DE102016206645A1 - Detergent with improved enzyme stability - Google Patents

Abstract

The present application is directed to the use of a surfactant system for stabilizing at least one enzyme in enzyme-containing detergents, in particular liquid detergents, wherein the surfactant system comprises at least one secondary alkanesulfonate, at least one linear alkylbenzenesulfonate, at least one alkyl ether sulfate and at least one alkyl ether.

Description

The present application is directed to the use of a surfactant system for stabilizing at least one enzyme in enzyme-containing detergents, in particular liquid detergents, wherein the surfactant system comprises at least one secondary alkanesulfonate, at least one linear alkylbenzene sulfonate, at least one alkyl ether sulfate and at least one alkyl ether.

High-quality detergents available today contain a wide variety of enzymes in order to completely remove enzyme-sensitive soiling, such as fats and proteins, on textiles during the washing process. In particular, hydrolytic enzymes such as proteases, amylases, lipases and cellulases are used as enzymes for this purpose.

When storing such enzyme-containing detergents or their basic masses, the stability of the enzymes decreases markedly over time, since, in particular proteases tend to cleave other enzymes contained in the detergent. Therefore, in enzyme-containing detergents usually enzyme stabilizer systems, such as boric acid in combination with 1,2-propanediol, used to stabilize the enzymes contained in the detergent during storage. However, the stabilizers used must be chosen so that they do not over-stabilize the enzymes, otherwise the enzymes do not develop their desired cleaning power during the washing process. For this reason, conventional stabilizer systems always represent a compromise between storage stability on the one hand and maintenance of the functionality of the enzymes on the other hand. It is therefore still a general endeavor to provide detergents, especially liquid detergents, with improved enzyme storage stability.

It has now surprisingly been found that enzyme-containing detergents, in particular liquid detergents which comprise a surfactant system which comprises at least one secondary alkanesulfonate, at least one linear alkylbenzene sulfonate, at least one alkyl ether sulfate and at least one alkyl ether, have increased enzyme stability, in particular storage stability. Furthermore, the stabilized enzyme is completely released during the washing process and can thus unfold its full enzymatic action and remove enzyme-sensitive soiling on textiles, without the stabilizer having a negative effect on the detergency of the detergent, in particular the enzyme action. Finally, liquid bases based on this surfactant system are highly perfumable, so that a lesser amount of perfume is needed to achieve a comparable odor intensity with conventional means.

• (a) mindestens ein sekundäres Alkansulfonat in einer Menge von 3 bis 20 Gew.-%, vorzugsweise von 8 bis 18 Gew.-% und besonders bevorzugt 8–10 Gew.-% bezogen auf das enzymhaltige Waschmittel;
• (b) mindestens ein lineares Alkylbenzolsulfonat in einer Menge von 3 bis 20 Gew.-%, vorzugsweise von 8 bis 18 Gew.-% und besonders bevorzugt 8–10 Gew.-% bezogen auf das enzymhaltige Waschmittel;
• (c) mindestens ein Alkylethersulfat in einer Menge von 3 bis 20 Gew.-%, vorzugsweise von 8 bis 18 Gew.-% bezogen auf das enzymhaltige Waschmittel; und
• (d) mindestens ein Alkylether in einer in einer Menge von 3 bis 20 Gew.-%, vorzugsweise von 8 bis 18 Gew.-% bezogen auf das enzymhaltige Waschmittel.

In a first aspect, the present invention therefore relates to the use of a surfactant system for stabilizing at least one enzyme in enzyme-containing detergents, in particular liquid detergents, wherein the surfactant system comprises:

• (A) at least one secondary alkanesulfonate in an amount of 3 to 20 wt .-%, preferably from 8 to 18 wt .-% and particularly preferably 8-10 wt .-% based on the enzyme-containing detergent;
• (b) at least one linear alkylbenzenesulfonate in an amount of 3 to 20% by weight, preferably 8 to 18% by weight and more preferably 8 to 10% by weight, based on the enzyme-containing detergent;
• (C) at least one alkyl ether sulfate in an amount of 3 to 20 wt .-%, preferably from 8 to 18 wt .-% based on the enzyme-containing detergent; and
• (D) at least one alkyl ether in one in an amount of 3 to 20 wt .-%, preferably from 8 to 18 wt .-% based on the enzyme-containing detergent.

The surfactant system according to the invention is preferably contained in a total amount of from 20 to 50% by weight, particularly preferably from 35 to 45% by weight, in the detergents according to the invention.

In the context of the invention, the stabilization of at least one enzyme is understood to mean the reduction or complete suppression of the degradation or cleavage of the at least one enzyme in comparison to agents which do not contain the surfactant system. This information refers to the period of storage of a matrix of the agent, the intermediate of the agent during the manufacturing process and the actual finished detergent.

In the context of the invention, cleaning performance (detergency) is understood to mean the removal of one or more soiling, in particular laundry soils, which are bleach-sensitive, enzyme-sensitive or surfactant-sensitive, in particular enzyme-sensitive. The distance can be measured by a brightening of the soiling measured as well as assessed visually.

The detergents described herein may be detergents for textiles or natural fibers. Detergents in the context of the invention also include washing aids which are metered into the actual detergent during manual or automatic textile washing in order to achieve a further effect or to enhance an effect. Furthermore, detergents within the scope of the invention also include textile pre-treatment and post-treatment agents, ie those agents with which the item of laundry is brought into contact before the actual washing, for example for dissolving stubborn soiling, and also agents which are in a downstream of the actual textile laundry step give the laundry further desirable properties such as comfortable grip, crease resistance or low static charge. Amongst others, the fabric softeners are calculated.

