Antimicrobial composition

Abstract

The present invention relates to a composition comprising: (A) at least one compound selected from the group consisting of: a compound # imgabs0 # of formula (I) wherein R is selected from the group consisting of saturated hydrocarbon chains having 5 to 23 carbon atoms, unsaturated hydrocarbon chains having 5 to 23 carbon atoms and mixtures thereof, sorbitan esters, isosorbide esters, glyceryl ethers and glycerides; and (B) at least one hydroxyacetophenone.

Description

[0001] The present invention relates to antimicrobial compositions, their use as antimicrobial agents, and formulations comprising the antimicrobial compositions.

[0002] Preservation of household formulations and cosmetic formulations extends their shelf life and thus provides consumers with better value for money.

[0003] In addition, preservatives prevent consumers from spreading microorganisms throughout their homes or onto their bodies and thus provide health benefits. Antimicrobial agents are well described in the art and many antimicrobial agents with excellent properties are available.

[0004] However, there is a desire to provide a range of advanced preservation systems that provide excellent antimicrobial performance and also keep the content of antimicrobial actives to a minimum. For example, many well-known antimicrobial actives with excellent efficacy are not preferred due to reduced consumer acceptance, health concerns or due to regulatory restrictions. The content of such actives may also be restricted (legally) for the same reasons. In addition, it is desirable that all elements of the preservation system meet sustainability goals and ensure that household formulations and cosmetic formulations are as environmentally friendly as possible.

[0005] Accordingly, there is a need to provide more advanced preservation systems that provide excellent antimicrobial action and are also highly acceptable to consumers, do not raise health or regulatory concerns, and have excellent sustainability and environmentally friendly properties.

[0006] The present invention relates to a composition comprising:

[0007] (A) at least one compound selected from:

[0008] compounds of formula (I)

[0009]

[0010] wherein R is selected from saturated hydrocarbon chains having 5 to 23 carbon atoms, unsaturated hydrocarbon chains having 5 to 23 carbon atoms, and mixtures thereof,

[0011] sorbitan esters, isosorbide esters, glycerol ethers and glycerol esters; and

[0012] (B) at least one hydroxyacetophenone.

[0013] Advantageously, the compositions of the present invention show a synergistic effect against a broad spectrum of microorganisms. This results in the advantage that smaller amounts of preservatives can be used to preserve formulations such as cosmetic formulations or household formulations, reducing the likelihood of negative effects from the antimicrobial actives, and saving resources. Advantageously, the compositions of the present invention have a high renewable carbon content. The compositions of the present invention are sustainable.

[0014] The composition of the present invention comprises (A) at least one compound selected from: compounds of formula (I)

[0015]

[0016] wherein R is selected from saturated hydrocarbon chains having 5 to 23 carbon atoms, unsaturated hydrocarbon chains having 5 to 23 carbon atoms, and mixtures thereof,

[0017] sorbitan esters, isosorbide esters, glycerol ethers, and glycerol esters.

[0018] In one embodiment, the composition of the present invention comprises (A) at least one compound selected from compounds of formula (I)

[0019]

[0020] wherein R is selected from saturated hydrocarbon chains having 5 to 23 carbon atoms, unsaturated hydrocarbon chains having 5 to 23 carbon atoms, and mixtures thereof.

[0021] Preferably, R in formula (I) is selected from saturated hydrocarbon chains having 5 to 17 carbon atoms, unsaturated hydrocarbon chains having 5 to 17 carbon atoms, and mixtures thereof.

[0022] More preferably, R in formula (I) is selected from saturated hydrocarbon chains having 5 to 13 carbon atoms, unsaturated hydrocarbon chains having 5 to 13 carbon atoms, and mixtures thereof.

[0023] Particularly preferably, R in formula (I) is selected from saturated hydrocarbon chains having 7 to 9 carbon atoms, unsaturated hydrocarbon chains having 7 to 9 carbon atoms, and mixtures thereof.

[0024] In at least one embodiment, R in formula (I) is selected from -(CH2)6CH3, -(CH2)8CH3, and mixtures thereof; or R in formula (I) is selected from -(CH2) 10 CH3, -(CH2) 12 CH3, and mixtures thereof; or R in formula (I) is selected from -(CH2)7CH═CH2, -(CH2)7CH═CHCH2CH3, and mixtures thereof; or the R-C═O residue in formula (I) is derived from coconut oil fatty acids; or the R-C═O residue in formula (I) is derived from soybean fatty acids.

[0025] In at least one embodiment, R in formula (I) is selected from -(CH2)6CH3, -(CH2)8CH3, and mixtures thereof. In at least one embodiment, R in formula (I) is selected from -(CH2) 10 CH3, -(CH2) 12CH3 and its mixtures. In at least one embodiment, R in formula (I) is selected from -(CH2)7CH=CH2, -(CH2)7CH=CHCH2CH3 and their mixtures. In at least one embodiment, the R-C=O residue in formula (I) is derived from coconut oil fatty acids. In at least one embodiment, the R-C=O residue in formula (I) is derived from soybean fatty acids.

[0026] As used herein, the expression "the R-C=O residue in formula (I) is derived from coconut oil fatty acids" preferably means that the carbon chain length distribution in the R-C=O residue in formula (I) corresponds to the carbon chain length distribution of the fatty acids in coconut oil (e.g., bound as triglycerides).

[0027] As used herein, the expression "the R-C=O residue in formula (I) is derived from soybean fatty acids" preferably means that the carbon chain length distribution in the R-C=O residue in formula (I) corresponds to the carbon chain length distribution of the fatty acids in soybean oil (e.g., bound as triglycerides).

[0028] Preferably, the weight ratio of the compound of formula (I) wherein R is -(CH2)6CH3 to the compound of formula (I) wherein R is -(CH2)8CH3 is from 1:9 to 9:1, preferably from 3:7 to 7:3.

[0029] Preferably, the 10 compound of formula (I) wherein R is -(CH2) 12 CH3 to the compound of formula (I) wherein R is -(CH2)

[0030] Preferably, the weight ratio of the compound of formula (I) wherein R is -(CH2)7CH=CH2 to the compound of formula (I) wherein R is -(CH2)7CH=CHCH2CH3 is from 1:9 to 9:1, preferably from 3:7 to 7:3.

[0031] The compounds of formula (I) are described, for example, in WO 2018 / 002100 and EP application number EP21200587.0.

[0032] In one embodiment, the composition of the present invention comprises (A) at least one compound selected from sorbitan esters and isosorbide esters.

[0033] In one embodiment, the composition of the present invention comprises (A) at least one compound selected from sorbitan esters.

[0034] Preferably, the sorbitan ester is a monoester, diester or triester of sorbitan and one or more C6-C20 fatty acids. More preferably, the sorbitan ester is a monoester or diester of sorbitan and one or more C8-C14 fatty acids. Particularly preferably, the sorbitan ester is a monoester or diester of sorbitan and caprylic acid.

[0035] Preferably, the sorbitan ester is selected from sorbitan octanoate, sorbitan stearate, sorbitan oleate, sorbitan oliveate, sorbitan decanoate, sorbitan laurate, sorbitan myristate, sorbitan hexanoate and mixtures thereof. Particularly preferably, the sorbitan ester is sorbitan octanoate.

[0036] In one embodiment, the composition of the present invention comprises (A) at least one compound selected from isosorbide esters.

[0037] Preferably, the isosorbide ester is a monoester or diester of isosorbide and one or more C6-C20 fatty acids. More preferably, the isosorbide ester is a monoester or diester of isosorbide and one or more C8-C14 fatty acids. Particularly preferably, the isosorbide ester is a monoester or diester of isosorbide and caprylic acid.

[0038] Preferably, the isosorbide ester is selected from isosorbide octanoate, isosorbide stearate, isosorbide oleate, isosorbide oliveate, isosorbide decanoate, isosorbide laurate, isosorbide myristate, isosorbide hexanoate and mixtures thereof. Particularly preferably, the isosorbide ester is isosorbide octanoate.

[0039] In one embodiment, the composition of the present invention comprises (A) at least one compound selected from glycerol ethers.

[0040] Preferably, the glycerol ether is a monoether or diether of glycerol and one or more C6-C20 fatty alcohols. More preferably, the glycerol ether is a monoether or diether of glycerol and one or more C8-C14 fatty alcohols. Particularly preferably, the glycerol ether is a monoether of glycerol and one or more C8 fatty alcohols.

[0041] In at least one embodiment, the glycerol ether is selected from ethylhexyl glycerin, methylheptyl glycerin, octyl glycerol ether and mixtures thereof.

[0042] In one embodiment, the composition of the present invention comprises (A) at least one compound selected from glycerol esters.

[0043] In at least one embodiment, the glycerol ester is selected from glycerol octanoate, glycerol decanoate and mixtures thereof. In one embodiment, the glycerol ester is glycerol octanoate / decanoate.

[0044] In one embodiment, the composition of the present invention comprises (A) at least one compound selected from sorbitan esters, wherein the hydroxyl value of at least one compound selected from sorbitan esters is preferably less than or equal to 320, more preferably less than or equal to 285, still more preferably less than or equal to 245, and particularly preferably less than or equal to 225.

[0045] In one embodiment, the composition of the present invention comprises (A) at least one compound selected from isosorbide esters, wherein the hydroxyl value of at least one compound selected from isosorbide esters is preferably less than or equal to 320, more preferably less than or equal to 285, still more preferably less than or equal to 245, and particularly preferably less than or equal to 225.

[0046] In one embodiment, the composition of the present invention comprises (A) a mixture of at least one compound selected from sorbitan esters and at least one compound selected from isosorbide esters. In one embodiment, the composition of the present invention comprises (A) a mixture of at least one compound selected from sorbitan esters and at least one compound selected from isosorbide esters, wherein the hydroxyl value of the mixture is preferably less than or equal to 320, more preferably less than or equal to 285, still more preferably less than or equal to 245, and particularly preferably less than or equal to 225.

[0047] The hydroxyl value of a substance should be understood to mean the amount of KOH in mg equivalent to the amount of acetic acid bound during the acetylation of 1 g of the substance.

[0048] Suitable methods for determining the hydroxyl value are, for example, DGF C-V 17a(53), Ph.Eur. 2.5.3 Method A and DIN 53240.

[0049] In the context of the present invention, the hydroxyl value is determined analogously to DIN 53240-2. The following procedure is employed here: Weigh out 1 g of the homogeneous sample to be measured, accurate to 0.1 mg. Add 20.00 ml of the acetylation mixture (acetylation mixture: Stir 50 ml of acetic anhydride into 1 l of pyridine). Dissolve the sample completely in the acetylation mixture, stirring and heating if necessary. Add 5 ml of the catalyst solution (catalyst solution: Dissolve 2 g of 4-dimethylaminopyridine in 100 ml of pyridine). Close the reaction vessel and place it in a water bath, pre-heating to 55 °C for 10 minutes while stirring. Then add 10 ml of completely deionized water to the reaction solution, close the reaction vessel again and react the mixture in the water bath once more, shaking for 10 minutes. Then cool the sample to room temperature (25 °C). Then add 50 ml of 2-propanol and 2 drops of phenolphthalein. Titrate the solution (Va) with an aqueous sodium hydroxide solution (aqueous sodium hydroxide solution c = 0.5 mol / l). Under the same conditions, but without adding any sample, determine the efficacy (Vb) of the acetylation mixture.

[0050] The hydroxyl value (OHV) is calculated using the following formula from the determination of the efficacy and the consumption of the aqueous sodium hydroxide solution in the titration of the sample.

[0051]

[0052] OHV = hydroxyl value in mg KOH / g of substance

[0053] Va = volume in ml of the aqueous sodium hydroxide solution consumed during the titration of the sample

[0054] Vb = volume in ml of the aqueous sodium hydroxide solution consumed during the titration of the efficacy

[0055] c = molar concentration of the aqueous sodium hydroxide solution in mol / l

[0056] t = titer of the aqueous sodium hydroxide solution

[0057] M = molar mass of KOH = 56.11 g / mol

[0058] E = mass in g of the weighed-out sample

[0059] (Vb - Va) is the volume in ml of the aqueous sodium hydroxide solution used, which is equivalent to the amount of acetic acid bound during the acetylation of the sample to be measured described above.

[0060] The composition of the present invention comprises (B) at least one hydroxyacetophenone.

[0061] Preferably, hydroxyacetophenone is selected from 2-hydroxyacetophenone, 3-hydroxyacetophenone, 4-hydroxyacetophenone, and mixtures thereof.

[0062] As used herein, 2-hydroxyacetophenone refers to a compound having the following formula:

[0063]

[0064] As used herein, 3-hydroxyacetophenone refers to a compound having the following formula:

[0065]

[0066] As used herein, 4-hydroxyacetophenone refers to a compound having the following formula:

[0067]

[0068] Particularly preferably, hydroxyacetophenone is 4-hydroxyacetophenone.

[0069] Hydroxyacetophenone is described, for example, in WO 2014 / 135650 A1.

[0070] Preferably, the weight ratio of (A) at least one compound selected from compounds of formula (I), sorbitan esters, isosorbide esters, glycerol ethers, and glycerol esters to (B) at least one hydroxyacetophenone is from 20:1 to 1:5, more preferably from 15:1 to 1:2, still more preferably from 12:1 to 1:1, particularly preferably from 10:1 to 3:1, such as from 6:1 to 7:1.

[0071] In a preferred embodiment, the composition of the present invention comprises (A) at least one compound selected from compounds of formula (I)

[0072]

[0073] wherein R is selected from a saturated hydrocarbon chain having 5 to 23 carbon atoms, an unsaturated hydrocarbon chain having 5 to 23 carbon atoms, and mixtures thereof; and

[0074] (B) at least one hydroxyacetophenone.

[0075] In a preferred embodiment, the composition of the present invention comprises (A) at least one compound selected from compounds of formula (I)

[0076]

[0077] wherein R is selected from a saturated hydrocarbon chain having 5 to 13 carbon atoms, an unsaturated hydrocarbon chain having 5 to 13 carbon atoms, and mixtures thereof; and

[0078] (B) At least one hydroxyacetophenone, wherein the hydroxyacetophenone is selected from 2-hydroxyacetophenone, 3-hydroxyacetophenone, 4-hydroxyacetophenone, and mixtures thereof.

[0079] In a particularly preferred embodiment, the composition of the present invention comprises:

[0080] (A) At least one compound selected from the compounds of formula (I)

[0081]

[0082] wherein R is selected from -(CH2)6CH3, -(CH2)8CH3, and mixtures thereof; and

[0083] (B) At least one hydroxyacetophenone, wherein the hydroxyacetophenone is 4-hydroxyacetophenone.

[0084] In at least one embodiment, the composition of the present invention is a blend.

