WO2017102471A1

WO2017102471A1 - Liquid detergents or cleaning agents containing acyl hydrazone

Info

Publication number: WO2017102471A1
Application number: PCT/EP2016/079980
Authority: WO
Inventors: André HÄTZELT; Christian Kropf
Original assignee: Henkel Ag & Co. Kgaa
Priority date: 2015-12-18
Filing date: 2016-12-07
Publication date: 2017-06-22
Also published as: EP3390608B1; EP3390608A1; DE102015225874A1

Abstract

The aim of the invention is to improve the dirt cleaning performance of liquid detergents and cleaning agents containing surfactants and enzymes. This aim is achieved essentially by incorporating specific acyl hydrazones.

Description

Liquid detergents or cleaners containing acylhydrazone

The present application relates to liquid detergents or cleaners containing surfactant, enzyme and certain acylhydrazone as well as the use of such acylhydrazone to improve the soil removal performance of liquid detergents or cleaners.

For incorporation into liquid surfactant compositions, in particular detergents or cleaners, either those ingredients are suitable which dissolve in the liquid phase of the composition or can be suspended in an undissolved, homogeneous manner. In the case of insoluble ingredients, a stable, homogeneous suspension is necessary for the function and aesthetics of the detergent. Sedimented solid particles can agglomerate and, when used, lead to local overconcentration of the ingredient and thus uneven dosage per wash load. Visible clumps, greasy precipitates, or solid ingredient deposits on an e.g. transparent wall of the storage vessel also mean an aesthetic flaw.

The incorporation of some optionally colored solid particles recognizable by the naked human eye in suspension in a transparent or translucent liquid phase as individualized particles are often referred to as speckies. Corresponding particles have for this purpose a corresponding particle size and offer the consumer an aesthetic appeal. Microcapsules are also solid ingredients and include any type of capsule known to those skilled in the art, but especially core-shell capsules and matrix capsules. Matrix capsules are porous shaped bodies that have a structure similar to a sponge. Core-shell capsules are shaped bodies having a core and a shell.

Sedimentation of suspended particles can be avoided by the use of liquid surfactant compositions having a yield point. A yield point can be generated by the selection of special surfactant combinations usually in the presence of an electrolyte salt by establishing a lamellar phase. The use of polymeric thickeners is also possible for generating a yield point. International patent application WO 2009/124855 A1 discloses metal complexes with acyl hydrazone ligands which carry electron-withdrawing substituents in the vicinity of the acyl group. International Patent Application WO 2012/08088 A1 relates to acylhydrazones having cyclic ammonium groups as substituents in the vicinity of the acyl group. International patent application WO 2013/104631 A1 discloses the use of certain acylhydrazones for improving the soil removal performance of detergents or cleaners against soiling from polysaccharide-containing food residues.

The object of the present invention is to provide liquid washing or cleaning compositions which, even without a content of peroxidic bleach, have an excellent detergency or detergency against stains which are conventionally at least partially removed by the use of peroxygen bleaching systems.

Surprisingly, it has been found that this can be achieved by the use of acylhydrazones.

An object of the invention is the use of acylhydrazones of general formula I,

in the R is a CF3 or a Ci-28-alkyl, C2-alkenyl, C2-22-alkynyl, -i2-cycloalkyl, -12-cycloalkenyl, phenyl, naphthyl, -9-aralkyl , -2o-heteroalkyl or -12-cycloheteroalkyl group,

R ² and R ³ independently of one another represent hydrogen or an optionally substituted C 1-28 -alkyl, C 2-6 alkenyl, C 2-12 -alkynyl, -i 2 -cycloalkyl, -i 2 -cycloalkenyl, -9-aralkyl-, Heteroalkyl, -i2-cycloheteroalkyl, -i6-heteroaralkyl, phenyl, naphthyl or heteroaryl or R ² and R ³ together with the carbon atom connecting them to an optionally substituted 5-, 6-, 7 -, 8- or 9-membered ring, which may optionally contain heteroatoms, and

R ^{4 is} hydrogen or a C 1 -28-alkyl, C 2 -alkenyl, C 2-12 -alkynyl, -i 2 -cycloalkyl, -12-cycloalkenyl, -9-aralkyl, -2o-heteroalkyl-, i2-cycloheteroalkyl, -i6-heteroaralkyl or an optionally substituted phenyl or naphthyl or heteroaryl group

stand,

for improving the dirt removal performance of liquid enzyme and surfactant-containing detergents or cleaners.

Another object of the invention are liquid detergents or cleaners containing 1 wt .-% to 70 wt .-%, preferably 1, 5 wt .-% to 50 wt .-% and in particular 2 wt .-% to 40 wt .-% of at least one surfactant,

at least one enzyme, and

at least one acylhydrazone of the general formula I,

in the R is a CF3 or for a Ο-28-alkyl, C2-alkenyl, C2-22-alkynyl, -i2-cycloalkyl, -12-cycloalkenyl, phenyl, naphthyl, -9-aralkyl , 2o-heteroalkyl or -i2-cycloheteroalkyl group, R ² and R ³ independently of one another represent hydrogen or an optionally substituted C 1-28 -alkyl, C 2-6 alkenyl, C 2-22 -alkynyl, -i 2 -cycloalkyl-, -i2-cycloalkenyl, -9-aralkyl, -28-heteroalkyl, -i2-cycloheteroalkyl, -i6-heteroaralkyl, phenyl, naphthyl or heteroaryl or R ² and R ³ together with the connecting them Carbon atom for an optionally substituted 5-, 6-, 7-, 8- or 9-membered ring, which may optionally contain heteroatoms, and

stand, as well

Water.

