WO2020074140A1 - Détergent liquide contenant un composé catéchol - Google Patents

Détergent liquide contenant un composé catéchol Download PDF

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Publication number
WO2020074140A1
WO2020074140A1 PCT/EP2019/065980 EP2019065980W WO2020074140A1 WO 2020074140 A1 WO2020074140 A1 WO 2020074140A1 EP 2019065980 W EP2019065980 W EP 2019065980W WO 2020074140 A1 WO2020074140 A1 WO 2020074140A1
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WIPO (PCT)
Prior art keywords
weight
liquid
particularly preferably
formula
liquid composition
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PCT/EP2019/065980
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German (de)
English (en)
Inventor
Mareile Job
Ulrich Pegelow
Simone BERGMANN-DALKILIC
Frank Meier
Christian Kropf
Eva SCHIMANSKI
Original Assignee
Henkel Ag & Co. Kgaa
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Priority to EP19732318.1A priority Critical patent/EP3864120A1/fr
Publication of WO2020074140A1 publication Critical patent/WO2020074140A1/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
    • 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
    • C11D17/042—Water soluble or water disintegrable containers or substrates containing cleaning compositions or additives for cleaning compositions
    • C11D17/045—Multi-compartment
    • 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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0084—Antioxidants; Free-radical scavengers
    • 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
    • C11D3/34—Organic compounds containing sulfur

Definitions

  • the present invention relates to the use of catechol compounds which are used together with (preferably concentrated), liquid detergent compositions to improve the washing and cleaning performance.
  • the polymerizable substances are mainly polyphenolic dyes, preferably flavonoids, in particular from the class of anthocyanidins or anthocyanins.
  • the soiling can in particular be caused by
  • 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.
  • Gallic acid esters such as propyl gallate in detergents and cleaning agents for improved removal of soils which contain polymerizable substances are known.
  • the international patent application WO 2013/092263 A1 relates to the improvement of the performance of detergents and cleaning agents through the use of oligohydroxybenzoic acid amides.
  • the German patent applications DE 102016214660 A1 and DE 102014222833 relate to the use of dihydroxy terephthalic acid derivatives in detergents and cleaning agents to improve the washing or cleaning performance.
  • the detergents and cleaning agents in these publications have an alkaline pH.
  • Composition forms. This discoloration is undesirable.
  • Dihydroxy terephthalic acid diamides the washing or cleaning performance of liquid (especially concentrated) detergents, particularly with regard to bleachable soiling, can be significantly improved. If said catechol compound is incorporated into an aqueous composition with a pH of at most pH 7, undesirable rust-brown to red discoloration of the detergents is prevented at the same time. The discoloration is particularly pronounced in the case of liquid surfactant compositions containing alkanolamine.
  • a multicomponent detergent is preferred, which comprises said liquid, acidic catechol derivative composition in combination with a liquid, alkaline, alkanolamine-containing composition.
  • a first subject of the present invention is therefore the use of at least one catechol compound of the formula (I)
  • X represents a sulfone group -SO2R 1 or an amide group -C-NH-R 2 ,
  • Y 1 and Y 2 stand for a hydrogen atom, for a sulfone group -SO2R 3 or
  • R 1 and R 3 independently represent hydroxy, a group -OZ + , or a group
  • R a and R b independently represent hydrogen or a cyclic or acyclic, straight-chain or branched-chain, aliphatic or aromatic
  • Hydrocarbon radical with 1 to 20 carbon atoms the backbone of which may be broken by one or more non-adjacent heteroatoms (in particular selected from O and / or N) and / or which is substituted on C-atoms not connected with heteroatoms with OH groups or NH2 groups
  • R a and R b can also be part of a heterocycle formed from them and the N atom bound to them,
  • R ' , R “ and R " independently of one another represent H or a straight-chain or branched-chain aliphatic hydrocarbon radical 1 to 3, preferably 1 to 2 carbon atoms and A represent an anion, in a liquid, aqueous composition with a pH (at 20 ° C.) of pH 1 to 6.9, in particular pH 4 to 5.5, to improve the washing or cleaning performance and / or to avoid rust-brown to red discoloration of liquid detergents.
  • a preferred first subject of the present invention is the use of at least one catechol compound of the formula (Ia) wherein
  • R 2 and R 4 independently of one another for a hydrocarbon radical having 1 to 20
  • carbon atoms which is optionally substituted with at least one radical selected from hydroxy, (Ci-C4) alkoxy, (Ci-C4) alkoxy (CH2CH20) n -, -NR ' R “ or
  • R ' , R " and R " independently of one another represent H or a straight-chain or branched-chain aliphatic hydrocarbon radical having 1 to 3, preferably 1 to 2 carbon atoms and X- stand for an anion,
  • aqueous composition with a pH (at 20 ° C) of pH 1 to 6.9, in particular pH 4 to 5.5, to improve the washing or cleaning performance and / or to avoid a rusty brown to red Discoloration of liquid, detergent.
  • 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).
  • the pH is determined at 20 ° C.
  • Liquid as used herein in relation to compositions according to the invention includes all compositions which are flowable under standard conditions (20 ° C., 1013 mbar) in the form of liquids and in particular includes liquids, gels and pasty compositions. In particular, the term also includes non-Newtonian liquids which have a yield point. As is known, granular mixtures (flowable solids such as powders or granules) are not liquids and are therefore not included.
  • At least one refers to 1 or more, for example 1, 2, 3, 4, 5, 6, 7, 8, 9 or more. In connection with components of those described herein
  • 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.
  • the quantity information relates to the total quantity of the correspondingly designated type of constituent, as already defined above.
  • a second subject of the invention is a liquid composition for providing a textile detergent, the liquid composition having a pH (20 ° C.) from 1 to 6.9, in particular from 4 to 5.5, and
  • X represents a sulfone group -SO2R 1 or an amide group -C-NH-R 2 ,
  • Y 1 and Y 2 stand for a hydrogen atom, for a sulfone group -SO2R 3 or
  • one of the radicals from Y 1 and Y 2 represents a hydrogen atom
  • the other radical from Y 1 and Y 2 is selected with the proviso that if X is a sulfone group, this other radical is also selected from a sulfone group and if X represents an amide group, this other radical is selected from an amide group,
  • R 1 and R 3 independently represent hydroxy, a group -OZ + , or one group
  • R a and R b independently represent hydrogen or a cyclic or acyclic, straight-chain or branched-chain, aliphatic or aromatic
  • Hydrocarbon radical with 1 to 20 carbon atoms the backbone of which may be broken by one or more non-adjacent heteroatoms (in particular selected from O and / or N) and / or which is substituted on C-atoms not connected with heteroatoms with OH groups or NH2 groups
  • R a and R b can also be part of a heterocycle formed from them and the N atom bound to them,
  • R ' , R " and R " independently of one another represent H or a straight-chain or branched-chain aliphatic hydrocarbon radical with 1 to 3, preferably 1 to 2 carbon atoms and A- represent an anion, and
  • Y 1 is selected from said sulfone group and Y 2 represents a hydrogen atom.
  • the catechol compounds of formula (I) contained in the composition are selected from 1,2-dihydroxybenzene-3,5-disulfonic acid (Tiron ) or its salt.
  • R a and R b are preferably the same.
