EP3472290B1 - Concentrated isotropic liquid detergents containing polymers - Google Patents

Description

The present application is aimed at highly concentrated isotropic liquid detergents with surfactant contents of 30% by weight and more, which also contain organic, non-surfactant components and have optimized product stability, which is made possible by a specially adapted surfactant system. Methods for washing textiles using the detergents described and their use are also recorded.

Liquid detergents are well known in the art and have become increasingly popular with consumers in recent years because they offer a number of advantages over solid detergents. These include, among other things, easier dosing, addition and dissolution in the washing liquor. In addition, they are perceived as safer and less aggressive towards the textiles and the environment. Especially for washing colored textiles, they have gained more and more popularity since their market launch.

There is a general trend on the market towards more highly concentrated liquid detergents, as these are associated with lower use of resources, which is due in particular to the lower transport weight and smaller bottle size. In addition, such highly concentrated agents are preferred by consumers because they take up little storage space in the household. Liquid detergents with a high concentration of surfactants are among others WO2013092049 , WO2013092052 , DE10153183 , DE102005015328 and DE2527793 known.

Although such compositions are advantageous from the point of view of handling and consumer acceptance, the known compositions suffer from disadvantages with regard to their stability, especially with longer storage times. These disadvantages are further intensified by the trend towards more highly concentrated products. For highly concentrated liquid detergents, the challenge is to accommodate more of the necessary performers (e.g. surfactants, polymers, enzymes, complexing agents, perfume, optical brighteners) in a smaller volume of liquid.

In order to achieve good washing performance from the consumer's point of view, polymer components are increasingly being used in modern liquid detergents. These are often essentially nonionic or anionic polymers of different functionality. Important groups are the so-called soil release polymers (soil-releasing polymers), the dye transfer inhibitors (DTIs), anti-redeposition agents and polymeric dispersants. A particular challenge is to ensure stable incorporation of the polymers, since the compatibility of the polymer ingredients in a liquid formulation decreases with increasing surfactant concentration. As a result, turbidity, sedimentation or even phase separations occur. These not only affect the aesthetic appearance of the formulation, but also adversely affect the washing performance.

There is therefore a need for improved, highly concentrated liquid detergent formulations which, with regard to the problems mentioned, have improved properties, i.e. in particular allow relatively large amounts of polymeric constituents to be formulated in a stable manner.

Surprisingly, it has now been found that the above-mentioned disadvantages of highly concentrated liquid detergents, i.e. detergents with surfactant contents of 30% by weight or more, can be overcome by using a special surfactant combination that enables the stable formulation of polymeric components that improve stability adversely affect the formulation, in amounts of 1.0% by weight or more.

1. (A) mindestens 20 Gew.-%, mindestens eines anionischen Tensids A,
2. (B) mindestens 5 Gew.-% mindestens eines nichtionischen Tensids N mit einem HLB-Wert nach Griffin ≤12;
3. (C) mindestens 2 Gew.-% mindestens eines nichtionischen, amphoteren oder zwitterionischen Tensids N1, welches, wenn es ein nichtionisches Tensid ist, einen HLB-Wert nach Griffin >12 oder, wenn es ein amphoteres oder zwitterionisches Tensid ist, einen HLB-Wert nach Davies >5 aufweist, wobei das Gewichtsverhältnis von N1 zu N ≤1 ist; und
4. (D) mindestens 1 Gew.-% mindestens einer polymeren Verbindung P, ausgewählt aus schmutzfreisetzenden Polymeren (SRP; Soil-Release Polymeren), Farbübertragungsinhibitoren (DTI) und Antiredepositionsmitteln, insbesondere einem SRP und optional einem DTI..

In a first aspect, the present invention therefore relates to an isotropic liquid detergent with a total surfactant concentration of at least 30% by weight, based on the total weight of the detergent, preferably in the range from 30 to 70% by weight, more preferably 35 to 60% by weight. , comprising, based on the total weight of the product,

1. (A) at least 20% by weight of at least one anionic surfactant A,
2. (B) at least 5% by weight of at least one nonionic surfactant N having a Griffin HLB value of ≤12;
3. (C) at least 2 wt. Davies value >5, where the weight ratio of N1 to N is ≤1; and
4. (D) at least 1 wt.

In a further aspect, the present invention relates to the use of a liquid detergent according to the invention for washing textiles.

In a further aspect, the present invention relates to a method for cleaning textiles, characterized in that a liquid detergent according to the invention is used in at least one method step.

These and other aspects, features and advantages of the invention will become apparent to those skilled in the art from a study of the following detailed description and claims. Each feature from one aspect of the invention can be used in any other aspect of the invention. Furthermore, it is to be understood that the examples contained herein illustrate the invention describe and illustrate, but not limit them and in particular the invention is not limited to these examples. Unless otherwise stated, all percentages are by weight based on the total weight of the agent/composition. Numerical ranges given in the format "from x to y" include the stated values. Where multiple preferred numeric ranges are given in this format, it is understood that any ranges resulting from the combination of the different endpoints are also included.

"At least one" as used herein refers to 1, 2, 3, 4, 5, 6, 7, 8, 9 or more. In the context of components of the compositions described herein, this statement does not refer to the absolute amount of molecules but to the type of component. "At least one anionic surfactant" thus means, for example, one or more different anionic surfactants, i.e. one or more different types of anionic surfactants. Together with quantities, the quantities refer to the total quantity of the type of ingredient referred to.

"About", "approx." or "approximately" as used herein in relation to a numerical value refers to the corresponding numerical value ±10%, preferably ±5%.

"Isotropic," as used herein in relation to the agents described, refers to optically isotropic agents, i.e., agents that appear homogeneous and single-phase when viewed with the naked eye.

The detergents described herein can be detergents for fabrics or natural fibers. The detergents within the scope of the invention also include washing aids which are metered into the actual detergent in manual or machine laundry in order to achieve a further effect or to enhance an effect. Furthermore, detergents within the scope of the invention also include textile pre- and post-treatment agents, i.e. those agents with which the item of laundry is brought into contact before the actual wash, for example to loosen stubborn dirt, and also such agents in a step downstream of the actual textile wash give the laundry other desirable properties such as a pleasant feel, crease resistance or low static charge. The latter means include fabric softeners. In preferred embodiments, however, it is a textile detergent.

In various embodiments of the invention, the liquid detergents have a total surfactant content of 30 to 70% by weight, preferably 35-60% by weight. "Total surfactant content" refers to the sum of all compounds used with surfactant properties, ie in particular the sum of the amounts of surfactants A, N and N1. Possibly existing soaps are also considered to fall under the term "anionic surfactants" and accounted for in the total surfactant content.

As "soaps" as used herein are meant the water-soluble metal, ammonium or alkanolammonium salts, particularly the sodium or potassium salts, of saturated and unsaturated higher fatty acids, of rosin acids (yellow rosin soaps) and of naphthenic acids, available as solid or semi-solid mixtures used mainly for washing and cleaning purposes.

In preferred embodiments, the liquid detergents described herein contain no further surfactants apart from the surfactant mixture, i.e. the total surfactant content corresponds to the amount of surfactant mixture.

Anionic surfactants A are, in particular, those of the sulfonate type, preferably alkylbenzene sulfonates, olefin sulfonates, i.e. mixtures of alkene and hydroxyalkane sulfonates and disulfonates, such as those obtained, for example, from monoolefins having 12 to 18 carbon atoms with a terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products. Also suitable are alkanesulfonates having 12 to 18 carbon atoms and the esters of α-sulfofatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.

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.Alkyl benzene sulfonates are preferably selected from linear or branched alkyl benzene sulfonates of the formula

wherein R' and R" are independently hydrogen or alkyl and together contain 9 to 19, preferably 9 to 15 and more preferably 9 to 13 carbon atoms. A most preferred representative is sodium dodecyl benzyl sulfonate.

The alk(en)yl sulfates used are the salts of sulfuric acid monoesters of fatty alcohols having 12 to 18 carbon atoms, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the oxo alcohols having 10 to 20 carbon atoms and those half esters of secondary alcohols of these chain lengths are preferred. Alkyl sulfates having 12 to 16 carbon atoms and alkyl sulfates having 12 to 15 carbon atoms and alkyl sulfates having 14 and 15 carbon atoms are preferred for reasons of washing technology.

