Surfactant system containing a combination of mannosylerythritol lipids

Abstract

A surfactant system comprising a specific mixture of MELs is suitable for use in laundry detergents, cleaning agents or textile care products and results in improved washing efficiency.

Description

[0001] Henkel AG & Co. KGaA

[0002] Dr. Ludwig

[0003] "Surfactant system containing a combination of mannosylerythritol lipids"

[0004] The present application relates to a surfactant system containing a combination of specific mannosylerythritol lipids (MEL), and to washing, cleaning or textile care products based on such a surfactant system.

[0005] Furthermore, the present application relates to a method for cleaning and / or caring for textiles and to the use of the surfactant system to improve the washing performance of washing, cleaning and textile care products.

[0006] The use of surfactants in washing, cleaning and textile care products is established in the state of the art.

[0007] For good washing performance, conventional surfactants such as fatty alcohol ethoxylates (FAEO), linear alkylbenzenesulfonates (LAS), and / or fatty alcohol ether sulfates (FAEOS) are typically used in washing, cleaning, and textile care. These classic surfactants are produced from fossil raw materials or are available through a semi-fossil, semi-bio-based, so-called bio-mass-balanced process.

[0008] LAS have the additional disadvantage that they are not anaerobically degradable.

[0009] For sustainability reasons, there is a growing trend to use more bio-based surfactants in washing, cleaning, and textile care products, which is why so-called biosurfactants are steadily gaining in importance. Biosurfactants are derived from renewable raw materials and therefore have an improved CO2 footprint.

[0010] One disadvantage of biosurfactants currently available on the market is that they sometimes have different properties or interactions than conventional surfactants, which is why completely new surfactant systems have to be conceived and provided.

[0011] Mannosylerythritol lipids (MELs), which are obtained through fermentation from various microorganisms and are currently being investigated primarily for their use in cosmetic products, are among the biosurfactants that perform particularly well due to their hydrophobicity. There is a desire to also use this class of biosurfactants in detergents and cleaning agents, thereby replacing other, less environmentally friendly surfactants as much as possible. However, corresponding detergents have so far shown only very low and unsatisfactory cleaning performance. Therefore, there is a need to improve the cleaning performance of detergents containing MELs.

[0012] WO 2019 / 214968 discloses mixtures of various MELs with rhamnolipids for the removal of greasy and / or oily residues from textiles at low temperatures.

[0013] WO 2016 / 066464 concerns detergents containing MEL and other, conventional surfactants, preferably in a weight ratio of 1:18 to 10:18. Surprisingly, it has now been found that the combination of at least two different mannosylerythritol lipids in detergents leads to improved washing performance even at low washing temperatures, which is particularly evident in the removal of especially greasy or oily soils.

[0014] A first subject matter of the present application is therefore a surfactant system comprising at least two different mannosylerythritol lipids (MEL) (1a) and (1b) of the following general formula in which

[0015] (1a) R3 and R4 independently represent H or an acetyl group and

[0016] Ri and R2 independently represent saturated or unsaturated acyl groups with 8 to 12 carbon atoms,

[0017] (lb) R3 and R4 independently represent H or an acetyl group and

[0018] Ri and R2 independently represent saturated or unsaturated acyl groups with 4 to 16 carbon atoms, provided that the acyl residues differ in the number of carbon atoms in the chain by at least 6 carbon atoms.

[0019] Another subject of the invention is a washing, cleaning or textile care product based on the surfactant system from MEL according to formulas (1a) and (1b).

[0020] Another object of the invention is a method for cleaning and / or caring for textiles, in which a means containing this surfactant system is used.

[0021] Another object of this invention is the use of a surfactant system according to the invention to increase the washing performance of washing, cleaning or textile care products.

[0022] The present invention and preferred embodiments of the present invention are characterized by the following statements:

[0023] 1. Surfactant system comprising at least two different mannosylerythritol lipids (MEL) (1a) and (1b) of the following general formula

[0024] in which

[0025] (1a) R3 and R4 independently represent H or an acetyl group and

[0026] Ri and R2 independently represent saturated or unsaturated acyl groups with 8 to 12 carbon atoms,

[0027] (lb) R3 and R4 independently represent H or an acetyl group and

[0028] Ri and R2 independently represent saturated or unsaturated acyl groups with 4 to 16 carbon atoms, provided that the acyl residues differ in the number of carbon atoms in the chain by at least 6 carbon atoms.

[0029] 2. Surfactant system according to statement 1, containing MEL according to (1a) and (1b), wherein at least one of the residues Ri or R2 carries at least one double bond in the carbon chain.

[0030] 3. Surfactant system according to one of statements 1 or 2, containing MEL according to (1a) and (1b), wherein R3 represents H and R4 represents an acetyl group (MEL-B).

[0031] 4. Surfactant system according to one of statements 1 to 3, containing MEL according to (1a), wherein Ri and R2 represent Cs-Ci2 acyl groups with the same number of carbon atoms.

[0032] 5. Surfactant system according to one of statements 1 to 4, containing MEL according to (1a), wherein Ri and R2 represent Oo-acyl groups.

[0033] 6. Surfactant system according to one of statements 1 to 5, containing MEL according to (1a), wherein Ri represents a saturated Oo-acyl group and R2 represents a monounsaturated Oo-acyl group.

