EP3864119B1 - Flüssige zusammensetzung mit dihydroxyterephthalsäurediamid-verbindung und hoher tensidmenge - Google Patents
Flüssige zusammensetzung mit dihydroxyterephthalsäurediamid-verbindung und hoher tensidmenge Download PDFInfo
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- EP3864119B1 EP3864119B1 EP19733687.8A EP19733687A EP3864119B1 EP 3864119 B1 EP3864119 B1 EP 3864119B1 EP 19733687 A EP19733687 A EP 19733687A EP 3864119 B1 EP3864119 B1 EP 3864119B1
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- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
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-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/26—Organic compounds containing nitrogen
- C11D3/32—Amides; Substituted amides
-
- 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
Definitions
- the invention relates to liquid surfactant compositions with a high surfactant content which are particularly suitable as detergents for laundry.
- the washing process often even intensifies and/or worsens the removability of the soiling, which should not least be due to chemical reactions that have been initiated, which can consist, for example, in the polymerisation of certain dyes contained in the soiling.
- the polymerizable substances are primarily polyphenolic dyes, preferably flavonoids, especially from the class of anthocyanidins or anthocyanins.
- the soiling can in particular have been caused by food products or beverages that contain the corresponding dyes.
- the stains can in particular be fruit or vegetable stains or red wine stains, which in particular contain polyphenolic dyes, especially those from the class of anthocyanidins or anthocyanins.
- German patent application DE 102016214660 A1 and the pamphlet WO 2016/074936 A1 , or. U.S. 2017/240849 A1 relate to the use of dihydroxyterephthalic acid derivatives in detergents and cleaning agents to improve washing or cleaning performance.
- dihydroxyterephthalic diamides are difficult to incorporate into liquid surfactant compositions, since the dihydroxyterephthalic diamides sediment under storage conditions. This problem is particularly present in compositions with a high surfactant content.
- liquid surfactant compositions can be improved through the use of dihydroxyterephthalic acid diamides with specific substitution on the amide nitrogen atom.
- the dihydroxyterephthalic acid diamides used according to the invention can easily be incorporated into liquid surfactant compositions.
- the washing performance, especially with regard to bleachable soiling is significantly increased.
- Liquid as used herein in relation to compositions according to the invention includes all flowable compositions in the form of liquids at standard conditions (20°C, 1013 mbar) and encompasses in particular liquids, flowable gels and pasty compositions. In particular, the term also includes non-Newtonian liquids that have a yield point. It is known that granular mixtures (flowable solids such as powder or granulate mixtures) are not liquids and are therefore not included.
- a chemical compound or its structural unit is organic if its molecular structure contains at least one covalent bond between carbon and hydrogen.
- organic a chemical compound or its structural unit is inorganic if its molecular structure does not contain a covalent bond between carbon and hydrogen.
- the mean molar masses specified in this application for polymeric ingredients are always weight-average molar masses M w , which can be determined in principle by means of gel permeation chromatography using an RI detector, with the measurement being advantageously carried out against an external standard he follows.
- a “surfactant-containing liquor” is a liquid preparation for treating a substrate that can be obtained by using a surfactant-containing agent and diluting it with at least one solvent (preferably water). Fabrics or textiles (e.g. clothing) can be used as a substrate.
- the preparations according to the invention are preferably used to provide a surfactant-containing liquor in machine cleaning processes, such as those carried out, for example, in a washing machine for textiles.
- At least one refers to 1 or more, for example 1, 2, 3, 4, 5, 6, 7, 8, 9 or more. In the context of components of the compositions described herein, this statement does not refer to the absolute amount of molecules but to the type of component.
- At least one nonionic surfactant thus means, for example, one or more different nonionic surfactants, i.e. one or more different types of nonionic surfactants. Together with quantities, the quantities refer to the total quantity of the corresponding type of ingredient as already defined above.
- the range also includes the limit values.
- the water content as defined herein refers to the water content determined by Karl Fischer titration ( Angewandte Chemie 1935, 48, 394-396; ISBN 3-540-12846-8 Eugene Scholz ).
- composition according to the invention must contain surfactant in a total amount of 20 to 70% by weight, based on the weight of the liquid composition according to the invention. It is preferred here if surfactant is present in a total amount of from 25 to 65% by weight, preferably from 30 to 50% by weight, particularly preferably from 35 to 45% by weight.
- the group of surfactants includes the nonionic, the anionic, the cationic and the amphoteric surfactants.
- the liquid composition according to the invention can comprise one or more of the surfactants mentioned.
- the liquid composition according to the invention particularly preferably comprises at least one anionic surfactant.
- Anionic surfactant is particularly preferred in a total amount of 15 to 50% by weight, in particular from 20 to 40% by weight, from 15 to 35% by weight, in particular from 20 to 30% by weight, in each case based on the weight of the liquid composition.
- the at least one anionic surfactant is preferably selected from the group comprising C 8-18 alkyl benzene sulfonates, olefin sulfonates, C 12-18 alkane sulfonates, C 12-18 ester sulfonates, C 12-18 alkyl sulfates, C 12-18 alkenyl sulfates, C 12-18 fatty alcohol ether sulfates and mixtures thereof. It has been found that these sulfonate and sulfate surfactants are particularly useful in preparing stable liquid compositions with a yield point.
- Liquid compositions which comprise C 9 -C 13 alkyl benzene sulfonates and fatty alcohol ether sulfates as anionic surfactants have particularly good dispersing properties.
- Surfactants of the sulfonate type are preferably C 9 -C 13 -alkylbenzene sulfonates, olefin sulfonates, i.e.
- mixtures of alkene and hydroxyalkane sulfonates and disulfonates such as are obtained, for example, from C 12 -C 18 -monoolefins with a terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products.
- Alk(en)yl sulfates are the alkali and in particular the sodium salts of the sulfuric acid half esters of the C12 - C18 fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C10 - C20 oxo alcohols and those half esters of secondary alcohols of these chain lengths are preferred.
- C 12 -C 16 -alkyl sulfates and C 12 -C 15 -alkyl sulfates and also C 14 -C 15 -alkyl sulfates are preferred for reasons of washing technology.
- 2,3-Alkyl sulfates are also suitable anionic surfactants.
- Preferred alk(en)yl sulfates are the salts of the sulfuric acid monoesters of fatty alcohols having 12 to 18 carbon atoms, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or oxo alcohols having 10 to 20 carbon atoms and those half esters of secondary alcohols of these chain lengths are preferred.
- Alkyl sulfates having 12 to 16 carbon atoms and alkyl sulfates having 12 to 15 carbon atoms and alkyl sulfates having 14 and 15 carbon atoms are preferred for reasons of washing technology.
- 2,3-Alkyl sulfates are also suitable anionic surfactants.
- Fatty alcohol ether sulfates such as the sulfuric acid monoesters of the straight-chain or branched C 7 -C 21 alcohols ethoxylated with 1 to 6 moles of ethylene oxide, such as 2-methyl-branched C9-11 alcohols with an average of 3.5 moles of ethylene oxide (EO) or C12 18 fatty alcohols with 1 to 4 EO are suitable.
- Alkyl ether sulfates having the formula (A-1) are preferred R 1 -O-(AO) n -SO 3 - X + (A-1)
- R 1 is a linear or branched, substituted or unsubstituted alkyl radical, preferably a linear, unsubstituted alkyl radical, particularly preferably a fatty alcohol radical.
- Preferred radicals R 1 of the formula (A-1) are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl radicals and mixtures thereof, wherein the Representatives with an even number of carbon atoms are preferred.
- radicals R 1 of the formula (A-1) are derived from Fatty alcohols with 12 to 18 carbon atoms, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or oxo alcohols with 10 to 20 carbon atoms.
- AO in formula (A-1) represents an ethylene oxide (EO) or propylene oxide (PO) group, preferably an ethylene oxide group.
- the index n of the formula (A-1) is an integer from 1 to 50, preferably from 1 to 20 and in particular from 2 to 10. n is very particularly preferably 2, 3, 4, 5, 6, 7 or 8.
- X is a monovalent cation or the nth part of an n-valent cation, preference being given to the alkali metal ions and including Na + or K + , with Na + being extremely preferred. Further cations X+ can be selected from NH 4+ , 1 ⁇ 2 Zn 2+ , 1 ⁇ 2 Mg 2+ , 1 ⁇ 2 Ca 2+ , 1 ⁇ 2 Mn 2+ , and mixtures thereof .