  • the preferred compounds of the general formula (I) also include those in which R a and R b are selected independently of one another from hydrogen, the methyl group, the ethyl group, the n-propyl group and the iso-propyl group. If R a and R b are part of a heterocycle formed from them and the N atom, this is preferably a pyrrolidine, piperidine or morpholine ring.
  • Y 1 stands for a hydrogen atom and Y 2 from one of said
  • Amide group is selected.
  • a very particularly preferred second subject of the invention is therefore a liquid one
  • composition for providing a textile detergent the liquid
  • Composition has a pH (20 ° C) of 1 to 6.9, in particular 4 to 5.5 and a) at least one catechol compound of the formula (Ia)
  • R 2 and R 4 independently of one another for a hydrocarbon radical having 1 to 20
  • R ' , R " and R " independently of one another are H or a straight-chain or branched-chain aliphatic hydrocarbon radical having 1 to 3, preferably 1 to 2 carbon atoms and A is an anion, b) water
  • Compounds of the general formulas (I) and (Ia) preferably have a solubility in demineralized water of pH 4 at 20 ° C. of at least 10 mg / l, in particular at least 20 mg / l.
  • the at least one catechol compound according to formula (I) in a total amount of 0.001 % By weight to 90% by weight, in particular from 0.01% by weight to 85% by weight, preferably from 1.0% by weight to 80% by weight, more preferably from 2.5% by weight .-% to 75 wt .-%, is included.
  • hydrocarbon radicals having 1 to 20 carbon atoms according to formula (I) and formula (la) can be linear or branched, saturated or unsaturated, cyclic or alicyclic or aromatic.
  • compositions which contain at least one catechol compound of the formula (I) or of the formula (Ia) in which the radicals R 2 and R 4 independently of one another represent an alkyl group (such as methyl, ethyl, n-propyl or i- Propyl) an alkoxyalkyl group (such as methoxyethyl, methoxypropyl, (2-methoxy) ethoxyethyl, ethoxyethyl, ethoxypropyl or (2-ethoxy) ethoxyethyl), a hydroxyalkyl group (such as 2-hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, 1, 2-dihydroxypropyl), a hydroxyalkyloxyalkyl group (such as 2-hydroxyethoxyethyl), (N-hydroxyethyl) aminoethyl, (N-methoxyethyl) aminoethyl or (N-ethoxyethyl) aminoethy
  • Preferred alkyl groups according to formula (I) or formula (la) are linear (C-i-C-io) alkyl groups or branched (C3-Cio) alkyl groups, Cs-Ce cycloalkyl.
  • radicals R 2 and R 4 are the same according to formulas (I) and (Ia).
  • m and n independently of one another represent 0 to 5 and A and B independently of one another represent a hydrogen atom, -NR 1 R 2 , -N + R 1 R 2 R 3 X-, and R 1 , R 2 and R 3 independently from each other are H or a straight-chain or branched-chain aliphatic hydrocarbon radical having 1 to 3, preferably 1 to 2 carbon atoms and X is an anion.
  • Preferred compounds of the general formula (Ib) are those in which A and B are the same.
  • A is in the formulas (I) and (la) and X in formula (Ib) is preferably from the group comprising lactate, citrate, tartrate, succinate, perchlorate, tetrafluoroborate, hexafluorophosphate, alkyl sulfonate, alkyl sulfate, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate , Phosphate, isocyanate, rhodanide, nitrate, fluoride, chloride, bromide, hydrogen carbonate and carbonate and mixtures of at least two of these are selected, the charge balance in the presence of polyvalent anions being present by the presence of a plurality of cationic backbones of the corresponding general formula or, if appropriate, by the presence additional cations such as sodium or ammonium ions can be guaranteed.
  • a and B represent a hydrogen atom.
  • catechol compounds of the formula (I) are the compounds of the formulas (Ic)
  • the liquid composition contains at least one surfactant. It is again particularly preferred if, based on the weight of the liquid composition according to the invention, surfactant in a total amount of 10 to 70% by weight, in particular 20 to 65% by weight, very particularly preferably 30 to 65% by weight, in particular 30 to 60 wt .-% is included.
  • the group of surfactants includes the nonionic, anionic, cationic and amphoteric surfactants.
  • the liquid composition of the second subject matter of the invention can comprise one or more of the surfactants mentioned. It particularly preferably comprises at least one or more anionic surfactants, which are preferably present in a total amount of 15 to 50% by weight, in particular 20 to 40% 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 C9-Ci3-alkylbenzenesulfonates, olefin sulfonates, Ci2-Ci8-alkanesulfonates, ester sulfonates,
  • compositions with a yield point are suitable.
  • Liquid compositions which comprise C9-Ci3-alkylbenzenesulfonates and fatty alcohol ether sulfates as anionic surfactant have particularly good, dispersing properties.
  • Preferred surfactants of the sulfonate type are C9-Ci3-alkylbenzenesulfonates, olefin sulfonates, that is to say mixtures of alkene and
  • Ci2-Ci8 alkane sulfonates and disulfonates such as those obtained, for example, from Ci2-Ci8 monoolefins with a terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products.
  • Ci2-Ci8 alkane sulfonates and the esters of a-sulfo fatty acids (ester sulfonates) 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 especially the sodium salts of
  • Sulfuric acid half-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 of 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 C9-1 1 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 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, the representatives with an even number of carbon atoms being preferred.
  • radicals R 1 of the formula (A-1) are derived from fatty alcohols with 12 to 18 carbon atoms, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or from 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 n-th 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 C9-13-alkylbenzenesulfonates and optionally additionally fatty alcohol ether sulfates as the anionic surfactant.
  • the liquid composition contains at least one anionic surfactant of the formula (A-3) Y
  • R ' and R " are independently 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.
  • the composition can also contain soaps.
  • 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 soap mixtures derived from natural fatty acids, for example coconut, palm kernel, olive oil or tallow fatty acids.
  • anionic surfactants and the soaps can be in the form of their sodium, potassium or
  • the anionic surfactants are preferably in the form of their ammonium salts, said ammonium ion being derived from at least one (C2-C6) alkanolamine.
  • Other preferred counterions for the anionic surfactants are the protonated forms of choline, triethylamine, monoethanolamine,
  • Triethanolamine or methylethylamine Triethanolamine or methylethylamine.
  • the liquid composition can (preferably together with at least one anionic surfactant) also have at least one nonionic surfactant.
  • the nonionic surfactant includes alkoxylated fatty alcohols, alkoxylated fatty acid alkyl esters, fatty acid amides, alkoxylated
  • Fatty acid amides polyhydroxy fatty acid amides, alkylphenol polyglycol ethers, amine oxides,
  • nonionic surfactant is present in a total amount of 10 to 40% by weight, in particular 15 to 35% 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 linear 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.
  • Preferred ethoxylated alcohols include
  • C12-14 alcohols with 4 EO or 7 EO 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 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.
  • 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 Ci6-Ci8 fatty alcohol with 7 EO and 2-propylheptanol with 7 EO.
  • the washing, cleaning, post-treatment or particularly preferably contains
  • Washing aids use a Ci2-Ci8 fatty alcohol with 7 EO or a Ci3-Ci5-oxo alcohol with 7 EO as a non-ionic 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.