[0034] 7. Surfactant system according to one of statements 1 to 6, containing MEL according to (Ib), wherein one of the residues Ri and R2 represents a Ci2-Ci6 acyl group and the other represents a C4-Cs acyl group.

[0035] 8. Surfactant system according to one of statements 1 to 7, containing MEL according to (Ib), wherein Ri represents a saturated C4 acyl group and R2 represents a monounsaturated Ci6 acyl group.

[0036] 9. Surfactant system according to any one of statements 1 to 8, containing MEL according to (1a) and (1b) in a mass ratio (1a) : (1b) in a range of 5 : 1 to 1 : 1, more preferably 4 : 1 to 1 : 1 and in particular 3 : 1 to 1 : 1.

[0037] 10. Washing, cleaning or textile care products containing a surfactant system according to any of the preceding statements.

[0038] 11. Washing, cleaning or textile care product according to statement 10, containing the surfactant system in a weight fraction of 0.1 to 30 wt.%, more preferably 0.5 to 25 wt.%, and particularly 1 to 20 wt.% of the total weight of the washing, cleaning or textile care product. Washing, cleaning and textile care product according to one of statements 10 or 11, additionally containing at least one further surfactant in a weight fraction of 1 to 35 wt.% of the total weight of the washing, cleaning or textile care product, wherein the at least one further surfactant is selected from the group consisting of a. anionic surfactants and / or b. non-ionic surfactants. Washing, cleaning and textile care product according to statement 12, containing as an anionic surfactant a. alkali or ammonium salts of the following compounds i. - xiv. i. linear or branched Cio-Ci6 alkyl sulfates ii. linear or branched Cio-Ci6 alkyl(ether) sulfates with 1-4 ethoxy groups iii. Ethercarboxylic acids of the formula RO-(CH2-CH2O)X-CH2-COOH, wherein R is a linear or branched, saturated or unsaturated alkyl group with 8 to 30 C atoms and x = 0 or 1 to 16 iv. Sulfo-Cio-Ci6-alkylates v. Cio-Ci6-alkylmethyltaurates vi. C8-C24-acylsarcosides vii. C8-C24-acylglutamates viii. Cs-C24-acylglycinates ix. C8-C24-acylaspartates x. Linear or branched di-C6-C20-alkylsulfosuccinates xi. Linear or branched C6-C20-alkyl(polyglycolether)sulfosuccinates xii. Cio-Ci6-alkylmethylisethionates xiii. alpha-olefin sulfonates xiv. linear Cio-Ci6-alkylbenzenesulfonates and / or xv. any mixtures of i. - xiv. Washing, cleaning and textile care products according to one of statements 12 or 13, containing as an anionic surfactant a. Cio-Ci6-alkyl(ether) sulfates with 1-4 ethoxy groups (a.ii.) and / or linear Cio-Ci6-alkylbenzenesulfonates (a.xiv.). Washing, cleaning and textile care products according to one of statements 12 or 13, containing as a non-ionic surfactant b. at least one i. sugar surfactant and / or ii.a biosurfactant other than (1a) and (1b) and / or iii. an ethoxylation product of linear or branched alcohols having 12 to 18 carbon atoms in the alkyl moiety. Washing, cleaning and textile care compositions according to any one of statements 10 to 15, wherein the weight ratio of the surfactant system (comprising all MEL (1a) and (1b)) to the sum of all additional surfactants a. and b. is in the range of 1:20 to 1:2, more preferably 1:15 to 1:4 and particularly 1:10 to 1:3. 17.Washing, cleaning or textile care products according to any one of statements 10 to 16, containing at least one further active ingredient, preferably selected from the group comprising one or more further surfactants, builders, bleaching agents, bleach activators, enzymes, electrolytes, pH adjusters, perfumes, perfume carriers, fluorescent agents, dyes, hydrotopes, foam inhibitors, anti-redeposition agents, anti-graying agents, dirt-removing polymers, shrinkage inhibitors, anti-crease agents, color transfer inhibitors, antimicrobial agents, solvents, germicides, fungicides, antioxidants, preservatives, corrosion inhibitors, antistatic agents, bittering agents, ironing aids, phobic and impregnating agents, skin-conditioning agents, swelling and slip-resistant agents, plasticizing components and UV absorbers.

[0039] 18. Washing, cleaning or textile care product according to any one of statements 10 to 17, wherein the washing, cleaning or textile care product is liquid and contains water in a weight fraction of 5 to 95 wt.%, more preferably 30 to 95 wt.% and particularly 50 to 90 wt.% of the total weight of the washing, cleaning or textile care product.

[0040] 19. Single dose comprising a washing, cleaning or textile care product according to any of statements 10 to 17 in a water-soluble coating, in particular a water-soluble coating made of a water-soluble film material, wherein the water-soluble film material preferably contains polyvinyl alcohol or a polyvinyl alcohol copolymer.

[0041] 20. Method for cleaning and / or caring for textiles, comprising the process steps: a. Providing a washing solution, comprising a washing, cleaning or textile care product according to any of statements 10 to 19; b. Bringing a textile into contact with the washing solution according to a.

[0042] 21. Use of a surfactant system according to one of statements 1 to 9 to improve the washing performance of a washing, cleaning or textile care product.

