given in weight percent, the agent contains the proteases in an amount of 0.00001 weight percent to 10 weight percent, preferably 0.0001 weight percent to 5 weight percent, more preferably 0.001 weight percent to 5 weight percent, most preferably 0.00025 weight percent to 2.5 Percent by weight and most preferably from 0.005% to 2% by weight. The quantities shown contain the first protease and the second protease.
Erfindungsgemäße Mittel können ausschließlich die beiden vorstehend beschriebenen Proteasen enthalten. Alternativ können sie auch weitere Proteasen oder andere Enzyme in einer für die Wirksamkeit des Mittels zweckmäßigen Konzentration enthalten. Einen weiteren Gegenstand der Erfindung stellen somit Mittel dar, die ferner eines oder mehrere weitere Enzyme umfassen, wobei prinzipiell alle im Stand der Technik für diese Zwecke etablierten Enzyme einsetzbar sind. Als weitere Enzyme bevorzugt einsetzbar sind alle Enzyme, die in dem erfindungsgemäßen Mittel eine katalytische Aktivität entfalten können, insbesondere Proteasen, Amylasen, Cellulasen, Hemicellulasen, Mannanasen, Tannasen, Xylanasen, Xanthanasen, ß-Glucosidasen, Carrageenasen, Oxidasen, Oxidoreduktasen, Pektin-abbauende Enzyme (Pektinasen) oder Lipasen, sowie vorzugsweise deren Gemische. Diese Enzyme sind im Prinzip natürlichen Ursprungs; ausgehend von den natürlichen Molekülen stehen für den Einsatz in Wasch- und Reinigungsmitteln verbesserte Varianten zur Verfügung, die entsprechend bevorzugt eingesetzt werden. Erfindungsgemäße Mittel enthalten Enzyme vorzugsweise in Gesamtmengen von 1 x 10~8 bis 5 Gewichts-Prozent bezogen auf aktives Protein. Bevorzugt sind die Enzyme von 0,00001 bis 5
Gew.-%, weiter bevorzugt von 0,0001 bis 2,5 Gew.-%, noch weiter bevorzugt von 0,0001 bis 1 Gew.-% und besonders bevorzugt von 0,0001 bis 0,072 Gew.-% in erfindungsgemäßen Mitteln enthalten, wobei jedes enthaltene Enzym in den genannten Mengenverhältnissen vorliegen kann.Compositions according to the invention may contain exclusively the two proteases described above. Alternatively, they may also contain other proteases or other enzymes in a concentration effective for the effectiveness of the agent. A further subject of the invention thus represents agents which further comprise one or more further enzymes, wherein in principle all enzymes established in the prior art for these purposes can be used. As other enzymes preferably used are all enzymes that can develop a catalytic activity in the agent of the invention, in particular proteases, amylases, cellulases, hemicellulases, mannanases, tannases, xylanases, xanthanases, ß-glucosidases, carrageenases, oxidases, oxidoreductases, pectin-degrading Enzymes (pectinases) or lipases, and preferably mixtures thereof. These enzymes are basically of natural origin; Starting from the natural molecules, improved variants are available for use in detergents and cleaners, which are preferably used accordingly. Compositions according to the invention preferably contain enzymes in total amounts of 1 × 10 -8 to 5 percent by weight, based on active protein. Preferably, the enzymes are from 0.00001 to 5 Wt .-%, more preferably from 0.0001 to 2.5 wt .-%, even more preferably from 0.0001 to 1 wt .-% and particularly preferably from 0.0001 to 0.072 wt .-% in inventive compositions , Wherein each enzyme contained can be present in the stated proportions.
Die Proteinkonzentration kann mit Hilfe bekannter Methoden, zum Beispiel dem BCA-Verfahren (Bicinchoninsäure; 2,2'-Bichinolyl-4,4'-dicarbonsäure) oder dem Biuret-Verfahren (A. G. Gornall, C. S. Bardawill und M. M. David, J. Biol. Chem., 177 (1948), S. 751-766) bestimmt werden. Besonders bevorzugt unterstützen die weiteren Enzyme die Wirkung des Mittels, beispielsweise die Reinigungsleistung eines Wasch- oder Reinigungsmittels, hinsichtlich bestimmter Anschmutzungen oder Flecken. Besonders bevorzugt zeigen die Enzyme synergistische Effekte hinsichtlich ihrer Wirkung gegenüber bestimmter Anschmutzungen oder Flecken, d.h. die in der Mittelzusammensetzung enthaltenen Enzyme unterstützen sich in ihrer Reinigungsleistung gegenseitig. Synergistische Effekte können nicht nur zwischen verschiedenen Enzymen, sondern auch zwischen einem oder mehreren Enzymen und weiteren Inhaltsstoffen des erfindungsgemäßen Mittels auftreten. In einer weiteren bevorzugten Ausführungsform der Erfindung ist das erfindungsgemäße Mittel somit dadurch gekennzeichnet, dass es mindestens ein weiteres Enzym enthält, welches eine Protease, Amylase, Cellulase, Hemicellulase, Mannanase, Tannase, Xylanase, Xanthanase, ß-Glucosidase, Carrageenase, Oxidase, Oxidoreduktase, Pektinabbauendes Enzym oder eine Lipase ist.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 further enzymes particularly preferably support the effect of the agent, for example the cleaning performance of a washing or cleaning agent, with regard to certain stains or stains. Most preferably, the enzymes exhibit synergistic effects on their action against certain soils or stains, i. the enzymes contained in the middle composition mutually support each other in their cleaning performance. Synergistic effects can occur not only between different enzymes, but also between one or more enzymes and other ingredients of the composition according to the invention. In a further preferred embodiment of the invention, the agent according to the invention is therefore characterized in that it contains at least one further enzyme which comprises a protease, amylase, cellulase, hemicellulase, mannanase, tannase, xylanase, xanthanase, β-glucosidase, carrageenase, oxidase, oxidoreductase , Pectin degrading enzyme or lipase.
Bei dem Vergleich der Leistungen zweier Enzyme, ist zwischen proteingleichem und aktivitätsgleichem Einsatz zu unterscheiden. Insbesondere bei gentechnisch erhaltenen, weitgehend nebenaktivitätsfreien Präparationen ist der proteingleiche Einsatz angebracht. Denn damit ist eine Aussage darüber möglich, ob dieselben Proteinmengen - beispielsweise als Maß für den Ertrag einer fermentativen Produktion - zu vergleichbaren Ergebnissen führen. Klaffen die jeweiligen Verhältnisse von Aktivsubstanz zu Gesamtprotein (die Werte der spezifischen Aktivität) auseinander, so ist ein aktivitätsgleicher Vergleich zu empfehlen, weil hierüber die jeweiligen enzymatischen Eigenschaften verglichen werden. Generell gilt, daß eine niedrige spezifische Aktivität durch Zugabe einer größeren Proteinmenge ausgeglichen werden kann. Hierbei handelt es sich letztlich um eine ökonomische Erwägung.When comparing the performance of two enzymes, a distinction must be made between protein-like and activity-like use. Particularly in the case of genetically engineered, largely side-activity-free preparations, the use of the same protein is appropriate. Because this is a statement on whether the same amounts of protein - for example, as a measure of the yield of a fermentative production - lead to comparable results. If the respective ratios of active substance to total protein (the values of the specific activity) diverge, then an activity-equivalent comparison is recommended because this compares the respective enzymatic properties. In general, a low specific activity can be compensated by adding a larger amount of protein. This is ultimately an economic consideration.
Die Proteaseaktivität in derartigen Mitteln kann nach der in Tenside, Band 7 (1970), S. 125-132 beschriebenen Methode ermittelt werden. Sie wird entsprechend in PE (Protease-Einheiten) angegeben.The protease activity in such agents can be determined by the method described in Tenside, Vol. 7 (1970), pp. 125-132. It is given in PE (protease units) accordingly.
Die in erfindungsgemäßen Mitteln eingesetzten Enzyme stammen entweder ursprünglich aus Mikroorganismen, etwa der Gattungen Bacillus, Streptomyces, Humicola, oder Pseudomonas, und/oder werden nach an sich bekannten biotechnologischen Verfahren durch geeignete
Mikroorganismen produziert, beispielsweise durch transgene Expressionswirte der Gattungen Bacillus oder durch filamentöse Fungi.The enzymes used in the compositions according to the invention are either originally derived from microorganisms, for example the genera Bacillus, Streptomyces, Humicola or Pseudomonas, and / or are prepared by suitable biotechnological processes Microorganisms produced, for example, by transgenic expression hosts of the genera Bacillus or by filamentous fungi.
Einen eigenen Erfindungsgegenstand stellt die Verwendung eines oben beschriebenen erfindungsgemäßen Mittels zur Entfernung von protease-sensitiven Anschmutzungen auf Textilien oder harten Oberflächen, d.h. zur Reinigung von Textilien oder von harten Oberflächen, dar.A separate subject of the invention is the use of an above-described agent according to the invention for the removal of protease-sensitive stains on textiles or hard surfaces, i. for cleaning textiles or hard surfaces.
Denn erfindungsgemäße Mittel können, insbesondere entsprechend den oben beschriebenen Eigenschaften, dazu verwendet werden, um von Textilien oder von harten Oberflächen proteinhaltige Verunreinigungen zu beseitigen. Ausführungsformen stellen beispielsweise die Handwäsche, die manuelle Entfernung von Flecken von Textilien oder von harten Oberflächen oder die Verwendung im Zusammenhang mit einem maschinellen Verfahren dar.For agents according to the invention can be used, in particular in accordance with the properties described above, to remove proteinaceous impurities from textiles or from hard surfaces. Embodiments include, for example, hand washing, manual removal of stains from fabrics or hard surfaces, or use in conjunction with a machine process.