  • the agent according to the invention can be mixtures of nonionic surfactants included that 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
  • Such fatty alcohol or oxo alcohol ethoxylates are available under the trade names Dehydol LT7 ® (BASF) Lutensol ® A07 (BASF) Lutensol ® M7 (BASF), and Neodol ® 45-7 (Shell Chemicals).
  • At least one catechol compound of the formula (I) in a total amount from 0.001% by weight to 90% by weight, in particular from 0.01% by weight to 85% by weight, preferably from 1.0% by weight up to 80% by weight, more preferably from 2.5% by weight to 75% by weight,
  • 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:
  • 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, - skin care products or
  • At least one active substance is preferably selected from enzymes, optical brighteners, builders, solvents, anti-redeposition agents, color transfer inhibitors,
  • 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 already 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 substitutions of one amino acid for another
  • “Exchange in position 320” means, for example, that a variant in the position which has the position 320 in the sequence of a reference protein 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 according to the invention designated by the present application are not limited to the fact that they are the only exchanges in which the variant in question differs from the wild-type molecule. It is state of the art known that the advantageous properties of individual point mutations can complement each other. 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 class E.C. 3.4 falls according to the invention (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 subtilases (and the subtilases)
  • Serine proteases characterized in that, in addition to said serine with histidine and aspartame, they have two further amino acid residues in the active center.
  • 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:
  • the 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).
  • the 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.
  • a protease of the type of the alkaline protease from Bacillus lentus DSM 5483 or a protease sufficiently similar to this (based on the sequence identity), which exhibits several of these changes in combination, is particularly suitable for use in and in the liquid surfactant composition according to the invention is advantageously improved stabilized. Advantages of using this protease thus arise in particular with regard to washing performance and / or stability.
  • 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.
  • Gapped BLAST and PSI-BLAST a new generation of protein database search programs "; Nucleic Acids Res., 25, S.3389-3402) and is principally done in that similar sequences of nucleotides or amino acids in the nucleic acid or amino acid sequences are assigned to one another become. A tabular assignment of the relevant positions is called alignment.
  • Another algorithm available in the prior art is the FASTA algorithm. Sequence comparisons (alignments), in particular multiple sequence comparisons, are created using 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.
  • Such a comparison also allows a statement about the similarity of the compared sequences to one another. It is usually given in percent identity, that is to say the proportion of identical nucleotides or amino acid residues in the same positions or in an alignment corresponding to one another.
  • the broader concept of homology also includes conserved amino acid exchanges in amino acid sequences, i.e. amino acids with similar chemical activity, since these usually have similar chemical functions within the protein
  • Identity and / or homology information can be applied to entire polypeptides or genes or only to 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 amino acid sequence specified in each case.
  • 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 inactivation.
  • compositions according to the invention can be added to the enzymes obtained in any form established according to the prior art. This includes in particular the through
  • the enzymes can also be encapsulated, for example by
  • 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 dextrinase 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
  • Celluzyme® is offered.
  • 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®. They can also be used, for example
  • Ecostone® and Biotouch® are available, and are based at least in part on the 20 kD EG from Melanocarpus.
  • 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 is available from Danisco / Genencor 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 international patent publication WO 98/12307, made from cellulases
  • Melanocarpus especially Melanocarpus albomyces, which is used in the international
  • Publication WO 97/14804 discloses cellulases of the EGIII type from Trichoderma reesei, which are disclosed in European patent application EP 1 305 432 or variants obtainable therefrom, in particular those which are disclosed in European ones
  • 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 produced in genetically engineered Trichoderma reseei transformants. Cellulases which have a homology of over 80% can also be used for the purposes of the present invention.
  • 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 amount of enzyme that produces reducing sugars in an amount corresponding to 1 nmol glucose per second), especially of 2 NCU / g to 400 NCU / g and particularly preferably from 6 NCU / g to 200 NCU / g.
  • 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).
  • first cellulase from Melanocarpus sp. or Myriococcum sp. available 20K cellulase or those which have a homology of over 80% (increasingly preferred of 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%) additionally has at least one more of the first cellulase
  • 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 have at least one lipase which is naturally present in a microorganism of the species Thermomyces lanuginosus or is derived from the aforementioned lipases which are naturally present in Thermomyces lanuginosus by mutagenesis.
  • naturally present means that the lipase is a separate enzyme of the microorganism.
  • the lipase can thus be expressed in the microorganism by a nucleic acid sequence that 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. In contrast, one would not be
  • Nucleic acid sequence was 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.
  • Thermomyces lanuginosus, Rhizopus oryzae and Mucor javanicus are the biological ones
  • 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 found in Rhizopus oryzae available.
  • 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%) is identical to the wild-type lipase from the strain DSM 4109 Thermomyces lanuginosus. It is again preferred if, based on said wild-type lipase from strain DSM 4109, there is at least the amino acid change
  • lipases derived from the wild-type lipase from strain DSM 4109 which are selected from at least one lipase enzyme according to at least one of the
  • 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.
  • a highly preferred lipase is commercially available from Novozymes (Denmark) under the trade name Lipex® and can advantageously be used in the cleaning compositions according to the invention. Lipase Lipex® is particularly preferred
  • compositions are characterized in that, based on the total weight of the composition, said lipase enzyme from Lipex® 100 L in a total amount of 0.01 to 1.0% by weight, in particular 0.02 to 0.1% by weight. % is included.
  • the liquid compositions according to the invention can additionally contain at least one mannanase as enzyme.
  • a mannanase contained in the composition according to the invention (in particular in a washing and cleaning agent for textiles preferred according to the invention) catalyzes the hydrolysis of 1,4-beta-D-mannosidic bonds in mannans, galactomannans, glucomannans and in the context of its mannanase activity
  • 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 under catalog number 1-AZGMA from Megazyme (http://www.megazyme.com), introduced.
  • AZGL galactomannan carob
  • Substrate for the endo-1,4-beta-D-mannanase essay available under catalog number 1-AZGMA from Megazyme (http://www.megazyme.com), introduced.
  • 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 mannanase in a total amount of 0.01 to, based on the total weight of the composition
  • Mannanase polypeptides from strains of the Thermoanaerobacter group, such as caldicellulose ruptor 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, can also be used in the context of the invention.
  • 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 stearothermophilus, Bacillus alkalophilus, Bacillus amyloliquefaciens, Bacillus coagulans, Bacillus circulans, Bacillus lautus, Bacillus thuringiensis, Bacillus cheniformis, and Bacillus sp., especially preferably selected from at least one representative 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 which 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%, 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% or 99.8%) sequence identity to the polypeptide according to SEQ ID No.1 (cf.
  • 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 the 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 lentus 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, at least one a-amylase .
  • a-Amylases (E.C. 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, the 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.
  • DNA Detected dinitrosalicylic acid
  • the activity is obtained in pmol of reducing sugars (based on maltose) per min and ml; this results in activity values in TAU.
  • the same enzyme can be determined by different methods, the respective
  • Conversion factors may vary depending on the enzyme and must therefore be determined using a standard. You can roughly calculate that 1 KNU corresponds to approx. 50 TAU. Another activity determination method is measurement using the Quick-Start ® test kit from Abbott, Abott Park, Illinois, USA.