The term "% by weight" here and below refers to the total weight of the composition, unless stated otherwise.

The liquid agents can be detergents for, for example, textiles, carpets or natural fibers. Detergents in the context of the invention also include washing auxiliaries which are metered into the actual detergent during manual or automatic textile washing in order to achieve a further effect which is not provided by the actual detergent or is provided only to an insufficient extent. Furthermore, laundry detergents within the scope of the invention also include laundry pre-treatment and aftertreatment agents, ie those agents with which the laundry item is brought into contact before or after the actual laundry, for example to dissolve stubborn stains or to achieve a soft feel and comfortable wearing behavior.

"Liquid" means that the detergent or cleaner at room temperature, that is at about 20 ° C, in liquid form and in particular is flowable and thus can be distributed, for example, from a container. In the liquid compositions of the invention or in the context of the use according to the invention, enzyme and / or acylhydrazone may be in dissolved or suspended form; in the latter embodiment, they or at least one of them may be present in the form of powders or, if desired, conventional inert carrier materials containing granules, which may also be coated in a manner known in principle.

Preferred embodiments of the acylhydrazones include those of the general formula (II),

in the R for a Ο-4-alkyl group having a substituent selected from

_R 10 _R 10 _R 1Q _R 10

\ ^"~ Λ \ ₊ \\ i \ i _ft

- NO A-; -NS A-; -NI A-; -NIA ^"

\ / \ / V- O \ - S

in which R ^{0 is} hydrogen or a Ο-28-alkyl, C 2-18 alkenyl, C 2-22 alkynyl, C 3-12 cycloalkyl, C 3-12 cycloalkenyl, Cz-g -Aralkyl, C3-2o-heteroalkyl, C3-i2-cycloheteroalkyl, C5-i6 heteroaralkyl group and A ^"represents the anion of an organic or inorganic acid,

R ² and R ^{4 have} the meaning given for formula (I) and

R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently R, hydrogen, halogen, hydroxy, amino, optionally substituted N-mono or di-O-4-alkyl or C 2-4 hydroxyalkylamino -, N-phenyl or N-naphthyl-amino, Ci-28-alkyl, Ci-28-alkoxy, phenoxy, C2-28-alkenyl, C2-22-alkynyl, C3-i2-cycloalkyl -, C3-i2-cycloalkenyl, Cz-g-aralkyl, C3-2o-heteroalkyl, C3-i2-cycloheteroalkyl, Cs-ie- heteroaralkyl, phenyl or naphthyl group, wherein the substituents are selected from Ci 4-alkyl, hydroxy, sulfo, sulfato, halogen, cyano, nitro, carboxy, phenylphenoxy, naphthoxy, amino, N-mono or di-Ci-4-alkyl or C2-4-hydroxyalkylamino, N-phenyl or N-naphthylamino groups, or

R ⁵ and R ⁶ or R ⁶ and R ⁷ or R ⁷ and R ⁸ to form 1, 2 or 3 carbocyclic or O, NR ¹⁰ - or S-heterocyclic, optionally aromatic and / or optionally C 1-6 alkyl-substituted rings connected to each other.

The anion A ^" is preferably carboxylate, such as lactate, citrate, tartrate or succinate, perchlorate, tetrafluoroborate, hexafluorophosphate, alkyl sulfonate, alkyl sulfate, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, phosphate, isocyanate, rhodanide, nitrate, fluoride, chloride, Bromide, Hydrogen carbonate or carbonate, wherein polyvalent anions, the charge balance can be achieved by the presence of additional cations such as sodium or ammonium ions.

Particular preference is given to the acylhydrazone of the formula (III)

The use according to the invention and the use of an agent according to the invention improve the removal of bleachable stains, in particular without the presence of bleaching agents. Likewise, the removal of enzyme-sensitive stains is improved, that is, the presence of the acylhydrazone enhances the performance of the enzymes.

Bleachable soils are to be understood as meaning those which are colored and, after washing, are removed more strongly in the presence of a peroxidic bleaching agent, such as, for example, sodium percarbonate, and optionally a bleach activator, such as Ν, Ν, Ν ', Ν'-tetraacetylethylenediamine or at least a lighter shade than after washing without the peroxidic bleach and optionally the bleach activator. The bleachable stains usually contain polymerizable substances, in particular dyes, wherein the dyes are preferably polyphenolic dyes, in particular flavonoids, especially anthocyanidins or anthocyanins or oligomers of these compounds. In addition to removing stains in the colors green, yellow, red or blue, stains in intermediate colors, in particular violet, purple, brown, purple or pink, as well as stains, which are green, yellow, red and violet, come into consideration Purple, brown, purple, pink or blue tint, without essentially being made entirely of this color itself. The colors mentioned can also be light or dark in each case. These are preferably stains, in particular stains of grass, fruits or vegetables, in particular soiling by food products, such as spices, sauces, chutneys, curries, purees and jams, or drinks, such as coffee, tea, wines and Juices containing the corresponding green, yellow, red, purple, purple, brown, purple, pink and / or blue dyes.