In einer bevorzugten Ausführungsform dieser Verwendung werden die betreffenden erfindungsgemäßen Mittel, vorzugsweise Wasch- beziehungsweise Reinigungsmittel, nach einer der oben ausgeführten Ausführungsformen bereitgestellt.In a preferred embodiment of this use, the relevant agents according to the invention, preferably detergents or cleaning agents, are provided according to one of the above-described embodiments.
Einen weiteren eigenen Erfindungsgegenstand stellen Verfahren zur Reinigung von Textilien oder von harten Oberflächen dar, bei denen wenigstens in einem der Verfahrensschritte ein erfindungsgemäßes Mittel verwendet wird. Das Verfahren zur Reinigung von Textilien oder harten Oberflächen ist demnach dadurch gekennzeichnet, dass in mindestens einem Verfahrensschritt ein erfindungsgemäßes Mittel angewendet ist.A further subject of the invention are processes for the cleaning of textiles or of hard surfaces, in which an agent according to the invention is used at least in one of the process steps. The process for the cleaning of textiles or hard surfaces is accordingly characterized in that an agent according to the invention is used in at least one process step.
Hierunter fallen sowohl manuelle als auch maschinelle Verfahren, wobei maschinelle Verfahren aufgrund ihrer präziseren Steuerbarkeit, was beispielsweise die eingesetzten Mengen und Einwirkzeiten angeht, bevorzugt sind.This includes both manual and mechanical processes, with mechanical processes being preferred on account of their more precise controllability, for example with regard to the quantities and reaction times used.
Verfahren zur Reinigung von Textilien zeichnen sich im allgemeinen dadurch aus, dass in mehreren Verfahrensschritten verschiedene reinigungsaktive Substanzen auf das Reinigungsgut aufgebracht und nach der Einwirkzeit abgewaschen werden, oder dass das Reinigungsgut in sonstiger Weise mit einem Waschmittel oder einer Lösung dieses Mittels behandelt wird. Das gleiche gilt für Verfahren zur Reinigung von allen anderen Materialien als Textilien, welche unter dem Begriff harte Oberflächen zusammengefasst werden. Alle denkbaren Wasch- oder Reinigungsverfahren können in wenigstens einem der Verfahrensschritte um ein erfindungsgemäßes Mittel bereichert werden, und stellen dann Ausführungsformen der vorliegenden Erfindung dar.
Da bevorzugte erfindungsgemäße Proteasekombinationen natürlicherweise bereits eine proteinauflösende Aktivität besitzen und diese auch in Medien entfalten, die sonst keine Reinigungskraft besitzen, wie beispielsweise in bloßem Puffer, kann ein einzelner Teilschritt eines solchen Verfahrens zur Reinigung, insbesondere zur maschinellen Reinigung, von Textilien oder harten Oberflächen darin bestehen, daß gewünschtenfalls neben stabilisierenden Verbindungen, Salzen oder Puffersubstanzen als einzige reinigungsaktive Komponente ein erfindungsgemäße Enzymmischung aufgebracht wird. Dies stellt eine besonders vereinfachte Ausführungsform der vorliegenden Erfindung dar.Methods for cleaning textiles are generally distinguished by the fact that various cleaning-active substances are applied to the items to be cleaned in a plurality of process steps and washed off after the action time, or that the items to be cleaned are otherwise treated with a detergent or a solution of this agent. The same applies to processes for cleaning all other materials than textiles, which are summarized by the term hard surfaces. All conceivable washing or cleaning methods can be enriched in at least one of the method steps by an agent according to the invention, and then represent embodiments of the present invention. Since preferred protease combinations according to the invention naturally already have a protein-dissolving activity and also unfold them in media which otherwise have no cleaning power, for example in bare buffer, a single substep of such a process may be for cleaning, in particular for machine cleaning, textiles or hard surfaces therein If desired, in addition to stabilizing compounds, salts or buffer substances, an enzyme mixture according to the invention is applied as sole cleaning-active component. This represents a particularly simplified embodiment of the present invention.
Einen weiteren Gegenstand der Erfindung stellen Verfahren zur Reinigung von Textilien oder harten Oberflächen dar, die dadurch gekennzeichnet sind, dass in mindestens einem Verfahrensschritt eine erste Protease und eine zweite Protease proteolytisch aktiv sind, wobei die erste Protease ausgewählt ist aus a) einer Protease, die eine Aminosäuresequenz umfasst, die zu der in SEQ ID NO.1 angegebenen Aminosäuresequenz mindestens zu 80% identisch ist; b) einer Protease, die eine Aminosäuresequenz umfasst, die zu der in SEQ ID NO.2 angegebenen Aminosäuresequenz mindestens zu 80% identisch ist; c) einer Protease, die eine Aminosäuresequenz umfasst, die zu der in SEQ ID NO.2 angegebenen Aminosäuresequenz mindestens zu 80% identisch ist und zusätzlich mindestens eine zusätzliche Aminosäure im Vergleich mit SEQ ID NO.2 aufweist; und die zweite Protease eine Aminosäuresequenz umfasst, die zu der in SEQ ID NO.3 angegebenen Aminosäuresequenz mindestens zu 80% identisch ist.Another object of the invention are methods for the purification of textiles or hard surfaces, which are characterized in that in at least one method step, a first protease and a second protease are proteolytically active, wherein the first protease is selected from a) a protease, the an amino acid sequence which is at least 80% identical to the amino acid sequence given in SEQ ID NO.1; b) a protease comprising an amino acid sequence which is at least 80% identical to the amino acid sequence given in SEQ ID NO. 2; c) a protease which comprises an amino acid sequence which is at least 80% identical to the amino acid sequence given in SEQ ID NO. 2 and additionally has at least one additional amino acid in comparison with SEQ ID NO. 2; and the second protease comprises an amino acid sequence which is at least 80% identical to the amino acid sequence given in SEQ ID NO.3.
In einer bevorzugten Ausführungsform des Verfahrens ist die erste Protease ausgewählt aus a) einer Protease, die eine Aminosäuresequenz umfasst, die zu der in SEQ ID NO.1 angegebenen Aminosäuresequenz zunehmend bevorzugt zu mindestens 82,5%, 85%, 87,5%, 90%, 91 %, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, 99,5% und ganz besonders bevorzugt zu 100% identisch ist. b) einer Protease, die eine Aminosäuresequenz umfasst, die zu der in SEQ ID NO.2 angegebenen Aminosäuresequenz zunehmend bevorzugt zu mindestens 82,5%, 85%, 87,5%, 90%, 91 %, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, 99,5% und ganz besonders bevorzugt zu 100% identisch ist. c) einer Protease, die eine Aminosäuresequenz umfasst, die zu der in SEQ ID NO.2 angegebenen Aminosäuresequenz zunehmend bevorzugt zu mindestens 82,5%, 85%, 87,5%, 90%, 91 %, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, 99,5% und ganz besonders bevorzugt zu 100% identisch ist und mindestens eine zusätzliche Aminosäure im Vergleich mit SEQ ID NO.2 aufweist.
In einer weiteren bevorzugten Ausführungsform ist das Verfahren dadurch gekennzeichnet, dass die zusätzliche Aminosäure der ersten Protease nach einer der folgenden Positionen in der Zählweise gemäß SEQ ID NO.2 eingefügt ist: 33, 34, 35, 36, 37, 38, 39, 40, 41 , 42, 43, 95, 96, 97, 98, 99, 100, 101 , 102, 103, 125, 126, 127, 126, 129, 130, 131 , 132, 153, 154, 155, 156, 157, 158, 159, 160, 161 , 162, 163, 164, 165, 166, 167, 168, 169, 170, 171 , 172, 173, 181 , 182, 183, 184, 185, 186, 187, 188, 189, 190, 191 , 192, 193, 194, 195, 202, 203, 204, 218, 219. Denn verschiedene Proteasen, die erfindungsgemäß als erste Protease in einem entsprechenden Verfahren einsetzbar sind, weisen eine entsprechende Insertion von zumindest einer Aminosäure oder auch von mehreren Aminosäuren, bevorzugt an einer oder mehreren der genannten Positionen, auf. Dies gilt - wie bereits vorstehend für erfindungsgemäße Mittel beschrieben - beispielsweise für Proteasen, die in der europäischen Patentanmeldung EP 1 032 655 beschrieben sind. Diese weisen beispielsweise mindestens eine zusätzliche Aminosäure auf in der Zählweise gemäß SEQ ID NO.2 (das heißt in der Zählweise der Savinase®, in der genannten Anmeldung bezeichnet als BLSAVI), in den Positionen 33 bis 43, 95 bis 103, 125 bis 132, 153 bis 173, 181 bis 195, 202 bis 204 und/oder Position 218 bis 219. Weitere Proteasen, die eine Insertion von mindestens einer Aminosäure aufweisen und erfindungsgemäß als erste Protease einsetzbar sind, gehen aus der internationalen Patentanmeldung WO 00/37599 und der internationalen Patentanmeldung WO 01/44452 hervor.In a preferred embodiment of the method, the first protease is selected from a) a protease which comprises an amino acid sequence which is increasingly preferably at least 82.5%, 85%, 87.5% to the amino acid sequence given in SEQ ID NO. 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, 99.5%, and most preferably 100% identical. b) a protease comprising an amino acid sequence which is more preferably at least 82.5%, 85%, 87.5%, 90%, 91%, 92%, 93%, of the amino acid sequence given in SEQ ID NO. 94%, 95%, 96%, 97%, 98%, 99%, 99.5% and most preferably 100% identical. c) a protease comprising an amino acid sequence which is more preferably at least 82.5%, 85%, 87.5%, 90%, 91%, 92%, 93% to the amino acid sequence given in SEQ ID NO. Is 94%, 95%, 96%, 97%, 98%, 99%, 99.5% and most preferably 100% identical and has at least one additional amino acid compared to SEQ ID NO.2. In a further preferred embodiment, the method is characterized in that the additional amino acid of the first protease is inserted in one of the following positions in the counting manner according to SEQ ID NO. 2: 33, 34, 35, 36, 37, 38, 39, 40 , 41, 42, 43, 95, 96, 97, 98, 99, 100, 101, 102, 103, 125, 126, 127, 126, 129, 130, 131, 132, 153, 154, 155, 156, 157 , 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 171, 172, 173, 181, 182, 183, 184, 185, 186, 187, 188, 189 , 190, 191, 192, 193, 194, 195, 202, 203, 204, 218, 219. For different proteases, which are used according to the invention as the first protease in a corresponding method, have a corresponding insertion of at least one amino acid or of a plurality of amino acids, preferably at one or more of said positions on. This applies - as already described above for agents according to the invention - for example for proteases, which are described in the European patent application EP 1 032 655. These have, for example, at least one additional amino acid in the counting method according to SEQ ID NO. 2 (that is to say in the counting method of Savinase®, referred to in the named application as BLSAVI), in positions 33 to 43, 95 to 103, 125 to 132 , 153 to 173, 181 to 195, 202 to 204 and / or position 218 to 219. Further proteases which have an insertion of at least one amino acid and can be used according to the invention as the first protease, are derived from the international patent application WO 00/37599 and the international patent application WO 01/44452.