The secondary alkanesulfonates are also particularly suitable. "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 attached still has two covalent bonds to two organic (alkylic) radicals, i.e. carbon atoms, and has a covalent bond to a hydrogen atom. Together with the carbon atom to which they are attached, the two organic (alkylic) groups form a linear or branched alkyl of 1 to 50 carbon atoms.

• wobei jeweils R¹ und R² unabhängig ein lineares oder verzweigtes Alkyl mit 1 bis 20 Kohlenstoffatomen ist und mit dem Kohlenstoffatom, an das sie gebunden sind, ein lineares oder verzweigtes Alkyl bilden, vorzugsweise mit 10 bis 30 Kohlenstoffatomen, bevorzugt mit 10 bis 20 Kohlenstoffatomen und X⁺ ausgewählt ist aus der Gruppe Na⁺, K⁺, NH₄ ⁺, ½ Zn²⁺, ½ Mg²⁺, ½ Ca²⁺, ½ Mn²⁺ und deren Mischungen, bevorzugt Na⁺. Besonders bevorzugt sind sekundäre Alkansulfonate der Formel
  
          H₃C-(CH₂)_n-CH(SO₃ ^-X⁺)-(CH₂)_m-CH₃,
  
  
• wobei m und n unabhängig voneinander eine ganze Zahl zwischen 0 und 15 sind. Vorzugsweise sind m und n unabhängig voneinander eine ganze Zahl zwischen 7 und 15 und bevorzugt zwischen 11 und 14. X⁺ ist ferner ausgewählt aus der Gruppe Na⁺, K⁺, NH₄ ⁺, ½ Zn²⁺, ½ Mg²⁺, ½ Ca²⁺, ½ Mn²⁺ und deren Mischungen, bevorzugt Na⁺.

In various embodiments of the invention, the secondary alkane sulfonate is one of the formula

R ¹ CH(SO ₃ ^- X ⁺ )R ² ,

• wherein each R ¹ and R ² is independently linear or branched alkyl of 1 to 20 carbon atoms and, with the carbon atom to which they are attached, form linear or branched alkyl, preferably of 10 to 30 carbon atoms, preferably 10 to 20 carbon atoms and X ⁺ is selected from the group of Na ⁺ , K ⁺ , NH ₄ ⁺ , ½ Zn ²⁺ , ½ Mg ²⁺ , ½ Ca ²⁺ , ½ Mn ²⁺ and mixtures thereof, preferably Na ⁺ . Secondary alkanesulfonates of the formula are particularly preferred
  
  H ₃ C-(CH ₂ ) _n -CH(SO ₃ ^- X ⁺ )-(CH ₂ ) _m -CH ₃ ,
  
  
• where m and n are independently an integer between 0 and 15. Preferably m and n are independently an integer between 7 and 15 and preferably between 11 and 14. X ⁺ is also selected from the group Na ⁺ , K ⁺ , NH ₄ ⁺ , ½ Zn ²⁺ , ½ Mg ²⁺ , ½ Ca ²⁺ , ½ Mn ²⁺ and mixtures thereof, preferably Na ⁺ .

Other suitable anionic surfactants are those of the sulfate type and in particular the alkyl ether sulfates.

Preferred alkyl ether sulfates are those of the formula below

R ³ -O-(AO) _n -SO ₃ ^- X ⁺ ,

wherein R ³ is linear or branched alkyl of 5 to 30 carbon atoms, preferably 7 to 25 carbon atoms, and preferably 10 to 19 carbon atoms. Furthermore, AO in the above formula stands for an ethylene oxide (EO) or propylene oxide (PO) moiety, preferably an ethylene oxide (EO) moiety and n is an integer from 1 to 50, preferably from 1 to 20 and preferably from is 2 to 10. X ⁺ is any cation and is preferably selected from the group of Na ⁺ , K ⁺ , NH ₄ ⁺ , 1/2 Zn ²⁺ , 1/2 Mg ²⁺ , 1/2 Ca ²⁺ , 1/2 Mn ² and mixtures thereof, particularly preferably Na ⁺ .

In the above formula, R ³ represents a linear or branched, substituted or unsubstituted alkyl radical. In a preferred embodiment of the present invention, R ³ is a linear or branched, preferably unsubstituted, alkyl radical having 5 to 30 carbon atoms, preferably having 7 to 25 carbon atoms and in particular having 10 to 19 carbon atoms. Preferred radicals R ³ are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl radicals and mixtures thereof, representatives with an even number of carbon atoms being preferred. Particularly preferred radicals R ³ are derived from fatty alcohols having 12 to 18 carbon atoms, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or from oxo alcohols having 10 to 19 carbon atoms.

AO 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 agent according to the invention can contain mixtures of nonionic surfactants which have different degrees of ethoxylation.

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). 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 alkyl ether sulfate is preferably one of the formula

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). The degree of ethoxylation given represents a statistical average, which can be a whole or a fractional number for a specific product. In general, the degrees of alkoxylation given represent statistical averages, which can be an integer or a fractional number for a specific product. Preferred alkoxylates/ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).

Other suitable anionic surfactants are, for example, the bisalkyl sulfosuccinates.

Preferred anionic surfactants are the alkyl benzene sulfonates and the alkyl ether sulfates and, in particular, combinations of both. It goes without saying that several different representatives of the respective surfactant class can also be used in each case. Soaps are considered anionic surfactants in the context of this invention, i.e. the amounts of anionic surfactants given include soaps, if any.

Any cation may be included in all of the anionic surfactants described above to balance the negative charge of the sulfonate group. The cation is preferably selected from the group consisting of Na ⁺ , K ⁺ , NH ₄ ⁺ , 1/2 Zn ²⁺ , 1/2 Mg ²⁺ , 1/2 Ca ²⁺ , 1/2 Mn ²⁺ and mixtures thereof, particularly preferably Na ⁺ .

The anionic surfactants A are preferably present in the detergents according to the invention in amounts of at least 20% by weight, based on the total weight of the detergent. Preferred amounts are from 20 to 65% by weight, more preferably from 20 to 55% by weight. Concentrations in the range of 25 to 35% by weight are most preferred. The amounts given relate to the total amounts of anionic surfactants contained in the agent.

• Alkylethern, insbesondere Fettalkoholalkoxylaten, wie Fettalkoholethoxylaten
• Alkyl(poly)glycosiden (APG) und Anlagerungsproducten von Alkylenoxid(en), insbesondere Propylenoxid/Ethylenoxid, an Alkyl(poly)glycoside
• Polyolfettsäureestern,
• (alkoxylierten) Triglyceriden,
• (alkoxylierten) Fettsäurealkylestern,
• Hydroxymischethern
• Sorbitanfettsäureestern und Anlagerungeprodukten von Alkylenoxid(en), insbesondere Propylenoxid/Ethylenoxid, an Sorbitanfettsäureester wie beispielsweise die Polysorbate (ethoxylierte Polysorbate),
• Zuckerfettsäureestern und Anlagerungsprodukten von Alkylenoxid(en), insbesondere Propylenoxid/Ethylenoxid, an Zuckerfettsäureester,
• Anlagerungsprodukten von Alkylenoxid(en), insbesondere Propylenoxid/Ethylenoxid, an Fettsäurealkanolamide und Fettamine,
• Fettsäure-N-Alkyl-polyhydroxyamide, insbesondere Fettsäure-N-Alkylglucamide, und
• N-Alkylglyconamide, insbesondere N-Alkylgluconamide.

