Preparation method of piroctone, including crystallization or precipitation, and preparation method of piroctone particles and piroctone olamine salt

Abstract

The invention relates to a method for crystallizing or precipitating piroctone, comprising the following steps: a) dissolving a piroctone-containing product in a solvent; b) cooling the solution; and c) separating the crystalline or precipitated piroctone.

Description

[0001] The present invention relates to a method for crystallizing or precipitating piroctone and piroctone particles with a certain particle size. The present invention also relates to the use of piroctone in the manufacture of a cosmetic composition, a cosmetic composition containing piroctone, and the use of piroctone as an antidandruff agent or as a preservative.

[0002] Preservation of cosmetic and household formulations extends their shelf life, thereby providing consumers with a better value for money. Additionally, preservatives prevent consumers from spreading microorganisms into their homes or on their bodies, thereby providing health benefits. Antimicrobial actives are well described in the art, and many are available that offer excellent performance.

[0003] Piroctone Olamine, also known as (Clariant) and piroctone ethanolamine are compounds used to treat fungal infections. The chemical name for piroctone ethanolamine is the monoethanolamine salt of 1-hydroxy-4-methyl-6-(2,4,4-trimethylpentyl)-2(1H)-pyridinone. Therefore, piroctone ethanolamine is the ethanolamine salt of the hydroxamic acid derivative piroctone.

[0004] Piroctone olamine salt is often used in anti-dandruff shampoos as a safe alternative to the commonly used compound pyrithione zinc.

[0005] GB 1440975, EP 0158481 and WO 2006 / 081969, among others, describe the use of piroctone olamine salts as antidandruff agents and / or preservatives.

[0006] However, there is a desire for improved preservative and antifungal systems. In particular, it is desirable to reduce the concentration of such systems - but this requires improved efficacy to ensure adequate inhibition of microbial growth. Consumers are generally becoming more aware of the contents of cosmetics and household products, and they desire a reduction in the content of "chemicals", especially those known to inhibit microbial growth.

[0007] In view of the foregoing, there remains a need for more effective preservative and antifungal substances that meet current performance demands and the expectations and desires of modern consumers.

[0008] In piroctone olamine salt, the ethanolamine counterion accounts for approximately 20% of the total weight of the piroctone olamine salt, but does not contribute to its anti-dandruff activity. Thus, piroctone does not have an ethanolamine counterion and therefore has a higher activity to weight ratio than piroctone olamine salt.

[0009] However, although piroctone olamine salt is often used in cosmetic compositions such as shampoos, to our knowledge, there are no commercially available examples containing piroctone (based on a Mintel search), despite it being listed as a permitted preservative in Annex V to Regulation (EC) No. 1223 / 2009 of the European Parliament. Using piroctone in cosmetic compositions such as shampoos is very challenging. In particular, dissolving piroctone in these formulations is very challenging.

[0010] Surprisingly, it has been found that piroctone can be isolated and purified by crystallization or precipitation. Such crystallization or precipitation provides piroctone with the desired particle size.

[0011] The present invention relates to a method for crystallizing or precipitating piroctone, comprising the following steps:

[0012] a) dissolving the piroctone-containing product in a solvent;

[0013] b) cooling the solution; and

[0014] c) isolating the crystallized or precipitated piroctone.

[0015] Advantageously, the process of the present invention provides piroctone in good yield and high purity. The piroctone of the present invention has a desired particle size. In particular, d 90 Such piroctone is soluble in formulations containing surfactants.

[0016] Another advantage of the method of the present invention is that the crude product obtained by the method for preparing piroctone can be directly used to achieve the desired particle size by chemical methods. The mechanical method of screening after grinding or milling is not necessary. Therefore, the yield loss due to the additional method can be avoided.

[0017] The advantage of piroctone is that it has a better activity to weight ratio than piroctone olamine salt, that is, a higher efficacy per molecular weight of active substance. The ethanolamine counterion in piroctone olamine salt accounts for about 20% of the total mass of piroctone olamine salt, but does not contribute to its anti-dandruff activity.

[0018] As used herein, piroctone is also known as 1-hydroxy-4-methyl-6-(2,4,4-trimethylpentyl)-2(1H)-pyridone and refers to the compound of the formula:

[0019]

[0020] As used herein, Pyron is also known as 1-hydroxy-4-methyl-6-(2,4,4-trimethylpentyl)-2(1H)-pyrone and refers to the compound of the formula:

[0021]

[0022] Regarding the particle size distribution metric used in this paper, d 50 , d(50) or D50, median value, is defined as the diameter below which half of the particle population lies. Similarly, 10% of the particle population lies below d 10 , d(10) or D10 diameter and 90% of the particle population is located at d 90 , d(90) or D90 diameter. If not otherwise indicated, d 50 d 10 d 90 Values are based on volume distribution.

[0023] The method of the present invention comprises the following step a): dissolving the piroctone-containing product in a solvent.

[0024] According to the present invention, the piroctone-containing product used in step a) comprises piroctone.

[0025] In a preferred embodiment, the piroctone-containing product used in step a) comprises at least 10% by weight, preferably at least 20% by weight, more preferably at least 30% by weight, more preferably at least 40% by weight, still more preferably at least 50% by weight, still more preferably at least 55% by weight and particularly preferably at least 60% by weight of piroctone, based on the total weight of the piroctone-containing product.

[0026] In a preferred embodiment, the piroctone-containing product used in step a) comprises at least 70% by weight, preferably at least 80% by weight, more preferably at least 90% by weight, even more preferably at least 95% by weight and particularly preferably at least 98% by weight of piroctone, based on the total weight of the piroctone-containing product.

[0027] The piroctone-containing product can be, for example, a crude product obtained by a method for preparing piroctone. In a preferred embodiment, the piroctone-containing product is a crude product obtained by a method comprising reacting pyron with hydroxylamine or a hydroxylammonium compound. Therefore, the piroctone-containing product can, for example, also contain one or more by-products or by-products of such a method, or pyron.

[0028] Alternatively, the piroctone-containing product can be, for example, relatively pure or pure piroctone, i.e., essentially consisting of piroctone or consisting of piroctone. It can still be useful to subject such piroctone to the process of the present invention, because this can change the particle size distribution of piroctone.