By using the surfactant system described herein, enzymes can be stabilized in enzyme-containing detergents, preferably liquid detergents. Thus, the storage stability is significantly improved. Further, the surfactant system described herein has very good detergency and perfumability properties, so that fewer amounts of perfume are required to achieve the same perfume intensity compared to conventional detergents.

All amounts stated in connection with the constituents of the detergent described herein are, unless stated otherwise, by weight in each case based on the total weight of the detergent. Further, such amounts referring to at least one ingredient always refer to the total amount of that type of ingredient contained in the detergent, unless explicitly stated otherwise. That is, such amounts, for example in connection with "at least one nonionic surfactant", refer to the total amount of nonionic surfactants contained in the detergent.

"At least one" as used herein refers to 1 or more, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9 or more. In the context of ingredients of the compositions described herein, this indication does not refer to the absolute amount of molecules but to the nature of the ingredient. Thus, for example, "at least one surfactant" means one or more different surfactants, i. one or more different types of surfactants. Together with quantities, the quantities refer to the total amount of the corresponding designated type of ingredient as defined above.

"Approximately" as used herein in reference to a numerical value means the referenced numerical value ± 10%, preferably ± 5%.

The surfactant system according to the invention stabilizes the at least one enzyme in enzyme-containing detergents.

The at least one enzyme may be any enzyme known in the art capable of exhibiting catalytic activity in a detergent or cleaning agent, and includes but is not limited to, for example, proteases, amylases, lipases, cellulases, hemicellulases, mannanases, pectin cleaving enzymes, tannases, xylanases, xanthanases, β-glucosidases, carrageenases, perhydrolases, oxidases, oxidoreductases and mixtures thereof. In a preferred embodiment, the at least one enzyme is selected from the group consisting of proteases, amylases, lipases, cellulases and mixtures thereof. These enzymes are, in principle, of natural origin, but starting from the natural molecules, improved variants are available for use in detergents or cleaners, which are preferably used accordingly.

Among the proteases, those of the subtilisin type are preferable. Examples of these 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 derived under the name BLAP ^® protease variants derived. Other usable proteases are, for example, under the trade names Durazym ^®, relase ^®, Everlase® ^®, Nafizym ^®, Natalase ^®, Kannase® ^® and Ovozyme ^® from Novozymes, the ^® under the trade names Purafect ^®, Purafect ^® OxP, Purafect Prime, Excellase ^® and Properase.RTM ^® from 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 ^® from Amano Pharmaceuticals Ltd., Nagoya, Japan, and the enzyme available under the name Proteinase K-16 from Kao Corp., Tokyo, Japan. Particular preference is also given to using the proteases from Bacillus gibsonii and Bacillus pumilus.

Examples of amylases are the α-amylases from Bacillus licheniformis, from B. amyloliquefaciens or from B. stearothermophilus and their further developments for use in detergents or 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 derived variants from the α- amylase from B. stearothermophilus under the names BSG ^® and Novamyl ^®, likewise from Novozymes. Furthermore, for this purpose, the α-amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948). Likewise, fusion products of all the molecules mentioned can be used. In addition, the enhancements available under the trade names Fungamyl.RTM ^® by the company Novozymes of α-amylase from Aspergillus niger and A. oryzae, which are. Other advantageous commercial products are for example the Amylase-LT ^® and Stainzyme® ^® or ultra Stainzyme® ^® or Stainzyme® plus ^®, the latter also from the company Novozymes. Also variants of these enzymes obtainable by point mutations can be used according to the invention.

Examples of useful lipases or cutinases, which are contained in particular because of their Triglyceridspaltenden activities, but also to generate from suitable precursors in situ peracids are the lipacases originally 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 ^®, LipoPrime® ^®, Lipozyme® ^® and Lipex ^®. Furthermore, for example, the cutinases can be used, which have been originally isolated from Fusarium solani pisi and Humicola insolens. Lipases which are likewise useful are sold by Amano under the names Lipase ^CE® , Lipase ^P® , Lipase ^B® or Lipase ^CES® , Lipase ^AKG® , Bacillus 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 the originally marketed by Gist-Brocades preparations M1 Lipase ^® and Lipomax® ^® and the enzymes marketed by Meito Sangyo KK, Japan under the names Lipase MY-30 ^®, Lipase OF ^® and lipase PL ^® to mention also the product Lumafast® ^® from Genencor.

Depending on the purpose, cellulases may be present as pure enzymes, as enzyme preparations or in the form of mixtures in which the individual components advantageously complement each other in terms of their various performance aspects. These performance aspects include in particular the contributions of the cellulase to the primary washing performance of the composition (cleaning performance), to the secondary washing performance of the composition (anti-redeposition effect or graying inhibition), to softening (fabric effect) or to the exercise of a "stone washed" effect. A useful fungal, Endoglucanase (EG) -rich cellulase preparation, or their developments is offered by the company Novozymes under the trade name Celluzyme ^® . The products Endolase® ^® and Carezyme ^®, likewise available from Novozymes, are based on the 50 kD EG and 43 kD EG from H. insolens DSM 1800. Further commercial products of this company are Cellusoft® ^{®, ®} and Renozyme Celluclean ^®. Also usable are for example the 20 kD EG Melanocarpus, which are available from AB Enzymes, Finland, under the trade names Ecostone ^® and Biotouch ^®. Further commercial products from AB Enzymes are Econase® ^® and ECOPULP ^®. Other suitable cellulases are from Bacillus sp. CBS 670.93 and CBS 669.93, those derived from Bacillus sp. CBS 670.93 from the company Genencor under the trade name Puradax ^{® is} available. Further commercial products of the company Genencor are "Genencor detergent cellulase L" and lndiAge ^® Neutra. Also variants of these enzymes obtainable by point mutations can be used according to the invention. Particularly preferred cellulases are Thielavia terrestris cellulase variants, cellulases from melanocarpus, in particular melanocarpus albomyces, cellulases of the EGIII type from Trichoderma reesei or variants obtainable therefrom.