- the degree of ethoxylation given represents a statistical average, which can be a whole or a fractional number for a specific product.
- the degrees of alkoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
- Preferred alkoxylates/ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
- the liquid composition contains a mixture of sulphonate and sulphate surfactants.
- the composition contains at least one C9-13 alkyl benzene sulfonate and optionally additionally at least one C 12-18 fatty alcohol ether sulfate as anionic surfactant.
- the liquid composition contains at least one anionic surfactant of the formula (A-3), in the R' and R" are independently H or alkyl and together contain 9 to 19, preferably 9 to 15 and in particular 9 to 13 carbon atoms, and Y + is a monovalent cation or the nth part of an n-valent cation (in particular Na + ) mean.
- the composition can also contain soaps as an anionic surfactant.
- Saturated and unsaturated fatty acid soaps such as the salts of lauric acid, myristic acid, palmitic acid, Stearic acid, (hydrogenated) erucic acid and behenic acid and, in particular, soap mixtures derived from natural fatty acids, for example coconut, palm kernel, olive oil or tallow fatty acids.
- the anionic surfactants can be in the form of their sodium, potassium or magnesium or ammonium salts.
- the anionic surfactants are in the form of their ammonium salts, said ammonium ion being derived from at least one said (C 2 -C 6 )alkanolamine.
- Other preferred counterions for the anionic surfactants are also the protonated forms of choline, triethylamine, monoethanolamine, triethanolamine or methylethylamine.
- the liquid composition may (preferably together with at least one anionic surfactant) also contain at least one nonionic surfactant.
- the weight ratio of anionic to nonionic surfactant is in the weight ratio range from 1:1 to 3:1, in particular from 1.5:1 to 2.5:1 , lies.
- the nonionic surfactant includes alkoxylated fatty alcohols, alkoxylated fatty acid alkyl esters, fatty acid amides, alkoxylated fatty acid amides, polyhydroxy fatty acid amides, alkyl phenol polyglycol ethers, amine oxides, alkyl polyglucosides, and mixtures thereof. It is again especially preferred if nonionic surfactant is present in a total amount of from 5 to 40% by weight, especially from 7 to 35% by weight, more preferably from 5 to 20% by weight, based on the weight of the liquid composition according to the invention preferably from 10 to 15% by weight.
- the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols preferably having 8 to 18 carbon atoms and an average of 4 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, such as are usually present in oxo alcohol radicals.
- EO ethylene oxide
- alcohol ethoxylates with linear radicals from alcohols of natural origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, and an average of 5 to 8 EO per mole of alcohol are preferred.
- Preferred ethoxylated alcohols include, for example, C12-14 alcohols with 4 EO or 7 EO, C9-11 alcohol with 7 EO, C13-15 alcohols with 5 EO, 7 EO or 8 EO, C12 - C18 alcohols with 5 EO or 7 EO and mixtures of these.
- the degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
- Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
- fatty alcohols with more than 12 EO can also be used. Examples of this are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
- Nonionic surfactants which contain EO and PO (propylene oxide) groups together in the molecule can also be used according to the invention. Also suitable are a mixture of a (more) branched ethoxylated fatty alcohol and an unbranched ethoxylated fatty alcohol, such as a mixture of a C 16 -C 18 fatty alcohol with 7 EO and 2-propylheptanol with 7 EO.
- the washing, cleaning, after-treatment or auxiliary washing agent particularly preferably contains a C 12 -C 18 fatty alcohol with 7 EO or a C 13 -C 15 oxo alcohol with 7 EO as nonionic surfactant.
- R 1 represents a linear or branched, substituted or unsubstituted alkyl group.
- R 1 is a linear or branched alkyl radical having 5 to 30 carbon atoms, preferably having 7 to 25 carbon atoms and in particular having 10 to 19 carbon atoms.
- Preferred radicals R 1 are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl radicals and mixtures thereof, representatives with an even number of carbon atoms being preferred .
- radicals R 1 are derived from fatty alcohols having 12 to 19 carbon atoms, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or from oxo alcohols having 10 to 19 carbon atoms.
- AO of formula (N-1) is an ethylene oxide (EO) or propylene oxide (PO) moiety, preferably an ethylene oxide moiety.
- the index m of the formula (N-1) is an integer from 1 to 50, preferably 2 to 20 and preferably 2 to 10. In particular, m is 3, 4, 5, 6 or 7.
- the agent according to the invention can contain mixtures of nonionic surfactants included, which have different degrees of ethoxylation. Surfactants with degrees of alkoxylation/ethoxylation of at least 5 are preferred.
- Such fatty alcohol or oxo alcohol ethoxylates are available under the trade names Dehydol® LT7 (BASF), Lutensol® AO7 (BASF), Lutensol® M7 (BASF) and Neodol® 45-7 (Shell Chemicals).
- compositions according to the invention particularly preferably contain water. It is very particularly preferred if the composition, based on its total weight, contains water in a total amount of 1 to 50% by weight, more preferably 2 to 30% by weight, particularly preferably 3 to 25% by weight, very particularly preferably from 5 to 25% by weight, in particular from 5 and 45% by weight, more preferably from 10 and 40% by weight, more preferably from 5 to 30% by weight, very particularly preferably from 8 to 25% by weight.
- the liquid composition preferably additionally contains at least one organic solvent.
- Suitable organic solvents include monohydric or polyhydric alcohols or glycol ethers, such as ethanol, n-propanol, isopropanol, butanols, glycol, propanediol, butanediol, methylpropanediol, glycerol, glycols such as diglycol, propyldiglycol, butyldiglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether , ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol methyl ether, propylene glycol methyl ether, propylene glycol methyl ether, propylene glycol methyl ether, propylene glycol methyl ether, propylene glycol methyl ether,
- the solvents are preferably selected from ethanol, n-propanol, i-propanol, butanols, glycol, propanediol, butanediol, methylpropanediol, glycerol, diglycol, propyldiglycol, butyldiglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol methyl 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, methoxytriglycol, ethoxytriglycol, butoxytriglycol, 1-butoxyethoxy-2-propanol,
- Organic solvents are advantageously present in a total amount of from 5% by weight to 20% by weight, particularly preferably from 10% by weight to 15% by weight, based in each case on the total weight of the composition.
- composition according to the invention also contains at least one catechol compound according to formula (I) in addition to the said amount of surfactant.
- the catechol compounds according to formula (I) can be analogous to the synthesis instructions according to Example 2 of WO 2016/074936 A1 provide.
- the at least one catechol compound according to formula (I) is present in a total amount of 0.05 to 10.0% by weight, more preferably 0.1 to 4% by weight, more preferably of 0.2 to 2.0% by weight, very particularly preferably from 0.3 to 3.0% by weight.
- the at least one catechol compound of the formula (I) of the liquid composition is selected as one or more Catechol compounds of the formula (I) in which R 1 and R 2 independently represent a carbon radical having 3 to 20 carbon atoms, preferably having 3 to 10 carbon atoms, particularly preferably having 3 to 6 carbon atoms.
- radicals R 1 and R 2 of the formula (I) independently represent a linear or branched C 3 -C 20 alkyl group, a linear or branched C 3 -C 10 alkyl group, a linear or branched C 3 -C 6 -alkyl group, a linear or branched C 3 -C 20 alkenyl group, a linear or branched C 3 -C 10 alkenyl group, a linear or branched C 3 -C 6 alkenyl group, a cyclic C 3 -C 10 alkyl group, a propyl group, a phenyl group or a benzyl group.
- R 1 and R 2 of the formula (I) are very particularly preferably, independently of one another, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl , tert-pentyl, 2,2-dimethylpropyl, 1,2-dimethylpropyl, cyclopentyl, n-hexyl, iso-hexyl, neo-hexyl, cyclohexyl, allyl, but-2-enyl or benzyl.
- n-Propyl and isopropyl are in turn the most preferred groups of the radicals R 1 and R 2 .
- radicals R 1 and R 2 can be different or the same. A symmetrical substitution proves to be favorable in particular for the synthesis of the catechol compounds of the formula (I).
- the radicals R 1 and R 2 according to formula (I) are therefore very particularly preferably identical.
- At least one active substance is preferably selected from enzymes, optical brighteners, builders, solvents, antiredeposition agents, color transfer inhibitors, preservatives, perfume or mixtures of at least two of the aforementioned active substances.