  • a preferred area of use of the liquid surfactant compositions according to the invention is in 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 almost still one
  • 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 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 amino acid exchanges in 10 different positions on the a-amylases from two different microorganisms and claims those for all amylases with a homology of at least 96% identity to them.
  • WO 01/66712 A2 denotes 31 different amino acid positions, some of which are identical with the abovementioned, which have been mutated in one of the two a-amylases mentioned in the application WO 00/60060 A2.
  • 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
  • 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.
  • Liquid compositions preferred according to the invention contain ⁇ -amylase in a total amount of 0.01 to 1.0% by weight, in particular 0.02 to 0.1% by weight.
  • At least one optical brightener tyrylbiphenyle from the substance classes of the diskette, the stilbenes, the 4,4-diamino-2,2-stilbenedisulfonic acids, 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-thiophenediyl) bis [5-1, 1-
  • the liquid composition can further comprise builders.
  • Polymeric polycarboxylates 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 are understood to mean those carboxylic acids which carry more than one acid function. For example, 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 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 also suitable, in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with
  • the polymers can also be used to improve water solubility
  • Allylsulfonic acids such as allyloxybenzenesulfonic acid and methallylsulfonic acid, as a monomer.
  • Soluble builders such as acrylic polymers with a molecular weight of 1,000 to 5,000 g / mol, are preferably used in liquid detergents.
  • soluble builders such as citric acid, or acrylic polymers with a molecular weight of 1,000 to 5,000 g / mol are particularly preferably used.
  • the liquid composition preferably additionally contains one or more non-aqueous solvents.
  • suitable non-aqueous solvents include monohydric or polyhydric alcohols or glycol ethers, such as, for example, ethanol, n-propanol, i-propanol, butanols, glycol, propanediol, butanediol, methyl propanediol, glycerol, glycols, such as diglycol, propyl diglycol, Butyl diglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether,
  • Propylene glycol propyl ether dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, methoxytriglycol, ethoxytriglycol, butoxytriglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, 2,2-dimethyl-4-hydroxymethyl-1, 3-dioxolane, propylene glycol butyl ether, di-n-octyl ether and low molecular weight polyalkylene glycols, such as PEG 400, and mixtures of these solvents.
  • the solvents are preferably selected from ethanol, n-propanol, i-propanol, butanols, glycol, propanediol, butanediol, methylpropanediol, glycerol, diglycol, propyl diglycol, butyl diglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether,
  • Propylene 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 Mi-di-octyl ether
  • liquid compositions according to the invention can additionally also contain components which have a positive effect on the oil and fat washability from textiles
  • 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 of 15 to 30% by weight and of hydroxypropoxyl groups of 1 to 15% by weight, in each case based on the nonionic
  • 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 of these are commercially available, for example, under the trade name Texcare ® .
  • Antiredeposition agents which can be used are in particular based on (co) polymers based on polyethyleneimine, polyvinyl acetate and polyethylene glycol, preferably in mixtures with
  • the liquid composition can preferably also contain color transfer inhibitors, preferably in amounts of 0.1% by weight to 2% by weight, in particular 0.1% by weight to 1% by weight, which
  • color transfer inhibitors preferably in amounts of 0.1% by weight to 2% by weight, in particular 0.1% by weight to 1% by weight, which
  • 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, can preferably be used.
  • the color transfer inhibitor is a polymer or copolymer of cyclic amines such as vinyl pyrrolidone and / or vinyl imidazole.
  • Color transfer inhibitor-suitable polymers include polyvinyl pyrrolidone (PVP),
  • Polyvinylimidazole (PVI), copolymers of vinylpyrrolidone and vinylimidazole (PVP / PVI),
  • Polyvinylpyrrolidone (PVP), polyvinylimidazole (PVI) or copolymers of vinylpyrrolidone and vinylimidazole (PVP / PVI) are particularly preferably used as color transfer inhibitors.
  • 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 extremely preferred color transfer inhibitor is polyethylene glycol-modified copolymers of vinylpyrrolidone and vinylimidazole, which are available, for example, under the name Sokalan® HP 66 from BASF are.
  • the liquid composition of the second subject of the invention is used in a washing process for textiles.
  • the liquid compositions of the second subject matter of the invention described here are suitable on the one hand as washing aids which are used as textile pre-treatment and post-treatment agents in textile laundry, i.e. as agents with which the item of laundry is brought into contact before the actual laundry, for example for dissolving stubborn soiling, and also those agents which, in a step following the actual textile washing, add further desirable properties to the laundry, such as Give a comfortable grip, wrinkle-free or low static charge.
  • the last mentioned means include fabric softener.
  • a surfactant-containing (in particular concentrated) detergent to provide a surfactant-containing liquor (in particular for the main wash in a washing machine).
  • the said additive and the detergent composition can be metered either in two steps in succession, or with the aid of a multi-component detergent provided as a kit in one step using an appropriate metering aid, such as one for one
  • Wash pre-made portion e.g. as a water-soluble multi-chamber pouch
  • a multi-chamber storage container with a possible mixing chamber.
  • a surfactant-containing liquor is a liquid preparation for the treatment of a substrate which can be obtained by using a surfactant-containing agent and diluted with at least one solvent (preferably water). Fabrics or textiles (such as clothing) can be used as substrates.
  • the liquid compositions according to the invention of the second subject of 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.
  • the liquid composition according to the invention of the second subject of the invention is particularly preferably used as part of a liquid multicomponent detergent.
  • the further components of the multi-component detergent can be present in any dosage form established according to the prior art and / or in any expedient form. These include, for example, liquid, gel-like or pasty dosage forms. Furthermore, pouches with one, two, three, four, five, six or more chambers are included, both in large containers and packaged in portions. It is preferred if the multicomponent detergent of the invention as a liquid multicomponent detergent in addition to at least one liquid composition of the second subject of the invention as the first composition and at least one further liquid composition as the second
  • Composition includes.
  • at least one solid composition can also be present as the third composition.
  • the second liquid composition in turn preferably has a pH (20 ° C.) greater than or equal to 7.
  • a solution of 1 g of the multi-component detergent in 100 ml of water very particularly preferably has a pH (20 ° C.) of> 7
  • a “multicomponent liquid detergent” thus contains, by definition, at least two liquid compositions, one of these compositions comprising at least one Composition of the second subject of the invention.
  • the detergent may also contain at least one solid component. It is important that the liquid component consists of at least two liquid compositions, ie of more than one component. However, it is very particularly preferred according to the invention if the liquid multi-component detergent comprises only liquid components, the liquid components preferably being packaged separately from one another.
  • the multi-component detergent is a liquid multi-component color detergent, that is, a
  • a third subject of the invention is a liquid multicomponent detergent comprising as components at least two liquid compositions, a solution of 1 g of the multicomponent detergent in 100 ml water having a pH (20 ° C.) of> 7, characterized in that it based on the weight of the total detergent, each in a total amount contains:
  • At least one alkalizing agent preferably at least one (C2-C6) alkanolamine or its salt of 1 to 20% by weight, preferably 2 to 15% by weight, in particular 3 to 10% by weight, in each case to the basic form,
  • At least one surfactant preferably in a total amount of 5 to 70% by weight
  • Multi-component detergent contains at least one catechol compound of the formula (I) and has a pH (20 ° C.) of pH 1 to 6.9, preferably of pH 4 to 5.5, and at least one different second liquid composition of the multi-component detergent at least one surfactant and at least one
  • alkalizing agent in particular at least one (C2-C6) alkanolamine or its salt and has a pH (20 ° C) of at least pH 7.0.