[0043] These and other aspects, features, and advantages of the invention will become apparent to the person skilled in the art upon studying the following detailed description and claims. Each feature from one aspect of the invention can be incorporated into any other aspect of the invention. Furthermore, it is understood that the examples contained herein are intended to describe and illustrate the invention, but do not limit it, and in particular, the invention is not limited to these examples.

[0044] Unless otherwise stated, all percentages are weight percentages based on the total weight of the agent / composition.

[0045] Numerical ranges specified in the format "from x to y" include the values ​​mentioned. If multiple preferred numerical ranges are specified in this format, it is understood that all 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 constituents of the compositions described herein, this refers not to the absolute quantity of molecules but to the type of constituent.

[0046] "At least one anionic surfactant" therefore means, for example, one or more different anionic surfactants, i.e., one or more different types of anionic surfactants. Along with quantity specifications, the quantities refer to the total amount of the respective named type of ingredient.

[0047] The surfactant system according to the invention contains at least two different mannosylerythritol lipids (MEL) (1a) and (1b).

[0048] Mannosylerythritol lipids (MELs) are surfactants consisting of a hydrophilic part, 4-O-β-D-mannopyranosyl-mesoerythritol, and several hydrophobic parts, which are C4-C20 acyl chains with varying degrees of acetylation. They are obtained by fermentation from various microorganisms, primarily yeasts such as Pseudozyma antarctica (also known as Candida arctica or Mesosziomyces). Other microorganisms suitable for MEL production include Pseudozyma sp. and Ustilago maydis. Fungi of the Ustilaginaceae family, such as Moesziomyces aphidis (Front. Bioeng. Biotechnol., 17 May 2022; See. Industrial Biotechnology; Volume 10 - 2022), are also particularly well-suited for fermentation. Due to their origin, MELs are classified as biosurfactants. The MELs used according to this invention obey the following general formula. and signify the specific MEL (1a) and (1b), wherein the residues Ri to R4 have the following meanings:

[0049] (1a) R3 and R4 independently represent H or an acetyl group and

[0050] Ri and R2 independently represent saturated or unsaturated acyl groups with 8 to 12 carbon atoms, respectively.

[0051] (lb) R3 and R4 independently represent H or an acetyl group and

[0052] Ri and R2 independently represent saturated or unsaturated acyl groups with 4 to 16 carbon atoms, provided that the acyl groups differ in the number of carbon atoms in the chain by at least 6 carbon atoms. The combination of at least two MELs with different lipophilic chain lengths according to formulas (1a) and (Ib) leads to improved performance. Compared to the individual MELs, the combination exhibits lower interfacial tension between the oily and aqueous phases and an increased adsorption rate at the surface. The synergistic effect of the two MELs according to (1a) and (Ib), which leads to a reduction in interfacial tension, was highest with two very specific MELs produced by different microorganisms and therefore having different chain lengths. MELs according to (1a) and (Ib) are described in more detail below.

[0053] Preferred MELs (according to (1a) and (1b)) bear residues Ri or R2, at least one of which has a double bond in the carbon chain.

[0054] MELs (according to (1a) and (1b)) are also preferred, where R3 represents H and R4 represents an acetyl group. Such MELs are referred to as MEL-B.

[0055] Furthermore, MEL according to (1a) are preferred, wherein Ri and R2 represent Ca-Ci2 acyl groups with the same number of carbon atoms, particularly preferably wherein Ri and R2 represent Oo-acyl groups. In particularly preferred MEL according to (1a), Ri has a saturated Cio-acyl group and R2 a monounsaturated Oo-acyl group.

[0056] Furthermore, MEL according to (Ib) are preferred, wherein one of the residues Ri and R2 represents a Ci2-Ci6-acyl group and the other represents a C4-Cs-acyl group, particularly preferably wherein Ri represents a saturated C4-acyl group and R2 represents a monounsaturated Ci6-acyl group.

[0057] The synergistic effect of the MEL, which leads to a particularly significant reduction in interfacial tension, is especially strong when the following MELs are mixed according to (1a) and (1b):

[0058] MEL-B according to (1a) with two Oo-acyl groups, one of which (R2) is preferably monounsaturated (MEL-1 B1) and

[0059] MEL-B according to (Ib) with a C4 acyl group and a Ci6 acyl group, one of which acyl group (R2) is preferably monounsaturated (MEL-3B1).

[0060] A further advantage for achieving the aforementioned synergy is that the MELs according to (1a) and (1b), in particular the previously described MEL-1 B1 and MEL-3B1, are present in a specific mass ratio. Therefore, the mass ratio of the two aforementioned MEL types is preferably in the range of 5:1 to 1:1, more preferably 4:1 to 1:1, and particularly 3:1 to 1:1.

[0061] A second object of the invention is a washing, cleaning or textile care product containing the surfactant system described above. Preferably, washing, cleaning or textile care products suitable according to the invention contain the surfactant system in a weight fraction of 0.1 to 30 wt.%, more preferably 0.5 to 25 wt.% and particularly 1 to 20 wt.% of the total weight of the washing, cleaning or textile care product.

[0062] According to a preferred embodiment, the washing, cleaning or textile care products can contain the surfactant system according to the invention as the only washing-active component.