Hinsichtlich der zweiten Protease, die in erfindungsgemäßen Verfahren mit der ersten Protease kombiniert wird, ist das Verfahren dadurch gekennzeichnet, dass die zweite Protease eine Aminosäuresequenz umfasst, die zu der in SEQ ID NO.3 angegebenen Aminosäuresequenz zunehmend bevorzugt zu mindestens 82,5%, 85%, 87,5%, 90%, 91 %, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, 99,5% und ganz besonders bevorzugt zu 100% identisch ist.With regard to the second protease which is combined in the method according to the invention with the first protease, the method is characterized in that the second protease comprises an amino acid sequence which is increasingly preferably at least 82.5% to the amino acid sequence given in SEQ ID NO. 85%, 87.5%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, 99.5%, and most preferably 100% identical is.
Bevorzugt werden die Proteasen in einer Menge von 40 μg bis 4 g, vorzugsweise von 50 μg bis 3 g, besonders bevorzugt von 100 μg bis 2 g und ganz besonders bevorzugt von 200 μg bis 1 g pro Anwendung eingesetzt. In den dargestellten Mengenangaben sind die erste Protease und die zweite Protease enthalten.The proteases are preferably used in an amount of from 40 μg to 4 g, preferably from 50 μg to 3 g, particularly preferably from 100 μg to 2 g and very particularly preferably from 200 μg to 1 g per application. The quantities shown contain the first protease and the second protease.
Weitere Ausführungsformen dieses Erfindungsgegenstandes stellen Verfahren zur Behandlung von Textilrohstoffen oder zur Textilpflege dar, bei denen in wenigstens einem der Verfahrensschritte eine erfindungsgemäße Proteasekombination aktiv wird.Further embodiments of this subject matter of the invention are processes for the treatment of textile raw materials or for textile care in which a protease combination according to the invention becomes active in at least one of the process steps.
Hierunter sind Verfahren für Textilrohstoffe, Fasern oder Textilien mit natürlichen Bestandteilen bevorzugt, und ganz besonders für solche mit Wolle oder Seide.
Es kann sich dabei beispielsweise um Verfahren handeln, in denen Materialien zur Verarbeitung in Textilien vorbereitet werden, etwa zur Antifilzausrüstung, oder beispielsweise um Verfahren, welche die Reinigung getragener Textilien um eine pflegende Komponente bereichern. Wegen der oben beschriebenen Wirkung von Proteasen auf natürliche, proteinhaltige Rohstoffe handelt es sich in bevorzugten Ausführungsformen um Verfahren zur Behandlung von Textilrohstoffen, Fasern oder Textilien mit natürlichen Bestandteilen, insbesondere mit Wolle oder Seide.Among these, methods for textile raw materials, fibers or textiles with natural components are preferred, and especially for those with wool or silk. These may be, for example, processes in which materials for processing in textiles are prepared, for example for anti-fungal finishing, or, for example, for processes which enrich the cleaning of worn textiles with a nourishing component. Because of the above-described effect of proteases on natural, proteinaceous raw materials, in preferred embodiments, they are processes for the treatment of textile raw materials, fibers or textiles with natural constituents, in particular with wool or silk.
Einen weiteren eigenen Erfindungsgegenstand stellt die Verwendung einer ersten Protease und einer zweiten Protease zur Reinigung von Textilien oder harten Oberflächen, dadurch gekennzeichnet, dass die erste Protease ausgewählt ist aus a) einer Protease, die eine Aminosäuresequenz umfasst, die zu der in SEQ ID NO.1 angegebenen Aminosäuresequenz mindestens zu 80% identisch ist; b) einer Protease, die eine Aminosäuresequenz umfasst, die zu der in SEQ ID NO.2 angegebenen Aminosäuresequenz mindestens zu 80% identisch ist; c) einer Protease, die eine Aminosäuresequenz umfasst, die zu der in SEQ ID NO.2 angegebenen Aminosäuresequenz mindestens zu 80% identisch ist und zusätzlich mindestens eine zusätzliche Aminosäure im Vergleich mit SEQ ID NO.2 aufweist; und die zweite Protease eine Aminosäuresequenz umfasst, die zu der in SEQ ID NO.3 angegebenen Aminosäuresequenz mindestens zu 80% identisch ist.A further inventive subject matter is the use of a first protease and a second protease for the purification of textiles or hard surfaces, characterized in that the first protease is selected from a) a protease comprising an amino acid sequence corresponding to the amino acid sequence shown in SEQ ID NO. 1 amino acid sequence is at least 80% identical; b) a protease comprising an amino acid sequence which is at least 80% identical to the amino acid sequence given in SEQ ID NO. 2; c) a protease which comprises an amino acid sequence which is at least 80% identical to the amino acid sequence given in SEQ ID NO. 2 and additionally has at least one additional amino acid in comparison with SEQ ID NO. 2; and the second protease comprises an amino acid sequence which is at least 80% identical to the amino acid sequence given in SEQ ID NO.3.
Denn erfindungsgemäße Kombinationen von Proteasen können, insbesondere auf Grund der vorstehend beschriebenen Eigenschaften, dazu verwendet werden, um von Textilien oder von harten Oberflächen proteinhaltige Verunreinigungen zu beseitigen. Ausführungsformen stellen beispielsweise die Handwäsche, die manuelle Entfernung von Flecken von Textilien oder von harten Oberflächen oder die Verwendung im Zusammenhang mit einem maschinellen Verfahren dar. In einer bevorzugten Ausführungsform dieser Verwendung werden die betreffenden erfindungsgemäßen Kombinationen von Proteasen nach einer der vorstehend ausgeführten Rezepturen bereitgestellt.Because combinations of proteases according to the invention can be used, in particular because of the properties described above, to eliminate proteinaceous impurities from textiles or from hard surfaces. Embodiments include, for example, hand washing, manual removal of stains from fabrics or hard surfaces, or use in conjunction with a machine process. In a preferred embodiment of this use, the subject combinations of proteases of this invention are provided according to any of the above recipes.
In einer bevorzugten Ausführungsform dieser Verwendung ist die erste Protease ausgewählt aus a) einer Protease, die eine Aminosäuresequenz umfasst, die zu der in SEQ ID NO.1 angegebenen Aminosäuresequenz zunehmend bevorzugt zu mindestens 82,5%, 85%, 87,5%, 90%, 91 %, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, 99,5% und ganz besonders bevorzugt zu 100% identisch ist. b) einer Protease, die eine Aminosäuresequenz umfasst, die zu der in SEQ ID NO.2 angegebenen Aminosäuresequenz zunehmend bevorzugt zu mindestens 82,5%, 85%, 87,5%,
90%, 91 %, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, 99,5% und ganz besonders bevorzugt zu 100% identisch ist. c) einer Protease, die eine Aminosäuresequenz umfasst, die zu der in SEQ ID NO.2 angegebenen Aminosäuresequenz zunehmend bevorzugt zu mindestens 82,5%, 85%, 87,5%, 90%, 91 %, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, 99,5% und ganz besonders bevorzugt zu 100% identisch ist und mindestens eine zusätzliche Aminosäure im Vergleich mit SEQ ID NO.2 aufweist.In a preferred embodiment of this use, the first protease is selected from a) a protease which comprises an amino acid sequence which is more preferably at least 82.5%, 85%, 87.5% to the amino acid sequence given in SEQ ID NO. 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, 99.5%, and most preferably 100% identical. b) a protease which comprises an amino acid sequence which is more preferably at least 82.5%, 85%, 87.5% to the amino acid sequence given in SEQ ID NO. 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, 99.5%, and most preferably 100% identical. c) a protease comprising an amino acid sequence which is more preferably at least 82.5%, 85%, 87.5%, 90%, 91%, 92%, 93% to the amino acid sequence given in SEQ ID NO. Is 94%, 95%, 96%, 97%, 98%, 99%, 99.5% and most preferably 100% identical and has at least one additional amino acid compared to SEQ ID NO.2.