  • the liquid multi-component detergent preferably contains a total amount of 0.1 to 10.0% by weight, particularly preferably 0.3 to 3.0% by weight, of the catechol compound according to formula (I), in each case based on the weight of the entire liquid multi-component detergent.
  • the preferred compounds of the formula (I) (vide supra) mentioned above for the second subject of the invention are very particularly preferred.
  • Composition of the liquid multi-component detergent which has a pH (20 ° C.) of> 7, compound of the formula (I) in a total amount of 0 to 0.001% by weight, preferably 0 to 0.0001% by weight , particularly preferably 0 to 0.00001% by weight, each based on the total weight of the said composition.
  • liquid multi-component detergents according to the invention containing at least one alkalizing agent or its salt in a total amount of 1 to 20% by weight, preferably 2 to 15% by weight. It is imperative that alkalizing agent is contained in the at least one second liquid composition.
  • the total amount of the alkalizing agent and its salt, or the total amount of all of the following preferred representatives, is calculated on the basis of the base form, i.e. if that
  • Alkalizing agent in the detergent according to the invention (partially) in its salt form, the counter ion is neglected in the quantity calculation and only the base form without the proton taken up is assumed for the salt fraction.
  • the alkalizing agents are preferably selected from (C2 to C6) alkanolamine,
  • (C2 to C6) alkanolamine is to be understood as meaning organic amine compounds which have a carbon skeleton of two to six carbon atoms to which at least one amino group (preferably exactly one amino group) and at least one hydroxyl group (again preferably precisely one hydroxyl group) binds .
  • Preferred (C2 to C6) alkanolamines according to the invention are preferably primary amines.
  • At least one (C2 to C6) alkanolamine with exactly one amino group is preferred.
  • this is preferably a primary amine.
  • the agent according to the invention preferably contains at least one (C2 to C6) alkanolamine selected from 2-aminoethan-1-ol (monoethanolamine), tris (2-hydroxyethyl) amine (triethanolamine), 3-aminopropan-1-ol, 4-aminobutane 1-ol, 5-aminopentan-1-ol, 1-aminopropan-2-ol, 1-aminobutan-2-ol, 1-aminopentan-2-ol, 1-aminopentan-3-ol, 1-aminopentan-4- ol, 3-amino-2-methylpropan-1-ol, 1-amino-2-methylpropan-2-ol, 3-aminopropan-1, 2-diol, 2-amino-2-methylpropan-1, 3-diol
  • Monoethanolamine has proven to be a very particularly suitable (C2 to C6) alkanolamine
  • (C2 to C6) alkanolamine or its salt is particularly preferably present in a total amount of 1 to 20% by weight, preferably 2 to 15% by weight, in the detergents according to the invention, in each case based on the basic form.
  • the liquid multi-component detergent necessarily contains at least one surfactant, preferably based on the total weight of the liquid multi-component detergent in one
  • surfactant is contained in the at least one second liquid composition.
  • surfactant can preferably also be present in the at least one first composition.
  • the liquid multi-component detergent also preferably contains at least one additional active substance, in particular selected from the group of enzymes,
  • Graying inhibitors anti-shrink agents, anti-crease agents, color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, preservatives, Corrosion inhibitors, antistatic agents, bittering agents, ironing aids, phobing and impregnating agents,
  • the at least one first liquid composition of the liquid multi-component detergent is a liquid composition of the second subject of the invention, in particular its preferred embodiment (vide supra).
  • a particularly preferred liquid multi-component detergent is characterized in that the catechol compound of the formula (I) in the first liquid composition, based on the total weight of this first liquid composition, in a total amount of 0.001% by weight to 90% by weight, in particular of 0.01% by weight to 85% by weight, preferably from 1.0% by weight to 80% by weight, more preferably from 2.5% by weight to 75% by weight, is contained .
  • the preferred total amounts of water and surfactant are realized, ie more surfactant is contained. In this case, therefore, the total amount of
  • Catechol compound of the formula (I) to a total amount of 0.001% by weight to 50% by weight, in particular from 0.01% by weight to 40% by weight, preferably from 1.0% by weight to 30% by weight %, more preferably from 2.5% to 25% by weight.
  • the liquid multi-component detergent preferably contains a total amount of 0.1 to 10.0% by weight, particularly preferably 0.3 to 3.0% by weight, of the catechol compound according to formula (I), in each case based on the weight of the entire liquid multi-component detergent. It is again advantageous if the first liquid composition contains said catechol compound of the formula (I) in the preferred amounts described above.
  • a particularly preferred liquid multi-component detergent is characterized in that it comprises at least one first liquid composition having a pH (20 ° C.) of pH 1 to 6.9, in particular pH 4 to 5.5, as a component each based on the total weight of the first liquid composition
  • 0.001% by weight to 50% by weight in particular from 0.01% by weight to 40% by weight, preferably from 1.0% by weight to 30% by weight, more preferably from 2.5 % By weight to 25% by weight c) at least one surfactant, in particular in a total amount from 25% by weight to 65% by weight, preferably from 30% by weight to 65% by weight,
  • Multi-component detergent a total amount of 0.1 to 10.0 wt .-%, particularly preferably from 0.3 to 3.0 wt .-%, of the catechol compound according to formula (I), each based on the weight of the total liquid multicomponent - Detergent, contains.
  • a liquid multi-component detergent according to the invention (in particular in the presence of a preferred first liquid composition) is characterized in that it has at least one second liquid composition with a pH (20 ° C.) of at least pH 7, in particular of pH 7 to 1 1, particularly preferably from pH 7.3 to 9.5, comprises as a component, each based on the total weight of the second liquid composition
  • At least one surfactant in particular in a total amount from 25% by weight to 65% by weight, preferably from 30% by weight to 65% by weight,
  • At least one alkalizing agent in particular at least one (C2-C6) -alkanolamine or its salt in a total amount of 1 to 20% by weight, preferably 2 to 15% by weight, in particular 3 to 10% by weight % each based on the basic form.
  • Multi-component detergent a total amount of 0.1 to 10.0 wt .-%, particularly preferably from 0.3 to 3.0 wt .-%, of the catechol compound according to formula (I), each based on the weight of the total liquid multicomponent - Detergent, contains.
  • the liquid composition of the second is
  • the container for the said liquid multi-component detergent comprises at least two spatially separate chambers (multi-chamber pouch), for example 2, 3, 4, 5, 6 or 7 chambers. These chambers are separated from one another in such a way that the liquid compositions of the detergent contained do not come into contact with one another. This separation can be done, for example, by a wall made of the same material as the container itself.
  • liquid multi-component detergent of the third subject matter of the invention in a container made of water-soluble material with at least two separate chambers, the at least one first liquid composition in at least one chamber and at least one chamber different therefrom which are at least a second liquid composition.
  • a material is water-soluble if at 20 ° C 0.1 g of the material is stirred
  • the water solubility of the material used for the production of pouches for wrapping in the form of a film can be determined with the aid of a square film of said material (film: 22 x 22 mm with a thickness of) fixed in a square frame (edge length on the inside: 20 mm) 76 pm) can be determined according to the following measurement protocol.