In this context, enzyme-sensitive soiling should be understood as meaning those which are more strongly removed after washing in the presence of enzymes or, if they are colored, one lighter shade than after washing without the enzyme. Preferably, it is proteinaceous, polysaccharide-containing and / or fatty soils, such as egg, blood, starch, mannan, grass, or sauces.

The inventive and preferably also used in the context of the inventive use agent contains a total amount of 1 to 70 wt .-% of at least one surfactant. It is inventively preferred if the agent contains a total amount of 1, 5 wt .-% to 50 wt .-%, in particular from 2 wt .-% to 40 wt .-%, surfactant.

The liquid agent preferably contains at least one anionic surfactant, in particular selected from the group consisting of Cs -is-alkylbenzenesulfonates, olefinsulfonates, C 12 -is-alkanesulfonates, ester sulfonates, alk (en) ylsulfates, fatty alcohol ether sulfates and mixtures thereof.

It is preferred if the agent contains at least one anionic surfactant of formula (T1)

R ^ _/ S0 ₃ ^" Y ⁺

^A (T1)

wherein

R is a linear or branched, substituted or unsubstituted radical selected from alkyl, aryl or alkylaryl radicals and

the grouping -A- is a direct chemical bond or a radical - (OZ) _n -O-, where Z is an alkylene group having 2 to 4 C atoms, in particular an ethylene and / or propylene group, and n is an integer from 1 to 50, preferably from 1 to 20 and especially from 2 to 10, most preferably 2, 3, 4, 5, 6, 7 or 8, and

Y ^{+ is} a monovalent cation or the nth part of an n-valent cation.

R is preferably a linear, unsubstituted alkyl radical, more preferably a fatty alcohol radical. Preferred radicals R are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl radicals and mixtures thereof, where the representatives with even number of carbon atoms are preferred. Particularly preferred radicals R are derived from C 12-18 fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or from C 10 -cis oxo alcohols, and mixtures of these.

OZ is preferably an ethylene oxide group. The stated degrees of alkoxylation n represent statistical averages, which may be an integer or a fractional number for a surfactant material which can be used in real terms. Preferred cations Y ⁺ are the alkali metal ions and include Na ⁺ or K ⁺ , with Na ^{+ being} highly preferred. ^_1/2 _a ^_1/2 Zn ^2+, ^_1/2 Mg ^2+, Ca ^2+, ¹ / - more cations Y ⁺ may be selected from NH ₄ ^+, (HA) _a N ⁺ (B-OH) ₄ ₂ Mn ²⁺ , and mixtures thereof, wherein A an alkylene group having 1 to 4 C atoms, B is an alkylene group having 2 to 3 C atoms and a is a number from 0 to 4.

The liquid agents may contain as anionic surfactant at least one alkyl ether sulfate of the formula (T1-1)

with k = 1 1 to 19, n = 2, 3, 4, 5, 6, 7 or 8. Very particularly preferred representatives are Na-Ci2-14 fatty alcohol ether sulfates with 2 EO (k = 1 1-13, n = 2 in Formula T1-1)

The liquid agents may contain as anionic surfactant at least one compound of formula (T1 -2)

in the

R ^' and R ^" independently of one another are H or alkyl groups and together contain 9 to 19, preferably 9 to 15 and in particular 9 to 13 C atoms, and for Y ⁺ the formula given above for formula T1 applies describe by the formula (T1-2a):

In addition to synthetic anionic surfactant of the sulfonate and / or sulfate type, the liquid agent may also contain soaps. Suitable are saturated and unsaturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, (hydrogenated) erucic acid and behenic acid and, in particular, soap mixtures derived from natural fatty acids, for example coconut, palm kernel, olive oil or tallow fatty acids.

The liquid agent may contain, instead of or preferably in addition to anionic surfactant, at least one nonionic surfactant. Suitable nonionic surfactants include alkoxylated Fatty acid alkyl esters, alkoxylated fatty acid amides, hydroxylated alkyl glycol ethers, polyhydroxy fatty acid amides, alkylphenol polyglycol ethers, amine oxides, alkyl (poly) glucosides and mixtures thereof.

The agent may contain as nonionic surfactant at least one compound of the formula (T2-1)

R ² -O- (XO) _m -H (T2-1) in the

R ^{2 is} a linear or branched Cs-Os-alkyl radical, an aryl radical or alkylaryl radical,

XO is an ethylene oxide (EO) or propylene oxide (PO) group or mixtures thereof, and m is a number from 1 to 50.

Particularly preferred radicals R ² in the compounds of the formula (T2-1) are derived from C 12 -C 18 -fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or from Cs-Os-oxo alcohols. XO is preferably an ethylene oxide group according to formula (T2-1). The degree of alkoxylation m according to formula (T2-1) is preferably from 1 to 20 and in particular from 2 to 10, very particularly preferably from 2 to 8. It represents a statistical average which is suitable for real use Ten- sidmaterial can be a whole or a fractional number.