[0029] Preferably, the solvent in step a) is selected from heptane, hexane, cyclohexane, methylcyclohexane, dimethylcyclohexane, toluene, benzene, dichloromethane, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, tert-amyl alcohol, dimethylformamide, dimethyl sulfoxide, tetrahydrofuran, acetonitrile, 2-aminopyridine, methyl tert-butyl ether, dibutyl ether, diisopropyl ether, water and mixtures thereof.

[0030] More preferably, the solvent in step a) is selected from heptane, hexane, cyclohexane, methylcyclohexane, dimethylcyclohexane, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, tert-amyl alcohol, methyl tert-butyl ether, dibutyl ether, diisopropyl ether, water and mixtures thereof.

[0031] Still more preferably, the solvent in step a) is selected from the group consisting of heptane, hexane, cyclohexane, methylcyclohexane, dimethylcyclohexane, methyl tert-butyl ether, dibutyl ether, diisopropyl ether and mixtures thereof. Particularly preferably, the solvent in step a) is heptane.

[0032] In a preferred embodiment, the solvent in step a) is a mixture of alcohol and water. Preferably, alcohol is selected from methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butanol, isopropyl alcohol, sec-butyl alcohol, the tert-butyl alcohol, tert-amyl alcohol and mixtures thereof. In a particularly preferred embodiment, the solvent in step a) is a mixture of isopropyl alcohol and water. Preferably, the solvent comprises at least 30 % by weight of alcohol (preferably isopropyl alcohol) and 70 % by weight of water based on the total weight of the solvent. More preferably, the solvent comprises 40 to 70 % by weight of alcohol (preferably isopropyl alcohol) and 30 to 60 % by weight of water based on the total weight of the solvent. Particularly preferably, the solvent comprises 50 to 60 % by weight of alcohol (preferably isopropyl alcohol) and 40 to 50 % by weight of water based on the total weight of the solvent.

[0033] In a preferred embodiment, at least 50 ml, preferably at least 100 ml, more preferably at least 300 ml, particularly preferably at least 500 ml of solvent are used per 100 g of piroctone-containing product in step a). In one embodiment, at least 1000 ml of solvent are used per 100 g of piroctone-containing product in step a).

[0034] In a preferred embodiment, 50 to 1000 ml, preferably 100 to 900 ml, more preferably 300 to 800 ml, and particularly preferably 500 to 750 ml of solvent are used per 100 g of piroctone-containing product in step a). In a preferred embodiment, 400 to 700 ml, preferably 450 to 650 ml, more preferably 450 to 600 ml, and particularly preferably 500 to 600 ml of solvent are used per 100 g of piroctone-containing product in step a). In one embodiment, 1000 to 1500 ml of solvent are used per 100 g of piroctone-containing product in step a).

[0035] In a preferred embodiment, the piroctone-containing product is dissolved in a solvent in step a) at a temperature in the range of 30 to 100° C., preferably 40 to 90° C., more preferably 50 to 80° C., particularly preferably 60 to 80° C. In a preferred embodiment, the piroctone-containing product is dissolved in a solvent in step a) at a temperature in the range of 55 to 85° C., preferably 60 to 80° C., more preferably 65 to 80° C., particularly preferably 70 to 75° C.

[0036] The method of the present invention comprises the following step b): cooling the solution.

[0037] In one embodiment, the solution is cooled in step b) to a temperature in the range of -10 to 80° C. In a preferred embodiment, the solution is cooled in step b) to a temperature in the range of -5 to 50° C., preferably 0 to 35° C., more preferably 0 to 25° C., particularly preferably 0 to 20° C. In a preferred embodiment, the solution is cooled in step b) to a temperature in the range of -5 to 20° C., preferably 0 to 15° C., more preferably 0 to 10° C., particularly preferably 0 to 5° C. In a preferred embodiment, the solution is cooled in step b) to a temperature in the range of 0 to 35° C., preferably 5 to 30° C., more preferably 10 to 25° C., particularly preferably 15 to 20° C.

[0038] The process of the present invention comprises the following step c): isolating the crystallized or precipitated piroctone.

[0039] In a preferred embodiment, the crystallized or precipitated piroctone is isolated by filtration. Preferably, the filtration is followed by washing with a solvent (preferably the solvent used in step a)) and drying.

[0040] In a preferred embodiment, the piroctone-containing product used in step a) is prepared by reacting pyron with hydroxylamine or a hydroxylammonium compound, preferably a hydroxylammonium compound.

[0041] In one embodiment, the pyron is reacted with hydroxylamine. Hydroxylamine can be used, for example, in the form of an aqueous solution. Hydroxylamine is commercially available, for example, as a 50% aqueous solution.

[0042] In a preferred embodiment, the pyron is reacted with a hydroxylammonium compound. Hydroxyllammonium compounds are particularly preferred. Suitable hydroxylammonium compounds are known to those skilled in the art. Preferred hydroxylammonium compounds are selected from the group consisting of hydroxylammonium sulfate, hydroxylammonium chloride, hydroxylammonium acetate, hydroxylammonium phosphate, hydroxylammonium nitrate, hydroxylammonium perchlorate, hydroxylammonium oxalate, hydroxylammonium hydrogen sulfate, 4-methylbenzenesulfonate, and hydroxylammonium bromide. More preferred hydroxylammonium compounds are selected from the group consisting of hydroxylammonium sulfate, hydroxylammonium chloride, and hydroxylammonium acetate. Even more preferred hydroxylammonium compounds are selected from the group consisting of hydroxylammonium sulfate and hydroxylammonium chloride. A particularly preferred hydroxylammonium compound is hydroxylammonium sulfate. Another particularly preferred hydroxylammonium compound is hydroxylammonium chloride.

[0043] Preferably, the molar ratio of pyron to hydroxylamine equivalents is from 1.0:1.0 to 1.0:4.0, more preferably from 1.0:1.8 to 1.0:3.0, still more preferably from 1.0:2.0 to 1.0:2.6, particularly preferably from 1.0:2.0 to 1.0:2.4, for example 1.0:2.2.

[0044] In a preferred embodiment, the molar ratio of pyron to hydroxylammonium compound is 1.0:0.5 to 1.0:2.0, more preferably 1.0:0.9 to 1.0:1.5, even more preferably 1.0:1.0 to 1.0:1.3, particularly preferably 1.0:1.0 to 1.0:1.2, for example 1.0:1.1. Such a molar ratio is preferred, for example, when hydroxylammonium sulfate is used as the hydroxylammonium compound.