Furthermore, in particular for the removal of certain problem soiling, further enzymes can be used, which are summarized by the term hemicellulases. These include, for example, mannanases, xanthan lyases, xanthanases, xyloglucanases, xylanases, pullulanases, pectin-splitting enzymes and β-glucanases. The obtained from Bacillus subtilis beta-glucanase under the name of Cereflo ^® available from Novozymes. According to the invention particularly preferred hemicellulases are mannanases, which are marketed under the trade names man Away ^® by the company Novozymes or Purabrite ^® by the company Genencor. The pectin-destroying enzymes in the context of the present invention are also counted enzymes with the designations pectinase, pectate lyase, pectin esterase, pectin methoxylase, pectin methoxylase, pectin methyl esterase, pectase, pectin methyl esterase, pectin esterase, pectin-pectin hydrolase, pectin-polymerase, endopolygalacturonase, pectolase, pectin hydrolase, pectin-polygalacturonase, Endo-polygalacturonase, poly-α-1,4-galacturonide glycanohydrolase, endogalacturonase, endo-D-galacturonase, galacturan 1,4-α-galacturonidase, exopolygalacturonase, poly (galacturonate) hydrolase, exo-D-galacturonase, exo-D Galacturonanase, exopoly-D-galacturonase, exo-poly-α-galacturonosidase, exopolygalacturonosidase or exopolygalacturanosidase. Examples in this regard, suitable enzymes for example, under the name Gamanase ^®, Pektinex AR ^®, X-Pect ^® or Pectaway ^® by the company Novozymes, UF under the name Rohapect ^®, Rohapect TPL ^®, Rohapect PTE100 ^®, Rohapect MPE ^®, Rohapect MA available plus HC, Rohapect DA12L ^®, Rohapect 10L ^®, Rohapect B1L ^® by the company AB Enzymes and under the name Pyrolase® ^® by the company Diversa Corp., San Diego, CA, United States.

Of all these enzymes, particular preference is given to those which have been stabilized per se with respect to oxidation in a comparatively stable manner or, for example, via point mutagenesis. Among the above-mentioned commercial products Everlase ^® and Purafect ^® OxP as examples of such proteases and Duramyl ^® are particular to cite as an example of such an α-amylase.

To increase the bleaching effect, oxidoreductases, for example oxidases, oxygenases, catalases (which react as peroxidase at low H ₂ O ₂ concentrations), peroxidases, such as halo-, chloro-, bromo-, lignin, can also be used in the detergents, especially liquid detergents , Glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases). Suitable commercial products Denilite® ^® 1 and 2 from Novozymes should be mentioned.

The detergents, in particular liquid detergents, contain the at least one enzyme in amounts established in the prior art. Thus, the at least one enzyme in a total amount of 1 × 10 ^-8 to 5 wt .-% based on active protein or in a total amount of 0.001 to 3 wt .-%, or 0.01 to 1.5 parts by weight. % or 0.05 to 1.25 wt .-% contained. The amounts given are to be understood so that any enzyme contained can be contained in the stated amounts. In liquid formulations, the enzymes are preferably used as enzyme liquid formulation (s).

The at least one enzyme present in a detergent or cleanser aids the cleaning performance of the agent on certain soils or stains. Particularly preferably, an agent according to the invention contains a plurality of enzymes, wherein the enzymes may belong to the same or different enzyme classes. Most preferably, the enzymes exhibit synergistic effects in their action against certain soils or stains, i. The enzymes contained in the composition support each other in their cleaning performance.

The surfactant system for stabilization comprises at least one secondary alkanesulfonate. The at least one secondary alkanesulfonate may be any known secondary alkanesulfonate suitable for the purpose of this invention. Secondary, as used herein, refers to the well-known chemical meaning of this term, and indicates that the carbon atom to which the sulfonate group is covalently bonded continues to have two covalent bonds to two organic (alkylic) residues, i. Carbon atoms, and having a covalent bond to a hydrogen atom.

Together with the carbon atom to which they are attached, the two organic (alkylic) radicals form one or branched alkyl of 1 to 50 carbon atoms. In order to compensate for the negative charge of the sulfonate group, the alkanesulfonate according to the invention further comprises any cation, preferably selected from the group Na ⁺ , K ⁺ , NH ₄ ⁺ , ½Zn ²⁺ , ½Mg ²⁺ , ½Ca ²⁺ , ½Mn ²⁺ and their mixtures, more preferably Na ⁺ .

In a preferred embodiment of the present invention, the at least one secondary alkanesulfonate has the formula (I) R ¹ CH (SO ₃ ^- X ⁺ ) R ² (I) wherein each of R ¹ and R ^{2 is} independently a linear or branched alkyl of 1 to 20 carbon atoms and form with the carbon atom to which they are attached a linear or branched alkyl, preferably of 10 to 30 carbon atoms, preferably 10 to 20 carbon atoms and X ^{+ is} selected from the group Na ⁺ , K ⁺ , NH4 ⁺ , ½Zn ²⁺ , ½Mg ²⁺ , ½Ca ²⁺ , ½Mn ²⁺ and mixtures thereof, preferably Na ⁺ .