[0085] In at least one embodiment, the blend comprises:

[0086] 25 to 99% by weight, preferably 40 to 80% by weight, more preferably 55 to 70% by weight, particularly preferably 60 to 65% by weight, based on the total weight of the blend, of (A) at least one compound selected from the compounds of formula (I), sorbitan esters, isosorbide esters, glycerol ethers, and glycerol esters; and

[0087] 1 to 50% by weight, preferably 2 to 20% by weight, more preferably 5 to 15% by weight, particularly preferably 8 to 12% by weight, based on the total weight of the blend, of (B) at least one hydroxyacetophenone.

[0088] In at least one embodiment, the blend is an aqueous solution.

[0089] In at least one embodiment, the blend comprises a solvent. In at least one embodiment, the blend comprises a solvent, wherein the solvent comprises water and / or an alcohol. The solvent is useful for providing the compounds used in the present invention in liquid form. In at least one embodiment, the solvent is cosmetically acceptable. In at least one embodiment, the blend comprises at least 10% by weight, preferably at least 20% by weight, more preferably at least 30% by weight, still more preferably at least 50% by weight of water. Water is useful both for economic reasons and because of its cosmetic acceptability. Optionally, the blend comprises a solvent that is miscible with or soluble in water, such as a lower alkyl alcohol. In at least one embodiment, the blend comprises a C1-C5 alkyl monohydric alcohol, preferably a C2-C3 alkyl monohydric alcohol. The alcohol that may be present is especially a lower monohydric or polyhydric alcohol having 1 to 4 carbon atoms, which is commonly used for cosmetic purposes, such as preferably ethanol or isopropanol.

[0090] Optionally, the blend comprises a water-soluble polyol. In at least one embodiment, the water-soluble polyol is a polyol having two or more hydroxyl groups in the molecule. In at least one embodiment, the water-soluble polyol is selected from: diols such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, tetramethylene glycol, 2,3-butanediol, 1,5-pentanediol, 2-butene-1,4-diol, hexanediol, octanediol; triols such as glycerol, trimethylolpropane, 1,2,6-hexanetriol, etc.; tetrols such as pentaerythritol; pentols such as xylytol; hexols such as sorbitol, mannitol; polyol polymers such as diethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, tetraethylene glycol, diglycerol, polyethylene glycol, triglycerol, tetraglycerol, polyglycerol; diol alkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monophenyl ether, ethylene glycol monohexyl ether, ethylene glycol mono-2-methylhexyl ether, ethylene glycol isoamyl ether, ethylene glycol benzyl ether, ethylene glycol isopropyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether; diol alkyl ethers such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol butyl ether, diethylene glycol methyl ethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol isopropyl ether, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, dipropylene glycol butyl ether; diol ether esters such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, ethylene glycol diadipate, ethylene glycol dibutanedioate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monophenyl ether acetate, glycerol monoalkyl ethers such as xyl alcohol, selachyl alcohol, batyl alcohol; sugar alcohols such as sorbitol, maltitol, maltotriose, mannitol, sucrose, erythritol, glucose, fructose, starch sugar, maltose, xylose, starch sugar reducing alcohol, glysolid, tetrahydrofurfuryl alcohol, POE tetrahydrofurfuryl alcohol, POP butyl ether, POP POE butyl ether, tripropylene glycol glycerol ether, POP glycerol ether, POP glycerol ether phosphate, POP POE pentaerythritol ether and mixtures thereof.

[0091] In a preferred embodiment, the blend comprises a solvent selected from water, diols, ethanol and mixtures thereof. In a preferred embodiment, the blend comprises water.

[0092] In a preferred embodiment, the blend comprises an aqueous, alcoholic or aqueous-alcoholic solvent, wherein the aqueous, alcoholic or aqueous-alcoholic solvent comprises water, ethanol, propanol, isopropanol, 1,2-propanediol, 1,3-propanediol, isobutanol, butanol, butyl glycol, butyl diglycol, glycerol or a mixture thereof; preferably wherein the aqueous, alcoholic or aqueous-alcoholic solvent comprises water, ethanol, propanol, isopropanol, 1,2-propanediol, 1,3-propanediol, glycerol or a mixture thereof; more preferably wherein the aqueous, alcoholic or aqueous-alcoholic solvent comprises water, isopropanol, 1,2-propanediol, 1,3-propanediol or a mixture thereof; still more preferably wherein the aqueous, alcoholic or aqueous-alcoholic solvent consists of water or consists of water and an alcohol, wherein the alcohol is selected from isopropanol, 1,2-propanediol and 1,3-propanediol.

[0093] Optionally, the composition of the present invention comprises (C) at least one additional antimicrobial agent.

[0094] Optionally, the blend of the present invention comprises (C) at least one additional antimicrobial agent.

[0095] In at least one embodiment, the antimicrobial agent is selected from aromatic alcohols, organic acids and their salts, hydroxamic acids and their salts, compounds according to formula (P), alkyl diols, halogenated compounds, isothiazolinones and mixtures thereof; wherein formula (P) is as follows:

[0096]

[0097] wherein

[0098] R1’ is H, a branched or unbranched C1-C 20 -alkyl group which is unsubstituted or halogen-substituted, a C5-C8-cycloalkyl group which is unsubstituted or halogen-substituted, a C6-C 10 -aryl group which is unsubstituted or halogen-substituted or a branched or unbranched C7-C 20 -aralkyl group;

[0099] R2’ is O or S;

[0100] R3’ is H or a C1-C4-alkyl group;

[0101] X + is a cation.

[0102] Preferably, R3’ is methyl.

[0103] In at least one embodiment, the aromatic alcohols are selected from benzyl alcohol, phenoxyethanol, veratryl alcohol, propylene phenoxyethanol, phenethyl alcohol, phenylpropyl alcohol, vanillin, 2-methyl-1-phenyl-2-propanol and mixtures thereof.

[0104] In at least one embodiment, the organic acid and its salts are selected from benzoic acid, sorbic acid, dehydroacetic acid, lactic acid, salicylic acid, p-methoxybenzoic acid, undecylenic acid, glycolic acid, propionic acid, levulinic acid, and mixtures thereof.

[0105] In at least one embodiment, the hydroxamic acid is selected from hydroxamic acids of formula (III)

[0106]

[0107] wherein R 1 is selected from saturated hydrocarbon chains having 5 to 23 carbon atoms, unsaturated hydrocarbon chains having 5 to 23 carbon atoms, and mixtures thereof.

[0108] Preferably, R in formula (III) 1 is selected from saturated hydrocarbon chains having 5 to 17 carbon atoms, unsaturated hydrocarbon chains having 5 to 17 carbon atoms, and mixtures thereof. More preferably, R in formula (III) 1 is selected from saturated hydrocarbon chains having 5 to 13 carbon atoms, unsaturated hydrocarbon chains having 5 to 13 carbon atoms, and mixtures thereof. Particularly preferably, R in formula (III) 1 is selected from saturated hydrocarbon chains having 7 carbon atoms, unsaturated hydrocarbon chains having 7 carbon atoms, and mixtures thereof.

[0109] Preferred hydroxamic acids are selected from octyl hydroxamic acid, hexyl hydroxamic acid, hexahydroxamic acid, lauryl hydroxamic acid, and mixtures thereof. Particularly preferred hydroxamic acid is octyl hydroxamic acid. Octyl hydroxamic acid can also be referred to as octanohydroxamic acid or caprylhydroxamic acid. Hydroxamic acids are described, for example, in EP2224973.

[0110] Examples of salts of hydroxamic acids are alkali metal salts of hydroxamic acids (e.g., sodium salt of hydroxamic acid or potassium salt of hydroxamic acid) or alkaline earth metal salts of hydroxamic acids (e.g., magnesium salt of hydroxamic acid or calcium salt of hydroxamic acid).

[0111] In at least one embodiment, the compounds according to formula (P) are selected from 2-hydroxypyridine-N-oxide, 2-mercaptopyridine-1-oxide and its salts, 1-hydroxy-4-methyl-6-(2,4,4-trimethylpentyl)-2(1H)-pyridone and its salts (preferably monoethanolamine salt), and mixtures thereof. Formula (P) discloses and encompasses the tautomeric equivalents of these compounds, due to the equilibrium that always exists. In at least one embodiment, the compound according to formula (P) is octopirox (octopirox ethanolamine salt).

[0112] In at least one embodiment, the alkyl diol is selected from 1,2-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 1,2-octanediol, 1,2-heptanediol, 1,2-decanediol, methylpropanediol, and mixtures thereof.

[0113] In at least one embodiment, the halogenated compound is selected from chlorhexidine and its salts, triclosan, chlorphenesin, trichlorocarban, chloroxylenol, iodopropynyl butylcarbamate, bronopol, clotrimazole, and mixtures thereof.

[0114] In at least one embodiment, the isothiazolinone is selected from methylisothiazolinone, methylchloroisothiazolinone, benzylisothiazolinone, and mixtures thereof.

[0115] In at least one embodiment, the antimicrobial agent is selected from aromatic alcohols, organic acids and their salts, hydroxamic acids and their salts, hydroxypyridines, alkyl diols, halogenated compounds, isothiazolinones, and mixtures thereof.

[0116] In at least one embodiment, the antimicrobial agent is selected from phenoxyethanol, benzyl alcohol, phenethyl alcohol, benzoic acid and its salts, octyl hydroxamic acid, piroctone olamine, and mixtures thereof.

[0117] In a preferred embodiment, the antimicrobial agent is 1,2-octanediol, particularly bio-based 1,2-octanediol, such as the bio-1,2-octanediol disclosed in WO 2019 / 152569.

[0118] Suitable antimicrobial agents are also listed in Annex V (updated on 28 / 09 / 2022) of Regulation (EC) No 1223 / 2009 of the European Parliament and of the Council of 30 November 2009 concerning cosmetic products.

[0119] The compositions of the present invention can be prepared by methods known in the art, such as by mixing its components.

[0120] The blends of the present invention can be prepared by methods known in the art, such as by mixing its components.

[0121] The present invention also relates to a formulation comprising:

[0122] (A) at least one compound selected from:

[0123] a compound of formula (I)

[0124]

[0125] wherein R is selected from a saturated hydrocarbon chain having 5 to 23 carbon atoms, an unsaturated hydrocarbon chain having 5 to 23 carbon atoms, and mixtures thereof,

[0126] Sorbitan esters, isosorbide glycerol ethers and glycerol esters; and

[0127] (B) at least one hydroxyacetophenone.

[0128] In one embodiment, the present invention relates to a formulation comprising:

[0129] (A) 0.1 to 10% by weight, preferably 0.2 to 3% by weight, particularly preferably 0.3 to 1.5% by weight, based on the total weight of the formulation, of at least one compound selected from:

[0130] compounds of formula (I)

[0131]

[0132] wherein R is selected from saturated hydrocarbon chains having 5 to 23 carbon atoms, unsaturated hydrocarbon chains having 5 to 23 carbon atoms and mixtures thereof,

[0133] Sorbitan esters, isosorbide esters, glycerol ethers and glycerol esters; and

[0134] (B) 0.01 to 1.5% by weight, preferably 0.05 to 0.5% by weight, particularly preferably 0.1 to 0.3% by weight, based on the total weight of the formulation, of at least one hydroxyacetophenone.

[0135] In at least one embodiment, the formulation is selected from cosmetic formulations and household cleaning formulations.

[0136] In at least one embodiment, the formulation is selected from shampoo, body wash, facial cleanser, facial mask, bubble bath, intimate wash, bath oil, cleansing milk, micellar water, makeup remover, cleansing wipes, hair mask, perfume, liquid soap, shaving soap, shaving foam, cleansing foam, day cream, anti-aging cream, body lotion, body milk, body mousse, facial essence, eye cream, sunscreen lotion, sunscreen, face cream, aftershave lotion, pre-shave cream, hair removal cream, skin whitening gel, self-tanning cream, anti-acne gel, mascara, foundation, makeup primer, concealer, rouge, contour powder, repair (BB) cream, eyeliner, night cream, eyebrow gel, brightener, lip gloss, hand sanitizer, hair oil, nail polish remover, conditioner, hairspray, styling milk, anti-frizz essence, scalp treatment, hair dye, split end fluid, deodorant, antiperspirant, baby cream, insect repellent, hand cream, sunscreen gel, foot cream, exfoliant, body scrub, cellulite treatment, soap bar, epidermal cream, lip balm, hair care agent, eyeshadow, bath additive, body spray, eau de toilette, mouthwash, toothpaste, lubricating gel, moisturizer, essence, skin care lotion, aqua sorbet, cream gel, styling mousse, dry shampoo, lip balm, lip gloss, hydro-alcoholic gel, body oil, body wash, brightening cream, lip pencil, hair spray, grooming cream, and sunscreen agent.

[0137] In at least one embodiment, the formulation is a cosmetic formulation for cleaning hair and / or skin.

[0138] In at least one embodiment, the formulation is a cosmetic formulation, preferably a skin care formulation, more preferably a leave-on skin care formulation.

[0139] In at least one embodiment, the formulation is an aqueous solution.

[0140] In at least one embodiment, the formulation contains a solvent. In at least one embodiment, the formulation contains a solvent, wherein the solvent contains water and / or alcohol. The solvent is useful for providing the compound in liquid form. In at least one embodiment, the solvent is cosmetically acceptable. In at least one embodiment, the formulation contains at least 10% by weight, preferably at least 20% by weight, more preferably at least 30% by weight, still more preferably at least 50% by weight of water. Water is useful both for economic reasons and because it is cosmetically acceptable. Optionally, the formulation contains a solvent that is miscible with or soluble in water, such as a lower alkyl alcohol. In at least one embodiment, the formulation contains a C1-C5 alkyl monohydric alcohol, preferably a C2-C3 alkyl monohydric alcohol. The alcohols that may be present are especially lower monohydric or polyhydric alcohols having 1 to 4 carbon atoms, which are commonly used for cosmetic purposes, such as preferably ethanol and isopropanol.