[0045] In another preferred embodiment, the molar ratio of pyron to hydroxylamine or hydroxylammonium compound is 1.0:1.0 to 1.0:4.0, more preferably 1.0:1.8 to 1.0:3.0, even more preferably 1.0:2.0 to 1.0:2.6, particularly preferably 1.0:2.0 to 1.0:2.4, for example 1.0:2.2. Such a molar ratio is preferred, for example, when hydroxylammonium chloride or hydroxylammonium acetate is used as the hydroxylammonium compound.

[0046] In a preferred embodiment, the pyron is reacted with hydroxylamine or a hydroxylammonium compound in the presence of a base. In one embodiment, the pyron is reacted with hydroxylamine in the presence of a base. In another embodiment, the pyron is reacted with hydroxylamine in the absence of a base. In a preferred embodiment, the pyron is reacted with a hydroxylammonium compound in the presence of a base.

[0047] Suitable bases are known to those skilled in the art. Examples of suitable bases are metal carbonates, metal bicarbonates, or metal hydroxides, such as alkali metal carbonates, alkali metal bicarbonates, alkali metal hydroxides, alkaline earth metal carbonates, alkaline earth metal bicarbonates, or alkaline earth metal hydroxides. Preferred bases are selected from alkali metal carbonates, alkali metal bicarbonates, alkali metal hydroxides, and mixtures thereof. More preferred bases are selected from alkali metal carbonates, alkali metal bicarbonates, and mixtures thereof. Even more preferred bases are selected from alkali metal carbonates.

[0048] Examples of suitable bases are lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, lithium bicarbonate, sodium bicarbonate, potassium bicarbonate, cesium bicarbonate, lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, calcium carbonate, magnesium carbonate, barium carbonate, nickel carbonate, zirconium carbonate, calcium hydroxide, magnesium hydroxide, barium hydroxide, nickel hydroxide, or zirconium hydroxide. Preferred bases are selected from lithium carbonate, sodium carbonate, potassium carbonate, lithium bicarbonate, sodium bicarbonate, potassium bicarbonate, sodium hydroxide, potassium hydroxide, and mixtures thereof. More preferred bases are selected from lithium carbonate, sodium carbonate, potassium carbonate, lithium bicarbonate, sodium bicarbonate, potassium bicarbonate, and mixtures thereof. Even more preferred bases are selected from lithium carbonate, sodium carbonate, potassium carbonate, and mixtures thereof. Even more preferred bases are selected from sodium carbonate, sodium bicarbonate, and mixtures thereof. A particularly preferred base is sodium carbonate.

[0049] Preferably, the molar ratio of hydroxylamine equivalents to base equivalents is 1.0:0.5 to 1.0:3.0, more preferably 1.0:0.8 to 1.0:2.0, still more preferably 1.0:1.0 to 1.0:1.5, still more preferably 1.0:1.0 to 1.0:1.2, particularly preferably 1.0:1.0 to 1.0:1.1, for example 1.0:1.0.

[0050] In a preferred embodiment, the molar ratio of the hydroxylammonium compound to the base is 1.0:0.5 to 1.0:3.0, more preferably 1.0:0.8 to 1.0:2.0, even more preferably 1.0:1.0 to 1.0:1.5, even more preferably 1.0:1.0 to 1.0:1.2, particularly preferably 1.0:1.0 to 1.0:1.1, for example 1.0:1.0. Such a molar ratio is preferred, for example, when hydroxylammonium sulfate is used as the hydroxylammonium compound and an alkali metal carbonate (e.g., sodium carbonate) is used as the base.

[0051] In a preferred embodiment, the pyron is reacted with hydroxylamine or a hydroxylammonium compound in the presence of a solvent. Suitable solvents are known to those skilled in the art.

[0052] Preferred solvents are selected from organic solvents, water, and mixtures thereof. Preferred organic solvents are selected from heptane, hexane, cyclohexane, methylcyclohexane, dimethylcyclohexane, toluene, benzene, dichloromethane, methanol, ethanol, isopropyl alcohol, tert-butyl alcohol, tert-amyl alcohol, dimethylformamide, dimethyl sulfoxide, tetrahydrofuran, acetonitrile, 2-aminopyridine, and mixtures thereof. More preferred organic solvents are selected from heptane, hexane, cyclohexane, methylcyclohexane, toluene, 2-aminopyridine, and mixtures thereof. Even more preferred organic solvents are selected from heptane, toluene, and mixtures thereof. Particularly preferred organic solvents are heptanes. Another particularly preferred organic solvent is toluene.

[0053] In a preferred embodiment, solvent is a mixture of an organic solvent and water. In a more preferred embodiment, solvent is a mixture of an organic solvent and water, wherein the organic solvent is selected from heptane, hexane, cyclohexane, methylcyclohexane, dimethylcyclohexane, toluene, benzene, methylene chloride, methanol, ethanol, isopropyl alcohol, the tert-butyl alcohol, tert-amyl alcohol, dimethylformamide, dimethyl sulfoxide, tetrahydrofuran (THF), acetonitrile, 2-aminopyridine and mixture thereof. In an even more preferred embodiment, solvent is a mixture of an organic solvent and water, wherein the organic solvent is selected from heptane, hexane, cyclohexane, methylcyclohexane, toluene, 2-aminopyridine and mixture thereof. In an even more preferred embodiment, solvent is a mixture of an organic solvent and water, wherein the organic solvent is selected from heptane, toluene and mixture thereof. In a particularly preferred embodiment, solvent is a mixture of an organic solvent and water, wherein the organic solvent is heptane. In another particularly preferred embodiment, solvent is a mixture of an organic solvent and water, wherein the organic solvent is toluene.

[0054] Preferably, the solvent comprises at least 80% by weight, more preferably at least 90% by weight, even more preferably at least 95% by weight, and particularly preferably at least 98% by weight of an organic solvent, based on the total weight of the solvent. In a preferred embodiment, the solvent comprises at least 80% by weight, more preferably at least 90% by weight, even more preferably at least 95% by weight, and particularly preferably at least 98% by weight of heptane or toluene, based on the total weight of the solvent.

[0055] Preferably, the pyron is reacted with hydroxylamine or a hydroxylammonium compound at a temperature of 50 to 120°C, more preferably 60 to 100°C, still more preferably 70 to 90°C, particularly preferably 80 to 90°C.