In still another preferred embodiment, the at least one secondary alkanesulfonate has the following formula (II) H ₃ C- (CH _{2) n} -CH (SO ₃ ^- X ⁺⁾ - (CH _{2) m} -CH ₃ (II) on, where m and n are independently an integer between 0 and 20. Preferably, m + n is an integer between 7 and 17, preferably 10 to 14 and X ⁺ is selected from the group Na ⁺ , K ⁺ , NH4 ⁺ , ½Zn ²⁺ , ½Mg ²⁺ , ½Ca ²⁺ , ½Mn ²⁺ and their mixtures, preferably Na ⁺ .

In a particularly preferred embodiment, the at least one secondary alkanesulfonate is secondary C _14-17 sodium alkanesulfonate.

Such a secondary C _14-17 sodium alkanesulfonate is marketed, for example, by the company Clariant under the trade name "Hostapur SAS60".

It should be explicitly pointed out at this point that the surfactant system described herein can contain several secondary alkanesulfonates according to the invention.

Furthermore, the surfactant system / detergent described herein contains further anionic surfactants, such as, for example, sulfates and / or sulfonates, namely at least one alkylbenzenesulfonate and at least one alkyl ether sulfate. Such anionic surfactants can be used in the form of their salts.

in der R´ und R´´ unabhängig Wasserstoff oder Alkyl sind und zusammen 9 bis 19, vorzugsweise 9 bis 15 und insbesondere 9 bis 13 Kohlenstoffatome enthalten. Ein ganz besonders bevorzugter Vertreter ist Natriumdodecylbenzylsulfonat. In anderen Ausführungsformen kann das Natrium in den Verbindungen der Formel (III) durch ein Kation ausgewählt aus K⁺, NH₄ ⁺, ½Zn²⁺,½Mg²⁺, ½Ca²⁺,½Mn²⁺ und deren Mischungen ersetzt sein, wobei Na⁺ allerdings bevorzugt ist. Alkylbenzenesulfonates are preferably selected from linear or branched alkylbenzenesulfonates of the formula (III)

in which R 'and R "are independently hydrogen or alkyl and together contain 9 to 19, preferably 9 to 15 and in particular 9 to 13 carbon atoms. A most preferred representative is sodium dodecylbenzylsulfonate. In other embodiments, the sodium in the compounds of formula (III) may be replaced by a cation selected from K ⁺ , NH ₄ ⁺ , ½Zn ²⁺ , ½Mg ²⁺ , ½Ca ²⁺ , ½Mn ²⁺ and mixtures thereof, wherein Na ⁺ however, it is preferred.

In a preferred embodiment, the at least one alkyl ether sulfate is a fatty alcohol ether sulfate of the following formula (IV) R ^{4 is} -O- (AO) _n -SO ₃ ^- X ⁺ (IV), wherein R ^{4 is} a linear or branched alkyl having 5 to 30 carbon atoms, preferably having 7 to 25 carbon atoms, and preferably having 10 to 19 carbon atoms. Further, AO in the above formula is an ethylene oxide (EO) or propylene oxide (PO) group, preferably an ethylene oxide (EO) group, and n is an integer of 1 to 50, preferably 1 to 20, and preferably of 2 to 10 is. X ⁺ is any cation and is preferably selected from the group Na ⁺ , K ⁺ , NH ₄ ⁺ , ½Zn ²⁺ , ½Mg ²⁺ , ½Ca ²⁺ , ½Mn ² and mixtures thereof, more preferably Na ⁺ .

In the above formula, R ^{4 is} a linear or branched, substituted or unsubstituted alkyl radical. In a preferred embodiment of the present invention, R ^{4 is} a linear or branched alkyl radical having from 5 to 30 carbon atoms, preferably from 7 to 25 carbon atoms and especially from 10 to 19 carbon atoms. Preferred radicals R ⁴ are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and mixtures thereof, with the even number of carbon atoms being preferred. Especially preferred radicals R ⁴ are derived from fatty alcohols having 12 to 19 carbon atoms, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or oxo alcohols having 10 to 19 carbon atoms.

AO is an ethylene oxide (EO) or propylene oxide (PO) moiety, preferably an ethylene oxide moiety. The index m 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 composition according to the invention can comprise mixtures of nonionic surfactants which have different degrees of ethoxylation.

sein, wobei k = 11 bis 19, n = 2, 3, 4, 5, 6, 7 oder 8 ist. Ganz besonders bevorzugte Vertreter sind Na Fettalkoholethersulfate mit 12 bis 18 Kohlenstoffatomen und 2 EO (k = 11 bis 13, n = 2 in Formel IV-1). Der angegebenen Ethoxylierungsgrad stellt einen statistischen Mittelwert dar, der für ein spezielles Produkt eine ganze oder eine gebrochene Zahl sein kann. Allgemein stellen die angegebenen Alkoxylierungsgrade statistische Mittelwerte dar, die für ein spezielles Produkt eine ganze oder eine gebrochene Zahl sein können. Bevorzugte Alkoxylate/Ethoxylate weisen eine eingeengte Homologenverteilung auf (narrow range ethoxylates, NRE). The fatty alcohol ether sulfate used according to the invention can also be one of the formula IV-1

where k = 11 to 19, n = 2, 3, 4, 5, 6, 7 or 8. Very particularly preferred representatives are Na fatty alcohol ether sulfates having 12 to 18 carbon atoms and 2 EO (k = 11 to 13, n = 2 in formula IV-1). The stated degree of ethoxylation represents a statistical average that may be an integer or a fractional number for a particular product. Generally, the degrees of alkoxylation indicated represent statistical means which, for a particular product, may be an integer or a fractional number. Preferred alkoxylates / ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).