In einer weiteren bevorzugten Ausführungsform ist die Verwendung dadurch gekennzeichnet, dass die zusätzliche Aminosäure der ersten Protease nach einer der folgenden Positionen in der Zählweise gemäß SEQ ID NO.2 eingefügt ist: 33, 34, 35, 36, 37, 38, 39, 40, 41 , 42, 43, 95, 96, 97, 98, 99, 100, 101 , 102, 103, 125, 126, 127, 126, 129, 130, 131 , 132, 153, 154, 155, 156, 157, 158, 159, 160, 161 , 162, 163, 164, 165, 166, 167, 168, 169, 170, 171 , 172, 173, 181 , 182, 183, 184, 185, 186, 187, 188, 189, 190, 191 , 192, 193, 194, 195, 202, 203, 204, 218, 219. Denn verschiedene Proteasen, die erfindungsgemäß als erste Protease verwendbar sind, weisen eine entsprechende Insertion von zumindest einer Aminosäure auf. Beispiele für derartige Enzyme, die eine entsprechende Insertion aufweisen, sind in der vorliegenden Anmeldung bereits vorstehend für die erfindungsgemäßen Mittel und die erfindungsgemäßen Verfahren erörtert.In a further preferred embodiment, the use is characterized in that the additional amino acid of the first protease is inserted in one of the following positions in the counting manner according to SEQ ID NO.2: 33, 34, 35, 36, 37, 38, 39, 40 , 41, 42, 43, 95, 96, 97, 98, 99, 100, 101, 102, 103, 125, 126, 127, 126, 129, 130, 131, 132, 153, 154, 155, 156, 157 , 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 171, 172, 173, 181, 182, 183, 184, 185, 186, 187, 188, 189 , 190, 191, 192, 193, 194, 195, 202, 203, 204, 218, 219. For different proteases, which are useful according to the invention as the first protease, have a corresponding insertion of at least one amino acid. Examples of such enzymes which have a corresponding insertion are already discussed above in the present application for the agents according to the invention and the methods according to the invention.
Hinsichtlich der zweiten Protease, die in einer erfindungsgemäßen Verwendung mit der ersten Protease kombiniert wird, ist die Verwendung dadurch gekennzeichnet, dass die zweite Protease eine Aminosäuresequenz umfasst, die zu der in SEQ ID NO.3 angegebenen Aminosäuresequenz zunehmend bevorzugt zu mindestens 82,5%, 85%, 87,5%, 90%, 91 %, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, 99,5% und ganz besonders bevorzugt zu 100% identisch ist.With regard to the second protease which is combined in a use according to the invention with the first protease, the use is characterized in that the second protease comprises an amino acid sequence which is increasingly preferably at least 82.5% to the amino acid sequence given in SEQ ID NO. , 85%, 87.5%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, 99.5% and most preferably 100% is identical.
Bevorzugt zeichnet sich eine erfindungsgemäße Verwendung einer erfindungsgemäßen Kombination von Proteasen dadurch aus, dass die Proteasen in einer Menge von 40 μg bis 4 g, vorzugsweise von 50 μg bis 3 g, besonders bevorzugt von 100 μg bis 2 g und ganz besonders bevorzugt von 200 μg bis 1 g pro Anwendung eingesetzt sind. In den dargestellten Mengenangaben sind die erste Protease und die zweite Protease enthalten.A preferred use of a combination of proteases according to the invention is characterized in that the proteases are present in an amount of from 40 μg to 4 g, preferably from 50 μg to 3 g, more preferably from 100 μg to 2 g and most preferably from 200 μg to 1 g per application are used. The quantities shown contain the first protease and the second protease.
Die folgenden Beispiele dienen der weiteren Erläuterung der Erfindung, ohne sie jedoch darauf einzuschränken:
Beispiel 1 : Synergistische Leistung der Protease-Variante S99SD+S99A gemäß WO 01/44452 und der Alkalischen Protease aus Bacillus gibsonii (DSM 14391 )The following examples serve to further illustrate the invention without, however, limiting it to: Example 1 Synergistic Performance of the Protease Variant S99SD + S99A According to WO 01/44452 and the Alkaline Protease from Bacillus Gibsonii (DSM 14391)
Zum Vergleich erfindungsgemäßer Mischungen mit dem Stand der Technik wurde zunächst folgende Rahmenrezeptur für ein festes maschinelles Geschirrspülmittel hergestellt:For comparison of inventive mixtures with the prior art, the following frame formulation for a solid machine dishwashing detergent was first prepared:
Inhaltsstoff Gehalt [Gew.-%]Ingredient Content [wt%]
Na-Tripolyphosphat 30 - 45Na tripolyphosphate 30-45
Nichtionisches Tensid 3 - 8Nonionic surfactant 3 - 8
Acrylsäure/Sulfonsäure-Copolymer 5 - 10Acrylic acid / sulfonic acid copolymer 5 - 10
Acrylsäurepolymer 5 - 10Acrylic acid polymer 5-10
Na-percarbonat 8-12Na-percarbonate 8-12
Na-carbonat 10 - 15Na carbonate 10 - 15
Amylase-Granulat gemäß DE 102005062984.9 0,5 - 1 ,5Amylase granules according to DE 102005062984.9 0.5-1.5
Zinkacetat 0,5 - 1 ,5Zinc acetate 0.5-1.5
Proteasen (siehe nachstehend)Proteases (see below)
Wasser, Salze, Farbstoffe ad 100%Water, salts, dyes ad 100%
In solch eine Rezeptur wurden die reinen Enzymgranulate und Mischungen der Protease, die als Subtilase 309 (auch bezeichnet als Subtilisin 309 oder Savinase®)-Variante S99SD+S99A in der internationalen Patentanmeldung WO 01/44452 offenbart ist (vgl. insbesondere die Beispiele 1 und 2 der WO 01/44452), als einem Vertreter der ersten Protease und der Alkalischen Protease aus Bacillus gibsonii (DSM 14391 ) als einem Vertreter der zweiten Protease eingearbeitet. Die Mischung wurde proportional zu den Einsätzen der Einzelenzyme berechnet. Das Granulat der Alkalischen Protease aus Bacillus gibsonii (DSM 14391 ) wurde gemäß WO 97/40128 A1 hergestellt und gemäß WO 98/26037 A2 beschichtet.In such a formulation, the pure enzyme granules and mixtures of the protease disclosed as Subtilase 309 (also referred to as Subtilisin 309 or Savinase®) variant S99SD + S99A are disclosed in international patent application WO 01/44452 (see especially Examples 1 and 2 of WO 01/44452) as a representative of the first protease and the alkaline protease from Bacillus gibsonii (DSM 14391) as a representative of the second protease. The mixture was calculated in proportion to the insertions of the single enzymes. The granules of the alkaline protease from Bacillus gibsonii (DSM 14391) were prepared according to WO 97/40128 A1 and coated according to WO 98/26037 A2.
Aus den Rezepturen wurden in einer Tablettierungspresse der Firma Paul-Otto Weber Maschinen + Apparatebau GmbH (Remshalden, Deutschland) unter einem Druck von 25 N Einphasen- Tabletten gepresst. Gefäße mit harten, glatten Oberflächen wurden standardisiert mit einer Ei/Milch-Anschmutzung (gemäß SÖFW (Seifen Öle Fette Wachse)-Journal 132 3-2006 ) versehen und mit einer handelsüblichen Haushaltsgeschirrspülmaschine gespült, nämlich bei 5O0C mit dem Normalprogramm der Geschirrspülmaschine des Typs Bosch SGS 59 A02. Pro Spülgang wurden jeweils 23 g Spülmittel verwendet. Die Wasserhärte betrug 21 ° deutscher Härte. Die Leistung wurde als Abtrag an Weicheiblechen gemäß SÖFW-Journal Ausgabe 3-2006, S. 132 (IKW- Arbeitskreis Maschinengeschirrspüimittei: Methoden zur Bestimmung der Reinigungsleistung von maschinellen Geschirrspülmittein (Teil B. aktualisiert 2005)), bestimmt. Nach dem Spülen wurde der Abtrag der Anschmutzungen gravimetrisch in Prozent ermittelt. Dafür wurde die Differenz aus
dem Gewicht des verschmutzten und anschließend gespülten Gefäßes und dem Anfangsgewicht des Gefäßes in Relation zu der Gewichtsdifferenz des nicht gespülten Gefäßes zum Anfangsgewicht gesetzt. Diese Relation kann als Prozent Abtrag angesehen werden. Die erhaltenen Ergebnisse werden in folgender Tabelle 1 zusammengestellt. Angegeben sind dort die Mittelwerte aus jeweils 9 Messungen.From the formulations were pressed in a tableting press of Paul-Otto Weber Maschinen + Apparatebau GmbH (Remshalden, Germany) under a pressure of 25 N single-phase tablets. Vessels with hard, smooth surfaces were standardized with an egg / milk soiling (according to SÖFW (Soaps Oils Fat Waxes) Journal 132 3-2006) and rinsed with a commercial household dishwasher, namely at 5O 0 C with the normal program of the dishwasher Type Bosch SGS 59 A02. Each rinse used 23 g of rinse each. The water hardness was 21 ° German hardness. The performance was determined as removal of soft sheets according to SÖFW-Journal issue 3-2006, p. 132 (IKW-Arbeitskreis Maschinengeschirrspüimittei: Methods for determining the cleaning performance of automatic dishwashing agents (Part B. updated 2005)). After rinsing, the removal of soiling was determined gravimetrically in percent. That was the difference the weight of the contaminated and subsequently rinsed vessel and the initial weight of the vessel in relation to the weight difference of the non-rinsed vessel to the initial weight set. This relation can be regarded as percent removal. The results obtained are summarized in Table 1 below. Indicated there are the mean values from 9 measurements each.
