EP3408367B1 - Improved anti-pilling on polyester textiles through use of a cutinase - Google Patents
Improved anti-pilling on polyester textiles through use of a cutinase Download PDFInfo
- Publication number
- EP3408367B1 EP3408367B1 EP17701292.9A EP17701292A EP3408367B1 EP 3408367 B1 EP3408367 B1 EP 3408367B1 EP 17701292 A EP17701292 A EP 17701292A EP 3408367 B1 EP3408367 B1 EP 3408367B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- cutinase
- washing agent
- weight
- amino acid
- agents
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/38—Products with no well-defined composition, e.g. natural products
- C11D3/386—Preparations containing enzymes, e.g. protease or amylase
- C11D3/38636—Preparations containing enzymes, e.g. protease or amylase containing enzymes other than protease, amylase, lipase, cellulase, oxidase or reductase
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
- D06M16/003—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic with enzymes or microorganisms
-
- 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
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
- C11D2111/10—Objects to be cleaned
- C11D2111/12—Soft surfaces, e.g. textile
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/32—Polyesters
Definitions
- the present invention is in the field of enzyme technology, in particular the anti-pilling effect of enzymes such as are used, for example, in detergents.
- the invention relates to a detergent which contains a cutinase as defined herein.
- the present invention also relates to a method for cleaning textiles and the use of the agent according to the invention for removing soiling. Furthermore, the invention is directed to the use of a cutinase to reduce pilling effects and anti-gray in a detergent.
- Pilling is the name given to the formation of pebbles or fluff in fabrics. These small lint appear especially in short-fiber fabrics. With long-fiber and twisted fibers, on the other hand, pilling is less pronounced. In general, these nodules are caused by loose fibers in the fabric or those that have become detached from the fabric. Due to their smooth surface, synthetic fibers tend to pilling more than natural fibers, because synthetic fibers can be detached from the fabric more quickly than rough natural fibers. In the case of woolen fabrics, these fibers "felt” mainly through mechanical friction and form pebbles on the surface.
- Pilling Due to the formation of pods on the surface, fabrics quickly look used and older than they are. In contrast, the functionality of the material is hardly or not at all impaired. For example, the constant thinning of the fabric even increases the breathability. Pilling takes place particularly in areas subject to high mechanical stress, usually the shoulder and waistband areas. Due to the continuous thinning of the fabric, these stressed areas in particular are at risk of forming holes or even tearing.
- a cutinase from Thermomonospora curvata DSM 43183 shows an anti-pilling effect in the washing process.
- pre-pilled tissue or new tissue is less pilled after 20 washes with a detergent which contains the cutinase according to the invention.
- the object described above, on which the present application is based, is achieved in that a cutinase is added to detergents which has at least 70% sequence identity with the amino acid sequence given in SEQ ID NO: 1 over its entire length.
- the addition of the cutinase has the effect that textiles washed with the agents according to the invention, in particular polyester textiles, have a significantly reduced pilling compared to a control detergent without cutinase.
- the present invention is therefore directed to a detergent, characterized in that it contains a cutinase, the cutinase being a cutinase which has at least 70% sequence identity with the amino acid sequence given in SEQ ID NO: 1 over its entire length.
- the present invention is directed to processes for cleaning textiles, characterized in that an agent according to the invention is used in at least one process step.
- the present invention is also directed to the use of a detergent as described herein, particularly preferably liquid detergent, for removing soiling.
- another aspect of the invention includes the use of a cutinase for reducing pilling effects of a detergent, particularly preferably a liquid detergent, the agent containing the cutinase, the cutinase being a cutinase which has at least 70% sequence identity with that in SEQ ID NO: 1 has indicated amino acid sequence over its entire length.
- a cutinase (EC 3.1.1.74) or cutin hydrolase is an enzyme that belongs to the ⁇ / ⁇ hydrolases and hydrolyses cutin. Cutinase is produced, among other things, by some phytopathogenic fungi and bacteria are formed (through the cutinase the fungi are able to break down the ester bond of the cutin in the cuticula of the plants and thus penetrate the plants).
- the cutinase is a cutinase from Thermomonospora curvata, in particular the cutinase with the amino acid sequence according to SEQ ID NO: 1, or a cutinase derived therefrom, for example by means of mutagenesis.
- the agents according to the invention contain the cutinase in an amount of 0.00001-1% by weight, preferably in an amount of 0.0001-0.5% by weight, particularly preferably in an amount of 0.001-0.1% by weight. -% based on the active protein.
- the cutinase comprises an amino acid sequence which is at least 70%, 71%, 72%, 73%, 74%, 75%, 76%, 77% of the total length of the amino acid sequence given in SEQ ID NO: 1 , 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 90.5%, 91%, 91, 5%, 92%, 92.5%, 93%, 93.5%, 94%, 94.5%, 95%, 95.5%, 96%, 96.5%, 97%, 97.5% , 98%, 98.5% and 98.8% are identical.
- nucleic acid or amino acid sequences is determined by a sequence comparison.
- This sequence comparison is based on the BLAST algorithm established and commonly used in the prior art (cf. for example Altschul, SF, Gish, W., Miller, W., Myers, EW & Lipman, DJ (1990) "Basic local alignment search tool.” J. Mol. Biol. 215: 403-410 , and Altschul, Stephan F., Thomas L. Madden, Alejandro A. Schaffer, Jinghui Zhang, Hheng Zhang, Webb Miller, and David J. Lipman (1997): "Gapped BLAST and PSI-BLAST: a new generation of protein database search programs "; Nucleic Acids Res., 25, pp.
- Sequence comparisons are also possible with the computer program Vector NTI® Suite 10.3 (Invitrogen Corporation, 1600 Faraday Avenue, Carlsbad, California, USA) with the specified standard parameters, whose AlignX module for the sequence comparisons is based on ClustalW.
- Such a comparison also allows a statement to be made about the similarity of the compared sequences to one another. It is usually given in percent identity, that is to say the proportion of identical nucleotides or amino acid residues in the same positions or positions corresponding to one another in an alignment.
- the broader term of homology includes conserved amino acid exchanges in the case of amino acid sequences, i.e. amino acids with similar chemical activity, since these usually exert similar chemical activities within the protein. Therefore, the similarity of the compared sequences can also be given as percent homology or percent similarity. Identity and / or homology information can be made over entire polypeptides or genes or only over individual areas. Homologous or identical regions of different nucleic acid or amino acid sequences are therefore defined by matches in the sequences.
- Such areas often have identical functions. They can be small and only contain a few nucleotides or amino acids. Such small areas often have essential functions for the overall activity of the protein. It can therefore be useful to relate sequence matches only to individual, possibly small areas. Unless otherwise stated, identity or homology details in the present application refer to the total length of the nucleic acid or amino acid sequence specified in each case.
- the cutinase is characterized in that its anti-pilling performance is not significantly reduced compared to that of a cutinase which comprises an amino acid sequence which corresponds to the amino acid sequences given in SEQ ID NO: 1, ie at least 70% , 75%, 80%, 85%, 90%, 95% of the reference anti-pilling performance.
- the anti-pilling performance can be determined in a washing system that contains a detergent in a dosage between 4.5 and 7.0 grams per liter of washing liquor as well as the cutinase, with the cutinases to be compared being used in the same concentration (based on active protein) and the anti-pilling performance is determined as described herein.
- the washing process can take place for 60 minutes at a temperature of 60 ° C and the water has a water hardness between 15.5 and 16.5 ° (German hardness).
- the concentration of cutinase in the detergent intended for this washing system is from 0.00001 - 1% by weight, preferably from 0.0001-0.5% by weight, particularly preferably from 0.001-0.1% by weight, based on active, purified protein.
- a preferred liquid detergent for such a washing system is composed as follows (all data in percent by weight): 4.4% alkylbenzenesulfonic acid, 5.6% anionic surfactants, 2.4% C12-C18 Na salts of fatty acids, 4.4 % non-ionic surfactants, 0.2% phosphonates, 1.4% citric acid, 0.95% NaOH, 0.01% antifoam, 2% glycerine, 0.08% preservatives, 1% ethanol, 1.6% enzyme mix ( Protease, amylase, cellulase, mannase), the remainder demineralized water.
- the dosage of the liquid detergent is preferably between 4.5 and 6.0 grams per liter of wash liquor, for example 4.7, 4.9 or 5.9 grams per liter of wash liquor. Washing is preferably carried out in a pH range between pH 8 and pH 10.5, preferably between pH 8 and pH 9.
- the anti-pilling performance is determined at 60 ° C. using a liquid detergent as indicated above, the washing process preferably taking place for 60 minutes.
- the anti-pilling performance can be tracked using visual sampling.
- a group of examiners assigns the laundry to be examined a value on a scale from 1-5.
- the respective cutinase for the same level of activity, it is ensured that the respective enzymatic properties, e.g. the anti-pilling performance, are compared even if there is a gap in the ratio of active substance to total protein (the values of the specific activity). In general, a low specific activity can be compensated for by adding a larger amount of protein.
- Proteins can be combined into groups of immunologically related proteins by reacting with an antiserum or a specific antibody. Members of such a group are distinguished by the fact that they have the same antigenic determinant recognized by an antibody. They are therefore structurally so similar to one another that they can be recognized by an antiserum or certain antibodies.
- Another subject matter of the invention is therefore cutinases, which are characterized in that they have at least one and increasingly preferably two, three or four matching antigenic determinants with a cutinase used in an agent according to the invention. Due to their immunological similarities, such cutinases are structurally so similar to the cutinases used in the agents according to the invention that a similar function can also be assumed.
- cutinases used in the agents according to the invention can have further amino acid changes compared to the cutinase described in SEQ ID NO: 1, in particular amino acid substitutions, insertions or deletions.
- Such cutinases are further developed, for example, through targeted genetic modification, i.e. through mutagenesis processes, and optimized for specific purposes or with regard to special properties (for example with regard to their catalytic activity, stability, etc.).
- nucleic acids that encode the cutinases used can be introduced into recombination batches and thus used to generate completely new types of cutinases or other polypeptides.
- the aim is to introduce specific mutations such as substitutions, insertions or deletions into the known molecules in order, for example, to improve the cleaning performance of enzymes according to the invention.
- specific mutations such as substitutions, insertions or deletions into the known molecules in order, for example, to improve the cleaning performance of enzymes according to the invention.
- the surface charges and / or the isoelectric point of the molecules and thereby their interactions with the substrate can be changed.
- the net charge of the enzymes can be changed in order to influence the substrate binding, especially for use in detergents and cleaning agents.
- one or more corresponding mutations can increase the stability of the cutinase even further and thereby improve its cleaning performance.
- Advantageous properties of individual mutations, e.g. individual substitutions can complement each other.
- a cutinase that has already been optimized with regard to certain properties, for example with regard to its activity and / or its anti-pilling performance, can therefore be further developed within the scope of the invention.
- the invention therefore also relates to an agent containing a cutinase, which is characterized in that it can be obtained from a cutinase as described above as the starting molecule by single or multiple conservative amino acid substitutions.
- conservative amino acid substitution means the exchange (substitution) of an amino acid residue for another amino acid residue, this exchange not leading to a change in polarity or charge at the position of the exchanged amino acid, e.g. B. the exchange of a non-polar amino acid residue for another non-polar amino acid residue.
- the cutinase is characterized in that it can be obtained from a cutinase contained in an agent according to the invention as a starting molecule by fragmentation, deletion, insertion or substitution mutagenesis and comprises an amino acid sequence that is at least 210, 220, 230, 240, 250, 260, 270, 280 or 289 contiguous amino acids match the parent molecule.
- the enzymes advantageously retain their hydrolytic activity even after the mutagenesis, i.e. their hydrolytic activity corresponds at least to that of the starting enzyme, i.e. in a preferred embodiment the hydrolytic activity is at least 80, preferably at least 90% of the activity of the starting enzyme. Further substitutions can also have advantageous effects. Both single and several connected amino acids can be exchanged for other amino acids.
- fatty acids or fatty alcohols or their derivatives - unless otherwise stated - represent branched or unbranched carboxylic acids or alcohols or their derivatives with preferably 6 to 22 carbon atoms.
- the oxo alcohols or their derivatives obtainable, for example, by ROELEN's oxo synthesis, or their derivatives can also be used accordingly.
- alkaline earth metals are mentioned in the following as counterions for monovalent anions, this means that the alkaline earth metal is of course only present in half the amount of substance - sufficient to balance the charge - as the anion.
- An object of the invention is a detergent which is characterized in that it contains a cutinase as defined herein.
- This subject matter of the invention includes all conceivable types of detergent, both concentrates and agents to be used undiluted, for use on a commercial scale, in the washing machine or in hand washing.
- detergents for textiles, carpets, or natural fibers, for which the term detergent is used.
- the detergents within the scope of the invention also include washing auxiliaries which are added to the actual detergent in manual or machine washing in order to achieve a further effect.
- laundry detergents in the context of the invention also include textile pretreatment and aftertreatment agents, i.e.
- agents with which the item of laundry is brought into contact before the actual washing for example to loosen stubborn dirt
- agents that are used in a step following the actual textile washing the laundry has other desirable properties such as pleasant Provide grip, wrinkle-free or low static charge.
- the last-mentioned agents include fabric softeners.
- the detergents according to the invention which can be present as pulverulent solids, in re-compacted particle form, as homogeneous solutions or suspensions, can contain, in addition to the cutinase described above, all known ingredients common in such agents, with at least one further ingredient preferably being present in the agent.
- the agents according to the invention can in particular contain surfactants, builders, bleaching agents, in particular peroxygen compounds, or bleach activators. Furthermore, they can contain water-miscible organic solvents, further enzymes, sequestering agents, electrolytes, pH regulators and / or further auxiliaries such as optical brighteners, graying inhibitors, foam regulators and dyes and fragrances and combinations thereof.
- a combination of the agent according to the invention with one or more further ingredient (s) is advantageous, since such an agent in preferred embodiments according to the invention has an improved cleaning performance due to resulting synergisms.
- Such a synergism can be achieved in particular by combining the agent according to the invention with a surfactant and / or a builder and / or a peroxygen compound and / or a bleach activator.
- the agent according to the invention can also be a compound from the class of anionic surfactants of the formula (I) R-SO 3 - Y + (I) contain.
- R stands for a linear or branched unsubstituted alkylaryl radical.
- Y stands for a monovalent cation or the nth part of an n-valent cation, preferred are the alkali metal ions, including Na + or K + , Na + being extremely preferred. Further cations Y + can be selected from NH4 + , 1 ⁇ 2 Zn 2+ , 1 ⁇ 2 Mg 2+ , 1 ⁇ 2 Ca 2+ , 1 ⁇ 2 Mn 2+ , and mixtures thereof.
- Alkylaryl refers to organic radicals consisting of an alkyl radical and an aromatic radical. Typical examples of such groups include, but are not limited to, alkylbenzene groups such as benzyl, butylbenzene groups, nonylbenzene groups, decylbenzene groups, undecylbenzene groups, dodecylbenzene groups, tridecylbenzene groups, and the like.
- such surfactants are selected from linear or branched alkylbenzenesulfonates of the formula A-1 in which R 'and R "together contain 9 to 19, preferably 11 to 15 and in particular 11 to 13 carbon atoms.
- R 'and R together contain 9 to 19, preferably 11 to 15 and in particular 11 to 13 carbon atoms.
- a very particularly preferred representative can be described by the formula A-1a:
- the compound of the formula (I) is preferably the sodium salt of a linear alkylbenzenesulfonate.
- the at least one compound from the class of the anionic surfactants of the formula (I) is present in an amount of 0.001 to 30% by weight, preferably 0.001-10% by weight, furthermore preferably 2-6% by weight, even more preferably 3-5% by weight, contained in the detergent, in each case based on the total weight of the detergent.
- the agent can contain at least one other surfactant in addition to the at least one compound of the formula (I) or as an alternative thereto.
- the agents according to the invention preferably contain at least one anionic surfactant, in particular an anionic surfactant of the formula R 1 -O- (AO) n -SO 3 -X + (II).
- R 1 represents a linear or branched, substituted or unsubstituted alkyl, aryl or alkylaryl radical, preferably a linear, unsubstituted alkyl radical, particularly preferably a fatty alcohol radical.
- Preferred radicals R 1 are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl radicals and mixtures thereof, the representatives with an even number of C- Atoms are preferred.
- radicals R 1 are derived from C 12 -C 18 fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or from C 10 -C 20 oxo alcohols.
- AO stands for an ethylene oxide (EO) or propylene oxide (PO) group, preferably for an ethylene oxide group.
- the index n stands for an integer from 1 to 50, preferably from 1 to 20 and in particular from 2 to 10. Very particularly preferably n stands for the numbers 2, 3, 4, 5, 6, 7 or 8.
- X stands for a monovalent cation or the n-th part of an n-valent cation, preferred are the alkali metal ions, including Na + or K + , Na + being extremely preferred. Further cations X + can be selected from NH4 + , 1 ⁇ 2 Zn 2+ , 1 ⁇ 2 Mg 2+ , 1 ⁇ 2 Ca 2+ , 1 ⁇ 2 Mn 2+ , and mixtures thereof.
- the detergent contains the at least one anionic surfactant of the formula (II) in an amount of 2-10% by weight, preferably 3-8% by weight, based on the total weight of the detergent.
- alkyl sulfates of the formula R 2 -O-SO 3 - X + (III).
- R 2 represents a linear or branched, substituted or unsubstituted alkyl radical, preferably a linear, unsubstituted alkyl radical, particularly preferably a fatty alcohol radical.
- Preferred radicals R 2 are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl radicals and mixtures thereof, the representatives with an even number of C- Atoms are preferred.
- radicals R 2 are derived from C 12 -C 18 fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or from C 10 -C 20 oxo alcohols.
- Y stands for a monovalent cation or the nth part of an n-valent cation, preferred are the alkali metal ions, including Na + or K + , Na + being extremely preferred. Further cations Y + can be selected from NH4 + , 1 ⁇ 2 Zn 2+ , 1 ⁇ 2 Mg 2+ , 1 ⁇ 2 Ca 2+ , 1 ⁇ 2 Mn 2+ , and mixtures thereof.
- R 3 represents a linear or branched, substituted or unsubstituted alkyl radical, preferably a linear, unsubstituted alkyl radical, particularly preferably a fatty alcohol radical.
- Preferred radicals R 2 are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl radicals and mixtures thereof, the representatives with an even number of C- Atoms are preferred.
- radicals R 3 are derived from C 12 -C 18 fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or from C 10 -C 20 oxo alcohols.
- AO stands for an ethylene oxide (EO) or propylene oxide (PO) group, preferably for an ethylene oxide group.
- the index m stands for an integer from 1 to 50, preferably from 1 to 20 and in particular from 2 to 10. m is very particularly preferably the numbers 2, 3, 4, 5, 6, 7 or 8.
- nonionic surfactants which can be contained in the agents described for the purposes of the present invention include, but are not limited to, alkyl glycosides, alkoxylated fatty acid alkyl esters, amine oxides, fatty acid alkanolamides, hydroxy mixed ethers, sorbitan fatty acid esters, polyhydroxy fatty acid amides and alkoxylated alcohols.