[0141] Optionally, the formulation comprises a water-soluble polyol. In at least one embodiment, the water-soluble polyol is a polyol having two or more hydroxyl groups in the molecule. In at least one embodiment, the water-soluble polyol is selected from: diols such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, tetramethylene glycol, 2,3-butanediol, 1,5-pentanediol, 2-butene-1,4-diol, hexanediol, octanediol; triols such as glycerol, trimethylolpropane, 1,2,6-hexanetriol, etc.; tetrols such as pentaerythritol; pentols such as xylytol; hexols such as sorbitol, mannitol; polyol polymers such as diethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, tetraethylene glycol, diglycerol, polyethylene glycol, triglycerol, tetraglycerol, polyglycerol; diol alkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monophenyl ether, ethylene glycol monohexyl ether, ethylene glycol mono-2-methylhexyl ether, ethylene glycol isoamyl ether, ethylene glycol benzyl ether, ethylene glycol isopropyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether; diol alkyl ethers such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol butyl ether, diethylene glycol methyl ethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol isopropyl ether, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, dipropylene glycol butyl ether; diol ether esters such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, ethylene glycol diadipate, ethylene glycol dibutyrate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monophenyl ether acetate, glycerol monoalkyl ethers such as xyl alcohol, selachyl alcohol, batyl alcohol, sugar alcohols such as sorbitol, maltitol, maltotriose, mannitol, sucrose, erythritol, glucose, fructose, starch sugar, maltose, xylose, starch sugar reducing alcohol, glysolid, tetrahydrofurfuryl alcohol, POE tetrahydrofurfuryl alcohol, POP butyl ether, POP POE butyl ether, tripropylene glycol glycerol ether, POP glycerol ether, POP glycerol ether phosphate, POP POE pentaerythritol ether and mixtures thereof.

[0142] In a preferred embodiment, the formulation comprises a solvent selected from water, ethylene glycol, ethanol and mixtures thereof. In a preferred embodiment, the formulation comprises water.

[0143] In a preferred embodiment, the formulation comprises an aqueous, alcoholic or aqueous-alcoholic solvent, wherein the aqueous, alcoholic or aqueous-alcoholic solvent comprises water, ethanol, propanol, isopropanol, 1,2-propanediol, 1,3-propanediol, isobutanol, butanol, butyl glycol, butyl diglycol, glycerol or a mixture thereof; preferably wherein the aqueous, alcoholic or aqueous-alcoholic solvent comprises water, ethanol, propanol, isopropanol, 1,2-propanediol, 1,3-propanediol, glycerol or a mixture thereof; more preferably wherein the aqueous, alcoholic or aqueous-alcoholic solvent comprises water, isopropanol, 1,2-propanediol, 1,3-propanediol or a mixture thereof; still more preferably wherein the aqueous, alcoholic or aqueous-alcoholic solvent consists of water or consists of a mixture of water and an alcohol, wherein the alcohol is selected from isopropanol, 1,2-propanediol and 1,3-propanediol.

[0144] In at least one embodiment, the formulation comprises additives common in cosmetics, pharmacy and dermatology, which are hereinafter referred to as adjuvants herein. In at least one embodiment, the adjuvants are selected from oily substances, emulsifiers, co-emulsifiers, cationic polymers, film formers, emollients, stabilizers, active biomaterials, glycerol, preservatives, pearlescent agents, dyes and fragrances, solvents, opacifiers, functional acids, and also protein derivatives such as gelatin, hydrolyzed collagen, natural or synthetic-based polypeptides, egg yolk, lecithin, lanolin and lanolin derivatives, fatty alcohols, silicones, deodorants, substances having a keratolytic and keratinogenic action, enzymes and / or carriers / solvents.

[0145] In at least one embodiment, the formulation comprises water-soluble vitamins and their derivatives, water-soluble amino acids and their salts and / or derivatives, viscosity regulators, dyes, non-volatile solvents or diluents (water-soluble and water-insoluble), pearlescent aids, thickeners, foam boosters, additional surfactants or non-ionic co-surfactants, pediculicides, pH regulators, fragrances, preservatives, chelating agents, proteins, skin actives, sunscreens, UV absorbers, vitamins, niacinamide, caffeine, minoxidil and combinations thereof. In at least one embodiment, the formulation comprises from 0 wt% to 5 wt% of vitamins and amino acids, based on the total weight of the formulation. The formulation may also comprise pigment materials such as inorganic, nitroso, monoazo, diazo, carotenoid, triphenylmethane, triarylmethane, xanthene, quinoline, oxazine, azine, anthraquinone, indigoid, thionindigoid, quinacridone, phthalocyanine, vegetable, natural pigments, including: water-soluble components such as those having a C.I. name. The formulation may comprise 0 wt%, preferably from 0.0001 wt% to 5 wt% of the pigment material.

[0146] In at least one embodiment, the formulation comprises an oily substance, which is any fatty substance that is liquid at room temperature (25 °C). In at least one embodiment, the formulation comprises an oily substance selected from volatile or non-volatile, linear, branched or cyclic, optionally organically modified silicone oils; phenylsilicones; silicone resins and silicones; mineral oils such as paraffin oil or petrolatum oil; oils of animal origin such as perhydrosqualene, lanolin; oils of plant origin such as liquid triglycerides, such as sunflower oil, corn oil, soybean oil, rice oil, jojoba oil, babassu oil, pumpkin oil, grape seed oil, sesame oil, walnut oil, almond oil, macadamia nut oil, avocado oil, sweet almond oil, oxalis oil, castor oil, triglycerides of caprylic / capric acid, olive oil, peanut oil, rapeseed oil, argan oil, abyssinian oil and coconut oil; synthetic oils such as purcellin oil, isoparaffins, linear and / or branched fatty alcohols and fatty acid esters, preferably guerbet alcohols having 6 to 18, preferably 8 to 10 carbon atoms; esters of linear (C6-C 13 ) fatty acids with linear (C6-C 20 ) fatty alcohols; esters of branched (C6-C 13 ) carboxylic acids with linear (C6-C 20 ) fatty alcohols, esters of linear (C6-C 18 ) fatty acids with branched alcohols, in particular 2-ethylhexanol; esters of linear and / or branched fatty acids with polyols (such as di- or tri-glycols) and / or guerbet alcohols; triglycerides based on (C6-C 10 ) fatty acids; esters such as dioctyl adipate, diisopropyl dimer dilinoleate; propylene glycol / dioctanoate or waxes such as beeswax, paraffin wax or microcrystalline wax, alone or in combination with a hydrophilic wax such as cetearyl alcohol; fluorinated and perfluorinated oils; fluorinated silicone oils; mixtures of the above compounds.

[0147] In at least one embodiment, the formulation comprises a non-ionic co-emulsifier. In at least one embodiment, the non-ionic co-emulsifier is selected from adducts of 0 to 30 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide with linear fatty alcohols having 8 to 22 carbon atoms, with fatty acids having 12 to 22 carbon atoms, with alkylphenols having 8 to 15 carbon atoms in the alkyl group, and with sorbitan or sorbitol esters; adducts of 0 to 30 moles of ethylene oxide with glycerol of (C 12 -C 18)Fatty acid monoesters and diesters; glycerol monoesters and diesters of saturated and unsaturated fatty acids having 6 to 22 carbon atoms and sorbitan monoesters and diesters and, where appropriate, their ethylene oxide adducts; adducts of 15 to 60 moles of ethylene oxide with castor oil and / or hydrogenated castor oil; polyol esters and especially polyglycerol esters, such as polyglycerol polyricinoleate and polyglycerol poly-12-hydroxystearate. Also suitable are mixtures of compounds from one or more of these classes of substances. Examples of suitable ionic co-emulsifiers include anionic emulsifiers, such as mono-phosphates, di-phosphates or tri-phosphates, and also cationic emulsifiers such as mono-alkyl quaternary ammonium compounds, di-alkyl quaternary ammonium compounds or tri-alkyl quaternary ammonium compounds and their polymeric derivatives.

[0148] In at least one embodiment, the formulation comprises a cationic polymer. Suitable cationic polymers include those known by the INCI name “Polyquaternium”, in particular polyquaternium-31, polyquaternium-16, polyquaternium-24, polyquaternium-7, polyquaternium-22, polyquaternium-39, polyquaternium-28, polyquaternium-2, polyquaternium-10, polyquaternium-11 and also polyquaternium 37 and mineral oil and PPG trideceth (Salcare SC95), PVP-dimethylaminoethyl methacrylate copolymer, guar hydroxypropyltrimonium chloride, and also calcium alginate and ammonium alginate. Also feasible is to employ cationic cellulose derivatives; cationic starch; copolymers of diallyl ammonium salts and acrylamide; quaternized vinylpyrrolidone / vinylimidazole polymers; condensation products of polyglycols and amines; quaternized collagen polypeptides; quaternized wheat polypeptides; polyethyleneimine; cationic silicone polymers, such as amido poly dimethyl siloxane; copolymers of adipic acid and dimethylaminohydroxypropyl diethylenetriamine; polyamino polyamides and cationic chitin derivatives such as chitosan.

[0149] In at least one embodiment, the formulation comprises a fat-rich agent. The following substances can be used as fat-rich agents: for example, polyethoxylated lanolin derivatives, lecithin derivatives, polyol fatty acid esters, monoglycerides or fatty acid alkanolamides, the latter also acting as foam stabilizers. Available humectants include, for example, isopropyl palmitate, glycerol and / or sorbitol.

[0150] In at least one embodiment, the formulation comprises a stabilizer. Metal salts of fatty acids can be used as stabilizers, such as magnesium stearate, aluminum stearate and / or zinc stearate.

[0151] In at least one embodiment, the formulation comprises a care additive. The formulation can be blended with conventional ceramides, pseudoceramides, fatty acid N-alkyl polyhydroxyalkylamides, cholesterol, cholesterol fatty acid esters, fatty acids, triglycerides, cerebrosides, phospholipids, panthenol, and similar substances as care additives.

[0152] In at least one embodiment, the formulation comprises an antifungal substance. In at least one embodiment, the antifungal substance is selected from ketoconazole, oxiconazole, bifonazole, butoconazole, clotrimazole, econazole, enilconazole, fenticonazole, isoconazole, miconazole, sulconazole, tioconazole, fluconazole, itraconazole, terconazole, naftifine, terbinafine, zinc pyrithione, octopirox, and combinations thereof. In at least one embodiment, the formulation comprises an antifungal substance in an amount of from 0.1% to 1% by weight of the total amount of the formulation. In at least one embodiment, the formulation comprises pyrithione antidandruff granules. For example, 1-hydroxy-2-pyridinethione salts are highly preferred particulate antidandruff agents. The concentration of the pyrithione antidandruff granules can range from 0.1% to 4% by weight, preferably from 0.1% to 3% by weight, more preferably from 0.3% to 2% by weight of the total weight of the formulation. Preferred pyrithione salts include those formed from heavy metals such as zinc, tin, cadmium, magnesium, aluminum, or zirconium, preferably zinc, more preferably the zinc salt of 1-hydroxy-2-pyridinethione (referred to as "zinc pyrithione" or "ZPT"), and more preferably 1-hydroxy-2-pyridinethione salts in the form of flaky particles. Salts formed from other cations such as sodium can also be suitable.

[0153] Functional acids are acidic substances that impart clinical functions to the skin or hair upon application. Suitable functional acids include alpha-hydroxy acids, beta-hydroxy acids, lactic acid, retinoic acid, and the like.

[0154] In at least one embodiment, the formulation comprises an astringent. In at least one embodiment, the astringent is selected from magnesium oxide, aluminum oxide, titanium dioxide, zirconium dioxide, zinc oxide, hydrated oxides, aluminum hydroxide hydrates (boehmite), and hydroxides, chlorohydrates of calcium, magnesium, aluminum, titanium, zirconium, or zinc. In at least one embodiment, the formulation comprises an astringent in an amount of from 0.001% to 10% by weight, or from 0.01% to 9% by weight, or from 0.05% to 8% by weight, or from 0.1% to 5% by weight.

[0155] In at least one embodiment, the formulation comprises a deodorant. In at least one embodiment, the deodorant is selected from allantoin, bisabolol, and combinations thereof. In at least one embodiment, the formulation comprises from 0.001 wt% to 10 wt%, or from 0.01 wt% to 9 wt%, or from 0.05 wt% to 8 wt%, or from 0.1 wt% to 5 wt% of the deodorant.