[0056] Preferably, the reaction of the pyron with hydroxylamine or a hydroxylammonium compound is continued for at least 4 hours, more preferably at least 8 hours, even more preferably at least 12 hours, particularly preferably at least 15 hours. For example, the reaction of the pyron with hydroxylamine or a hydroxylammonium compound is continued for 8 to 24 hours, preferably 12 to 20 hours, particularly preferably 15 to 18 hours.

[0057] In a preferred embodiment, the crystallized or precipitated piroctone has a d value of 250 μm or less, preferably 200 μm or less, more preferably 150 μm or less, particularly preferably 100 μm or less. 90 In a preferred embodiment, the crystallized or precipitated piroctone has a d in the range of 30 to 250 μm, preferably 40 to 200 μm, more preferably 50 to 150 μm, particularly preferably 60 to 100 μm. 90 .

[0058] In a more preferred embodiment, the crystallized or precipitated piroctone has a d value of 90 μm or less, preferably 85 μm or less. 90 In a more preferred embodiment, the crystallized or precipitated piroctone has a d in the range of 65 to 90 μm, preferably 70 to 90 μm, more preferably 70 to 85 μm, particularly preferably 75 to 85 μm. 90 .

[0059] In a preferred embodiment, the crystallized or precipitated piroctone has a d of 90 μm or less, preferably 80 μm or less, more preferably 75 μm or less, particularly preferably 70 μm or less. 50 In a preferred embodiment, the crystallized or precipitated piroctone has a d in the range of 10 to 90 μm, preferably 15 to 80 μm, more preferably 20 to 75 μm, particularly preferably 25 to 70 μm. 50 .

[0060] In a more preferred embodiment, the crystallized or precipitated piroctone has a d value of 60 μm or less, preferably 50 μm or less, more preferably 40 μm or less, particularly preferably 35 μm or less. 50 In a more preferred embodiment, the crystallized or precipitated piroctone has a d in the range of 15 to 60 μm, preferably 20 to 50 μm, more preferably 25 to 40 μm, particularly preferably 28 to 35 μm. 50 .

[0061] In a preferred embodiment, the crystallized or precipitated piroctone has a d of 30 μm or less, preferably 25 μm or less, more preferably 20 μm or less, particularly preferably 15 μm or less. 10 In a preferred embodiment, the crystallized or precipitated piroctone has a d in the range of 2 to 30 μm, preferably 3 to 25 μm, more preferably 4 to 20 μm, particularly preferably 5 to 15 μm. 10 .

[0062] In a more preferred embodiment, the crystallized or precipitated piroctone has a d value of 12 μm or less, preferably 10 μm or less. 10In a more preferred embodiment, the crystallized or precipitated piroctone has a d in the range of 4 to 12 μm, preferably 5 to 10 μm. 10 .

[0063] The present invention also relates to crystallized or precipitated piroctone obtainable by the process of the present invention.

[0064] The present invention also relates to a device having a d of 250 μm or less 90 In a preferred embodiment, the piroctone particles have a d of 200 μm or less, preferably 150 μm or less, particularly preferably 100 μm or less. 90 In a preferred embodiment, the piroctone particles have a d in the range of 30 to 250 μm, preferably 40 to 200 μm, more preferably 50 to 150 μm, particularly preferably 60 to 100 μm. 90 .

[0065] In a more preferred embodiment, the piroctone particles have a d of 90 μm or less, preferably 85 μm or less. 90 In a more preferred embodiment, the piroctone particles have a d in the range of 65 to 90 μm, preferably 70 to 90 μm, more preferably 70 to 85 μm, particularly preferably 75 to 85 μm. 90 .

[0066] In a preferred embodiment, the piroctone particles have a d of 90 μm or less, preferably 80 μm or less, more preferably 75 μm or less, particularly preferably 70 μm or less. 50 In a preferred embodiment, the piroctone particles have a d in the range of 10 to 90 μm, preferably 15 to 80 μm, more preferably 20 to 75 μm, particularly preferably 25 to 70 μm. 50 .

[0067] In a more preferred embodiment, the piroctone particles have a d of 60 μm or less, preferably 50 μm or less, more preferably 40 μm or less, particularly preferably 35 μm or less. 50 In a more preferred embodiment, the piroctone particles have a d in the range of 15 to 60 μm, preferably 20 to 50 μm, more preferably 25 to 40 μm, particularly preferably 28 to 35 μm. 50 .

[0068] In a preferred embodiment, the piroctone particles have a d of 30 μm or less, preferably 25 μm or less, more preferably 20 μm or less, particularly preferably 15 μm or less. 10 In a preferred embodiment, the piroctone particles have a d in the range of 2 to 30 μm, preferably 3 to 25 μm, more preferably 4 to 20 μm, particularly preferably 5 to 15 μm.10 .

[0069] In a more preferred embodiment, the piroctone particles have a d of 12 μm or less, preferably 10 μm or less. 10 In a more preferred embodiment, the piroctone particles have a d in the range of 4 to 12 μm, preferably 5 to 10 μm. 10 .

[0070] In a preferred embodiment, piroctone particles are obtained by the process of the present invention.

[0071] The present invention also relates to a method for preparing piroctone, comprising the following steps:

[0072] 1) reacting pyron with hydroxylamine or a hydroxylammonium compound in solvent S1; and

[0073] 2) crystallizing or precipitating piroctone from solvent S2,

[0074] The prerequisite is that if the solvent S2 used in step 2) is heptane, the solvent S1 used in step 1) is not heptane.

[0075] Preferably, the solvent S1 in step 1) is selected from heptane, hexane, cyclohexane, methylcyclohexane, dimethylcyclohexane, toluene, benzene, dichloromethane, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, tert-amyl alcohol, dimethylformamide, dimethyl sulfoxide, tetrahydrofuran, acetonitrile, 2-aminopyridine, methyl tert-butyl ether, dibutyl ether, diisopropyl ether, water and mixtures thereof.

[0076] More preferably, the solvent S1 in step 1) is selected from heptane, hexane, cyclohexane, methylcyclohexane, toluene, 2-aminopyridine and mixtures thereof.

[0077] Still more preferably, the solvent S1 in step 1) is selected from heptane, toluene and mixtures thereof. Particularly preferably, the solvent S1 in step 1) is heptane. Still more preferably, the solvent S1 in step 1) is toluene.