- liquid composition according to the invention additionally contains at least one enzyme, in particular selected from protease, amylase, lipase, mannanase, cellulase, pectate lyase or mixtures thereof.
- at least one enzyme in particular selected from protease, amylase, lipase, mannanase, cellulase, pectate lyase or mixtures thereof.
- Variant at the protein level is the equivalent term to "mutant" at the nucleic acid level.
- the precursor or starting molecules can be wild-type enzymes, ie those obtainable from natural sources. It can also be an enzyme that is already a variant, ie compared to the wild type molecule have been changed. This includes, for example, point mutants, those with changes in the amino acid sequence over several positions or longer contiguous regions, or also hybrid molecules which are composed of mutually complementary sections of different wild-type enzymes.
- Amino acid exchanges are to be understood as meaning substitutions of one amino acid for another amino acid. According to the invention, such substitutions are given in the internationally customary one-letter code, indicating the positions in which the exchange takes place, optionally combined with the relevant amino acids.
- "Exchange in position 320” means, for example, that a variant has a different amino acid in the position which has position 320 in the sequence of a reference protein. Such exchanges are usually carried out at the DNA level via mutations of individual base pairs (see above).
- “R320K” means, for example, that the reference enzyme has the amino acid arginine at position 320, while the variant under consideration has the amino acid lysine at the position that can be homologated with it.
- 320K means that any amino acid, that is, as a rule, a naturally predetermined amino acid at a position that corresponds to position 320, is replaced by a lysine, which is located precisely at this point in the present molecule.
- R320K,L means that the amino acid arginine at position 320 is replaced with lysine or leucine.
- R320X means that the amino acid arginine in position 320 has been replaced by any other amino acid in principle.
- amino acid substitutions according to the invention referred to in the present application are not restricted to being the only substitutions in which the relevant variant differs from the wild-type molecule. It is known in the prior art that the advantageous properties of individual point mutations can complement one another. Thus, embodiments of the present invention encompass all variants which, in addition to other substitutions compared to the wild-type molecule, also have the substitutions according to the invention.
- a protease is an enzyme that cleaves peptide bonds by hydrolysis.
- Each of the enzymes from class EC 3.4 is included according to the invention (including each of the thirteen subclasses included).
- the EC number corresponds to the Enzyme Nomenclature 1992 of the NC-IUBMB, Academic Press, San Diego, California , including supplements 1 to 5, published in Eur. J. Biochem. 1994, 223, 1-5 ; Eur. J. Biochem. 1995, 232, 1-6 ; Eur. J. Biochem. 1996, 237, 1-5 ; Eur. J. Biochem. 1997, 250, 1-6 ; other Eur. J. Biochem. 1999, 264, 610-650 .
- Subtilase names a subgroup of the serine proteases.
- the serine proteases or serine peptidases are a subgroup of proteases that have serine in the active site of the enzyme that forms a covalent adduct with the substrate.
- the subtilases (and the serine proteases) are characterized in that, in addition to said serine, they have two further amino acid residues in the active center with histidine and aspartame.
- the subtilases can be divided into 6 subclasses, namely the subtilisin family, the thermitase family, the proteinase K family, the lantibiotic peptidase family, the kexin family and the pyrolysin family.
- the proteases which are preferably excluded from or preferably contained in reduced amounts as a component of the compositions according to the invention are endopeptidases (EC 3.4.21).
- proteolytic activity is present according to the invention if the enzyme has proteolytic activity (EC 3.4).
- protease activity Different types are known: The three main types are: trypsin-like, with cleavage of the amide substrate after amino acids Arg or Lys at P1; chymotrypsin-like, with cleavage occurring after one of the hydrophobic amino acids at P1; and elastase-like, with cleavage of the amide substrate to Ala at P1.
- the protease activity can be determined according to the in Surfactants, Vol. 7 (1970), pp. 125-132 method described can be determined. Accordingly, it is given in PU (protease units).
- the protease activity of an enzyme can be determined according to common standard methods, such as in particular using BSA as a substrate (bovine albumin) and/or using the AAPF method.
- a protease of the alkaline protease type from Bacillus lentus DSM 5483 or a protease sufficiently similar thereto (based on the sequence identity), which has several of these changes in combination, is particularly suitable for use in the liquid surfactant composition according to the invention and therein is advantageously improved stabilized. Advantages of using this protease thus result in particular with regard to washing performance and/or stability.
- sequence comparison is based on the BLAST algorithm that is 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.
- the Clustal series for example, is frequently used (cf. e.g Chenna et al. (2003): Multiple sequence alignment with the Clustal series of programs. Nucleic Acid Research 31 , 3497-3500 ), T-Coffee (cf. for example Notredame et al. (2000): T-Coffee: A novel method for multiple sequence alignments. J. Mol. Biol. 302, 205-217 ) or programs based on these programs or algorithms.
- Such a comparison also allows a statement to be made about the similarity of the compared sequences to one another. It is usually given as a percentage of identity, ie the proportion of identical nucleotides or amino acid residues in the same positions or in positions that correspond to one another in an alignment.
- identity ie the proportion of identical nucleotides or amino acid residues in the same positions or in positions that correspond to one another in an alignment.
- amino acid sequences the broader concept of homology includes conserved amino acid exchanges, i.e. amino acids with similar chemical activity, since these usually have similar chemical activities within the protein. Therefore, the similarity of the compared sequences can also be indicated as percent homology or percent similarity. Identity and/or homology statements can be made about entire polypeptides or genes or only about individual regions.
- homologous or identical regions of different nucleic acid or amino acid sequences are therefore defined by similarities in the sequences. Such areas often have identical functions. They can be small, containing only a few nucleotides or amino acids. Such small regions often perform essential functions for the overall activity of the protein. It can therefore make sense to relate sequence matches only to individual, possibly small areas. However, unless otherwise stated, identity or homology statements in the present application relate to the total length of the particular nucleic acid or amino acid sequence stated.
- the concentration of the protease in the liquid composition is from 0.001-0.1% by weight, preferably from 0.01 to 0.06% by weight, based on active protein.
- liquid surfactant compositions according to the invention (particularly preferably in addition to the protease) preferably contain at least one enzyme selected from ⁇ -amylase, cellulase, mannanase, lipase, pectate lyase as the enzyme.
- the enzymes contained in a composition according to the invention can be adsorbed on carriers and/or embedded in encapsulating substances in order to protect them against premature inactivation.
- the enzymes obtained can be added to compositions according to the invention in any form established in the prior art. These include, in particular, the solid preparations obtained by granulation, extrusion or lyophilization, advantageously as concentrated as possible, low in water and/or mixed with stabilizers.
- the enzymes can also be encapsulated, 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 from Core-shell type in which an enzyme-containing core is coated with a water, air and/or chemical impermeable protective layer.
- additional active ingredients such as stabilizers, emulsifiers, pigments, bleaches or dyes are applied.
- Such capsules are applied by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes.
- such granules for example due to the application of polymeric film formers, produce little dust and are stable in storage due to the coating.
- the liquid compositions preferably additionally contain at least one cellulase.
- a cellulase is an enzyme. Synonymous terms can be used for cellulases, in particular endoglucanase, endo-1,4-beta-glucanase, carboxymethyl cellulase, endo-1,4-beta-D-glucanase, beta-1,4-glucanase, beta-1,4-endoglucan hydrolase , celludextrinase or avicelase.
- the decisive factor in determining whether an enzyme is a cellulase within the meaning of the invention is its ability to hydrolyze 1,4- ⁇ -D-glucosidic bonds in cellulose.
- Cellulases which can be prepared according to the invention include, for example, the fungal cellulase preparation rich in endoglucanase (EG) or its further developments, which is offered by the company Novozymes under the trade name Celluzyme® .
- the products Endolase ® and Carezyme ® which are also available from the company Novozymes, are based on the 50 kD EG or the 43 kD EG from Humicola insolens DSM 1800.
- Other usable commercial products from this company are Cellusoft ® , Renozyme ® and Celluclean ® .
- cellulases which are available from AB Enzymes, Finland, under the trade names Ecostone® and Biotouch® and which are at least partly based on the 20 kD EG from Melanocarpus.
- Other cellulases from the company AB Enzymes are Econase ® and Ecopulp ® .
- suitable cellulases are from Bacillus sp. CBS 670.93 and CBS 669.93, wherein the Bacillus sp. CBS 670.93 is available from the Danisco/Genencor company under the tradename Puradax® .