[0156] In at least one embodiment, the formulation comprises a sunscreen and / or a UV filter. Suitable sunscreens and UV filters are disclosed in WO-2013 / 017262A1, pages 32, line 11 to the end of page 33. In at least one embodiment, the sunscreen and / or UV filter is selected from 4-aminobenzoic acid, 3-(4’-trimethylammonium)-benzylide-boran-2-one-methylsulfate, camphor benzalkonium methyl sulfate, 3,3,5-trimethyl-cyclohexyl salicylate, 2-hydroxy-4-methoxybenzophenone, 2-phenylbenzimidazole-5-sulfonic acid and its potassium, sodium and triethanolamine salts, 3,3’-(1,4-phenylenedimethylene)-bis-(7,7-dimethyl-2-oxobicyclo[2.2.1]-heptane-1-methanesulfonic acid) and its salts, 1-(4-tert-butylphenyl)-3-(4-methoxyphenyl)propane-1,3-dione, 3-(4’-sulfo)-benzylide-bornan-2-one and its salts, 2-cyano-3,3-diphenyl-acrylic acid-(2-ethylhexyl ester), polymer of N-[2(and 4)-(2-oxoborn-3-ylidenmethyl)benzyl]-acrylamide, 2-ethylhexyl 4-methoxycinnamate, ethoxylated ethyl 4-aminobenzoate, isopentyl 4-methoxycinnamate, 2,4,6-tris-[p-(2-ethylhexyloxycarbonyl)anilino]-1,3,5-triazine, 2-(2H-benzotriazol-2-yl)-4-methyl-6-(2-methyl-3-(1,3,3,3-tetramethyl-1-(trimethylsilanoxy)-disiloxanyl)-propyl)phenol, 4,4’-[(6-[4-((1,1-dimethylethyl)-aminocarbonyl)phenylamino]-1,3,5-triazine-2,4-yl)diimino]bis-(2-ethylhexyl benzoate), 3-benzophenone, 4-benzophenone, 3(4’-methylbenzylidene)D,L-camphor, 3-benzylidene-camphor, 2-ethylhexyl salicylate, 2-ethylhexyl 4-dimethylaminobenzoate, hydroxy-4-methoxy-benzophenone-5-sulfonic acid and its sodium salt, 4-isopropylbenzyl salicylate, N,N,N-trimethyl-4-(2-oxoborn-3-ylidenmethyl)anilinium methyl sulfate (N,N,N-trimethyl-4-(2-oxoborn-3-ylidenemethyl)anilium methyl sulfate, Homosalate (INN), Oxybenzone (INN), 2-phenylbenzimidazole-5-sulfonic acid and its sodium, potassium and triethanolamine salts, Octyl methoxycinnamate, Isoamyl-4-methoxycinnamate, Isoamyl-p-methoxycinnamate, 2,4,6-trianilino-(p-carbo-2'-ethylhexyl-1'-oxy)-1,3,5-triazine (Octyl triazone) phenol, 2,2(2H-benzotriazol-2-yl)-4-methyl-6-(2-methyl-3-(1,3,3,3-tetramethyl-1-(trimethylsilyloxy)-disiloxanyl)propyl (Tinosorb M) benzoic acid, 4,4-((6-(((1,1-dimethylethyl)amino)carbonyl)phenyl)amino)-1,3,5-triazine-2,4-diyl)diimino)bis, bis(2-ethylhexyl) ester) benzoic acid, 4,4-((6-(((1,1-dimethylethyl)amino)-carbonyl)phenyl)amino)-1,3,5-triazine-2,4-diyl)diimino)bis, bis(2-ethylhexyl) ester), 3-(4'-methylbenzylidene)-D,L-camphor (4-methylbenzylidene camphor), Benzylidene-camphor-sulfonic acid, Octocrylene, Polyacrylamidomethyl-benzylidene-camphor, 2-ethylhexyl-salicylate (Octyl salicylate), 4-dimethyl-aminobenzoic acid ethyl-2-hexyl ester (Octyl dimethyl PABA), PEG-25 PABA, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid (5-Benzophenone) and its sodium salt, 2,2'-methylenebis-6-(2H-benzotriazol-2-yl)-4-(tetramethyl-butyl)-1,1,3,3-phenol, Sodium salt of 2-2'-bis-(1,4-benzylidene)1H-benzimidazole-4,6-disulfonic acid, (1,3,5)-triazine-2,4-bis((4-(2-ethyl-hexyloxy)-2-hydroxy)-phenyl)-6-(4-methoxyphenyl), 2-ethylhexyl-2-cyano-3,3-diphenyl-2-propionate, Glyceryl caprylate, Di-p-methoxycinnamic acid, p-aminobenzoic acid and its esters, 4-tert-butyl-4'-methoxydibenzoylmethane, 4-(2-β-glucopyranosyloxy)propoxy-2-hydroxybenzophenone, Octyl salicylate, Methyl-2,5-diisopropylcinnamate, Cinoxate, Dihydroxy-dimethoxybenzophenone, Disodium salt of 2,2'-dihydroxy-4,4'-dimethoxy-5,5'-disulfonyldibenzophenone, Dihydroxybenzophenone, 1,3,4-dimethoxyphenyl-4,4-dimethyl-1,3 - Pentanedione, 2 - ethylhexyl - dimethoxybenzylidene dioxoimidazolidine propionate, methylene - bis - benzotriazolyl tetramethylbutylphenol, phenyl dibenzimidazole tetrasulfonate, bis - ethylhexyloxyphenol - methoxyphenol - triazine, tetrahydroxybenzophenone, terephthalylidene dicamphor - sulfonic acid, 2,4,6 - tris[4,2 - ethylhexyloxycarbonyl) anilino] - 1,3,5 - triazine, methyl - bis(trimethylsilyloxy) silyl - isopentyl trimethoxycinnamate, pentyl - p - dimethylaminobenzoate, pentyl - p - dimethylaminobenzoate, 2 - ethylhexyl - p - dimethylaminobenzoate, isopropyl - p - methoxycinnamate / diisopropyl cinnamate, 2 - ethylhexyl - p - methoxycinnamate, 2 - hydroxy - 4 - methoxybenzophenone, 2 - hydroxy - 4 - methoxybenzophenone - 5 - sulfonic acid and its trihydrate, sodium salt of 2 - hydroxy - 4 - methoxybenzophenone - 5 - sulfonate, phenyl - benzimidazole sulfonic acid and combinations thereof. In at least one embodiment, the formulation comprises from 0.001 wt% to 10 wt%, preferably from 0.05 wt% to 5 wt%, still more preferably from 0.1 wt% to 3 wt%, and most preferably from 0.05 wt% to 1 wt% of a sunscreen agent and / or UV filter. In at least one embodiment, the formulation comprises an amount of a photoprotective substance from 0.01 to 10 wt%, or from 0.1 to 5 wt%, more preferably from 0.2 to 2 wt%. Suitable photoprotective substances include in particular all photoprotective substances specified in EP1084696A1, which is incorporated herein by reference. In a preferred embodiment, the photoprotective substance is selected from 2 - ethylhexyl 4 - methoxycinnamate, methyl methoxycinnamate, 2 - hydroxy - 4 - methoxybenzophenone - 5 - sulfonic acid, polyethoxylated p - aminobenzoate and combinations thereof.,

[0157] In at least one embodiment, the formulation comprises an antioxidant. In at least one embodiment, the antioxidant is selected from amino acids, peptides, sugars, imidazoles, carotenoids, carotenes, chlorogenic acid, lipoic acid, thiols, thiol glycosyl esters, thiol N-acetyl esters, thiol methyl esters, thiol ethyl esters, thiol propyl esters, thiol pentyl esters, thiol butyl esters, thiol lauryl esters, thiol palmitoyl esters, thiol oleyl esters, thiol linoleyl esters, thiol cholesteryl esters, thiol glycerol esters, dilauryl thiodipropionate, distearyl thiodipropionate, thiodipropionic acid, metal chelators, hydroxy acids, fatty acids, folic acid, vitamin C, tocopherols, vitamin A, stilbenes, their derivatives, and combinations thereof. In at least one embodiment, the antioxidant is selected from glycine, histidine, tyrosine, tryptophan, urocanic acid, D,L-carnosine, D-carnosine, L-carnosine, β-carotene, α-carotene, lycopene, dihydrolipoic acid, aurothioglucose, propylthiouracil, thioredoxin, glutathione, cysteine, cystine, cystamine, buthioninsulfoximine, homocysteinsulfoximine, buthionine sulfone, pentathioninsulfoximine, hexathioninsulfoximine, heptathioninsulfoximine, hydroxy fatty acids, palmitic acid, phytanic acid, lactoferrin, citric acid, lactic acid, malic acid, humic acid, bile acids, bilirubin, biliverdin, EDTA, EGTA, linoleic acid, linolenic acid, oleic acid, butylated hydroxyanisole, trihydroxybutyrophenone, ubiquinone, panthenol, ascorbyl palmitate, ascorbyl magnesium phosphate, ascorbyl acetate, vitamin E acetate, vitamin A palmitate, carnosine, mannose, ZnO, ZnSO4, methionine selenium, stilbene, superoxide dismutase, and combinations thereof. In at least one embodiment, the antioxidant is selected from vitamin A, vitamin A derivatives, vitamin E, vitamin E derivatives, and combinations thereof. In at least one embodiment, the formulation comprises from 0.001 wt% to 10 wt%, preferably from 0.05 wt% to 5 wt%, particularly preferably from 0.1 wt% to 3 wt%, and even more particularly preferably from 0.05 wt% to 1 wt% of the antioxidant.

[0158] In at least one embodiment, the formulation comprises a dye or a pigment. In at least one embodiment, the formulation comprises at least one pigment. Suitable dyes and pigments are disclosed in the table on pages 36 to 43 of WO2013 / 017262A1. These can be colored pigments that impart color to the product material or hair, or they can be luster effect pigments that impart a luster effect to the product material or hair. The color or luster effect on the hair is preferably short-term, i.e., they last until the next hair wash and can be removed again by washing the hair with a conventional shampoo. In at least one embodiment, the formulation comprises from 0.01% to 25% by weight, preferably from 5% to 15% by weight in total, of pigments. In at least one embodiment, the particle size of the pigments is from 1 micron to 200 microns, preferably from 3 microns to 150 microns, more preferably from 10 microns to 100 microns. Pigments are colorants that are poorly soluble in the application medium and can be inorganic or organic. Inorganic-organic mixed pigments are also feasible. Inorganic pigments are preferred. The advantage of inorganic pigments is their excellent light, weather and temperature resistance. Inorganic pigments can be of natural origin. In at least one embodiment, the inorganic pigments are selected from chalk, ochre, umber, green earth, burnt ochre, graphite and combinations thereof. The pigments can be white pigments such as titanium dioxide or zinc oxide, black pigments such as iron oxide black, colored pigments such as ultramarine or iron oxide red, luster pigments, metal effect pigments, pearlescent pigments and fluorescent or phosphorescent pigments, wherein preferably at least one pigment is a colored, non-white pigment. In at least one embodiment, the pigments are selected from metal oxides, hydroxides and hydrated oxides, mixed phase pigments, sulfur-containing silicates, metal sulfides, complex metal cyanides, metal sulfates, chromates and molybdates and the metals themselves (copper pigments) and combinations thereof. In at least one embodiment, the pigments are selected from titanium dioxide (CI77891), iron oxide black (CI 77499), iron oxide yellow (CI 77492), iron oxide red and iron oxide brown (CI 77491), manganese violet (CI 77742), ultramarine (sodium aluminosilicate sulfonate, CI 77007, Pigment Blue 29), hydrated chromium oxide (CI 77289), Prussian blue (ferric ferrocyanide, CI 77510), carmine and combinations thereof. In at least one embodiment, the pigments are selected from mica-based pearlescent and colored pigments coated with metal oxides or metal chlorooxides, such as titanium dioxide or bismuth oxychloride and optionally additional color-imparting substances such as iron oxides, Prussian blue, ultramarine, carmine, etc., and wherein the color can be determined by changing the layer thickness. Such pigments are available from Merck, for example and for sale under the trademark name. In at least one embodiment, the pigment is selected from organic pigments such as sepia, gamboge, bone charcoal, Cassel brown, indigo, chlorophyll and other plant pigments. In at least one embodiment, the pigment is selected from synthetic organic pigments such as azo pigments, anthraquinoid, indigoid, dioxazine, quinacridone, phthalocyanine, isoindolinone, perylene and perinone, metal complexes, basic blue and diketopyrrolopyrrole pigments.

[0159] In at least one embodiment, the formulation comprises from 0.01% to 10% by weight, preferably from 0.05% to 5% by weight of at least one particulate matter. Suitable substances are, for example, substances that are solid at room temperature (25 °C) and are in particulate form. In at least one embodiment, the particulate matter is selected from silica, silicates, aluminates, clays, micas, insoluble salts, especially insoluble inorganic metal salts, metal oxides such as titanium dioxide, minerals and insoluble polymer particles are suitable. The particles may be present in the formulation in undissolved form, preferably in a stable dispersion, and after application to the keratin substrate and evaporation of the solvent, may be deposited on the substrate in solid form. A stable dispersion can be achieved by providing a formulation with a yield point large enough to prevent the solid particles from sinking. A suitable amount of a suitable gelling agent can be used to establish a sufficient yield point. In at least one embodiment, the particulate matter is selected from silica (silica gel, silica) and metal salts, especially inorganic metal salts, with silica being particularly preferred. Metal salts are, for example, alkali metal or alkaline earth metal halides such as sodium chloride or potassium chloride; alkali metal or alkaline earth metal sulfates such as sodium sulfate or magnesium sulfate.

[0160] In at least one embodiment, the formulation comprises a direct dye. Preferred among the direct dyes are the following compounds (alone or in combination with each other): hydroxyethyl-2-nitro-p-toluidine, 2-hydroxyethyl picramic acid, 4-nitrophenyl semicarbazide, tris(4-amino-3-methylphenyl) carbonium chloride (Basic Violet 2), 1,4-di-amino-9,10-anthracenedione (Disperse Violet 1), 1-(2-hydroxyethyl)amino-2-nitro-4-[bis(2-hydroxyethyl)amino]benzene (HC Blue No. 2), 4-[ethyl-(2-hydroxyethyl)amino]-1-[(2-hydroxyethyl)amino]-2-nitrobenzene hydrochloride (HC Blue No. 12), 1-amino-4-[bis(2-hydroxyethyl)amino]-2-nitrobenzene hydrochloride (HC Red No. 13), 4-amino-1-[(2-hydroxyethyl)amino]-2-nitrobenzene (HC Red No. 3), 4-amino-3-nitrophenol, 4-[(2-hydroxyethyl)amino]-3-nitrophenol, 1-amino-5-chloro-4-[(2,3-dihydroxypropyl)amino]-2-nitrobenzene (HC Red No. 10), 5-chloro-1,4-[bis(2,3-dihydroxypropyl)amino]-2-nitrobenzene (HC Red No. 11), 2-chloro-6-ethylamino-4-nitrophenol, 2-amino-6-chloro-4-nitrophenol, 4-[(2-hydroxyethyl)amino]-3-nitro-1-trifluoromethylbenzene (HC Yellow No. 13), 8-amino-2-bromo-5-hydroxy-4-imino-6-{[3-(trimethylammonio)phenyl]amino}-1(4H)-naphthone chloride (C.I. 56059; Basic Blue 99), 1-[(4-aminophenyl)azo]-7-(trimethylammonio)-2-naphthol chloride (C.I. 12250; Basic Brown 16), 1-[(4-amino-2-nitrophenyl)azo]-7-(trimethylammonio)-2-naphthol chloride (Basic Brown 17), 2-hydroxy-1-[(2-methoxyphenyl)azo]-7-(trimethylammonio)naphthalene chloride (C.I. 12245; Basic Red 76), 3-methyl-1-phenyl-4-{[3-(trimethylammonio)phenyl]azo}pyrazol-5-one chloride (C.I. 12719; Basic Yellow 57) and 2,6-diamino-3-[(pyridin-3-yl)azo]pyridine and its salts.Particularly preferred among the above direct dyes are the following compounds (alone or in combination with each other): hydroxyethyl-2-nitro-p-toluidine, 2-hydroxyethyl picramic acid, 4-nitrophenyl semicarbazide, tris(4-amino-3-methylphenyl) carbonium chloride (Basic Violet 2), 1,4-diamino-9,10-anthraquinone (Disperse Violet 1), 1-(2-hydroxyethyl)amino-2-nitro-4-[bis(2-hydroxyethyl)amino]benzene (HC Blue No. 2), 4-[ethyl-(2-hydroxyethyl)amino]-1-[(2-hydroxyethyl)amino]-2-nitrobenzene hydrochloride (HC Blue No. 12), 1-amino-4-[bis(2-hydroxyethyl)amino]-2-nitrobenzene hydrochloride (HC Red No. 13), 4-amino-1-[(2-hydroxyethyl)amino]-2-nitrobenzene (HC Red No. 3), 4-amino-3-nitrophenol, 4-[(2-hydroxyethyl)amino]-3-nitrophenol, 1-amino-5-chloro-4-[(2,3-dihydroxypropyl)amino]-2-nitrobenzene (HC Red No. 10), 5-chloro-1,4-[bis(2,3-dihydroxypropyl)amino]-2-nitrobenzene (HC Red No. 11), 2-chloro-6-ethylamino-4-nitrophenol, 2-amino-6-chloro-4-nitrophenol, 4-[(2-hydroxyethyl)amino]-3-nitro-1-trifluoromethylbenzene (HC Yellow No. 13), 8-amino-2-bromo-5-hydroxy-4-imino-6-{[3-(trimethylammonio)phenyl]amino}-1(4H)-naphthone chloride (C.I. 56059; Basic Blue No. 99), 1-[(4-aminophenyl)azo]-7-(trimethylammonio)-2-naphthol chloride (C.I. 12250; Basic Brown No. 16), 1-[(4-amino-2-nitrophenyl)azo]-7-(trimethylammonio)-2-naphthol chloride (Basic Brown No. 17), 2-hydroxy-1-[(2-methoxyphenyl)azo]-7-(trimethylammonio)naphthalene chloride (C.I. 12245; Basic Red No. 76), 3-methyl-1-phenyl-4-{[3-(trimethylammonio)phenyl]azo}pyrazol-5-one chloride (C.I. 12719; Basic Yellow No. 57), and 2,6-diamino-3-[(pyridin-3-yl)azo]pyridine and its salts. In at least one embodiment, the total amount of the direct dye in the formulation totals 0.01 to 15% by weight, preferably 0.1 to 10% by weight, and most preferably 0.5 to 8% by weight.

