EP3864119A1 - Composition liquide comportant un composé de diamide d'acide dihydroxytéréphtalique et une quantité élevée de tensioactif - Google Patents

Composition liquide comportant un composé de diamide d'acide dihydroxytéréphtalique et une quantité élevée de tensioactif

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Publication number
EP3864119A1
EP3864119A1 EP19733687.8A EP19733687A EP3864119A1 EP 3864119 A1 EP3864119 A1 EP 3864119A1 EP 19733687 A EP19733687 A EP 19733687A EP 3864119 A1 EP3864119 A1 EP 3864119A1
Authority
EP
European Patent Office
Prior art keywords
weight
liquid composition
composition according
formula
preferred
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.)
Granted
Application number
EP19733687.8A
Other languages
German (de)
English (en)
Other versions
EP3864119B1 (fr
Inventor
Ulrich Pegelow
Sabine Schuemann
Mareile Job
Frank Meier
Christian Kropf
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Publication date
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Publication of EP3864119A1 publication Critical patent/EP3864119A1/fr
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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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • 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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2003—Alcohols; Phenols
    • C11D3/2041—Dihydric alcohols
    • C11D3/2058—Dihydric alcohols aromatic
    • 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 laundry detergents.
  • Soiling which is normally removed in particular due to the bleaching agent contained, is correspondingly frequently only removed in an inadequate manner.
  • a similar problem also exists for bleach-free color detergents in which the bleach is omitted in order to protect the dyes in the textile and prevent them from fading. In the absence of bleach, this is made more difficult by the fact that instead of removing the so-called bleachable stains, which are normally at least partially removed by the use of peroxygen-based bleach, on the contrary, often one
  • Intensification and / or deterioration of the removability of the soiling is brought about, which should not least be due to initiated chemical reactions, which may consist, for example, in the polymerization of certain dyes contained in the soiling.
  • the polymerizable substances are mainly polyphenolic dyes, preferably flavonoids, in particular from the class of anthocyanidins or anthocyanins.
  • the soiling can have been caused in particular by food products or beverages containing appropriate dyes.
  • the soiling can be, in particular, stains from fruits or vegetables or also 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 publication WO 2016/074936 A1 relate to the use of dihydroxy terephthalic acid derivatives in detergents and cleaning agents to improve the washing or cleaning performance.
  • Dihydroxy terephthalic acid diamides with special substitution on the amide nitrogen atom can improve the stability of liquid surfactant compositions.
  • Dihydroxy terephthalic acid diamides are easily incorporated into liquid surfactant compositions.
  • the washing performance especially with regard to bleachable soiling, is significantly increased.
  • a first object of the present invention is therefore a liquid (and preferred
  • R 1 and R 2 independently of one another for a hydrocarbon radical having at least 3
  • Liquid as used herein in relation to compositions of the invention includes all compositions flowable under standard conditions (20 ° C, 1013 mbar) in the form of
  • compositions in particular, the term also includes non-Newtonian liquids which have a yield point.
  • Granular batches flowable solids such as powder or
  • Mixture of granules are known not to be 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.
  • a “surfactant-containing liquor” is a liquid that can be obtained by using a surfactant-containing agent diluted with at least one solvent (preferably water)
  • Preparation for the treatment of a substrate Fabrics or textiles (such as clothing) can be used as substrates.
  • the preparations according to the invention are preferably used to provide a surfactant-containing liquor in the course of machine cleaning processes, such as those e.g. run by 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 connection with constituents of the compositions described herein, this information does not refer to the absolute amount of molecules but to the type of constituent. "At least one nonionic surfactant” therefore means, for example, one or more different nonionic surfactants, i.e. one or more different types of nonionic surfactants. Together with quantity information, the quantity information relates to the total quantity of the correspondingly designated type of constituent, as already defined above.
  • the water content as defined herein relates to the water content determined by means of the Karl Fischer titration (Angewandte Chemie 1935, 48, 394-396; ISBN 3-540-12846-8 Eugen Scholz).
  • composition according to the invention contains, based on the weight of the liquid composition according to the invention, surfactant in a total amount of 20 to 70% by weight. It is preferred if surfactant is contained in a total amount of 25 to 65% by weight, preferably 30 to 50% by weight, particularly preferably 35 to 45% by weight.
  • the group of surfactants includes the nonionic, anionic, cationic and amphoteric surfactants. According to the invention, the liquid
  • 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 Cs -is alkylbenzenesulfonates, olefin sulfonates, Ci2-i8 alkanesulfonates, Ci2-i8 ester sulfonates, C 12-18 alkyl sulfates, Ci2-18 alkenyl sulfates, Ci2-i8- Fatty alcohol ether sulfates and mixtures thereof. It has been shown that these sulfonate and sulfate surfactants are particularly suitable for producing stable liquid compositions with a flow limit.
  • Liquid compositions which comprise C9-Ci3-alkylbenzenesulfonates and fatty alcohol ether sulfates as anionic surfactant have particularly good, dispersing properties.
  • the surfactants of the sulfonate type are preferably C9-Ci3-alkylbenzenesulfonates, olefin sulfonates, that is to say mixtures of alkene and hydroxyalkanesulfonates, and disulfonates such as are obtained, for example, from Ci2-Ci8 monoolefins having an end or internal double bond by sulfonating with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products is considered.
  • Ci2-Ci8 alkane sulfonates and the esters of a-sulfo fatty acids are also suitable, for example the a-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.
  • alk (en) yl sulfates the alkali and in particular the sodium salts of the sulfuric acid semi-esters of the Ci2-Ci8 fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the Cio-C2o-oxo alcohols and those half esters, are secondary Alcohols of these chain lengths are preferred.
  • the Ci2-Ci6-alkyl sulfates and Ci 2 -Ci5-alkyl sulfates and Ci 4 -Ci5-alkyl sulfates are preferred from the point of view of washing technology. 2,3-Alkyl sulfates are also suitable anionic surfactants.
  • Preferred alk (en) yl sulfates are the salts of the sulfuric acid half-esters of fatty alcohols with 12 to 18 carbon atoms, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the oxo alcohols with 10 to 20 carbon atoms and those half-esters of secondary alcohols of this chain length are preferred.