- Suitable amphoteric surfactants are, for example, betaines of the formula (R iii ) (R iv ) (R v ) N + CH 2 COO - , in which R iii is an alkyl radical with 8 to 25, preferably 10 to 21 carbon atoms, optionally interrupted by heteroatoms or heteroatom groups, and iv and R v denote identical or different alkyl radicals with 1 to 3 carbon atoms, in particular C 10 -C 18 -alkyl-dimethylcarboxymethylbetaine and C 11 -C 17 -alkylamidopropyl-dimethylcarboxymethylbetaine.
- Suitable cationic surfactants include the quaternary ammonium compounds of the formula (R vi ) (R vii ) (R viii ) (R ix ) N + X - , in which R vi to R ix represent four identical or different types, in particular two long and two short-chain, alkyl radicals and X - stand for an anion, in particular a halide ion, for example didecyldimethylammonium chloride, alkylbenzyldidecylammonium chloride and mixtures thereof.
- quaternary surface-active compounds in particular with a sulfonium, phosphonium, iodonium or arsonium group, which are also known as antimicrobial agents.
- quaternary surface-active compounds with an antimicrobial effect, the agent can be designed with an antimicrobial effect or its antimicrobial effect, which may already be present due to other ingredients, can be improved.
- the total amount of surfactants based on the weight of the agent is 2 to 30% by weight, preferably 5 to 25% by weight, more preferably 10 to 20% by weight, most preferably 14 to 18% by weight , where the (linear) alkylbenzenesulfonates are based at most in an amount of 0.001 to 30% by weight, preferably 0.001-10% by weight, furthermore preferably 2-6% by weight, even more preferably 3-5% by weight based on the weight of the remedy.
- Detergents according to the invention can contain further enzymes in addition to the cutinase. These can be hydrolytic enzymes or other enzymes in a concentration suitable for the effectiveness of the agent.
- An embodiment of the invention thus represent agents which comprise one or more enzymes.
- Preferred enzymes that can be used are all enzymes which can develop a catalytic activity in the agent according to the invention, in particular a protease, amylase, cellulase, hemicellulase, mannanase, tannase, xylanase, xanthanase, xyloglucanase, ⁇ -glucosidase, pectinase, carrageenase, perhydrolase, oxidase , Oxidoreductase or a lipase, and mixtures thereof.
- Enzymes are advantageously contained in the agent in an amount of 1 ⁇ 10 ⁇ 8 to 5% by weight, based on active protein. Increasingly, each enzyme is used in an amount of 1 ⁇ 10 -7 -3% by weight, from 0.00001-1% by weight, from 0.00005-0.5% by weight, from 0.0001 to 0.1% by weight and particularly preferably from 0.0001 to 0.05% by weight in agents according to the invention, based on active protein.
- the enzymes particularly preferably show synergistic cleaning performance with respect to certain soiling or stains, ie the enzymes contained in the agent composition mutually support one another 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 agent according to the invention.
- the amylase (s) is preferably an ⁇ -amylase.
- the hemicellulase is preferably a ⁇ -glucanase, a pectinase, a pullulanase and / or a mannanase.
- the cellulase is preferably a cellulase mixture or a one-component cellulase, preferably or predominantly an endoglucanase and / or a cellobiohydrolase.
- the oxidoreductase is preferably an oxidase, in particular a choline oxidase, or a perhydrolase.
- the proteases used are preferably alkaline serine proteases. They act as unspecific endopeptidases, that is, they hydrolyze any acid amide bonds that are inside peptides or proteins, thereby breaking down protein-containing soiling on the items to be cleaned. Their pH optimum is usually in the clearly alkaline range.
- the protein concentration can be determined with the aid of known methods, for example the BCA method (bicinchoninic acid; 2,2'-bichinolyl-4,4'-dicarboxylic acid) or the biuret method.
- the active protein concentration is determined by titrating the active centers using a suitable irreversible inhibitor (for proteases, for example, phenylmethylsulfonyl fluoride (PMSF)) and determining the residual activity (cf. M. Bender et al., J. Am. Chem. Soc. 88, 24 (1966), pp. 5890-5913 ).
- a suitable irreversible inhibitor for proteases, for example, phenylmethylsulfonyl fluoride (PMSF)
- the enzymes to be used can also be packaged together with accompanying substances, for example from fermentation.
- the enzymes are preferably used as liquid enzyme formulation (s).
- the enzymes are not provided in the form of the pure protein, but rather in the form of stabilized, storable and transportable preparations.
- These ready-made preparations include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, in particular in the case of liquid or gel-like agents, solutions of the enzymes, advantageously as concentrated as possible, with little water and / or with stabilizers or other auxiliaries.
- the enzymes can be encapsulated both for the solid and for the liquid dosage form, for example by spray drying or extrusion of the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are enclosed as in a solidified gel or in those of the core-shell type, in which an enzyme-containing core is coated with a protective layer impermeable to water, air and / or chemicals.
- Additional active ingredients for example stabilizers, emulsifiers, pigments, bleaches or dyes, can also be applied in superimposed layers.
- Such capsules are applied by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes. Such granulates are advantageously low in dust, for example through the application of polymeric film-forming agents, and due to the coating are stable in storage.
- the agent according to the invention can have one or more enzyme stabilizers.
- the agent according to the invention can therefore also contain an enzyme stabilizer selected, for example, from the group consisting of sodium formate, sodium sulfate, lower aliphatic alcohols and boric acid and their esters and salts.
- an enzyme stabilizer selected, for example, from the group consisting of sodium formate, sodium sulfate, lower aliphatic alcohols and boric acid and their esters and salts.
- two or more of these compounds can also be used in combination.
- the salts of the compounds mentioned can also be used in the form of hydrates, such as, for example, sodium sulfate decahydrate.
- lower aliphatic alcohols as used herein includes monoalcohols, diols and higher alcohols having up to 6 carbon atoms.
- polyols for example glycerol, (mono) ethylene glycol, (mono) propylene glycol or sorbitol may be mentioned as belonging to the group of lower aliphatic alcohols, without the invention being restricted to these.
- an agent according to the invention can also contain at least one further stabilizer.
- Such stabilizers are known in the prior art.
- Reversible protease inhibitors protect the enzymes contained in a detergent from proteolytic degradation by reversibly inhibiting the enzymatic activity of the proteases contained in the agent.
- Benzamidine hydrochloride, boronic acids or their salts or esters are often used as reversible protease inhibitors, including in particular derivatives with aromatic groups, such as ortho-, meta- or para-substituted phenylboronic acids, in particular 4-formylphenylboronic acid, or the salts or esters of named compounds.
- Peptide aldehydes that is to say oligopeptides with a reduced C-terminus, in particular those made from 2 to 50 monomers, are also used for this purpose.
- the peptide reversible protease inhibitors include ovomucoid and leupeptin.
- Further enzyme stabilizers are amino alcohols such as mono-, di-, triethanol- and propanolamine and mixtures thereof, aliphatic carboxylic acids up to C 12 , such as, for example, succinic acid, other dicarboxylic acids or salts of the acids mentioned. End-capped fatty acid amide alkoxylates are also suitable for this purpose. Some organic acids used as builders are also able to stabilize an enzyme. Calcium and / or magnesium salts are also used for this purpose, such as calcium acetate. Polyamide oligomers or polymeric compounds such as lignin, water-soluble vinyl copolymers or cellulose ethers, acrylic polymers and / or polyamides stabilize the enzyme preparation against, among other things, physical influences or fluctuations in the pH value.
- Polymers containing polyamine-N-oxide act simultaneously as enzyme stabilizers and as color transfer inhibitors.
- Other polymeric stabilizers are linear C 8 -C 18 polyoxyalkylenes.
- Alkyl polyglycosides can also stabilize the enzymatic components of the agent according to the invention and are preferably able to additionally increase their performance.
- Crosslinked N-containing compounds preferably fulfill a double function as soil release agents and as enzyme stabilizers.
- Hydrophobic, nonionic polymer stabilizes in particular any cellulase it may contain.
- Reducing agents and antioxidants increase the stability of the enzymes against oxidative decay; for this purpose, sulfur-containing reducing agents, for example sodium sulfite and reducing sugars, are common.
- the compositions according to the present invention are liquid and contain water as the main solvent, i.e. they are aqueous compositions.
- the water content of the aqueous agent according to the invention is usually 15 to 70% by weight, preferably 20 to 60% by weight. In various embodiments, the water content is more than 5% by weight, preferably more than 15% by weight and particularly preferably more than 50% by weight, based in each case on the total amount of agent.
- non-aqueous solvents can be added to the agent.
- Suitable non-aqueous solvents include monohydric or polyhydric alcohols, alkanolamines or glycol ethers, provided they are miscible with water in the specified concentration range.
- the solvents are preferably selected from ethanol, n-propanol, i-propanol, butanols, glycol, propanediol, butanediol, methylpropanediol, glycerol, diglycol, propyl diglycol, butyl diglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol ether, ethylene glycol propyl ether, Diethylene glycol ethyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, methoxy triglycol, ethoxy triglycol, butoxy triglycol, 1-butoxyethoxy-2-propanol, propylene-butoxyethoxy-2-propan
- the one or more non-aqueous solvents is / are usually contained in an amount of 0.1 to 10% by weight, preferably 1 to 8% by weight, based on the total composition.
- the agents according to the invention can contain further ingredients which further improve the application-related and / or aesthetic properties of the detergent.
- these include, for example, additives to improve the drainage and drying behavior, to adjust the viscosity and / or for stabilization, as well as other auxiliaries and additives common in cleaning agents, such as UV stabilizers, perfumes, pearlescent agents, dyes, corrosion inhibitors, preservatives, bitter substances, organic Salts, disinfectants, structuring polymers, defoamers, encapsulated ingredients (eg encapsulated perfume), pH adjusters and additives that improve or care for the skin.
- additives to improve the drainage and drying behavior to adjust the viscosity and / or for stabilization
- other auxiliaries and additives common in cleaning agents such as UV stabilizers, perfumes, pearlescent agents, dyes, corrosion inhibitors, preservatives, bitter substances, organic Salts, disinfectants, structuring polymers, defoamers, encapsulated ingredients (eg encapsulated perfume), pH adjusters and additive
- a detergent according to the invention preferably contains at least one water-soluble and / or water-insoluble, organic and / or inorganic builder (builder).
- the builders that can generally be used include in particular the aminocarboxylic acids and their salts, zeolites, silicates, carbonates, organic (co) builders and - where there are no ecological prejudices against their use - also the phosphates.
- the agents are preferably free of phosphates.
- 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 as well as polyaspartic acid, polyphosphonic acids, in particular aminotris (methylenephosphonic acid) and 1, 1-methylenediphosphonic acid, in particular aminotris (methylenephosphonophosphonic acid, 1, 1-methyleniphosphonic acid, and 1-methylenephosphonophosphonic acid), especially aminotris (methylenephosphonic acid), especially aminotris (methylenephosphonic acid) and 1, 1-methylenephosphonic acid, in particular aminotris (methylenephosphonic acid) and 1-methylenediphosphonic acid, monomeric and polymeric aminopolycarboxylic acids, monomeric and polymeric aminopolycarboxylic acids, in particular aminotris (methylenephosphonic acid) and 1, 1 polymeric hydroxy compounds such as dextrin and polymeric
- Suitable, albeit less preferred, compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinyl methyl ethers, vinyl esters, ethylene, propylene and styrene, in which the acid makes up at least 50% by weight.
- the organic builder substances can, in particular for the production of liquid agents, be used 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 salts.
- Organic builder substances can, if desired, 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 upper limit mentioned are preferably used in pasty or liquid, in particular water-containing, agents according to the invention. Laundry post-treatment agents according to the invention, such as, for example, fabric softeners, can optionally also be free from organic builders.
- Particularly suitable water-soluble inorganic builder materials are alkali metal silicates and polyphosphates, preferably sodium triphosphate.
- water-insoluble, water-dispersible inorganic builder materials in particular crystalline or amorphous alkali metal aluminosilicates, if desired, 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 used.
- the crystalline sodium aluminosilicates in detergent quality in particular zeolite A, P and optionally X, are preferred. Quantities close to the upper limit mentioned are preferably used in solid, particulate compositions.
- Suitable aluminosilicates in particular do not have any particles with a grain size of more than 30 ⁇ m and preferably consist of at least 80% by weight of particles with a size of less than 10 ⁇ m.
- Suitable substitutes or partial substitutes for said aluminosilicate are crystalline alkali metal silicates, which can be present alone or in a mixture with amorphous silicates.
- the alkali silicates which can be used as builders in the agents according to the invention preferably have a molar ratio of alkali oxide to SiO 2 below 0.95, in particular from 1: 1.1 to 1:12, and can be amorphous or crystalline.
- Preferred alkali silicates are the sodium silicates, in particular the amorphous sodium silicates, with a molar ratio Na 2 O: SiO 2 of 1: 2 to 1: 2.8.
- the crystalline silicates used alone or in a mixture with amorphous silicates are preferably crystalline sheet silicates of the general formula Na 2 Si x O 2x + 1 y H 2 O, in which x, the so-called module, is a number of 1, 9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4.
- Preferred crystalline sheet silicates are those in which x in the general formula mentioned assumes the values 2 or 3.
- both beta and delta sodium disilicates Na 2 Si 2 O 5 ⁇ y H 2 O
- Virtually anhydrous crystalline alkali silicates of the above general formula, in which x is a number from 1.9 to 2.1, prepared from amorphous alkali silicates, can also be used in agents according to the invention.
- a crystalline layered sodium silicate with a module of 2 to 3, as can be produced from sand and soda is used.
- Crystalline sodium silicates with a modulus in the range from 1.9 to 3.5 are used in a further preferred embodiment of agents according to the invention.
- the weight ratio of aluminosilicate to silicate is preferably 1:10 to 10: 1.
- the weight ratio of amorphous alkali silicate to crystalline alkali silicate is preferably 1: 2 to 2: 1 and in particular 1: 1 to 2: 1.
- builder substances are contained in the agents according to the invention preferably in amounts of up to 60% by weight, in particular from 5% by weight to 40% by weight.
- Laundry post-treatment agents such as fabric softeners, are preferably free of inorganic builders.
- Polymeric thickeners for the purposes of the present invention are the polycarboxylates that act as polyelectrolytes, preferably homopolymers and copolymers of acrylic acid, in particular acrylic acid copolymers such as acrylic acid-methacrylic acid copolymers, and the polysaccharides, in particular heteropolysaccharides, and other conventional thickening polymers.
- Suitable polysaccharides or heteropolysaccharides are the polysaccharide gums, for example gum arabic, agar, alginates, carrageenans and their salts, guar, guaran, tragacanth, gellan, ramsan, dextran or xanthan and their derivatives, e.g.
- propoxylated guar and their mixtures.
- Other polysaccharide thickeners such as starches or cellulose derivatives, can be used as an alternative, but preferably in addition to a polysaccharide gum, for example starches of various origins and starch derivatives, e.g. hydroxyethyl starch, starch phosphate esters or starch acetates, or carboxymethyl cellulose or its sodium salt, methyl, ethyl, hydroxyethyl, Hydroxypropyl-, hydroxypropyl-methyl- or hydroxyethyl-methyl-cellulose or cellulose acetate.
- Acrylic acid polymers suitable as polymeric thickeners are, for example, high molecular weight homopolymers of acrylic acid (INCI Carbomer) crosslinked with a polyalkenyl polyether, in particular an allyl ether of sucrose, pentaerythritol or propylene, which are also referred to as carboxyvinyl polymers.
- a polyalkenyl polyether in particular an allyl ether of sucrose, pentaerythritol or propylene, which are also referred to as carboxyvinyl polymers.
- acrylic acid copolymers are the following acrylic acid copolymers: (i) Copolymers of two or more monomers from the group of acrylic acid, methacrylic acid and their simple esters, preferably formed with C 1-4 alkanols (INCI Acrylates Copolymers), to which such as the copolymers of methacrylic acid, butyl acrylate and methyl methacrylate (CAS 25035-69-2) or of butyl acrylate and methyl methacrylate (CAS 25852-37-3); (ii) crosslinked high molecular weight acrylic acid copolymers, including the copolymers of C 10-30 alkyl acrylates crosslinked with an allyl ether of sucrose or pentaerythritol with one or more monomers from the group of acrylic acid, methacrylic acid and their simple, preferably C 1-4 - Alkanols formed, include esters (INCI Acrylates / C10-30 Alkyl Acrylate Crosspolymer).
- the content of polymeric thickener is usually not more than 8% by weight, preferably between 0.1 and 7% by weight, particularly preferably between 0.5 and 6% by weight, in particular between 1 and 5% by weight and extremely preferably between 1.5 and 4% by weight, for example between 2 and 2.5% by weight, based on the total weight of the detergent.
- one or more dicarboxylic acids and / or their salts can be added, in particular a composition of sodium salts of adipic, succinic and glutaric acid, such as those available under the trade name Sokalan® DSC is. They are advantageously used in amounts of 0.1 to 8% by weight, preferably 0.5 to 7% by weight, in particular 1.3 to 6% by weight and particularly preferably 2 to 4% by weight, based on the total weight of the detergent.
- the agent according to the invention is preferably free from dicarboxylic acid (salts).
- the detergents according to the invention can be compared with reference detergents in order to determine the increased anti-pilling performance of the agents according to the invention.
- a washing system can be composed as follows (all data in percent by weight): Reference agent: 4.4% alkylbenzenesulfonic acid, 5.6% other anionic surfactants, 2.4% C12-C18 Na salts of fatty acids (soaps), 4 , 4% non-ionic surfactants, 0.2% phosphonates, 1.4% citric acid, 0.95% NaOH, 0.01% defoamer, 2.0% glycerine, 0.08% preservatives, 1% ethanol, 1, 6% enzyme mix (protease, amylase, cellulase, mannase), the remainder demineralized water.
- Reference agent 4.4% alkylbenzenesulfonic acid, 5.6% other anionic surfactants, 2.4% C12-C18 Na salts of fatty acids (soaps), 4 , 4% non-i
- Agent according to the invention 4.4% alkylbenzenesulfonic acid, 5.6% other anionic surfactants, 2.4% C12-C18 Na salts of fatty acids (soaps), 4.4% non-ionic surfactants, 0.2% phosphonates, 1, 4% citric acid, 0.95% NaOH, 0.01% defoamer, 2.0% glycerine, 0.08% preservatives, 1% ethanol, 1.6% enzyme mix (protease, amylase, cellulase, mannase), 0.009% cutinase , Rest demineralized water.
- the dosage of the liquid detergent is preferably between 4.5 and 6.0 grams per liter of wash liquor, for example 4.7, 4.9 or 5.9 grams per liter of wash liquor. Washing is preferably carried out in a pH range between pH 8 and pH 10.5, preferably between pH 8 and pH 9.
- the aforementioned embodiments of the present invention include all solid, powdery, liquid, gel-like or pasty dosage forms of agents according to the invention, which can optionally also consist of several phases and can be in compressed or uncompressed form.
- the agent can be in the form of a free-flowing powder, in particular with a bulk density of 300 g / l to 1200 g / l, in particular 500 g / l to 900 g / l or 600 g / l to 850 g / l.
- the solid dosage forms of the agent also include extrudates, granules, tablets or pouches.
- the agent can also be liquid, gel-like or pasty, for example 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 can be in the form of a one-component system. Such means consist of a phase. Alternatively, a means can also consist of several phases. Such a means is therefore divided into several components.
- Another subject matter of the invention is a method for cleaning textiles, which is characterized in that a detergent according to the invention is used in at least one method step.