Furthermore, the surfactant system / detergent described herein contains at least one nonionic surfactant from the group of the alkyl ethers, in particular at least one fatty alcohol alkoxylate with the following formula (V) R ^{3 is} -O- (AO) _m -H (V), wherein R ^{3 is} a linear or branched alkyl radical, AO is an ethylene oxide (EO) or propylene oxide (PO) moiety and m is an integer from 1 to 50. In the above formula, R ^{3 is} a linear or branched, substituted or unsubstituted alkyl radical. In a preferred embodiment of the present invention, R ^{3 is} a linear or branched alkyl radical having from 5 to 30 carbon atoms, preferably from 7 to 25 carbon atoms and especially from 10 to 19 carbon atoms. Preferred radicals R ³ are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and mixtures thereof, with the even number of carbon atoms being preferred. Particularly preferred radicals R ³ are derived from fatty alcohols having 12 to 19 carbon atoms, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or oxo alcohols having 10 to 19 carbon atoms.

AO is an ethylene oxide (EO) or propylene oxide (PO) moiety, preferably an ethylene oxide moiety. The index m 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 composition according to the invention can comprise mixtures of nonionic surfactants which have different degrees of ethoxylation.

mit k = 9 bis 17, m = 3, 4, 5, 6, oder 7. Ganz besonders bevorzugte Vertreter sind Fettalkohole mit 10 bis 18 Kohlenstoffatomen und mit 7 EO (k = 11 bis 17, m = 7 in Formel V-1). In summary, particularly preferred fatty alcohol alkoxylates are those of the formula

with k = 9 to 17, m = 3, 4, 5, 6, or 7. Very particularly preferred representatives are fatty alcohols having 10 to 18 carbon atoms and 7 EO (k = 11 to 17, m = 7 in formula V-1 ).

Such fatty alcohol ethoxylates are available under the brand names 45-7 Dehydol LT7 ^® (Cognis), Lutensol AO7 ^® (BASF) Lutensol ^® M7 (BASF), and Neodol ^® (Shell Chemicals).

Further, the surfactant system / detergent may contain alkyl sulfates. Preferred alkyl sulfates are the salts of the sulfuric acid half-esters of fatty alcohols having 12 to 18 carbon atoms, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the oxo alcohols having 10 to 20 carbon atoms and those half-esters of secondary alcohols of these chain lengths. Out In terms of washing technology, the alkyl sulfates having 12 to 16 carbon atoms and alkyl sulfates having 12 to 15 carbon atoms and alkyl sulfates having 14 and 15 carbon atoms are preferred. 2,3-alkyl sulfates are also suitable anionic surfactants. Alkyl sulfates may be included, for example, in amounts of 0.1 to 10, preferably 0.1 to 5 wt .-% based on the total weight of the detergent.

Furthermore, the detergent may contain amine oxide. As amine oxide, in principle all amine oxides established for this purpose in the prior art are compounds which have the formula R ¹ R ² R ³ NO, in which each R ¹ , R ² and R ^{3 is} independently of the others an optionally substituted hydrocarbon chain having 1 to 30 carbon atoms, can be used. Particularly preferred amine oxides are those in which R ^{1 is} alkyl of 12 to 18 carbon atoms and R ² and R ^{3 are} each independently alkyl of 1 to 4 carbon atoms, especially alkyl dimethylamine oxides of 12 to 18 carbon atoms. 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.

Other nonionic surfactants which may be included in the described compositions within the meaning of the present invention include, but are not limited to, alkyl (poly) glycosides, alkoxylated fatty acid alkyl esters, fatty acid alkanolamides, hydroxy mixed ethers, sorbitan fatty acid esters and polyhydroxy fatty acid amides.

Suitable alkyl (poly) glycosides are, for example, those of the formula R ² O- [G] _p , where R ^{2 is} a branched or branched alkyl having 12 to 16 carbon atoms, G is a sugar residue having 5 or 6 carbon atoms, in particular glucose, and the index p is 1 to 10. These may, for example, be present in amounts of up to 5% by weight in the detergent.

Furthermore, the detergent may contain at least one further anionic surfactant, in particular a fatty acid soap. The anionic surfactants including the fatty acid soaps may be in the form of their sodium, potassium or magnesium or ammonium salts. Preferably, the anionic surfactants are in the form of their sodium salts and / or ammonium salts. As additional surfactants of the sulfonate type, for example, olefin sulfonates, i. Mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as obtained for example from monoolefins having 12 to 18 carbon atoms with terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation into consideration. Also suitable are alkanesulfonates having 12 to 18 carbon atoms and the esters of α-sulfo fatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.

It has proved to be advantageous for the cold washing performance if the detergents additionally contain soap (s). Preferred detergents are therefore characterized in that they contain, based on their weight, from 0.25 to 15% by weight, preferably from 0.5 to 12.5% by weight, more preferably from 1 to 10% by weight, still further preferably from 1.5 to 7.5% by weight and in particular from 2 to 6% by weight of soap (s). Particularly preferred are soaps of fatty acids having 12 to 18 carbon atoms.

Finally, the surfactant system / detergent may also contain amphoteric surfactants and / or cationic surfactants.