The nonionic surfactants N and, if N1 is a nonionic surfactant, also N1 can be selected from:

• Alkyl ethers, in particular fatty alcohol alkoxylates, such as fatty alcohol ethoxylates
• Alkyl(poly)glycosides (APG) and addition products of alkylene oxide(s), in particular propylene oxide/ethylene oxide, onto alkyl(poly)glycosides
• polyol fatty acid esters,
• (alkoxylated) triglycerides,
• (alkoxylated) fatty acid alkyl esters,
• hydroxy mixed ethers
• Sorbitan fatty acid esters and adducts of alkylene oxide(s), in particular propylene oxide/ethylene oxide, with sorbitan fatty acid esters such as polysorbates (ethoxylated polysorbates),
• Sugar fatty acid esters and adducts of alkylene oxide(s), in particular propylene oxide/ethylene oxide, on sugar fatty acid esters,
• Adducts of alkylene oxide(s), in particular propylene oxide/ethylene oxide, onto fatty acid alkanolamides and fatty amines,
• Fatty acid N-alkyl polyhydroxyamides, in particular fatty acid N-alkyl glucamides, and
• N-alkyl glyconamides, in particular N-alkyl gluconamides.

In various embodiments, the nonionic surfactants can include at least one alkyl ether. In a preferred embodiment of the invention the contained herein means described as nonionic surfactant at least one fatty alcohol alkoxylate with the following formula

R ⁴ -O-(AO) _m -H,

wherein R ⁴ 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 ⁴ represents a linear or branched, substituted or unsubstituted alkyl group. In a preferred embodiment of the present invention, R ¹ is a linear or branched, preferably unsubstituted, alkyl radical having 5 to 30 carbon atoms, preferably having 7 to 25 carbon atoms and in particular having 10 to 19 carbon atoms. Preferred radicals R ¹ are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl radicals and mixtures thereof, representatives with an even number of carbon atoms being preferred. Particularly preferred radicals R ⁴ are derived from fatty alcohols (fatty alcohol alkoxylates) having 12 to 19 carbon atoms, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or from oxo alcohols having 10 to 19 carbon atoms.

AO 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 agent according to the invention can contain 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 5 oder 7 EO (k = 11 bis 17, m = 5 oder 7).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 with 10 to 18 carbon atoms and with 5 or 7 EO (k=11 to 17, m=5 or 7) .

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

Suitable alkyl (poly)glycosides are, in particular, those of the formula

R ⁵ O-[G] _p ,

in which R ⁵ is a linear or branched alkyl having 4 to 26, preferably 8 to 20, more preferably 8 to 18, 8 to 10 or 12 to 16 carbon atoms, G is a sugar residue having 5 or 6 carbon atoms and p is a number from 1 to 100, preferably 1 to 10.

G stands for residues of sugars with 5 (pentoses) or 6 (hexoses) carbon atoms, where the sugars can be ketoses or aldoses. Preferred monosaccharides include, but are not limited to, glucose, galactose, fructose, mannose, or ribose, especially glucose. In addition to the monosaccharides, G can also stand for sugar derivatives, in particular sugar alcohols, sugar acids, amino sugars (glycosamines) or thio sugars. Sugar alcohols result from the corresponding monosaccharide by reduction of the aldehyde or ketone function, for example glucose results in sorbitol (glucitol) and mannose in mannitol. Saccharic acids arise from the corresponding monosaccharide by oxidation of the aldehyde function (aldonic acids) or a terminal hydroxyl function (uronic acids) or both (aldaric acids), for example glucose gives gluconic acid, glucuronic acid or glucaric acid. Amino sugars result from replacing a hydroxyl function with an amino function. A preferred example is glucosamine. Thiosugars result from replacing a hydroxyl function with a thiol function. An example is thioglucose.

It goes without saying that, although the sugars and sugar derivatives are described as such above, they occur in the alkyl (poly)glycosides of the above formula as sugar radicals and the radical R ⁵ replaces a hydrogen atom in the corresponding sugar or sugar derivative.

The degree of oligomerization p can be from 1 to 100, preferably from 1 to 10, it being possible for each G to stand independently for a simple sugar. When p is 2 or more, then the different units G are preferably linked to each other via glycosidic bonds. It may be preferred that the R ⁵ group is attached to a terminal sugar group, but it may also be attached to a non-terminal sugar moiety in a corresponding oligomer.

When p=2, the sugar residue is a disaccharide residue. For example, one G can be glucose and the second G can be fructose, thus forming sucrose (α-D-glucopyranosyl-(1-2)-β-D-fructofuranoside). However, it is preferred that all G's in a molecule are the same simple sugar, such as glucose. Examples of suitable disaccharides are, without limitation, maltose (α -D-glucopyranosyl-(1→4)-α-D-glucopyranose), isomaltose (α - D-glucopyranosyl-(1→6) -α -D-glucopyranose) and lactose ( β -D-galactopyranosyl-(1→4)-D-glucopyranose).

When p=3, the sugar residue is a trisaccharide residue. Examples of suitable trisaccharides include, but are not limited to, raffinose, panose, and especially maltotriose.

When p=4, the sugar residue is a tetrasaccharide residue, particularly preferred is maltotetraose.

When p=5 or more, the units are preferably glucose units, especially those linked 1,4-glycosidically.

In all embodiments in which p is 2 or more, individual, several or all sugar moieties can be replaced by the corresponding sugar derivatives defined above. For example, aminoglycosides and thioglycosides, in which the bond to the next moiety is via the nitrogen or sulfur atom, respectively, can be used.

in der n für 7 bis 15, insbesondere 7 bis 9 oder 11 bis 15, und p für Zahlen von 1 bis 100, vorzugsweise 1 bis 10, steht.Particularly preferred alkyl (poly)glycosides are derived from glucose and can be described by the formula:

in which n is 7 to 15, in particular 7 to 9 or 11 to 15, and p is a number from 1 to 100, preferably 1 to 10.

The degree of oligomerization p in the formulas given above is preferably <8, more preferably <6, even more preferably <4 and in particular <2. Surfactants in which p is a number from 1.4 to 1.8 are particularly preferred. These fractional degrees of oligomerization are accomplished by mixtures containing varying amounts of surfactants of the above formulas where p is an integer, preferably 1, 2, 3 or 4, for the individual molecule.

• n-Decyl- oder n-Dodecyl-β-D-Maltosid;
• n-Octyl-, 2-Ethylhexyl-, n-Decyl- oder n-Dodecyl-β-D-Glucosid; und
• n-Octyl-, 2-Ethylhexyl-, n-Decyl- oder n-Dodecyl-α-D-Glucosid;

Examples of particularly suitable surfactants include, without limitation:

• n-decyl or n-dodecyl-β-D-maltoside;
• n-octyl, 2-ethylhexyl, n-decyl or n-dodecyl β-D-glucoside; and
• n-octyl, 2-ethylhexyl, n-decyl or n-dodecyl α-D-glucoside;

Detergents according to the invention can contain, for example _, C _8-16 , in particular C _8-10 or C _12-16 -alkyl-oligo(1,4)-glucoside. Suitable alkyl (poly) glycosides are, for example, among the Trade names ^Plantacare® or ^Plantaren® are available from BASF (BASF SE, DE) and include, inter alia, ^Plantacare® 220 UP (APG 220 UP) and ^Plantaren® 1200 UP NP (APG 600 UP).

Sugar fatty acid esters can be compounds of the formula R ⁵ C(O)O-[G] _p where R ⁵ , p and G can be as defined above for the alkyl polyglycosides. However, R ⁵ preferably contains 7 to 19, more preferably 7 to 17, 7 to 9 or 11 to 15 carbon atoms. An example of such compounds is sucrose cocoate (INCI: sucrose cocoate), ie the ester of sucrose with fatty acids derived from coconut oil.

In addition to or instead of the sugar fatty acid esters, the corresponding polyol fatty acid esters, which result from using the corresponding sugar alcohols instead of the sugars, can also be used. Examples are sorbitol esters. These can also satisfy the above formula R ⁵ C(O)O-[G] _p , although G is a corresponding polyol, in particular a sugar alcohol. Also suitable are sorbitan fatty acid esters, ie esters of 1,4-sorbitan anhydride with 1-4, preferably 1 or 3, esterified fatty acid residues, in particular C _12-18 fatty acids, especially those selected from laurate, palmitate, stearate and oleate. These can also be alkoxylated, in particular ethoxylated, such as the polysorbates.