- the method described above is characterized in that the detergent according to the invention is at a temperature of 0-100 ° C, preferably 0-80 ° C, more preferably 30-70 ° C and most preferably 40-60 ° C is used.
- Processes for cleaning textiles are generally characterized in that various active cleaning substances are applied to the items to be cleaned in several process steps and washed off after the exposure time, or that the items to be cleaned are treated in some other way with a detergent or a solution or dilution of this agent. All conceivable washing or cleaning processes can be enriched in at least one of the process steps by the use of a detergent according to the invention and then represent embodiments of the present invention. All facts, subjects and embodiments that are described for agents according to the invention are also applicable to this subject matter of the invention. For this reason, reference is expressly made at this point to the disclosure at the corresponding point with the note that this disclosure also applies to the above methods according to the invention.
- a single and / or the only step of such a process can consist in the fact that the only active cleaning component is a cutinase with the Soiling is brought into contact, preferably in a buffer solution or in water.
- Alternative embodiments of this subject matter of the invention also represent processes for treating raw textile materials or for textile care, in which an agent according to the invention becomes active in at least one process step.
- processes for textile raw materials, fibers or textiles with natural components are preferred, and very particularly for those with wool or silk.
- the invention also covers the use of the agent described herein, for example as a washing agent as described above, for the (improved) removal of soiling, for example from textiles, in particular polyester textiles.
- the invention also relates to the use of a cutinase for reducing the pilling effects of an agent, preferably a detergent, particularly preferably a liquid detergent, the agent containing the cutinase.
- an agent preferably a detergent, particularly preferably a liquid detergent, the agent containing the cutinase.
- the cutinase can be a cutinase as defined herein.
- the cutinase is in an amount of 0.00001-1% by weight, preferably in an amount of 0.0001-0.5% by weight, particularly preferably in an amount of 0.001-0.1 % By weight, contained in the agent.
- the cutinase which brings about a reduction in the pilling effect, is applied to textiles, in particular textiles which are made of polyester or comprise polyester.
- the pre-pilled fabrics are produced by washing cycles repeated 20 times at 40 ° C in commercially available washing machines.
- a change of 0.5 units is to be regarded as significant.
- the cutinase according to the invention significantly improves the appearance of the pill.
- a technically similar cutinase does not improve the pill picture.
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Description
Die vorliegende Erfindung liegt auf dem Gebiet der Enzymtechnologie, insbesondere der Anti-Pilling Wirkung von Enzymen, wie sie zum Beispiel in Waschmitteln, verwendet werden. Die Erfindung betrifft ein Waschmittel, welches eine Cutinase, wie hierin definiert, enthält. Ferner betrifft die vorliegende Erfindung ein Verfahren zur Reinigung von Textilien sowie die Verwendung des erfindungsgemäßen Mittels zur Entfernung von Anschmutzungen. Des Weiteren richtet sich die Erfindung auf die Verwendung einer Cutinase zur Verringerung von Pilling-Effekten und Anti-Grau in einem Waschmittel.The present invention is in the field of enzyme technology, in particular the anti-pilling effect of enzymes such as are used, for example, in detergents. The invention relates to a detergent which contains a cutinase as defined herein. The present invention also relates to a method for cleaning textiles and the use of the agent according to the invention for removing soiling. Furthermore, the invention is directed to the use of a cutinase to reduce pilling effects and anti-gray in a detergent.
Bei mehrfacher Wäsche von Kleidungsstücken weisen diese mit der Zeit ein Pilling auf. Dies gilt für Textilien jeglicher Art und ist vom Konsumenten unerwünscht, da das Kleidungsstück dadurch älter und unansehnlich wirkt. Als Pilling bezeichnet man die Knötchen- oder Fusselbildung bei Stoffen. Diese kleinen Fussel entstehen insbesondere bei kurzfaserigen Stoffen. Bei langfaserigen und verzwirnten Fasern entsteht Pilling dagegen weniger stark. Allgemein entstehen diese Knötchen durch lose Fasern im Stoff oder solche die sich aus dem Gewebe gelöst haben. Synthetische Fasern neigen, durch ihre glatte Oberfläche, eher zum Pilling als Naturfasern, weil synthetische Fasern schneller aus dem Gewebe gelöst werden können als raue Naturfasern. Bei Wollstoffen "verfilzen" diese Fasern hauptsächlich durch mechanische Reibung und bilden Knötchen an der Oberfläche.If items of clothing are washed several times, they will pilling over time. This applies to all types of textiles and is undesirable by the consumer, as it makes the item of clothing look older and unsightly. Pilling is the name given to the formation of pebbles or fluff in fabrics. These small lint appear especially in short-fiber fabrics. With long-fiber and twisted fibers, on the other hand, pilling is less pronounced. In general, these nodules are caused by loose fibers in the fabric or those that have become detached from the fabric. Due to their smooth surface, synthetic fibers tend to pilling more than natural fibers, because synthetic fibers can be detached from the fabric more quickly than rough natural fibers. In the case of woolen fabrics, these fibers "felt" mainly through mechanical friction and form pebbles on the surface.
Die Hauptauswirkung von Pilling ist eine Optische. Durch die Knötchenbildung an der Oberfläche sehen Stoffe schnell gebraucht und älter aus als sie sind. Dagegen wird die Funktionalität des Stoffes kaum bis gar nicht beeinträchtigt. Zum Beispiel wird durch die andauernde Ausdünnung des Stoffes wird die Atmungsaktivität sogar gesteigert. Pilling findet insbesondere an mechanisch stark beanspruchten Stellen statt, meist sind dies Schulter- und Bundbereich. Durch die fortlaufende Ausdünnung des Stoffes sind vor allem diese beanspruchten Bereiche gefährdet Löcher zu bilden oder gar zu reißen.The main effect of pilling is optical. Due to the formation of pods on the surface, fabrics quickly look used and older than they are. In contrast, the functionality of the material is hardly or not at all impaired. For example, the constant thinning of the fabric even increases the breathability. Pilling takes place particularly in areas subject to high mechanical stress, usually the shoulder and waistband areas. Due to the continuous thinning of the fabric, these stressed areas in particular are at risk of forming holes or even tearing.
Eine technische Lösung, um den Pilling-Effekt zu verringern liegt für Baumwoll-Textilien vor. Hierbei werden Cellulasen im Reinigungsmittel verwendet, um den Pilling-Effekt zu verringern (
Es ist wünschenswert und es besteht eine Nachfrage nach weiteren und verbesserten Lösungen, die das Pilling von Textilien, insbesondere Textilien, die synthetische Fasern wie Polyester enthalten, reduzieren.It is desirable and there is a need for further and improved solutions that reduce pilling of textiles, particularly textiles containing synthetic fibers such as polyester.
Überraschenderweise haben die Erfinder der vorliegenden Erfindung gefunden, dass eine Cutinase aus Thermomonospora curvata DSM 43183 eine Anti-Pilling Wirkung im Waschprozess zeigt. Im Vergleich zu Waschmittel ohne Cutinase/PET-Esterase, ist vorgepilltes Gewebe bzw. neues Gewebe nach 20 Wäschen mit einem Waschmittel, das die erfindungsgemäße Cutinase enthält, weniger gepillt.Surprisingly, the inventors of the present invention have found that a cutinase from Thermomonospora curvata DSM 43183 shows an anti-pilling effect in the washing process. Compared to detergents without cutinase / PET esterase, pre-pilled tissue or new tissue is less pilled after 20 washes with a detergent which contains the cutinase according to the invention.
Die oben beschriebene Aufgabe, die der vorliegenden Anmeldung zugrunde liegt, wird dadurch gelöst, dass Waschmitteln eine Cutinase zugesetzt wird, die mindestens 70% Sequenzidentität mit der in SEQ ID NO:1 angegebenen Aminosäuresequenz über deren Gesamtlänge aufweist. Der Zusatz der Cutinase bewirkt, dass mit den erfindungsgemäßen Mitteln gewaschene Textilien, insbesondere Polyester Textilien, ein signifikant verringertes Pilling im Vergleich zu einem Kontrollwaschmittel ohne Cutinase aufweisen.The object described above, on which the present application is based, is achieved in that a cutinase is added to detergents which has at least 70% sequence identity with the amino acid sequence given in SEQ ID NO: 1 over its entire length. The addition of the cutinase has the effect that textiles washed with the agents according to the invention, in particular polyester textiles, have a significantly reduced pilling compared to a control detergent without cutinase.
Daher richtet sich in einem ersten Aspekt die vorliegende Erfindung auf ein Waschmittel, dadurch gekennzeichnet, dass es eine Cutinase enthält, wobei die Cutinase eine Cutinase ist, die mindestens 70% Sequenzidentität mit der in SEQ ID NO:1 angegebenen Aminosäuresequenz über deren Gesamtlänge aufweist.In a first aspect, the present invention is therefore directed to a detergent, characterized in that it contains a cutinase, the cutinase being a cutinase which has at least 70% sequence identity with the amino acid sequence given in SEQ ID NO: 1 over its entire length.
In einem weiteren Aspekt richtet sich die vorliegende Erfindung auf Verfahren zur Reinigung von Textilien, dadurch gekennzeichnet, dass in mindestens einem Verfahrensschritt ein erfindungsgemäßes Mittel angewendet wird.In a further aspect, the present invention is directed to processes for cleaning textiles, characterized in that an agent according to the invention is used in at least one process step.
In noch einem Aspekt richtet sich die vorliegende Erfindung ferner auf die Verwendung eines wie hierin beschriebenen Waschmittels, besonders bevorzugt flüssige Waschmittel, zur Entfernung von Anschmutzungen.In yet another aspect, the present invention is also directed to the use of a detergent as described herein, particularly preferably liquid detergent, for removing soiling.
Darüber hinaus beinhaltet ein weiterer Aspekt der Erfindung, die Verwendung einer Cutinase zur Verringerung von Pilling-Effekten eines Waschmittels, besonders bevorzugt eines Flüssigwaschmittels, wobei das Mittel die Cutinase enthält, wobei die Cutinase eine Cutinase ist, die mindestens 70% Sequenzidentität mit der in SEQ ID NO:1 angegebenen Aminosäuresequenz über deren Gesamtlänge aufweist.In addition, another aspect of the invention includes the use of a cutinase for reducing pilling effects of a detergent, particularly preferably a liquid detergent, the agent containing the cutinase, the cutinase being a cutinase which has at least 70% sequence identity with that in SEQ ID NO: 1 has indicated amino acid sequence over its entire length.
Eine Cutinase (EC 3.1.1.74) oder auch Cutin Hydrolase ist ein Enzym, das zu den α/β-Hydrolasen gehört und Cutin hydrolisiert. Cutinase wird unter anderem von einigen pflanzenpathogenen Pilzen und Bakterien gebildet (durch die Cutinase sind die Pilze in der Lage, die Esterbindung des Cutins in der Cuticula der Pflanzen abzubauen und so in die Pflanzen einzudringen).A cutinase (EC 3.1.1.74) or cutin hydrolase is an enzyme that belongs to the α / β hydrolases and hydrolyses cutin. Cutinase is produced, among other things, by some phytopathogenic fungi and bacteria are formed (through the cutinase the fungi are able to break down the ester bond of the cutin in the cuticula of the plants and thus penetrate the plants).
In verschiedenen bevorzugten Ausführungsformen handelt es sich bei der Cutinase um eine Cutinase aus Thermomonospora curvata, insbesondere die Cutinase mit der Aminosäuresequenz gemäß SEQ ID NO:1, bzw. eine davon, beispielsweise mittels Mutagenese, abgeleitete Cutinase.In various preferred embodiments, the cutinase is a cutinase from Thermomonospora curvata, in particular the cutinase with the amino acid sequence according to SEQ ID NO: 1, or a cutinase derived therefrom, for example by means of mutagenesis.
In verschiedenen weiteren Ausführungsformen ist das Mittel dadurch gekennzeichnet, dass
- (a) die Cutinase aus einer wie oben definierten Cutinase als Ausgangsmolekül durch ein- oder mehrfache konservative Aminosäuresubstitution erhältlich ist; und/oder
- (b) die Cutinase aus einer wie oben definierten Cutinase als Ausgangsmolekül erhältlich ist durch Fragmentierung, Deletions-, Insertions- oder Substitutionsmutagenese und eine Aminosäuresequenz umfasst, die über eine Länge von mindestens 210, 220, 230, 240, 250, 260, 270, 280 oder 289 zusammenhängenden Aminosäuren mit dem Ausgangsmolekül übereinstimmt.
- (a) the cutinase can be obtained from a cutinase as defined above as the starting molecule by one or more conservative amino acid substitutions; and or
- (b) the cutinase can be obtained from a cutinase as defined above as the starting molecule by fragmentation, deletion, insertion or substitution mutagenesis and comprises an amino acid sequence which is at least 210, 220, 230, 240, 250, 260, 270, 280 or 289 contiguous amino acids match the parent molecule.
Die erfindungsgemäßen Mittel enthalten die Cutinase in einer Menge von 0,00001 - 1 Gew.-%, bevorzugt in einer Menge von 0,0001 - 0,5 Gew.-%, besonders bevorzugt in einer Menge von 0,001 - 0,1 Gew.-% bezogen auf das aktive Protein.The agents according to the invention contain the cutinase in an amount of 0.00001-1% by weight, preferably in an amount of 0.0001-0.5% by weight, particularly preferably in an amount of 0.001-0.1% by weight. -% based on the active protein.
In verschiedenen Ausführungsformen der Erfindung umfasst die Cutinase eine Aminosäuresequenz, die zu der in SEQ ID NO:1 angegebenen Aminosäuresequenz über deren Gesamtlänge zu mindestens 70%, 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 90,5%, 91%, 91,5%, 92%, 92,5%, 93%, 93,5%, 94%, 94,5%, 95%, 95,5%, 96%, 96,5%, 97%, 97,5%, 98%, 98,5% und 98,8% identisch ist.In various embodiments of the invention, the cutinase comprises an amino acid sequence which is at least 70%, 71%, 72%, 73%, 74%, 75%, 76%, 77% of the total length of the amino acid sequence given in SEQ ID NO: 1 , 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 90.5%, 91%, 91, 5%, 92%, 92.5%, 93%, 93.5%, 94%, 94.5%, 95%, 95.5%, 96%, 96.5%, 97%, 97.5% , 98%, 98.5% and 98.8% are identical.
Die Bestimmung der Identität von Nukleinsäure- oder Aminosäuresequenzen erfolgt durch einen Sequenzvergleich. Dieser Sequenzvergleich basiert auf dem im Stand der Technik etablierten und üblicherweise genutzten BLAST-Algorithmus (vgl. beispielsweise
Solch ein Vergleich erlaubt auch eine Aussage über die Ähnlichkeit der verglichenen Sequenzen zueinander. Sie wird üblicherweise in Prozent Identität, das heißt dem Anteil der identischen Nukleotide oder Aminosäurereste an denselben oder in einem Alignment einander entsprechenden Positionen angegeben. Der weiter gefasste Begriff der Homologie bezieht bei Aminosäuresequenzen konservierte Aminosäure-Austausche in die Betrachtung mit ein, also Aminosäuren mit ähnlicher chemischer Aktivität, da diese innerhalb des Proteins meist ähnliche chemische Aktivitäten ausüben. Daher kann die Ähnlichkeit der verglichenen Sequenzen auch Prozent Homologie oder Prozent Ähnlichkeit angegeben sein. Identitäts- und/oder Homologieangaben können über ganze Polypeptide oder Gene oder nur über einzelne Bereiche getroffen werden. Homologe oder identische Bereiche von verschiedenen Nukleinsäure- oder Aminosäuresequenzen sind daher durch Übereinstimmungen in den Sequenzen definiert. Solche Bereiche weisen oftmals identische Funktionen auf. Sie können klein sein und nur wenige Nukleotide oder Aminosäuren umfassen. Oftmals üben solche kleinen Bereiche für die Gesamtaktivität des Proteins essentielle Funktionen aus. Es kann daher sinnvoll sein, Sequenzübereinstimmungen nur auf einzelne, gegebenenfalls kleine Bereiche zu beziehen. Soweit nicht anders angegeben beziehen sich Identitäts- oder Homologieangaben in der vorliegenden Anmeldung aber auf die Gesamtlänge der jeweils angegebenen Nukleinsäure- oder Aminosäuresäuresequenz.Such a comparison also allows a statement to be made about the similarity of the compared sequences to one another. It is usually given in percent identity, that is to say the proportion of identical nucleotides or amino acid residues in the same positions or positions corresponding to one another in an alignment. The broader term of homology includes conserved amino acid exchanges in the case of amino acid sequences, i.e. amino acids with similar chemical activity, since these usually exert similar chemical activities within the protein. Therefore, the similarity of the compared sequences can also be given as percent homology or percent similarity. Identity and / or homology information can be made over entire polypeptides or genes or only over individual areas. Homologous or identical regions of different nucleic acid or amino acid sequences are therefore defined by matches in the sequences. Such areas often have identical functions. They can be small and only contain a few nucleotides or amino acids. Such small areas often have essential functions for the overall activity of the protein. It can therefore be useful to relate sequence matches only to individual, possibly small areas. Unless otherwise stated, identity or homology details in the present application refer to the total length of the nucleic acid or amino acid sequence specified in each case.
In einer weiteren Ausführungsform der Erfindung ist die Cutinase dadurch gekennzeichnet, dass ihre Anti-Pilling-Leistung gegenüber derjenigen einer Cutinase, die eine Aminosäuresequenz umfasst, die der in SEQ ID NO:1 angegebenen Aminosäuresequenzen entspricht, nicht signifikant verringert ist, d.h. mindestens 70%, 75 %, 80 %, 85 %, 90 %, 95 % der Referenz-Anti-Pilling-leistung besitzt. Die Anti-Pilling-Leistung kann in einem Waschsystem bestimmt werden, das ein Waschmittel in einer Dosierung zwischen 4,5 und 7,0 Gramm pro Liter Waschflotte sowie die Cutinase enthält, wobei die zu vergleichenden Cutinasen konzentrationsgleich (bezogen auf aktives Protein) eingesetzt sind und die Anti-Pilling-Leistung wie hierin beschrieben ermittelt wird. Beispielsweise kann der Waschvorgang für 60 Minuten bei einer Temperatur von 60°C erfolgen und das Wasser eine Wasserhärte zwischen 15,5 und 16,5° (deutsche Härte) aufweisen. Die Konzentration der Cutinase in dem für dieses Waschsystem bestimmten Waschmittel beträgt von 0,00001 - 1 Gew.-%, bevorzugt von 0,0001 - 0,5 Gew.-%, besonders bevorzugt von 0,001 - 0,1 Gew.-%, bezogen auf aktives, gereinigtes Protein.In a further embodiment of the invention, the cutinase is characterized in that its anti-pilling performance is not significantly reduced compared to that of a cutinase which comprises an amino acid sequence which corresponds to the amino acid sequences given in SEQ ID NO: 1, ie at least 70% , 75%, 80%, 85%, 90%, 95% of the reference anti-pilling performance. The anti-pilling performance can be determined in a washing system that contains a detergent in a dosage between 4.5 and 7.0 grams per liter of washing liquor as well as the cutinase, with the cutinases to be compared being used in the same concentration (based on active protein) and the anti-pilling performance is determined as described herein. For example, the washing process can take place for 60 minutes at a temperature of 60 ° C and the water has a water hardness between 15.5 and 16.5 ° (German hardness). The concentration of cutinase in the detergent intended for this washing system is from 0.00001 - 1% by weight, preferably from 0.0001-0.5% by weight, particularly preferably from 0.001-0.1% by weight, based on active, purified protein.