  • the alkyl sulfates with 12 to 16 carbon atoms and alkyl sulfates with 12 to 15 carbon atoms and alkyl sulfates with 14 and 15 carbon atoms are preferred.
  • 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 C7-C 2i 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 represents a linear or branched, substituted or
  • 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, 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 oil 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 2, 3, 4, 5, 6, 7 or 8 is very particularly preferred.
  • X is a monovalent cation or the nth part of an n-valent cation, preference being given to the alkali metal ions and among them Na + or K + , Na + being extremely preferred. Further cations X + can be selected from NH 4 + , 1 Zn 2+ , 1 Mg 2+ , 1 Ca 2+ , 1 Mn 2+ , and mixtures thereof.
  • Particularly preferred detergents contain an alkyl ether sulfate selected from
  • the degree of ethoxylation indicated represents a statistical mean value, which can be an integer or a fraction 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 contain a mixture of sulfonate and sulfate surfactants.
  • the composition contains at least one C9-13-alkylbenzenesulfonate and optionally additionally at least one C 12-18-fatty alcohol ether sulfate as the anionic surfactant.
  • the liquid composition contains at least one anionic surfactant of the formula (A-3)
  • R ' and R " independently of one another are H or alkyl and together contain 9 to 19, preferably 9 to 15 and in particular 9 to 13 C atoms, and Y + is a monovalent cation or the nth part of an n-valent cation (in particular Na + ) mean.
  • composition can also contain soaps as an anionic surfactant.
  • Saturated and unsaturated fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, palmitic acid, Stearic acid, (hydrogenated) erucic acid and behenic acid and in particular from natural
  • Fatty acids for example coconut, palm kernel, olive oil or tallow fatty acids, derived
  • the anionic surfactants can be in the form of their sodium, potassium or magnesium or
  • ammonium salts are present.
  • the anionic surfactants are preferably in the form of their
  • Further preferred counterions for the anionic surfactants are also the protonated forms of choline, triethylamine, monoethanolamine, triethanolamine or
  • the liquid composition can (preferably together with at least one anionic surfactant) also have at least one nonionic surfactant.
  • the weight ratio of anionic to nonionic surfactant is in the weight ratio range from 1 to 1 to 3 to 1, in particular from 1.5 to 1 to 2.5 to 1 , lies.
  • the nonionic surfactant comprises alkoxylated fatty alcohols, alkoxylated fatty acid alkyl esters,
  • nonionic surfactant in a total amount of 5 to 40% by weight, in particular 7 to 35% by weight, more preferably 5 to 20% by weight, particularly preferably from 10 to 15% by weight.
  • the nonionic surfactant used is preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 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 linearly or preferably methyl-branched in the 2-position or can contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
  • EO ethylene oxide
  • alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow fat or oleyl alcohol, and an average of 5 to 8 EO per mole of alcohol are particularly preferred.
  • the preferred ethoxylated alcohols include, for example, C12-14 alcohols with 4 EO or 7 EO, C9-1 1 alcohol with 7 EO, C13-15 alcohols with 5 EO, 7 EO or 8 EO, Ci2-Ci8 alcohols 5 EO or 7 EO and mixtures of these.
  • Degrees of ethoxylation are statistical averages, which can be an integer or a fraction for a specific product.
  • Preferred alcohol ethoxylates have a restricted one
  • fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • Nonionic surfactants which contain EO and PO (propylene oxide) groups together in the molecule can also be used according to the invention.
  • a mixture of a (more) branched ethoxylated fatty alcohol and an unbranched ethoxylated fatty alcohol such as a mixture of a C16-C18 Fatty alcohol with 7 EO and 2-propylheptanol with 7 EO.
  • the washing, cleaning, aftertreatment or auxiliary washing agent particularly preferably contains a Ci2-Ci8 fatty alcohol with 7 EO or a Ci3-Ci5-oxo alcohol with 7 EO as a nonionic surfactant.
  • the liquid composition particularly preferably contains at least one nonionic surfactant of the formula (N-1)
  • R 3 represents a linear or branched Cs-C-is-alkyl radical, an aryl radical or alkylaryl radical,
  • XO independently of one another for an ethylene oxide (EO) or propylene oxide (PO) group
  • EO ethylene oxide
  • PO propylene oxide
  • 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 C atoms, preferably having 7 to 25 C atoms and in particular having 10 to 19 C atoms.
  • Preferred radicals R 1 are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl radicals and mixtures thereof, the representatives with an even number of carbon atoms being preferred .
  • radicals R 1 are derived from fatty alcohols with 12 to 19 carbon atoms, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or from oxo alcohols with 10 to 19 carbon atoms.
  • AO of formula (N-1) is an ethylene oxide (EO) or propylene oxide (PO) group, preferably an ethylene oxide group.
  • 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. Das
  • Agents according to the invention can contain mixtures of nonionic surfactants which have different degrees of ethoxylation. Surfactants with degrees of alkoxylation / ethoxylation of at least 5 are preferred.
  • particularly preferred fatty alcohol alkoxylates are those of the formula (N-2)
  • compositions according to the invention particularly preferably contain water. It is very particularly preferred if, in the composition, based on its total weight, 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 5 up 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, i-propanol, butanols, glycol, propanediol, butanediol,
  • the solvents are preferably selected from ethanol, n-propanol, i-propanol, butanols, glycol, propanediol, butanediol, methyl propanediol, glycerol, diglycol, propyl diglycol, butyl diglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether,
  • Dipropylene glycol monomethyl ether dipropylene glycol monoethyl ether, methoxytriglycol, ethoxytriglycol, butoxytriglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene-glycol-t-butyl ether, di-n-octyl ether and mixtures of these solvents.
  • Organic solvents are advantageously present in a total amount of 5% by weight to 20% by weight, particularly preferably 10% by weight to 15% by weight, based in each case on the total weight of the composition.
  • composition according to the invention additionally contains at least one catechol compound of the formula (I) in addition to the said amount of surfactant.
  • the catechol compounds according to formula (I) can be provided analogously to the synthesis instructions according to example 2 of WO 2016/074936 A1.
  • the at least one catechol compound according to formula (I) 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 wt .-%, very particularly preferably from 0.3 to 3.0 wt .-%, is contained.