[0063] According to a further preferred embodiment, the washing, cleaning or textile care products contain, in addition to the described surfactant system, at least one further surfactant in a weight fraction of 1 to 35 wt.% of the total weight of the washing, cleaning or textile care product, wherein the at least one further surfactant is selected from the group of a. anionic surfactants and / or b. non-ionic surfactants.

[0064] The presence of additional surfactants a. and / or b. offers the advantage that the surfactants can pack even more densely by mixing and / or enhance the synergism of the MEL according to (1a) and (1b).

[0065] Suitable anionic surfactants are anionic surface-active substances that contain at least one water-soluble anionic group, such as a carboxylate, sulfate, sulfonate, or phosphate group, and at least one lipophilic alkyl group with approximately 8 to 30 carbon atoms. The molecule may also contain glycol or polyglycol ether groups, ester, ether, and / or amide groups, as well as hydroxyl groups.

[0066] Preferred anionic surfactants a., which can be combined as co-surfactants with the previously described MELs, include alkali or ammonium salts of i. linear or branched Cio-Ci6 alkyl sulfates ii. linear or branched Cio-Ci6 alkyl (ether) sulfates with 1-4 ethoxy groups iii. ether carboxylic acids of the formula RO-(CH2-CH2O) X-CH2-COOH, wherein R is a linear or branched, saturated or unsaturated alkyl group with 8 to 30 C atoms and x = 0 or 1 to 16 iv. Sulfo-Cio-Ci6-alkylates v. Cio-Ci6-alkylmethyltaurates vi. C8-C24-acylsarcosides vii. C8-C24-acylglutamates viii. Cs-C24-acylglycinates ix. C8-C24-acylaspartates x. Linear or branched di-C6-C20-alkylsulfosuccinates xi. Linear or branched C6-C20-alkyl(polyglycolether)sulfosuccinates xii. Cio-Ci6-alkylmethylisethionates xiii. alpha-olefin sulfonates xiv. linear Cio-Ci6-alkylbenzenesulfonates and / or xv. any mixtures of i. - xiv.

[0067] Very good synergy effects could be achieved when the surfactant system according to the invention was combined with one or more anionic surfactants a. selected from Cio-Ci6-alkyl(ether)sulfates with 1-4 ethoxy groups (ii.) and / or linear Cio-Ci6-alkylbenzenesulfonates (xiv.).

[0068] The anionic surfactant(s) a. can / can be used in the washing, cleaning or textile care products preferably in a weight fraction of 1 to 35 wt.%, more preferably 2 to 30 wt.% and in particular 5 to 25 wt.%, based on the total weight of the washing, cleaning or textile care products.

[0069] Suitable non-ionic surfactants b. in the sense of the present invention are preferably selected from i. sugar surfactants and / or ii. of (1a) and (1b) various biosurfactants and / or iii. ethoxylation products of linear or branched alcohols having 12 to 18 carbon atoms in the alkyl moiety.

[0070] For the purposes of the present invention, sugar surfactants bi are preferably understood to be alkyl or alkenyl oligoglycosides. These sugar surfactants are known nonionic surfactants according to formula R 1 O-[G] P dar, in the R 1G represents an alkyl or alkenyl group with 4 to 22 carbon atoms, G represents a sugar group with 5 or 6 carbon atoms, and p represents a number from 1 to 10. The alkyl and alkenyl oligoglycosides can be derived from aldoses or ketoses with 5 or 6 carbon atoms, preferably glucose. The preferred alkyl and / or alkenyl oligoglycosides are thus alkyl and / or alkenyl oligoglucosides. The index number p indicates the degree of oligomerization (DP), i.e., the distribution of mono- and oligoglycosides, and represents a number between 1 and 10. While p must always be an integer for a single molecule, and can primarily take the values ​​p = 1 to 6, the value p for a specific alkyl oligoglycoside is an analytically determined calculated quantity, which is usually a fraction. Preferably, alkyl and / or alkenyl oligoglycosides with a medium degree of oligomerization p of 1.1 to 3.0 are used.From an application-related perspective, alkyl and / or alkenyl oligoglycosides with a degree of oligomerization of less than 1.7, and particularly between 1.2 and 1.4, are preferred. The alkyl or alkenyl group R. 1 It can be derived from primary alcohols with 4 to 11, preferably 8 to 10 carbon atoms. Alkyl oligoglucosides based on hydrogenated Ci2 / 14 coconut alcohol (coco glucoside, lauryl glucoside) and / or Ca-Cio glucoside (decyl glucoside) with a DP of 1 to 3 are preferred.

[0071] In accordance with the present invention, sugar surfactants bi preferably include fatty acid N-alkyl polyhydroxyalkylamides of formula (III) understood, in which in the R 2 CO for an aliphatic acyl group with 6 to 22 carbon atoms, R 3[Z] represents hydrogen, an alkyl or hydroxyalkyl group with 1 to 4 carbon atoms, and [Z] represents a linear or branched polyhydroxyalkyl group with 3 to 12 carbon atoms and 3 to 10 hydroxyl groups. Preferably, the fatty acid N-alkylpolyhydroxyalkylamides are derived from reducing sugars with 5 or 6 carbon atoms, in particular from glucose. The preferred fatty acid N-alkylpolyhydroxyalkylamides are therefore fatty acid N-alkylglucamides, as represented by formula (IV):

[0072] Particularly preferred are fatty acid N-alkylglucamides of formula (IV), which are obtained by reductive amination of glucose with methylamine and subsequent acylation with lauric acid or Ci2 / i4-coconut fatty acid or a corresponding derivative. Furthermore, the polyhydroxyalkylamides can also be derived from maltose and palatinose.