Tabelle 1 : Ergebnisse des Leistungsvergleichs von einer Mischung von Proteasen im Vergleich zu den reinen Proteasen in einem maschinellen Geschirrspülmittel.Table 1: Results of the performance comparison of a mixture of proteases compared to the pure proteases in a machine dishwashing detergent.
Durch Vergleich der beiden Ansätze 1 und 2 mit dem Ansatz 3 wird deutlich, dass durch die proportionale Kombination der beiden Proteasen Subtilase 309 - Variante S99SD+S99A gemäß WO 01/44452 und Alkalische Protease aus Bacillus gibsonii (DSM 14391 ) bei geringerem Enzymproteingehalt im Vergleich zu Versuchsansätzen mit alleinig Subtilase 309 - Variante S99SD+S99A gemäß WO 01/44452 bzw. Alkalische Protease aus Bacillus gibsonii (DSM 14391 ) eine deutlich bessere, synergistische Leistung erhalten wird.By comparing the two approaches 1 and 2 with the approach 3 it is clear that by the proportional combination of the two proteases subtilase 309 - variant S99SD + S99A according to WO 01/44452 and alkaline protease from Bacillus gibsonii (DSM 14391) with a lower enzyme protein content in comparison to test assays with sole subtilase 309 variant S99SD + S99A according to WO 01/44452 or alkaline protease from Bacillus gibsonii (DSM 14391) a significantly better, synergistic performance is obtained.
Für eine Kalkulation der erwartbaren Reinigungsleistung einer Kombination von der Subtilase 309 - Variante S99SD+S99A gemäß WO 01/44452 und Alkalischen Protease aus Bacillus gibsonii (DSM 14391 ) werden zunächst die jeweiligen Mengen an Gesamtprotease zueinander ins Verhältnis gesetzt, wodurch sich ein Faktor von 0,52437 ergibt (44 mg + 18,4 mg Enzymprotein (Ansatz 3) geteilt durch 74 mg Enzymprotein (Ansatz 1 ) + 45 mg Enzymprotein (Ansatz 2)). Hieraus folgt, dass der theoretische Abtrag einer Kombination von der Subtilase 309 - Variante S99SD+S99A gemäß WO 01/44452 und der Alkalischen Protease aus Bacillus gibsonii (DSM 14391 ) (64% + 71 %) x 0,52437 = 70,8% beträgt. Im Vergleich hierzu beträgt der real vorhandene Abtrag 84%. Der Vergleich dieser beiden Werte verdeutlicht das Vorliegen einer synergistischen Reinigungsleistung durch die beiden verwendeten Proteasen.For a calculation of the expected cleaning performance of a combination of the subtilase 309 variant S99SD + S99A according to WO 01/44452 and alkaline protease from Bacillus gibsonii (DSM 14391), first the respective amounts of total protease are set in relation to each other, whereby a factor of 0 , 52437 (44 mg + 18.4 mg enzyme protein (batch 3) divided by 74 mg enzyme protein (batch 1) + 45 mg enzyme protein (batch 2)). It follows that the theoretical removal of a combination of the subtilase 309 variant S99SD + S99A according to WO 01/44452 and the alkaline protease from Bacillus gibsonii (DSM 14391) (64% + 71%) x 0.52437 = 70.8% is. Compared to this, the actual stock removal is 84%. The comparison of these two values illustrates the presence of a synergistic cleaning performance by the two proteases used.
Beispiel 2: Synergistische Leistung der Alkalischen Protease aus Bacillus lentus F49 und derExample 2: Synergistic Performance of the Bacillus lentus F49 Alkaline Protease and the
Alkalischen Protease aus Bacillus gibsonii (DSM 14391 )Alkaline protease from Bacillus gibsonii (DSM 14391)
Zum Vergleich erfindungsgemäßer Mischungen mit dem Stand der Technik wurde zunächst
folgende Rahmenrezeptur für ein festes maschinelles Geschirrspülmittel hergestellt:For comparison of inventive mixtures with the prior art was first following frame formulation for a solid machine dishwashing detergent prepared:
Inhaltsstoff Gehalt [Gew.-%]Ingredient Content [wt%]
Na-Tripolyphosphat 30 - 45Na tripolyphosphate 30-45
Nichtionisches Tensid 3 - 8Nonionic surfactant 3 - 8
Acrylsäure/Sulfonsäure-Copolymer 5 - 10Acrylic acid / sulfonic acid copolymer 5 - 10
Acrylsäurepolymer 5 - 10Acrylic acid polymer 5-10
Na-percarbonat 8-12Na-percarbonate 8-12
Na-carbonat 10 - 15Na carbonate 10 - 15
Amylase-Granulat gemäß DE 102005062984.9 0,5 - 1 ,5Amylase granules according to DE 102005062984.9 0.5-1.5
Zinkacetat 0,5 - 1 ,5Zinc acetate 0.5-1.5
Proteasen (siehe nachstehend)Proteases (see below)
Wasser, Salze, Farbstoffe ad 100%Water, salts, dyes ad 100%
In solch eine Rezeptur wurden die reinen Enzymgranulate und Mischungen von der Alkalischen Protease aus Bacillus lentus F49 als einem Vertreter der ersten Protease und der Alkalischen Protease aus Bacillus gibsonii (DSM 14391 ) als einem Vertreter der zweiten Protease eingearbeitet. Die Mischung wurde proportional zu den Einsätzen der Einzelenzyme berechnet. Das Granulat der Alkalischen Protease aus Bacillus gibsonii (DSM 14391 ) wurde gemäß WO 97/40128 A1 hergestellt und gemäß WO 98/26037 A2 beschichtet.In such a formulation, the pure enzyme granules and mixtures of the alkaline protease from Bacillus lentus F49 were incorporated as a representative of the first protease and the alkaline protease from Bacillus gibsonii (DSM 14391) as a representative of the second protease. The mixture was calculated in proportion to the insertions of the single enzymes. The granules of the alkaline protease from Bacillus gibsonii (DSM 14391) were prepared according to WO 97/40128 A1 and coated according to WO 98/26037 A2.
Aus den Rezepturen wurden in einer Tablettierungspresse der Firma Paul-Otto Weber Maschinen + Apparatebau GmbH unter einem Druck von 25 N Einphasen-Tabletten gepresst. Gefäße mit harten, glatten Oberflächen wurden standardisiert mit einer Ei/Milch-Anschmutzung versehen und mit einer handelsüblichen Haushaltsgeschirrspülmaschine gespült, nämlich bei 4O0C mit dem Normalprogramm der Geschirrspülmaschine des Typs Bosch SGS 59 A 02. Pro Spülgang wurden jeweils 23 g Spülmittel verwendet. Die Wasserhärte betrug 21 ° deutscher Härte. Die Leistung wurde als Abtrag an Weicheiblechen gemäß SÖFW-Journal 132 3-2006 bestimmt. Nach dem Spülen wurde der Abtrag der Anschmutzungen gravimetrisch in Prozent ermittelt. Dafür wurde die Differenz aus dem Gewicht des verschmutzten und anschließend gespülten Gefäßes und dem Anfangsgewicht des Gefäßes in Relation zu der Gewichtsdifferenz des nicht gespülten Gefäßes zum Anfangsgewicht gesetzt. Diese Relation kann als Prozent Abtrag angesehen werden. Die erhaltenen Ergebnisse werden in folgender Tabelle 2 zusammengestellt. Angegeben sind dort die Mittelwerte aus jeweils 9 Messungen für Ansätze 1 und 3 sowie 8 Messungen für Ansatz 2.From the formulations were pressed in a tabletting press of Paul-Otto Weber Maschinen + Apparatebau GmbH under a pressure of 25 N single-phase tablets. Vessels with hard, smooth surfaces were standardized with an egg / milk soiling and rinsed with a commercial household dishwasher, namely at 4O 0 C with the standard program of the dishwasher Bosch SGS 59 A 02. Per rinse, each 23 g of detergent were used. The water hardness was 21 ° German hardness. The performance was determined as removal of soft sheets according to SÖFW-Journal 132 3-2006. After rinsing, the removal of soiling was determined gravimetrically in percent. For this, the difference between the weight of the contaminated and subsequently rinsed vessel and the initial weight of the vessel was set in relation to the weight difference of the non-rinsed vessel to the initial weight. This relation can be regarded as percent removal. The results obtained are summarized in Table 2 below. Indicated there are the mean values from in each case 9 measurements for approaches 1 and 3 as well as 8 measurements for approach 2.
Tabelle 2: Ergebnisse des Leistungsvergleichs höherkonzentrierter Granulate mit niedriger konzentrierten Granulaten in einem maschinellen Geschirrspülmittel.
Table 2: Results of the performance comparison of higher concentrated granules with low concentrated granules in a machine dishwashing detergent.