Suitable amphoteric surfactants are, for example, betaines of the formula (R ⁱⁱⁱ ) (R ^iv ) (R ^v ) N ⁺ CH ₂ COO ^- , in which R ^{iii is} an alkyl radical optionally interrupted by hetero atoms or heteroatom groups having 8 to 25, preferably 10 to 21 carbon atoms and R ^iv and R ^{v are} identical or different alkyl radicals having 1 to 3 carbon atoms, in particular C ₁₀ -C ₁₈ -Alkyldimethylcarboxymethylbetain and C ₁₁ -C ₁₇ -Alkylamidopropyl-dimethylcarboxymethylbetain.

Suitable cationic surfactants include the quaternary ammonium compounds of the formula (R ^vi ) (R ^vii ) (R ^viii ) (R ^ix ) N ⁺ X ^- , in which R ^vi to R ^{ix are} four identical or different, in particular two long and two short-chain, alkyl radicals and X ^{- are} an anion, in particular a halide ion, for example, didecyldimethylammonium chloride, Alkylbenzyldidecylammoniumchlorid and mixtures thereof. Further suitable cationic surfactants are the quaternary surface-active compounds, in particular having a sulfonium, phosphonium, iodonium or arsonium group, which are also known as antimicrobial agents. Through the use of quaternary surface-active compounds with antimicrobial action, the agent can be designed with an antimicrobial effect or its possibly existing antimicrobial effect due to other ingredients can be improved.

In addition, the detergent may contain other ingredients that further improve the performance and / or aesthetic properties of the detergent. In the context of the present invention, the detergent preferably additionally contains one or more substances from the group of builders / complexing agents, bleaching agents, electrolytes, perfumes, perfume carriers, fluorescers, dyes, hydrotropes, foam inhibitors, silicone oils, anti redeposition agents, grayness inhibitors, anti-shrinkage agents, anti-crease agents, color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, preservatives, corrosion inhibitors, antistatic agents, bittering agents, ironing auxiliaries, repellents and impregnating agents, swelling and anti-slip agents, plasticizing components, pH adjusters and UV absorbers.

As anti-redeposition agents are in particular polymers terephthalate-PEG-based, such as are commercially available for example under the trade name Texcare ^®, can be used. Alternatively (co) polymers based on polyethyleneimine, polyvinyl acetate and polyethylene glycol can also be used.

As a bleaching agent can serve all substances that destroy or absorb dyes by oxidation, reduction or adsorption and thereby discolor materials. These include, among others, hypohalite-containing bleach, hydrogen peroxide, perborate, percarbonate, peroxoacetic acid, diperoxoazelaic acid, diperoxododecanedioic acid, and oxidative enzyme systems. However, liquid detergents are typically free of non-enzymatic bleaches.

Suitable builders which may be present in the detergent are, in particular, silicates, aluminum silicates (in particular zeolites), carbonates, phosphonates, organic di- and polycarboxylic acids or salts thereof and mixtures of these substances.

Organic builders which may be present in the detergent are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. For example, these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, and mixtures of these. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures thereof.

As builders further polymeric polycarboxylates are suitable. These are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example, those having a molecular weight of 600 to 750,000 g / mol.

Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of from 1,000 to 15,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molecular weights of from 1,000 to 10,000 g / mol, and particularly preferably from 1,000 to 5,000 g / mol, may again be preferred from this group.

Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. To improve the water solubility, the polymers may also contain allylsulfonic acids, such as allyloxybenzenesulfonic acid and methallylsulfonic acid, as a monomer.

In liquid detergents, preference is given to using soluble builders, such as, for example, citric acid, or acrylic polymers having a molar mass of from 1,000 to 5,000 g / mol.

The detergents may additionally contain phosphonates, such as HEDP (1-hydroxyethane-1,1-diphosphonic acid), as builders and complexing agents.

Preferred liquid detergents preferably have a viscosity of from 100 to 1500 mPas (Brookfield, spindle 3, 20 rpm, 20 ° C.).

Further, preferred liquid detergents preferably contain water as the main solvent. It is preferred that the detergent more than 5 wt .-%, preferably more than 15 wt .-% and particularly preferably more than 25 wt .-%, each based on the total amount of detergent, water. Particularly preferred liquid detergents contain - based on their weight - 5 to 75 wt .-%, preferably 10 to 65 wt .-%, particularly preferably 25 to 60 wt .-% and in particular 35 to 50 wt .-% water. Alternatively, the liquid detergents may be low-water to water-free detergents, the In a preferred embodiment, the content of water is less than 10% by weight and more preferably less than 8% by weight, based in each case on the total liquid detergent.

In addition, nonaqueous solvents may be added to the detergent. Suitable non-aqueous solvents include mono- or polyhydric alcohols, alkanolamines or glycol ethers, provided that they are miscible with water in the specified concentration range. Preferably, the solvents are selected from ethanol, n-propanol, i-propanol, butanols, glycol, propanediol, butanediol, methylpropanediol, glycerol, diglycol, propyldiglycol, butyldiglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether, Diethylene glycol ethyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, methoxytriglycol, ethoxytriglycol, butoxytriglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene glycol t-butyl ether, di-n-octyl ether and mixtures thereof Solvent. However, it is preferred that the detergent contains an alcohol, in particular ethanol and / or glycerol, in amounts of between 0.5 and 5 wt .-%, based on the total detergent.

The detergents described herein may be filled into a water-soluble wrapper and thus be part of a water-soluble wrapper. When the detergent is packaged in a water-soluble casing, it is preferred that the content of water be less than 10% by weight, based on the total detergent, and that anionic surfactants, if present, be in the form of their ammonium salts.