  • Said framed film is immersed in 800 ml of distilled water at a temperature of 20 ° C. in a 1 liter beaker with a circular base (Schott, Mainz, beaker 1000 mL, low form), so that the surface of the clamped film is at a right angle to Bottom surface of the beaker is arranged, the upper 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 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 arranged above the center of the radius of the beaker bottom.
  • 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 water-soluble or water-dispersible material can comprise a polymer, a copolymer or mixtures thereof.
  • Water-soluble polymers in the sense of the invention are those polymers which are more than 2.5% by weight soluble in water at room temperature.
  • Preferred water-soluble materials preferably comprise at least partly at least one substance from the group consisting of (acetalized) polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene oxide, gelatin, polyvinyl alcohols substituted with sulphate, carbonate and / or citrate, polyalkylene oxides, acrylamides, cellulose esters, cellulose ethers, cellulose amides, cellulose, polyvinyl acetates , Polycarboxylic acids and their salts, polyamino acids or peptides, polyamides, polyacrylamides, copolymers of maleic acid and acrylic acid, copolymers of acrylamides and (meth) acrylic acid, polysaccharides, such as starch or guar derivatives, Gelatine and under the INCI names Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27.
  • the water-soluble material is particularly preferred
  • the water-soluble material comprises mixtures of different substances. Such mixtures enable the mechanical properties of the container to be adjusted and can influence the degree of water solubility.
  • 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 which in small proportions (approx. 2%) also structural units of the type
  • 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.
  • 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 impenetrable for gases such as oxygen, nitrogen, helium, hydrogen, carbon dioxide, however, leave
  • 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
  • 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 increased by post-treatment with
  • Aldehydes (acetalization) or ketones (ketalization) can be changed.
  • 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.
  • 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 also be added to the film material suitable as water-soluble material.
  • Suitable water-soluble films for use as the water-soluble material of the water-soluble potion 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.
  • HPMC Hydroxypropylmethyl cellulose
  • Hydroxypropoxyl groups per anhydroglucose unit of cellulose from 0.1 to 0.3, preferably from 0.15 to 0.25.
  • Polyvinylpyrrolidones are produced by radical polymerization of 1-vinylpyrrolidone.
  • Commercial PVPs have molecular weights in the range of approx.
  • Polyethylene oxides, PEOX for short, are polyalkylene glycols of the general formula
  • H- [0-CH 2 -CH 2 ] n-0H which are produced industrially by base-catalyzed polyaddition of ethylene oxide (oxirane) in mostly small amounts of water-containing systems with ethylene glycol as the starting molecule. They usually have molar masses in the range from approx. 200 to 5,000,000 g / mol, corresponding to degrees of polymerization n from approx. 5 to> 100,000. Polyethylene oxides have an extremely low concentration of reactive hydroxyl end groups and show only weak glycol properties.
  • Gelatin is a polypeptide (molecular weight: approx. 15,000 to> 250,000 g / mol), which is primarily obtained by hydrolysis of the collagen contained in the skin and bones of animals under acidic or alkaline conditions.
  • the amino acid composition of the gelatin largely corresponds to that of the collagen from which it was obtained and varies in
  • gelatin Dependence on its provenance.
  • the use of gelatin as a water soluble Envelope material is particularly widespread in the pharmaceutical industry in the form of hard or soft gelatin capsules.
  • gelatin In the form of films, gelatin is used only to a minor extent because of its high price in comparison to the abovementioned polymers.
  • water-soluble materials which comprise a polymer from the group starch and starch derivatives, cellulose and cellulose derivatives,
  • methyl cellulose in particular include methyl cellulose and mixtures thereof.
  • Starch is a homoglycan, with the glucose units linked a-glycosidically. Starch is made up of two components of different molecular weights (MW): approx. 20 to 30% straight-chain amylose (MW approx. 50,000 to 150,000) and 70 to 80% branched-chain
  • Amylopectin (MW approx. 300,000 to 2,000,000). It also contains small amounts of lipids, phosphoric acid and cations. While the amylose forms long, helical, intertwined chains with about 300 to 1,200 glucose molecules as a result of the binding in the 1,4 position, the chain in the amylopectin branches after an average of 25 glucose units through 1,6 binding to form a knot-like structure with about 1,500 to 12,000 molecules of glucose.
  • starch derivatives which can be obtained from polymer-analogous reactions from starch are also suitable for the production of water-soluble containers in the context of the present invention. Such chemically modified starches include, for example, products
  • Starches in which the hydroxyl groups have been replaced by functional groups which are not bound via an oxygen atom can also be used as starch derivatives.
  • the group of starch derivatives includes, for example, alkali starches, carboxymethyl starch (CMS), starch esters and starches and amino starches.
  • Pure cellulose has the formal gross composition (C6H10O5) and, formally speaking, is a ß-1, 4-polyacetal of cellobiose, which in turn is made up of two molecules of glucose. Suitable celluloses consist of approximately 500 to 5,000 glucose units and consequently have average molecular weights of 50,000 to 500,000.
  • Cellulose-based disintegrants which can be used in the context of the present invention are also cellulose derivatives which can be obtained from cellulose by polymer-analogous reactions. Such chemically modified celluloses include, for example, products from esterifications
  • celluloses in which the hydroxyl groups have been replaced by functional groups which are not bound via an oxygen atom can also be used as cellulose derivatives.
  • the group of cellulose derivatives includes, for example, alkali celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers and aminocelluloses.
  • the water-soluble material can have other additives. These are, for example, plasticizers, such as, for example, dipropylene glycol, ethylene glycol or diethylene glycol, water or disintegrating agents.
  • Polyvinyl alcohol is particularly preferably used as the water-soluble material. On the one hand, this is easy to process and inexpensive to maintain. In addition, it is particularly soluble in water and thus enables the container to be used in a variety of ways.
  • At least one bittering agent is contained in the water-soluble material to increase product safety.
  • Preferred bittering agents have a bitter value of at least 1,000, preferably at least 10,000, particularly preferably at least 200,000.
  • the standardized procedure described in the European Pharmacopoeia (5th edition Grundtechnik, Stuttgart 2005, Volume 1 General Part Monograph Groups, 2.8.15 Bitter Value p. 278) is used to determine the bitter value.
  • the inter-individual taste differences in the organoleptic examination of bitterness are compensated by a correction factor.
  • bittering agents are selected from denatonium benzoate, glycosides, isoprenoids, alkaloids, amino acids and mixtures thereof, particularly preferred
  • Glycosides are organic compounds of the general structure R-O-Z, in which an alcohol (R-OH) is linked to a sugar part (Z) via a glycosidic bond.
  • Suitable glycosides are, for example, flavonoids such as quercetin or naringin or
  • Iridoid glycosides such as aucubin and in particular secoiridoid such as amarogentin, dihydrofoliamentin, gentiopicroside, gentiopikrin, swertiamarin, sweroside, gentioflavoside, centauroside, methiafolin, harpagoside and centapikrin, sailicin or condurangin.
  • Isoprenoids are compounds that are formally derived from isoprene. Examples are in particular terpenes and terpenoids.