  • the at least one catechol compound of the formula (I) of the liquid composition is selected one or more Catechol compounds of formula (I) in which R 1 and R 2 independently of one another 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 of one another stand for a linear or branched C3-C 2 o-alkyl group, a linear or branched C3-Cio-alkyl group, a linear or branched C3-C6-alkyl group, a linear or branched C3-C2o-alkenyl group, a linear or branched C3-Cio-alkenyl group, a linear or branched C3-C6-alkenyl, a cyclic C3-Cio-alkyl group, a propyl group, a phenyl group or a benzyl group.
  • R 1 and R 2 of the formula (I) very particularly preferably independently of one another stand for 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 iso-propyl are 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 has proven to be particularly advantageous 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 the same.
  • compositions according to the invention preferably additionally contain at least one further active substance.
  • Active substances in the sense of the present invention are in particular:
  • Re-soiling bleaching agents, bleach activators, enzymes, silicone oils, anti-redeposition agents, optical brighteners, graying inhibitors, anti-shrink agents, anti-crease agents,
  • Color transfer inhibitors antimicrobial agents, germicides, fungicides, antioxidants, antistatic agents, ironing aids, swelling and anti-slip agents, UV absorbers, cationic polymers,
  • At least one active substance is preferably selected from enzymes, optical brighteners,
  • Builders solvents, anti-redeposition agents, color transfer inhibitors, preservatives, perfume or mixtures of at least two of the aforementioned active ingredients.
  • 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 is the term corresponding to "mutant” at the nucleic acid level.
  • the precursor or starting molecules can be wild-type enzymes, that is to say those which are obtainable from natural sources. They can also be enzymes that are already variants in themselves, that is, compared to the wild-type molecules have been changed. These include, for example, point mutants, those with changes in the amino acid sequence, over several positions or longer contiguous regions, or else hybrid molecules which are composed of mutually complementary sections of different wild-type enzymes.
  • Amino acid exchanges are to be understood as substitutions of one amino acid for another amino acid. According to the invention, such substitutions are specified in the internationally customary single-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 in the position that is in the sequence of a reference protein Position 320 has a different amino acid. 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 at position 320 contains the amino acid arginine, while the variant under consideration at the position that can be homologated via the amino acid lysine
  • 320K means that any, that is to say usually a naturally prescribed, amino acid at a position which corresponds to position 320 is replaced by a lysine which is located at precisely this point in the present molecule.
  • R320K, L means that the amino acid arginine at position 320 is replaced by lysine or leucine.
  • R320X means that the amino acid arginine in position 320 is replaced by any other amino acid.
  • Amino acid exchanges are not limited to being the only exchanges in which the variant in question 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 include all variants which, in addition to other exchanges with the wild-type molecule, also have the exchanges 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 (including each of the thirteen subclasses).
  • 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; and Eur. J. Biochem. 1999, 264, 610-650.
  • Subtilase names a subset of the serine proteases.
  • the serine proteases or serine peptidases are a subset of the proteases that have serine in the active center of the enzyme that forms a covalent adduct with the substrate.
  • the subtilases (and the serine proteases) are characterized in that they have two further amino acid residues in the active center in addition to said serine with histidine and aspartame.
  • the subtilases can be divided into 6 subclasses, namely the subtilisin family, the thermitase family, the proteinase K family, the family of lantibiotic peptidases, the kexin family and the pyrolysine family.
  • the proteases which are preferably excluded or preferably contained in reduced amounts as part of the compositions according to the invention are endopeptidases (EC 3.4.21).
  • proteolytic activity is present if the enzyme has proteolytic activity (EC 3.4).
  • proteolytic activity EC 3.4
  • Different types of protease activity are known: The three main types are:
  • protease activity can be determined by the method described in Tenside, Volume 7 (1970), pp. 125-132. Accordingly, it is given in PE (protease units).
  • Protease activity of an enzyme can be carried out according to standard methods, such as in particular using BSA as substrate (bovine albumin) and / or using the AAPF method.
  • 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.
  • Amino acid sequences can be assigned to each other. A tabular assignment of the relevant positions is called alignment. Another algorithm available in the prior art is the FASTA algorithm. Sequence comparisons (alignments), especially multiple
  • Sequence comparisons are made with computer programs.
  • the Clustal series cf. for example 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
  • all sequence comparisons were created 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 .
  • nucleotides or amino acid residues are indicated at the same or in an alignment corresponding positions.
  • the broader concept of homology also includes conserved amino acid exchanges in amino acid sequences, that is, 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 given as percent homology or percent similarity.
  • Identity and / or homology information can be made about 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 contain only a few nucleotides or amino acids. Such small areas often have essential functions for the overall activity of the protein. It can therefore make sense to relate sequence matches only to individual, possibly small, areas. Unless otherwise stated, identity or homology information in the present application relates to the total length of the nucleic acid or
  • 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 coating substances in order to protect them against premature
  • compositions according to the invention can be added to the enzymes obtained in any form established according to 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 in a solidified gel or in those of Core-shell type in which an enzyme-containing core is coated with a protective layer impermeable to water, air and / or chemicals.
  • layered layers can additional active ingredients, for example stabilizers, emulsifiers, pigments, bleaches or dyes, are additionally applied.
  • active ingredients for example stabilizers, emulsifiers, pigments, bleaches or dyes.
  • Capsules of this type are applied by methods known per se, for example by churning or roll granulation or in fluid-bed processes.
  • Such granules are advantageously low in dust, for example by applying polymeric film formers, and are stable on 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 , Cellulose extrinase or avicelase.
  • the decisive factor for whether an enzyme is a cellulase in the sense of the invention is its ability to hydrolize 1,4- ⁇ -D-glucosidic bonds in cellulose.
  • Ready-to-use cellulases include, for example, the fungal cellulase preparation rich in endoglucanase (EG) or its preparation
  • Novozymes under the Celluzyme® trade name.
  • the products Endolase® and Carezyme® which are also available from Novozymes, are based on the 50 kD-EG and 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 based at least in part on the 20 kD EG from melanocarpus can also be used, for example.
  • Other cellulases from AB Enzymes are Econase® and Ecopulp®.
  • Other suitable cellulases are from Bacillus sp. CBS 670.93 and CBS 669.93, where the from Bacillus sp. CBS 670.93 from that
  • Danisco / Genencor is available under the trade name Puradax®.