The neutralization with amines, unlike bases such as NaOH or KOH, does not lead to the formation of water. Thus, low-water detergents can be prepared which are directly suitable for use in water-soluble wraps.

A water-soluble packaging contains, in addition to the detergent, a water-soluble coating. The water-soluble coating is preferably formed by a water-soluble film material.

Such water-soluble packages can be made by either vertical fill-seal (VFFS) or thermoforming techniques.

The thermoforming process generally includes forming a first layer of water-soluble sheet material to form protrusions for receiving a composition therein, filling the composition into the protrusions, covering the composition-filled protrusions with a second layer of water-soluble sheet material, and sealing the first and second layers at least around the bulges.

The water-soluble coating is preferably formed from a water-soluble film material selected from the group consisting of polymers or polymer blends. The wrapper may be formed of one or two or more layers of the water-soluble film material. The water-soluble film material of the first layer and the further layers, if present, may be the same or different.

The water-soluble package comprising the detergent and the water-soluble wrapper may have one or more chambers. The liquid detergent may be contained in one or more chambers, if any, of the water-soluble coating. The amount of liquid detergent preferably corresponds to the full or half dose needed for a wash.

It is preferable that the water-soluble coating contains polyvinyl alcohol or a polyvinyl alcohol copolymer.

Suitable water-soluble films for producing the water-soluble coating are preferably based on a polyvinyl alcohol or a polyvinyl alcohol copolymer whose molecular weight is in the range of 10,000 to 1,000,000 g / mol, preferably 20,000 to 500,000 g / mol, more preferably 30,000 to 100,000 g / mol and especially from 40,000 to 80,000 g / mol.

A suitable for preparing the water-soluble coating sheet material may additionally polymers, selected from the group comprising acrylic acid-containing polymers, polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters, polyether polylactic acid, and / or mixtures of the above polymers may be added.

Preferred polyvinyl alcohol copolymers include, in addition to vinyl alcohol, dicarboxylic acids as further monomers. Suitable dicarboxylic acids are itaconic acid, malonic acid, succinic acid and mixtures thereof, with itaconic acid being preferred.

Likewise preferred polyvinyl alcohol copolymers include, in addition to vinyl alcohol, an ethylenically unsaturated carboxylic acid, its salt or its esters. Such polyvinyl alcohol copolymers particularly preferably contain, in addition to vinyl alcohol, acrylic acid, methacrylic acid, acrylates, methacrylates or mixtures thereof.

Suitable water-soluble films for use in the casings of the water-soluble packaging according to the invention are films sold by the company MonoSol LLC, for example under the designation M8630, C8400 or M8900. Other suitable films include films with the label Solublon ^® PT, Solublon ^® GA, Solublon KC ^® or Solublon ^® KL by Aicello Chemical Europe GmbH, or VF-HP film available from Kuraray.

The water-soluble packages may have a substantially dimensionally stable spherical and pillow-shaped configuration with a circular, elliptical, square or rectangular basic shape.

The water soluble package may include one or more chambers for storing one or more agents. If the water-soluble packaging has two or more chambers, at least one chamber contains a liquid detergent. The other chambers may each contain a solid or a liquid detergent.

In a further aspect, the invention relates to a process for the stabilization of enzymes in an enzyme-containing detergent, in particular liquid detergent, wherein the detergent contains a surfactant system, characterized in that the surfactant system comprises at least one secondary alkanesulfonate.

The embodiments described herein in connection with the uses according to the invention are equally applicable to the described methods and vice versa. Examples: Table 1: Formulations (in% by weight of active substance) component E1 E2 E3 E4 E5 E6 E7 E8 E9 E10 boric acid 1.00 citric acid 3.00 propylene glycol 10.00 10.00 8.00 8.00 10.00 12,00 10.00 8.00 8.00 10.00 READ 8.22 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 10.36 FAS (C _12-18 ) 4.85 2.00 2.00 2.00 2.00 2.28 2.00 2.00 6.00 2.00 SAS 8.00 8.00 8.00 12,97 12.77 8.00 8.00 8.00 8.33 11.00 FAEOS (C _12-14 ) with 2 EO 8.00 8.00 13,30 8.00 13.23 8.00 12.92 8.00 8.00 8.00 FAEO with 7 EO 8.00 18,00 8.00 8.00 8.00 14.07 8.00 8.00 8.14 8.12 APG C _12-14 6.82 - - - - - 5.04 8.00 1.61 1.53 Genaminox LA; C12 (lauryl) AO, - - - - - 0.22 - - 0.85 - Betaine (cocoamidopropyl betaine) 0.12 - - - - 2.97 - 2.00 0.06 - DTPMP Na7H3 1.00 fatty acid 1.00 1.00 1.00 1.00 1.00 1.47 1.04 1.00 4.00 4.00 Monoethanolamine 5.42 5.27 5.29 5.29 5.32 5.51 5.42 5.47 6.17 6.73 ethanol 2.00 Soil Repellent Polymer 1.00 Perfume 0.90 lipase 0.20 protease 0.64 cellulase 0.17 amylase 0.44 mannanase 0.20 Water demin. ad 100 colour green appearance Clear cloudy clear Clear Clear cloudy clear clear clear clear LAS = linear alkylbenzenesulfonate (dodecylbenzenesulfonate)
FAS = fatty alcohol sulfate (alkyl sulfate, FAS C12-18)
SAS = secondary alkylsulfonate (here: Hostapur SAS 60)
FAEOS = fatty alcohol ether sulfate
FAEO = fatty alcohol ethers (here: Dehydol LT7)
APG = alkyl polyglucoside (here: C12-14 APG)
DTPMP = diethylenetriamine-penta (methylenephosphonic acid)