[0161] In at least one embodiment, the formulation comprises a conditioning agent. In at least one embodiment, the conditioning agent is a water-insoluble, water-dispersible, non-volatile liquid that forms emulsified liquid particles. In at least one embodiment, the conditioning agent is a silicone (such as a silicone oil, a cationic silicone, a silicone gum, a high refractive index silicone, or a silicone resin), an organic conditioning oil (such as a hydrocarbon oil, a polyolefin, or a fatty ester), a cationic conditioning surfactant, a high melting point fatty compound, or a combination thereof.

[0162] In at least one embodiment, the conditioning agent is a silicone, and the formulation comprises from 0.01% to 10% or from 0.1% to 5% of the silicone conditioning agent, based on the total weight of the formulation. Suitable silicone conditioning agents and optional suspending agents for silicones are described in US-5,104,646. In at least one embodiment, the formulation comprises a silicone gum selected from polydimethylsiloxane, (polydimethylsiloxane)(methylvinylsiloxane) copolymer, poly(dimethylsiloxane)(diphenylsiloxane)(methylvinylsiloxane) copolymer, and mixtures thereof.

[0163] In at least one embodiment, the formulation comprises a terminal amino silicone. As used herein, "terminal amino silicone" means a silicone that contains one or more amino groups at one or both ends of the silicone backbone. In at least one embodiment, the formulation is substantially free of any silicone compounds containing pendant amino groups. In an embodiment, the formulation is substantially free of any silicone compounds that are non-terminal amino silicones. In at least one embodiment, the amino group at at least one end of the silicone backbone of the terminal amino silicone is selected from primary amines, secondary amines, and tertiary amines. In at least one embodiment, the formulation comprises a terminal amino silicone conforming to formula (S):

[0164] (R F ) a G 3-a -Si-(-OSiG2) n -O-SiG 3-a (R F ) a (S)

[0165] where

[0166] G is hydrogen, phenyl, hydroxy, or a C1-C8 alkyl group, preferably methyl;

[0167] a is an integer having a value of from 1 to 3, preferably 1;

[0168] b is 0, 1, or 2, preferably 1;

[0169] n is a number from 0 to 1999;

[0170] RF is a monovalent group conforming to the general formula C q H 2q L, where q is an integer having a value of 2 to 8 and L is selected from the following groups: -N(R T )CH2-CH2-N(R T )2; -N(R T )2; -N(R T )3A - ; -N(R T )CH2-CH2-NR T H2A - ; where R T is hydrogen, phenyl, benzyl or a saturated hydrocarbon group, preferably an alkyl group having 1 to 20 carbon atoms; A - is a halide ion.

[0171] In at least one embodiment, the terminal amino organosilicon corresponding to formula (S) has a = 1, q = 3, G = methyl, n is from 1000 to 2500, alternatively from 1500 to 1700, and L is -N(CH3)2. Suitable terminal amino organosilicons corresponding to formula (S) have a = 0, G = methyl, n is from 100 to 1500, or from 200 to 800, and L is selected from the following groups: -N(R T )CH2-CH2-N(R T )2; -N(R T )2; -N(R T )3A - ; -N(R T )CH2-CH2-NR T H2A - ; where R T is hydrogen, phenyl, benzyl or a saturated hydrocarbon group, preferably an alkyl group having 1 to 20 carbon atoms; A - is a halide ion, alternatively L is -NH2. In at least one embodiment, the terminal amino organosilicon is selected from bis-aminomethyl polydimethylsiloxane, bis-aminoethyl polydimethylsiloxane, bis-aminopropyl polydimethylsiloxane, bis-aminobutyl polydimethylsiloxane and mixtures thereof. In an embodiment, the terminal amino organosilicon has a viscosity measured at 25 °C of from 1000 to 30000 cPs, or from 5000 to 20000 cPs. In at least one embodiment, the formulation comprises from 0.1% to 20%, or from 0.5% to 10%, or from 1% to 6% by total weight of the formulation of the terminal amino organosilicon.

[0172] In at least one embodiment, the formulation comprises a high melting point fatty compound. The high melting point fatty compound has a melting point of 25 °C or higher. In at least one embodiment, the high melting point fatty compound is selected from fatty alcohols, fatty acids, fatty alcohol derivatives, fatty acid derivatives, and mixtures thereof. Non-limiting examples of high melting point compounds are found in the International Cosmetic Ingredient Dictionary, 5th Edition, 1993 and the CTFA Cosmetic Ingredient Handbook, 2nd Edition, 1992. The formulation may comprise from 0.1% to 40%, or from 1% to 30%, or from 1.5% to 16%, or from 1.5% to 8% by weight of the total weight of the formulation of the high melting point fatty compound. This is advantageous in view of providing improved conditioning benefits such as a smooth feel during application to wet hair and a softening and moisturizing feel on dry hair. In at least one embodiment, the fatty alcohol is selected from cetyl alcohol, stearyl alcohol, behenyl alcohol, and mixtures thereof. In at least one embodiment, the formulation comprises a linear fatty alcohol, wherein the linear fatty alcohol is incorporated in a lamellar gel matrix. The lamellar gel matrix is suitable for providing various conditioning benefits such as a smooth feel during application to wet hair and a softening and moisturizing feel on dry hair. The linear fatty alcohol may contain from 8 to 24 carbon atoms. In an embodiment, the linear fatty alcohol is selected from cetyl alcohol, stearyl alcohol, and mixtures thereof. In an embodiment, the weight ratio of the total linear fatty alcohol to the terminal amino silicone is from 0.5:1 to 10:1, or from 1:1 to 5:1, or from 2.4:1 to 2.7:1.

[0173] In at least one embodiment, the lamellar gel matrix comprises a cationic conditioning surfactant and a high melting point fatty compound. In view of providing a lamellar gel matrix, the cationic conditioning surfactant and the high melting point fatty compound are present in such amounts that the weight ratio of the cationic surfactant to the high melting point fatty compound is in the range of from 1:1 to 1:10, or from 1:1 to 1:6.

[0174] In at least one embodiment, the formulation comprises a cationic conditioning surfactant. In at least one embodiment, the formulation comprises from 0.05% to 3.0%, or from 0.075% to 2.0%, or from 0.1% to 1.0% by weight of the total weight of the formulation of the cationic conditioning surfactant. In at least one embodiment, the cationic conditioning surfactant is incorporated in the lamellar gel matrix. In other words, the formulation comprises a lamellar gel matrix and the lamellar gel matrix comprises a cationic conditioning surfactant. In an embodiment, the cationic conditioning surfactant is according to formula (C):

[0175]

[0176] wherein R71 , R 72 , R 73 and R 74 At least one of and R is selected from aliphatic groups having 8 to 30 carbon atoms, aromatic groups, alkoxy groups, polyoxyalkylene groups, alkylacylamino groups, hydroxyalkyl groups, aryl groups or alkylaryl groups having at most 22 carbon atoms; the remaining R 71 , R 72 , R 73 and R 74 are independently selected from aliphatic groups having 1 to 22 carbon atoms, and aromatic groups, alkoxy groups, polyoxyalkylene groups, alkylacylamino groups, hydroxyalkyl groups, aryl groups or alkylaryl groups having at most 22 carbon atoms;

[0177] X is selected from halogen, acetate, citrate, lactate, glycolate, phosphate, nitrate, sulfonate, sulfate, alkyl sulfate, alkyl sulfonate and combinations thereof.

[0178] In at least one embodiment, the cationic conditioning surfactant is selected from behenyl trimethyl ammonium chloride, behenyl trimethyl methyl sulfate or behenyl trimethyl ethyl sulfate, and stearyl trimethyl ammonium chloride, stearyl trimethyl methyl sulfate or stearyl trimethyl ethyl sulfate. It is believed that the longer alkyl groups provide improved smoothness and soft feel on wet and dry hair compared to cationic surfactants having shorter alkyl groups. It is also believed that such cationic surfactants may provide reduced irritation compared to those having shorter alkyl groups.

[0179] In at least one embodiment, the cationic surfactant is a di-long alkyl quaternary ammonium salt selected from: dialkyl (C14-C18) dimethyl ammonium chloride, ditallow alkyl dimethyl ammonium chloride, dihydrogenated tallow alkyl dimethyl ammonium chloride, distearyl dimethyl ammonium chloride, dicetyl dimethyl ammonium chloride and mixtures thereof.

[0180] In at least one embodiment, the cationic surfactant is a tertiary acylaminoamine having an alkyl group with 12 to 22 carbon atoms. The tertiary acylaminoamine may be selected from stearoyl aminopropyl dimethylamine, stearoyl aminopropyl diethylamine, stearoyl aminoethyl diethylamine, stearoyl aminoethyl dimethylamine, palmitoyl aminopropyl dimethylamine, palmitoyl aminopropyl diethylamine, palmitoyl aminoethyl diethylamine, palmitoyl aminoethyl dimethylamine, behenoyl aminopropyl dimethylamine, behenoyl aminopropyl diethylamine, behenoyl aminoethyl diethylamine, behenoyl aminoethyl dimethylamine, arachidoyl aminopropyl dimethylamine, arachidoyl aminopropyl diethylamine, arachidoyl aminoethyl diethylamine, arachidoyl aminoethyl dimethylamine, diethylaminoethyl stearamide, and mixtures thereof. The tertiary acylaminoamine may be used in combination with an acid. The acid is typically used as a salt-forming anion. In an embodiment, the acid is selected from lactic acid, malic acid, hydrochloric acid, L-glutamic acid, acetic acid, citric acid, and mixtures thereof.

[0181] In at least one embodiment, the cationic surfactant is selected from cetyltrimethylammonium chloride (CTAC), stearyltrimethylammonium chloride (STAC), behenyltrimethylammonium methyl sulfate, stearoyl aminopropyl dimethylamine (SAPDMA), distearyldimethylammonium chloride, and mixtures thereof.

[0182] In at least one embodiment, the formulation comprises a surfactant system. In at least one embodiment, the surfactant system comprises a surfactant selected from anionic surfactants, cationic surfactants, nonionic surfactants, zwitterionic surfactants, and / or amphoteric surfactants. In at least one embodiment, the formulation comprises from 0.01 wt% to 70 wt%, from 0.1 wt% to 40 wt%, from 1 wt% to 30%, from 2 wt% to 20% of the total amount of surfactant.

[0183] In at least one embodiment, the formulation comprises an anionic surfactant. In at least one embodiment, the anionic surfactant is selected from (C 10 -C 20) - Alkyl and alkylene carboxylates (esters), alkyl ether carboxylates (esters), fatty alcohol sulfates (esters), fatty alcohol ether sulfates (esters), alkylamide sulfates (esters) and sulfonates (esters), fatty acid alkylamide polyethylene glycol ether sulfates (esters), alkyl sulfonates (esters) and hydroxyalkyl sulfonates (esters), olefin sulfonates (esters), acyl esters of hydroxyethyl sulfonates (esters), α-sulfo fatty acid esters, alkylbenzene sulfonates (esters), alkylphenol diol ether sulfonates (esters), sulfosuccinates (esters), sulfosuccinic acid mono- and diesters, fatty alcohol ether phosphates, protein / fatty acid condensation products, alkyl monoglyceride sulfates (esters) and sulfonates (esters), alkyl glyceride ether sulfonates (esters), fatty acid methyl taurates (esters), fatty acid sarcosinates (esters), sulforicinates (esters), acyl glutamates (esters) and mixtures thereof. The anionic surfactant (and mixtures thereof) can be used in the form of their water-soluble or water-dispersible salts (esters), examples being sodium salts, potassium salts, magnesium salts, ammonium salts, monoethanolammonium, diethanolammonium and triethanolammonium and similar alkylammonium salts. In at least one embodiment, the anionic surfactant is a salt of an anionic surfactant containing 12 to 14 carbon atoms. In at least one embodiment, the anionic surfactant is selected from sodium lauryl sulfate, sodium laureth sulfate, sodium tridecyl sulfate, sodium trideceth sulfate, sodium myristyl sulfate, sodium myreth sulfate and mixtures thereof.

[0184] In at least one embodiment, the formulation comprises an acylglycinate (acylglycine) surfactant. In at least one embodiment, the acylglycinate (acylglycine) surfactant conforms to formula (Y):

[0185]

[0186] wherein

[0187] R 1a is a linear or branched saturated alkyl group having 6 to 30, preferably 8 to 22, particularly preferably 8 to 18 carbon atoms, or is a linear or branched mono- or polyunsaturated alkenyl group having 6 to 30, preferably 8 to 22, particularly preferably 12 to 18 carbon atoms, and

[0188] Q a + is a cation.

[0189] In at least one embodiment, Q a + is selected from Li + 、Na + 、K + 、Mg ++ 、Ca ++ 、Al+++ 、 NH4 + 、 monoalkylammonium ions, dialkylammonium ions, trialkylammonium ions, and tetraalkylammonium ions, or combinations thereof. In at least one embodiment, the acylglycinate (acylglycine) surfactant is selected from sodium cocoyl glycinate and potassium cocoyl glycinate. In at least one embodiment, the acylglycinate surfactant is selected from those conforming to formula (Y), where R is a C 12 alkyl or a C 14 alkyl. In at least one embodiment, the acylglycinate (acylglycine) surfactant is selected from those conforming to formula (Y), where R is a C 16 alkyl or a C 18 alkyl.

[0190] In at least one embodiment, the formulation comprises a glutamate (glutamic acid) surfactant corresponding to formula (Z) or a salt thereof:

[0191]

[0192] where

[0193] R’ is HOOC-CH2-CH2- or M +- OOC-CH2-CH2- where M + is a cation;

[0194] R is a linear or branched saturated alkyl group having 6 to 30, preferably 8 to 22, more preferably 8 to 18 carbon atoms, or is a linear or branched mono- or poly-unsaturated alkenyl group having 6 to 30, preferably 8 to 22, more preferably 12 to 18 carbon atoms. In at least one embodiment, M + is a metal cation. In at least one embodiment, M + is selected from Li + 、 Na + 、 K + 、 Mg ++ 、 Ca ++ 、 Al +++ 、 NH4 + 、 monoalkylammonium ions, dialkylammonium ions, trialkylammonium ions, and tetraalkylammonium ions, or combinations thereof.