Ein bevorzugtes flüssiges Waschmittel für ein solches Waschsystem ist wie folgt zusammengesetzt (alle Angaben in Gewichts-Prozent): 4,4% Alkylbenzolsulfonsäure, 5,6% anionische Tenside, 2,4% C12-C18 Na-Salze von Fettsäuren, 4,4% nicht-ionische Tenside, 0,2% Phosphonate, 1,4% Zitronensäure, 0,95% NaOH, 0,01% Antischaum, 2% Glycerin, 0,08% Konservierungsstoffe, 1% Ethanol, 1,6% Enzymmix (Protease, Amylase, Cellulase, Mannase), Rest demineralisiertes Wasser. Bevorzugt beträgt die Dosierung des flüssigen Waschmittels zwischen 4,5 und 6,0 Gramm pro Liter Waschflotte, beispielsweise 4,7, 4,9 oder 5,9 Gramm pro Liter Waschflotte. Bevorzugt wird gewaschen in einem pH-Wertebereich zwischen pH 8 und pH 10,5, bevorzugt zwischen pH 8 und pH 9.A preferred liquid detergent for such a washing system is composed as follows (all data in percent by weight): 4.4% alkylbenzenesulfonic acid, 5.6% anionic surfactants, 2.4% C12-C18 Na salts of fatty acids, 4.4 % non-ionic surfactants, 0.2% phosphonates, 1.4% citric acid, 0.95% NaOH, 0.01% antifoam, 2% glycerine, 0.08% preservatives, 1% ethanol, 1.6% enzyme mix ( Protease, amylase, cellulase, mannase), the remainder demineralized water. The dosage of the liquid detergent is preferably between 4.5 and 6.0 grams per liter of wash liquor, for example 4.7, 4.9 or 5.9 grams per liter of wash liquor. Washing is preferably carried out in a pH range between pH 8 and pH 10.5, preferably between pH 8 and pH 9.
Im Rahmen der Erfindung erfolgt die Bestimmung der Anti-Pilling-Leistung bei 60°C unter Verwendung eines flüssigen Waschmittels wie vorstehend angegeben, wobei der Waschvorgang vorzugsweise für 60 Minuten erfolgt.In the context of the invention, the anti-pilling performance is determined at 60 ° C. using a liquid detergent as indicated above, the washing process preferably taking place for 60 minutes.
Die Anti-Pilling-Leistung kann anhand von visueller Abmusterung verfolgen. Eine Prüfergruppe ordnet in diesem Fall der zu untersuchenden Wäsche einen Wert einer Skala von 1-5 zu. Dabei steht der Wert = 1 für sehr stark gepillte Wäsche, während der Wert = 5 nicht gepillter Wäsche zugeordnet wird.The anti-pilling performance can be tracked using visual sampling. In this case, a group of examiners assigns the laundry to be examined a value on a scale from 1-5. The value = 1 stands for very heavily pillaged laundry, while the value = 5 is assigned to non-pillaged laundry.
Durch den aktivitätsgleichen Einsatz der jeweiligen Cutinase wird sichergestellt, dass auch bei einem etwaigen Auseinanderklaffen des Verhältnisses von Aktivsubstanz zu Gesamtprotein (die Werte der spezifischen Aktivität) die jeweiligen enzymatischen Eigenschaften, also beispielsweise die Anti-Pilling-Leistung, verglichen werden. Generell gilt, dass eine niedrige spezifische Aktivität durch Zugabe einer größeren Proteinmenge ausgeglichen werden kann.By using the respective cutinase for the same level of activity, it is ensured that the respective enzymatic properties, e.g. the anti-pilling performance, are compared even if there is a gap in the ratio of active substance to total protein (the values of the specific activity). In general, a low specific activity can be compensated for by adding a larger amount of protein.
Proteine können über die Reaktion mit einem Antiserum oder einem bestimmten Antikörper zu Gruppen immunologisch verwandter Proteine zusammengefasst werden. Die Angehörigen einer solchen Gruppe zeichnen sich dadurch aus, dass sie dieselbe, von einem Antikörper erkannte antigene Determinante aufweisen. Sie sind daher einander strukturell so ähnlich, dass sie von einem Antiserum oder bestimmten Antikörpern erkannt werden. Einen weiteren Erfindungsgegenstand bilden daher Cutinasen, die dadurch gekennzeichnet sind, dass sie mindestens eine und zunehmend bevorzugt zwei, drei oder vier übereinstimmende antigene Determinanten mit einer in einem erfindungsgemäßen Mittel verwendeten Cutinase aufweisen. Solche Cutinasen sind auf Grund ihrer immunologischen Übereinstimmungen den in den erfindungsgemäßen Mitteln verwendeten Cutinasen strukturell so ähnlich, dass auch von einer gleichartigen Funktion auszugehen ist.Proteins can be combined into groups of immunologically related proteins by reacting with an antiserum or a specific antibody. Members of such a group are distinguished by the fact that they have the same antigenic determinant recognized by an antibody. They are therefore structurally so similar to one another that they can be recognized by an antiserum or certain antibodies. Another subject matter of the invention is therefore cutinases, which are characterized in that they have at least one and increasingly preferably two, three or four matching antigenic determinants with a cutinase used in an agent according to the invention. Due to their immunological similarities, such cutinases are structurally so similar to the cutinases used in the agents according to the invention that a similar function can also be assumed.
Weitere in den erfindungsgemäßen Mitteln verwendete Cutinasen können im Vergleich zu der in SEQ ID NO:1 beschriebenen Cutinase weitere Aminosäureveränderungen, insbesondere Aminosäure-Substitutionen, -Insertionen oder -Deletionen, aufweisen. Solche Cutinasen sind beispielsweise durch gezielte genetische Veränderung, d.h. durch Mutageneseverfahren, weiterentwickelt und für bestimmte Einsatzzwecke oder hinsichtlich spezieller Eigenschaften (beispielsweise hinsichtlich ihrer katalytischen Aktivität, Stabilität, usw.) optimiert. Ferner können Nukleinsäuren, die die verwendeten Cutinasen kodieren, in Rekombinationsansätze eingebracht und damit zur Erzeugung völlig neuartiger Cutinasen oder anderer Polypeptide genutzt werden.Further cutinases used in the agents according to the invention can have further amino acid changes compared to the cutinase described in SEQ ID NO: 1, in particular amino acid substitutions, insertions or deletions. Such cutinases are further developed, for example, through targeted genetic modification, i.e. through mutagenesis processes, and optimized for specific purposes or with regard to special properties (for example with regard to their catalytic activity, stability, etc.). Furthermore, nucleic acids that encode the cutinases used can be introduced into recombination batches and thus used to generate completely new types of cutinases or other polypeptides.
Das Ziel ist es, in die bekannten Moleküle gezielte Mutationen wie Substitutionen, Insertionen oder Deletionen einzuführen, um beispielsweise die Reinigungsleistung von erfindungsgemäßen Enzymen zu verbessern. Hierzu können insbesondere die Oberflächenladungen und/oder der isoelektrische Punkt der Moleküle und dadurch ihre Wechselwirkungen mit dem Substrat verändert werden. So kann beispielsweise die Nettoladung der Enzyme verändert werden, um darüber die Substratbindung insbesondere für den Einsatz in Wasch- und Reinigungsmitteln zu beeinflussen. Alternativ oder ergänzend kann durch eine oder mehrere entsprechende Mutationen die Stabilität der Cutinase noch weiter erhöht und dadurch ihre Reinigungsleistung verbessert werden. Vorteilhafte Eigenschaften einzelner Mutationen, z.B. einzelner Substitutionen, können sich ergänzen. Eine hinsichtlich bestimmter Eigenschaften bereits optimierte Cutinasen, zum Beispiel hinsichtlich ihrer Aktivität und/oder ihrer Anti-Pilling-Leistung, kann daher im Rahmen der Erfindung zusätzlich weiterentwickelt sein.The aim is to introduce specific mutations such as substitutions, insertions or deletions into the known molecules in order, for example, to improve the cleaning performance of enzymes according to the invention. For this purpose, in particular the surface charges and / or the isoelectric point of the molecules and thereby their interactions with the substrate can be changed. For example, the net charge of the enzymes can be changed in order to influence the substrate binding, especially for use in detergents and cleaning agents. Alternatively or in addition, one or more corresponding mutations can increase the stability of the cutinase even further and thereby improve its cleaning performance. Advantageous properties of individual mutations, e.g. individual substitutions, can complement each other. A cutinase that has already been optimized with regard to certain properties, for example with regard to its activity and / or its anti-pilling performance, can therefore be further developed within the scope of the invention.
Ein weiterer Gegenstand der Erfindung ist daher ein Mittel enthaltend eine Cutinase, die dadurch gekennzeichnet ist, dass sie aus einer Cutinase wie vorstehend beschrieben als Ausgangsmolekül erhältlich ist durch ein- oder mehrfache konservative Aminosäuresubstitution. Der Begriff "konservative Aminosäuresubstitution" bedeutet den Austausch (Substitution) eines Aminosäurerestes gegen einen anderen Aminosäurerest, wobei dieser Austausch nicht zu einer Änderung der Polarität oder Ladung an der Position der ausgetauschten Aminosäure führt, z. B. der Austausch eines unpolaren Aminosäurerestes gegen einen anderen unpolaren Aminosäurerest. Konservative Aminosäuresubstitutionen im Rahmen der Erfindung umfassen beispielsweise: G=A=S, I=V=L=M, D=E, N=Q, K=R, Y=F, S=T, G=A=I=V=L=M=Y=F=W=P=S=T.The invention therefore also relates to an agent containing a cutinase, which is characterized in that it can be obtained from a cutinase as described above as the starting molecule by single or multiple conservative amino acid substitutions. The term "conservative amino acid substitution" means the exchange (substitution) of an amino acid residue for another amino acid residue, this exchange not leading to a change in polarity or charge at the position of the exchanged amino acid, e.g. B. the exchange of a non-polar amino acid residue for another non-polar amino acid residue. Conservative amino acid substitutions within the scope of the invention include, for example: G = A = S, I = V = L = M, D = E, N = Q, K = R, Y = F, S = T, G = A = I = V = L = M = Y = F = W = P = S = T.
Alternativ oder ergänzend ist die Cutinase dadurch gekennzeichnet, dass sie aus einer in einem erfindungsgemäßen Mittel enthaltenen Cutinase als Ausgangsmolekül erhältlich ist durch Fragmentierung, Deletions-, Insertions- oder Substitutionsmutagenese und eine Aminosäuresequenz umfasst, die über eine Länge von mindestens 210, 220, 230, 240, 250, 260, 270, 280 oder 289 zusammenhängenden Aminosäuren mit dem Ausgangsmolekül übereinstimmt.Alternatively or in addition, the cutinase is characterized in that it can be obtained from a cutinase contained in an agent according to the invention as a starting molecule by fragmentation, deletion, insertion or substitution mutagenesis and comprises an amino acid sequence that is at least 210, 220, 230, 240, 250, 260, 270, 280 or 289 contiguous amino acids match the parent molecule.
So ist es beispielsweise möglich, an den Termini oder in den Loops des Enzyms einzelne Aminosäuren zu deletieren, ohne dass dadurch die hydrolytische Aktivität verloren oder vermindert wird. Ferner kann durch derartige Fragmentierung, Deletions-, Insertions- oder Substitutionsmutagenese beispielsweise auch die Allergenizität betreffender Enzyme gesenkt und somit insgesamt ihre Einsetzbarkeit verbessert werden. Vorteilhafterweise behalten die Enzyme auch nach der Mutagenese ihre hydrolytische Aktivität, d.h. ihre hydrolytische Aktivität entspricht mindestens derjenigen des Ausgangsenzyms, d.h. in einer bevorzugten Ausführungsform beträgt die hydrolytische Aktivität mindestens 80, vorzugsweise mindestens 90 % der Aktivität des Ausgangsenzyms. Auch weitere Substitutionen können vorteilhafte Wirkungen zeigen. Sowohl einzelne wie auch mehrere zusammenhängende Aminosäuren können gegen andere Aminosäuren ausgetauscht werden.For example, it is possible to delete individual amino acids at the termini or in the loops of the enzyme without losing or reducing the hydrolytic activity. Furthermore, such fragmentation, deletion, insertion or substitution mutagenesis can also, for example, reduce the allergenicity of enzymes concerned and thus improve their usability overall. The enzymes advantageously retain their hydrolytic activity even after the mutagenesis, i.e. their hydrolytic activity corresponds at least to that of the starting enzyme, i.e. in a preferred embodiment the hydrolytic activity is at least 80, preferably at least 90% of the activity of the starting enzyme. Further substitutions can also have advantageous effects. Both single and several connected amino acids can be exchanged for other amino acids.
Alle Prozentangaben, die im Zusammenhang mit den hierin beschriebenen Zusammensetzungen gemacht werden, beziehen sich, sofern nicht explizit anders angegeben auf Gew.-%, jeweils bezogen auf die betreffende Mischung.All percentages given in connection with the compositions described herein relate, unless explicitly stated otherwise, to% by weight, in each case based on the mixture in question.
Im Rahmen der vorliegenden Erfindung stehen Fettsäuren bzw. Fettalkohole bzw. deren Derivate - soweit nicht anders angegeben - stellvertretend für verzweigte oder unverzweigte Carbonsäuren bzw. Alkohole bzw. deren Derivate mit vorzugsweise 6 bis 22 Kohlenstoffatomen. Insbesondere sind auch die beispielsweise nach der ROELENschen Oxo-Synthese erhältlichen Oxo-Alkohole bzw. deren Derivate entsprechend einsetzbar.In the context of the present invention, fatty acids or fatty alcohols or their derivatives - unless otherwise stated - represent branched or unbranched carboxylic acids or alcohols or their derivatives with preferably 6 to 22 carbon atoms. In particular, the oxo alcohols or their derivatives obtainable, for example, by ROELEN's oxo synthesis, or their derivatives can also be used accordingly.
Wann immer im Folgenden Erdalkalimetalle als Gegenionen für einwertige Anionen genannt sind, so bedeutet das, dass das Erdalkalimetall natürlich nur in der halben - zum Ladungsausgleich ausreichenden - Stoffmenge wie das Anion vorliegt.Whenever alkaline earth metals are mentioned in the following as counterions for monovalent anions, this means that the alkaline earth metal is of course only present in half the amount of substance - sufficient to balance the charge - as the anion.
Ein Gegenstand der Erfindung ist ein Waschmittel, das dadurch gekennzeichnet ist, dass es eine Cutinase, wie hierin definiert, enthält.An object of the invention is a detergent which is characterized in that it contains a cutinase as defined herein.
Zu diesem Erfindungsgegenstand zählen alle denkbaren Waschmittelarten, sowohl Konzentrate als auch unverdünnt anzuwendende Mittel, zum Einsatz im kommerziellen Maßstab, in der Waschmaschine oder in der Handwäsche. Dazu gehören beispielsweise Waschmittel für Textilien, Teppiche, oder Naturfasern, für die die Bezeichnung Waschmittel verwendet wird. Zu den Waschmittel im Rahmen der Erfindung zählen ferner Waschhilfsmittel, die bei der manuellen oder maschinellen Textilwäsche zum eigentlichen Waschmittel hinzudosiert werden, um eine weitere Wirkung zu erzielen. Ferner zählen zu Waschmittel im Rahmen der Erfindung auch Textilvor- und Nachbehandlungsmittel, also solche Mittel, mit denen das Wäschestück vor der eigentlichen Wäsche in Kontakt gebracht wird, beispielsweise zum Anlösen hartnäckiger Verschmutzungen, und auch solche Mittel, die in einem der eigentlichen Textilwäsche nachgeschalteten Schritt dem Waschgut weitere wünschenswerte Eigenschaften wie angenehmen Griff, Knitterfreiheit oder geringe statische Aufladung verleihen. Zu letztgenannten Mittel werden u.a. die Weichspüler gerechnet.This subject matter of the invention includes all conceivable types of detergent, both concentrates and agents to be used undiluted, for use on a commercial scale, in the washing machine or in hand washing. These include, for example, detergents for textiles, carpets, or natural fibers, for which the term detergent is used. The detergents within the scope of the invention also include washing auxiliaries which are added to the actual detergent in manual or machine washing in order to achieve a further effect. Furthermore, laundry detergents in the context of the invention also include textile pretreatment and aftertreatment agents, i.e. those agents with which the item of laundry is brought into contact before the actual washing, for example to loosen stubborn dirt, and also those agents that are used in a step following the actual textile washing the laundry has other desirable properties such as pleasant Provide grip, wrinkle-free or low static charge. The last-mentioned agents include fabric softeners.
Die erfindungsgemäßen Waschmittel, die als pulverförmige Feststoffe, in nachverdichteter Teilchenform, als homogene Lösungen oder Suspensionen vorliegen können, können neben der oben beschriebenen Cutinase alle bekannten und in derartigen Mitteln üblichen Inhaltsstoffe enthalten, wobei bevorzugt mindestens ein weiterer Inhaltsstoff in dem Mittel vorhanden ist. Die erfindungsgemäßen Mittel können insbesondere Tenside, Builder (Gerüststoffe), Bleichmittel, insbesondere Persauerstoffverbindungen, oder Bleichaktivatoren enthalten. Ferner können sie wassermischbare organische Lösungsmittel, weitere Enzyme, Sequestrierungsmittel, Elektrolyte, pH-Regulatoren und/oder weitere Hilfsstoffe wie optische Aufheller, Vergrauungsinhibitoren, Schaumregulatoren sowie Farb- und Duftstoffe sowie Kombinationen hiervon enthalten.The detergents according to the invention, which can be present as pulverulent solids, in re-compacted particle form, as homogeneous solutions or suspensions, can contain, in addition to the cutinase described above, all known ingredients common in such agents, with at least one further ingredient preferably being present in the agent. The agents according to the invention can in particular contain surfactants, builders, bleaching agents, in particular peroxygen compounds, or bleach activators. Furthermore, they can contain water-miscible organic solvents, further enzymes, sequestering agents, electrolytes, pH regulators and / or further auxiliaries such as optical brighteners, graying inhibitors, foam regulators and dyes and fragrances and combinations thereof.
Insbesondere eine Kombination des erfindungsgemäßen Mittels mit einem oder mehreren weiteren Inhaltsstoff(en) ist vorteilhaft, da ein solches Mittel in bevorzugten erfindungsgemäßen Ausgestaltungen eine verbesserte Reinigungsleistung durch sich ergebende Synergismen aufweist. Insbesondere durch die Kombination des erfindungsgemäßen Mittels mit einem Tensid und/oder einem Builder (Gerüststoff) und/oder einer Persauerstoffverbindung und/oder einem Bleichaktivator kann ein solcher Synergismus erreicht werden.In particular, a combination of the agent according to the invention with one or more further ingredient (s) is advantageous, since such an agent in preferred embodiments according to the invention has an improved cleaning performance due to resulting synergisms. Such a synergism can be achieved in particular by combining the agent according to the invention with a surfactant and / or a builder and / or a peroxygen compound and / or a bleach activator.