The nonionic surfactant used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 4 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as they are usually present in Oxoalkoholresten. In particular, however, alcohol ethoxylates with linear radicals of alcohols of native origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 4 to 8 EO per mole of alcohol are preferred. The preferred ethoxylated alcohols include, for example, C12-14-alcohols with 4 EO or 7 EO, Cg-n-alcohol with 7 EO, cis-is alcohols with 5 EO, 7 EO or 8 EO, Ci2-i8-alcohols with 5 EO or 7 EO and mixtures of these. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow rank ethoxylates, NRE). In addition to or instead of these preferred nonionic surfactants, fatty alcohols containing more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO. Nonionic surfactants containing EO and PO groups together in the molecule can also be used according to the invention. Also suitable are also a mixture of a (more) branched ethoxylated fatty alcohol and an unbranched ethoxylated fatty alcohol, such as a mixture of a Ci6-i8-fatty alcohol with 7 EO and 2-propylheptanol with 7 EO. In particular, the agent preferably contains a C 12-18 fatty alcohol with 7 EO or a C 13-15 oxo alcohol with 7 EO as nonionic surfactant. As nonionic surfactants, the agent may also have amine oxides of the formula (T2-2) RR ² R ³ NO (T2-2) wherein each R, R ² and R ^{3 is} independently of the others an optionally substituted C 1 to C 30 hydrocarbon chain. Preferred amine oxides are those in which R is C 12 -C 18 -alkyl and R ² and R ^{3 are} each independently of the other C 1 -C 4 -alkyl, in particular C 12 -C 18 -alkyldimethylamine oxides. Exemplary representatives of suitable amine oxides are N-cocoalkyl-N, N-dimethylamine oxide, N-tallowalkyl-N, N-dihydroxyethylamine oxide, myristyl / cetyldimethylamine oxide or lauryldimethylamine oxide.

The composition according to the invention or used in the context of the use according to the invention contains at least one enzyme, in particular selected from protease, amylase, lipase, cellulase and / or hemicellulase, such as mannanase and mixtures thereof. Such enzymes are in principle of natural origin; Starting from the natural molecules, improved variants are often available for use in detergents and cleaning agents, which are preferably used accordingly. Agents according to the invention contain enzyme, based on active protein, preferably in amounts of from 1 × 10 ^-6 % by weight to 5% by weight. The protein concentration can be determined by known methods, for example the BCA method (bicinchoninic acid, 2,2'-biquinolyl-4,4'-dicarboxylic acid) or the biuret method.

Among the proteases, those of the subtilisin type are preferable. Examples thereof are the subtilisins BPN 'and Carlsberg, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the enzymes thermitase, proteinase K and the subtilases, but not the subtilisins in the narrower sense Proteases TW3 and TW7. Subtilisin Carlsberg in a developed form under the trade names Alcalase ^® from Novozymes A / S, Bagsvaerd, Denmark. The subtilisins 147 and 309 are sold under the trade names Esperase ^® or Savinase ^® from Novozymes. From the protease from Bacillus lentus DSM 5483 different variants are derived, which can be used. Other useful proteases are from various Bacillus sp. and B. gibsonii. Other usable proteases are, for example, under the trade names Durazym ^®, relase ^®, Everlase® ^®, Nafizym ^®, Natalase ^®, Kannase® ^® and Ovozymes ^® from Novozymes, under the trade names Purafect ^®, Purafect ^® OxP and Properase.RTM ^® by the company Genencor, that under the trade name Protosol® ^® from Advanced Biochemicals Ltd., Thane, India, under the trade name Wuxi ^® from Wuxi Snyder Bioproducts Ltd., China, under the trade names Proleather® ^® and protease P ^® by the company Amano Pharmaceuticals Ltd., Nagoya, Japan, and the enzyme available under the name Proteinase K-16 from Kao Corp., Tokyo, Japan. Examples of amylases are the α-amylases from Bacillus Iicheniformis, from B. amyloliquefaciens or from B. stearothermophilus and their further developments for use in detergents and cleaners. The enzyme from B. licheniformis is available from Novozymes under the name Termamyl ^® and from Genencor under the name Purastar® ^® ST. Development products of this α-amylase are available from Novozymes under the trade names Duramyl ^® and Termamyl ^® ultra, from Genencor under the name Purastar® ^® OxAm and from Daiwa Seiko Inc., Tokyo, Japan, as Keistase ^®. The α-amylase from B. amyloliquefaciens is marketed by Novozymes under the name BAN ^®, and variants derived from the α-amylase from B. stearothermophilus under the names BSG ^® and No- vamyl ^®, likewise from Novozymes. Furthermore, the α-amylase from Bacillus sp. A 7-7 (DSM 12368) and cyclodextrin glucanotransferase (CGTase) from B. agaradherens

(DSM 9948). Likewise, fusion products of said molecules can be used. In addition, the enhancements available under the trade names Fungamyl.RTM ^® by Novozymes of α-amylase from Aspergillus niger and A. oryzae, which are. Other commercial products are, for example amylase LT ^® and Stainzyme®.