[0195] In at least one embodiment, the glutamate (glutamic acid) surfactant is selected from sodium cocoyl glutamate and potassium cocoyl glutamate. In at least one embodiment, the glutamate (glutamic acid) surfactant is selected from those conforming to formula (Z), where R is a C 12 alkyl or a C 14 alkyl. In at least one embodiment, the glutamate (glutamic acid) surfactant is selected from those conforming to formula (Z), where R is a C 16alkyl or C 18 alkyl group.

[0196] In at least one embodiment, the formulation comprises from 0.01% to 30% by weight, preferably from 1% to 25% by weight, more preferably from 5% to 20% by weight, particularly preferably from 12% to 18% by weight of an anionic surfactant.

[0197] In at least one embodiment, the formulation comprises a nonionic surfactant. In at least one embodiment, the nonionic surfactant has an HLB (hydrophilic-lipophilic balance value) greater than 12. Optionally, the nonionic surfactant is selected from ethoxylated or ethoxylated / propoxylated fatty alcohols having a fatty chain with 12 to 22 carbon atoms, ethoxylated sterols such as stearyl alcohol or lauryl alcohol (EO-7), PEG-16 soy sterol or PEG-10 soy sterol, polyoxyethylene polyoxypropylene block polymers (poloxamers), and mixtures thereof.

[0198] In at least one embodiment, the nonionic surfactant is selected from ethoxylated fatty alcohols, fatty acids, fatty acid glycerides or alkylphenols, in particular addition products of 2 to 30 moles of ethylene oxide and / or 1 to 5 moles of propylene oxide to C8- to C 22 - fatty alcohols, to C 12 - to C 22 - fatty acids or to alkylphenols having 8 to 15 carbon atoms in the alkyl group, addition products of 1 to 30 moles of ethylene oxide to glycerol, addition products of 5 to 60 moles of ethylene oxide to castor oil or to hydrogenated castor oil of C 12 - to C 22 - fatty acid monoesters and diesters, fatty acid sugar esters, in particular esters of sucrose and one or two C8- to C 22 - fatty acids, INCI: sucrose cocoate, sucrose dilaurate, sucrose distearate, sucrose laurate, sucrose myristate, sucrose oleate, sucrose palmitate, sucrose ricinoleate, sucrose stearate, sorbitan esters with one, two or three C8- to C 22 - fatty acids and polyglycerol fatty acid esters with an ethoxylation degree of 4 to 20, in particular polyglycerol fatty acid esters of one, two or more C8- to C 22 - fatty acids and polyglycerol having preferably 2 to 20 glycerol units, alkyl glucosides, alkyl oligoglucosides and alkyl polyglucosides having a C8 to C 22 - alkyl group, such as decyl glucoside or lauryl glucoside, and mixtures thereof.

[0199] In at least one embodiment, the nonionic surfactant is selected from fatty alcohol ethoxylates (alkyl polyethylene glycols), alkylphenol polyethylene glycols, alkylthiol polyethylene glycols, fatty amine ethoxylates (alkylamino polyethylene glycols), fatty acid ethoxylates (acyl polyethylene glycols), polypropylene glycol ethoxylates (e.g., ), fatty acid alkylolamides (fatty acid amide polyethylene glycols), N-alkyl-, N-alkoxypolyhydroxy-fatty acid amides, sucrose esters, sorbitan esters, polyglycol ethers, and mixtures thereof.

[0200] In at least one embodiment, the formulation comprises a fatty N-methyl-N-glucamide surfactant, wherein the fatty N-methyl-N-glucamide surfactant conforms to formula (X):

[0201]

[0202] wherein R is selected from saturated or unsaturated hydrocarbon chains having 5 to 23 carbon atoms. Preferably, R in formula (X) is selected from saturated or unsaturated hydrocarbon chains having 7 to 17 carbon atoms. More preferably, the R—C═O residue in formula (X) is derived from caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, coconut oil fatty acids, or mixtures thereof. Even more preferably, the R—C═O residue in formula (X) is derived from 9-decenoic acid, 9-dodecenoic acid, or mixtures thereof.

[0203] Particularly preferred N-methyl-N-acylglucosamines of formula (X) are octanoyl / hexanoyl methyl glucamide, lauroyl / myristoyl methyl glucamide, cocoyl methyl glucamide, oleoyl methyl glucamide, or mixtures thereof. Such N-methyl-N-acylglucosamines are commercially available from Clariant ( Clear, Plus, Flex, Care, Sense).

[0204] Also particularly preferred N-methyl-N-acylglucosamines of formula (X) are N-9-decenoyl-N-methyl glucamine, N-9-dodecenoyl-N-methyl glucamine, or mixtures thereof.

[0205] In at least one embodiment, the formulation comprises 1 wt% to 20 wt%, preferably 2 wt% to 10 wt%, more preferably 3 wt% to 7 wt% of the nonionic surfactant.

[0206] In at least one embodiment, the amphoteric surfactant is selected from N-(C 12 -C 18)-alkyl-β-aminopropionate and N-(C 12 -C 18 )-alkyl-β-imino dipropionate as alkali metal salts and mono-, di- and tri-alkyl ammonium salts; N-acylaminoalkyl-N,N-dimethylacetobetaines, preferably N-(C8-C 18 )-acylaminopropyl-N,N-dimethylacetobetaine, (C 12 -C 18 )-alkyl-dimethyl-sulfopropyl betaines, imidazoline-based zwitterionic surfactants (e.g., ), preferably the sodium salt of 1-(β-carboxymethoxyethyl)-1-(carboxymethyl)-2-laurylimidazoline; amine oxides, e.g., (C 12 -C 18 )-alkyl dimethyl amine oxides, fatty acid aminoalkyl dimethyl amine oxides and mixtures thereof.

[0207] In at least one embodiment, the formulation comprises a betaine surfactant. Optionally, the betaine surfactant is selected from C8- to C 18 -alkyl betaines. In at least one embodiment, the betaine surfactant is selected from coco dimethyl carboxymethyl betaine, lauryl dimethyl carboxymethyl betaine, lauryl dimethyl α-carboxyethyl betaine, cetyl dimethyl carboxymethyl betaine, oleyl dimethyl γ-carboxypropyl betaine and lauryl bis(2-hydroxypropyl) α-carboxyethyl betaine and combinations thereof. Optionally, the betaine surfactant is selected from C8- to C 18 -sulfobetaines. In at least one embodiment, the betaine surfactant is selected from coco dimethyl sulfopropyl betaine, stearyl dimethyl sulfopropyl betaine, lauryl dimethyl sulfethyl betaine, lauryl bis(2-hydroxyethyl) sulfopropyl betaine and combinations thereof. Optionally, the betaine surfactant is selected from carboxy derivatives of imidazole, C8- to C 18 -alkyl dimethyl ammonium acetate, C8- to C 18 -alkyl dimethyl carbonylmethyl ammonium salts and C8- to C 18 -fatty acid alkylamido betaines and mixtures thereof. Optionally, the C8- to C 18 -fatty acid alkylamido betaines are selected from coco fatty acid amido propyl betaine, N-coco fatty acid amido ethyl-N-[2-(carboxymethoxy)ethyl] glycerol (CTFA name: cocoamphocarboxyglycinate) and mixtures thereof.

[0208] In at least one embodiment, the formulation comprises 0.5 wt% to 20 wt%, preferably 1 wt% to 10 wt% of a zwitterionic surfactant.

[0209] In at least one embodiment, the formulation comprises a surfactant system. In at least one embodiment, the surfactant system comprises at least one surfactant selected from lauryl sulfate, laureth sulfate, cocamidopropyl betaine, sodium cocoyl glutamate, lauroamphoacetate, and mixtures thereof. In at least one embodiment, the surfactant system comprises sodium laureth sulfate, sodium lauryl sulfate, and optionally cocamidopropyl betaine. In at least one embodiment, the surfactant system comprises sodium laureth sulfate, potassium cocoyl glutamate, and cocamidopropyl betaine.

[0210] In at least one embodiment, the formulation further comprises a hair styling polymer. In at least one embodiment, the hair styling polymer is selected from amphoteric hair styling polymers, zwitterionic hair styling polymers, anionic hair styling polymers, nonionic hair styling polymers, cationic hair styling polymers, and mixtures thereof. In at least one embodiment, the formulation comprises from 0.01% to 20%, or from 0.01% to 16%, or from 0.01% to 10%, or from 1% to 8%, or from 2% to 6% of the hair styling polymer. Suitable hair styling polymers are disclosed, for example, in WO2018 / 002100 (pages 55 - 63).

[0211] In at least one embodiment, the formulation has a viscosity of from 0 cPs to 20000 cPs. In at least one embodiment, the formulation has a viscosity of from 0.1 cPs to 10000 cPs, or from 1 cPs to 5000 cPs, or from 5 cPs to 3500 cPs.

[0212] The viscosity measurement conditions are defined in the definition section above. Viscosity is important for anti - drip reasons. Dripping is inconvenient for the user. Additionally, a more viscous formulation can be useful for measuring the dosage. In at least one embodiment, the formulation has a viscosity of from 0 cPs to 1000 cPs. This viscosity range is advantageous when the formulation is in the form of a facial cleanser, given the need for the ability to distribute on the skin and rinse off.

[0213] In at least one embodiment, the formulation further comprises a viscosity - regulating substance. The viscosity - regulating substance is preferably a thickening polymer.

[0214] In at least one embodiment, the thickening polymer is based on acrylamidomethylpropanesulfonic acid Polymers. These polymers show good thickening properties even at pH values ​​of 7 or lower. Particularly preferably, the thickening polymer is selected from homopolymers or copolymers of acrylamidomethylpropanesulfonic acid and its salts. Of the polymers just mentioned, preference is given to polymers having at least 20 mol % of units based on acrylamidomethylpropanesulfonic acid and / or its salts, and particular preference is given to polymers having at least 50 mol % of units based on acrylamidomethylpropanesulfonic acid and / or its salts, the molar numbers in each case being related to the overall polymer. In the case of copolymers, in addition to structural units based on acrylamidomethylpropanesulfonic acid and / or its salts, preference is given to the presence in the copolymer of one or more structural units based on the following comonomers: acrylic acid, methacrylic acid, acrylamide, dimethylacrylamide, vinylpyrrolidone (VP), hydroxyethyl acrylate, hydroxyethyl methacrylate, ethoxylated alcohols RO-(CH2CH2O) m H, wherein R is an alkyl group having 12 to 30 carbon atoms and m is a number from 3 to 30, and CH2=CH-COO-(CH2CH2-COO) n X, wherein n is a number from 0 to 10 and X is a counterion and is preferably H + 、Na + and / or NH4 + The polymers selected from homopolymers or copolymers of acrylamidomethylpropanesulfonic acid and its salts may be crosslinked or non-crosslinked. In the case of crosslinking, they contain structural units based on monomers having 2 or more olefinic double bonds. In the case of crosslinking, preferably 0.1 to 10 mol % of such structural units, based on the overall polymer, are present in the homopolymer or copolymer. If one or more structural units based on acrylamidomethylpropanesulfonic acid and / or its salts in the homopolymer or copolymer of acrylamidomethylpropanesulfonic acid and / or its salts have one or more olefinic double bonds other than H + These other counterions are preferably selected from Na + and NH4 + Suitable polymers are mentioned in publications including EP-0816403, EP-1069142, EP-1116733 and DE-10 2009 014877 (Clariant), EP-1347736 (L'Oréal) or EP-1496081 (Seppic). Examples include AVC (ammonium acryloyldimethyltaurate / VP copolymer), AVS (sodium acryloyldimethyl taurate / VP cross-linked polymer), TAC (ammonium acryloyldimethyltaurate carboxyethyl acrylate crosspolymer), AMPS (ammonium polyacryloyl dimethyl taurate), HMB (ammonium acryloyldimethyltaurate / beheneth-25 methacrylate crosspolymer), BLV (ammonium acryloyldimethyltaurate / beheneth-25 methacrylate crosspolymer), HMS (ammonium acryloyldimethyltaurate / steareth-25 methacrylate crosspolymer), SNC (ammonium acryloyldimethyltaurate / steareth-8 methacrylate copolymer), LNC (ammonium acryloyldimethyltaurate / laureth-7 methacrylate copolymer) or EMT 10 (hydroxyethyl acrylate / sodium acryloyldimethyltaurate copolymer), 305.

[0215] In at least one embodiment, the thickening polymer is selected from copolymers of at least one first monomer type and at least one second monomer type, the first monomer type being selected from acrylic acid and methacrylic acid, and the second monomer type being selected from esters of acrylic acid and ethoxylated fatty alcohols; crosslinked polyacrylic acid; crosslinked copolymers of at least one first monomer type and at least one second monomer type, the first monomer type being selected from acrylic acid and methacrylic acid, and the second monomer type being selected from esters of acrylic acid and C 10 - to C 30 - alcohols; copolymers of at least one first monomer type and at least one second monomer type, the first monomer type being selected from acrylic acid and methacrylic acid, and the second monomer type being selected from esters of itaconic acid and ethoxylated fatty alcohols; copolymers of at least one first monomer type, at least one second monomer type and a third monomer type, the first monomer type being selected from acrylic acid and methacrylic acid, and the second monomer type being selected from esters of itaconic acid and ethoxylated C 10 - to C 30- esters of alcohols, the third monomer being selected from C1- to C4-aminoalkyl acrylates; copolymers of two or more monomers selected from acrylic acid, methacrylic acid, acrylates and methacrylates; copolymers of vinylpyrrolidone and acryloyldimethyltaurine ammonium; copolymers of acryloyldimethyltaurine ammonium and monomers selected from esters of methacrylic acid and ethoxylated fatty alcohols; hydroxyethyl cellulose; hydroxypropyl cellulose, hydroxypropyl guar gum; glyceryl polyacrylate; glyceryl polymethacrylate; copolymers of at least one C2-, C3- or C4-olefin and styrene; polyurethanes; hydroxypropyl starch phosphate; polyacrylamide; copolymers of methyl vinyl ether and maleic anhydride crosslinked with decadiene; carob seed flour; guar gum; xanthan gum; dehydroxanthan gum; carrageenan; karaya gum, hydrolyzed corn starch; copolymers of polyoxyethylene, fatty alcohols and saturated diphenylmethylene diisocyanate (e.g. PEG-150 / stearyl alcohol / SMDI copolymer) and mixtures thereof.

[0216] In at least one embodiment, the formulation has a pH value of from 2.0 to 12.0, preferably from 3.0 to 9.0, more preferably from 4.5 to 7.5. By varying the pH value, the formulation can be made suitable for different applications.