Vorteilhafte Inhaltsstoffe erfindungsgemäßer Mittel sind offenbart in der internationalen Patentanmeldung
Diese und weitere Aspekte, Merkmale und Vorteile der Erfindung werden für den Fachmann aus dem Studium der folgenden detaillierten Beschreibung und Ansprüche ersichtlich. Dabei kann jedes Merkmal aus einem Aspekt der Erfindung in jedem anderen Aspekt der Erfindung eingesetzt werden. Ferner ist es selbstverständlich, dass die hierin enthaltenen Beispiele die Erfindung beschreiben und veranschaulichen sollen, diese aber nicht einschränken und insbesondere die Erfindung nicht auf diese Beispiele beschränkt ist. Alle Prozentangaben sind, sofern nicht anders angegeben, Gewichts-% bezogen auf das Gesamtgewicht der Zusammensetzung. Numerische Bereiche, die in dem Format "von x bis y" angegeben sind, schließen die genannten Werte ein. Wenn mehrere bevorzugte numerische Bereiche in diesem Format angegeben sind, ist es selbstverständlich, dass alle Bereiche, die durch die Kombination der verschiedenen Endpunkte entstehen, ebenfalls erfasst werden.These and other aspects, features, and advantages of the invention will become apparent to those skilled in the art from a study of the following detailed description and claims. Each feature from one aspect of the invention can be used in any other aspect of the invention. Furthermore, it goes without saying that the examples contained herein are intended to describe and illustrate the invention, but not to restrict it, and in particular the invention is not limited to these examples. Unless stated otherwise, all percentages are percentages by weight based on the total weight of the composition. Numeric ranges given in the format "from x to y" include the stated values. If several preferred numerical ranges are given in this format, it is understood that all ranges resulting from the combination of the various endpoints are also recorded.
Das erfindungsgemäße Mittel kann neben der Cutinase auch eine Verbindung aus der Klasse der anionischen Tenside der Formel (I)
R-SO3- Y+ (I)
enthalten.In addition to the cutinase, the agent according to the invention can also be a compound from the class of anionic surfactants of the formula (I)
R-SO 3 - Y + (I)
contain.
In dieser Formel (I) steht R für einen linearen oder verzweigten unsubstituierten Alkylarylrest. Y steht für ein einwertiges Kation oder den n-ten Teil eines n-wertigen Kations, bevorzugt sind dabei die Alkalimetallionen und darunter Na+ oder K+, wobei Na+ äußerst bevorzugt ist. Weitere Kationen Y+ können ausgewählt sein aus NH4+, ½ Zn2+,½ Mg2+,½ Ca2+,½ Mn2+, und deren Mischungen.In this formula (I), R stands for a linear or branched unsubstituted alkylaryl radical. Y stands for a monovalent cation or the nth part of an n-valent cation, preferred are the alkali metal ions, including Na + or K + , Na + being extremely preferred. Further cations Y + can be selected from NH4 + , ½ Zn 2+ , ½ Mg 2+ , ½ Ca 2+ , ½ Mn 2+ , and mixtures thereof.
"Alkylaryl", wie hierin verwendet, bezieht sich auf organische Reste, die aus einem Alkylrest und einem aromatischen Rest bestehen. Typische Beispiele für derartige Reste schließen ein, sind aber nicht beschränkt auf Alkylbenzolreste, wie Benzyl, Butylbenzolreste, Nonylbenzolreste, Decylbenzolreste, Undecylbenzolreste, Dodecylbenzolreste, Tridecylbenzolreste und ähnliche."Alkylaryl" as used herein refers to organic radicals consisting of an alkyl radical and an aromatic radical. Typical examples of such groups include, but are not limited to, alkylbenzene groups such as benzyl, butylbenzene groups, nonylbenzene groups, decylbenzene groups, undecylbenzene groups, dodecylbenzene groups, tridecylbenzene groups, and the like.
In verschiedenen Ausführungsformen sind derartige Tenside ausgewählt aus linearen oder verzweigten Alkylbenzolsulfonaten der Formel A-1
In verschiedenen Ausführungsformen handelt es sich bei der Verbindung der Formel (I) vorzugsweise um das Natriumsalz eines linearen Alkylbenzolsulfonats.In various embodiments, the compound of the formula (I) is preferably the sodium salt of a linear alkylbenzenesulfonate.
In erfindungsgemäßen Mitteln ist die mindestens eine Verbindung aus der Klasse der anionischen Tenside der Formel (I) in einer Menge von 0,001 bis 30 Gew.-%, vorzugsweise 0,001 - 10 Gew.-%, ferner bevorzugt 2 - 6 Gew.-%, noch bevorzugter 3 - 5 Gew.-%, in dem Waschmittel enthalten, jeweils bezogen auf das Gesamtgewicht des Waschmittels.In agents according to the invention, the at least one compound from the class of the anionic surfactants of the formula (I) is present in an amount of 0.001 to 30% by weight, preferably 0.001-10% by weight, furthermore preferably 2-6% by weight, even more preferably 3-5% by weight, contained in the detergent, in each case based on the total weight of the detergent.
In verschiedenen Ausführungsformen kann das Mittel neben der mindestens einen Verbindung der Formel (I) oder alternativ dazu mindestens ein anderes Tensid enthalten. Als alternative oder zusätzliche Tenside kommen insbesondere weitere anionische Tenside, nichtionische Tenside und deren Gemische, aber auch kationische, zwitterionische und amphotere Tenside in Frage.In various embodiments, the agent can contain at least one other surfactant in addition to the at least one compound of the formula (I) or as an alternative thereto. Other anionic surfactants, nonionic surfactants and mixtures thereof, but also cationic, zwitterionic and amphoteric surfactants, are particularly suitable as alternative or additional surfactants.
In verschiedenen Ausführungsformen enthalten die erfindungsgemäßen Mittel vorzugsweise mindestens ein anionisches Tensid, insbesondere ein anionisches Tensid der Formel R1-O-(AO)n-SO3-X+ (II).In various embodiments, the agents according to the invention preferably contain at least one anionic surfactant, in particular an anionic surfactant of the formula R 1 -O- (AO) n -SO 3 -X + (II).
In dieser Formel (II) steht R1 für einen linearen oder verzweigten, substituierten oder unsubstituierten Alkyl-, Aryl- oder Alkylarylrest, vorzugsweise für einen linearen, unsubstituierten Alkylrest, besonders bevorzugt für einen Fettalkoholrest. Bevorzugte Reste R1 sind ausgewählt aus Decyl-, Undecyl-, Dodecyl-, Tridecyl-, Tetradecyl, Pentadecyl-, Hexadecyl-, Heptadecyl-, Octadecyl-, Nonadecyl-, Eicosylresten und deren Mischungen, wobei die Vertreter mit gerader Anzahl an C-Atomen bevorzugt sind. Besonders bevorzugte Reste R1 sind abgeleitet von C12-C18-Fettalkoholen, beispielsweise von Kokosfettalkohol, Talgfettalkohol, Lauryl-, Myristyl-, Cetyl- oder Stearylalkohol oder von C10-C20-Oxoalkoholen.In this formula (II), R 1 represents a linear or branched, substituted or unsubstituted alkyl, aryl or alkylaryl radical, preferably a linear, unsubstituted alkyl radical, particularly preferably a fatty alcohol radical. Preferred radicals R 1 are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl radicals and mixtures thereof, the representatives with an even number of C- Atoms are preferred. Particularly preferred radicals R 1 are derived from C 12 -C 18 fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or from C 10 -C 20 oxo alcohols.
AO steht für eine Ethylenoxid- (EO) oder Propylenoxid- (PO) Gruppierung, vorzugsweise für eine Ethylenoxidgruppierung. Der Index n steht für eine ganze Zahl von 1 bis 50, vorzugsweise von 1 bis 20 und insbesondere von 2 bis 10. Ganz besonders bevorzugt steht n für die Zahlen 2, 3, 4, 5, 6, 7 oder 8. X steht für ein einwertiges Kation oder den n-ten Teil eines n-wertigen Kations, bevorzugt sind dabei die Alkalimetallionen und darunter Na+ oder K+, wobei Na+ äußerst bevorzugt ist. Weitere Kationen X+ können ausgewählt sein aus NH4+, ½ Zn2+, ½ Mg2+, ½ Ca2+, ½ Mn2+, und deren Mischungen.AO stands for an ethylene oxide (EO) or propylene oxide (PO) group, preferably for an ethylene oxide group. The index n stands for an integer from 1 to 50, preferably from 1 to 20 and in particular from 2 to 10. Very particularly preferably n stands for the numbers 2, 3, 4, 5, 6, 7 or 8. X stands for a monovalent cation or the n-th part of an n-valent cation, preferred are the alkali metal ions, including Na + or K + , Na + being extremely preferred. Further cations X + can be selected from NH4 + , ½ Zn 2+ , ½ Mg 2+ , ½ Ca 2+ , ½ Mn 2+ , and mixtures thereof.
Zusammenfassend enthalten Mittel in verschiedenen Ausführungsformen somit mindestens ein anionisches Tensid ausgewählt aus Fettalkoholethersulfaten der Formel A-2
In verschiedenen Ausführungsformen enthält das Waschmittel das mindestens eine anionische Tensid der Formel (II) in einer Menge von 2 - 10 Gew.-%, vorzugsweise 3 - 8 Gew.-%, bezogen auf das Gesamtgewicht des Waschmittels.In various embodiments, the detergent contains the at least one anionic surfactant of the formula (II) in an amount of 2-10% by weight, preferably 3-8% by weight, based on the total weight of the detergent.
Weitere einsetzbare anionische Tenside sind die Alkylsulfate der Formel
R2-O-SO3 - X+ (III).
Further usable anionic surfactants are the alkyl sulfates of the formula
R 2 -O-SO 3 - X + (III).
In dieser Formel (III) steht R2 für einen linearen oder verzweigten, substituierten oder unsubstituierten Alkylrest, vorzugsweise für einen linearen, unsubstituierten Alkylrest, besonders bevorzugt für einen Fettalkoholrest. Bevorzugte Reste R2 sind ausgewählt aus Decyl-, Undecyl-, Dodecyl-, Tridecyl-, Tetradecyl, Pentadecyl-, Hexadecyl-, Heptadecyl-, Octadecyl-, Nonadecyl-, Eicosylresten und deren Mischungen, wobei die Vertreter mit gerader Anzahl an C-Atomen bevorzugt sind. Besonders bevorzugte Reste R2 sind abgeleitet von C12-C18-Fettalkoholen, beispielsweise von Kokosfettalkohol, Talgfettalkohol, Lauryl-, Myristyl-, Cetyl- oder Stearylalkohol oder von C10-C20-Oxoalkoholen. Y steht für ein einwertiges Kation oder den n-ten Teil eines n-wertigen Kations, bevorzugt sind dabei die Alkalimetallionen und darunter Na+ oder K+, wobei Na+ äußerst bevorzugt ist. Weitere Kationen Y+ können ausgewählt sein aus NH4+, ½ Zn2+, ½ Mg2+, ½ Ca2+, ½ Mn2+, und deren Mischungen.In this formula (III), R 2 represents a linear or branched, substituted or unsubstituted alkyl radical, preferably a linear, unsubstituted alkyl radical, particularly preferably a fatty alcohol radical. Preferred radicals R 2 are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl radicals and mixtures thereof, the representatives with an even number of C- Atoms are preferred. Particularly preferred radicals R 2 are derived from C 12 -C 18 fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or from C 10 -C 20 oxo alcohols. Y stands for a monovalent cation or the nth part of an n-valent cation, preferred are the alkali metal ions, including Na + or K + , Na + being extremely preferred. Further cations Y + can be selected from NH4 + , ½ Zn 2+ , ½ Mg 2+ , ½ Ca 2+ , ½ Mn 2+ , and mixtures thereof.
In verschiedenen Ausführungsformen sind diese Tenside ausgewählt aus Fettalkoholsulfaten der Formel A-3
In verschiedenen Ausführungsformen umfassen die Mittel mindestens ein nichtionisches Tensid, insbesondere mindestens ein Fettalkoholalkoxylat. In verschiedenen Ausführungsformen enthalten die Waschmittel daher mindestens ein nichtionisches Tensid der Formel
R3-O-(AO)m-H (IV),
in der
- R3
- für einen linearen oder verzweigten, substituierten oder unsubstituierten Alkylrest,
- AO
- für eine Ethylenoxid- (EO) oder Propylenoxid- (PO) Gruppierung,
- m
- für ganze Zahlen von 1 bis 50 stehen.
R 3 -O- (AO) m -H (IV),
in the
- R 3
- for a linear or branched, substituted or unsubstituted alkyl radical,
- AO
- for an ethylene oxide (EO) or propylene oxide (PO) group,
- m
- stand for whole numbers from 1 to 50.
In der vorstehend genannten Formel (IV) steht R3 für einen linearen oder verzweigten, substituierten oder unsubstituierten Alkylrest, vorzugsweise für einen linearen, unsubstituierten Alkylrest, besonders bevorzugt für einen Fettalkoholrest. Bevorzugte Reste R2 sind ausgewählt aus Decyl-, Undecyl-, Dodecyl-, Tridecyl-, Tetradecyl, Pentadecyl-, Hexadecyl-, Heptadecyl-, Octadecyl-, Nonadecyl-, Eicosylresten und deren Mischungen, wobei die Vertreter mit gerader Anzahl an C-Atomen bevorzugt sind. Besonders bevorzugte Reste R3 sind abgeleitet von C12-C18-Fettalkoholen, beispielsweise von Kokosfettalkohol, Talgfettalkohol, Lauryl-, Myristyl-, Cetyl- oder Stearylalkohol oder von C10-C20-Oxoalkoholen.In the above formula (IV), R 3 represents a linear or branched, substituted or unsubstituted alkyl radical, preferably a linear, unsubstituted alkyl radical, particularly preferably a fatty alcohol radical. Preferred radicals R 2 are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl radicals and mixtures thereof, the representatives with an even number of C- Atoms are preferred. Particularly preferred radicals R 3 are derived from C 12 -C 18 fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or from C 10 -C 20 oxo alcohols.
AO steht für eine Ethylenoxid- (EO) oder Propylenoxid- (PO) Gruppierung, vorzugsweise für eine Ethylenoxidgruppierung. Der Index m steht für eine ganze Zahl von 1 bis 50, vorzugsweise von 1 bis 20 und insbesondere von 2 bis 10. Ganz besonders bevorzugt steht m für die Zahlen 2, 3, 4, 5, 6, 7 oder 8.AO stands for an ethylene oxide (EO) or propylene oxide (PO) group, preferably for an ethylene oxide group. The index m stands for an integer from 1 to 50, preferably from 1 to 20 and in particular from 2 to 10. m is very particularly preferably the numbers 2, 3, 4, 5, 6, 7 or 8.
Zusammenfassend handelt es sich bei vorzugsweise einzusetzenden Fettalkoholalkoxylaten um Verbindungen der Formel
Weitere nichtionische Tenside, die im Sinne der vorliegenden Erfindung in den beschriebenen Mitteln enthalten sein können, schließen ein, sind aber nicht beschränkt auf Alkylglykoside, alkoxylierte Fettsäurealkylester, Aminoxide, Fettsäurealkanolamide, Hydroxymischether, Sorbitanfettsäurester, Polyhydroxyfettsäureamide und alkoxylierte Alkohole.Further nonionic surfactants which can be contained in the agents described for the purposes of the present invention include, but are not limited to, alkyl glycosides, alkoxylated fatty acid alkyl esters, amine oxides, fatty acid alkanolamides, hydroxy mixed ethers, sorbitan fatty acid esters, polyhydroxy fatty acid amides and alkoxylated alcohols.
Geeignete Amphotenside sind beispielsweise Betaine der Formel (Riii)(Riv)(Rv)N+CH2COO-, in der Riii einen gegebenenfalls durch Heteroatome oder Heteroatomgruppen unterbrochenen Alkylrest mit 8 bis 25, vorzugsweise 10 bis 21 Kohlenstoffatomen und Riv sowie Rv gleichartige oder verschiedene Alkylreste mit 1 bis 3 Kohlenstoffatomen bedeuten, insbesondere C10-C18-Alkyl-dimethylcarboxymethylbetain und C11-C17-Alkylamidopropyl-dimethylcarboxymethylbetain. Geeignete Kationtenside sind u.a. die quartären Ammoniumverbindungen der Formel (Rvi)(Rvii)(Rviii)(Rix)N+ X-, in der Rvi bis Rix für vier gleich- oder verschiedenartige, insbesondere zwei lang- und zwei kurzkettige, Alkylreste und X- für ein Anion, insbesondere ein Halogenidion, stehen, beispielsweise Didecyldimethylammoniumchlorid, Alkylbenzyldidecylammoniumchlorid und deren Mischungen. Weitere geeignete kationische Tenside sind die quaternären oberflächenaktiven Verbindungen, insbesondere mit einer Sulfonium-, Phosphonium-, Jodonium- oder Arsoniumgruppe, die auch als antimikrobielle Wirkstoffe bekannt sind. Durch den Einsatz von quaternären oberflächenaktiven Verbindungen mit antimikrobieller Wirkung kann das Mittel mit einer antimikrobiellen Wirkung ausgestaltet werden bzw. dessen gegebenenfalls aufgrund anderer Inhaltsstoffe bereits vorhandene antimikrobielle Wirkung verbessert werden.Suitable amphoteric surfactants are, for example, betaines of the formula (R iii ) (R iv ) (R v ) N + CH 2 COO - , in which R iii is an alkyl radical with 8 to 25, preferably 10 to 21 carbon atoms, optionally interrupted by heteroatoms or heteroatom groups, and iv and R v denote identical or different alkyl radicals with 1 to 3 carbon atoms, in particular C 10 -C 18 -alkyl-dimethylcarboxymethylbetaine and C 11 -C 17 -alkylamidopropyl-dimethylcarboxymethylbetaine. Suitable cationic surfactants include the quaternary ammonium compounds of the formula (R vi ) (R vii ) (R viii ) (R ix ) N + X - , in which R vi to R ix represent four identical or different types, in particular two long and two short-chain, alkyl radicals and X - stand for an anion, in particular a halide ion, for example didecyldimethylammonium chloride, alkylbenzyldidecylammonium chloride and mixtures thereof. Further suitable cationic surfactants are the quaternary surface-active compounds, in particular with a sulfonium, phosphonium, iodonium or arsonium group, which are also known as antimicrobial agents. By using quaternary surface-active compounds with an antimicrobial effect, the agent can be designed with an antimicrobial effect or its antimicrobial effect, which may already be present due to other ingredients, can be improved.
In verschiedenen Ausführungsformen beträgt die Gesamtmenge der Tenside bezogen auf das Gewicht des Mittels 2 bis 30 Gew.-%, vorzugsweise 5 bis 25 Gew.-%, noch bevorzugter 10 bis 20 Gew.-%, am bevorzugtesten 14 bis 18 Gew.-%, wobei die (linearen) Alkylbenzolsulfonate höchstens in einer Menge von 0,001 bis 30 Gew.-%, vorzugsweise 0,001 - 10 Gew.-%, ferner bevorzugt 2 - 6 Gew.-%, noch bevorzugter 3 - 5 Gew.-%, bezogen auf das Gewicht des Mittels vorliegen.In various embodiments, the total amount of surfactants based on the weight of the agent is 2 to 30% by weight, preferably 5 to 25% by weight, more preferably 10 to 20% by weight, most preferably 14 to 18% by weight , where the (linear) alkylbenzenesulfonates are based at most in an amount of 0.001 to 30% by weight, preferably 0.001-10% by weight, furthermore preferably 2-6% by weight, even more preferably 3-5% by weight based on the weight of the remedy.