The agents may contain lipases and / or cutinases. These include, for example, the lipases originally obtainable from Humicola lanuginosa (Thermomyces lanuginosus) or further developed, in particular those with the amino acid exchange D96L. They are sold, for example, by Novozymes under the trade names Lipolase ^®, Lipolase Ultra ^®, lip- oPrime ^®, Lipozyme® ^® and Lipex ^®. Furthermore, for example, the cutinases can be used, which were originally isolated from Fusarium solani pisi and Humicola insolens. Likewise useable lipases are available from Amano under the designations Lipase CE ^®, Lipase P ^®, Lipase B ^®, or lipase CES ^®, Lipase AKG ^®, Bacillis sp. ^Lipase® , Lipase ^AP® , Lipase M- ^AP® and Lipase ^{AML® are} available. By Genencor, for example, the lipases or cutinases can be used, the initial enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii. Other important commercial products are those originally marketed by Gist-Brocades

M1 Lipase Lipomax ^® and ^® and the enzymes marketed by Meito Sangyo KK, Japan under the name Lipase MY-30 ^®, ^® Lipase OF and Lipase PL ^® to mention also the product Lumafast ^® from Genencor.

The agents may contain cellulases, depending on the purpose as pure enzymes, as enzyme preparations or in the form of mixtures in which the individual components complement each other advantageously in terms of their various performance aspects. These performance aspects include, in particular, contributions to the primary washing performance, to the secondary washing performance of the agent (antiredeposition effect or graying inhibition) and finishing (tissue effect), right through to exercise a "stone washecT effect. A useful fungal, endoglucanase (EG) -rich cellulase preparation and developments thereof are offered by Novozymes under the trade name Celluzyme ^®. The products are also available from Novozymes Endolase® ^® and Carezyme ^® are based on the 50 kD EG and 43 kD EG from H. insolens DSM 1800. Further commercial products of this company Cellusoft® ^® and Renozyme ^®. It is also possible the use of cellulase 20 kD EG Melanocarpus from AB Enzymes , Finland, is sold under the trade names Ecostone® ^® and Biotouch ^® available. Further commercial products from AB Enzymes are Econase® ^® and ECOPULP ^®. the Bacillus sp.

CBS 670.93 derived cellulase is from the company Genencor under the trade name

Puradax ^® available. Further commercial products of the company Genencor are "Genencor detergent cellulase L" and lndiAge ^® Neutra.

The agents may contain other enzymes, which are summarized by the term hemicellulases. These include, for example, mannanases, xanthan lyases, pectin lyases

(= Pectinases), pectin esterases, pectate lyases, xyloglucanases (= xylanases), pullulanases and ß-glucanases. Suitable mannanases include, for example, under the names Gamanase ^®, Pekti- nex AR ^® and Mannaway ^® from Novozymes under the name ^® Rohapec B1L by AB Enzymes and under the name ^® Pyrolase® from Diversa Corp. available. The obtained from B. subtilis beta-glucanase is available under the name Cereflo ^® from Novozymes.

The enzymes are produced by biotechnological methods known per se by suitable microorganisms, for example by transgenic expression hosts such as the genera Bacillus or filamentous fungi.

An enzyme, in particular during storage, can be protected against damage such as inactivation, denaturation or decomposition by, for example, physical influences, oxidation or proteolytic cleavage. The agents may contain enzyme stabilizers for this purpose. One group of enzyme stabilizers are reversible protease inhibitors. Frequently, benzamidine hydrochloride, borax, boric acids, boronic acids or their salts or esters are used, in particular derivatives with aromatic groups, for example ortho-substituted, meta-substituted or para-substituted phenylboronic acids or their salts or esters, and / or peptide aldehydes, that is, oligopeptides with reduced C-terminus, ovomucoid, and / or leupeptin. Further enzyme stabilizers are amino alcohols such as mono-, di-, triethanol- and -propanolamine and mixtures thereof, aliphatic carboxylic acids up to C 12 such as succinic acid, other dicarboxylic acids or salts of said acids, end-capped fatty acid amide alkoxylates, lower aliphatic alcohols such as ethanol or propanol, above all, however, polyols, such as, for example, glycerol, ethylene glycol, propylene glycol or sorbitol, but also di- Glycerol phosphate, calcium salts such as calcium acetate or calcium formate, and magnesium salts. Preference is given to using combinations of stabilizers, for example of polyols, boric acid and / or borax, or of boric acid or borate, reducing salts and succinic acid or other dicarboxylic acids, or of boric acid or borate with polyols or polyamino compounds and with reducing salts.

The compositions according to the invention and those used in the context of the use according to the invention are liquid and contain water. It is preferred that the agent contains more than 5 wt .-%, preferably more than 15 wt .-% and in particular more than 25 wt .-% water. Particularly preferred liquid detergents contain from 5% by weight to 90% by weight, preferably from 10% by weight to 85% by weight, particularly preferably from 25% by weight to 75% by weight and in particular 35% by weight to 65% by weight of water. Alternatively, the detergents may be low-water agents, with the level of water in preferred embodiments being less than 10% by weight and more preferably less than 8% by weight.

Besides, the agent may contain non-aqueous water-miscible organic solvents. Suitable non-aqueous solvents include monohydric or polyhydric alcohols, alkanolamines or glycol ethers. The solvents are preferably selected from ethanol, n-propanol, isopropanol, butanols, glycol, propanediol, butanediol, methylpropanediol, glycerol, diglycol, propyldiglycol, butyldiglycol, hexyleneglycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylglycolpropyl ether, ethylene glycol mono-n- butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, methoxytriglycol, ethoxytriglycol, butoxytriglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene glycol t-butyl ether, Di-n-octyl ether and mixtures of these solvents. Preferably, the composition contains non-aqueous water-miscible organic solvents, especially at least one alcohol, in amounts of from 0.5% to 5% by weight; the amount of non-aqueous water-miscible organic solvent optionally contained as an enzyme stabilizer or component of an enzyme stabilizer system in the agent is thereby included.