Claims (10)

Use of a surfactant system for stabilizing at least one enzyme in enzyme-containing detergents, especially liquid detergents, characterized in that the surfactant system comprises: (a) at least one secondary alkanesulfonate in an amount of 3 to 20 wt.%, Preferably 8 to 18 wt. % and more preferably 8-10 wt .-% based on the enzyme-containing detergent; (b) at least one linear alkylbenzenesulfonate in an amount of 3 to 20% by weight, preferably 8 to 18% by weight and more preferably 8 to 10% by weight, based on the enzyme-containing detergent; (C) at least one alkyl ether sulfate in an amount of 3 to 20 wt .-%, preferably from 8 to 18 wt .-% based on the enzyme-containing detergent; and (d) at least one alkyl ether in an amount of from 3 to 20% by weight, preferably from 8 to 18% by weight, based on the enzyme-containing detergent. Use of a surfactant system according to claim 1, characterized in that the at least one secondary alkanesulfonate has the formula (I) R ¹ CH (SO ₃ ^- X ⁺ ) R ² (I) wherein each of R ¹ and R ^{2 is} independently a linear or branched alkyl having 1 to 20 carbon atoms and with the carbon atom to which they are attached form a linear or branched alkyl, preferably having 10 to 30 carbon atoms, preferably 10 to 20 carbon atoms and X ^{+ is} selected from the group Na ⁺ , K ⁺ , NH4 ⁺ , ½Zn ²⁺ , ½Mg ²⁺ , ½Ca ²⁺ , ½Mn ²⁺ and mixtures thereof, preferably Na ⁺ . Use of a surfactant system according to claim 1 or 2, characterized in that the at least one secondary alkanesulfonate has the formula (II) H ₃ C- (CH _{2) n} -CH (SO ₃ ^- X ⁺⁾ - (CH _{2) m} -CH ₃ (II) having, m and n are independently an integer between 0 and 20, preferably m + n is an integer between 7 and 17, preferably 10 to 14 and X ^{+ is} selected from the group Na ⁺ , K ⁺ , NH4 ⁺ , ½Zn ^{2 +} , ½Mg ²⁺ , ½Ca ²⁺ , ½Mn ²⁺ and mixtures thereof, preferably Na ⁺ . Use of a surfactant system according to any one of claims 1 to 3, characterized in that the at least one linear alkylbenzenesulfonate is a compound of formula (III)

wherein R 'and R "are independently hydrogen or alkyl and together contain 9 to 19, preferably 9 to 15, and especially 9 to 13, carbon atoms. Use of a surfactant system according to one of claims 1 to 4, characterized in that the at least one alkyl ether sulfate is a fatty alcohol ether sulfate of the formula (IV) R ⁴ -O- (AO) _n -SO ₃ ^- X ⁺ (IV) where R ^{4 is} a linear or branched alkyl having 5 to 30 carbon atoms, preferably 7 to 25 carbon atoms, and preferably 10 to 19 carbon atoms, AO is an ethylene oxide (EO) or propylene oxide (PO) moiety, preferably an ethylene oxide (EO) moiety, n is an integer from 1 to 50, preferably from 1 to 20, and preferably from 2 to 10, and X ⁺ is selected from the group Na ⁺ , K ⁺ , NH ₄ ⁺ , ½Zn ²⁺ , ½Mg ²⁺ , ½Ca ²⁺ , ½Mn ² and mixtures thereof, preferably Na ⁺ . Use of a surfactant system according to one of claims 1 to 5, characterized in that the at least one alkyl ether is a fatty alcohol alkoxylate of the formula (V) R ^{3 is} -O- (AO) _m -H (V) where R ^{3 is} a linear or branched alkyl having 5 to 30 carbon atoms, preferably having 7 to 25 carbon atoms and preferably having 10 to 19 carbon atoms, AO is an ethylene oxide (EO) or propylene oxide (PO) grouping, preferably an ethylene oxide (EO) grouping and m is an integer from 1 to 50, preferably 2 to 20 and preferably 2 to 10. Use of a surfactant system according to any one of claims 1 to 6, characterized in that the surfactant system further contains at least one alkyl sulfate, preferably a C12-18 alkyl sulfate, in particular in an amount of 0.1 to 10 wt .-%, preferably of 0.1 to 5 wt .-% based on the enzyme-containing detergent. Use of a surfactant system according to any one of claims 1 to 7, characterized in that the surfactant system contains one or more other surfactants selected from soaps of C10-18 fatty acids, alkyl polyglycosides, betaines and amine oxides. Use of a surfactant system according to any one of claims 1 to 8, characterized in that the detergent comprises the surfactant system in a total amount of 25 to 50 wt .-%, preferably from 35 to 45 wt .-%. Use of a surfactant system according to any one of claims 1 to 9, characterized in that the detergent further comprises at least one further constituent selected from the group consisting of builders, bleaches, electrolytes, perfumes, perfume carriers, fluorescers, dyes, hydrotropes, foam inhibitors, silicone oils, anti redeposition agents, Grayness inhibitors, inlet preventer, Anti-wrinkling agents, color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, preservatives, corrosion inhibitors, antistatic agents, bittering agents, ironing aids, repellents and impregnating agents, swelling and anti-slip agents, softening components, pH adjusters and UV absorbers.