[0217] In at least one embodiment, the formulation contains a basifying agent or pH regulator. In at least one embodiment, ammonia or caustic soda is suitable, but water-soluble, physiologically acceptable salts of organic or inorganic bases can also be considered. Optionally, the pH regulator is selected from ammonium bicarbonate, ammonia, monoethanolamine, ammonium carbonate. In at least one embodiment, the basifying agent or pH regulator is selected from 2-amino-2-methyl-1-propanol, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-ethyl-1,3-propanediol, tris(hydroxymethyl)-aminomethane, 2-amino-1-butanol, tris(2-hydroxypropyl)-amine, 2,2-imino-bisethanol, lysine, iminourea (guanidine carbonate), tetrahydro-1,4-oxazine, 2-amino-5-guanidino-valeric acid, 2-aminoethanesulfonic acid, diethanolamine, triethanolamine, N-methylethanolamine, isopropanolamine, diisopropanolamine, triisopropanolamine, glucosamine, sodium hydroxide, potassium hydroxide, lithium hydroxide, magnesium oxide and mixtures thereof.

[0218] To establish an acidic pH value, an acid can be included. In at least one embodiment, the formulation contains an acid selected from hydrochloric acid, phosphoric acid, acetic acid, formic acid, sulfuric acid, citric acid and mixtures thereof. Citric acid is most preferred because of its high consumer acceptance. In at least one embodiment, a buffer such as a phosphate buffer, a TRIS buffer or a citrate buffer is used to adjust the acidic pH. The buffer can be used alone or in combination with an acid.

[0219] In at least one embodiment, the formulation is in liquid form. In an alternative embodiment, the formulation is in solid form. Optionally, the formulation is in the form of a powder or granules. This is advantageous as there is no need to transport the usually heavy liquids over long distances, which has economic and environmental benefits. The solid form can be achieved by spray drying the formulation or by using a rotary evaporator. The formulation can be converted into liquid form, for example, by adding water after transportation.

[0220] In at least one embodiment, the formulation is a household cleaning formulation.

[0221] In at least one embodiment, the formulation is a dishwashing formulation for hand washing. In at least one embodiment, the dishwashing formulation for hand washing contains an anionic surfactant. In at least one embodiment, the dishwashing formulation for hand washing contains 5 wt% to 25 wt% of an anionic surfactant. In at least one embodiment, the dishwashing formulation for hand washing contains a surfactant system, the surfactant system containing at least one anionic surfactant and an additional surfactant selected from nonionic surfactants, amphoteric surfactants, zwitterionic surfactants, and combinations thereof.

[0222] Preferably, the dishwashing formulation for hand washing contains cocamidopropyl betaine or amine oxide. Preferably, the amine oxide is lauryl amine oxide, coconut acyl amine oxide, or a combination thereof. In at least one embodiment, the pH value of the dishwashing formulation for hand washing is from pH 5.0 to pH 10, preferably from pH 5.5 to pH 9.0. In the case where the dishwashing formulation for hand washing contains amine oxide, the dishwashing formulation for hand washing preferably has a pH of from pH 7.5 to pH 9.5, most preferably from pH 8.0 to pH 9.0.

[0223] In at least one embodiment, the formulation is a hard surface cleaner. In at least one embodiment, the hard surface cleaner contains an anionic surfactant. In at least one embodiment, the hard surface cleaner contains 1 wt% to 10 wt% of an anionic surfactant. In at least one embodiment, the hard surface cleaner contains a nonionic surfactant. In at least one embodiment, the hard surface cleaner contains 1 wt% to 10 wt% of a nonionic surfactant. In at least one embodiment, the hard surface cleaner contains a surfactant system, the surfactant system containing at least one anionic surfactant and an additional surfactant selected from nonionic surfactants, amphoteric surfactants, zwitterionic surfactants, and combinations thereof. Preferably, the hard surface cleaner contains linear alkylbenzene sulfonate and fatty alcohol ethoxylate. In at least one embodiment, the pH value of the hard surface cleaner is from pH 5.0 to pH 11, preferably from pH 6.0 to pH 9.0.

[0224] In at least one embodiment, the formulation is a liquid laundry detergent formulation comprising one or more surfactants. Preferably, the one or more surfactants of the liquid laundry detergent formulation are selected from anionic, nonionic, cationic, and zwitterionic surfactants, and more preferably from anionic, nonionic, and zwitterionic surfactants.

[0225] Anionic surfactant

[0226] In at least one embodiment, the formulation comprises an anionic surfactant. Anionic surfactants are particularly useful in cleaning formulations such as household cleaning formulations. Preferred anionic surfactants are alkyl sulfonates(esters) and alkyl ether sulfates(esters). Preferred alkyl sulfonates are alkyl benzene sulfonates, especially linear alkyl benzene sulfonates (LAS) having a C8-C 15 , preferably C 12 -C 14 alkyl chain length. Feasible counterions for concentrated alkaline liquids are ammonium ions, such as those produced by the neutralization of alkyl benzene sulfonic acid with one or more ethanolamines such as monoethanolamine (MEA) and triethanolamine (TEA), or alternatively, alkali metals, such as those resulting from the neutralization of alkyl benzene sulfonic acid with alkali metal hydroxides. Preferred alkyl ether sulfates (AES) are alkyl polyethoxylated sulfate anionic surfactants.

[0227] Nonionic surfactant

[0228] In at least one embodiment, the formulation comprises a nonionic surfactant. Nonionic surfactants include primary alcohol ethoxylates and secondary alcohol ethoxylates, especially C8-C 20 aliphatic alcohols ethoxylated with 1 to 20 moles of ethylene oxide per mole of alcohol, and more especially C 10 -C 15 primary and secondary aliphatic alcohols ethoxylated with 1 to 10 moles of ethylene oxide per mole of alcohol. Non-ethoxylated nonionic surfactants include alkyl polyglycosides, glycerol monoethers, and polyhydroxyamides (glucamides). Mixtures of nonionic surfactants can also be used.

[0229] When included therein, household cleaning formulations, especially liquid laundry detergent formulations, preferably contain from 0.2% to 40% by weight, more preferably from 1% to 20% by weight, of nonionic surfactants such as alcohol ethoxylates, nonylphenol ethoxylates, alkyl polyglycosides, alkyl dimethylamine oxides, ethoxylated fatty acid monoethanolamides, fatty acid monoethanolamides, polyhydroxyalkyl fatty acid amides, N-acyl N-alkyl derivatives of glucosamine (glucamides), or combinations thereof. The nonionic surfactants that can be used include primary alcohol ethoxylates and secondary alcohol ethoxylates, especially C8-C 20 aliphatic alcohols, and more especially C 10 -C 15 primary aliphatic alcohols and secondary aliphatic alcohols ethoxylated with from 1 to 10 moles of ethylene oxide per mole of alcohol.

[0230] zwitterionic surfactants

[0231] In at least one embodiment, the formulation contains a zwitterionic surfactant. The liquid laundry detergent formulation can contain a zwitterionic surfactant such as amine oxide or betaine, preferably in an amount of up to 10% by weight based on the total weight of the liquid laundry detergent formulation. The betaine can be alkyl dimethyl betaine or alkylamidobetaine, where the alkyl group has C 12 -C 18 chains.

[0232] Additional surfactants

[0233] In at least one embodiment, the liquid laundry detergent formulation contains surfactants selected from anionic surfactants, nonionic surfactants, and mixtures thereof; preferably the surfactants are selected from linear alkylbenzene sulfonates, alkyl ether sulfates, nonionic surfactants, amine oxides, and betaines; and more preferably from linear alkylbenzene sulfonates, alkyl ether sulfates, and nonionic surfactants. Surfactants other than the preferred LAS, AES, and nonionic surfactants can also be added. Although less preferred, alkyl sulfate surfactants, especially non-ethoxylated C 12 -C 15 primary and secondary alkyl sulfates can also be used. Soaps can also be used. The content of soap is preferably less than 10% by weight.

[0234] Preferably, one or more surfactants in the liquid laundry detergent formulation are present in an amount of at least 5% by weight, preferably 5% to 65% by weight, more preferably 6% to 60% by weight, and particularly preferably 7% to 55% by weight, in each case based on the total weight of the liquid laundry detergent formulation.

[0235] Additional optional ingredients

[0236] Household cleaning formulations may contain one or more optional ingredients. For example, they may contain conventional ingredients commonly used in detergent compositions, especially laundry detergent compositions. Examples of optional ingredients include, but are not limited to, synergists, bleaches, bleach-active compounds, bleach activators, bleach catalysts, optical bleaches, dye transfer inhibitors, color protectants, anti-redeposition agents, dispersants, fabric softeners and antistatic agents, optical brighteners, enzymes, enzyme stabilizers, foam regulators, defoamers, deodorants, preservatives, disinfectants, hydrotropes, fiber lubricants, anti-shrinkage agents, buffers, fragrances, processing aids, colorants, dyes, pigments, corrosion inhibitors, fillers, stabilizers or other conventional ingredients for washing or laundry detergent compositions.

[0237] Polymer

[0238] To enhance detergency, it can be advantageous to use polymers in household cleaning formulations, especially in liquid laundry detergent formulations. The polymer is preferably polyalkoxylated polyethyleneimine (EPEI). Polyethyleneimine is a material composed of ethyleneimine units -CH2CH2NH-, and when branched, the hydrogen on the nitrogen is replaced by a chain of additional ethyleneimine units. These polyethyleneimines can be prepared, for example, by polymerizing ethyleneimine in the presence of a catalyst such as carbon dioxide, sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid, acetic acid, etc. Specific methods for preparing these polyamine backbones are disclosed in US 2,182,306, US 3,033,746, US 2,208,095, US 2,806,839 and US 2,553,696.

[0239] Household cleaning formulations, especially liquid laundry detergent formulations, may contain other polymeric materials, such as: dye transfer inhibiting polymers, anti-redeposition polymers or cotton soil release polymers, especially those based on modified cellulose materials. In particular, when EPEI is absent, the formulation may additionally contain a polymer of polyethylene glycol and vinyl acetate, such as the lightly grafted copolymer described in WO 2007 / 138054. Such amphiphilic graft polymers based on water-soluble polyoxyalkylene as the graft base and side chains formed by the polymerization of vinyl ester components have the ability to reduce the surfactant content while maintaining a high level of removal of oily soil.

[0240] Hydrotrope

[0241] In at least one embodiment, the formulation comprises a hydrotrope. As used herein, a "hydrotrope" is neither water nor a conventional surfactant, but rather a solvent that aids in solubilizing surfactants and other components, particularly any polymers and / or chelating agents, in a liquid to render it isotropic. Hydrotropes are particularly useful in household cleaning formulations. Among suitable hydrotropes are the following: monopropylene glycol (MPG), glycerol, sodium cumenesulfonate, ethanol, other diols such as dipropylene glycol, diethers, and ureas. MPG and glycerol are preferred hydrotropes.

[0242] Enzyme

[0243] In at least one embodiment, the formulation, particularly a liquid laundry detergent formulation, comprises an enzyme. In at least one embodiment, the enzyme is selected from proteases, mannanases, pectin lyases, cutinases, esterases, lipases, amylases, cellulases, and combinations thereof. Sub-preferred additional enzymes may be selected from peroxidases and oxidases. The enzyme is preferably present together with a corresponding enzyme stabilizer. The total enzyme content in the formulation is preferably from 0 wt% to 5 wt%, more preferably from 0.5 wt% to 5 wt%, and still more preferably from 1 wt% to 4 wt% of the total weight of the formulation.

[0244] Chelating agent

[0245] The formulation, particularly a household cleaning formulation, preferably comprises a chelating agent. Preferred chelating agents include, for example, organic phosphonates, alkane hydroxy phosphonates, and carboxylates that can be obtained from Thermphos under the trademark DEQUEST. The preferred chelating agent content is less than 10 wt% and preferably less than 5 wt% of the total weight of the formulation. A particularly preferred chelating agent is, for example, HEDP (1-hydroxyethylidene-1,1-diphosphonic acid) sold as Dequest2010. Also suitable is 2066 (diethylenetriamine penta(methylene-phosphonic acid) or DTPMP heptasodium).

[0246] Buffer

[0247] In at least one embodiment, the formulation, particularly a liquid laundry detergent formulation, comprises a buffer. The buffer is preferably present to control the pH, in addition to any reagents optionally included for the generation of anionic surfactants from, for example, LAS or fatty acids. Feasible buffers are one or more ethanolamines, such as monoethanolamine (MEA) or triethanolamine (TEA). They are preferably used in the formulation in an amount of from 1.0 wt% to 15 wt%. Other suitable amino alcohol buffer materials may be selected from compounds having a molecular weight greater than 61 g / mol, which includes MEA. In addition to the materials already mentioned, suitable materials also include: monoisopropanolamine, diisopropanolamine, triisopropanolamine, monoaminohexanol, 2-[(2-methoxyethyl)methylamino]-ethanol, propanolamine, N-methylethanolamine, diethanolamine, monobutanolamine, isobutanolamine, monopentanolamine, 1-amino-3-(2-methoxyethoxy)-2-propanol, 2-methyl-4-(methylamino)-2-butanol, or mixtures thereof. A feasible alternative to the amino alcohol buffer is an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide.

[0248] The invention also relates to the use of the composition of the invention as an antimicrobial agent.

[0249] In at least one embodiment, the antimicrobial agent is an antibacterial (antibacterial agent) or an antifungal agent. In at least one embodiment, the antimicrobial agent is an antibacterial (antibacterial agent). In at least one embodiment, the antimicrobial agent is an antifungal agent.

[0250] The invention also relates to a method of reducing the effect of microorganisms in a formulation, wherein the method comprises adding the composition of the invention to the formulation.

[0251] In at least one embodiment, the microorganisms are bacteria or fungi. In at least one embodiment, the microorganisms are bacteria. In at least one embodiment, the microorganisms are fungi. The fungi can be, for example, yeasts or molds.