- Other usable commercial products from the company Danisco/Genencor are “Genencor detergent cellulase L” and IndiAge® Neutra.
- Variants of these enzymes obtainable by point mutations can also be used according to the invention.
- Particularly preferred cellulases are Thielavia terrestris cellulase variants described in International Laid-Open Specification WO 98/12307 are disclosed, cellulases from Melanocarpus, in particular Melanocarpus albomyces, which are disclosed in International Offenlegungsschrift WO 97/14804 are disclosed, EGIII-type cellulases from Trichoderma reesei, which are disclosed in European patent application EP 1 305 432 are disclosed or variants obtainable therefrom, in particular those disclosed in the European patent applications EP1240525 and EP1305432 , as well as cellulases disclosed in the International Laid-Open Specifications WO1992006165 , WO 96/29397 and WO 02/099091 . Reference is therefore expressly made to their respective disclosure or their relevant disclosure content is therefore expressly included in the present patent application.
- Liquid compositions which are particularly preferred according to the invention are characterized in that at least one cellulase from Melanocarpus sp. or Myriococcum sp. available 20K cellulase or those sharing over 80% homology (increasingly favored by over 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 90.5%, 91%, 91.5%, 92%, 92.5 %, 93%, 93.5%, 94%, 94.5%, 95%, 95.5%, 96%, 96.5%, 97%, 97.5%, 98%, 98.5%, 99.0%, 99.1%, 99.2%, 99.3%, 99.4%, 99.5%, 99.6%, 99.7%, 99.8%, 99.9%) has to.
- the from Melanocarpus sp. or Myriococcum sp. available 20K cellulase is from the international patent application WO 97/14804 known. As described there, it has a molecular weight of about 20 kDa and has at least 80% of its maximum activity at 50° C. in the pH range from 4 to 9, with almost 50% of the maximum activity remaining at pH 10. As also described there, it can be isolated from Melanocarpus albomyces and produced in genetically engineered Trichoderma reseei transformants.
- cellulases which have a homology greater than 80% (increasingly preferably greater than 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90 %, 90.5%, 91%, 91.5%, 92%, 92.5%, 93%, 93.5%, 94%, 94.5%, 95%, 95.5%, 96%, 96.5%, 97%, 97.5%, 98%, 98.5%, 99.0%, 99.1%, 99.2%, 99.3%, 99.4%, 99.5% , 99.6%, 99.7%, 99.8%, 99.9%) to 20K cellulase.
- K20 cellulase is preferably used in such amounts that a composition according to the invention has a cellulolytic activity of 1 NCU / g to 500 NCU / g (determinable by hydrolyzing 1 weight percent carboxymethylcellulose at 50 ° C and neutral pH and determining the reducing thereby released Sugar using dinitrosalicylic acid, as described by MJ Bailey et al. in Enzyme Microb. technol. 3:153 (1981 ) described; 1 NCU defines the amount of enzyme that generates reducing sugars in an amount corresponding to 1 nmol glucose per second), in particular from 2 NCU/g to 400 NCU/g and more preferably from 6 NCU/g to 200 NCU/g.
- the composition according to the invention can optionally contain other cellulases.
- a liquid composition according to the invention preferably contains from 0.001 mg to 0.5 mg, in particular from 0.02 mg to 0.3 mg, of cellulolytic protein per gram of the total composition.
- Protein concentration can be determined using known methods, for example, the bicinchonic acid method (BCA method, Pierce Chemical Co., Rockford, IL) or the biuret method ( AG Gornall, CS Bardawill and MM David, J. Biol. Chem. 177, 751-766, 1948 ) are determined.
- liquid compositions according to the invention additionally contain at least one lipase.
- Lipase enzymes preferred according to the invention are selected from at least one enzyme from the group formed from triacylglycerol lipase (EC 3.1.1.3) and lipoprotein lipase (EC 3.1.1.34) and monoglyceride lipase (EC 3.1.1.23).
- the lipase preferably contained in a liquid composition according to the invention is naturally present in a microorganism of the species Thermomyces lanuginosus or Rhizopus oryzae or Mucor javanicus or is derived from the aforementioned naturally present lipases by mutagenesis.
- the compositions according to the invention particularly preferably contain at least one lipase which is naturally present in a microorganism of the species Thermomyces lanuginosus or which is derived by mutagenesis from the aforementioned lipases which are naturally present in Thermomyces lanuginosus .
- the lipase is an enzyme of the microorganism itself.
- the lipase can thus be expressed in the microorganism from a nucleic acid sequence which is part of the chromosomal DNA of the microorganism in its wild-type form. It or the nucleic acid sequence coding for it is consequently present in the wild-type form of the microorganism and/or can be isolated from the wild-type form of the microorganism.
- a lipase not naturally present in the microorganism or the nucleic acid sequence coding for it would have been specifically introduced into the microorganism with the aid of genetic engineering methods, so that the microorganism would have been enriched by the lipase or the nucleic acid sequence coding for it.
- a lipase which is naturally present in a microorganism of the species Thermomyces lanuginosus or Rhizopus oryzae or Mucor javanicus may well have been produced recombinantly by another organism.
- the fungus Thermomyces lanuginosus (also known as Humicola lanuginosa ) belongs to the class Eurotiomycetes (subclass Eurotiomycetidae), herein to the order Eurotiales and herein to the family Trichocomaceae and the genus Thermomyces.
- the fungus Rhizopus oryzae belongs to the class of Zygomycetes (subclass Incertae sedis), here to the order Mucorales and here in turn to the family Mucoraceae and the genus Rhizopus.
- the fungus Mucor javanicus also belongs to the class of zygomycetes (subclass Incertae sedis), here to the order Mucorales and here in turn to the family Mucoraceae, here then to the genus Mucor.
- the designations Thermomyces lanuginosus, Rhizopus oryzae and Mucor javanicus are the biological species designations within the respective genus.
- preferred lipases are the lipase enzymes available from Amano Pharmaceuticals under the names Lipase M- AP10® , Lipase LE® and Lipase F® (also Lipase JV® ).
- the lipase F ® is naturally present in Rhizopus oryzae.
- the lipase M- AP10® is naturally present in Mucor javanicus.
- compositions of a most preferred embodiment of the invention contain at least one lipase selected from at least one or more polypeptides having an amino acid sequence that is at least 90% (and more preferably at least 81%, 82%, 83%, 84%, 85% %, 86%, 87%, 88%, 89%, 90%, 90.5%, 91%, 91.5%, 92%, 92.5%, 93%, 93.5%, 94%, 94 .5%, 95%, 95.5%, 96%, 96.5%, 97%, 97.5%, 98%, 98.5%, 99.0%, 99.1%, 99.2% , 99.3%, 99.4%, 99.5%, 99.6%, 99.7%, 99.8%, 99.9%) to wild-type lipase from strain DSM 4109
- Thermomyces lanuginosus is identical. It is again preferred if, starting from said wild-type lipase from strain DSM 4109, at least the amino acid change N233R is present.
- those lipases derived from the wild-type lipase from the DSM 4109 strain can preferably be used according to the invention, which are selected from at least one lipase enzyme according to at least one of claims 1 to 13 of the publication WO 00/60063 A1 .
- the revelation pamphlet WO 00/60063 A1 is expressly referred to in its entirety.
- At least one lipase is particularly preferably used in the compositions of the invention, which is derived from the wild-type lipase from the strain DSM 4109 and in which, starting from said wild-type lipase, at least one substitution of an electrically neutral or negatively charged amino acid by a positively charged amino acid took place.
- the charge is determined in water at pH 10.
- Negative amino acids within the meaning of the invention are E, D, Y and C.
- Positively charged amino acids within the meaning of the invention are R, K and H, in particular R and K.
- Neutral amino acids within the meaning of the invention are G, A, V, L, I , P, F, W, S, T, M, N, Q and C when C forms a disulfide bridge.
- At least one of the following amino acid substitutions is present in positions D96L, T213R and/or N233R, particularly preferably T213R and N233R.
- a highly preferred lipase is commercially available under the trade name Lipex® from the company Novozymes (Denmark) and can be used advantageously in the cleaning compositions according to the invention.
- the lipase Lipex® 100 L (ex Novozymes A/S, Denmark) is particularly preferred here.