The liquid agent may additionally contain other ingredients that further improve its performance and / or aesthetic properties depending on the intended use. In the context of the present invention, agents, in particular if they are used as textile treatment agents (for example as detergents or softeners), may be builders, esterquats, silicone oils, emulsifiers, thickeners, electrolytes, pH regulators, fluorescers, dyes, hydrotopes, foam inhibitors, anti redeposition agents , Solvents, optical brighteners, scorch inhibitors, shrinkage inhibitors, anti-crease agents, dye transfer inhibitors, color protectants, wetting improvers, antimicrobial agents, germicides, fungicides, antioxidants, corrosion inhibitors, preservatives, antistatic agents, ironing auxiliaries, repellents and imitations. contain impregnating agents, polymers, swelling and anti-sliding agents and / or UV absorbers. An agent according to the invention is preferably free of bleaching agents.

An agent suitable as a textile treatment or cleaning agent preferably contains at least one water-soluble or water-insoluble, organic or inorganic builder. The water-soluble organic builder substances include polycarboxylic acids, in particular citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid and sugar acids, monomeric and polymeric aminopolycarboxylic acids, in particular methylglycinediacetic acid, nitrilotriacetic acid and ethylenediaminetetraacetic acid and polyaspartic acid, polyphosphonic acids, in particular aminotris (methylenephosphonic acid) , Ethylenediaminetrakis (methylenephosphonic acid) and 1-hydroxyethane-1, 1-diphosphonic acid, polymeric hydroxy compounds such as dextrin and polymeric (poly) carboxylic acids, polymeric acrylic acids, methacrylic acids, maleic acids and copolymers thereof, which polymerize even small amounts - Can contain substances in copolymerized form without carboxylic acid functionality. Suitable, although less preferred, compounds of this class are copolymers of acrylic or methacrylic acid with vinyl ethers, such as vinylmethyl ethers, vinyl esters, ethylene, propylene and styrene, in which the acid content is at least 50% by weight. The organic builders may be used to prepare the liquid agents, in the form of aqueous solutions, such as in the form of 30 to 50 weight percent aqueous solutions. All of the acids mentioned are generally used in the form of their water-soluble salts, in particular their alkali metal salts. Preferred are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures thereof. Builders may, if desired, be included in the compositions in amounts of up to 40% by weight, more preferably up to 25% by weight, and preferably from 1% to 8% by weight. Laundry aftertreatment agents, such as fabric softeners, may optionally also be free of builder.

Optical brighteners are preferably selected from the substance classes of distyrylbiphenyls, the Silibene, the ^{^{diamino-2,2-stilbenedisulfonic}} acids 4.4, the coumarins, the dihydroquinolinones, the 1, 3-diaryl pyrazolines, naphthalimides of the benzoxazole systems, Benzisoxazole systems, the benzimidazole systems, heterocyclic substituted pyrene derivatives, and mixtures thereof. Particularly preferred optical brighteners include disodium 4,4'-bis (2-morpholino-4-anilino-s-triazin-6-ylamino) stilbene disulfonate (available, for example, as Tinopal® DMS from BASF SE), disodium 2,2 '. bis (phenyl-styryl) disulfonate (available, for example, as Tinopal® CBS from BASF SE), 4,4'-bis [(4-anilino-6- [bis (2-hydroxyethyl) amino] -1, 3.5 -triazin-2-yl) -amino] stilbene-2,2'-disulfonic acid (available, for example, as Tinopal® UNPA from BASF SE), 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) (obtainable, for example, as Tinopal® SFP from BASF SE), 2, 2 '- (2,5-thiophenediyl) bis [5-1, 1-dimethylethyl) benzoxazole (available, for example, as Tinopal® SFP from BASF SE) and / or 2,5-bis (benzoxazol-2-yl) thiophene. In addition, the agents suitable as textile treatment or cleaning agents may also contain components which positively influence the oil and Fettauswaschbarkeit from textiles, so-called soil release agents. This effect becomes particularly clear when a textile is soiled, which has been previously washed several times with an agent containing this oil and fat dissolving component. The preferred oil and fat dissolving components include, for example, nonionic cellulose ethers such as methylcellulose and methylhydroxypropylcellulose with a proportion of methoxy groups of 15 to 30 wt .-% and hydroxypropoxyl groups of 1 to 15 wt .-%, each based on the nonionic cellulose ethers, as well as the known from the prior art polymers of phthalic acid and / or terephthalic acid or derivatives thereof with monomeric and / or polymeric diols, especially polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionic and / or nonionic modified derivatives of these.