Erfindungsgemäße Waschmittel können neben der Cutinase weitere Enzyme enthalten. Dies können hydrolytische Enzyme oder andere Enzyme in einer für die Wirksamkeit des Mittels zweckmäßigen Konzentration sein. Eine Ausführungsform der Erfindung stellen somit Mittel dar, die eines oder mehrere Enzyme umfassen. Als Enzyme bevorzugt einsetzbar sind alle Enzyme, die in dem erfindungsgemäßen Mittel eine katalytische Aktivität entfalten können, insbesondere eine Protease, Amylase, Cellulase, Hemicellulase, Mannanase, Tannase, Xylanase, Xanthanase, Xyloglucanase, β-Glucosidase, Pektinase, Carrageenase, Perhydrolase, Oxidase, Oxidoreduktase oder eine Lipase, sowie deren Gemische. Enzyme sind in dem Mittel vorteilhafterweise jeweils in einer Menge von 1 x 10-8 bis 5 Gew.-%bezogen auf aktives Protein enthalten. Zunehmend bevorzugt ist jedes Enzym in einer Menge von 1 x 10-7-3 Gew.-%, von 0,00001-1 Gew.-%, von 0,00005-0,5 Gew.-%, von 0,0001 bis 0,1 Gew.-% und besonders bevorzugt von 0,0001 bis 0,05 Gew.-% in erfindungsgemäßen Mitteln enthalten, bezogen auf aktives Protein. Besonders bevorzugt zeigen die Enzyme synergistische Reinigungsleistungen gegenüber bestimmten 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.Detergents according to the invention can contain further enzymes in addition to the cutinase. These can be hydrolytic enzymes or other enzymes in a concentration suitable for the effectiveness of the agent. An embodiment of the invention thus represent agents which comprise one or more enzymes. Preferred enzymes that can be used are all enzymes which can develop a catalytic activity in the agent according to the invention, in particular a protease, amylase, cellulase, hemicellulase, mannanase, tannase, xylanase, xanthanase, xyloglucanase, β-glucosidase, pectinase, carrageenase, perhydrolase, oxidase , Oxidoreductase or a lipase, and mixtures thereof. Enzymes are advantageously contained in the agent in an amount of 1 × 10 −8 to 5% by weight, based on active protein. Increasingly, each enzyme is used in an amount of 1 × 10 -7 -3% by weight, from 0.00001-1% by weight, from 0.00005-0.5% by weight, from 0.0001 to 0.1% by weight and particularly preferably from 0.0001 to 0.05% by weight in agents according to the invention, based on active protein. The enzymes particularly preferably show synergistic cleaning performance with respect to certain soiling or stains, ie the enzymes contained in the agent composition mutually support one another 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 agent according to the invention.
Bei der/den Amylase(n) handelt es sich vorzugsweise um eine α-Amylase. Bei der Hemicellulase handelt es sich vorzugsweise um eine β-Glucanase, eine Pektinase, eine Pullulanase und/oder eine Mannanase. Bei der Cellulase handelt es sich vorzugsweise um ein Cellulase-Gemisch oder eine Einkomponenten-Cellulase, vorzugsweise bzw. überwiegend um eine Endoglucanase und/oder eine Cellobiohydrolase. Bei der Oxidoreduktase handelt es sich vorzugsweise um eine Oxidase, insbesondere eine Cholin-Oxidase, oder um eine Perhydrolase.The amylase (s) is preferably an α-amylase. The hemicellulase is preferably a β-glucanase, a pectinase, a pullulanase and / or a mannanase. The cellulase is preferably a cellulase mixture or a one-component cellulase, preferably or predominantly an endoglucanase and / or a cellobiohydrolase. The oxidoreductase is preferably an oxidase, in particular a choline oxidase, or a perhydrolase.
Die eingesetzten Proteasen sind vorzugsweise alkalische Serin-Proteasen. Sie wirken als unspezifische Endopeptidasen, das heißt, sie hydrolysieren beliebige Säureamidbindungen, die im Inneren von Peptiden oder Proteinen liegen und bewirken dadurch den Abbau proteinhaltiger Anschmutzungen auf dem Reinigungsgut. Ihr pH-Optimum liegt meist im deutlich alkalischen Bereich.The proteases used are preferably alkaline serine proteases. They act as unspecific endopeptidases, that is, they hydrolyze any acid amide bonds that are inside peptides or proteins, thereby breaking down protein-containing soiling on the items to be cleaned. Their pH optimum is usually in the clearly alkaline range.
Die Proteinkonzentration kann mit Hilfe bekannter Methoden, zum Beispiel dem BCA-Verfahren (Bicinchoninsäure; 2,2'-Bichinolyl-4,4'-dicarbonsäure) oder dem Biuret-Verfahren bestimmt werden. Die Bestimmung der Aktivproteinkonzentration erfolgt diesbezüglich über eine Titration der aktiven Zentren unter Verwendung eines geeigneten irreversiblen Inhibitors (für Proteasen beispielsweise Phenylmethylsulfonylfluorid (PMSF)) und Bestimmung der Restaktivität (vgl.
In den hierin beschriebenen Reinigungsmitteln können die einzusetzenden Enzyme ferner zusammen mit Begleitstoffen, etwa aus der Fermentation, konfektioniert sein. In flüssigen Formulierungen werden die Enzyme bevorzugt als Enzymflüssigformulierung(en) eingesetzt.In the cleaning agents described herein, the enzymes to be used can also be packaged together with accompanying substances, for example from fermentation. In liquid formulations, the enzymes are preferably used as liquid enzyme formulation (s).
Die Enzyme werden in der Regel nicht in Form des reinen Proteins, sondern vielmehr in Form stabilisierter, lager- und transportfähiger Zubereitungen bereitgestellt. Zu diesen vorkonfektionierten Zubereitungen zählen beispielsweise die durch Granulation, Extrusion oder Lyophilisierung erhaltenen festen Präparationen oder, insbesondere bei flüssigen oder gelförmigen Mitteln, Lösungen der Enzyme, vorteilhafterweise möglichst konzentriert, wasserarm und/oder mit Stabilisatoren oder weiteren Hilfsmitteln versetzt.As a rule, the enzymes are not provided in the form of the pure protein, but rather in the form of stabilized, storable and transportable preparations. These ready-made preparations include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, in particular in the case of liquid or gel-like agents, solutions of the enzymes, advantageously as concentrated as possible, with little water and / or with stabilizers or other auxiliaries.
Alternativ können die Enzyme sowohl für die feste als auch für die flüssige Darreichungsform verkapselt werden, beispielsweise durch Sprühtrocknung oder Extrusion der Enzymlösung zusammen mit einem vorzugsweise natürlichen Polymer oder in Form von Kapseln, beispielsweise solchen, bei denen die Enzyme wie in einem erstarrten Gel eingeschlossen sind oder in solchen vom Kern-Schale-Typ, bei dem ein enzymhaltiger Kern mit einer Wasser-, Luft- und/oder Chemikalienundurchlässigen Schutzschicht überzogen ist. In aufgelagerten Schichten können zusätzlich weitere Wirkstoffe, beispielsweise Stabilisatoren, Emulgatoren, Pigmente, Bleich- oder Farbstoffe aufgebracht werden. Derartige Kapseln werden nach an sich bekannten Methoden, beispielsweise durch Schüttel- oder Rollgranulation oder in Fluid-bed-Prozessen aufgebracht. Vorteilhafterweise sind derartige Granulate, beispielsweise durch Aufbringen polymerer Filmbildner, staubarm und aufgrund der Beschichtung lagerstabil.Alternatively, the enzymes can be encapsulated both for the solid and for the liquid dosage form, for example by spray drying or extrusion of the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are enclosed as in a solidified gel or in those of the core-shell type, in which an enzyme-containing core is coated with a protective layer impermeable to water, air and / or chemicals. Additional active ingredients, for example stabilizers, emulsifiers, pigments, bleaches or dyes, can also be applied in superimposed layers. Such capsules are applied by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes. Such granulates are advantageously low in dust, for example through the application of polymeric film-forming agents, and due to the coating are stable in storage.
Weiterhin ist es möglich, zwei oder mehrere Enzyme zusammen zu konfektionieren, so dass ein einzelnes Granulat mehrere Enzymaktivitäten aufweist.It is also possible to pack two or more enzymes together so that a single granulate has several enzyme activities.
In verschiedenen Ausführungsformen kann das erfindungsgemäße Mittel einen oder mehrere Enzymstabilisatoren aufweisen. Daher kann das erfindungsgemäße Mittel ferner einen Enzymstabilisator beispielsweise ausgewählt aus der Gruppe bestehend aus Natriumformiat, Natriumsulfat, niederen aliphatischen Alkoholen und Borsäure sowie deren Estern und Salzen enthalten. Natürlich können auch zwei oder mehr dieser Verbindungen in Kombination eingesetzt werden. Die Salze der genannten Verbindungen können auch in Form von Hydraten, wie beispielsweise Natriumsulfat Dekahydrat, eingesetzt werden.In various embodiments, the agent according to the invention can have one or more enzyme stabilizers. The agent according to the invention can therefore also contain an enzyme stabilizer selected, for example, from the group consisting of sodium formate, sodium sulfate, lower aliphatic alcohols and boric acid and their esters and salts. Of course, two or more of these compounds can also be used in combination. The salts of the compounds mentioned can also be used in the form of hydrates, such as, for example, sodium sulfate decahydrate.
Der Begriff "niedere aliphatische Alkohole", wie hierin verwendet, schließt Monoalkohole, Diole und höherwertige Alkohole mit bis zu 6 Kohlenstoffatomen ein. Als zu der Gruppe der niederen aliphatischen Alkohole gehörend seien in diesem Zusammenhang insbesondere Polyole, beispielsweise Glycerin, (Mono)Ethylenglykol, (Mono)Propylenglykol oder Sorbit genannt, ohne dass die Erfindung auf diese beschränkt ist.The term "lower aliphatic alcohols" as used herein includes monoalcohols, diols and higher alcohols having up to 6 carbon atoms. In this context, polyols, for example glycerol, (mono) ethylene glycol, (mono) propylene glycol or sorbitol may be mentioned as belonging to the group of lower aliphatic alcohols, without the invention being restricted to these.
Neben dem mindestens einen Enzymstabilisator, ausgewählt aus der obenstehenden Gruppe, kann ein erfindungsgemäßes Mittel auch mindestens einen weiteren Stabilisator enthalten. Derartige Stabilisatoren sind im Stand der Technik bekannt.In addition to the at least one enzyme stabilizer selected from the above group, an agent according to the invention can also contain at least one further stabilizer. Such stabilizers are known in the prior art.
Reversible Proteaseinhibitoren schützen die in einem Waschmittel enthaltenen Enzyme vor proteolytischem Abbau, indem die enzymatische Tätigkeit der in dem Mittel enthaltenen Proteasen reversibel inhibiert wird. Als reversible Proteaseinhibitoren werden häufig Benzamidin-Hydrochlorid, Boronsäuren oder deren Salze oder Ester eingesetzt, darunter vor allem Derivate mit aromatischen Gruppen, etwa ortho-, meta- oder para-substituierte Phenylboronsäuren, insbesondere 4-Formylphenyl-Boronsäure, beziehungsweise die Salze oder Ester der genannten Verbindungen. Auch Peptidaldehyde, das heißt Oligopeptide mit reduziertem C-Terminus, insbesondere solche aus 2 bis 50 Monomeren werden zu diesem Zweck eingesetzt. Zu den peptidischen reversiblen Proteaseinhibitoren gehören unter anderem Ovomucoid und Leupeptin.Reversible protease inhibitors protect the enzymes contained in a detergent from proteolytic degradation by reversibly inhibiting the enzymatic activity of the proteases contained in the agent. Benzamidine hydrochloride, boronic acids or their salts or esters are often used as reversible protease inhibitors, including in particular derivatives with aromatic groups, such as ortho-, meta- or para-substituted phenylboronic acids, in particular 4-formylphenylboronic acid, or the salts or esters of named compounds. Peptide aldehydes, that is to say oligopeptides with a reduced C-terminus, in particular those made from 2 to 50 monomers, are also used for this purpose. The peptide reversible protease inhibitors include ovomucoid and leupeptin.
Weitere Enzymstabilisatoren sind Aminoalkohole wie Mono-, Di-, Triethanol- und -Propanolamin und deren Mischungen, aliphatische Carbonsäuren bis zu C12, wie beispielsweise Bernsteinsäure, andere Dicarbonsäuren oder Salze der genannten Säuren. Auch endgruppenverschlossene Fettsäureamidalkoxylate sind für diesen Zweck geeignet. Auch manche als Builder eingesetzte organische Säuren vermögen zusätzlich ein Enzym zu stabilisieren. Auch Calcium- und/oder Magnesiumsalze werden zu diesem Zwecke eingesetzt, wie beispielsweise Calciumacetat. Polyamid-Oligomere oder polymere Verbindungen wie Lignin, wasserlösliche Vinyl-Copolymere oder Cellulose-Ether, Acryl-Polymere und/oder Polyamide stabilisieren die Enzym-Präparation unter anderem gegenüber physikalischen Einflüssen oder pH-Wert-Schwankungen. Polyamin-N-Oxid-enthaltende Polymere wirken gleichzeitig als Enzymstabilisatoren und als Farbübertragungsinhibitoren. Andere polymere Stabilisatoren sind lineare C8-C18 Polyoxyalkylene. Auch Alkylpolyglycoside können die enzymatischen Komponenten des erfindungsgemäßen Mittels stabilisieren und vermögen vorzugsweise, diese zusätzlich in ihrer Leistung zu steigern. Vernetzte N-haltige Verbindungen erfüllen vorzugsweise eine Doppelfunktion als Soil-release-Agentien und als EnzymStabilisatoren. Hydrophobes, nichtionisches Polymer stabilisiert insbesondere eine gegebenenfalls enthaltene Cellulase.Further enzyme stabilizers are amino alcohols such as mono-, di-, triethanol- and propanolamine and mixtures thereof, aliphatic carboxylic acids up to C 12 , such as, for example, succinic acid, other dicarboxylic acids or salts of the acids mentioned. End-capped fatty acid amide alkoxylates are also suitable for this purpose. Some organic acids used as builders are also able to stabilize an enzyme. Calcium and / or magnesium salts are also used for this purpose, such as calcium acetate. Polyamide oligomers or polymeric compounds such as lignin, water-soluble vinyl copolymers or cellulose ethers, acrylic polymers and / or polyamides stabilize the enzyme preparation against, among other things, physical influences or fluctuations in the pH value. Polymers containing polyamine-N-oxide act simultaneously as enzyme stabilizers and as color transfer inhibitors. Other polymeric stabilizers are linear C 8 -C 18 polyoxyalkylenes. Alkyl polyglycosides can also stabilize the enzymatic components of the agent according to the invention and are preferably able to additionally increase their performance. Crosslinked N-containing compounds preferably fulfill a double function as soil release agents and as enzyme stabilizers. Hydrophobic, nonionic polymer stabilizes in particular any cellulase it may contain.
Reduktionsmittel und Antioxidantien erhöhen die Stabilität der Enzyme gegenüber oxidativem Zerfall; hierfür sind beispielsweise schwefelhaltige Reduktionsmittel geläufig, etwa Natrium-Sulfit und reduzierende Zucker.Reducing agents and antioxidants increase the stability of the enzymes against oxidative decay; for this purpose, sulfur-containing reducing agents, for example sodium sulfite and reducing sugars, are common.
In einer Ausführungsform sind die Mittel gemäß der vorliegenden Erfindung flüssig und enthalten Wasser als Hauptlösungsmittel, d.h. es handelt sich um wässrige Mittel. Der Wassergehalt des erfindungsgemäßen wässrigen Mittels beträgt üblicherweise 15 bis 70 Gew.-%, vorzugsweise 20 bis 60 Gew.-%. In verschiedenen Ausführungsformen beträgt der Wassergehalt mehr als 5 Gew.-%, bevorzugt mehr als 15 Gew.-% und insbesondere bevorzugt mehr als 50 Gew.-%, jeweils bezogen auf die Gesamtmenge an Mittel.In one embodiment, the compositions according to the present invention are liquid and contain water as the main solvent, i.e. they are aqueous compositions. The water content of the aqueous agent according to the invention is usually 15 to 70% by weight, preferably 20 to 60% by weight. In various embodiments, the water content is more than 5% by weight, preferably more than 15% by weight and particularly preferably more than 50% by weight, based in each case on the total amount of agent.
Daneben können dem Mittel nichtwässrige Lösungsmittel zugesetzt werden. Geeignete nichtwässrige Lösungsmittel umfassen ein- oder mehrwertige Alkohole, Alkanolamine oder Glykolether, sofern sie im angegebenen Konzentrationsbereich mit Wasser mischbar sind. Vorzugsweise werden die Lösungsmittel ausgewählt aus Ethanol, n-Propanol, i-Propanol, Butanolen, Glykol, Propandiol, Butandiol, Methylpropandiol, Glycerin, Diglykol, Propyldiglycol, Butyldiglykol, Hexylenglycol, Ethylenglykolmethylether, Ethylenglykolethylether, Ethylenglykolpropylether, Ethylenglykolmono-n-butylether, Diethylenglykolmethylether, Diethylenglykolethylether, Propylenglykolmethylether, Propylenglykolethylether, Propylenglykolpropylether, Dipropylenglykolmonomethylether, Dipropylenglykolmonoethylether, Methoxytriglykol, Ethoxytriglykol, Butoxytriglykol, 1-Butoxyethoxy-2-propanol, 3-Methyl-3-methoxybutanol, Propylen-glykol-t-butylether, Di-n-octylether sowie Mischungen dieser Lösungsmittel.In addition, non-aqueous solvents can be added to the agent. Suitable non-aqueous solvents include monohydric or polyhydric alcohols, alkanolamines or glycol ethers, provided they are miscible with water in the specified concentration range. The solvents are preferably selected from ethanol, n-propanol, i-propanol, butanols, glycol, propanediol, butanediol, methylpropanediol, glycerol, diglycol, propyl diglycol, butyl diglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol ether, ethylene glycol propyl ether, Diethylene glycol ethyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, methoxy triglycol, ethoxy triglycol, butoxy triglycol, 1-butoxyethoxy-2-propanol, propylene-butoxyethoxy-2-propanol, propylene-butoxy-3-butyl ether, and mixtures of these n-butoxyethoxy-2-propanol, 3-butyl-3-butylether, propylene, propylene-octanol, propylene-octanolether, propylene-butyl-3-ethanol, propylene-butoxyethoxy-2-propanol, propylene-butoxyethoxy-2-propanol, propylene-butoxy-3-butylether, propylene-butoxyethoxy-2-propanol, propylene-butoxyethoxy-2-propanol, propylene-butoxy-3-ether, propylene-butoxy-3-ether, propylene glycol propylether, dipropylene glycol monomethylether, 3-butyl-3-meth Solvent.
Das eine oder die mehreren nichtwässrigen Lösungsmittel ist/sind üblicherweise in einer Menge von 0,1 bis 10 Gew.-%, vorzugsweise 1 bis 8 Gew.-% bezogen auf die Gesamtzusammensetzung enthalten.The one or more non-aqueous solvents is / are usually contained in an amount of 0.1 to 10% by weight, preferably 1 to 8% by weight, based on the total composition.