[0073] Biosurfactants b.ii., which are different from MEL according to (1a) and (1b), are in principle glycolipids produced by fermentation.

[0074] Raw materials for the production of biosurfactants b.ii. can include carbohydrates, especially sugars such as glucose and / or lipophilic carbon sources such as fats, oils, partial glycerides, fatty acids, fatty alcohols, long-chain saturated or unsaturated hydrocarbons.

[0075] Particularly preferred biosurfactants b.ii. in the sense of the present invention are rhamnolipids, sophorolipids, glucose lipids, cellulose lipids and / or trehalose lipids; rhamnolipids and / or sophorolipids are especially preferred.

[0076] Suitable biosurfactants b.ii. are known in the prior art and can be obtained, for example, from the companies Soliance or Evonik.

[0077] Nonionic surfactants (b.iii.) are understood to be ethoxylation products of linear or branched alcohols with 12 to 18 carbon atoms in the alkyl group. These follow the formula R-O-(AO)mH, in which R represents a linear or branched, substituted or unsubstituted alkyl group with 12 to 18 carbon atoms, AO represents an ethylene oxide (EO) or propylene oxide (PO) group, and m represents integers from 1 to 50. In the above formula, R preferably represents groups derived from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl, or stearyl alcohol. AO stands for an ethylene oxide (EO) or propylene oxide (PO) grouping, preferably for an ethylene oxide grouping, and the index m stands for an integer from 1 to 50, more preferably from 1 to 20, particularly preferably from 1 to 15 and particularly from 2 to 10. Most preferably, m stands for the numbers 2, 3, 4, 5, 6, 7 or 8.Preferably, a C12-18 fatty alcohol ethoxylate with 7 EO is used.

[0078] The non-ionic surfactant(s) b. can / can be used in the washing, cleaning or textile care products preferably in a weight fraction of 0.5 to 30 wt.%, more preferably 1 to 25 wt.% and in particular 1 to 20 wt.%, based on the total weight of the washing, cleaning or textile care products.

[0079] In a further preferred embodiment, washing, cleaning and textile care products contain the surfactant system according to the invention (comprising all MEL (1a) and (1b)) to the sum of all additional surfactants a. and b. in a weight proportion in the range of 1:20 to 1:2, more preferably 1:15 to 1:4 and in particular 1:10 to 1:3.

[0080] In addition to the surfactant system and the optional additional surfactants, the washing, cleaning or textile care product may preferably contain at least one further active ingredient, preferably selected from the group comprising one or more further surfactants, builders, bleaching agents, bleach activators, enzymes, electrolytes, pH adjusters, perfumes, perfume carriers, fluorescent agents, dyes, hydrotopes, foam inhibitors, anti-reposition agents, anti-graying inhibitors, dirt-removing polymers, shrinkage inhibitors, anti-crease agents, color transfer inhibitors, antimicrobial agents, solvents, germicides, fungicides, antioxidants, preservatives, corrosion inhibitors, antistatic agents, bittering agents, ironing aids, phobic and impregnating agents, skin-conditioning agents, swelling and slip-resistant agents, plasticizing components and UV absorbers.

[0081] In addition to the surfactants already mentioned above, other nonionic surfactants can also be used. These include, for example, alkoxylated fatty acid alkyl esters, fatty acid amides, alkoxylated fatty acid amides, polyhydroxy fatty acid amides, alkylphenol polyglycol ethers, amine oxides, and mixtures thereof.

[0082] Zwitterionic or amphoteric surfactants can also be used, for example betaines, sulfobetaines or amphoacetates.

[0083] Cationic surfactants can also be used, such as quaternary ammonium compounds, especially esterquats.

[0084] In a preferred embodiment, however, the washing, cleaning, or textile care agent is free of cationic or amphoteric surfactants. A washing, cleaning, or textile care agent according to the invention preferably contains at least one water-soluble and / or water-insoluble, organic and / or inorganic builder. The water-soluble organic builder substances include polycarboxylic acids, in particular citric acid and sugar acids, monomeric and polymeric aminopolycarboxylic acids and their salts, in particular glutamic acid N,N-diacetic acid (GLDA), methylglycine diacetic acid (MGDA), nitrilotriacetic acid (NTA), and iminodisuccinates such as ethylenediamine N.N'-disuccinic acid (EDDS) and hydroxyiminodisuccinates (HIDS), ethylenediaminetetraacetic acid (EDTA) as well as polyaspartic acid, polyphosphonic acids, in particular aminotris(methylenephosphonic acid), ethylenediaminetetrakis(methylenephosphonic acid), lysinetetra(methylenephosphonic acid) and 1-hydroxyethane1,1-diphosphonic acid, polymeric hydroxy compounds such as dextrin as well as polymeric (poly-)carboxylic acids, in particular polycarboxylates accessible by oxidation of polysaccharides, polymeric acrylic acids, methacrylic acids, maleic acids and copolymers of these, which may also contain small amounts of polymerizable substances without carboxylic acid functionality polymerized into the polymer. The relative mean molecular mass of the homopolymers of unsaturated carboxylic acids is generally between 5,000 g / mol and 200,000 g / mol, that of the copolymers between 2,000 g / mol and 200,000 g / mol, preferably 50,000 g / mol to 120,000 g / mol, in each case based on free acid.A particularly preferred acrylic acid-maleic acid copolymer has a relative mean molecular mass of 50,000 to 100,000. Suitable, though less preferred, compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinyl methyl ethers, vinyl esters, ethylene, propylene, and styrene, in which the acid content is at least 50% by weight. Terpolymers containing as monomers two unsaturated acids and / or their salts, and as a third monomer vinyl alcohol and / or a vinyl alcohol derivative or a carbohydrate, can also be used as water-soluble organic builder substances.