  • Suitable isoprenoids include, for example, sequiterpene lactones such as absinthin, artabsin, cnicin, lactucin, lactucopikrin or salonitenolide, monoterpene ketones (thujones) such as
  • tetranortriterpenes such as deoxylimones, Desoxylimonic acid, limonin, ichangin, iso-obacunonic acid, obacunon, obacunonic acid, nomilin or nomilic acid, terpenes such as marrubin, premarrubin, carnosol, carnosolic acid or quassin.
  • Alkaloids refer to naturally occurring, chemically heterogeneous, mostly alkaline, nitrogen-containing organic compounds of secondary metabolism that act on the animal or human organism.
  • Suitable alkaloids are, for example, quinine hydrochloride, quinine hydrogen sulfate,
  • Suitable amino acids include, for example, threonine, methionine, phenylalanine, tryptophan, arginine, histidine, valine and aspartic acid.
  • Denatonium benzoate (eg available as Bitrex ® ).
  • the water-soluble material preferably contains bittering agents (particularly preferably denatonium benzoate) in a total amount of at most 1 part by weight of bitter substance to 250 parts by weight of viscoelastic, solid surfactant composition (1: 250), particularly preferably at most 1: 500, very particularly preferably at most 1: 1000.
  • bittering agents particularly preferably denatonium benzoate
  • a liquid multicomponent detergent in a container made of water-soluble material with at least two separate chambers, comprising as components at least two liquid compositions, a solution of 1 g of the multicomponent detergent in 100 ml of water has a pH value (20 ° C) of> 7, characterized in that it contains in total in relation to the weight of the total detergent:
  • X, Y 1 and Y 2 are defined as previously described,
  • At least one alkalizing agent preferably at least one (C2-C6) alkanolamine or its salt of 1 to 20% by weight, preferably 2 to 15% by weight, in particular 3 to 10% by weight, in each case to the basic form,
  • At least one surfactant preferably in a total amount of 5 to 70% by weight
  • Multi-component detergent contains at least one catechol compound of the formula (I) and has a pH (20 ° C) of pH 1 to 6.9, preferably pH 4 to 5.5, and a) water in a total amount of 1 to 50% by weight, preferably 2 to 30% by weight, particularly preferably 3 to 25% by weight, very particularly preferably 5 to 25% by weight, in particular 5 to 35% by weight, preferably 5 to 30% by weight, particularly preferably 5 to 25% by weight, very particularly preferably 8 to 25% by weight
  • 0.001% by weight to 50% by weight in particular from 0.01% by weight to 40% by weight, preferably from 1.0% by weight to 30% by weight, more preferably from 2.5 % By weight to 25% by weight, c) at least one surfactant, in particular in a total amount from 25% by weight to 65% by weight, preferably from 30% by weight to 65% by weight,
  • At least one surfactant in particular in a total amount from 25% by weight to 65% by weight, preferably from 30% by weight to 65% by weight,
  • At least one alkalizing agent in particular at least one (C2-C6) -alkanolamine or its salt in a total amount of 1 to 20% by weight, preferably 2 to 15% by weight, in particular 3 to 10% by weight % each based on the basic form.
  • a fourth subject of the invention is the use of a liquid composition of the second subject of the invention, as an additive for detergents.
  • liquid composition of the second subject of the invention for washing textiles, in particular for removing stains based on constituents and residues of deodorants, rust, berries, tea and red wine.
  • a fifth object of the invention is a method for washing textiles, characterized in that a liquid composition of the second object of the invention is used to provide a liquid liquor.
  • Subject of the invention is used as a component of a liquid multi-component detergent of the third subject of the invention.
  • the soiling with the composition according to the invention of the second subject of the invention can be pretreated for the actual washing process and / or a surfactant-containing liquor can first be made available as a washing solution which contains the liquid multi-component detergent according to the invention and which subsequently contains the textile to be cleaned Is brought into contact.
  • Processes for cleaning textiles are generally distinguished by the fact that, in several process steps, different cleaning-active substances are applied to the items to be cleaned 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.
  • temperatures of 60 ° C. or less, for example 40 ° C. or less are used in various embodiments of the invention. These temperature specifications relate to the temperatures used in the washing steps.
  • Multi-component detergent of the third subject of the invention is metered into the drum of a washing machine.
  • Liquid multi-component detergent comprising as components at least two liquid compositions, a solution of 1 g of the detergent in 100 ml of water having a pH at 20 ° C of> 7, characterized in that it is based on the weight of the total
  • the total amount of detergent contains:
  • water of 1 to 50% by weight preferably 2 to 30% by weight, particularly preferably 3 to 25% by weight, very particularly preferably 5 to 25% by weight, in particular 5 to 35% by weight, preferably 5 to 30 %
  • X represents a sulfone group -SO2R 1 or an amide group -C-NH-R 2 ,
  • Y 1 and Y 2 stand for a hydrogen atom, for a sulfone group -SO2R 3 or
  • one of the radicals from Y 1 and Y 2 represents a hydrogen atom
  • the other radical from Y 1 and Y 2 is selected with the proviso that if X is a sulfone group, this other radical is also selected from a sulfone group and if X represents an amide group, this other radical is selected from an amide group,
  • R 1 and R 3 independently represent hydroxy, a group -OZ + , or a group
  • R a and R b independently represent hydrogen or a cyclic or acyclic, straight-chain or branched-chain, aliphatic or aromatic
  • Hydrocarbon radical with 1 to 20 carbon atoms the backbone of which may be broken by one or more non-adjacent heteroatoms (in particular selected from O and / or N) and / or which is substituted on C-atoms not connected with heteroatoms with OH groups or NH2 groups
  • R a and R b can also be part of a heterocycle formed from them and the N atom bound to them,
  • R ' , R “ and R " independently of one another represent H or a straight-chain or branched-chain aliphatic hydrocarbon radical 1 to 3, preferably 1 to 2 carbon atoms and A- represent an anion, c) at least one alkalizing agent (in particular at least one (C2-C6) alkanolamine) or its salt from 1 to 20% by weight, preferably from 2 to 15% by weight, in particular from 3 to 10% by weight, based in each case on the basic form,
  • At least one surfactant preferably in a total amount of 5 to 70% by weight
  • Multi-component detergent contains at least one catechol compound of the formula (I) and has a pH at 20 ° C. of pH 1 to 6.9, preferably of pH 4 to 5.5, and at least one second liquid composition of the different
  • Multi-component detergent at least one surfactant and at least one
  • Liquid multi-component detergent according to item 1 characterized in that when X is selected from said sulfone group according to formula (I), Y 1 is selected from said sulfone group and Y 2 represents a hydrogen atom.
  • Multicomponent liquid detergent according to one of the preceding points characterized in that when X is selected from said amide group according to formula (I), Y 1 represents a hydrogen atom and Y 2 is selected from said amide group.
  • Liquid multi-component detergent according to item 3 characterized in that the catechol compound of the formula (I) is selected from at least one catechol compound of the formula (Ia)
  • R 2 and R 4 independently of one another for a hydrocarbon radical having 1 to 20
  • R ' , R " and R " independently of one another represent H or a straight-chain or branched-chain aliphatic hydrocarbon radical having 1 to 3, preferably 1 to 2 carbon atoms and A standing for an anion, liquid multi-component Detergent according to one of the preceding items, characterized in that, according to formula (I) or formula (la), the radicals R 2 and R 4 independently of one another represent an alkyl group (such as methyl, ethyl, n-propyl or i-propyl) an alkoxyalkyl group (such as methoxyethyl, methoxypropyl, (2-methoxy) ethoxyethyl, eth
  • Liquid multi-component detergent according to one of the preceding items characterized in that the radicals R 2 and R 4 are the same according to formula (I) or formula (Ia).