Neben den bisher genannten Komponenten können die erfindungsgemäßen Mittel weitere Inhaltsstoffe enthalten, die die anwendungstechnischen und/oder ästhetischen Eigenschaften des Waschmittels weiter verbessern. Hierzu zählen beispielsweise Additive zur Verbesserung des Ablauf- und Trocknungsverhaltens, zur Einstellung der Viskosität und/oder zur Stabilisierung, sowie weitere in Reinigungsmitteln übliche Hilfs- und Zusatzstoffe, etwa UV-Stabilisatoren, Parfüm, Perlglanzmittel, Farbstoffe, Korrosionsinhibitoren, Konservierungsmittel, Bitterstoffe, organische Salze, Desinfektionsmittel, strukturgebende Polymere, Entschäumer, verkapselte Inhaltsstoffe (z.B. verkapseltes Parfüm), pH-Stellmittel sowie Hautgefühl-verbessernde oder pflegende Additive.In addition to the components mentioned above, the agents according to the invention can contain further ingredients which further improve the application-related and / or aesthetic properties of the detergent. These include, for example, additives to improve the drainage and drying behavior, to adjust the viscosity and / or for stabilization, as well as other auxiliaries and additives common in cleaning agents, such as UV stabilizers, perfumes, pearlescent agents, dyes, corrosion inhibitors, preservatives, bitter substances, organic Salts, disinfectants, structuring polymers, defoamers, encapsulated ingredients (eg encapsulated perfume), pH adjusters and additives that improve or care for the skin.
Ein erfindungsgemäßes Waschmittel enthält vorzugsweise mindestens einen wasserlöslichen und/oder wasserunlöslichen, organischen und/oder anorganischen Builder (Gerüststoffe).A detergent according to the invention preferably contains at least one water-soluble and / or water-insoluble, organic and / or inorganic builder (builder).
Zu den generell einsetzbaren Gerüststoffen zählen insbesondere die Aminocarbonsäuren und deren Salze, Zeolithe, Silikate, Carbonate, organische (Co)Builder und - wo keine ökologischen Vorurteile gegen ihren Einsatz bestehen - auch die Phosphate. Vorzugsweise sind die Mittel aber phosphatfrei.The builders that can generally be used include in particular the aminocarboxylic acids and their salts, zeolites, silicates, carbonates, organic (co) builders and - where there are no ecological prejudices against their use - also the phosphates. However, the agents are preferably free of phosphates.
Zu den wasserlöslichen organischen Buildersubstanzen gehören Polycarbonsäuren, insbesondere Citronensäure und Zuckersäuren, monomere und polymere Aminopolycarbonsäuren, insbesondere Methylglycindiessigsäure, Nitrilotriessigsäure und Ethylendiamintetraessigsäure sowie Polyasparaginsäure, Polyphosphonsäuren, insbesondere Aminotris(methylenphosphonsäure), Ethylendiamintetrakis(methylenphosphonsäure) und 1-Hydroxyethan-1,1-diphosphonsäure, polymere Hydroxyverbindungen wie Dextrin sowie polymere (Poly-)carbonsäuren, polymere Acrylsäuren, Methacrylsäuren, Maleinsäuren und Mischpolymere aus diesen, die auch geringe Anteile polymerisierbarer Substanzen ohne Carbonsäurefunktionalität einpolymerisiert enthalten können. Geeignete, wenn auch weniger bevorzugte Verbindungen dieser Klasse sind Copolymere der Acrylsäure oder Methacrylsäure mit Vinylethern, wie Vinylmethylethern, Vinylester, Ethylen, Propylen und Styrol, in denen der Anteil der Säure mindestens 50 Gew.-% beträgt. 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.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 as well as polyaspartic acid, polyphosphonic acids, in particular aminotris (methylenephosphonic acid) and 1, 1-methylenediphosphonic acid, in particular aminotris (methylenephosphonophosphonic acid, 1, 1-methyleniphosphonic acid, and 1-methylenephosphonophosphonic acid), especially aminotris (methylenephosphonic acid), especially aminotris (methylenephosphonic acid) and 1, 1-methylenephosphonic acid, in particular aminotris (methylenephosphonic acid) and 1-methylenediphosphonic acid, monomeric and polymeric aminopolycarboxylic acids, monomeric and polymeric aminopolycarboxylic acids, in particular aminotris (methylenephosphonic acid) and 1, 1 polymeric hydroxy compounds such as dextrin and polymeric (poly) carboxylic acids, polymeric acrylic acids, methacrylic acids, maleic acids and copolymers of these, which can also contain small amounts of polymerizable substances without carboxylic acid functionality in polymerized form. Suitable, albeit less preferred, compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinyl methyl ethers, vinyl esters, ethylene, propylene and styrene, in which the acid makes up at least 50% by weight. The organic builder substances can, in particular for the production of liquid agents, be used 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 salts.
Organische Buildersubstanzen können, falls gewünscht, 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. Erfindungsgemäße Wäschenachbehandlungsmittel, wie z.B. Weichspüler, können gegebenenfalls auch frei von organischem Builder sein.Organic builder substances can, if desired, 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 upper limit mentioned are preferably used in pasty or liquid, in particular water-containing, agents according to the invention. Laundry post-treatment agents according to the invention, such as, for example, fabric softeners, can optionally also be free from organic builders.
Als wasserlösliche anorganische Buildermaterialien kommen insbesondere Alkalisilikate und Polyphosphate, vorzugsweise Natriumtriphosphat, in Betracht. Als wasserunlösliche, wasserdispergierbare anorganische Buildermaterialien können insbesondere kristalline oder amorphe Alkalialumosilikate, falls gewünscht, in Mengen von bis zu 50 Gew.-%, vorzugsweise nicht über 40 Gew.-% und in flüssigen Mitteln insbesondere von 1 Gew.-% bis 5 Gew.-%, eingesetzt werden. Unter diesen sind die kristallinen Natriumalumosilikate in Waschmittelqualität, insbesondere Zeolith A, P und gegebenenfalls X, 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.Particularly suitable water-soluble inorganic builder materials are alkali metal silicates and polyphosphates, preferably sodium triphosphate. As water-insoluble, water-dispersible inorganic builder materials, in particular crystalline or amorphous alkali metal aluminosilicates, if desired, 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 used. Among these, the crystalline sodium aluminosilicates in detergent quality, in particular zeolite A, P and optionally X, are preferred. Quantities close to the upper limit mentioned are preferably used in solid, particulate compositions. Suitable aluminosilicates in particular do not have any particles with a grain size of more than 30 μm and preferably consist of at least 80% by weight of particles with a size of less than 10 μm.
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 4 und y eine Zahl von 0 bis 20 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 beta- als auch delta-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. Falls als zusätzliche Buildersubstanz auch Alkalialumosilikat, insbesondere Zeolith, vorhanden ist, beträgt das Gewichtsverhältnis Alumosilikat zu Silikat, jeweils bezogen auf wasserfreie Aktivsubstanzen, vorzugsweise 1:10 bis 10:1. In Mitteln, die sowohl amorphe als auch kristalline Alkalisilikate enthalten, beträgt das Gewichtsverhältnis von amorphem Alkalisilikat zu kristallinem Alkalisilikat vorzugsweise 1:2 bis 2:1 und insbesondere 1:1 bis 2:1.Suitable substitutes or partial substitutes for said aluminosilicate are crystalline alkali metal silicates, which can be present alone or in a mixture with amorphous silicates. The alkali silicates which can be used as builders in the agents according to the invention preferably have a molar ratio of alkali oxide to SiO 2 below 0.95, in particular from 1: 1.1 to 1:12, and can be amorphous or crystalline. Preferred alkali silicates are the sodium silicates, in particular the amorphous sodium silicates, with a molar ratio Na 2 O: SiO 2 of 1: 2 to 1: 2.8. The crystalline silicates used alone or in a mixture with amorphous silicates are preferably crystalline sheet silicates of the general formula Na 2 Si x O 2x + 1 y H 2 O, in which x, the so-called module, is a number of 1, 9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4. Preferred crystalline sheet silicates are those in which x in the general formula mentioned assumes the values 2 or 3. In particular, both beta and delta sodium disilicates (Na 2 Si 2 O 5 · y H 2 O) are preferred. Virtually anhydrous crystalline alkali silicates of the above general formula, in which x is a number from 1.9 to 2.1, prepared from amorphous alkali silicates, can also be used in agents according to the invention. In a further preferred embodiment of agents according to the invention, a crystalline layered sodium silicate with a module of 2 to 3, as can be produced from sand and soda, is used. Crystalline sodium silicates with a modulus in the range from 1.9 to 3.5 are used in a further preferred embodiment of agents according to the invention. If alkali aluminosilicate, in particular zeolite, is also present as an additional builder substance, the weight ratio of aluminosilicate to silicate, based in each case on anhydrous active substances, is preferably 1:10 to 10: 1. In agents which contain both amorphous and crystalline alkali silicates, the weight ratio of amorphous alkali silicate to crystalline alkali silicate is preferably 1: 2 to 2: 1 and in particular 1: 1 to 2: 1.
Buildersubstanzen sind, falls gewünscht, in den erfindungsgemäßen Mitteln vorzugsweise in Mengen bis zu 60 Gew.-%, insbesondere von 5 Gew.-% bis 40 Gew.-%, enthalten. Erfindungsgemäße Wäschenachbehandlungsmittel, wie z.B. Weichspüler, sind vorzugsweise frei von anorganischem Builder.If desired, builder substances are contained in the agents according to the invention preferably in amounts of up to 60% by weight, in particular from 5% by weight to 40% by weight. According to the invention Laundry post-treatment agents, such as fabric softeners, are preferably free of inorganic builders.
Polymere Verdickungsmittel im Sinne der vorliegenden Erfindung sind die als Polyelektrolyte verdickend wirkenden Polycarboxylate, vorzugsweise Homo- und Copolymerisate der Acrylsäure, insbesondere Acrylsäure-Copolymere wie Acrylsäure-Methacrylsäure-Copolymere, und die Polysaccharide, insbesondere Heteropolysaccharide, sowie andere übliche verdickende Polymere. Geeignete Polysaccharide bzw. Heteropolysaccharide sind die Polysaccharidgummen, beispielsweise Gummi arabicum, Agar, Alginate, Carrageene und ihre Salze, Guar, Guaran, Tragacant, Gellan, Ramsan, Dextran oder Xanthan und ihre Derivate, z.B. propoxyliertes Guar, sowie ihre Mischungen. Andere Polysaccharidverdicker, wie Stärken oder Cellulosederivate, können alternativ, vorzugsweise aber zusätzlich zu einem Polysaccharidgummi eingesetzt werden, beispielsweise Stärken verschiedensten Ursprungs und Stärkederivate, z.B. Hydroxyethylstärke, Stärkephosphatester oder Stärkeacetate, oder Carboxymethylcellulose bzw. ihr Natriumsalz, Methyl-, Ethyl-, Hydroxyethyl-, Hydroxypropyl-, Hydroxypropyl-methyl- oder Hydroxyethyl-methyl-cellulose oder Celluloseacetat.Polymeric thickeners for the purposes of the present invention are the polycarboxylates that act as polyelectrolytes, preferably homopolymers and copolymers of acrylic acid, in particular acrylic acid copolymers such as acrylic acid-methacrylic acid copolymers, and the polysaccharides, in particular heteropolysaccharides, and other conventional thickening polymers. Suitable polysaccharides or heteropolysaccharides are the polysaccharide gums, for example gum arabic, agar, alginates, carrageenans and their salts, guar, guaran, tragacanth, gellan, ramsan, dextran or xanthan and their derivatives, e.g. propoxylated guar, and their mixtures. Other polysaccharide thickeners, such as starches or cellulose derivatives, can be used as an alternative, but preferably in addition to a polysaccharide gum, for example starches of various origins and starch derivatives, e.g. hydroxyethyl starch, starch phosphate esters or starch acetates, or carboxymethyl cellulose or its sodium salt, methyl, ethyl, hydroxyethyl, Hydroxypropyl-, hydroxypropyl-methyl- or hydroxyethyl-methyl-cellulose or cellulose acetate.
Als polymere Verdickungsmittel geeignete Acrylsäure-Polymere sind beispielsweise hochmolekulare mit einem Polyalkenylpolyether, insbesondere einem Allylether von Saccharose, Pentaerythrit oder Propylen, vernetzte Homopolymere der Acrylsäure (INCI Carbomer), die auch als Carboxyvinylpolymere bezeichnet werden.Acrylic acid polymers suitable as polymeric thickeners are, for example, high molecular weight homopolymers of acrylic acid (INCI Carbomer) crosslinked with a polyalkenyl polyether, in particular an allyl ether of sucrose, pentaerythritol or propylene, which are also referred to as carboxyvinyl polymers.
Besonders geeignete polymere Verdickungsmittel sind aber folgende Acrylsäure-Copolymere: (i) Copolymere von zwei oder mehr Monomeren aus der Gruppe der Acrylsäure, Methacrylsäure und ihrer einfachen, vorzugsweise mit C1-4-Alkanolen gebildeten, Ester (INCI Acrylates Copolymer), zu denen etwa die Copolymere von Methacrylsäure, Butylacrylat und Methylmethacrylat (CAS 25035-69-2) oder von Butylacrylat und Methylmethacrylat (CAS 25852-37-3) gehören; (ii) vernetzte hochmolekulare Acrylsäurecopolymere, zu denen etwa die mit einem Allylether der Saccharose oder des Pentaerythrits vernetzten Copolymere von C10-30-Alkylacrylaten mit einem oder mehreren Monomeren aus der Gruppe der Acrylsäure, Methacrylsäure und ihrer einfachen, vorzugsweise mit C1-4-Alkanolen gebildeten, Ester (INCI Acrylates/C10-30 Alkyl Acrylate Crosspolymer) gehören.However, particularly suitable polymeric thickeners are the following acrylic acid copolymers: (i) Copolymers of two or more monomers from the group of acrylic acid, methacrylic acid and their simple esters, preferably formed with C 1-4 alkanols (INCI Acrylates Copolymers), to which such as the copolymers of methacrylic acid, butyl acrylate and methyl methacrylate (CAS 25035-69-2) or of butyl acrylate and methyl methacrylate (CAS 25852-37-3); (ii) crosslinked high molecular weight acrylic acid copolymers, including the copolymers of C 10-30 alkyl acrylates crosslinked with an allyl ether of sucrose or pentaerythritol with one or more monomers from the group of acrylic acid, methacrylic acid and their simple, preferably C 1-4 - Alkanols formed, include esters (INCI Acrylates / C10-30 Alkyl Acrylate Crosspolymer).
Der Gehalt an polymerem Verdickungsmittel beträgt üblicherweise nicht mehr als 8 Gew.-%, vorzugsweise zwischen 0,1 und 7 Gew.-%, besonders bevorzugt zwischen 0,5 und 6 Gew.-%, insbesondere zwischen 1 und 5 Gew.-% und äußerst bevorzugt zwischen 1,5 und 4 Gew.-%, beispielsweise zwischen 2 und 2,5 Gew.-%, bezogen auf das Gesamtgewicht des Waschmittels.The content of polymeric thickener is usually not more than 8% by weight, preferably between 0.1 and 7% by weight, particularly preferably between 0.5 and 6% by weight, in particular between 1 and 5% by weight and extremely preferably between 1.5 and 4% by weight, for example between 2 and 2.5% by weight, based on the total weight of the detergent.
Zur Stabilisierung des erfindungsgemäßen Mittels, insbesondere bei hohem Tensidgehalt, können ein oder mehrere Dicarbonsäuren und/oder deren Salze zugesetzt werden, insbesondere eine Zusammensetzung aus Na-Salzen der Adipin-, Bernstein- und Glutarsäure, wie sie z.B. unter dem Handelsnamen Sokalan® DSC erhältlich ist. Der Einsatz erfolgt hierbei vorteilhafterweise in Mengen von 0,1 bis 8 Gew.-%, vorzugsweise 0,5 bis 7 Gew.-%, insbesondere 1,3 bis 6 Gew.-% und besonders bevorzugt 2 bis 4 Gew.-%, bezogen auf das Gesamtgewicht des Waschmittels.To stabilize the agent according to the invention, especially with a high surfactant content, one or more dicarboxylic acids and / or their salts can be added, in particular a composition of sodium salts of adipic, succinic and glutaric acid, such as those available under the trade name Sokalan® DSC is. They are advantageously used in amounts of 0.1 to 8% by weight, preferably 0.5 to 7% by weight, in particular 1.3 to 6% by weight and particularly preferably 2 to 4% by weight, based on the total weight of the detergent.
Kann jedoch auf deren Einsatz verzichtet werden, so ist das erfindungsgemäße Mittel vorzugsweise frei von Dicarbonsäure(salze)n.However, if their use can be dispensed with, the agent according to the invention is preferably free from dicarboxylic acid (salts).
Die erfindungsgemäßen Waschmittel können mit Referenzwaschmitteln verglichen werden, um die erhöhte Anti-Pilling-Leistung der erfindungsgemäßen Mittel festzustellen. Ein solches Waschsystem kann wie folgt zusammengesetzt sein (alle Angaben in Gewichts-Prozent): Referenzmittel: 4,4% Alkylbenzolsulfonsäure, 5,6% weitere anionische Tenside, 2,4% C12-C18 Na-Salze von Fettsäuren (Seifen), 4,4% nicht-ionische Tenside, 0,2% Phosphonate, 1,4% Zitronensäure, 0,95% NaOH, 0,01% Entschäumer, 2,0% Glycerin, 0,08% Konservierungsstoffe, 1% Ethanol, 1,6% Enzymmix (Protease, Amylase, Cellulase, Mannase), Rest demineralisiertes Wasser. Erfindungsgemäßes Mittel: 4,4% Alkylbenzolsulfonsäure, 5,6% weitere anionische Tenside, 2,4% C12-C18 Na-Salze von Fettsäuren (Seifen), 4,4% nicht-ionische Tenside, 0,2% Phosphonate, 1,4% Zitronensäure, 0,95% NaOH, 0,01% Entschäumer, 2,0% Glycerin, 0,08% Konservierungsstoffe, 1% Ethanol, 1,6% Enzymmix (Protease, Amylase, Cellulase, Mannase), 0,009 % Cutinase, Rest demineralisiertes Wasser. Bevorzugt beträgt die Dosierung des flüssigen Waschmittels zwischen 4,5 und 6,0 Gramm pro Liter Waschflotte, beispielsweise 4,7, 4,9 oder 5,9 Gramm pro Liter Waschflotte. Bevorzugt wird gewaschen in einem pH-Wertebereich zwischen pH 8 und pH 10,5, bevorzugt zwischen pH 8 und pH 9.The detergents according to the invention can be compared with reference detergents in order to determine the increased anti-pilling performance of the agents according to the invention. Such a washing system can be composed as follows (all data in percent by weight): Reference agent: 4.4% alkylbenzenesulfonic acid, 5.6% other anionic surfactants, 2.4% C12-C18 Na salts of fatty acids (soaps), 4 , 4% non-ionic surfactants, 0.2% phosphonates, 1.4% citric acid, 0.95% NaOH, 0.01% defoamer, 2.0% glycerine, 0.08% preservatives, 1% ethanol, 1, 6% enzyme mix (protease, amylase, cellulase, mannase), the remainder demineralized water. Agent according to the invention: 4.4% alkylbenzenesulfonic acid, 5.6% other anionic surfactants, 2.4% C12-C18 Na salts of fatty acids (soaps), 4.4% non-ionic surfactants, 0.2% phosphonates, 1, 4% citric acid, 0.95% NaOH, 0.01% defoamer, 2.0% glycerine, 0.08% preservatives, 1% ethanol, 1.6% enzyme mix (protease, amylase, cellulase, mannase), 0.009% cutinase , Rest demineralized water. The dosage of the liquid detergent is preferably between 4.5 and 6.0 grams per liter of wash liquor, for example 4.7, 4.9 or 5.9 grams per liter of wash liquor. Washing is preferably carried out in a pH range between pH 8 and pH 10.5, preferably between pH 8 and pH 9.