[0252] In this document, in all embodiments including all aspects of the present invention, the following definitions apply, unless otherwise specifically indicated. All percentages are by weight (w / w) of the total composition. All ratios are weight ratios. "Weight %" means weight percentage. References to 'parts' such as a mixture of 1 part of X and 3 parts of Y are weight ratios. "QS" or "QSP" means an amount sufficient for 100% or for 100 g. + / - represents the standard deviation. All ranges are inclusive of the endpoints and combinable. The number of significant figures neither represents a limitation on the amount indicated nor on the accuracy of the measurement. All measurements are understood to be made at 23 °C and under ambient conditions, where "ambient conditions" means at a pressure of 1 atmosphere (atm) and 50% relative humidity. "Relative humidity" refers to the ratio (expressed as a percentage) of the water content of air to the saturated water content at the same temperature and pressure. A hygrometer, especially a probe hygrometer from International, can be used to measure relative humidity. In this document, "min" means "minute (singular)" or "minutes (plural)". In this document, "mol" means mole. In this document, "g" after a number means "gram (singular)" or "gram (singular)". In this document, "comprising" means that other steps or other ingredients may additionally be present. "Comprising" encompasses the terms "consisting of" and "consisting essentially of". The compositions, formulations, methods, uses, and processes of the present invention may comprise the elements and limitations of the invention described herein and any additional or optional ingredients, components, steps, or limitations described herein, consist of them, and consist essentially of them. The embodiments and aspects described herein may comprise the elements, features, or components of other embodiments and / or aspects or may be combined with them, even though no explicit combination examples are shown, unless incompatibility is indicated. "In at least one embodiment" means that one or more embodiments of the present invention, optionally all embodiments or a large subset of the embodiments, have the features described subsequently. In cases where ranges of amounts are provided, they should be understood as the total amount of the ingredient(s) in the composition, or, in cases where more than one substance falls within the definition of the ingredient, as the total amount of all ingredients in the composition that meet that definition.

[0253] "Molecular weight" or "M.Wt" or "MW" and grammatical equivalents mean number-average molecular weight.

[0254] "Viscosity" is measured at 25 °C using a HAAKE rotational viscometer VT550 with a cooling / heating container and a sensor system according to DIN 53019 at a shear rate of 12.9 s -1 .

[0255] "Water-soluble" refers to any material that is sufficiently soluble in water at a concentration of 0.1% by weight (based on the material in water) at 25°C to form a clear solution to the naked eye. The term "water-insoluble" refers to any material that is not "water-soluble".

[0256] "Dry" or "substantially dry" means a compound or composition that contains less than 5%, less than 3%, less than 2%, less than 1%, or about 0% of any compound or composition in liquid form when measured at 25° C. under ambient conditions. Such compounds or compositions in liquid form include water, oils, organic solvents, and other wetting agents. "Anhydrous" means that the composition contains less than 5%, less than 3%, less than 2%, less than 1%, or about 0% water by total weight of the composition.

[0257] "Substantially free" or "substantially free of" means less than 1%, or less than 0.8%, or less than 0.5%, or less than 0.3%, or about 0% of the total weight of the composition or formulation.

[0258] "Derivatives" include, but are not limited to, amide, ether, ester, amino, carboxyl, acetyl, acid, salt and / or alcohol derivatives of a given compound. In at least one embodiment, "derivatives thereof" means amide, ether, ester, amino, carboxyl, acetyl, acid, salt and alcohol derivatives.

[0259] The examples which follow are intended to illustrate the subject-matter of the invention without restricting it thereto. Example

[0260] Material

[0261] Flex is commercially available from Clariant. Chemical name: Capryloyl / hexanoyl anhydrous methyl glucamide (and) water, active content: 70% by weight. Capryloyl / hexanoyl anhydrous methyl glucamide is a mixture of a compound of formula (I) wherein R is -(CH2)8CH3 and a compound of formula (I) wherein R is -(CH2)6CH3.

[0262] SC is commercially available from Clariant. Chemical name: Sorbitan octanoate.

[0263] CGE is commercially available from Clariant. Chemical name: Caprylyl Glyceryl Ether.

[0264] 4-Hydroxyacetophenone is commercially available from Sigma Aldrich.

[0265] Example 1

[0266] The antimicrobial properties of Velsan Flex, 4-hydroxyacetophenone, and their combination against bacteria, yeasts, and molds were studied: To test the inhibition against bacteria, Velsan Flex, 4-hydroxyacetophenone, or their combination was diluted in butyl polyethylene glycol and added to liquid Caso-Agar at different concentrations at 50 °C and buffered to pH 7 (+ / -0.2). To test the inhibition against yeasts and molds, Velsan Flex, 4-hydroxyacetophenone, or their combination was diluted in butyl polyethylene glycol and added to liquid Sabouraud-4% Dextrose-Agar at different concentrations at 50 °C and buffered to pH 5.6 (+ / -0.2). Each solution was poured into Petri dishes and inoculated with the same amount of bacteria, yeast, or mold respectively. The minimum inhibitory concentration (MIC) is the lowest concentration of each composition that inhibits the growth of each microorganism, where the next lowest dilution does not inhibit the growth of the microorganism. The experiments were conducted under scientifically fair conditions so that appropriate comparisons and conclusions could be drawn.

[0267] The results are shown in the following table:

[0268]

[0269] It can be seen that since the MIC of the combination is lower than that of the single component, the combination of the two components shows a synergistic effect. This effect was observed in a broad spectrum of microorganisms including both bacteria and fungi. This leads to the advantages that a smaller amount of a single preservative can be used to preserve formulations such as cosmetic formulations or household formulations, reducing the likelihood of negative effects from antimicrobial actives, and saving resources.

[0270] The antimicrobial properties of Velsan SC, 4-hydroxyacetophenone, and their combination against bacteria, yeasts, and molds were studied in experiments similar to those described above.

[0271] The results are shown in the following table:

[0272]

[0273]

[0274] It can be seen that since the MIC of the combination is lower than that of the single component, the combination of Velsan SC and hydroxyacetophenone shows a synergistic effect. This effect was observed in a broad spectrum of microorganisms including both bacteria and fungi. This leads to the advantages that a smaller amount of a single preservative can be used to preserve formulations such as cosmetic formulations or household formulations, reducing the likelihood of negative effects from antimicrobial actives, and saving resources.

[0275] Example 2

[0276] Antiseptic ability demonstrated in challenge tests:

[0277] The synergistic effect and ability to preserve typical cosmetic formulations for wash-free applications are also shown. The following examples show the challenge test results according to Chapter 5.1.3 of the 10th Edition of the EUROPEAN PHARMACOPOEIA. The following test bacteria are used as representative microorganisms: Pseudomonas aeruginosa (Gram-negative bacterium, abbreviated as "P.a."), Staphylococcus aureus (Gram-positive bacterium, abbreviated as "S.a."), Escherichia coli (Gram-negative bacterium, abbreviated as "E.c."), Candida albicans (yeast, abbreviated as "C.a.") and Aspergillus brasiliensis (mold, abbreviated as "A.b.").

[0278] Standard A represents the recommended efficacy to be achieved. In reasonable cases where Standard A cannot be achieved, for example due to an increased risk of negative reactions, Standard B must be met. Standard A is associated with excellent protection of the formulation, and Standard B requires showing sufficient protection but requires the application of additional risk elimination measures related to packaging and raw material quality. In the case where any of the tested organisms is Standard F, the entire challenge test fails and the antiseptic / protection of the formulation is insufficient.

[0279] The unpreserved samples of each formulation were also tested as a reference. A formulation difficult to preserve was used as the test system:

[0280] Wash-free: O / W-cream gel

[0281]

[0282] The results of the challenge tests of the formulations tested at pH 7 are shown in the following table:

[0283]

[0284] The non-preserved test system failed the challenge test for all test bacteria at pH 7 (item 7). The use level of 0.5% hydroxyacetophenone was insufficient to preserve the formulation as it failed to resist E.c. (item 6) and only reached the B-standard for S.a. Additionally, Velsan SC, Velsan Flex, or Velsan CGE alone was insufficient to preserve the formulation (items 8 - 11). In contrast, the combination of Velsan Flex and hydroxyacetophenone at use levels of 0.5% and 0.5% (item 1) reached the A-standard for all test microorganisms, providing excellent protection for the formulation. The same formulation also reached the A-standard for all test bacteria at pH 7 when using 0.5% and 0.5% of Velsan SC and hydroxyacetophenone (item 2), providing excellent protection for the formulation. The same effect was observed when using a combination of 0.25% and 0.5% use levels of Velsan CGE with hydroxyacetophenone, reaching the A-standard for all microorganisms (item 4). The combination of 0.5% Velsan CGE with hydroxyacetophenone could even reduce the amount of hydroxyacetophenone to 0.25% (item 3), resulting in the A-standard for all test microorganisms. However, when using 0.25% hydroxyacetophenone as the sole preservative, only the F-standard was obtained for all test microorganisms (item 5).

[0285] As can be seen from the results shown in Example 2, the combination of hydroxyacetophenone with Velsan Flex, Velsan SC, or Velsan CGE showed a synergistic effect, because when the use concentration of hydroxyacetophenone was 0.5%, it could already pass the challenge test, while hydroxyacetophenone alone or Velsan Flex, Velsan SC, or Velsan CGE was insufficient to fully protect the cosmetic formulation at this concentration. This leads to the advantage that a smaller amount of preservative can be used to preserve formulations such as cosmetic formulations or household formulations, reducing the likelihood of negative effects from antimicrobial actives.

[0286] Example 3

[0287] Example compositions of the present invention (amounts are provided in wt%)

[0288]

[0289] Note:

[0290] * = compound according to formula (I) where R is -(CH2)8CH3; # = compound according to formula (I) where R is -(CH2)6CH3. The compositions were prepared by mixing their components at room temperature.

[0291] Example 4

[0292] Example compositions of the present invention (amounts are provided in wt%)

[0293]

[0294] The composition is prepared by mixing its components at room temperature.

[0295] Example 5

[0296] Example compositions of the present invention (amounts are provided in wt%)

[0297]

[0298] The composition is prepared by mixing its components at room temperature.

[0299] Example 6

[0300] Example formulations of the present invention (amounts are provided in wt%)

[0301]

[0302]

[0303] Example 7

[0304] Example formulations of the present invention (amounts are provided in wt%)

[0305]

[0306] Example 8

[0307] Example formulations of the present invention (amounts are provided in wt%)

[0308]

[0309]

[0310]

[0311] Example 9

[0312] Example formulations of the present invention (amounts are provided in wt%)

[0313]

[0314]

[0315] Example 10

[0316] Example formulations of the present invention (amounts are provided in wt%)

[0317]

[0318] Example 11

[0319] Formulations of the embodiments of the present invention (amounts are provided in wt%)

[0320]

[0321]

Claims

1. A composition comprising: (A) at least one compound selected from: compounds of formula (I) wherein R is selected from saturated hydrocarbon chains having 5 to 23 carbon atoms, unsaturated hydrocarbon chains having 5 to 23 carbon atoms, and mixtures thereof, sorbitan esters, isosorbide esters, glycerol ethers, and glycerol esters; and (B) at least one hydroxyacetophenone.

2. The composition according to claim 1, wherein R in formula (I) is selected from saturated hydrocarbon chains having 5 to 17 carbon atoms, unsaturated hydrocarbon chains having 5 to 17 carbon atoms, and mixtures thereof, preferably selected from saturated hydrocarbon chains having 5 to 13 carbon atoms, unsaturated hydrocarbon chains having 5 to 13 carbon atoms, and mixtures thereof, more preferably selected from saturated hydrocarbon chains having 7 to 9 carbon atoms, unsaturated hydrocarbon chains having 7 to 9 carbon atoms, and mixtures thereof.

3. The composition according to claim 1 or 2, wherein the sorbitan ester is a monoester, diester, or triester of sorbitan with one or more C6-C20 fatty acids, preferably a monoester or diester of sorbitan with one or more C8-C14 fatty acids, more preferably a monoester or diester of sorbitan with octanoic acid.

4. The composition according to any one of claims 1 to 3, wherein the sorbitan ester is selected from sorbitan octanoate, sorbitan stearate, sorbitan oleate, sorbitan oleate, sorbitan decanoate, sorbitan laurate, sorbitan myristate, sorbitan caproate, and mixtures thereof, preferably sorbitan octanoate.

5. The composition according to any one of claims 1 to 4, wherein the isosorbide ester is a monoester or diester of isosorbide with one or more C6-C20 fatty acids, preferably a monoester or diester of isosorbide with one or more C8-C14 fatty acids, more preferably a monoester or diester of isosorbide with octanoic acid.

6. The composition according to any one of claims 1 to 5, wherein the isosorbide ester is selected from isosorbide octanoate, isosorbide stearate, isosorbide oleate, isosorbide oleate, isosorbide decanoate, isosorbide laurate, isosorbide myristate, isosorbide caproate, and mixtures thereof, preferably isosorbide octanoate.

7. The composition according to any one of claims 1 to 6, wherein the glycerol ether is a monoether or diether of glycerol with one or more C6-C20 fatty alcohols, preferably a monoether or diether of glycerol with one or more C8-C14 fatty alcohols, and particularly preferably a monoether of glycerol with one or more C8 fatty alcohols.

8. The composition according to any one of claims 1 to 7, wherein the hydroxyacetophenone is selected from 2-hydroxyacetophenone, 3-hydroxyacetophenone, 4-hydroxyacetophenone, and mixtures thereof.

9. The composition according to claim 8, wherein the hydroxyacetophenone is 4-hydroxyacetophenone.

10. The composition according to any one of claims 1 to 9, wherein the weight ratio of (A) at least one compound selected from the group consisting of the compounds of formula (I), sorbitan esters, isosorbide esters, glycerol ethers, and glycerol esters to (B) at least one hydroxyacetophenone is from 20:1 to 1:5, preferably from 15:1 to 1:2, more preferably from 12:1 to 1:1, particularly preferably from 10:1 to 3:1, such as from 6:1 to 7:

1.

11. The composition according to any one of claims 1 to 10, wherein the composition is a blend.

12. The composition according to claim 11, wherein the blend comprises: 25 to 99% by weight, preferably 40 to 80% by weight, more preferably 55 to 70% by weight, particularly preferably 60 to 65% by weight, based on the total weight of the blend, of (A) at least one compound selected from the group consisting of the compounds of formula (I), sorbitan esters, isosorbide esters, glycerol ethers, and glycerol esters; and 1 to 50% by weight, preferably 2 to 20% by weight, more preferably 5 to 15% by weight, particularly preferably 8 to 12% by weight, based on the total weight of the blend, of (B) at least one hydroxyacetophenone.

13. Use of the composition defined in any one of claims 1 to 12 as an antimicrobial agent.

14. A method for reducing the action of microorganisms in a formulation, wherein the method comprises adding to the formulation the composition defined in any one of claims 1 to 12.

15. A formulation comprising (A) 0.1 to 10% by weight, preferably 0.2 to 3% by weight, particularly preferably 0.3 to 1.5% by weight, based on the total weight of the formulation, of at least one compound selected from the compounds of formula (I) wherein R is selected from a saturated hydrocarbon chain having 5 to 23 carbon atoms, an unsaturated hydrocarbon chain having 5 to 23 carbon atoms, and mixtures thereof, sorbitan esters, isosorbide esters, glycerol ethers, and glycerol esters; and (B) at least one hydroxyacetophenone in an amount of 0.01 to 1.5% by weight, preferably 0.05 to 0.5% by weight, particularly preferably 0.1 to 0.3% by weight, based on the total weight of the formulation.

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