  • Other usable commercial products from Danisco / Genencor are “Genencor detergent cellulase L” and lndiAge®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, which are disclosed in the international patent application WO 98/12307, cellulases from Melanocarpus, in particular Melanocarpus albomyces, which are disclosed in the international patent application WO 97/14804, cellulases of the EGIII type from Trichoderma reesei, which in the European
  • Patent application EP 1 305 432 are disclosed or variants obtainable therefrom, in particular those which are disclosed in European patent applications EP 1240525 and EP 1305432, and cellulases which are disclosed in international patent applications WO 1992006165, WO 96/29397 and WO 02 / 099091. Reference is therefore expressly made to their respective disclosures, and their disclosure content in this regard 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 that have a homology of over 80% (increasingly preferred from Over 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 90.5%, 91%, 91, 5%, 92%, 92.5 %,
  • the from Melanocarpus sp. or Myriococcum sp. Available 20K cellulase is known from international patent application WO 97/14804. 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 genetically produced
  • Trichoderma reseei transformants are produced.
  • Cellulases which have a homology of more than 80% are also usable in the context of the present invention %, 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%) for 20K cellulase.
  • K20 cellulase is preferably used in amounts such that a composition according to the invention has a cellulolytic activity of 1 NCU / g to 500 NCU / g (can be determined by the hydrolysis of 1% by weight carboxymethyl cellulose at 50 ° C. and neutral pH and determination of the reducing substances released in the process Sugar using dinitrosalicylic acid, as described by MJBailey et al. In Enzyme Microb. Technol. 3: 153 (1981); 1 NCU defines the
  • the composition according to the invention can optionally contain further cellulases.
  • a liquid composition according to the invention preferably contains 0.001 mg to 0.5 mg, in particular 0.02 mg to 0.3 mg, of cellulolytic protein per gram of the total
  • the 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).
  • BCA method Pierce Chemical Co., Rockford, IL
  • biuret method AG Gornall, CS Bardawill and MM David, J. Biol. Chem. 177 , 751-766, 1948).
  • the 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 which is 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.
  • compositions according to the invention particularly preferably comprise at least one lipase which is naturally present in a microorganism of the type Thermomyces lanuginosus or is derived by mutagenesis from the aforementioned lipases which are naturally present in Thermomyces lanuginosus.
  • the lipase is a separate enzyme of the microorganism.
  • the lipase can therefore be found in the microorganism of one
  • Nucleic acid sequence are expressed, 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 derived from the wild-type form of the
  • Microorganism can be isolated from this.
  • a lipase that is not naturally present in the microorganism or the nucleic acid sequence coding for it would have been introduced into the microorganism in a targeted manner using genetic engineering methods, so that the
  • Microorganism would have been enriched with the lipase or the nucleic acid sequence coding for it.
  • a lipase that is naturally present in a microorganism of the species Thermomyces lanuginosus or Rhizopus oryzae or Mucor javanicus may have been produced recombinantly by another organism.
  • the fungus Thermomyces lanuginosus (also known as Humicola lanuginosa) belongs to the class of Eurotiomycetes (subclass Eurotiomycetidae), here to the order of the Eurotiales and here to the family Trichocomaceae and the genus Thermomyces.
  • the fungus Rhizopus oryzae belongs to the class of the Zygomycetes (subclass Incertae sedis), here to the order Mucorales and here again to the family Mucoraceae and the genus Rhizopus.
  • the fungus Mucor javanicus also belongs to the class of the Zygomycetes (subclass Incertae sedis), here to the order Mucorales and again to the Mucoraceae family, and then to the genus Mucor.
  • the names Thermomyces lanuginosus, Rhizopus oryzae and Mucor javanicus are the biological species names within the respective genus.
  • Preferred lipases according to the invention are the lipase enzymes available from Amano Pharmaceuticals under the names Lipase M-AP10®, Lipase LE® and Lipase F® (also Lipase JV®).
  • Lipase F® is naturally present in Rhizopus oryzae.
  • Lipase M-AP10® for example, is naturally present in Mucor javanicus.
  • compositions of a very particularly preferred embodiment of the invention contain at least one lipase which is selected from at least one or more polypeptides with an amino acid sequence which is at least 90% (and increasingly preferred 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%) for the wild-type lipase from the strain DSM 4109 Thermomyces lanuginosus is identical. It is again preferred if, based on said wild-type lipase from strain DSM 4109, there is at least the amino acid change N
  • lipases derived from the wild-type lipase from strain DSM 4109 are preferably 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 publication WO 00/60063 A1. Reference is expressly made in full to the disclosure in publication WO 00/60063 A1.
  • At least one lipase in the compositions of the invention which is derived from the wild-type lipase from strain DSM 4109 and in which, based on said wild-type lipase, at least one substitution of an electrically neutral or negatively charged amino acid by a positively charged amino acid was carried out.
  • the charge is determined in water at pH 10.
  • Negative amino acids in the sense of the invention are E, D, Y and C.
  • Positively charged amino acids in the sense of the invention are R, K and H, in particular R and K.
  • Neutral amino acids in the sense of the invention are G, A, V, L, I , P, F, W, S, T, M, N, Q and C if C forms a disulfide bridge.
  • At least one of the following amino acid exchanges is present in positions D96L, T213R and / or N233R, particularly preferably T213R and N233R.
  • a most preferred lipase is commercially available under the trade name Lipex®
  • Lipase Lipex® 100 L (ex Novozymes A / S, Denmark) is particularly preferred.
  • Preferred compositions are characterized in that, based on the total weight of the composition, said lipase enzyme from Lipex®
  • the liquid compositions according to the invention can additionally contain at least one mannanase as enzyme.
  • One contained in the composition according to the invention in particular in a washing and cleaning agent for textiles preferred according to the invention)
  • mannanase As part of its mannanase activity, mannanase catalyzes the hydrolysis of 1,4-beta-D-mannosidic bonds in mannans, galactomannans, glucomannans and
  • Galactoglucomannans Said mannanase enzymes according to the invention are, according to the enzyme nomenclature, as E.C. 3.2.1.78 classified.
  • the mannanase activity of a polypeptide or enzyme can be according to the literature
  • Test methods can be determined. For example, a test solution is placed in 4 mm diameter holes of an agar plate containing 0.2% by weight of AZGL galactomannan (carob), i.e. Substrate for the endo-1, 4-beta-D-mannanase essay, available from the company under catalog number I-AZGMA
  • compositions according to the invention contain, for example, mannanase, which is marketed under the name Mannaway® by Novozymes.