- Preferred compositions are characterized in that said lipase enzyme from Lipex ® 100 L is present in a total amount of from 0.01 to 1.0% by weight, in particular from 0.02 to 0.1% by weight, based on the total weight of the composition. %, is included.
- the liquid compositions according to the invention can additionally contain at least one mannanase as an enzyme.
- a mannanase contained in the composition according to the invention (in particular in a detergent and cleaning agent preferred according to the invention for textiles) catalyzes the hydrolysis of 1,4-beta-D-mannosidic bonds in mannans, galactomannans, glucomannans and galactoglucomannans as part of its mannanase activity.
- said mannanase enzymes according to the invention are referred to as E.C. 3.2.1.78 classified.
- the mannanase activity of a polypeptide or enzyme can be determined according to test methods known from the literature. For example, a test solution in holes with a diameter of 4 mm of an agar plate containing 0.2% by weight of AZGL galactomannan (carob), ie substrate for the endo-1,4-beta-D-mannanase assay, available under catalog number I-AZGMA of company Megazyme (http://www.megazyme.com).
- compositions according to the invention contain, for example, the mannanase which is marketed under the name Mannaway® by the Novozymes company.
- Mannanase enzymes have been identified in numerous Bacillus organisms: WO 99/64619 discloses examples of liquid, protease-containing detergent compositions with a high total surfactant content of at least 20% by weight, which additionally comprise mannanase enzyme.
- compositions according to the invention preferably contain mannanase in a total amount of from 0.01 to 1.0% by weight, in particular from 0.02 to 0.1% by weight, based on the total weight of the composition.
- Mannanase polypeptides from strains of the Thermoanaerobacter group, such as Caldicellulosiruptor, are preferably suitable according to the invention.
- mannanase polypeptides of the fungi Humicola or Scytalidium in particular of the species Humicola insolens or Scytalidium thermophilum.
- compositions according to the invention contain at least one mannanase polypeptide from gram-positive alkalophilic strains of Bacillus, in particular selected from at least one representative of the group consisting of Bacillus subtilis, Bacillus lentus, Bacillus clausii, Bacillus agaradhaerens, Bacillus brevis, Bacillus stearothermophilus, Bacillus alkalophilus, Bacillus amyloliquefaciens, Bacillus coagulans, Bacillus circulans, Bacillus lautus, Bacillus thuringiensis, Bacillus cheniformis, and Bacillus sp., particularly preferably selected from at least one representative of the group consisting of Bacillus sp. 1633, Bacillus sp. AAI12, Bacillus clausii, Bacillus agaradhaerens and Bacillus licheniformis.
- said preferred mannanase in a total amount of 0.01 to 1.0 wt .-%, in particular from 0.02 to 0.1 wt .-%, each based on the total weight of the composition, in the composition according to the invention is included.
- the liquid surfactant composition according to the invention particularly preferably contains at least one ⁇ -amylase in addition to the preferred protease of the alkaline protease type from Bacillus lentus DSM 5483 or in addition to the protease sufficiently similar thereto (based on the sequence identity) which has several of these changes in combination .
- ⁇ -amylases hydrolyze internal ⁇ -1,4-glycosidic bonds of starch and starch-like polymers.
- This ⁇ -amylase activity is, for example, the applications WO 97/03160 A1 and GB1296839 measured in KNU (kilo novo units).
- 1 KNU stands for the amount of enzyme which hydrolyzes 5.25 g of starch (available from Merck, Darmstadt, Germany) per hour at 37° C., pH 5.6 and in the presence of 0.0043 M calcium ions.
- An alternative activity determination method is the so-called DNS method, which is used, for example, in the application WO 02/10356 A2 is described.
- the oligosaccharides, disaccharides and glucose units released by the enzyme during the hydrolysis of starch are detected by oxidation of the reducing ends with dinitrosalicylic acid (DNA).
- DNA dinitrosalicylic acid
- the activity is obtained in ⁇ mol of reducing sugars (relative to maltose) per min and ml; this results in activity values in TAU.
- the same enzyme can be determined using different methods, whereby the respective conversion factors can vary depending on the enzyme and must therefore be determined using a standard. It can be roughly calculated that 1 KNU corresponds to approx. 50 TAU.
- Another activity determination method is measurement using the Quick-Start ® test kit from Abbott, Abbott Park, Illinois, USA.
- a preferred area of use according to the invention for the liquid surfactant compositions according to the invention is the cleaning of textiles. Because detergents and cleaning agents for textiles predominantly have alkaline pH values, ⁇ -amylases in particular, which are active in an alkaline medium, are used for this purpose. Such are produced and secreted by microorganisms, ie fungi or bacteria, especially those of the genera Aspergillus and Bacillus. Based on these natural enzymes, there is still an almost unmanageable wealth of variants that have been derived via mutagenesis and have specific advantages depending on the area of application.
- ⁇ -amylases from Bacillus licheniformis, from B. amyloliquefaciens and from B. stearothermophilus and their improved further developments for use in detergents or cleaning agents.
- the enzyme from B. licheniformis is available from Novozymes under the name Termamyl® and from Genencor under the name Purastar® ST. Further development products of this ⁇ -amylase are available from Novozymes under the trade names Duramyl® and Termamyl® ultra, from Genencor under the name Purastar® OxAm and from Daiwa Seiko Inc., Tokyo, Japan, as Keistase® .
- amyloliquefaciens is marketed by the company Novozymes under the name BAN® , and variants derived from the ⁇ -amylase from B. stearothermophilus under the names BSG® and Novamyl® , also from the company Novozymes.
- ⁇ -amylases from other organisms are the further developments of ⁇ -amylase from Aspergillus niger and A. oryzae available under the trade name Fungamyl® from Novozymes.
- Another commercial product is, for example, Amylase-LT ® .
- the state of the art includes the three Patent applications WO 96/23873 A1 , WO 00/60060 A2 and WO 01/66712 A2 , which have been registered by the company Novozymes.
- WO 96/23873 A1 partly describes several different point mutations in a total of more than 30 different positions in four different wild-type amylases and claims such for all amylases with at least 80% identity to one of these four; they should have altered enzymatic properties with regard to thermal stability, oxidation stability and calcium dependence.
- the registration WO 00/60060 A2 also names a large number of possible amino acid substitutions in 10 different positions on the ⁇ -amylases from two different microorganisms and claims such for all amylases with a homology of at least 96% identity to these.
- WO 01/66712 A2 designates 31 different amino acid positions, some of which are identical to those mentioned above, which are present in one of the two in the application WO 00/60060 A2 mentioned ⁇ -amylases have been mutated.
- WO 96/23873 A1 shows, for example, the concrete possibility of replacing an M in position 9 according to the count of AA560 with an L, in position 202 M with L and those in positions 182 and 183 (or 183 and 184) in the ⁇ -amylases mentioned delete amino acids.
- WO 00/60060 A2 specifically discloses, inter alia, the amino acid variation N195X (i.e. in principle against any other amino acid).
- WO 01/66712 A2 discloses, inter alia, the amino acid variations R118K, G186X (including in particular the replacement G186R which is not relevant here), N299X (including in particular the replacement N299A which is not relevant here), R320K, E345R and R458K.
- the liquid surfactant composition according to the invention contains at least one ⁇ -amylase in addition to the preferred protease of the alkaline protease type from Bacillus lentus DSM 5483 or a protease sufficiently similar thereto (based on the sequence identity) which has several of these changes in combination , which has a higher activity at temperatures between 10 and 20 ° C than the amylase with the trade name "Stainzyme 12 L" from Novozymes.
- Liquid compositions preferred according to the invention contain ⁇ -amylase in a total amount of from 0.01 to 1.0% by weight, in particular from 0.02 to 0.1% by weight.
- the liquid composition contains at least one optical brightener.
- the optical brighteners are preferably from the substance classes of distyrylbiphenyls, stilbenes, 4,4'-diamino-2,2'-stilbenedisulfonic acids, coumarins, dihydroquinolinones, 1,3-diarylpyrazolines, naphthalic acid imides, benzoxazole systems, the benzisoxazole systems, the benzimidazole systems, the pyrene derivatives substituted by heterocycles and mixtures thereof.
- These substance classes of optical brighteners have high stability, high light and oxygen resistance and a high affinity for fibers.