[0078] Preferably, the solvent S2 in step 2) is selected from heptane, hexane, cyclohexane, methylcyclohexane, dimethylcyclohexane, toluene, benzene, dichloromethane, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, tert-amyl alcohol, dimethylformamide, dimethyl sulfoxide, tetrahydrofuran, acetonitrile, 2-aminopyridine, methyl tert-butyl ether, dibutyl ether, diisopropyl ether, water and mixtures thereof.

[0079] More preferably, the solvent S2 in step 2) is selected from heptane, hexane, cyclohexane, methylcyclohexane, dimethylcyclohexane, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, methyl tert-butyl ether, dibutyl ether, diisopropyl ether, water and mixtures thereof.

[0080] Still more preferably, the solvent S2 in step 2) is selected from heptane, hexane, cyclohexane, isopropyl alcohol, diisopropyl ether, water, and mixtures thereof. Still more preferably, the solvent S2 in step 2) is selected from heptane, hexane, cyclohexane, diisopropyl ether, and a mixture of isopropyl alcohol and water. Particularly preferably, the solvent S2 in step 2) is selected from heptane.

[0081] In a preferred embodiment, step 2) the solvent S2 is a mixture of alcohol and water.Preferably, alcohol is selected from methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butanol, isopropyl alcohol, sec-butyl alcohol, the tert-butyl alcohol, tert-amyl alcohol and mixtures thereof.In a particularly preferred embodiment, step 2) the solvent S2 is a mixture of isopropyl alcohol and water.Preferably, solvent S2 comprises at least 30 % by weight of alcohol (preferably isopropyl alcohol) and 70 % by weight water at the most based on the gross weight of solvent S2. More preferably, solvent S2 comprises 40 to 70 % by weight of alcohol (preferably isopropyl alcohol) and 30 to 60 % by weight water based on the gross weight of solvent S2. Particularly preferably, solvent S2 comprises 50 to 60 % by weight of alcohol (preferably isopropyl alcohol) and 40 to 50 % by weight water based on the gross weight of solvent S2.

[0082] In a preferred embodiment, the solvent S1 in step 1) is heptane; and the solvent S2 in step 2) is selected from hexane, cyclohexane, isopropanol, diisopropyl ether, water and mixtures thereof.

[0083] In a preferred embodiment, the solvent S1 in step 1) is heptane; and the solvent S2 in step 2) is selected from hexane, cyclohexane, diisopropyl ether, and a mixture of isopropanol and water.

[0084] In a preferred embodiment, the solvent S1 in step 1) is toluene; and the solvent S2 in step 2) is selected from heptane, hexane, cyclohexane, isopropanol, diisopropyl ether, water and mixtures thereof.

[0085] In a preferred embodiment, the solvent S1 in step 1) is toluene; and the solvent S2 in step 2) is selected from heptane, hexane, cyclohexane, diisopropyl ether, and a mixture of isopropanol and water.

[0086] In a particularly preferred embodiment, the solvent S1 in step 1) is toluene; and the solvent S2 in step 2) is heptane.

[0087] Pyron is reacted with hydroxylamine or a hydroxylammonium compound. In one embodiment, pyron is reacted with hydroxylamine. In a preferred embodiment, pyron is reacted with a hydroxylammonium compound. Preferred hydroxylammonium compounds are further described above. Preferred molar ratios of pyron to hydroxylamine equivalents are further described above.

[0088] In a preferred embodiment, the pyron is reacted with hydroxylamine or a hydroxylammonium compound in the presence of a base. In one embodiment, the pyron is reacted with hydroxylamine in the presence of a base. In another embodiment, the pyron is reacted with hydroxylamine in the absence of a base. In a preferred embodiment, the pyron is reacted with the hydroxylammonium compound in the presence of a base. Preferred bases are further described above. Preferred molar ratios of hydroxylamine equivalents to base equivalents are further described above.

[0089] Preferably, the pyron is reacted with hydroxylamine or a hydroxylammonium compound at a temperature of 50 to 120°C, more preferably 60 to 100°C, still more preferably 70 to 90°C, particularly preferably 80 to 90°C.

[0090] Preferably, the reaction of the pyron with hydroxylamine or a hydroxylammonium compound is continued for at least 4 hours, more preferably at least 8 hours, even more preferably at least 12 hours, particularly preferably at least 15 hours. For example, the reaction of the pyron with hydroxylamine or a hydroxylammonium compound is continued for 8 to 24 hours, preferably 12 to 20 hours, particularly preferably 15 to 18 hours.

[0091] Preferably, piroctone is crystallized or precipitated at a temperature of -5 to 25°C, more preferably 0 to 25°C, even more preferably 0 to 20°C, particularly preferably 0 to 5°C, yet particularly preferably 15 to 20°C.

[0092] Preferably, piroctone is crystallized or precipitated from a solution of piroctone in solvent S2, wherein solvent S2 has a temperature of 50 to 85° C., preferably 60 to 80° C., particularly preferably 70 to 75° C. Preferably, the solution of piroctone is cooled to a temperature of −5 to 25° C., more preferably 0 to 25° C., even more preferably 0 to 20° C., particularly preferably 0 to 5° C., yet particularly preferably 15 to 20° C.

[0093] The crystallized or precipitated piroctone obtained by the method of the present invention or the piroctone particles of the present invention can be dissolved in a cosmetic composition, such as shampoo. Consistent with this, the crystallized or precipitated piroctone obtained by the method of the present invention or the piroctone particles of the present invention are suitable for use in a cosmetic composition, such as shampoo.

[0094] The present invention also relates to the use of the crystallized or precipitated piroctone obtained by the process according to the invention or the piroctone particles according to the invention for the manufacture of a cosmetic composition.

[0095] In a preferred embodiment, 0.01 to 10% by weight, preferably 0.05 to 5% by weight, more preferably 0.1 to 2.0% by weight, even more preferably 0.1 to 1.0% by weight and particularly preferably 0.1 to 0.5% by weight of piroctone, based on the total weight of the cosmetic composition, are used for the production of the cosmetic composition.

[0096] For example, the cosmetic composition can be selected from shampoo, conditioner, hair tonic, cream rinse, shower gel, bubble bath, bath oil, facial cleanser, cleansing mask, cleansing milk, micellar water, makeup remover, cleansing wipes, perfume, soap, shaving soap, shaving foam, cleansing foam, facial mask, facial cream, hand cream and body lotion.

[0097] Preferably, the cosmetic composition is a hair care composition, a scalp care composition, or a skin care composition. More preferably, the cosmetic composition is a hair care or scalp care composition, particularly preferably a hair care and scalp care composition. Even more preferably, the cosmetic composition is a skin care composition.