Also suitable are fatty acid N-alkyl polyhydroxyamides, in particular fatty acid N-alkyl glucamides, ie amides of fatty acids with the amines derived from sugars. Usually such compounds are obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid ester or a fatty acid chloride. Examples of suitable compounds satisfy the formula R ⁶ C(O)NR ⁷ Z where R ⁶ is a linear or branched, saturated or unsaturated alkyl group having from 7 to 21 carbon atoms, Z is a polyhydroxyhydrocarbyl group having at least three hydroxyl or alkoxy groups, and R ^{7 is} C ₁ - C ₈ alkyl, a group of the formula -(CH ₂ ) _x NR ⁸ R ⁹ or R ¹⁰ is O(CH ₂ ) _n - where R ⁸ and R ⁹ are C ₁ -C ₄ alkyl or C ₂ -C ₄ -Hydroxyalkyl, R ¹⁰ is C ₁ -C ₄ -alkyl, n is a number from 2 to 4 and x is a number from 2 to 10. Particularly preferred compounds are those in which R ⁶ is C ₇ -C ₁₇ alkyl, preferably linear and saturated, R ⁷ is methyl and Z is a glucose-derived radical of the formula -CH ₂ -(CHOH)-(CHOH)-(CHOH)- CHOH)-CH ₂ OH. C ₁₂ -C ₁₈ -acyl-N-methylglucamides, such as C ₁₂ -acyl-N-methylglucamide, are particularly preferred.

Also suitable are N-alkylglyconamides, in particular N-alkylgluconamides, ie amides of alkylamines with the acids derived from sugars. Exemplary compounds satisfy the formula R ⁶ NR ⁷ C(O)Z where R ⁶ , R ⁷ and Z are as defined above, where R ⁷ can also be H and not Z alone but the group C(O)Z as a whole a residue derived from a sugar such as glucose, such as -C(O)-(CHOH)-(CHOH)-(CHOH)-CHOH)-CH2OH. Examples of suitable compounds are NC ₈ -C ₁₈ -alkyl-D-gluconamides, such as N-octyl-, N-decyl- and N-dodecyl-D-gluconamides and the corresponding N,N-dialkyl-D-gluconamides, in particular NC ₈ -C ₁₈ -alkyl-N-methyl-D-gluconamides.

Fatty acid amidoalkoxylates of the formula R ¹¹ -CON(R ¹² )(R ¹³ ) are also suitable, where R ¹¹ is an alkyl group or alkenyl group having 7 to 21 carbon atoms, R ^{12 is} hydrogen or a group --(AO) _x H, R ¹³ is a group -(AO) _x H, A is a group of the formula -C ₂ H ₄ -, -C ₃ H ₆ - or -C ₄ H ₈ - and x is a number from 1 to 20.

In addition, alkoxylated fatty acid alkyl esters are also suitable, especially those of the formula R ¹⁴ CO-(OCH ₂ CHR ¹⁵ ) _w OR ¹⁶ , in which R ¹⁴ CO is a linear or branched, saturated and/or unsaturated acyl radical having 6 to 22 carbon atoms, R ¹⁵ is hydrogen or methyl and R ¹⁶ is linear or branched alkyl radicals having 1 to 4 carbon atoms and w is 1 to 20.

• R¹⁷ für H oder, bevorzugt, einen linearen oder verzweigten Kohlenwasserstoffrest mit 2 bis 26 Kohlenstoffatomen steht;
• jedes von R¹⁸, R¹⁹, R²⁰ und R²¹ jeweils unabhängig voneinander ausgewählt ist aus -H, -CH₃, -CH₂CH₃, -CH₂CH₂CH₃, -CH(CH₃)₂, vorzugsweise -H oder -CH₃;
• R²² ausgewählt ist aus -CH₂CH(OH)R²³;
• R²³ für einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C_2-26-Alkyl- oder Alkenylrest steht; und
• w, x, y und z für Werte zwischen 1 und 120 stehen, wobei x, y und/oder z auch 0 sein können.

Also suitable are hydroxy mixed ethers, in particular those of the formula

R ¹⁷ -O-(CH ₂ -CH(R ¹⁸ )-O) _w -(CH ₂ -CH(R ¹⁹ )-O) _x -(CH ₂ -CH(R ²⁰ )-O) _y -(CH ₂ -CH( ^R21 )-O) _z ^-R22

whereby

• R ¹⁷ is H or, preferably, a linear or branched hydrocarbon radical having 2 to 26 carbon atoms;
• each of R ¹⁸ , R ¹⁹ , R ²⁰ and R ²¹ is independently selected from -H, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH(CH ₃ ) ₂ , preferably - H or -CH ₃ ;
• R ²² is selected from -CH ₂ CH(OH)R ²³ ;
• R ²³ is a straight-chain or branched, saturated or mono- or polyunsaturated C _2-26 -alkyl or alkenyl radical; and
• w, x, y and z stand for values between 1 and 120, where x, y and/or z can also be 0.

In certain embodiments in such surfactants, R ¹⁷ is a linear or branched hydrocarbon radical having from 2 to 26 carbon atoms, R ¹⁸ is H, R ²² is -CH ₂ CH(OH)R ²³ , where R ²³ is a straight-chain or branched, saturated or mono- or polyunsaturated C _6-26 -alkyl or alkenyl radical and w=1 to 120, preferably 10 to 80, in particular 15 to 40 and x,y,z=0. Examples of such surfactants are the C _4-22 fatty alcohol (EO) _10-80 -2-hydroxyalkyl ethers, in particular the C _8-12 fatty alcohol (EO) ₂₂ -2-hydroxydecyl ether and the C _4-22 fatty alcohol (EO ) _40-80 -2-hydroxyalkyl ether.

Alternatively, R ¹⁷ can be a linear or branched hydrocarbon radical having 2 to 26, preferably 4 to 18 carbon atoms, y and z are 0, R ¹⁸ is CH ₃ and R ¹⁹ is H, R ²² is -CH ₂ CH(OH)R ²³ , where R ²³ is a straight-chain or branched, saturated or mono- or polyunsaturated C _6-26 alkyl or alkenyl radical, preferably having 8 to 14 carbon atoms, and w=1 or 2 and x=at least 15. Examples of such surfactants are the C _2-26 fatty alcohol (PO) ₁ -(EO) _15-40 -2-hydroxyalkyl ethers, in particular also the C _8-10 fatty alcohol (PO) ₁ -(EO) ₂₂ -2-hydroxydecyl ether. In alternative embodiments, R ¹⁸ H and R ¹⁹ can also be -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ -CH ₃ , or -CH(CH ₃ ) ₂ , but preferably -CH ₃ . R ¹⁷ and R ²² /R ²³ are as defined above, but w and x independently represent values between 1 and 32, where nonionic surfactants with R ¹⁹ = -CH ₃ and values for w from 15 to 32 and x from 0 and 2 (in the case of mixtures of such products also numerical values between 0 and 2) are very particularly preferred.

Amine oxides, for example, can be used as alternative (zwitterionic/amphoteric) surfactants N1. In principle, all amine oxides established in the prior art for these purposes, i.e. compounds which have the formula R ¹ R ² R ³ NO, in which each R ¹ , R ² and R ³ independently of the others is an optionally substituted hydrocarbon chain with 1 to 30 carbon atoms can be used. Particularly preferred amine oxides employed 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 dimethyl amine 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 suitable amphoteric/zwitterionic surfactants are the betaines and sulfaines. Betaines are preferably compounds of the formula (R ⁱⁱⁱ )(R ^iv )(R ^v )N ⁺ CH ₂ COO ^- , in which R ⁱⁱⁱ is an alkyl radical having 8 to 25, preferably 10 to 21 carbon atoms and which is optionally interrupted by heteroatoms or heteroatom groups, and R ^iv and R ^v are identical or different alkyl radicals having 1 to 3 carbon atoms, in particular compounds of the formula

R ²⁴ -C(O)-NH-(CH ₂ ) ₃ -N ⁺ (CH ₃ ) ₂ -CH ₂ -COO ^-

where R ²⁴ is a linear or branched hydrocarbon radical having 2 to 26, preferably 5 to 21 carbon atoms, preferably a straight-chain or branched, saturated or mono- or polyunsaturated C _2-26 -alkyl or alkenyl radical, preferably having 5 to 21 carbon atoms . Examples are C ₁₀ -C ₁₈ alkyl dimethyl carboxymethyl betaine and C ₁₁ -C ₁₇ alkyl amidopropyl dimethyl carboxymethyl betaine.