- optical brighteners which are selected from the group consisting of disodium 4,4'-bis-(2-morpholino-4-anilino-s-triazin-6-ylamino)stilbene disulfonate, disodium 2,2 '-bis(phenyl-styryl)disulfonate, 4,4'-bis[(4-anilino-6-[bis(2-hydroxyethyl)amino]-1,3,5-triazin-2-yl)amino]stilbene -2,2'-disulfonic acid, hexasodium 2,2'-[vinylenebis[(3-sulphonato-4,1-phenylene)imino[6-(diethylamino)-1,3,5-triazine-4,2-diyl ]imino]]bis(benzene-1,4-disulfonate), 2,2'-(2,5-thiophenediyl)bis[5-1,1-dimethyl,4
- the liquid composition can further comprise builders.
- Polymeric polycarboxylates for example, are suitable as builders. These are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 600 to 750,000 g/mol.
- Suitable polymers are, in particular, polyacrylates, which preferably have a molecular weight of 1000 to 15,000 g/mol. Due to their superior solubility, the short-chain polyacrylates which have molar masses of 1000 to 10,000 g/mol, and particularly preferably of 1000 to 5000 g/mol, can be preferred from this group.
- copolymeric polycarboxylates in particular those of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid.
- the polymers can also contain allyl sulfonic acids, such as allyloxybenzene sulfonic acid and methallyl sulfonic acid, as a monomer.
- silicates aluminum silicates (in particular zeolites), carbonates, salts of organic di- and polycarboxylic acids and mixtures of these substances should also be mentioned as builders which can be present in the composition according to the invention.
- Organic builders are particularly suitable as additional builders, for example the polycarboxylic acids which can be used in the form of their sodium salts or also as acids, polycarboxylic acids being understood to mean those carboxylic acids which carry more than one acid function.
- these are adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, in particular glutamic acid-N,N-diacetic acid (GLDA) and methylglycine-N,N-diacetic acid (MGDA), and mixtures of these.
- Polymeric polycarboxylates are also suitable as builders. These are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 600 to 750,000 g/mol. Suitable polymers are, in particular, polyacrylates, which preferably have a molecular weight of 1000 to 15,000 g/mol.
- the short-chain polyacrylates which have molar masses from 1000 to 10,000 g/mol, and particularly preferably from 1000 to 5000 g/mol, may in turn be preferred from this group.
- copolymeric polycarboxylates in particular those of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid.
- the polymers can also contain allyl sulfonic acids, such as allyloxybenzene sulfonic acid and methallyl sulfonic acid, as a monomer.
- Soluble builders such as acrylic polymers with a molar mass of 1000 to 5000 g/mol, are preferably used in liquid detergents.
- soluble builders such as citric acid, or acrylic polymers with a molar mass of 1000 to 5000 g/mol are particularly preferably used.
- the liquid compositions according to the invention can also contain components which have a positive effect on the ability to be washed out of oil and grease from textiles, so-called soil-release active ingredients.
- the liquid composition preferably additionally contains at least one dirt-repellent polymer (also known as SRP).
- SRP dirt-repellent polymer
- the preferred oil and fat-dissolving components include, for example, non-ionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose containing 15 to 30% by weight of methoxyl groups and 1 to 15% by weight of hydroxypropoxyl groups, based in each case on the nonionic cellulose ether, and the polymers known from the prior art of phthalic acid and/or terephthalic acid or derivatives thereof with monomeric and/or polymeric diols, in particular polymers of ethylene terephthalates and/or polyethylene glycol terephthalates or anionically and/or nonionically modified derivatives of this.
- non-ionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose containing 15 to 30% by weight of methoxyl groups and 1 to 15% by weight of hydroxypropoxyl groups, based in each case on the nonionic cellulose ether
- Anti-redeposition agents are chosen in particular from copolymers based on polyethyleneimine, based on polyvinyl acetate and based on polyethylene glycol.
- the liquid composition may preferably also contain at least one dye transfer inhibiting polymer.
- Such color transfer inhibitors are preferably contained in amounts of 0.1% by weight to 2% by weight, in particular 0.1% by weight to 1% by weight, which in a preferred embodiment of the invention contain polymers of vinylpyrrolidone, vinylimidazole, vinylpyridine-N -oxide or copolymers thereof.
- Graying inhibitors have the task of keeping the dirt detached from the textile fibers suspended in the liquor.
- Water-soluble colloids usually of an organic nature, are suitable for this purpose, for example starch, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
- Water-soluble polyamides containing acidic groups are also suitable for this purpose.
- starch derivatives other than those mentioned above can be used, for example aldehyde starches.
- Cellulose ethers such as carboxymethyl cellulose (Na salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof can preferably be used, for example in amounts of 0.1 to 5% by weight, based on the composition according to the invention.
- the dye transfer inhibitor is a polymer or copolymer of cyclic amines such as vinyl pyrrolidone and/or vinyl imidazole.
- Polymers useful as dye transfer inhibitors include polyvinylpyrrolidone (PVP), polyvinylimidazole (PVI), copolymers of vinylpyrrolidone and vinylimidazole (PVP/PVI), polyvinylpyridine N-oxide, poly-N-carboxymethyl-4-vinylpyridium chloride, polyethylene glycol-modified copolymers of vinylpyrrolidone and vinylimidazole and mixtures thereof.
- Polyvinylpyrrolidone (PVP), polyvinylimidazole (PVI) or copolymers of vinylpyrrolidone and vinylimidazole (PVP/PVI) are particularly preferred as color transfer inhibitor deployed.
- the polyvinylpyrrolidones (PVP) used preferably have an average molecular weight of 2,500 to 400,000 and are commercially available from ISP Chemicals as PVP K 15, PVP K 30, PVP K 60 or PVP K 90 or from BASF as Sokalan® HP 50 or Sokalan® HP 53 available.
- the copolymers of vinylpyrrolidone and vinylimidazole (PVP/PVI) used preferably have a molecular weight in the range from 5,000 to 100,000.
- a PVP/PVI copolymer is commercially available, for example from BASF under the name Sokalan® HP 56.
- Another color transfer inhibitor that can be used with extreme preference are polyethylene glycol-modified copolymers of vinylpyrrolidone and vinylimidazole, which are available, for example, under the name Sokalan® HP 66 from BASF are.
- Preferred liquid compositions of the invention additionally contain at least one bluing agent.
- a "bluing agent” is a blue to violet dye that turns white fabrics blue to violet to increase the whiteness of the fabric.
- One method of determining the presence of a bluing agent is to measure the Lab values colorimetrically, as described in the reference WO 2014/089386 A1 on page 7, line 20 to page 9, line 6, to which reference is expressly made.
- a bluing agent is present, for example, if the blue to violet dye causes a DE* value of at least 2.0 DE* units, preferably at least 3.0 DE* units, particularly preferably at least 4.0 DE* units, on the textile according to the aforementioned test method .
- the bluing agent in solution or dispersion (ethanol, at 20° C.) has an absorption maximum in a wavelength range of 510 and 640 nm, particularly preferably from 530 to 620 nm.
- the bluing agent is preferably a dye whose maximum extinction coefficient in a wavelength range from 400 to 750 nm is preferably greater than 1000 L/mol/cm.
- the bluing agent is preferably not charged or has an anionic charge; the dye is particularly preferably nonionic.
- the bluing agent is a compound of the following general formula BL-1: in which F represents the monoazo dye.
- the aforesaid extinction coefficient relates to this dye F in the compound FH in an ethanolic solution.
- L according to formula BL-1 is an organic group which connects the monoazo dye F to the carboxyl group CO 2 M.
- This linking group L preferably has a molecular weight in the range from 14 to 1000 g/mol, especially from 14 to 600 g/mol preferably from 28 to 300 g/mol.
- the group L preferably comprises essentially exclusively carbon and hydrogen and optionally also oxygen and/or nitrogen.
- L particularly preferably represents a C 1-20 -alkyl group which optionally has ether and/or ester and/or amide groups as branching points. According to the invention, the alkyl chain can be substituted. Possible substituents are -OH, -CN, -NO 2 , -SO 2 CH 3 , -CL, -BR.
- M represents any counterion, usually hydrogen, sodium or potassium.
- Examples of short-chain alkyl and/or alkoxy radicals are methyl, ethyl, n-propyl, n-butyl, ethoxy and methoxy.