  • 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, based on the
  • Total weight of the mannanase composition in a total amount of 0.01 to 1.0% by weight, in particular 0.02 to 0.1% by weight.
  • Mannanase polypeptides from strains of the Thermoanaerobacter group, such as caldicellulose ruptor, are preferably suitable according to the invention. Can also be used within the scope of the invention
  • Mannanase polypeptides of the fungi Humicola or Scytalidium in particular the species Humicola insolens or Scytalidium thermophilum.
  • compositions according to the invention as mannanase enzyme have at least one mannanase polypeptide from gram-positive alkalophilic strains of Bacillus, in particular selected from at least one member of the group from Bacillus subtilis, Bacillus ientus, Bacillus clausii, Bacillus agaradhaerens, Bacillus brevis, Bacillus
  • 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 member of the group from Bacillus sp. 1633, Bacillus sp. AAI12, Bacillus clausii, Bacillus agaradhaerens and Bacillus licheniformis.
  • a preferred mannanase according to the invention is selected from at least one representative from the group that is formed from
  • polypeptides comprising an amino acid sequence that is at least 90% (more preferably at least 90.5%, 91%, 91, 5%, 92%, 92.5%, 93%, 93.5%, 94%, 94 , 5%, 95%, 95.5%,
  • said preferred mannanase in a total amount of 0.01 to 1.0% by weight, in particular 0.02 to 0.1% by weight, in each case based on the total weight of the composition in which composition according to the invention is included.
  • the liquid surfactant composition according to the invention contains, in addition to the preferred protease of the alkaline protease type from Bacillus Ientus DSM 5483 or in addition to the protease which is sufficiently similar to this (based on the sequence identity) and which has several of these changes in combination, additionally at least one a-amylase .
  • a-Amylases (EC 3.2.1.1) hydrolyze as internal enzyme a-1, 4-glycosidic bonds of starch and starch-like polymers. This a-amylase activity is measured, for example, according to the applications WO 97/03160 A1 and GB 1296839 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, for example in the
  • Another activity determination method is measurement using the Quick-Start ® test kit from Abbott, Abott Park, Illinois, USA.
  • Surfactant compositions is the cleaning of textiles. Because laundry detergents and cleaning agents for textiles mainly have alkaline pH values, a-amylases, which are active in the alkaline medium, are used in particular. These 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 abundance of variants that have been derived via mutagenesis and depending on
  • Examples of this are the a-amylases from Bacillus licheniformis, from B. amyloliquefaciens and from B. stearothermophilus as well as their 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.
  • a-amylases from other organisms are further developments of a-amylase sold under the trade names Fungamyl.RTM ® from Novozymes from Aspergillus niger and A. oryzae.
  • Fungamyl.RTM ® from Novozymes from Aspergillus niger and A. oryzae.
  • Another commercial product is the Amylase-LT ® .
  • WO 00/60060 A2 and WO 01/66712 A2 which have been registered by Novozymes.
  • WO 96/23873 A1 describes several different point mutations in a total of more than 30 different positions in four different wild-type amylases and claims them for all amylases with at least 80% identity to one of these four; they should have changed enzymatic properties with regard to thermal stability, oxidation stability and calcium dependence.
  • the application WO 00/60060 A2 also names a large number of possible ones
  • WO 00/60060 A2 called a-amylases have been mutated.
  • WO 96/23873 A1 concretely shows the possibility of replacing an M in position 9 in the a-amylases mentioned according to the AA560 count with an L, in position 202 M for L and that in positions 182 and 183 ( or 183 and 184) lying amino acids.
  • WO 00/60060 A2 specifically discloses the
  • Amino acid variation N195X (basically against any other amino acid).
  • WO 01/66712 A2 discloses, inter alia, the amino acid variations R1 18K, G186X (including, in particular, the G186R exchange not relevant here), N299X (including, in particular, the N299A exchange not relevant here), R320K, E345R and R458K.
  • the liquid surfactant composition according to the invention very particularly preferably contains, in addition to the preferred protease of the alkaline protease type from Bacillus lentus DSM 5483 or a protease which is sufficiently similar to this (based on the sequence identity) and which has several of these changes in combination, additionally at least one a-amylase , which has a higher activity at temperatures between 10 and 20 ° C than the amylase with the trade name "Stainzyme 12 L" from Novozymes.
  • Preferred liquid compositions according to the invention contain a-amylase in one
  • Total amount 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 preferred from the substance classes of distyrylbiphenyls, the stilbenes, the diamino-2,2-stilbenedisulfonic acids 4.4, the coumarins, the dihydroquinolinones, the 1, 3-diaryl pyrazolines, naphthalimides of the benzoxazole systems, the benzisoxazole systems, the benzimidazole systems, the heterocycle-substituted pyrene derivatives and mixtures thereof.
  • These substance classes of optical brighteners have a high stability, a 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, are particularly good and stable '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- Thiophendiyl) bis [5-1, 1-
  • 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 1,000 to 15,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molar masses of 1,000 to 10,000 g / mol, and particularly preferably 1,000 to 5,000 g / mol, can in turn be preferred from this group.
  • Copolymers of polycarboxylates are furthermore suitable, in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid.
  • the polymers can also contain allylsulfonic acids, such as allyloxybenzenesulfonic acid and methallylsulfonic acid, as monomers.
  • silicates As builders, which can be contained in the composition according to the invention, silicates, aluminum silicates (in particular zeolites), carbonates, salts of organic di- and polycarboxylic acids and mixtures of these substances are to be mentioned in particular.
  • 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, especially glutamic acid-N, N-diacetic acid (GLDA) and methylglycine-N, N-diacetic acid (MGDA), as well as 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 are preferably a
  • the short-chain polyacrylates which have molar masses of 1,000 to 10,000 g / mol, and particularly preferably 1,000 to 5,000 g / mol, can in turn be preferred from this group.
  • Copolymers of polycarboxylates are furthermore suitable, in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid.
  • the polymers can also contain allylsulfonic acids, such as allyloxybenzenesulfonic acid and methallylsulfonic acid, as monomers.