Examples of sultaines are compounds of the formula

R ²⁴ -C(O)-NH-(CH ₂ ) ₃ -N ⁺ (CH ₃ ) ₂ -CH ₂ -CH(OH)-CH ₂ -SO ₃ ^-

where R ²⁴ is as defined above.

The nonionic surfactants N have an HLB value of ≦12, in certain embodiments also ≦11, ≦10, ≦9, ≦8 or ≦7. The HLB value is a measure of the balance between hydrophilic and hydrophobic parts in a surfactant and is determined here, in particular for all nonionic surfactants, according to Griffin, unless otherwise stated ( Griffin, WC: "Classification of surface active agents by HLB", J. Soc. cosmetics Chem. 1, 1949 ). If several nonionic surfactants N are contained in the liquid detergent, the HLB value of each individual nonionic surfactant N is less than or equal to 12. Examples of such surfactants are low-ethoxylated alkyl ethers, such as C _12-18 alkyl ethers with ≤7 EO.

In addition to the nonionic surfactants N, the agent contains at least one surfactant N1, which can likewise be a nonionic, but also an amphoteric or zwitterionic surfactant. Suitable nonionic, zwitterionic and amphoteric surfactants are described above. The additional surfactant N1, if it is a nonionic surfactant, has an HLB value of >12. In various embodiments, the at least one surfactant N1 can also be a mixture of a plurality of surfactants. In such embodiments, each surfactant N1 has an HLB value of >12.

The difference between the HLB values of the surfactant(s) N1 and the surfactant(s) N determined by the Griffin method is preferably at least 1, more preferably 2 or more, even more preferably 3 or more.

If the surfactant N1 is an amphoteric or zwitterionic surfactant, the HLB value can alternatively be determined using the Davies increment method ( JT Davies, A quantitative kinetic theory of emulsion type, I. Physical chemistry of the emulsifying agent, in: Proceedings of Second International CongressSurface Activity, 1957, p. 426 ) are determined and is then preferably >5, more preferably >6, >7, >8, >9 or >10. Here too, however, the HLB value of the surfactant N1 according to Davies must be greater than the HLB value of the surfactant(s) N according to Davies. If the surfactant N1 is an amphoteric or zwitterionic surfactant, in various With a total surfactant content of 30% by weight, the ratio of the total amount of N+N1 to the total amount of anionic surfactants A is preferably 5:1 to 1:5, in particular 2:1 to 1:5, with a total surfactant content of 35% by weight. % preferably 5:2 to 1:6, in particular 4:3 to 1:6, with a total surfactant content of 40% by weight, preferably 5:3 to 1:7, in particular 1:1 to 1:3, with a total surfactant content of 45% by weight, preferably 5:4 to 1:8, in particular 4:5 to 2:7, with a total surfactant content of 50% by weight, preferably 1:1 to 1:9, in particular 2:3 to 1:4 a total surfactant content of 55% by weight, preferably 5:6 to 1:10, in particular 4:7 to 2:9, with a total surfactant content of 60% by weight, preferably 5:7 to 1:11, in particular 1:2 to 1 :5, with a total surfactant content of 65% by weight, preferably 5:8 to 1:12, in particular 4:9 to 2:11, and with a total surfactant content of 70% by weight, preferably 5:9 to 1:13, in particular 2:5 to 1:6. In the above embodiments, N1 makes up at most 50% by weight of the total amount of N + N1, and based on the total weight of the composition, preferably 2 to 10% by weight, more preferably 2 to 8 or 2 to 6% by weight .

In particular, fatty alcohol alkoxylates, such as those described above, are used as surfactants N, in particular those with up to 7 EO, preferably 2-5 EO.

Nonionic surfactants are used in particular as surfactants N1, for example alkyl polyglycosides, in particular n-decyl- or n-dodecyl-β-D-maltoside, n-octyl-, 2-ethylhexyl-, n-decyl- or n-dodecyl-β-D- Glucoside, n-octyl-, 2-ethylhexyl-, n-decyl- or n-dodecyl-α-D-glucoside _, or generally C _8-16 , in particular C _8-10 or C _12-16 -alkyl-oligo(1 ,4)-glucosides and the N-alkylgluconamides described above, in particular N-octyl-, N-decyl- and N-dodecyl-D-gluconamides and the corresponding N,N-dialkyl-D-gluconamides, in particular NC ₈ -C ₁₈ -Alkyl-N-Methyl-D-Gluconamides. In alternative embodiments, N1 is an amphoteric or zwitterionic surfactant, such as an amine oxide or a betaine.

In various embodiments, the agents of the invention contain alkyl ethers, in particular the fatty alcohol alkoxylates described above, as surfactant N, and the alkyl polyglycosides or N-alkylgluconamides described above as surfactant N1, in particular in weight ratios of 1:1 to 5:1, preferably 1:1 to 3 :1. The amount of alkyl ether/fatty alcohol alkoxylate can be, for example, 5 to 15% by weight, preferably 6 to 10% by weight, and/or the amount of alkyl (poly)glycoside can be, for example, 2 to 8% by weight, preferably 3 to 5% by weight % by weight, based in each case on the total weight of the composition.

In various embodiments, the liquid detergent contains no other nonionic surfactants apart from these two types of nonionic surfactants mentioned. Alternatively, the detergent can contain other nonionic surfactants, provided that the total content of nonionic surfactants in the composition preferably does not exceed 20% by weight. In such embodiments, the residual content of surfactants is preferably made up of anionic surfactants. In various embodiments, the agents therefore contain no cationic surfactants and preferably also no amphoteric or zwitterionic surfactants.

The surfactants described above are used in customary amounts, the amount being chosen such that the total surfactant content of the agents according to the invention, as described above, is ≥30% by weight, for example 30 to 70% by weight, preferably 35-60% by weight. -% amounts to. In various embodiments, the total surfactant content is up to 45% by weight, with preferred amounts of surfactant being in the range from 32 to 38% by weight.

In preferred embodiments, the agents contain at least one anionic, preferably at least two, anionic surfactants A and at least two nonionic surfactants N and N1, as defined above.

The anionic surfactants are preferably alkylbenzene sulfonates, as described above, which are usually present in the compositions in amounts of 10 to 25% by weight, preferably 12 to 20% by weight, particularly preferably 14 to 18% by weight . Additionally or alternatively, the agents can also contain alkyl ether sulfates, usually in amounts of 2 to 10% by weight, in particular 3 to 8% by weight.

In addition to the anionic surfactants, nonionic surfactants are present in amounts of at least 7% by weight, preferably 7% to 25% by weight. Preferred amounts for surfactants N and N1 have been defined above.

Furthermore, the detergent can contain at least one fatty acid soap. These are particularly beneficial for cold wash performance. Preferred detergents are therefore characterized in that they contain - based on their weight - 0.1 to 15% by weight, preferably 0.2 to 12.5% by weight, more preferably 0.5 to 3% by weight soap (n) included. Especially preferred are soaps of fatty acids having 12 to 18 carbon atoms. The fatty acid soaps can be in the form of their sodium, potassium or magnesium or ammonium salts. They are preferably in the form of their sodium salts and/or ammonium salts.

The polymeric compound P is present in an amount of at least 1% by weight, preferably 2 or more% by weight, preferably up to 10% by weight, more preferably up to 5% by weight, based on the total weight of the agent included in this.

The compound P is a polymeric component selected from soil release polymers (soil release polymers or SRPs), anti-redeposition agents, dye transfer inhibitors (DTIs), polymeric dispersants and combinations of the aforementioned.

Particularly oligoesters obtainable as SRPs are preferably from terephthalic acid, isophthalic acid, sulfoisophthalic acid and/or their methyl esters, aliphatic dicarboxylic acids (saturated and/or unsaturated), for example adipic acid, and/or their anhydrides, aliphatic substituted dicarboxylic acids, for example nonylsuccinic acid, alkylene glycols (ethylene, 1,2-propylene-, 1,2-butylene glycol), polyethylene glycols, alkyl polyethylene glycols, polyethylene glycol benzoic esters, polyethylene glycol sulfobenzoic esters and optionally alkanolamines can be used. Preference is given to polymers based on terephthalate-PEG, such as are commercially available, for example, under the trade name ^Texcare® . Alternatively, (co)polymers based on polyethyleneimine, polyvinyl acetate and polyethylene glycol can also be used.