  • Liquid multi-component detergent according to one of the preceding items characterized in that each liquid composition functioning as a component having a pH (20 ° C.) of> 7 compound of the formula (I) in a total amount of 0 to 0.001% by weight. %, preferably 0 to 0.0001% by weight, particularly preferably 0 to 0.00001% by weight, each based on the total weight of the said composition.
  • Liquid multi-component detergent according to one of the preceding points, characterized in that it contains at least one (C2 to C6) alkanolamine as an alkalizing agent as a (C2 to C6) alkanolamine selected from 2-aminoethan-1-ol (monoethanolamine), tris ( 2-hydroxyethyl) amine (triethanolamine), 3-aminopropan-1-ol, 4-aminobutan-1-ol, 5-aminopentan-1-ol, 1-aminopropan-2-ol, 1-aminobutan-2-ol, 1 -Aminopentan-2-ol, 1-aminopentan-3-ol, 1-aminopentan-4-ol, 3-amino-2-methylpropan-1-ol, 1-amino-2-methylpropan-2-ol, 3-aminopropane -1, 2-diol, 2-amino-2-methylpropan-1, 3-diol (especially under 2-aminoethan-1-o
  • Liquid multi-component detergent according to one of the preceding points characterized in that it contains at least one anionic surfactant.
  • Liquid multi-component detergent according to one of the preceding items characterized in that at least one anionic surfactant selected from Cs-is-alkylbenzenesulfonates, Cs -is-olefinsulfonates, Ci2-i8-alkanesulfonates, ester sulfonates, alkyl sulfates, alkenyl sulfates, fatty alcohol ether sulfates or mixtures thereof is.
  • Liquid multi-component detergent according to one of the preceding items characterized in that it contains at least one anionic surfactant of the formula (A-3),
  • 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)
  • Liquid multi-component detergent according to one of the preceding items, characterized in that, based on the total weight of the liquid multi-component detergent, the catechol compound of the formula (I) or of the formula (Ia) in one
  • Liquid multi-component detergent according to one of the preceding items, characterized in that the catechol compound of the formula (I) or of the formula (Ia) in the first liquid composition, based on the total weight of this first liquid composition, in a total amount of 0.001% by weight up to 90% by weight, in particular from 0.01% by weight to 85% by weight, preferably from 1.0% by weight to 80% by weight, more preferably from 2.5% by weight to 75 wt .-%, is included.
  • Liquid multi-component detergent according to one of the preceding items, characterized in that it comprises at least one first liquid composition with a pH at 20 ° C. of pH 1 to 6.9, in particular pH 4 to 5.5, as a component, containing in each case based on the total weight of the first liquid composition a) water in a total amount of 1 to 50% by weight, preferably 2 to 30% by weight,
  • 0.001% by weight to 50% by weight in particular from 0.01% by weight to 40% by weight, preferably from 1.0% by weight to 30% by weight, more preferably from 2.5 % By weight to 25% by weight, c) at least one surfactant,
  • Liquid multi-component detergent according to one of the preceding items, characterized in that it has at least one second liquid composition with a pH at 20 ° C. of at least pH 7, in particular of pH 7 to 11, particularly preferably of pH 7.3 to 9.5, included as a component, each based on the total weight of the second liquid composition
  • Liquid multi-component detergent according to one of the preceding items, in a container made of water-soluble material with at least two separate ones
  • the at least one first liquid composition being in at least one chamber and the at least one second liquid composition being in at least one different chamber.
  • Liquid composition for providing a textile detergent the liquid composition having a pH at 20 ° C. from 1 to 6.9, in particular from 4 to 5.5, and
  • a) comprises at least one catechol compound of the formula (I) as defined in one of items 1 to 6,
  • 0.001% by weight to 50% by weight in particular from 0.01% by weight to 40% by weight, preferably from 1.0% by weight to 30% by weight, more preferably from 2.5 % By weight to 25% by weight, b) water in a total amount of from 1 to 50% by weight, preferably 2 to 30% by weight, particularly preferably 3 to 25% by weight, very particularly preferably 5 to 25% by weight .%, in particular 5 to 35% by weight, preferably 5 to 30% by weight, particularly preferably 5 to 25% by weight, very particularly preferably 8 to 25% by weight,
  • Liquid composition according to one of items 19 or 20, characterized in that it contains at least one anionic surfactant.
  • Liquid composition according to one of items 19 to 21 characterized in that at least one anionic surfactant selected from Cs -is-alkylbenzenesulfonates, Cs -is-olefin sulfonates, Ci2-i8-alkanesulfonates, ester sulfonates, alkyl sulfates, alkenyl sulfates, fatty alcohol ether sulfates or mixtures thereof is.
  • 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)
  • m stand for integers from 1 to 50.
  • Composition according to one of the items 19 to 25 is used to provide a surfactant-containing fleet.
  • liquid detergents from Table 1 were prepared by mixing the components. A homogeneous solution of the catechol compound in a mixture of the nonionic surfactant and the non-aqueous, organic solvent was first prepared. Then water and the alkalizing agent and the other constituents of the detergent were added and mixed. The enzymes were then added.
  • the pH of these wash liquors was 7.5.
  • the detergents of the compositions V2 and V3 differ from the composition V1 by the presence of a catechol compound and are therefore more intense, darker in color to an orange tone.
  • compositions E1 and E2 differ from the compositions V2 and V3 only in their pH. Compositions E1 and E2 show no discoloration to a darker shade despite the presence of a catechol compound.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
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  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Biochemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

La présente invention concerne l'utilisation d'au moins un composé catéchol spécifique dans des compositions liquides à pH acide en tant qu'additif de détergent ou composant d'un détergent liquide à plusieurs composants. L'invention améliore la performance de lavage et de nettoyage tout en empêchant une coloration brune-rouge de la composition détergente.
PCT/EP2019/065980 2018-10-11 2019-06-18 Détergent liquide contenant un composé catéchol WO2020074140A1 (fr)

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DE102018217398.2A DE102018217398A1 (de) 2018-10-11 2018-10-11 Flüssigwaschmittel mit Dihydroxyterephthalsäurediamid-Verbindung

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4170005A1 (fr) * 2021-10-19 2023-04-26 Henkel AG & Co. KGaA Préparation coulante et concentrée de détergent présentant des propriétés améliorées
EP4170006A1 (fr) * 2021-10-19 2023-04-26 Henkel AG & Co. KGaA Préparation coulante et concentrée de détergent présentant des propriétés améliorées

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4170005A1 (fr) * 2021-10-19 2023-04-26 Henkel AG & Co. KGaA Préparation coulante et concentrée de détergent présentant des propriétés améliorées
EP4170006A1 (fr) * 2021-10-19 2023-04-26 Henkel AG & Co. KGaA Préparation coulante et concentrée de détergent présentant des propriétés améliorées

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