[0085] Suitable water-soluble inorganic builder materials include polyphosphates, preferably sodium triphosphate, as well as water-soluble crystalline and / or amorphous alkali silicate builders. In a preferred embodiment, however, the washing, cleaning, or textile care products according to the invention are phosphate-free.

[0086] Water-insoluble inorganic builder materials, particularly crystalline or amorphous, water-dispersible alkali aluminosilicates, are used. Among these, crystalline sodium aluminosilicates of detergent quality, especially zeolite A, zeolite P, zeolite MAP, and optionally zeolite X, are preferred.

[0087] Bleaching agents can be any substances that destroy or absorb dyes through oxidation, reduction, or adsorption, thereby decolorizing materials. These include, among others, hypohalite-containing bleaching agents, hydrogen peroxide, perborate, percarbonate, peroxoacetic acid, diperoxoazelic acid, diperoxododecanedioic acid, and oxidative enzyme systems. The washing, cleaning, or textile care product may also contain one or more enzymes. In principle, all enzymes established in the prior art for these purposes can be used. Preferably, these are one or more enzymes that can exhibit catalytic activity in a detergent, in particular a protease, amylase, lipase, cellulase, hemicellulase, mannanase, pectin-splitting enzyme, tannase, xylanase, xanthanase, β-glucosidase, carrageenase, perhydrolase, oxidase, oxidoreductase, and mixtures thereof.Preferred hydrolytic enzymes include, in particular, proteases, amylases (especially α-amylases), cellulases, lipases, hemicellulases (especially pectinases), mannanases, β-glucanases, and mixtures thereof. Proteases, amylases, and / or lipases, as well as mixtures thereof, are particularly preferred, and proteases are especially preferred. These enzymes are, in principle, of natural origin; however, improved versions of the natural molecules are available for use in detergents and are therefore preferred. The enzymes can be adsorbed onto carrier substances and / or embedded in coating materials to protect them against premature inactivation. Furthermore, the enzymes to be used can be formulated together with accompanying substances, such as those obtained from fermentation, or with stabilizers.

[0088] To adjust a desired pH value that does not result automatically from the mixture of the other components, the agents according to the invention can contain system- and environmentally compatible acids, in particular citric acid, acetic acid, tartaric acid, malic acid, lactic acid, amino acids such as glycine, glutamic acid, arginine and / or aspartic acid, glycolic acid, maleic acid, fumaric acid, salicylic acid, succinic acid, glutaric acid and / or adipic acid, but optionally also mineral acids, in particular sulfuric acid, or bases, in particular ammonium or alkali hydroxides.

[0089] Anti-graying agents serve to keep the dirt detached from textile fibers suspended in the cleaning solution. Water-soluble colloids, mostly of organic origin, are suitable for this purpose, such as starch, glue, gelatin, salts of ethercarboxylic or ethersulfonic acids of starch or cellulose, or salts of acidic sulfuric acid esters of cellulose or starch. Water-soluble polyamides containing acidic groups are also suitable. Furthermore, starch derivatives other than those mentioned above can be used, for example, aldehyde starches. Cellulose ethers, such as carboxymethylcellulose (sodium salt), methylcellulose, hydroxyalkylcellulose, and mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose, and mixtures thereof, are preferred.

[0090] Furthermore, the product may contain dirt-removing polymers or soil release polymers (SRPs). SRPs available in particular include oligoesters of preferably 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 nonyl succinic acid, alkylene glycols (ethylene, 1,2-propylene, 1,2-butylene glycol), polyethylene glycols, alkyl polyethylene glycols, and polyethylene glycol succinic acid esters.

[0091] Polyethylene glycol sulfobenzoic acid esters and, optionally, alkanolamines can be used. Terephthalate-PEG-based polymers, such as those commercially available under the trade name Texcare®, are preferred. Alternatively, (co)polymers based on polyethyleneimine, polyvinyl acetate, and polyethylene glycol can also be used.

[0092] Suitable dirt-removing polymers are generally already sufficiently known from the prior art. In particular, all polymers known from the prior art for this purpose can therefore be used.