[0098] Preferably, the cosmetic composition is a shampoo composition or a conditioner composition. More preferably, the cosmetic composition is a shampoo composition, particularly preferably an anti-dandruff shampoo composition. Even more preferably, the cosmetic composition is a conditioner composition.

[0099] The cosmetic composition preferably comprises one or more additional components (F). Preferred additional components (F) and preferred amounts of such components are further described below. The additional components (F) and amounts thereof described in this document for use in the cosmetic composition of the present invention can also be used in the cosmetic composition produced according to the present invention.

[0100] The cosmetic composition can be manufactured by methods known in the art. For example, the cosmetic composition can be manufactured by mixing its ingredients. For example, piroctone can be mixed with other ingredients of the cosmetic composition.

[0101] The present invention also relates to a cosmetic composition comprising the crystallized or precipitated piroctone obtained by the process according to the invention or the piroctone particles according to the invention.

[0102] In a preferred embodiment, the cosmetic composition according to the invention comprises 0.01 to 10% by weight, preferably 0.05 to 5% by weight, more preferably 0.1 to 2.0% by weight, still more preferably 0.1 to 1.0% by weight, particularly preferably 0.1 to 0.5% by weight of piroctone, based on the total weight of the cosmetic composition.

[0103] For example, the cosmetic composition of the present invention can be selected from shampoo, conditioner, hair tonic, hair lotion, shower gel, bubble bath, bath oil, facial cleanser, cleansing mask, cleansing milk, micellar water, makeup remover, cleansing wipes, perfume, soap, shaving soap, shaving foam, cleansing foam, facial mask, facial cream, hand cream and body lotion.

[0104] Preferably, the cosmetic composition of the present invention is a hair care composition, a scalp care composition, or a skin care composition. More preferably, the cosmetic composition of the present invention is a hair care or scalp care composition, particularly preferably a hair care and scalp care composition. Even more preferably, the cosmetic composition of the present invention is a skin care composition.

[0105] Preferably, the cosmetic composition of the present invention is a shampoo composition or a conditioner composition. More preferably, the cosmetic composition of the present invention is a shampoo composition, particularly preferably an anti-dandruff shampoo composition. Even more preferably, the cosmetic composition of the present invention is a conditioner composition.

[0106] In a preferred embodiment, the cosmetic composition of the present invention is a shampoo composition. Shampoo compositions can be in the form of rinse-off products or "dry shampoo" products, can be opaque or transparent, and can be formulated into a variety of product forms, including creams, gels, lotions, mousses, and sprays. Preferably, the shampoo composition is in the form of a rinse-off product. The shampoo composition can be used, for example, on human hair and / or scalp or animal hair, preferably human hair and / or scalp.

[0107] In a preferred embodiment, the cosmetic composition of the present invention is a conditioner composition. Conditioner compositions can be in the form of rinse-off products or leave-on products, can be opaque or transparent, and can be formulated into a variety of product forms, including creams, gels, lotions, mousses, and sprays. Preferably, the conditioner composition is in the form of a rinse-off product.

[0108] In at least one embodiment, the cosmetic composition is in liquid form. In alternative embodiments, the cosmetic composition is in solid form. Optionally, the cosmetic composition is in powder or granular form. This is advantageous because it does not require long-distance transport of typically heavy liquids, which has economic and environmental benefits. The solid form can be achieved by spray drying the composition or by using a rotary evaporator. The solid form can also be achieved by extrusion or pressing. The composition can be converted into a liquid form after it has been transported, for example, by adding water.

[0109] The cosmetic composition of the present invention preferably comprises one or more additional components (F) in an amount of at least 0.01 wt. %, preferably at least 0.05 wt. %, more preferably at least 0.1 wt. %, still more preferably at least 0.5 wt. % based on the weight of the cosmetic composition.

[0110] Preferably, component (F) is selected from acidity regulators, colorants, conditioners, emulsifiers, film formers, fragrances, glossing agents, humectants, lubricants, moisturizers, pigments, preservatives, transdermal absorption enhancers, stabilizers, surfactants, thickeners and viscosity regulators. More preferably, component (F) is selected from acidity regulators, glossing agents, lubricants and surfactants.

[0111] Suitable lubricants are, for example, fatty alcohol components having 6 to 18 carbon atoms.

[0112] The surfactant may, for example, be chosen from non-polymeric cationic quaternary ammonium compounds, in particular cetyltrimethylammonium chloride (CTAC).

[0113] Suitable classical cationic conditioning agents include cationic quaternary ammonium salts. In at least one embodiment, component (F) is a cationic quaternary ammonium salt. Examples of such quaternary ammonium salts include benzyltriethylammonium chloride, cetyltrimethylammonium chloride (cetyltrimethylammonium chloride, CTAC), behenyltrimethylammonium chloride (BTAC) or cetylpyridinium chloride.

[0114] As the cationic component, various cationic polymers are suitable, including quaternized cellulose ethers, copolymers of vinyl pyrrolidone, acrylic polymers, homopolymers or copolymers including dimethyldiallylammonium chloride or acrylamide. Also suitable are various types of homopolymers or copolymers derived from acrylic acid or methacrylic acid, acrylamide, methacrylamide, diacetone-acrylamide.

[0115] In at least one embodiment, component (F) is a glossing agent. Typical glossing agents are silicones. Suitable silicones are volatile or non-volatile nonionic silicone fluids, silicone resins, and silicone semi-solids or solids. Volatile silicones are linear or cyclic silicones with a measurable vapor pressure, defined as a vapor pressure of at least 2 mm of mercury at 20°C. Also suitable are water-insoluble non-volatile silicone fluids including polyalkylsiloxanes, polyarylsiloxanes, polyalkylarylsiloxanes, polyethersiloxane copolymers, amine-functional silicones, or mixtures thereof.

[0116] The cosmetic composition of the present invention may contain 0.05 to 5% by weight, preferably 0.5 to 5% by weight, of at least one oil component. Typical oils are organic oils, often esters. The oil component may include glycerides or triglycerides of fatty acids, coconut oil, almond oil, apricot kernel oil, avocado oil, babassu oil, evening primrose oil, linseed oil, grapeseed oil, macadamia seed oil, corn oil, meadowfoam seed oil, mink oil, olive oil, palm kernel oil, safflower seed oil, sesame oil, soybean oil, sunflower oil, wheat germ oil, and camellia seed oil.