Suitable soil-removing polymers are generally already known to a sufficient extent from the prior art. In particular, therefore, all polymers known in the prior art for this purpose can be used.

In order to effectively suppress dye detachment and/or dye transfer to other textiles during washing and/or cleaning of colored textiles, the composition according to the invention may contain a dye transfer inhibitor. It is preferred that the dye transfer inhibitor is a polymer or copolymer of cyclic amines such as vinyl pyrrolidone and/or vinyl imidazole. Suitable polymers include polyvinylpyrrolidone (PVP), polyvinylimidazole (PVI), copolymers of vinylpyrrolidone and vinylimidazole (PVP/PVI), polyvinylpyridine-N-oxide, poly-N-carboxymethyl-4-vinylpyridium chloride, 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.

Polycarboxylates in particular come into consideration as anti-redeposition agents. Suitable materials can be prepared by the polymerization or copolymerization of unsaturated carboxylic acid monomers such as acrylic acid, maleic acid (or anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylmalonic acid. Acrylate polymers and acrylic/maleic acid copolymers are particularly preferred.

Suitable SRPs, anti-redeposition agents and DTls are also disclosed, for example, in International Patent Publication WO 2009/153184 A1 on pages 25-39 under the headings "dye transfer inhibitors", "anti redeposition agents" and "soil release polymers" are described.

In various embodiments of the invention, the polymers contained in the agents include at least one SRP and optionally at least one DTI.

The liquid detergents described herein also preferably contain at least one enzyme. The at least one enzyme can be any enzyme known in the prior art that can display catalytic activity in a detergent or cleaning agent and includes, without being 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. In principle, these enzymes are of natural origin, but based on the natural molecules, improved variants are available for use in detergents or cleaning agents, which are preferably used accordingly.

Among the proteases, those of the subtilisin type are preferred. 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 subtilases, but no longer the subtilisins in the narrower sense, thermitase enzymes, proteinase K and the proteases TW3 and TW7. Subtilisin Carlsberg is available in a further developed form under the trade name ^Alcalase® from Novozymes A/S, Bagsvaerd, Denmark. The subtilisins 147 and 309 are marketed under the trade names ^Esperase® and ^Savinase® by the Novozymes company. The protease variants listed under the name ^BLAP® are derived from the protease from Bacillus lentus DSM 5483. Other useful proteases are, for example, those sold under the trade names ^Durazym® , ^Relase® , ^Everlase® , ^Nafizym® , ^Natalase® , ^Kannase® and ^Ovozyme® from Novozymes, which are available under the trade names ^Purafect® , ^Purafect® OxP, ^Purafect® Prime, Excellase ^® and Properase ^® from Genencor, sold under the trade name Protosol ^® from Advanced Biochemicals Ltd., Thane, India, sold under the trade name Wuxi ^® from Wuxi Snyder Bioproducts Ltd., China, sold 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. The proteases from Bacillus gibsonii and Bacillus pumilus are also used with particular preference.

Examples of amylases are the α -amylases from Bacillus licheniformis, from B. amyloliquefaciens or from B . stearothermophilus and their improved developments for use in detergents or cleaning agents. The enzyme from B. licheniformis is available from Novozymes under the name ^Termamyl® and from Genencor under the name ^Purastar® ST. Further development products of this 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 of B . amyloliquefaciens is marketed by the company Novozymes under the name BAN ^® , and variants derived from the α-amylase from B . stearothermophilus under the names BSG ^® and Novamyl ^® , also from the company 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). Fusion products of all the molecules mentioned can also be used. In addition, the further developments of α-amylase from Aspergillus niger and A. oryzae available under the trade names ^Fungamyl® from the company Novozymes are suitable. Other commercial products that can be used advantageously are, for example, the Amylase-LTO and ^Stainzyme® or Stainzyme ^ultra® or Stainzyme ^plus® , the latter also from the company Novozymes. Variants of these enzymes obtainable by point mutations can also be used according to the invention.

Examples of usable lipases or cutinases, which are included in particular because of their triglyceride-splitting activities, but also to generate peracids in situ from suitable precursors, are the lipases originally available from Humicola lanuginosa ( Thermomyces lanuginosus ), or further developed ones, in particular those with amino acid substitution D96L. They are marketed, for example, by the Novozymes company under the trade names ^Lipolase® , ^Lipolase® Ultra, ^LipoPrime® , ^Lipozyme® and ^Lipex® . Furthermore, for example, the cutinases can be used which were originally isolated from Fusarium solani pisi and Humicola insolens . Lipases that can also be used are available from the Amano company 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 ^® available. For example, the lipases or cutinases from Genencor can be used, the starting enzymes of which were originally isolated from Pseudomonas mendocina and Fusarium solanii . Other important commercial products are the preparations M1 ^Lipase® and ^Lipomax® originally marketed by Gist-Brocades and the enzymes marketed by Meito Sangyo KK, Japan, under the names Lipase MY- ^30® , Lipase ^OF® and Lipase ^PL® Mention should also be made of the product ^Lumafast® from Genencor.

Depending on the purpose, cellulases can be used 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 aspects of performance may be present. These performance aspects include, in particular, the contributions of cellulase to the primary washing performance of the agent (cleaning performance), to the secondary washing performance of the agent (anti-redeposition effect or graying inhibition), to finishing (fabric effect) or to exerting a "stone washed" effect. A usable fungal, endoglucanase (EG)-rich cellulase preparation, or its further developments, is offered by the company Novozymes under the trade name ^Celluzyme® . The products ^Endolase® and ^Carezyme® , which are also available from Novozymes, are based on the 50 kD EG and the 43 kD EG, respectively, from H. insolens DSM 1800. Other commercial products from this company that can be used are ^Cellusoft® , ^Renozyme® and ^Celluclean® . Also usable are, for example, the 20 kD EG from Melanocarpus, which are available from AB Enzymes, Finland, under the trade names ^Ecostone® and ^Biotouch® . Other commercial products from AB Enzymes are ^Econase® and ^Ecopulp® . Other suitable cellulases are from Bacillus sp. CBS 670.93 and CBS 669.93, wherein the Bacillus sp. CBS 670.93 is available from Genencor under the trade name ^Puradax® . Other commercial products from Genencor are "Genencor detergent cellulase L" and ^IndiAge® Neutra. Variants of these enzymes obtainable by point mutations can also be used according to the invention. Particularly preferred cellulases are Thielavia terrestris cellulase variants, cellulases from Melanocarpus, in particular Melanocarpus albomyces, cellulases of the EGIII type from Trichoderma reesei or variants obtainable therefrom.

In addition, other enzymes, which are summarized under the term hemicellulases, can be used in particular to remove certain problem soils. These include, for example, mannanases, xanthan lyases, xanthanases, xyloglucanases, xylanases, pullulases, pectin-splitting enzymes and ß-glucanases. The β-glucanase obtained from Bacillus subtilis is available under the name ^Cereflo® from Novozymes. Hemicellulases that are particularly preferred according to the invention are mannanases, which are marketed, for example, under the trade names ^Mannaway® by the company Novozymes or ^Purabrite® by the company Genencor. In the context of the present invention, the pectin-cleaving enzymes also include enzymes with the designations pectinase, pectate lyase, pectin esterase, pectin demethoxylase, pectin methoxylase, pectin methyl esterase, pectase, pectin methyl esterase, pectinoesterase, pectin pectyl hydrolase, pectin depolymerase, endopolygalacturonase, pectolase, pectin hydrolase, pectin poly galacturonase, EndoPolygalacturonase, 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 of enzymes suitable in this regard are, for example, under the names ^Gamanase® , Pektinex ^AR® , X-Pect ^® or Pectaway ^® from the company Novozymes, under the name Rohapect UF ^® , Rohapect TPL ^® , Rohapect PTE100 ^® , Rohapect MPE ^® , Rohapect MA plus HC, Rohapect DA12L ^® , Rohapect 10L ^® , Rohapect B1L ^® from the company AB Enzymes and available under the name Pyrolase ^® from Diversa Corp., San Diego, CA, USA.