Durch Vergleich der beiden Ansätze 1 und 2 mit dem Ansatz 3 wird deutlich, dass durch die proportionale Kombination der beiden Proteasen (Bacillus lentus alkalische Protease F49 und Alkalische Protease aus Bacillus gibsonii (DSM 14391 )) bei geringerem Enzymproteingehalt im Vergleich zu Versuchsansätzen mit nur einer der genannten Proteasen alleine eine deutlich bessere, synergistische Leistung erhalten wird.By comparing the two approaches 1 and 2 with the approach 3 it is clear that by the proportional combination of the two proteases (Bacillus lentus alkaline protease F49 and alkaline protease from Bacillus gibsonii (DSM 14391)) with a lower enzyme protein content compared to experimental approaches with only one the proteases mentioned alone a significantly better, synergistic performance is obtained.
Für eine Kalkulation der erwartbaren Reinigungsleistung einer Kombination von der Alkalischen Protease aus Bacillus lentus F49 als einem Vertreter der ersten Protease und der Alkalischen Protease aus Bacillus gibsonii (DSM 14391 ) als einem Vertreter der zweiten Protease werden zunächst die jeweiligen Mengen an Gesamtprotease zueinander ins Verhältnis gesetzt, wodurch sich ein Faktor von 0,5 ergibt (20 mg + 10 mg Enzymprotein (Ansatz 3) geteilt durch 40 mg Enzymprotein (Ansatz 1 ) + 20 mg Enzymprotein (Ansatz 2)). Hieraus folgt, dass der theoretische Abtrag einer Kombination von Alkalischen Protease aus Bacillus lentus F49 und der Alkalischen Protease aus Bacillus gibsonii (DSM 14391 ) (53,2% + 52,8%) x 0,5 = 53,0% beträgt. Im Vergleich hierzu beträgt der real vorhandene Abtrag 56,7%. Der Vergleich dieser beiden Werte verdeutlicht das Vorliegen einer synergistischen Reinigungsleistung durch die beiden verwendeten Proteasen.For a calculation of the expected purification performance of a combination of the alkaline protease from Bacillus lentus F49 as a representative of the first protease and the alkaline protease from Bacillus gibsonii (DSM 14391) as a representative of the second protease, first the respective amounts of total protease are compared resulting in a factor of 0.5 (20 mg + 10 mg enzyme protein (batch 3) divided by 40 mg enzyme protein (batch 1) + 20 mg enzyme protein (batch 2)). It follows that the theoretical removal of a combination of Bacillus lentus F49 alkaline protease and Bacillus gibsonii alkaline protease (DSM 14391) (53.2% + 52.8%) is x 0.5 = 53.0%. In comparison, the actual stock removal is 56.7%. The comparison of these two values illustrates the presence of a synergistic cleaning performance by the two proteases used.
Beispiel 3: Erfindungsgemäße Anwendung in maschinellen Geschirrspülmitteln (MGSM) MGSM-Formulierungen, die folgender Rahmenrezeptur gehorchen wurde im Rahmen der Erfindung erzeugt:EXAMPLE 3 Application According to the Invention in Automatic Dishwashing Detergents (MGSM) MGSM formulations which obey the following general recipe were produced in the context of the invention:
Inhaltsstoff Gehalt [Gew.-%]Ingredient Content [wt%]
Na-Tripolyphosphat 30 - 45Na tripolyphosphate 30-45
Nichtionisches Tensid 3 - 8Nonionic surfactant 3 - 8
Acrylsäure/Sulfonsäure-Copolymer 5 - 10Acrylic acid / sulfonic acid copolymer 5 - 10
Acrylsäurepolymer 5 - 10Acrylic acid polymer 5-10
Na-percarbonat 10-15Na-percarbonate 10-15
Na-carbonat 10 - 15
Amylase-Granulat gemäß DE 102005062984.9 0,5 - 1 ,5Na carbonate 10 - 15 Amylase granules according to DE 102005062984.9 0.5-1.5
Zinkacetat 0,5 - 1Zinc acetate 0.5 - 1
Mn-Bleichkatalysatorcompound 0,52Mn bleach catalyst compound 0.52
Proteasen s.u.Proteases s.u.
Wasser, Salze, Farbstoffe ad 100%Water, salts, dyes ad 100%
Beispiel 4: Erfindungsgemäße Anwendung in festen WaschmittelnExample 4: Use according to the invention in solid detergents
Formulierungen für feste Waschmittel, die folgender Rahmenrezeptur gehorchen, wurden imFormulations for solid detergents which obey the following outline recipe have been published in the
Rahmen der Erfindung erzeugt.Frame of the invention produced.
Inhaltsstoff Gehalt [Gew.-%] lineares Alkylbenzolsulfonat (Natrium-Salz) 5 - 15Ingredient Content [% by weight] Linear alkyl benzene sulfonate (sodium salt) 5-15
Ci∑-Cis-Fettalkoholsulfat (Natrium-Salz) 1- 2Ci Σ- Cis fatty alcohol sulfate (sodium salt) 1-2
Ci2-Ci8-Fettalkohol mit 7 EO 1- 3Ci 2 -Ci 8 fatty alcohol with 7 EO 1-3
Natriumcarbonat 15- 30Sodium carbonate 15-30
Natriumhydrogencarbonat 2 - 10 amorphes Natriumdisilikat 2,5 - 8Sodium bicarbonate 2 - 10 amorphous sodium disilicate 2.5 - 8
Natriumcarbonat-peroxohydrat 10 - 22Sodium carbonate peroxohydrate 10 - 22
TAED 2 - 8TAED 2 - 8
Polyacrylat 0,5 - 5Polyacrylate 0.5 - 5
Carboxymethylcellulose 0 - 2Carboxymethyl cellulose 0-2
Phosphonat 0,5 - 2Phosphonate 0.5 - 2
Natriumsulfat 20 - 30Sodium sulfate 20-30
Proteasen 0,001 - 0,072 (reines Protein)Proteases 0.001-0.072 (pure protein)
Amylase 0 - 0,072 (reines Protein)Amylase 0 - 0.072 (pure protein)
Cellulase 0 - 0,072 (reines Protein)Cellulase 0 - 0.072 (pure protein)
Lipase 0 - 0,072 (reines Protein)Lipase 0 - 0.072 (pure protein)
Mannanase 0 - 0,072 (reines Protein)Mannanase 0 - 0.072 (pure protein)
Pectinase 0 - 0,072 (reines Protein) Rest: Schauminhibitoren, optischer Aufheller, DuftstoffePectinase 0 - 0.072 (pure protein) Balance: foam inhibitors, optical brightener, fragrances
Desweiteren wurden Formulierungen fester Waschmittel mit dieser Rahmenrezeptur im Rahmen der Erfindung erzeugt:Furthermore, formulations of solid detergents with this framework formulation were produced within the scope of the invention:
Inhaltsstoff Gehalt [Gew.-%] lineares Alkylbenzolsulfonat (Natrium-Salz) 2 - 6Ingredient Content [% by weight] Linear alkyl benzene sulfonate (sodium salt) 2-6
C12-C18-Fettalkoholsulfat (Natrium-Salz) 2 - 6
C12-C18-Fettalkohol mit 7 EO 3-7C12-C18 fatty alcohol sulfate (sodium salt) 2-6 C12-C18 fatty alcohol with 7 EO 3-7
Natrium-Seife 0,5-2Sodium soap 0.5-2
Natriumcarbonat 7-30 amorphes Natriumdisilikat 0,5-4Sodium carbonate 7-30 amorphous sodium disilicate 0.5-4
Natriumperborat-Tetrahydrat 0-30Sodium perborate tetrahydrate 0-30
TAED 0-20TAED 0-20
Zeolith A 10-35Zeolite A 10-35
Polycarboxylat 2,5-7Polycarboxylate 2.5-7
Phosphonat 0-1,5Phosphonate 0-1.5
Schauminhibitorgranulat 0,5-4Foam inhibitor granules 0.5-4
Natriumsulfat 2,5-8Sodium sulfate 2.5-8
Proteasen 0,001 - 0,072 (reines Protein)Proteases 0.001-0.072 (pure protein)
Amylase 0 - 0,072 (reines Protein)Amylase 0 - 0.072 (pure protein)
Cellulase 0 - 0,072 (reines Protein)Cellulase 0 - 0.072 (pure protein)
Lipase 0 - 0,072 (reines Protein)Lipase 0 - 0.072 (pure protein)
Mannanase 0 - 0,072 (reines Protein)Mannanase 0 - 0.072 (pure protein)
Pectinase 0 - 0,072 (reines Protein)Pectinase 0 - 0.072 (pure protein)
Rest: Wasser, optischer Aufheller, SalzeRemainder: water, optical brightener, salts
Beispiel 5: Erfindungsgemäße Anwendung in flüssigen WaschmittelnExample 5: Inventive Use in Liquid Detergents
Formulierungen für flüssige Waschmittel, die folgender Rahmenrezeptur gehorchen, wurden imFormulations for liquid detergents which obey the following outline recipe have been published in the
Rahmen der Erfindung erzeugt.Frame of the invention produced.