  • Soluble builders such as
  • Acrylic polymers with a molecular weight of 1,000 to 5,000 g / mol are used.
  • liquid compositions according to the invention can additionally additionally
  • the liquid composition preferably additionally contains at least one dirt-repellent polymer (also known as SRP).
  • SRP dirt-repellent polymer
  • the effect of SRP becomes particularly clear if a textile is soiled that has already been washed several times with an agent that contains this oil and fat-dissolving component.
  • the preferred oil and fat-dissolving components include, for example, non-ionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxyl groups from 15 to 30% by weight and of hydroxypropoxyl groups from 1 to 15% by weight, in each case based on the non-ionic
  • Cellulose ethers as well as the polymers of phthalic acid and / or terephthalic acid known from the prior art or of their derivatives with monomeric and / or polymeric diols, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives thereof. These are commercially available, for example, under the trade name Texcare ® .
  • Anti-redeposition agents are particularly selected from copolymers based on
  • Polyethyleneimine based on polyvinyl acetate and based on polyethylene glycol.
  • the liquid composition can preferably also contain at least one polymer that inhibits color transfer.
  • Such color transfer inhibitors are preferably present 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 comprise polymers of vinylpyrrolidone, vinylimidazole, vinylpyridine-N - Oxide or copolymers of these are.
  • Graying inhibitors have the task of keeping the dirt detached from the textile fibers suspended in the liquor.
  • Water-soluble colloids of mostly organic nature are suitable for this, 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 also be used, for example aldehyde starches.
  • Cellulose ethers such as carboxymethyl cellulose (sodium salt),
  • Methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof, for example in amounts of 0.1 to 5% by weight, based on the composition according to the invention.
  • the color transfer inhibitor is a polymer or copolymer of cyclic amines such as vinyl pyrrolidone and / or vinyl imidazole.
  • Polymers useful as a color transfer inhibitor 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 vinylpyridone and vinylpyridone as well as mixtures thereof.
  • Polyvinylpyrrolidone (PVP), polyvinylimidazole (PVI) or copolymers of vinylpyrrolidone and vinylimidazole (PVP / PVI) are particularly preferred as color transfer inhibitors used.
  • 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,
  • copolymers of vinylpyrrolidone and vinylimidazole 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 extremely preferred color transfer inhibitor is polyethylene glycol-modified
  • Copolymers of vinyl pyrrolidone and vinyl imidazole which are available, for example, from BASF under the name Sokalan® HP 66.
  • Preferred liquid compositions of the invention additionally contain at least one
  • a “bluing agent” is a blue to violet dye that dyes blue to violet to increase the whiteness of white textiles.
  • a method of determining the presence of a bluing agent is the colorimetric measurement of the Lab values, as described in the
  • a bluing agent is present, for example, if the blue to violet dye produces a DE * value on the textile according to the aforementioned test method of at least 2.0 DE * units, preferably at least 3.0 DE * units, particularly preferably at least 4.0 DE * units .
  • the blueing agent in solution or dispersion (ethanol, at 20 ° C.) has an absorption maximum in a wavelength range from 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 1,000 L / mol / cm.
  • the bluing agent is preferably not charged or has an anionic charge, and the dye is particularly preferably nonionic.
  • the bluing agent is preferably a compound of the following general formula BL-1:
  • F - L - CO2M (BL-1) in which F stands for the monoazo dye.
  • the extinction coefficient mentioned above relates to this dye F in the compound F-H in an ethanolic solution.
  • L according to formula BL-1 is an organic group which connects the monoazo dye F with the carboxyl group CO2M.
  • This connecting group L preferably has a molecular weight in the range from 14 to 1000 g / mol, in particular from 14 to 600 g / mol particularly 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-i-20-alkyl group which may have ether and / or ester and / or amide groups as branching sites.
  • the alkyl chain can be substituted according to the invention. Possible substituents are -OH, -CN, -NO2, -SO2CH3, -CL, -BR.
  • M stands for any counter ion, usually hydrogen, sodium or potassium.
  • the bluing agent comprises the following general formula BL-2:
  • R is a C 2-12 alkyl radical 1- 20, or C, which optionally contains ether and / or ester and / or amide groups as the branching points and the further Aklylkette
  • R 1 and R 2 are each independently selected and represent, for example, hydrogen; they are preferably each independently selected from electron-withdrawing groups such as, for example, -CN, -NO 2 , -SO 2 CH3, -CL, -BR;
  • Z is selected from an electron-withdrawing group and is preferably selected from cyano-, sulfamoyl, N: N-diethylsulfamoyl, N-ethylsulfamoyl, trifluoromethyl, ethylsulfonyl, nitrosylfonyl, N-methylsulfamoyl, chloro and bromo; in particular Z is a nitro group;
  • Y is hydrogen, a short (C-) alkyl radical, halogen, -NHCOR, preferably hydrogen, -CH3 or -CI;
  • X is hydrogen, a short (C 1-4 ) alkoxy chain or halogen, especially hydrogen, methoxy, ethoxy or chloride.
  • Examples of short-chain alkyl and / or alkoxy radicals are methyl, ethyl, n-propyl, n-butyl, ethoxy and methoxy.
  • Examples of the optionally substituted, short-chain alkyl radicals, which are represented by R in the general formula 2, are ⁇ -hydroxyethyl, ⁇ -cyanoethyl, ⁇ - (methoxy or ethoxy) ethyl, g-methoxypropyl, benzyl or ⁇ -phenylethyl, ß-methoxycarbonyl-ethyl or ß-acetoxyethyl.
  • the bluing agent according to the invention can have, for example, the following general formula BL-3:
  • Particularly preferred bluing agents are Basic Violet 10, Liquitint® Violet 200, Liquitint Violet CT or compounds of the following formula:
  • Subject of the invention can be in pre-portioned form (portion).
  • composition according to the invention is present in a container made 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 total agent.
  • 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 envelops at least one according to the invention
  • the water solubility of the material can be measured using a square frame
  • Beaker with a circular bottom surface (Schott, Mainz, beaker 1000 mL, low form) immersed 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 aligned parallel to the bottom surface of the beaker in such a way that the lower edge of the frame runs along the radius of the bottom surface of the beaker and the center of the lower edge of the frame is arranged above the center of the radius of the beaker base.