Of all these enzymes, particular preference is given to those which are comparatively stable to oxidation or have been stabilized, for example, by point mutagenesis. These include in particular the already mentioned commercial products ^Everlase® and ^Purafect® OxP as examples of such proteases and ^Duramyl® as an example of such an α-amylase.

To increase the bleaching effect, oxidoreductases, for example oxidases, oxygenases, catalases (which react as peroxidases at low H ₂ O ₂ concentrations), peroxidases such as halo-, chloro-, bromo-, lignin -, glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases). Suitable commercial products are ^Denilite® 1 and 2 from Novozymes.

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

The at least one enzyme that is present in a washing or cleaning agent supports the cleaning performance of the agent on specific soiling or stains. An agent according to the invention particularly preferably contains a number of enzymes, it being possible for the enzymes to belong to the same or different enzyme classes. The enzymes particularly preferably show synergistic effects with regard to their action on specific soiling or stains, i.e. the enzymes contained in the composition support each other in their cleaning performance.

In addition, the detergent can 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, bleaches, electrolytes, perfumes, perfume carriers, fluorescent agents, dyes, hydrotropes, foam inhibitors, silicone oils, graying inhibitors, shrinkage inhibitors, anti-crease agents, antimicrobial agents, germicides , fungicides, Antioxidants, preservatives, corrosion inhibitors, antistatic agents, bittering agents, ironing aids, repellents and impregnating agents, swelling and non-slip agents, softening components, pH adjusters and UV absorbers.

Any substance that destroys or absorbs dyes through oxidation, reduction or adsorption and thereby decolorizes materials can be used as a bleaching agent. These include hypohalite-containing bleaches, hydrogen peroxide, perborate, percarbonate, peroxoacetic acid, diperoxoazelaic acid, diperoxododecanedioic acid and oxidative enzyme systems. However, liquid detergents are typically free of non-enzymatic bleaches.

In particular, silicates, aluminum silicates (in particular zeolites), carbonates, phosphonates, organic di- and polycarboxylic acids or their salts and mixtures of these substances should be mentioned as builders which can be present in the detergent.

Organic builders which can be present in the detergent are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids being understood as 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 of these. Also suitable and preferred are aminocarboxylic acids, such as in particular glutamine diacetic acid (GLDA) and methylglycine diacetic acid (MGDA).

Polymeric polycarboxylates are also suitable as builders. These are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 600 to 750,000 g/mol.

Suitable polymers are, in particular, polyacrylates, which preferably have a molecular weight of 1000 to 15,000 g/mol. Due to their superior solubility, the short-chain polyacrylates which have molar masses from 1000 to 10,000 g/mol, and particularly preferably from 1000 to 5000 g/mol, can in turn be preferred from this group.

Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid.

To improve the solubility in water, it is also possible to use copolymeric polycarboxylates as polymers, which contain allylsulfonic acids, such as allyloxybenzenesulfonic acid and methallylsulfonic acid, included as a monomer. In various embodiments, such sulfopolymers are particularly preferred.

In liquid detergents, preference is given to using soluble builders, such as citric acid, or acrylic polymers with a molar mass of 1000 to 5000 g/mol.

Citrate is particularly preferred. The water-soluble organic builders described above can be used in various embodiments in amounts of 1 to 25% by weight, preferably 1.5 to 20% by weight, more preferably 2 to 15% by weight, most preferably 2.5 to 10% by weight %, based on the total weight of the agent. In particular, citrate is used in amounts of 2.5 to 5% by weight.

The detergents can also contain phosphonates, such as HEDP (1-hydroxyethane-1,1-diphosphonic acid) or DTPMP (diethylenetriaminepenta(methylenephosphonate), as builders and complexing agents. The phosphonates are preferred in various embodiments in amounts of up to 10% by weight up to 5% by weight, particularly preferably 0.5 to 4% by weight, based on the total weight of the agent.

Preferred liquid detergents preferably contain water as the main solvent. It is preferred that the detergent contains more than 5% by weight, preferably more than 15% by weight and particularly preferably more than 25% by weight, in each case based on the total amount of detergent, water. Particularly preferred liquid detergents contain--based on their weight--5 to 65% by weight, preferably 10 to 60% by weight, particularly preferably 25 to 55% by weight and in particular 30 to 50% by weight of water. Alternatively, the liquid detergents can be low-water or water-free detergents, with low-water liquid detergents having a water content of less than 20% by weight, preferably less than 15% by weight, more preferably less than 10% by weight and most most preferably less than 8% by weight, based in each case on the total liquid detergent. Anhydrous compositions contain less than 5%, preferably less than 3%, more preferably less than 2%, most preferably less than 1% by weight of water, based on the total weight of the composition.

In addition, non-aqueous solvents can be added to the detergent. Suitable non-aqueous solvents include monohydric or polyhydric alcohols, alkanolamines or glycol ethers, provided they are miscible with water in the specified concentration range. The solvents are preferably selected from ethanol, n-propanol, i-propanol, butanols, glycol, propanediol, butanediol, methylpropanediol, glycerol, diglycol, propyldiglycol, butyldiglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether, Diethylene glycol ethyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, methoxytriglycol, ethoxytriglycol, butoxytriglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene glycol t-butyl ether, di-n-octyl ether and mixtures of these Solvent. Particularly preferred are 1,2-propanediol and glycerol. It can be preferred that the detergent contains such an alcohol, in particular 1,2-propanediol and/or glycerol, very particularly preferably 1,2-propanediol, in amounts of between 0.5 and 15% by weight, based on the detergent as a whole contains.

To further improve the stability of the compositions, hydrotropes can be used in addition to the surfactant systems described herein. The term "hydrotrope" as used in the context of the present invention refers to additives or solvents that act to increase the water solubility of poorly soluble (hydrophobic) organic compounds. A second component (ie the hydrotrope) is added to the sparingly soluble substance, which itself is not a solvent. Such hydrotropes have hydrophilic and hydrophobic structural units (like surfactants) but without the tendency to form aggregates in water (in contrast to surfactants). In various embodiments, these hydrotropes have no micellar activity or the critical micellar concentration (CMC) is greater than 10 ^-4 mol/L, preferably greater than 10 ^-3 mol/L, and more preferably 10 ^-2 mol/L. The "critical micelle concentration" is, in accordance with the general understanding in the prior art, the concentration of the relevant substance above which it starts to form micelles and every further molecule that is added to the system goes into the micelles. The hydrotropes used typically have a molecular weight <10,000 g/mol, preferably <2500 g/mol, more preferably <1000 g/mol and most preferably <500 g/mol. They may be selected, for example, from mono-, di-, tri-, tetra- or penta-short chain alkyl benzene sulphonates, particularly C _1-6 alkyl benzene sulphonates, where the alkyl groups may be linear or branched including but not limited to cumene sulphonate, toluene sulphonate and/or Xylene sulfonate and butyl glycol, propylene glycol, 3-methoxy-3-methyl-1-butanol, 2,2-dimethyl-4-hydroxymethyl-1,2-dioxolane, propylene carbonate, butyl lactate, 2-isobutyl-2-methyl-1,3- dioxolane-4-methanol or mixtures thereof. The hydrotropic compounds are used preferably in a range from 0.1 to 5% by weight, more preferably from 1 to 2% by weight, based on the total weight of the detergent.

The detergents described herein, in particular the low-water to water-free liquid detergents described, can be filled into a water-soluble envelope and thus be part of a water-soluble packaging. If the detergent is packaged in a water-soluble envelope, it is preferred that the water content is less than 20 % by weight, preferably less than 15 or 10% by weight, based on the detergent as a whole.

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

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

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

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

The water-soluble packaging comprising the detergent and the water-soluble envelope can have one or more compartments. The liquid detergent may be contained in one or more compartments, if any, of the water-soluble envelope. The amount of liquid detergent preferably corresponds to the full or half dose required for one wash cycle.