Inhaltsstoff Gehalt [Gew.-%]Ingredient Content [wt%]
Polyacrylat-Verd icker 0-5%Polyacrylate thickener 0-5%
Anti-Schaummittel 0-4%Anti-foaming agent 0-4%
Glycerin 0-12%Glycerine 0-12%
Propylenglykol 0-14%Propylene glycol 0-14%
Ethanol 0-5%Ethanol 0-5%
FAEOS 0-7%FAEOS 0-7%
Lineare Alkylbenzolsulfonsäure 0-20%Linear alkylbenzene sulfonic acid 0-20%
Alyklpolyglycosid 0-5%Alyklpolyglycoside 0-5%
Nichtionische Tenside 5-25%Nonionic surfactants 5-25%
Borsäure 1-2%Boric acid 1-2%
Natriumeitrat (Dihydrat) 0,5-7%Sodium citrate (dihydrate) 0.5-7%
Soda 2-8%Soda 2-8%
Kokosnuss-Fettsäuren 0-12%
HEDP 0-1%Coconut fatty acids 0-12% HEDP 0-1%
DTPMP 0-2%DTPMP 0-2%
PVP 0-0,4PVP 0-0.4
PVP/PVI 0-1% optischer Aufheller 0-0,2%PVP / PVI 0-1% optical brightener 0-0.2%
Farbstoff 0-0,001Dye 0-0.001
Proteasen 0,001 - 0,072 (reines Protein)Proteases 0.001-0.072 (pure protein)
Amylase 0 - 0,072 (reines Protein)Amylase 0 - 0.072 (pure protein)
Cellulase 0 - 0,072 (reines Protein)Cellulase 0 - 0.072 (pure protein)
Lipase 0 - 0,072 (reines Protein)Lipase 0 - 0.072 (pure protein)
Mannanase 0 - 0,072 (reines Protein)Mannanase 0 - 0.072 (pure protein)
Pectinase 0 - 0,072 (reines Protein) demineralisiertes Wasser ad 100%Pectinase 0 - 0.072 (pure protein) demineralized water ad 100%
Beispiel 6: Erfindungsgemäße Anwendung in festen, hochschäumenden Waschmitteln Formulierungen für feste hochschäumende Waschmittel, die folgender Rahmenrezeptur gehorchen, wurden im Rahmen der Erfindung erzeugt.Example 6 Application According to the Invention in Solid, High-Foaming Detergents Formulations for solid high-foaming detergents which obey the following general formula were produced in the context of the invention.
Inhaltsstoff Gehalt [Gew.-%] lineares Alkylbenzolsulfonat (Natrium-Salz) 10-30Ingredient Content [wt%] Linear alkyl benzene sulfonate (sodium salt) 10-30
C12-C18-Fettalkoholsulfat (Natrium-Salz) 0,01 -5C12-C18 fatty alcohol sulfate (sodium salt) 0.01 -5
C12-C18-Fettalkohol mit 7 EO 0,01 -5C12-C18 fatty alcohol with 7 EO 0.01 -5
Natriumcarbonat 0-30Sodium carbonate 0-30
Natriumsilikat 0- 10Sodium silicate 0-10
Natriumperborat 0- 10Sodium perborate 0-10
TAED 0-8TAED 0-8
Zeolith A 0-15Zeolite A 0-15
Na-Tripolyphosphat 5-35Na tripolyphosphate 5-35
Na-Percarbonat 0-20Na-percarbonate 0-20
Polycarboxylat 1 -7Polycarboxylate 1 -7
Polyacrylat 0,5-5Polyacrylate 0.5-5
Phosphonat 0-2Phosphonate 0-2
Carboxymethylcellulose 0-2Carboxymethylcellulose 0-2
Natriumsulfat 10-50Sodium sulfate 10-50
Proteasen 0,001 - 0,072 (reines Protein)Proteases 0.001-0.072 (pure protein)
Amylase 0 - 0,072 (reines Protein)Amylase 0 - 0.072 (pure protein)
Cellulase 0 - 0,072 (reines Protein)
Lipase 0 - 0,072 (reines Protein)Cellulase 0 - 0.072 (pure protein) Lipase 0 - 0.072 (pure protein)
Mannanase 0 - 0,072 (reines Protein)Mannanase 0 - 0.072 (pure protein)
Pectinase 0 - 0,072 (reines Protein) Rest: Wasser, optischer Aufheller, Salze
Pectinase 0 - 0.072 (pure protein) Balance: water, optical brightener, salts
Claims
1. Mittel enthaltend eine erste Protease und eine zweite Protease, dadurch gekennzeichnet, dass die erste Protease ausgewählt ist aus a) einer Protease, die eine Aminosäuresequenz umfasst, die zu der in SEQ ID NO.1 angegebenen Aminosäuresequenz mindestens zu 80%, zunehmend bevorzugt zu mindestens 82,5%, 85%, 87,5%, 90%, 91 %, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, 99,5% und ganz besonders bevorzugt zu 100%, identisch ist; b) einer Protease, die eine Aminosäuresequenz umfasst, die zu der in SEQ ID NO.2 angegebenen Aminosäuresequenz mindestens zu 80%, zunehmend bevorzugt zu mindestens 82,5%, 85%, 87,5%, 90%, 91 %, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, 99,5% und ganz besonders bevorzugt zu 100%, identisch ist; c) einer Protease, die eine Aminosäuresequenz umfasst, die zu der in SEQ ID NO.2 angegebenen Aminosäuresequenz mindestens zu 80%, zunehmend bevorzugt zu mindestens 82,5%, 85%, 87,5%, 90%, 91 %, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, 99,5% und ganz besonders bevorzugt zu 100%, identisch ist und zusätzlich mindestens eine zusätzliche Aminosäure im Vergleich mit SEQ ID NO.2 aufweist; und die zweite Protease eine Aminosäuresequenz umfasst, die zu der in SEQ ID NO.3 angegebenen Aminosäuresequenz mindestens zu 80%, zunehmend bevorzugt zu mindestens 82,5%, 85%, 87,5%, 90%, 91 %, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, 99,5% und ganz besonders bevorzugt zu 100%, identisch ist, insbesondere ein Waschmittel, Handwaschmittel, Spülmittel, Handgeschirrspülmittel, Maschinengeschirrspülmittel, Reinigungsmittel, Zahnprothesen- oder Kontaktlinsenpflegemittel, Nachspülmittel, Desinfektionsmittel, kosmetisches Mittel, pharmazeutisches Mittel oder ein Mittel zur Behandlung von Filtermedien, Textilien, Pelzen, Papier, Fellen oder Leder, ist, besonders bevorzugt ein Wäschewaschmittel oder ein Geschirrspülmittel.A composition comprising a first protease and a second protease, characterized in that the first protease is selected from a) a protease which comprises an amino acid sequence which is at least 80% to the amino acid sequence given in SEQ ID NO. 1 at least 80% at least 82.5%, 85%, 87.5%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, 99.5% and most preferably 100% identical; b) a protease comprising an amino acid sequence which is at least 80%, more preferably at least 82.5%, 85%, 87.5%, 90%, 91%, 92% of the amino acid sequence given in SEQ ID NO %, 93%, 94%, 95%, 96%, 97%, 98%, 99%, 99.5%, and most preferably 100%, is identical; c) a protease which comprises an amino acid sequence which is at least 80%, more preferably at least 82.5%, 85%, 87.5%, 90%, 91%, 92, of the amino acid sequence given in SEQ ID NO %, 93%, 94%, 95%, 96%, 97%, 98%, 99%, 99.5% and most preferably 100%, is identical and additionally at least one additional amino acid in comparison with SEQ ID NO. 2 has; and the second protease comprises an amino acid sequence which is at least 80%, more preferably at least 82.5%, 85%, 87.5%, 90%, 91%, 92%, of the amino acid sequence given in SEQ ID NO. 93%, 94%, 95%, 96%, 97%, 98%, 99%, 99,5% and most preferably 100%, in particular a detergent, hand washing detergent, dishwashing detergent, hand dishwashing detergent, machine dishwashing detergent, cleaning agent, Denture or contact lens care product, rinse aid, disinfectant, cosmetic agent, pharmaceutical agent or a means for the treatment of filter media, textiles, furs, paper, skin or leather, is particularly preferably a laundry detergent or a dishwashing detergent.
2. Mittel nach Anspruch 1 , dadurch gekennzeichnet, dass die zusätzliche Aminosäure der ersten Protease nach einer der folgenden Positionen in der Zählweise gemäß SEQ ID NO.2 eingefügt ist: 33, 34, 35, 36, 37, 38, 39, 40, 41 , 42, 43, 95, 96, 97, 98, 99, 100, 101 , 102, 103, 125, 126, 127, 126, 129, 130, 131 , 132, 153, 154, 155, 156, 157, 158, 159, 160, 161 , 162, 163, 164, 165, 166, 167, 168, 169, 170, 171 , 172, 173, 181 , 182, 183, 184, 185, 186, 187, 188, 189, 190, 191 , 192, 193, 194, 195, 202, 203, 204, 218, 219.2. Composition according to claim 1, characterized in that the additional amino acid of the first protease is inserted after one of the following positions in the counting manner according to SEQ ID NO.2: 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 95, 96, 97, 98, 99, 100, 101, 102, 103, 125, 126, 127, 126, 129, 130, 131, 132, 153, 154, 155, 156, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 171, 172, 173, 181, 182, 183, 184, 185, 186, 187, 188, 189, 190, 191, 192, 193, 194, 195, 202, 203, 204, 218, 219.
3. Mittel nach einem der Ansprüche 1 oder 2, dadurch gekennzeichnet, dass die erste Protease in dem Mittel als Fragment, Deletionsvariante, chimäres Protein oder Derivat vorliegt und/oder die zweite Protease in dem Mittel als Fragment, Deletionsvariante, chimäres Protein oder Derivat vorliegt, wobei die erste und die zweite Protease weiterhin katalytisch aktiv sind.3. Composition according to one of claims 1 or 2, characterized in that the first protease is present in the agent as a fragment, deletion variant, chimeric protein or derivative and / or the second protease is present in the agent as a fragment, deletion variant, chimeric protein or derivative, wherein the first and second proteases are still catalytically active.