- Examples of the optionally substituted lower alkyl radicals represented by R in general formula 2 are ⁇ -hydroxyethyl, ⁇ -cyanoethyl, ⁇ -(methoxy or ethoxy)ethyl, ⁇ -methoxypropyl, benzyl or ⁇ -phenylethyl, ⁇ -methoxycarbonyl-ethyl or ⁇ -acetoxyethyl.
- the bluing agent according to the invention can, for example, have the following general formula BL-3: in which Z, R, X, Y and L represent the same radicals as already explained above for formula 1 and formula 2.
- low-water, liquid compositions according to the invention of the first subject matter of the invention can be present in pre-portioned form (portion).
- the composition of the invention is present in a container of water-soluble or water-dispersible material.
- composition according to the invention is packaged in a water-soluble or water-dispersible material, it is preferred that the water content is between 5 and 20% by weight, based on the composition as a whole.
- the container made of water-soluble material comprises at least one chamber, preferably at least two spatially separated chambers (multi-chamber pouch).
- the water-soluble material forms walls of the chamber and thereby encloses at least one composition according to the invention.
- the water solubility of the material can be determined using a square film of said material (film: 22 x 22 mm with a thickness of 76 ⁇ m) fixed in a square frame (edge length on the inside: 20 mm) according to the following measurement protocol.
- said The framed film is immersed in 800 mL of distilled water at a temperature of 20 °C in a 1 liter beaker with a circular bottom (Schott, Mainz, 1000 mL beaker, low shape) so that the surface of the clamped film is at right angles to the bottom surface of the beaker, the top edge of the frame is 1 cm below the water surface and the bottom edge of the frame is oriented parallel to the bottom surface of the beaker such that the bottom edge of the frame runs along the radius of the bottom surface of the beaker and the center of the bottom edge of the frame is above the center of the radius of the bottom of the beaker.
- the material should dissolve within 600 seconds with stirring (stirring speed, magnetic stirrer 300 rpm, stirring rod: 6.8 cm long, diameter 10 mm) in such a way that individual solid film particles are no longer visible to the naked eye.
- the walls are preferably made of a water-soluble film. According to the invention, this film can preferably have a thickness of at most 150 ⁇ m (particularly preferably at most 120 ⁇ m). Accordingly, preferred walls are made of a water-soluble film and have a thickness of at most 150 ⁇ m (particularly preferably at most 120 ⁇ m, very particularly preferably at most 90 ⁇ m).
- Such portions can be made by either vertical form fill seal (VFFS) processes or thermoforming processes.
- Walls of at least one chamber are particularly preferably created by sealing at least one film of water-soluble material, in particular by sealing using a form-fill-seal method.
- the thermoforming process generally includes forming a first layer of a water-soluble sheet material to form at least one recess for receiving at least one composition of the invention therein, filling the composition into each recess, covering the composition-filled recesses with a second layer of a water soluble sheet material and sealing the first and second layers together at least around the bulges.
- the water-soluble material preferably contains at least one water-soluble polymer.
- the water-soluble material preferably contains a water-soluble film material selected from polymers or polymer blends.
- the cover can be formed from one or from two or more layers of the water-soluble film material.
- the water-soluble film material of the first layer and the further layers, if any, can be the same or different.
- the water-soluble material contains polyvinyl alcohol or a polyvinyl alcohol copolymer.
- Suitable water-soluble films as the water-soluble material are preferably based on a polyvinyl alcohol or a polyvinyl alcohol copolymer whose molecular weight is in the range from 10,000 to 1,000,000 gmol -1 , preferably from 20,000 to 500,000 gmol -1 , particularly preferably from 30,000 to 100,000 gmol -1 and in particular from 40,000 to 80,000 gmol- 1 .
- Polyvinyl alcohol is usually produced by hydrolysis of polyvinyl acetate, since the direct synthesis route is not possible. The same applies to polyvinyl alcohol copolymers which are correspondingly produced from polyvinyl acetate copolymers.
- the water-soluble material preferably contains at least one polyvinyl alcohol and/or at least one polyvinyl alcohol copolymer.
- Polyvinyl alcohol (abbreviation PVAL or PVA, occasionally also PVOH) is the designation for polymers of the general structure which in small proportions (about 2%) also structural units of the type contain.
- polyvinyl alcohols which are available as yellowish-white powders or granules with a degree of polymerization in the range from about 100 to 2500 (molar masses from about 4000 to 100,000 g/mol), have degrees of hydrolysis of 98 to 99 mol% or 87 to 89 mol -%, so still contain a residual content of acetyl groups.
- the polyvinyl alcohols are characterized by the manufacturer by specifying the degree of polymerization of the starting polymer, the degree of hydrolysis, the saponification number or the solution viscosity.
- polyvinyl alcohols are soluble in water and a few strongly polar organic solvents (formamide, dimethylformamide, dimethyl sulfoxide); they are not attacked by (chlorinated) hydrocarbons, esters, fats and oils.
- Polyvinyl alcohols are classified as toxicologically harmless and are at least partially biodegradable.
- the water solubility can be reduced by post-treatment with aldehydes (acetalization), by complexing with Ni or Cu salts or by treatment with dichromates, boric acid or borax.
- the polyvinyl alcohol coatings are largely impervious to gases such as oxygen, nitrogen, helium, hydrogen, carbon dioxide, but allow water vapor to pass through.
- the water-soluble material at least partially comprises a polyvinyl alcohol whose degree of hydrolysis is 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol -% amounts to.
- the water-soluble material consists of at least 20% by weight, more preferably at least 40% by weight, very preferably at least 60% by weight and in particular at least 80% by weight of a polyvinyl alcohol, its Degree of hydrolysis is 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol%.
- polyvinyl alcohols described above are widely available commercially, for example under the trade name Mowiol® (Clariant).
- Mowiol® Commercially, for example under the trade name Mowiol® (Clariant).
- particularly suitable polyvinyl alcohols are, for example, Mowiol 3-83, Mowiol ® 4-88, Mowiol ® 5-88, Mowiol ® 8-88 and L648, L734, Mowiflex LPTC 221 ex KSE and the compounds from Texas Polymers such as for example Vinex 2034.
- preferred polyvinyl alcohol copolymers include dicarboxylic acids as further monomers. Suitable dicarboxylic acids are itaconic acid, malonic acid, succinic acid and mixtures thereof, with itaconic acid being preferred.
- polyvinyl alcohol copolymers include, in addition to vinyl alcohol, an ethylenically unsaturated carboxylic acid, its salt or its ester.
- Such polyvinyl alcohol copolymers particularly preferably contain, in addition to vinyl alcohol, acrylic acid, methacrylic acid, acrylic acid esters, methacrylic acid esters or mixtures thereof.
- polyvinyl alcohol polymer can be changed by post-treatment with aldehydes (acetalization) or ketones (ketalization).
- aldehydes acetalization
- ketones ketalization
- Polyvinyl alcohols which are acetalized or ketalized with the aldehyde or keto groups of saccharides or polysaccharides or mixtures thereof have proven to be particularly preferred and particularly advantageous due to their extremely good solubility in cold water.
- the water solubility can be changed by complexing with Ni or Cu salts or by treatment with dichromates, boric acid, borax and thus adjusted to desired values.
- PVAL films are largely impenetrable to gases such as oxygen, nitrogen, helium, hydrogen and carbon dioxide, but allow water vapor to pass through.
- polymers selected from the group comprising acrylic acid-containing polymers, polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters, polyethers, polylactic acid and/or mixtures of the above polymers can be added to the film material suitable as water-soluble material.
- the film material suitable as the water-soluble material can also contain polymers selected from the group consisting of polymers containing acrylic acid, polyacrylamides, oxazoline polymers, Polystyrene sulfonates, polyurethanes, polyesters, polyethers, polylactic acid, and/or mixtures of the above polymers may be added.
- Film material used as the water-soluble material of the walls has a preferred thickness in a range from 65 to 180 ⁇ m, in particular from 70 to 150 ⁇ m, more preferably 75 to 120 ⁇ m.
- a bittering agent is preferably incorporated into said water-soluble material of the walls of the portion to increase product safety.
- Corresponding embodiments of the water-soluble material with bittering agent are in the publications EP-B1-2 885 220 and EP-B1-2 885 221 described.
- a preferred bittering agent is denatonium benzoate.
- Suitable water-soluble films for use as the water-soluble material of the wall of the water-soluble portion according to the invention are films sold under the designation Monosol M8630 by MonoSol LLC.