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

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

A film material suitable for producing the water-soluble covering can additionally contain polymers selected from the group consisting of polymers containing acrylic acid, polyacrylamides, Oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters, polyethers, polylactic acid, and/or mixtures of the above polymers may be added.

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

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

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

The water-soluble packaging can have an essentially dimensionally stable spherical and cushion-shaped configuration with a circular, elliptical, square or rectangular basic shape.

The water-soluble packaging can have one or more chambers for storing one or more agents. If the water-soluble packaging has two or more compartments, at least one compartment contains a liquid detergent. The other chambers can each contain a solid or a liquid detergent.

Another subject of the invention is a method for cleaning textiles, which is characterized in that a detergent according to the invention is used in at least one method step and the use of a liquid detergent according to the invention for washing textiles.

This includes both manual and machine methods, with machine methods being preferred. Processes for cleaning textiles are generally characterized in that various cleaning-active substances are applied to the items to be cleaned in several process steps and washed off after the exposure time, or that the items to be cleaned are treated in some other way with a detergent or a solution or dilution of this agent. All conceivable washing methods can in at least one of the Method steps are enriched by the use of a detergent according to the invention and then represent embodiments of the present invention. All facts, objects and embodiments that are described for agents according to the invention are also applicable to this subject of the invention. Therefore, at this point, reference is expressly made to the disclosure at the appropriate point, with the indication that this disclosure also applies to the above methods and uses according to the invention.

examples Example 1: Detergent formulations

Table 1: Detergent formulation, components in % by weight E1 V1 v2 E2 substance Linear alkyl benzene sulfonate 14 14 14 14 fatty alcohol ether sulfate 5 5 5 5 fatty alcohol-7EO 15 5 15 15 Glucopon 215 CSUP 5 0 0 0 Glucopon 600 CSUP 0 0 0 5 Soap 1 1 1 1 DTPMP (phosphonate) 1 1 1 1 boric acid 1 1 1 1 citric acid 3 3 3 3 Optical brightener 0.1 0.1 0.1 0.1 monoethanolamine 7 7 7 7 SRP's 2 2 0 2 DTI 1 1 0 1 1,2-propylene glycol 11 11 11 11 enzymes 1.5 1.5 1.5 1.5 Water ad 100 ad 100 ad 100 ad 100 SBF 1 0.8 Glucopon 215 CSUP (C8-10 alkyl(poly)glucoside; DP 1.5; active ingredient 62-65% by weight)
Glucopon 600 CSUP (C12-14 alkyl(poly)glucoside; DP 1.4; active ingredient 50-53% by weight)

The formulations E1 and E2 according to the invention were stable after 12 weeks of storage at room temperature. A comparison formulation in which only fatty alcohol 7EO was contained as a nonionic surfactant component (C1) showed phase separation after just 2 weeks. Comparative formulation V2 serves as a reference and contains neither polymer (SRP) nor glucopon.

Claims (10)

1. Isotropic liquid detergent with a total surfactant concentration of at least 30% by weight based on the total weight of the composition, preferably in the range of 30 to 70 % by weight, more preferably 35 to 60 % by weight, including, based on the total weight of the composition,

   (A) at least 20% by weight of at least one anionic surfactant A,

   (B) at least 5% by weight of at least one non-ionic surfactant N with an HLB value according to Griffin ≤12 ;

   (C) at least 2% by weight of at least one nonionic, amphoteric or zwitterionic surfactant N1, which in the case of a nonionic surfactant has an HLB value according to Griffin > 12 or in the case of an amphoteric or zwitterionic surfactant has an HLB value according to Davies > 5, the weight ratio of N1 to N being ≤1; and

   (D) at least 1% by weight of at least one polymeric compound P selected from soil release polymers (SRP), colour transfer inhibitors (DTI) and anti-redeposition agents, in particular an SRP and optionally a DTI.
2. The isotropic liquid detergent of claim 1, characterized in that the at least one anionic surfactant A

   (i) are contained in the composition at a concentration of 20 to 65% by weight, preferably 20 to 55% by weight, based on the total weight of the composition; and/or

   (ii) are selected from sulphate and sulphonate surfactants, preferably alkylbenzene sulphonates, alkyl sulphates, alkyl ether sulphates and mixtures thereof, more preferably a combination of alkylbenzene sulphonates and alkyl ether sulphates in particular a combination of alkylbenzenesulphonates in quantities of 10 to 25 wt.%, preferably 12 to 20 wt.%, particularly preferably 14 to 18 wt.%, and alkyl ether sulphates in quantities of 2 to 10 wt.%, in particular 3 to 8 wt.%.
3. The isotropic liquid detergent of claim 1 or 2, characterized in that the surfactant(s) N

   (i) are contained in the composition at a concentration of 5 to 50, preferably 5 to 25, % by weight, based on the total weight of the composition; and/or

   (ii) are selected from fatty alcohol alkoxylates, in particular those containing up to 7EO.
4. Isotropic liquid detergent according to any of the preceding claims, characterized in that the surfactant N1 is selected from alkylpolyglycosides and N-alkylgluconamides, preferably from the group consisting of n-decyl- or n-dodecyl-β-Δ-maltoside, n-octyl-, 2-ethylhexyl-, n-decyl- or n-dodecyl-β-D-glucoside, n-octyl-, 2-ethylhexyl-, n-decyl- or n-dodecyl-α-D-glucoside, C_8-16, in particular C_8-10 or C_12-16 alkyl-oligo(1,4)-glucosides, N-octyl, N-decyl and N-dodecyl-D-gluconamide, and N,N-dialkyl-D-gluconamides, in particular N-C_8-18-alkyl-N-methyl-D-gluconamides.
5. Isotropic liquid detergent according to any of the preceding claims, characterized in that the concentration of the surfactant N1 is from 2 to 10% by weight and/or the amount of the surfactant N is from 5 to 20% by weight, based on the total weight of the detergent, preferably from 2 to 8% by weight of N1 and from 5 to 15% by weight of N.
6. Isotropic liquid detergent according to any of the preceding claims, characterized in that the ratio of the total amount of N + N1 to the total amount of anionic surfactants A is 5:1 to 1:5, in particular 2:1 to 1:5 at a total surfactant content of 30% by weight, 5:2 to 1:6, in particular 4:3 to 1:6 at a total surfactant content of >30 to 35% by weight, 5:3 to 1:7, in particular 1:1 to 1:3, at a total surfactant content of >35 to 40% by weight, 5:4 to 1:8, in particular 4:5 to 2:7 at a total surfactant content of >40 to 45 by weight, 1 :1 to 1 :9, in particular 2:3 to 1 :4 at a total surfactant content of >45 to 50% by weight, 5:6 to 1:10, in particular 4:7 to 2:9 at a total surfactant content of >50 to 55% by weight, 5:7 to 1:11, in particular 1:2 to 1:5, at a total surfactant content of >55 to 60% by weight, 5:8 and 1:12, in particular 4:9 to 2:11, at a total surfactant content of >60 to 65% by weight, and 5:9 to 1:13, in particular from 2:5 to 1:6, at a total surfactant content of >65 to 70% by weight.
7. The isotropic liquid detergent composition according to any one of the preceding claims, characterized in that the polymeric compound P is present in the composition at a concentration of from 1 to 20% by weight, preferably from 1 to 10% by weight, based on the total weight of the composition.
8. Liquid detergent composition according to one of the claims 1 to 7, characterized in that the composition

   (1) contains at least one enzyme; and/or

   (2) additionally comprises at least one other component selected from the group consisting of builders, bleaches, electrolytes, perfumes, perfume carriers, fluorescent agents, dyes, hydrotropes, foam inhibitors, silicone oils, greying inhibitors, anti-shrinkage agents, anti-crease agents, contains antimicrobial agents, germicides, fungicides, antioxidants, preservatives, corrosion inhibitors, antistatic agents, bittering agents, ironing aids, sealing and impregnating agents, swelling and gliding agents, softening components, pH adjusting agents and UV absorbers
9. Use of a liquid detergent according to any of claims 1 to 8 for washing textiles.
10. Method for cleaning textiles, characterized in that a liquid detergent according to one of claims 1 to 8 is used in at least one step of the method.