4. Mittel nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass es als Einkomponentensystem vorliegt oder dass es in mehrere Komponenten aufgeteilt ist, und insbesondere eines, das die Proteasen in einer Menge von 0,1 μg bis 100 mg, vorzugsweise von 1 μg bis 50 mg, weiter bevorzugt von 10 μg bis 50 mg, besonders bevorzugt von 25 μg bis 25 mg und ganz besonders bevorzugt von 50 μg bis 20 mg pro g des Mittels enthält.4. Composition according to one of claims 1 to 3, characterized in that it is present as a one-component system or that it is divided into several components, and in particular one which contains the proteases in an amount of 0.1 .mu.g to 100 mg, preferably from 1 μg to 50 mg, more preferably from 10 μg to 50 mg, more preferably from 25 μg to 25 mg and most preferably from 50 μg to 20 mg per g of the agent.
5. Mittel nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass es in fester Form vorliegt, insbesondere als rieselfähiges Pulver mit einem Schüttgewicht von 300 g/l bis 1200 g/l, insbesondere 500 g/l bis 900 g/l, oder dass es in pastöser oder in flüssiger Form vorliegt.5. Composition according to one of claims 1 to 4, characterized in that it is in solid form, in particular as a free-flowing powder having a bulk density of 300 g / l to 1200 g / l, in particular 500 g / l to 900 g / l, or that it is in pasty or liquid form.
6. Mittel nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass mindestens eine Protease mit einer bei Raumtemperatur oder bei Abwesenheit von Wasser für die Protease undurchlässigen Substanz umhüllt ist.6. A composition according to any one of claims 1 to 5, characterized in that at least one protease is coated with a at room temperature or in the absence of water for the protease impermeable substance.
7. Mittel nach einem der Ansprüche 1 bis 6, ferner umfassend eines oder mehrere weitere Enzyme, insbesondere eine Protease, Amylase, Cellulase, Hemicellulase, Mannanase, Tannase, Xylanase, Xanthanase, ß-Glucosidase, Carrageenase, Oxidase, Oxidoreduktase, Pektin-abbauendes Enzym oder Lipase.7. Composition according to one of claims 1 to 6, further comprising one or more further enzymes, in particular a protease, amylase, cellulase, hemicellulase, mannanase, tannase, xylanase, xanthanase, ß-glucosidase, carrageenase, oxidase, oxidoreductase, pectin-degrading Enzyme or lipase.
8. Mittel nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass es mindestens eine weitere Komponente enthält, ausgewählt aus der Gruppe bestehend aus Tensiden, Buildern, Säuren, alkalischen Substanzen, Hydrotropen, Lösungsmitteln, Verdickungsmitteln, Bleichmitteln, Farbstoffen, Parfüms, Korrosionsinhibitoren, Sequestriermitteln, Elektrolyten, optischen Aufhellern, Vergrauungsinhibitoren, Silberkorrosionsinhibitoren, Farbübertragungsinhibitoren, Schauminhibitoren, Desintegrationshilfsmittel, Abrasivstoffen, UV-Absorbenzien, Lösungsmitteln, Antistatika, Perlglanzmitteln und Hautschutzmitteln.8. Composition according to one of claims 1 to 7, characterized in that it contains at least one further component selected from the group consisting of surfactants, builders, acids, alkaline substances, hydrotropes, solvents, thickeners, bleaching agents, dyes, perfumes, corrosion inhibitors , Sequestering agents, electrolytes, optical brighteners, grayness inhibitors, silver corrosion inhibitors, color transfer inhibitors, foam inhibitors, disintegration aids, abrasives, UV absorbers, solvents, antistatic agents, pearlescers and skin protection agents.
9. Verwendung eines Mittels nach einem der Ansprüche 1 bis 8 zur Entfernung von protease- sensitiven Anschmutzungen auf Textilien oder harten Oberflächen.9. Use of a composition according to any one of claims 1 to 8 for the removal of protease-sensitive stains on textiles or hard surfaces.
10. Verfahren zur Reinigung von Textilien oder harten Oberflächen, dadurch gekennzeichnet, dass in mindestens einem Verfahrensschritt ein Mittel nach einem der Ansprüche 1 bis 8 angewendet ist. 10. A method for cleaning textiles or hard surfaces, characterized in that in at least one method step, an agent according to any one of claims 1 to 8 is applied.
11. Verfahren zur Reinigung von Textilien oder harten Oberflächen, dadurch gekennzeichnet, dass in mindestens einem Verfahrensschritt eine erste Protease und eine zweite Protease proteolytisch aktiv sind, wobei die erste Protease ausgewählt ist aus a) einer Protease, die eine Aminosäuresequenz umfasst, die zu der in SEQ ID NO.1 angegebenen Aminosäuresequenz mindestens zu 80% identisch ist; b) einer Protease, die eine Aminosäuresequenz umfasst, die zu der in SEQ ID NO.2 angegebenen Aminosäuresequenz mindestens zu 80% identisch ist; c) einer Protease, die eine Aminosäuresequenz umfasst, die zu der in SEQ ID NO.2 angegebenen Aminosäuresequenz mindestens zu 80% identisch ist und zusätzlich mindestens eine zusätzliche Aminosäure im Vergleich mit SEQ ID NO.2 aufweist; und die zweite Protease eine Aminosäuresequenz umfasst, die zu der in SEQ ID NO.3 angegebenen Aminosäuresequenz mindestens zu 80% identisch ist.11. A process for the purification of textiles or hard surfaces, characterized in that in at least one process step, a first protease and a second protease are proteolytically active, wherein the first protease is selected from a) a protease comprising an amino acid sequence corresponding to the at least 80% identical in amino acid sequence given in SEQ ID NO. 1; b) a protease comprising an amino acid sequence which is at least 80% identical to the amino acid sequence given in SEQ ID NO. 2; c) a protease which comprises an amino acid sequence which is at least 80% identical to the amino acid sequence given in SEQ ID NO. 2 and additionally has at least one additional amino acid in comparison with SEQ ID NO. 2; and the second protease comprises an amino acid sequence which is at least 80% identical to the amino acid sequence given in SEQ ID NO.3.
12. Verfahren nach Anspruch 1 1 , dadurch gekennzeichnet, dass die Proteasen in einer Menge von 40 μg bis 4 g, vorzugsweise von 50 μg bis 3 g, besonders bevorzugt von 100 μg bis 2 g und ganz besonders bevorzugt von 200 μg bis 1 g pro Anwendung eingesetzt sind.12. The method according to claim 1 1, characterized in that the proteases in an amount of 40 micrograms to 4 g, preferably from 50 micrograms to 3 g, more preferably from 100 micrograms to 2 g and most preferably from 200 micrograms to 1 g are used per application.
13. Verwendung einer ersten Protease und einer zweiten Protease zur Reinigung von Textilien oder harten Oberflächen, dadurch gekennzeichnet, dass die erste Protease ausgewählt ist aus a) einer Protease, die eine Aminosäuresequenz umfasst, die zu der in SEQ ID NO.1 angegebenen Aminosäuresequenz mindestens zu 80% identisch ist; b) einer Protease, die eine Aminosäuresequenz umfasst, die zu der in SEQ ID NO.2 angegebenen Aminosäuresequenz mindestens zu 80% identisch ist; c) einer Protease, die eine Aminosäuresequenz umfasst, die zu der in SEQ ID NO.2 angegebenen Aminosäuresequenz mindestens zu 80% identisch ist und zusätzlich mindestens eine zusätzliche Aminosäure im Vergleich mit SEQ ID NO.2 aufweist; und die zweite Protease eine Aminosäuresequenz umfasst, die zu der in SEQ ID NO.3 angegebenen Aminosäuresequenz mindestens zu 80% identisch ist.13. Use of a first protease and a second protease for purifying textiles or hard surfaces, characterized in that the first protease is selected from a) a protease which comprises an amino acid sequence which corresponds to the amino acid sequence given in SEQ ID NO is 80% identical; b) a protease comprising an amino acid sequence which is at least 80% identical to the amino acid sequence given in SEQ ID NO. 2; c) a protease which comprises an amino acid sequence which is at least 80% identical to the amino acid sequence given in SEQ ID NO. 2 and additionally has at least one additional amino acid in comparison with SEQ ID NO. 2; and the second protease comprises an amino acid sequence which is at least 80% identical to the amino acid sequence given in SEQ ID NO.3.
14. Verwendung nach Anspruch 13, dadurch gekennzeichnet, dass die Proteasen in einer Menge von 40 μg bis 4 g, vorzugsweise von 50 μg bis 3 g, besonders bevorzugt von 100 μg bis 2 g und ganz besonders bevorzugt von 200 μg bis 1 g pro Anwendung eingesetzt sind. 14. Use according to claim 13, characterized in that the proteases in an amount of 40 ug to 4 g, preferably from 50 micrograms to 3 g, more preferably from 100 micrograms to 2 g and most preferably from 200 micrograms to 1 g per Application are used.
Applications Claiming Priority (2)
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DE200710038031 DE102007038031A1 (en) | 2007-08-10 | 2007-08-10 | Agents containing proteases |
DE102007038031.5 | 2007-08-10 |
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WO2009021867A9 WO2009021867A9 (en) | 2010-06-10 |
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