Die zuvor genannten Ausführungsformen der vorliegenden Erfindung umfassen alle festen, pulverförmigen, flüssigen, gelförmigen oder pastösen Darreichungsformen erfindungsgemäßer Mittel, die gegebenenfalls auch aus mehreren Phasen bestehen können sowie in komprimierter oder nicht komprimierter Form vorliegen können. Das Mittel kann als rieselfähiges Pulver vorliegen, 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. Zu den festen Darreichungsformen des Mittels zählen ferner Extrudate, Granulate, Tabletten oder Pouches. Alternativ kann das Mittel auch flüssig, gelförmig oder pastös sein, beispielsweise in Form eines nicht-wässrigen Flüssigwaschmittels oder einer nicht-wässrigen Paste oder in Form eines wässrigen Flüssigwaschmittels oder einer wasserhaltigen Paste. Weiterhin kann das Mittel als Einkomponentensystem vorliegen. Solche Mittel bestehen aus einer Phase. Alternativ kann ein Mittel auch aus mehreren Phasen bestehen. Ein solches Mittel ist demnach in mehrere Komponenten aufgeteilt.The aforementioned embodiments of the present invention include all solid, powdery, liquid, gel-like or pasty dosage forms of agents according to the invention, which can optionally also consist of several phases and can be in compressed or uncompressed form. The agent can be in the form of a free-flowing powder, in particular with a bulk density of 300 g / l to 1200 g / l, in particular 500 g / l to 900 g / l or 600 g / l to 850 g / l. The solid dosage forms of the agent also include extrudates, granules, tablets or pouches. Alternatively, the agent can also be liquid, gel-like or pasty, for example 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. Furthermore, the agent can be in the form of a one-component system. Such means consist of a phase. Alternatively, a means can also consist of several phases. Such a means is therefore divided into several components.
Ein weiterer Erfindungsgegenstand ist ein Verfahren zur Reinigung von Textilien, das dadurch gekennzeichnet ist, dass in mindestens einem Verfahrensschritt ein erfindungsgemäßes Waschmittel angewendet wird.Another subject matter of the invention is a method for cleaning textiles, which is characterized in that a detergent according to the invention is used in at least one method step.
In verschiedenen Ausführungsformen zeichnet sich das oben beschriebene Verfahren dadurch aus, dass das erfindungsgemäße Waschmittel bei einer Temperatur von 0-100°C, bevorzugt 0-80°C, weiter bevorzugt 30-70°C und am meisten bevorzugt bei 40-60°C eingesetzt wird.In various embodiments, the method described above is characterized in that the detergent according to the invention is at a temperature of 0-100 ° C, preferably 0-80 ° C, more preferably 30-70 ° C and most preferably 40-60 ° C is used.
Hierunter fallen sowohl manuelle als auch maschinelle Verfahren, wobei maschinelle Verfahren bevorzugt sind. 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 oder Verdünnung dieses Mittels behandelt wird. Alle denkbaren Wasch- oder Reinigungsverfahren können in wenigstens einem der Verfahrensschritte um die Anwendung eines erfindungsgemäßen Waschmittels bereichert werden und stellen dann Ausführungsformen der vorliegenden Erfindung dar. Alle Sachverhalte, Gegenstände und Ausführungsformen, die für erfindungsgemäße Mittel beschrieben sind, sind auch auf diesen Erfindungsgegenstand anwendbar. Daher wird an dieser Stelle ausdrücklich auf die Offenbarung an entsprechender Stelle verwiesen mit dem Hinweis, dass diese Offenbarung auch für die vorstehenden erfindungsgemäßen Verfahren gilt.This includes both manual and machine processes, with machine processes being preferred. Processes for cleaning textiles are generally characterized in that various active cleaning substances are applied to the items to be cleaned in several process steps and washed off after the exposure time, or that the items to be cleaned are treated in some other way with a detergent or a solution or dilution of this agent. All conceivable washing or cleaning processes can be enriched in at least one of the process steps by the use of a detergent according to the invention and then represent embodiments of the present invention. All facts, subjects and embodiments that are described for agents according to the invention are also applicable to this subject matter of the invention. For this reason, reference is expressly made at this point to the disclosure at the corresponding point with the note that this disclosure also applies to the above methods according to the invention.
Da Enzyme natürlicherweise bereits eine katalytische Aktivität besitzen und diese auch in Medien entfalten, die sonst keine Reinigungskraft besitzen wie beispielsweise in bloßem Puffer, kann ein einzelner und/oder der einzige Schritt eines solchen Verfahrens darin bestehen, dass als einzige reinigungsaktive Komponente eine Cutinase mit der Anschmutzung in Kontakt gebracht wird, bevorzugt in einer Pufferlösung oder in Wasser. Dies stellt eine weitere Ausführungsform dieses Erfindungsgegenstandes dar.Since enzymes naturally already have a catalytic activity and also develop this in media that otherwise have no cleaning power such as mere buffers, a single and / or the only step of such a process can consist in the fact that the only active cleaning component is a cutinase with the Soiling is brought into contact, preferably in a buffer solution or in water. This represents a further embodiment of this subject matter of the invention.
Alternative Ausführungsformen dieses Erfindungsgegenstandes stellen auch Verfahren zur Behandlung von Textilrohstoffen oder zur Textilpflege dar, bei denen in wenigstens einem Verfahrensschritt ein erfindungsgemäßes Mittel aktiv wird. Hierunter sind Verfahren für Textilrohstoffe, Fasern oder Textilien mit natürlichen Bestandteilen bevorzugt, und ganz besonders für solche mit Wolle oder Seide.Alternative embodiments of this subject matter of the invention also represent processes for treating raw textile materials or for textile care, in which an agent according to the invention becomes active in at least one process step. Among these, processes for textile raw materials, fibers or textiles with natural components are preferred, and very particularly for those with wool or silk.
Des Weiteren erfasst die Erfindung auch die Verwendung des hierin beschriebenen Mittels, beispielsweise als Waschmittel wie oben beschrieben, zur (verbesserten) Entfernung von Anschmutzungen, beispielsweise von Textilien, insbesondere Polyester Textilien.Furthermore, the invention also covers the use of the agent described herein, for example as a washing agent as described above, for the (improved) removal of soiling, for example from textiles, in particular polyester textiles.
Schließlich bezieht sich die Erfindung auch auf die Verwendung einer Cutinase zur Verringerung von Pilling-Effekten eines Mittels, vorzugsweise eines Waschmittels, besonders bevorzugt eines Flüssigwaschmittels, wobei das Mittel die Cutinase enthält.Finally, the invention also relates to the use of a cutinase for reducing the pilling effects of an agent, preferably a detergent, particularly preferably a liquid detergent, the agent containing the cutinase.
Die Cutinase kann eine Cutinase sein wie sie hierin definiert ist. In verschiedenen Ausführungsformen der Verwendung ist die Cutinase in einer Menge von 0,00001 - 1 Gew.-%, bevorzugt in einer Menge von 0,0001 - 0,5 Gew.-%, besonders bevorzugt in einer Menge von 0,001 - 0,1 Gew.-%, in dem Mittel enthalten. In weiteren verschiedenen Ausführungsformen wird die Cutinase, die eine Verringerung des Pilling-Effekts bewirkt, auf Textilien, insbesondere Textilien, die aus Polyester bestehen oder Polyester umfassen, angewendet.The cutinase can be a cutinase as defined herein. In various embodiments of the use, the cutinase is in an amount of 0.00001-1% by weight, preferably in an amount of 0.0001-0.5% by weight, particularly preferably in an amount of 0.001-0.1 % By weight, contained in the agent. In further different embodiments, the cutinase, which brings about a reduction in the pilling effect, is applied to textiles, in particular textiles which are made of polyester or comprise polyester.
Alle Sachverhalte, Gegenstände und Ausführungsformen, die für erfindungsgemäßen Mittel und die Cutinase beschrieben sind, sind auch auf die weiteren Erfindungsgegenstände anwendbar. Daher wird an dieser Stelle ausdrücklich auf die Offenbarung an entsprechender Stelle verwiesen mit dem Hinweis, dass diese Offenbarung auch für das vorstehende erfindungsgemäße Verfahren und die erfindungsgemäßen Verwendungen gilt.All facts, subjects and embodiments that are described for the agents according to the invention and the cutinase are also applicable to the other subjects of the invention. Therefore, at this point, express reference is made to the disclosure at the appropriate point with the note that this disclosure also applies to the above method according to the invention and the uses according to the invention.
Dies ist eine handelsübliche Waschmittelmatrix (ohne opt. Aufheller, Parfüm und Farbstoffe), die für den Waschtest verwendet wurde:
In einer handelsüblichen Waschmaschine werden 20 identische Versuche hintereinander durchgeführt. Als zu beurteilende Textilien werden verschiedene Polyetser und Mischtextilien benutzt, welche einmal neu und einmal vorgepillt sind. Nach den 20 Versuchen wird die Pillreduktion der vorgepillten Gewebe und die Pillbildung der neuen Gewebe optisch beurteilt.20 identical tests are carried out one after the other in a commercially available washing machine. Various polyesters and mixed textiles are used as textiles to be assessed, one of which is new and one of which is pre-pilled. After the 20 tests, the pill reduction of the pre-pilled tissue and the pilling of the new tissue are visually assessed.
Die vorgepillten Gewebe werden durch 20-fach wiederholte Waschzyklen bei 40°C in handelsüblichen Waschmaschinen hergestellt.The pre-pilled fabrics are produced by washing cycles repeated 20 times at 40 ° C in commercially available washing machines.
Nach jedem Waschzyklus wird die komplette Wäsche im Trockner getrocknet.After each wash cycle, all laundry is dried in the dryer.
- Wasser mit 16°dH, 2,5 kg saubere Füllwäsche, 60°C Normalprogramm, 46 g Waschmittel wie oben beschrieben pro MaschineWater with 16 ° dH, 2.5 kg of clean laundry, 60 ° C normal program, 46 g of detergent per machine as described above
-
Dosierung der zu untersuchenden Cutinase: 4 mg Aktivenzym pro Waschmaschine
- Probe 1: nur Waschmittel wie oben beschrieben (Vergleichsreferenz)
- Probe 2: Waschmittel + 4 mg Cutinase Tcur1278 aus Thermomonospora curvata (SEQ ID NO:1) (erfindungsgemäß)
- Probe 3: Waschmittel + 4 mg Cutinase TfCut2 aus Thermobifida fusca (Vergleichsreferenz)
- Sample 1: only detergent as described above (comparison reference)
- Sample 2: detergent + 4 mg cutinase Tcur1278 from Thermomonospora curvata (SEQ ID NO: 1) ( according to the invention)
- Sample 3: detergent + 4 mg cutinase TfCut2 from Thermobifida fusca (comparison reference)
Ergebnis nach 20 Wäschen auf 100% Polyester Textil:
- Visuelle Abmusterung der Pills, Skala 1-5, sehr stark gepillt =1, nicht gepillt = 5
- Probe 1: 1,5
- Probe 2: 2,5
- Probe 3: 1,5
- Visual inspection of the pills, scale 1-5, very heavily pilled = 1, not pilled = 5
- Sample 1: 1.5
- Sample 2: 2.5
- Sample 3: 1.5
Eine Änderung von 0,5 Einheiten ist als signifikant anzusehen.A change of 0.5 units is to be regarded as significant.
Die erfindungsgemäße Cutinase verbessert das Pill-Erscheinungsbild signifikant. Eine technisch ähnlich anzusehende Cutinase verbessert das Pill-Bild hingegen nicht.The cutinase according to the invention significantly improves the appearance of the pill. A technically similar cutinase, however, does not improve the pill picture.
- <110> Henkel AG & Co. KGaA<110> Henkel AG & Co. KGaA
- <120> Verbessertes Anti-Pilling auf Polyester Textilien durch Einsatz einer Cutinase<120> Improved anti-pilling on polyester textiles through the use of a cutinase
-
<130>
<130>PT033704PCT PT033704PCT -
<150>
DE102016201173.1
<151> 2016-01-27<150>DE102016201173.1
<151> 2016-01-27 - <160> 2<160> 2
- <170> PatentIn version 3.5<170> Patent In version 3.5
-
<210> 1
<211> 289
<212> PRT
<213> Thermomonospora curvata<210> 1
<211> 289
<212> PRT
<213> Thermomonospora curvata - <400> 1 <400> 1
-
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<211> 870
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<213> Thermomonospora curvata<210> 2
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<213> Thermomonospora curvata - <400> 2 <400> 2
Claims (8)
- A washing agent, characterized in that it contains a cutinase, the cutinase being a cutinase which has at least 70% sequence identity with the amino acid sequence given in SEQ ID NO:1 over its entire length.
- The washing agent according to claim 1, characterized in that(a) the cutinase is obtainable from a cutinase according to claim 1 as a starting molecule by single or multiple conservative amino acid substitution; and/or(b) the cutinase is obtainable from a cutinase according to claim 1 as a starting molecule by means of fragmentation or deletion, insertion or substitution mutagenesis, and comprises an amino acid sequence which matches the starting molecule over a length of at least 210, 220, 230, 240, 250, 260, 270, 280 or 289 contiguous amino acids.
- The washing agent according to one of claims 1 to 2, wherein the cutinase is contained in the washing agent in an amount of from 0.00001 to 1 wt.%, preferably in an amount of from 0.0001 to 0.5 wt.%, particularly preferably in an amount of from 0.001 to 0.1 wt.%.
- The washing agent according to one of claims 1 to 3, characterized in that(a) it contains at least one additional ingredient selected from the group consisting of surfactants, builders, bleaching agents, bleach activators, water-miscible organic solvents, further enzymes, sequestering agents, electrolytes, pH regulators, optical brighteners, graying inhibitors, foam regulators, dyes and fragrances and combinations thereof; and/or(b) it is present in solid or liquid, preferably liquid, form.
- A method for cleaning textiles, characterized in that a washing agent according to one of claims 1 to 4 is applied in at least one method step.
- The use of a washing agent according to one of claims 1 to 4 for removing stains.
- The use of a cutinase for reducing pilling effects of a washing agent, preferably a liquid washing agent, the washing agent containing the cutinase, characterized in that the cutinase is a cutinase which has at least 70% sequence identity with the amino acid sequence given in SEQ ID NO: 1 over its entire length.
- The use according to claim 7, wherein(a) the cutinase is obtainable from a cutinase according to claim 7 as a starting molecule by single or multiple conservative amino acid substitution; and/or(b) the cutinase is obtainable from a cutinase according to claim 7 as a starting molecule by means of fragmentation or deletion, insertion or substitution mutagenesis, and comprises an amino acid sequence which matches the starting molecule over a length of at least 210, 220, 230, 240, 250, 260, 270, 280 or 289 contiguous amino acids; and/or(c) the cutinase is contained in the washing agent in an amount of from 0.00001 to 1 wt.%, preferably in an amount of from 0.0001 to 0.5 wt.%, particularly preferably in an amount of from 0.001 to 0.1 wt.%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PL17701292T PL3408367T3 (en) | 2016-01-27 | 2017-01-17 | Improved anti-pilling on polyester textiles through use of a cutinase |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102016201173.1A DE102016201173A1 (en) | 2016-01-27 | 2016-01-27 | Improved anti-pilling on polyester textiles by using a cutinase |
| PCT/EP2017/050848 WO2017129436A1 (en) | 2016-01-27 | 2017-01-17 | Improved anti-pilling on polyester textiles through use of a cutinase |
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|---|---|
| EP3408367A1 EP3408367A1 (en) | 2018-12-05 |
| EP3408367B1 true EP3408367B1 (en) | 2021-03-17 |
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| EP17701292.9A Active EP3408367B1 (en) | 2016-01-27 | 2017-01-17 | Improved anti-pilling on polyester textiles through use of a cutinase |
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| Country | Link |
|---|---|
| EP (1) | EP3408367B1 (en) |
| DE (1) | DE102016201173A1 (en) |
| ES (1) | ES2868649T3 (en) |
| PL (1) | PL3408367T3 (en) |
| WO (1) | WO2017129436A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| DE102018210608A1 (en) * | 2018-06-28 | 2020-01-02 | Henkel Ag & Co. Kgaa | Agent containing polyesterase I |
| DE102018210605A1 (en) | 2018-06-28 | 2020-01-02 | Henkel Ag & Co. Kgaa | Agent containing recombinant polyesterase |
| EP3699272A1 (en) * | 2019-02-21 | 2020-08-26 | Henkel AG & Co. KGaA | Improved caring properties on polyester textiles by use of a cutinase |
| EP4389864A1 (en) * | 2022-12-20 | 2024-06-26 | Basf Se | Cutinases |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5512203A (en) * | 1987-05-29 | 1996-04-30 | Genencor International, Inc. | Cutinase cleaning compositions |
| AU710006B2 (en) | 1995-04-28 | 1999-09-09 | Genencor International, Inc. | Detergents comprising cellulases |
| EP0996785B1 (en) * | 1997-07-04 | 2004-01-21 | Novozymes A/S | A method of treating polyester fabrics |
| JP4988124B2 (en) * | 2000-06-02 | 2012-08-01 | ノボザイムス アクティーゼルスカブ | Cutinase mutant |
| WO2004059075A1 (en) * | 2002-12-23 | 2004-07-15 | Novozymes North America, Inc. | A method of treating polyester fabrics |
| DE102008017103A1 (en) | 2008-04-02 | 2009-10-08 | Henkel Ag & Co. Kgaa | Detergents and cleaning agents containing proteases from Xanthomonas |
-
2016
- 2016-01-27 DE DE102016201173.1A patent/DE102016201173A1/en not_active Withdrawn
-
2017
- 2017-01-17 ES ES17701292T patent/ES2868649T3/en active Active
- 2017-01-17 WO PCT/EP2017/050848 patent/WO2017129436A1/en not_active Ceased
- 2017-01-17 EP EP17701292.9A patent/EP3408367B1/en active Active
- 2017-01-17 PL PL17701292T patent/PL3408367T3/en unknown
Non-Patent Citations (1)
| Title |
|---|
| DANIELA S GOMES ET AL: "Production of heterologous cutinases by E. coli and improved enzyme formulation for application on plastic degradation", ELECTRONIC JOURNAL OF BIOTECHNOLOGY, 15 September 2013 (2013-09-15), pages 1 - 13, XP055645815, Retrieved from the Internet <URL:http://www.bioline.org.br/pdf?ej13053> [retrieved on 20191122], DOI: 10.2225/vol16issue5-fulltext-12 * |
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| WO2017129436A1 (en) | 2017-08-03 |
| PL3408367T3 (en) | 2021-10-11 |
| ES2868649T3 (en) | 2021-10-21 |
| DE102016201173A1 (en) | 2017-07-27 |
| EP3408367A1 (en) | 2018-12-05 |
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