[0117] The cosmetic composition of the present invention may contain 0.05 to 5% by weight, preferably 0.5 to 5% by weight, of at least one emulsifier. Preferred emulsifiers are, for example, sorbitan esters.

[0118] The cosmetic composition of the present invention may contain 0.1 to 10% by weight, preferably 0.2 to 5% by weight, more preferably 0.2 to 3% by weight, and more preferably 0.5 to 5% by weight of at least one rheology modifier, in particular a gelling agent and a thickening agent. Examples are cellulosic thickeners, such as hydroxyethylcellulose, hydroxypropylcellulose and carboxymethylcellulose, guar gum, such as hydroxypropylguar gum, gums of microbial origin, such as xanthan gum and scleroglucan gum, and synthetic thickeners, such as crosslinked homopolymers or copolymers of acrylic acid and / or acrylamidopropanesulfonic acid. Other rheology modifiers include fatty acid amides such as coconut diethanolamide and coconut monoethanolamide, and oxyethylated monoethanolamides of carboxylic acid alkyl ethers.

[0119] Rheology modifiers are also known as structural materials. Common structural materials include polymeric materials known as "carbomers," including, for example, those available from Lubrizol Corporation under the trademark Another type of (meth)acrylic acid polymer is an alkali swellable emulsion (ASE) polymer. ASE polymers include, for example, 38 copolymers. Carbomer and ASE polymers belong to a class of materials known as hydrodynamic thickeners. These hydrodynamic thickeners contain acid groups in their polymer structure that, when deprotonated, form mutually repelling anionic charges, causing polymer chain expansion and entanglement. Expansion and chain entanglement can contribute to the thickening and suspending effects provided by the deprotonated polymers. The properties of these hydrodynamic thickeners are influenced by their molecular weight, acid group content, degree of crosslinking, and degree of swelling. These thickeners are also referred to as "space-filling" or "volume-excluding" and tend to increase both viscosity and yield point with increasing concentration. When used, hydrodynamic polymers typically cause compositions to exhibit shear-thinning or non-Newtonian behavior. Another type of (meth)acrylic acid-based rheology modifier is the hydrophobically modified alkali-swellable (HASE) polymer. Like ASE polymers, HASE polymers contain acid groups whose deprotonation causes the polymer to swell. Additionally, HASE polymers contain hydrophobic side groups, chains or blocks that cause associative interactions with each other and with other hydrophobic substances present in the composition employing the HASE polymer (e.g., hydrophobic groups of surfactants, fatty acids, other thickeners, etc.). The associative interactions create hydrophobic regions throughout the polymer chain network. This can also help improve the material's properties as a solubilizing agent. 22 and 28 copolymer and Aqua SF from Lubrizol Corporation These are commonly used HASE materials. U.S. Patent No. 4,529,773 (Witiak et al.) reports activation of alkali-soluble emulsion polymers by neutralization to a pH greater than 6.5 and subsequent acidification in the presence of a surfactant. These are described as useful thickeners in acidic compositions. The polymers are formed by copolymerization of a monomer system comprising: (1) methacrylic acid or acrylic acid, (2) a C8-C30 alkyl methacrylic acid or acrylic acid ester, or a hydrocarbyl monoether of a polyethylene glycol as more specifically described therein, (3) a C1-C4 alkyl acrylate or methacrylate, and optionally (4) a small amount of a polyethylenically unsaturated monomer.

[0120] The cosmetic composition of the present invention may further comprise a fatty compound as component (F). The fatty compound may be contained in the cosmetic composition in an amount of 0.1 to 20% by weight, preferably 1.0 to 10% by weight. The fatty compound is selected from fatty alcohols (e.g., cetyl alcohol, stearyl alcohol, or cetearyl alcohol), fatty acids, fatty alcohol derivatives, fatty acid derivatives, or mixtures thereof.

[0121] It should be understood that the disclosed components may fall into more than one classification in some cases, for example, some fatty alcohol derivatives may also be classified as fatty acid derivatives. However, a given classification is not intended to limit a particular compound, but is done for the convenience of classification and naming. Non-limiting examples are found in the International Cosmetic Ingredient Dictionary and Handbook, 14th edition (2014) and the CTFA Cosmetic Ingredient Handbook, 2nd edition, 1992. Preferably, the fatty alcohol has 14 to 30 or 16 to 22 carbon atoms. These fatty alcohols are saturated and can be linear or branched. Examples of fatty alcohols are cetyl alcohol, stearyl alcohol, behenyl alcohol and mixtures thereof. Preferred fatty acids have 10 to 30 or 12 to 22 carbon atoms. These fatty acids can be saturated and can be linear or branched. Salts of these fatty acids are also included herein. Examples of fatty acids are lauric acid, palmitic acid, stearic acid, behenic acid, sebacic acid or mixtures thereof.

[0122] Fatty alcohol derivatives and fatty acid derivatives useful herein include alkyl ethers of fatty alcohols, alkoxylated fatty alcohols, alkyl ethers of alkoxylated fatty alcohols, esters of fatty alcohols, fatty acid esters of compounds having esterifiable hydroxyl groups, hydroxy-substituted fatty acids, or mixtures thereof. Examples of fatty alcohol derivatives and fatty acid derivatives include methyl stearyl ether, polyoxyethylene ether of behenyl alcohol, ethyl stearate, cetyl stearate, cetyl palmitate, octadecyl stearate, myristyl myristate, polyoxyethylene cetyl ether stearate, polyoxyethylene stearyl ether stearate, polyoxyethylene lauryl ether stearate, ethylene glycol monostearate, polyoxyethylene monostearate, polyoxyethylene distearate, propylene glycol monostearate, propylene glycol distearate, trimethylolpropane distearate, sorbitan stearate, polyglyceryl stearate, glyceryl monostearate, glyceryl distearate, glyceryl tristearate, or mixtures thereof.

[0123] The cosmetic composition of the present invention may include an aqueous carrier. The content and type of the aqueous carrier are selected based on compatibility with the other components and other desired properties of the cosmetic composition. The aqueous carrier may, for example, be water or an aqueous solution of a lower alkanol or a polyhydric alcohol. The lower alkanol may, for example, be a monohydric alcohol having 1 to 6 carbon atoms, often ethanol and / or isopropyl alcohol. The polyhydric alcohol may, for example, be propylene glycol, hexylene glycol, glycerol and / or propylene glycol. Preferably, the aqueous carrier is essentially water. Deionized water is preferably used. Depending on the desired properties of the composition, water from natural sources, including mineral springs, may also be used. Typically, the cosmetic composition of the present invention may include up to 80% by weight, often even up to 95% by weight, of water.