[0093] To effectively suppress dye transfer and / or dye transfer to other textiles during washing and / or cleaning of dyed textiles, the composition according to the invention can contain a dye transfer inhibitor (DTI). It is preferred that the dye transfer inhibitor is a polymer or copolymer of cyclic amines such as vinylpyrrolidone and / or vinylimidazole. 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. Polyvinylpyrrolidone (PVP), polyvinylimidazole (PVI), or copolymers of vinylpyrrolidone and vinylimidazole (PVP / PVI) are particularly preferred as the dye transfer inhibitor.

[0094] Polycarboxylates are particularly suitable as anti-reposition agents. Appropriate 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 especially preferred.

[0095] Washing, cleaning, or textile care products can contain optical brighteners such as derivatives of diaminostilbene disulfonic acid or its alkali metal salts. However, color detergents are preferably free of optical brighteners. Suitable examples include salts of 4,4'-bis(2-anilino-4-morpholino-1,3,5-triazinyl-6-amino)stilbene-2,2'-disulfonic acid or similarly structured compounds that, instead of the morpholino group, bear a diethanolamino group, a methylamino group, an anilino group, or a 2-methoxyethylamino group. Furthermore, optical brighteners of the substituted diphenylstyryl type may be present, for example, the alkali salts of 4,4'-bis(2-sulfostyryl)diphenyl, 4,4'-bis(4-chloro-3-sulfostyryl)diphenyl, or 4-(4-chlorostyryl)-4'-(2-sulfostyryl)diphenyl. Mixtures of the aforementioned optical brighteners may also be used.Particularly when used in automated processes, it can be advantageous to add common foam inhibitors to washing, cleaning, or textile care products. Suitable foam inhibitors include, for example, soaps of natural or synthetic origin that have a high proportion of C18-C24 fatty acids. Suitable non-surfactant foam inhibitors include, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica, as well as paraffins, waxes, microcrystalline waxes, and their mixtures with silanized silica or bis-fatty acid alkylenediamides. Mixtures of different foam inhibitors, such as those of silicones, paraffins, or waxes, are also advantageously used. Preferably, the foam inhibitors, especially silicone- and / or paraffin-containing foam inhibitors, are bound to a granular, water-soluble or dispersible carrier substance.In particular, mixtures of paraffins and bistearylethylenediamide are preferred.

[0096] The washing, cleaning, or textile care agent can be in any known form, for example, solid, liquid, gel, paste, powder, granules, or tablet. Liquid agents contain solvents. In a preferred embodiment, the main solvent is water. In addition, non-aqueous solvents can be added to the agent. Suitable non-aqueous solvents include mono- or polyhydric alcohols, alkanolamines, or glycol ethers, provided they are miscible with water within the specified concentration range. Preferably, the solvents are selected from ethanol, n-propanol, i-propanol, butanols, glycol, propanediol, butanediol, methylpropanediol, glycerin, diglycylene, propyldiglycol, butyldiglycylene, 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.

[0097] 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 tert-butyl ether, di-n-octyl ether, and mixtures of these solvents. An alcohol, particularly ethanol and / or glycerol, is especially preferred.

[0098] In a preferred embodiment, the washing, cleaning or textile care agent is liquid and contains water in a weight fraction of 5 to 95 wt.%, more preferably 30 to 95 wt.% and particularly 50 to 90 wt.% of the total weight of the washing, cleaning or textile care agent.

[0099] To further improve the stability of the agents, hydrotropes can be used in addition to the surfactant systems described herein. The term "hydrotrope," as used in connection with the present invention, refers to additives or solvents that increase the water solubility of sparingly soluble (hydrophobic) organic compounds. A second component (i.e., the hydrotrope) is added to the sparingly soluble substance, but it is not itself a solvent. Such hydrotropes have hydrophilic and hydrophobic structural units (like surfactants) but without the tendency to form aggregates in water (unlike surfactants). In various embodiments, these hydrotropes have no micelle-forming activity, or the critical micelle concentration (CMC) is greater than 10⁻⁵. -4 mol / L, preferably greater than 10 -3 mol / L and even more preferably 10 -2mol / L. The "critical micelle formation concentration," in accordance with the general understanding in the prior art, is the concentration of the substance above which it begins to form micelles and any further molecule added to the system is converted into micelles. The hydrotropes used typically have a molecular weight < 10,000 g / mol, preferably < 2,500 g / mol, more preferably < 1,000 g / mol, and most preferably < 500 g / mol. They can be selected, for example, from short-chain mono-, di-, tri-, tetra- or penta-alkylbenzenesulfonates, in particular Ci-e alkylbenzenesulfonates, wherein the alkyl groups may be linear or branched, including but not limited to cumenesulfonate, toluenesulfonate and / or xylenesulfonate, as well as 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 preferably used in a range of 0.1 to 5 wt.%, more preferably from 1 to 2 wt.%, based on the total weight of the detergents.

[0100] In one embodiment, the washing, cleaning, or textile care product is offered as a pre-portioned single dose in a water-soluble coating. The water-soluble coating is preferably formed from a water-soluble film material.

[0101] Such individual doses can be manufactured either by vertical form-fill-seal (VFFS) or hot-forming processes. The hot-forming process generally involves forming a first layer of a water-soluble film material to create indentations for receiving a composition, filling the indentations with the composition, covering the composition-filled indentations with a second layer of a water-soluble film material, and sealing the first and second layers together, at least around the indentations.