The textile treatment or cleaning agents may also color transfer inhibitors, preferably in amounts of 0.1 wt .-% to 2 wt .-%, in particular 0.1 wt .-% to 1 wt .-%, containing, in a preferred embodiment of the invention polymers of vinylpyrrolidone , Vinylimidazole, vinylpyridine N-oxide or copolymers thereof. It is preferred that the color transfer inhibitor is a polymer or copolymer of cyclic amines such as vinylpyrrolidone and / or vinylimidazole. Suitable color transfer inhibiting polymers include polyvinylpyrrolidone (PVP), polyvinylimidazole (PVI), copolymers of vinylpyrrolidone and vinylimidazole (PVP / PVI), polyvinylpyridine-N-oxide, poly-N-carboxymethyl-4-vinylpyridium chloride, polyethyleneglycol-modified copolymers of vinylpyrrolidone and vinylimidazole and mixtures thereof. Particular preference is given to using polyvinylpyrrolidone (PVP), polyvinylimidazole (PVI) or copolymers of vinylpyrrolidone and vinylimidazole (PVP / PVI) as color transfer inhibitor. The polyvinylpyrrolidones (PVP) used preferably have an average molecular weight of from 2 500 g / mol to 400 000 g / mol and are commercially available from ISP Chemicals as PVP K 15, PVP K 30, PVP K 60 or PVP K 90 or from BASF SE 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 5000 g / mol to 100 000 g / mol. Commercially available is a PVP / PVI copolymer, for example, from BASF SE under the name Sokalan® HP 56. Another extremely preferably usable color transfer inhibitor are polyethylene glycol-modified copolymers of vinylpyrrolidone and vinylimidazole, which are available, for example, under the name Sokalan® HP 66 from BASF SE are.

Graying inhibitors have the task of keeping suspended from the textile fiber dirt suspended in the fleet. Water-soluble colloids of mostly organic nature are suitable for this purpose, for example starch, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or of cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Also, water-soluble polyamides containing acidic groups are suitable for this purpose. Furthermore, other than the above-mentioned starch derivatives can be used, for example aldehyde starches. Preference is given to using cellulose ethers, such as carboxymethylcellulose (Na salt), methylcellulose, hydroxyalkylcellulose and mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof, for example in amounts of from 0.1 to 5% by weight, based on the compositions become.

In yet another aspect, the invention is directed to a process for textile treatment comprising the process steps

(A) providing a solution comprising a detergent according to the invention, and

(b) contacting a soiled textile with the solution according to (a).

The solution can be prepared by dissolving a composition according to the invention or its individual constituents, it being possible for some of the constituents to be combined to form an agent, which may not then be inventive. In the context of the last-mentioned embodiment, it is possible to use an acylhydrazone-free agent and to add to the solution an acylhydrazone essential to the invention; It is also possible to use an enzyme-free or only certain enzymes containing agent and the solution to add at least one enzyme or at least one specific other enzyme, and also to use an enzyme and acylhydrazone-free agent and the solution to add an essential acylhydrazone invention and at least one enzyme. It is inventively preferred if 10 g to 1 10 g, in particular 15 g to 100 g of the composition with 5 l to 25 l of water, in particular with 10 l to 20 l of water are mixed to prepare said solution.

In the washing process, which can be carried out manually or by means of conventional washing machines, preferably temperatures of 60 ° C or less, in particular 50 ° C or less, and particularly preferably from 15 ° C to 45 ° C are used. These temperature data refer to the temperatures used in the washing steps.

Examples

Cotton fabrics, which were provided with the standardized stains set forth in the table below, were treated with wash liquors (from 16 ° dH water) at 4.1 g / l of enzyme and surfactant containing water at 40 ° C for 70 minutes , bleach-free liquid detergent or with an otherwise identical wash liquor, which is additionally 0.7 g / l of morpholinium 4- (2- (2 - ((2-hydroxyphenylmethyl) methylene) hydrazinyl) -2-oxoethyl) -4-methyl chloride, washed under the same conditions. The treated fabric substrates were subsequently dried and color-measured to determine the Y value (brightness value). The following table shows the difference in the brightness value of the measuring pieces (average of 3-fold determinations) between the wash with the acylhydrazone-containing wash and the wash with the acylhydrazone-free wash liquor with the error limits observed. It can be seen that the stain removal performance in the presence of the acylhydrazone was significantly higher than that without its addition.

Table 1: AY values

Soiling ΔΥ error limit

Grass 2,7 1, 4

Red wine, fresh 3.7 1, 9

Beetroot 2,3 1, 3

Red wine, aged 3,3 1, 7

Coffee 2,9 1, 3

Curry 1, 0 0.6

Blueberry juice 6,7 2,4

Claims

claims

1. Use of acylhydrazones of the general formula I,

in the R represents a CF3 or a Ο-28-alkyl, C2-alkenyl, C2-22-alkynyl, -i2-cycloalkyl, -i2-cycloalkenyl, phenyl, naphthyl, -9-aralkyl , -2o-heteroalkyl or -12-cycloheteroalkyl group,

R ² and R ³ independently of one another represent hydrogen or an optionally substituted C 1-6 -alkyl, C 2-6 alkenyl, C 2-12 -alkynyl, -i 2 -cycloalkyl, -i 2 -cycloalkenyl, -9-aralkyl-, 28- heteroalkyl, -i2-cycloheteroalkyl, -i6-heteroaralkyl, phenyl, naphthyl or heteroaryl group or R ² and R ³ together with the carbon atom connecting them for an optionally substituted 5-, 6-, 7- , 8- or 9-membered ring, which may optionally contain heteroatoms, and