  • the material should dissolve within 600 seconds while stirring (stirring speed magnetic stirrer 300 rpm, stirring rod: 6.8 cm long, diameter 10 mm) in such a way that no individual solid film particles are 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 pm (particularly preferably of at most 120 pm). Preferred walls are accordingly made of a water-soluble film and have a thickness of at most 150 pm (particularly preferably of at most 120 pm, very particularly preferably of at most 90 pm).
  • Such portions can be made by either vertical form fill sealing (VFFS) or thermoforming.
  • Walls of at least one chamber are particularly preferably created by sealing at least one film of water-soluble material, in particular by sealing in the context of a form-fill-seal process.
  • thermoforming process generally includes forming a first layer of a water-soluble sheet material to form at least one bulge for receiving at least one composition of the invention therein, filling the
  • composition in the respective bulge, covering the bulges filled with the composition with a second layer of a water-soluble film 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 mixtures.
  • the sheath can be formed from one or two or more layers of the water-soluble film material.
  • the water-soluble film material of the first layer and the further layers, if present, can be the same or different.
  • the water soluble material is a polyvinyl alcohol or a
  • Suitable water-soluble films as water-soluble material are preferably based on a
  • Polyvinyl alcohol or a polyvinyl alcohol copolymer whose molecular weight is in each case 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 route of synthesis is not possible. The same applies to polyvinyl alcohol copolymers which are produced from polyvinyl acetate copolymers accordingly.
  • 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 name for polymers of the general structure
  • Degrees of polymerization in the range of approximately 100 to 2500 (molar masses of approximately 4000 to 100,000 g / mol) are offered, have degrees of hydrolysis of 98 to 99 mol% or 87 to 89 mol%, and therefore still contain a residual content of acetyl groups .
  • 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 safe and are at least partially biodegradable. Water solubility can be achieved by post-treatment with aldehydes (acetalization)
  • the polyvinyl alcohol coatings are largely impermeable to gases such as oxygen, nitrogen, helium, hydrogen, carbon dioxide, but leave water vapor
  • the water-soluble material at least partially comprises a polyvinyl alcohol, the degree of hydrolysis of which is 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol -%.
  • the water-soluble material consists of at least 20% by weight, particularly preferably at least 40% by weight, very particularly preferably at least 60% by weight and in particular at least 80% by weight, of a polyvinyl alcohol, the 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 trademark Mowiol® (Clariant).
  • Polyvinyl alcohols which are particularly suitable in the context of the present invention are, for example, Mowiole 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 comprise dicarboxylic acids as further monomers.
  • Suitable dicarboxylic acids are itaconic acid, malonic acid, succinic acid and mixtures thereof, itaconic acid being preferred.
  • polyvinyl alcohol copolymers comprise, 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 ester, methacrylic acid ester or mixtures thereof.
  • the water solubility of polyvinyl alcohol polymer can be changed by post-treatment with aldehydes (acetalization) or ketones (ketalization).
  • Polyvinyl alcohols which have been acetalized or ketalized with the aldehyde or keto groups of saccharides or polysaccharides or mixtures thereof have turned out to be particularly preferred and particularly advantageous because of 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 the desired values.
  • PVAL films are largely impenetrable for gases such as oxygen, nitrogen, helium, hydrogen, carbon dioxide, but allow water vapor to pass through.
  • the film material suitable as a water-soluble material can additionally have 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.
  • the film material suitable as a water-soluble material can additionally contain polymers selected from the group comprising acrylic acid-containing polymers, polyacrylamides, oxazoline polymers, Polystyrene sulfonates, polyurethanes, polyesters, polyether polylactic acid, and / or mixtures of the above polymers may be added.
  • Foil material used as the water-soluble material of the walls has a preferred thickness in a range from 65 to 180 gm, in particular from 70 to 150 gm, more preferably 75 to 120 gm.
  • Product safety preferably incorporates a bittering agent.
  • a bittering agent Corresponding embodiments of the water-soluble material with bittering agent are described in the publications EP-B1-2 885 220 and EP-B1-2 885 221.
  • 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 which are sold under the name Monosol M8630 by MonoSol LLC.
  • Other suitable films include films with the designation Solublon® PT, Solublon® KA, Solublon® KC or Solublon® KL from Aicello Chemical Europe GmbH or the films VF-HP from Kuraray, or HiTorrent SH2312 from Nippon Gohsei.
  • a second subject of the invention is a method for substrate treatment, in particular textile treatment, comprising the process steps
  • inventive composition of the first subject of the invention are pretreated before step (a).
  • Processes for cleaning textiles are generally characterized in that various cleaning-active substances are applied to the items to be cleaned and washed off after the contact time in several process steps, or in that the items to be cleaned are treated in some other way with a detergent or a solution of this agent.
  • step (a) it is preferred in step (a) to provide an aqueous liquor by mixing 5.0 to 20.0 L of water with 5 to 75 g (in particular 10 to 55 g) of a composition of the first subject of the invention.
  • step (b) the aqueous liquor is set to temperatures of 60 ° C. or less, for example 40 ° C. or less.
  • 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 items 1 to 22 (vide infra)), for
  • Textile treatment in particular for cleaning textiles.
  • an aqueous liquor obtainable by mixing 5.0 to 20.0 L of water with 5 to 75 g (in particular 10 to 55 g) of a composition of the first subject of the invention.
  • Liquid composition in particular for textile washing, each based on their total weight
  • R 1 and R 2 independently of one another for a hydrocarbon radical having at least 3
  • Liquid composition according to item 1 characterized in that surfactant in one
  • Liquid composition according to one of the preceding points, characterized in that it contains at least one anionic surfactant.
  • Liquid composition according to item 3 characterized in that, based on the weight of the composition, a total amount of anionic surfactant from 15 to 35% by weight, in particular from 20 to 30% by weight, is contained.
  • Liquid composition according to one of items 3 or 4 characterized in that at least one anionic surfactant selected from the group consisting of Cs -is-alkylbenzenesulfonates, olefin sulfonates, Ci2-i8-alkanesulfonates, Ci2-i8-ester sulfonates, C12-18-alkylsulfates , Ci2-18 alkenyl sulfates, Ci2-i8 fatty alcohol ether sulfates and mixtures thereof.