[0102] The water-soluble coating is preferably formed from a water-soluble film material selected from the group consisting of polymers or polymer mixtures. The coating can be formed from one, two, or more layers of the water-soluble film material. The water-soluble film material of the first layer and any subsequent layers can be the same or different. The single dose, comprising the washing, cleaning, or textile care agent and the water-soluble coating, can also have one or more chambers. The agent can be contained in one or more chambers, if present, of the water-soluble coating. The amount of detergent preferably corresponds to the full or half dose required for one wash cycle.

[0103] It is preferred that the water-soluble coating contains polyvinyl alcohol or a polyvinyl alcohol copolymer. In addition, polymers selected from the group comprising acrylic acid-containing polymers, polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters, polyethers, polylactic acid, and / or mixtures of the aforementioned polymers may be added to the film material.

[0104] Preferred polyvinyl alcohol copolymers comprise, 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.

[0105] The single dose can have an essentially dimensionally stable spherical, rotationally ellipsoidal, cubic, cuboidal, or cushion-shaped form with a circular, elliptical, square, or rectangular base.

[0106] Furthermore, it may have one or more compartments for storing one or more substances. If the water-soluble packaging has two or more compartments, each compartment may contain a solid component or a liquid component, or one or more compartments may contain solid components and one or more other compartments may contain liquid components.

[0107] Another object of the invention is a method for cleaning and / or caring for textiles, comprising the process steps: a) providing a washing solution comprising a washing, cleaning or textile care agent containing the surfactant system according to the invention and b) bringing a textile into contact with the washing solution according to a).

[0108] This includes both manual and machine-based methods, with machine-based methods being preferred.

[0109] Another aspect of this invention is the use of the surfactant system according to the invention to improve the washing performance of a detergent, cleaning agent, or textile care product. Exemplary embodiments:

[0110] The following MELs and mixtures of MELs were investigated: a) MEL-1B1 b) MEL-3B1 c) MEL-1B1 + MEL-3B1 in a mass ratio of 1 : 3 d) MEL-1B1 + MEL-3B1 in a mass ratio of 1 : 1 e) MEL-1B1 + MEL-3B1 in a mass ratio of 3 : 1

[0111] The concentration of MEL in water was 0.5 g / L in each case, and the pH value (adjusted with a citrate buffer) was 8.

[0112] The interfacial tensions were measured at 25°C. The results are shown in the table below.

[0113] Measurements of the interfacial tension data show that it is very low for all investigated MELs and mixtures of MELs, especially compared to conventional surfactants. A clear synergism* can be observed particularly with the 1:1 and 3:1 mixtures of MEL-1 B1 and MEL-3B1.

[0114] It is known that the lower the surface tension, the better the dirt removal capacity and the better the emulsifiability. This means that particularly with MEL combinations, very high washing performance can be expected.

[0115] * Synergism can be assumed if the interfacial tension of the mixture of two surfactants is lower than the expected interfacial tension, which in a 50% mixture, for example, lies exactly between the two pure substances.

Claims

Patent claims:

1. Surfactant system comprising at least two different mannosylerythritol lipids (MEL) (1a) and (1b) of the following general formula in which (1a) R3 and R4 independently represent H or an acetyl group and Ri and R2 independently represent saturated or unsaturated acyl groups with 8 to 12 carbon atoms, (lb) R3 and R4 independently represent H or an acetyl group and Ri and R2 independently represent saturated or unsaturated acyl groups with 4 to 16 carbon atoms, provided that the acyl residues differ in the number of carbon atoms in the chain by at least 6 carbon atoms.

2. Surfactant system according to claim 1, comprising MEL according to (1a) and (1b), wherein at least one of the residues Ri or R2 carries at least one double bond in the carbon chain.

3. Surfactant system according to one of claims 1 or 2, comprising MEL according to (1a) and (1b), wherein R3 represents H and R4 represents an acetyl group (MEL-B).

4. Surfactant system according to one of claims 1 to 3, comprising MEL according to (1a), wherein Ri and R2 represent Cs-Ci2 acyl groups with the same number of carbon atoms.

5. Surfactant system according to one of claims 1 to 4, comprising MEL according to (Ib), wherein one of the residues Ri and R2 represents a Ci2-Ci6 acyl group and the other represents a C4-Cs acyl group.

6. Surfactant system according to any one of claims 1 to 5, comprising MEL according to (1a) and (1b) in a weight ratio (1a) : (1b) in a range of 5 : 1 to 1 : 1 .

7. Washing, cleaning or textile care product comprising a surfactant system according to any one of claims 1 to 6.

8. Washing, cleaning and textile care product according to claim 7, additionally comprising at least one further surfactant in a weight fraction of 1 to 35 wt.% of the total weight of the washing, cleaning or textile care product, wherein the at least one further surfactant is selected from the group of a. anionic surfactants and / or b. non-ionic surfactants.

9. Method for cleaning and / or caring for textiles, comprising the process steps a. providing a washing solution comprising a washing, cleaning or textile care agent according to claim 7 or 8 b. bringing a textile into contact with the washing solution according to a.

10. Use of a surfactant system according to any one of claims 1 to 6 for improving the washing performance of a washing, cleaning or textile care product.

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