R ^{4 is} hydrogen or a C 1 -28-alkyl, C 2 -alkenyl, C 2-12 -alkynyl, -i 2 -cycloalkyl, -12-cycloalkenyl, -9-aralkyl, -2o-heteroalkyl-, i2-cycloheteroalkyl, -16-heteroaralkyl or an optionally substituted phenyl or naphthyl or heteroaryl group

stand,

2. Use of acylhydrazones of the general formula (II)

in the R for a Ci-4-alkyl group, which is a substituent selected from

10 _R 10 _R 10 _R 10

R

\\ l

NO A-; -NS A-; -NI A-: -NIA ^'

\ / VJ o in which R ^{0 is} hydrogen or C 1 -C 28 -alkyl, C 2-28 alkenyl, C 2-22 alkynyl, C 3-12 cycloalkyl, C 3-12 cycloalkenyl, C 7-9 aralkyl -, C3-2o-heteroalkyl, C3-i2-cycloheteroalkyl, C5-16 heteroaralkyl and A ^"represents the anion of an organic or inorganic acid, R ² and R ^{4 have} the meaning given for formula (I) and

R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently R, hydrogen, halogen, a hydroxy, amino, an optionally substituted N-mono or di-O-4-alkyl or C 2-4 hydroxyalkylamino, N-phenyl or N-naphthylamino, Ci- 28 -alkyl-, Ci- 28 -alkoxy-, phenoxy-, C2-28-alkenyl-, C2-22-alkynyl-, C3- i2-cycloalkyl, C 3-12 cycloalkenyl, C 7-9 aralkyl, C 3-30 heteroalkyl, C 3-12 cycloheteroalkyl, C 5-6 heteroaralkyl, phenyl or naphthyl, be selected from Ο-4-alkyl, Ci-4-alkoxy, hydroxy, sulfo, sulfato, halogen, cyano, nitro, carboxy, phenyl, phenoxy, naphthoxy, amino , N-mono or di-C 1-4 -alkyl or C 2-4 -hydroxyalkylamino, N-phenyl or N-naphthylamino groups, or

R ⁵ and R ⁶ or R ⁶ and R ⁷ or R ⁷ and R ⁸ to form 1, 2 or 3 carbocyclic or O, NR ¹⁰ - or S-heterocyclic, optionally aromatic and / or optionally Ci-6-alkyl-substituted rings connected to each other,

Use according to claim 1 or 2, characterized in that one uses a liquid agent, the 1 wt .-% to 70 wt .-%, in particular 1, 5 wt .-% to 50 wt .-% surfactant and / or 1 x 10 ^{~ 6} wt .-% to 5 wt .-%, based on active protein, enzyme selected from protease, amylase, lipase, cellulase and / or hemicellulase and mixtures thereof.

Use according to one of claims 1 to 3, characterized in that the improvement of the dirt removal performance against bleachable and / or enzyme-sensitive soiling takes place.

Liquid washing or cleaning agent containing 1 wt .-% to 70 wt .-% of at least one surfactant, at least one enzyme, and at least one acylhydrazone of the general formula

in the R represents a CF 3 or a C-28-alkyl, C 2-30 alkenyl, C 2-22 alkynyl, C 3-12 cycloalkyl, C 3-12 cycloalkenyl, phenyl, naphthyl, C7-9 aralkyl, C3-2o heteroalkyl or C3-12 cycloheteroalkyl group, R ² and R ³ independently of one another represent hydrogen or an optionally substituted C 1-8-alkyl, C 2-30 -alkenyl, C 2-22 -alkynyl, C 3-12 -cycloalkyl, C 3-12 -cycloalkenyl, C 7- 9-aralkyl, C3-28 heteroalkyl, C3-i2-cycloheteroalkyl, C5-i6 heteroaralkyl, phenyl, naphthyl or heteroaryl group, or R ² and R ³ together with the carbon atom connecting them, optionally substituted 5-, 6-, 7-, 8- or 9-membered ring, which may optionally contain heteroatoms, and

R ^{4 is} hydrogen or a C-28-alkyl, C 2-30 alkenyl, C 2-22 alkynyl, C 3-12 cycloalkyl, C 3-12

Cycloalkenyl, C7-9 aralkyl, C3-2o heteroalkyl, C3-i2 cycloheteroalkyl, C5-16

Heteroaralkyl group or an optionally substituted phenyl or naphthyl or heteroaryl group

stand, as well

Water.

6. A composition according to claim 5, characterized in that it contains at least one anionic surfactant, in particular selected from the group consisting of Cs -is-alkylbenzenesulfonates, Olefinsulfonaten, Ci2-is-alkanesulfonates, ester sulfonates, alk (en) ylsulfaten, Fettalkoho- lethersulfaten and mixtures thereof.

7. Composition according to claim 5 or 6, characterized in that it contains at least one nonionic surfactant.

8. Use according to one of claims 1 to 4 or agent according to one of claims 5 to 7, characterized in that enzyme and / or acylhydrazone are in dissolved or suspended form and they or at least one of them in the latter embodiment in the form of powders or, if desired, conventional granules containing inert carrier materials which may also be coated in a manner known in principle.

9. A process for textile treatment, comprising the process steps

(A) providing a solution comprising a detergent according to any one of claims 5 to 8, and

(b) contacting a soiled textile with the solution according to (a).

10. The method according to claim 9, characterized in that temperatures of 60 ° C or less, in particular 50 ° C or less, and more preferably at 15 ° C to 45 ° C are used.