  • Liquid composition according to one of items 3 to 5, characterized in that it contains at least one anionic surfactant of the formula (A-3),
  • R ' and R " independently of one another are H or alkyl and together contain 9 to 19, preferably 9 to 15 and in particular 9 to 13 C atoms, and Y + is a monovalent cation or the nth part of an n-valent cation (in particular Na + ) mean.
  • Liquid composition according to one of the preceding points, characterized in that it contains at least one nonionic surfactant.
  • Liquid composition according to item 7 characterized in that, based on the weight of the composition, a total amount of nonionic surfactant of 5 to 20% by weight, in particular 10 to 15% by weight, is contained.
  • Liquid composition according to one of items 7 or 8, characterized in that at least one nonionic surfactant according to formula (N-1) is contained
  • R 3 represents a linear or branched Cs-C-is-alkyl radical, an aryl radical or alkylaryl radical,
  • XO independently of one another for an ethylene oxide (EO) or propylene oxide (PO) group
  • EO ethylene oxide
  • PO propylene oxide
  • Liquid composition according to one of items 1 to 9, characterized in that the weight ratio of anionic to nonionic surfactant is in the weight ratio range from 1 to 1 to 3 to 1, in particular from 1.5 to 1 to 2.5 to 1.
  • Liquid composition according to one of the preceding points, characterized in that water (preferably in a total amount of 5 and 45% by weight, more preferably 10 and 40% by weight, more preferably 5 to 30% by weight, very particularly preferably of 8 to 25% by weight) is contained.
  • Liquid composition according to one of the preceding points characterized in that at least one organic solvent (in particular in a total amount from 5% by weight to 20% by weight, particularly preferably from 10% by weight to 15% by weight) in each case based on the total weight of the composition) is included.
  • Liquid composition according to one of the preceding points characterized in that, according to formula (I), R 1 and R 2 independently of one another 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.
  • Liquid composition according to one of the preceding points, characterized in that according to formula (I) R 1 and R 2 independently of one another for a linear or branched C3-C2o-alkyl group, a linear or branched C3-Cio-alkyl group, a linear or branched C3 -C6-alkyl group, a linear or branched C3-C 2 o-alkenyl group, a linear or branched C3-Cio-alkenyl group, a linear or branched C3-C6-alkenyl group, a cyclic C3-Cio-alkyl group, a propyl group, a phenyl group or a benzyl group.
  • R 1 and R 2 independently of one another for a linear or branched C3-C2o-alkyl group, a linear or branched C3-Cio-alkyl group, a linear or branched C3 -C6-
  • Liquid composition according to one of the preceding points, characterized in that, according to formula (I), R 1 and R 2 independently of one another for n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, n -Pentyl, iso-pentyl, neopentyl, tert-pentyl, 2,2-dimethylpropyl, 1, 2-dimethylpropyl, cyclopentyl, n-hexyl, iso-hexyl, neo-hexyl, cyclohexyl, allyl, but-2-enyl or benzyl .
  • R 1 and R 2 independently of one another for n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, n -Pentyl, iso-pent
  • Liquid composition according to one of the preceding points, characterized in that according to formula (I) R 1 and R 2 are the same.
  • Liquid composition according to one of the preceding points, characterized in that, based on the total weight of the composition, the at least one
  • Catechol compound according to formula (I) in a total amount of 0.05 to 10.0% by weight, more preferably 0.1 to 4% by weight, more preferably 0.2 to 2.0% by weight, very particularly preferably from 0.3 to 3.0% by weight.
  • Liquid composition according to one of the preceding points characterized in that at least one enzyme, in particular at least one lipase, is additionally present.
  • Liquid composition according to one of the preceding points characterized in that it additionally contains at least one polymer which inhibits color transfer.
  • Liquid composition according to one of the preceding points, characterized in that it additionally contains at least one dirt-repellent polymer (SRP).
  • SRP dirt-repellent polymer
  • Liquid composition according to one of the preceding points, characterized in that it additionally contains at least one optical brightener.
  • Liquid composition according to one of the preceding points, characterized in that it additionally contains at least one bluing agent.
  • Process for substrate treatment comprising the process steps
  • an aqueous liquor obtainable by mixing 0.5 L to 40.0 L water with 0.5 to 100 g of a liquid composition according to one of items 1 to 22, for
  • compositions in Table 1 were prepared by mixing the components in a conventional manner.
  • compositions were then stored at 0 ° C for 8 weeks and then assessed visually.
  • Formula V1 not according to the invention showed a clear one

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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)

Abstract

Composition liquide, en particulier pour le lavage de textiles contenant à chaque fois par rapport à son poids total - une quantité totale de 20 à 70 % en poids de tensioactif , et - au moins un composé de catéchol de formule (I), dans laquelle R1 et R2 indépendamment l'un de l'autre représentent un radical hydrocarboné comportant au moins 3 atomes de carbone. Procédé pour le traitement d'un substrat comprenant les étapes de procédé (a) mise à disposition d'un bain aqueux par le mélange de 0,5 L à 40,0 L d'eau avec 0,5 à 100 g de ladite composition, et (b) mise en contact d'un substrat, en particulier d'un textile, avec le bain aqueux préparé selon (a). L'invention concerne également l'utilisation d'un bain aqueux, pouvant être obtenu par le mélange 0,5 L à 40,0 L d'eau avec 0,5 à 100 g de ladite composition pour le traitement de textiles, en particulier pour le nettoyage de textiles.
EP19733687.8A 2018-10-11 2019-06-18 Composition liquide comportant un composé de diamide d'acide dihydroxytéréphtalique et une quantité élevée de tensioactif Active EP3864119B1 (fr)

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 (fr) 2018-10-11 2019-06-18 Composition liquide comportant un composé de diamide d'acide dihydroxytéréphtalique et une quantité élevée de tensioactif

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EP3864119A1 true EP3864119A1 (fr) 2021-08-18
EP3864119B1 EP3864119B1 (fr) 2023-03-01

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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

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DE102016214660A1 (de) 2016-08-08 2018-02-08 Henkel Ag & Co. Kgaa Wasch- und Reinigungsmittel mit verbesserter Leistung

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WO2020074144A1 (fr) 2020-04-16
EP3864119B1 (fr) 2023-03-01
PL3864119T3 (pl) 2023-06-12

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