- Other suitable films include films with the name Solublon® PT, Solublon® KA, Solublon® KC or Solublon® KL from Aicello Chemical Europe GmbH or films VF-HP from Kuraray, or HiTorrent SH2312 from Nippon Gohsei.
- the soiling can be pretreated with the composition according to the invention of the first subject matter of the invention before step (a) in the context of a textile wash.
- Processes for cleaning textiles are generally characterized in that various cleaning-active 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 of this agent.
- an aqueous liquor in step (a) by mixing 5.0 to 20.0 L of water with 5 to 75 g (particularly 10 to 55 g) of a composition of the first subject of the invention.
- step (b) the aqueous liquor is adjusted to temperatures of 60° C. or less, for example 40° C. or less, in various embodiments of the invention.
- a third subject of the invention is the use of an aqueous liquor obtainable by mixing 0.5 L to 40.0 L of water with 0.5 to 100 g of a liquid composition of the first subject of the invention (in particular according to one of points 1 to 22 ( vide infra )), for textile treatment, especially for textile cleaning.
- an aqueous liquor obtainable by mixing 5.0 to 20.0 L of water with 5 to 75 g (particularly 10 to 55 g) of a composition of the first subject of the invention.
- Table 1 Liquid detergents E1 [% by weight] V1 [% by weight] C 11-13 alkyl benzene sulfonic acid 20.0 20.0 (C 12-14 )fatty alcohol ether sulphate with 2 units of ethylene oxide 5.0 5.0 Fatty alcohol ether ethoxylated with 7 moles of ethylene oxide 10.0 10.0 2-aminoethanol 8.0 8.0 sodium hydroxide 1.0 1.0 DTA-1 1 0.5 - DTA-2 2 - 0.5 C 12-18 fatty acid 3.0 3.0 Etidronic acid (HEDP) 0.6 0.6 citric acid 3.0 3.0 boric acid 2.0 2.0 1,2-propylene glycol 12.0 12.0 denatonium benzoate 0.001 0.001 Dye, protease, amylase, lipase, cellulase, stilbene type optical brightener 1.7 1.7 Perfume 1.0 1.0 distilled water to 100 to 100 1 2,3-di
- compositions were then stored at 0°C for a period of 8 weeks and then assessed visually.
- Formula V1 which was not according to the invention, showed significant sedimentation, whereas formula E1 according to the invention was stable.
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Detergent Compositions (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102018217399.0A DE102018217399A1 (de) | 2018-10-11 | 2018-10-11 | Flüssige Zusammensetzung mit Dihydroxyterephthalsäurediamid-Verbindung und hoher Tensidmenge |
| PCT/EP2019/065991 WO2020074144A1 (de) | 2018-10-11 | 2019-06-18 | Flüssige zusammensetzung mit dihydroxyterephthalsäurediamid-verbindung und hoher tensidmenge |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP3864119A1 EP3864119A1 (de) | 2021-08-18 |
| EP3864119B1 true EP3864119B1 (de) | 2023-03-01 |
Family
ID=67070798
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP19733687.8A Active EP3864119B1 (de) | 2018-10-11 | 2019-06-18 | Flüssige zusammensetzung mit dihydroxyterephthalsäurediamid-verbindung und hoher tensidmenge |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP3864119B1 (pl) |
| DE (1) | DE102018217399A1 (pl) |
| PL (1) | PL3864119T3 (pl) |
| WO (1) | WO2020074144A1 (pl) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102019219295A1 (de) * | 2019-12-11 | 2021-06-17 | Henkel Ag & Co. Kgaa | Verbesserte Waschleistung von Color Waschmitteln an bleichbaren Flecken ohne Farbschädigung |
| DE102022116728A1 (de) | 2022-07-05 | 2024-01-11 | Basf Se | Wasch- und Reinigungsmittel enthaltend amphiphile alkoxylierte Poly(ethylen/propylen)imin Copolymere sowie Catecholverbindungen |
Family Cites Families (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1296839A (pl) | 1969-05-29 | 1972-11-22 | ||
| US5049280A (en) * | 1989-03-29 | 1991-09-17 | The Regents Of The University Of California | 2,3-dihydroxyterephthalamides as highly effective metal ion sequestering compounds |
| DE69133633D1 (de) | 1991-06-11 | 2010-07-08 | Genencor Int | Cellulasezusammensetzungen mit einem Defizit an Komponenten des Typs-CBH I enthaltende Reinigungsmittelzusammensetzungen |
| AR000862A1 (es) | 1995-02-03 | 1997-08-06 | Novozymes As | Variantes de una ó-amilasa madre, un metodo para producir la misma, una estructura de adn y un vector de expresion, una celula transformada por dichaestructura de adn y vector, un aditivo para detergente, composicion detergente, una composicion para lavado de ropa y una composicion para la eliminacion del |
| CN102080070B (zh) | 1995-03-17 | 2016-01-20 | 诺沃奇梅兹有限公司 | 新的内切葡聚糖酶 |
| GB2303145A (en) | 1995-07-08 | 1997-02-12 | Procter & Gamble | Detergent compositions |
| EP0857216B1 (en) | 1995-10-17 | 2014-09-10 | AB Enzymes Oy | Cellulases, the genes encoding them and uses thereof |
| CN101085985B (zh) | 1996-09-17 | 2012-05-16 | 诺沃奇梅兹有限公司 | 纤维素酶变体 |
| KR20010052736A (ko) | 1998-06-10 | 2001-06-25 | 피아 스타르 | 신규한 만난나제 |
| EP1171581A1 (en) | 1999-03-31 | 2002-01-16 | Novozymes A/S | Lipase variant |
| JP4745503B2 (ja) | 1999-03-31 | 2011-08-10 | ノボザイムス アクティーゼルスカブ | アルカリα−アミラーゼ活性を有するポリペプチド及びそれらをコードする核酸 |
| JP2003518258A (ja) | 1999-12-23 | 2003-06-03 | ファルマシア・アンド・アップジョン・カンパニー | アミロイドβまたはその凝集体の標的としてのナトリウムチャネルの使用に基づくアッセイ方法ならびに診断および治療方法 |
| AU2001240473A1 (en) | 2000-03-08 | 2001-09-17 | Novozymes A/S | Variants with altered properties |
| DE50107849D1 (de) | 2000-07-28 | 2005-12-01 | Henkel Kgaa | Neues amylolytisches enzym aus bacillus sp. a 7-7 (dsm 12368) sowie wasch- und reinigungsmittel mit diesem neuen amylolytischen enzym |
| DE60143086D1 (de) | 2000-08-04 | 2010-10-28 | Genencor Int | Mutierte trichoderma reesei egiii cellulasen, dafür kodierende dna und verfahren zu deren herstellung |
| CN101864406B (zh) | 2001-06-06 | 2016-03-30 | 诺维信公司 | 内切-β-1,4-葡聚糖酶 |
| DE102012214607A1 (de) | 2012-08-16 | 2014-02-20 | Henkel Ag & Co. Kgaa | Wasserlösliche Verpackung mit Bittermittel I |
| DE102012214608A1 (de) | 2012-08-16 | 2014-02-20 | Henkel Ag & Co. Kgaa | Wasserlösliche Verpackung mit Bittermittel II |
| WO2014089386A1 (en) | 2012-12-06 | 2014-06-12 | The Procter & Gamble Company | Soluble pouch comprising hueing dye |
| DE102014222833A1 (de) * | 2014-11-10 | 2016-05-12 | Henkel Ag & Co. Kgaa | Wasch- und Reinigungsmittel mit verbesserter Leistung |
| DE102016214660A1 (de) | 2016-08-08 | 2018-02-08 | Henkel Ag & Co. Kgaa | Wasch- und Reinigungsmittel mit verbesserter Leistung |
-
2018
- 2018-10-11 DE DE102018217399.0A patent/DE102018217399A1/de not_active Withdrawn
-
2019
- 2019-06-18 EP EP19733687.8A patent/EP3864119B1/de active Active
- 2019-06-18 PL PL19733687.8T patent/PL3864119T3/pl unknown
- 2019-06-18 WO PCT/EP2019/065991 patent/WO2020074144A1/de unknown
Also Published As
| Publication number | Publication date |
|---|---|
| DE102018217399A1 (de) | 2020-04-16 |
| PL3864119T3 (pl) | 2023-06-12 |
| EP3864119A1 (de) | 2021-08-18 |
| WO2020074144A1 (de) | 2020-04-16 |
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