[0124] The cosmetic composition of the present invention may further comprise other components as additional components (F) which are useful in making the composition more cosmetically or aesthetically acceptable or providing additional benefits to the composition. Such other components may generally be used individually in amounts of 0.001% to 5% by weight. Various additional components (F) may be formulated into the cosmetic composition of the present invention. These include conditioning agents such as panthenol, panthenylethyl ether, proteins, hydrolyzed proteins (preferably of vegetable or animal origin, such as hydrolyzed collagen or hydrolyzed keratin), nutrients, antioxidants such as vitamin E; emollients such as PPG-3 myristyl ether, trimethylpentyl hydroxyethyl ether; hair styling polymers such as amphoteric styling polymers, cationic styling polymers, anionic styling polymers, nonionic styling polymers, silicone graft copolymers; preservatives such as benzyl alcohol, methylparaben, propylparaben, imidazolidinyl urea; pH adjusting agents such as citric acid, sodium citrate, succinic acid, phosphoric acid, sodium hydroxide, sodium carbonate; salts, typically such as potassium acetate or sodium chloride; colorants; hair oxidizing (bleaching) agents such as hydrogen peroxide, perborates or persulfates; hair reducing agents such as thioglycolates; fragrances; and chelating agents such as disodium EDTA.

[0125] Preferably, the salt is present in an amount of 0.1 to 1 wt. % of the total cosmetic composition to adjust the product viscosity. Preferably, NaOH is present in an amount of 0.1 to 1 wt. % of the total cosmetic composition to adjust the pH of the formulation.

[0126] The cosmetic composition of the present invention may contain a polysorbate as an additional component (F) to adjust rheological properties, for example polysorbate-20, polysorbate-21, polysorbate-40, polysorbate-60 or a mixture thereof. The polysorbate may be included in the cosmetic composition in an amount of up to 5% by weight (e.g., 0.1 to 5% by weight).

[0127] The cosmetic composition of the present invention may also contain polypropylene glycol as an additional component (F). Preferred polypropylene glycols are those having a weight average molecular weight of 200 to 100,000 g / mol. The polypropylene glycol may be water-soluble, water-insoluble, or have limited solubility in water, depending on the degree of polymerization and whether there are other structural moieties attached to it. The desired solubility of the polypropylene glycol in water will largely depend on the form of the composition (e.g., a leave-on composition, a rinse-off composition). The polypropylene glycol may be included in the cosmetic composition of the present invention in an amount of up to 10% by weight.

[0128] For example, in a rinse-off composition, the polypropylene glycol preferably has a solubility in water at 25° C. of less than about 1 g / 100 g of water, more preferably less than about 0.5 g / 100 g of water, and even more preferably less than about 0.1 g / 100 g of water. The polypropylene glycol may be included in the cosmetic composition of the present invention in an amount of up to 10% by weight.

[0129] The cosmetic composition of the present invention may also contain a low-melting-point oil as an additional component (F), the low-melting-point oil being selected from hydrocarbons having 10 to 40 carbon atoms; unsaturated fatty alcohols having 10 to 30 carbon atoms, such as oleyl alcohol; unsaturated fatty acids having from about 10 to about 30 carbon atoms; fatty acid derivatives; fatty alcohol derivatives; ester oils such as pentaerythritol ester oils, trimethylol ester oils, citrate oils, or glyceride oils; poly[α]-olefin oils, and mixtures thereof. Preferred low-melting-point oils are selected from ester oils such as pentaerythritol ester oils, trimethylol ester oils, citrate oils, or glyceride oils; poly[α]-olefin oils, and mixtures thereof. Particularly useful pentaerythritol ester oils and trimethylol ester oils are pentaerythritol tetraisostearate, pentaerythritol tetraoleate, trimethylolpropane triisostearate, trimethylolpropane trioleate, or mixtures thereof. Particularly useful glycerides are triisostearin, triolein, or trilinolein.

[0130] The cosmetic composition of the present invention may also contain a cationic polymer as an additional component (F). Cationic polymers may be present in the cosmetic composition of the present invention to further enhance deposition properties.

[0131] Suitable cationic polymers can be cationically substituted homopolymers or can be formed from two or more types of monomers. The weight average (Mw) molecular weight of the polymer will generally be 100,000 to 2,000,000 g / mol. The polymer will have groups containing nitrogen cations such as quaternary ammonium or protonated amino groups or combinations thereof. If the molecular weight of the polymer is too low, the conditioning effect will be poor. If too high, there may be a problem where high extensional viscosity causes the composition to draw when poured.

[0132] The group containing the nitrogen cation will generally exist as a substituent on a portion of the total monomer units of the cationic polymer. Therefore, when the polymer is not a homopolymer, it may contain a non-cationic spacer monomer unit. Such polymers are described in the CTFA Cosmetic Ingredient Directory, 3rd edition. The ratio of cationic and non-cationic monomer units is selected to provide a polymer with a cationic charge density within the desired range, typically 0.2 to 3.0 meq / gm. The cationic charge density of the polymer is suitably measured by the Kjeldahl method described in the chemical test for nitrogen determination in the United States Pharmacopoeia (US Pharmacopoeia).

[0133] Suitable cationic polymers include, for example, copolymers of vinyl monomers with cationic amine or quaternary ammonium functional groups and water-soluble spacer monomers, such as (meth) acrylamide, alkyl and dialkyl (meth) acrylamide, alkyl (meth) acrylate, vinyl caprolactone and vinyl pyrrolidine. Alkyl and dialkyl substituted monomers preferably have C1-C7 alkyl groups, more preferably C1-3 alkyl groups. Other suitable spacers include vinyl esters, vinyl alcohol, maleic anhydride, propylene glycol and ethylene glycol. Cationic amines can be primary amines, secondary amines or tertiary amines, depending on the specific material and pH of the composition. Generally, secondary amines and tertiary amines, particularly tertiary amines, are preferred. Amine-substituted vinyl monomers and amines can be polymerized in the form of amines and then converted into ammonium by quaternization. Cationic polymers can include monomer units derived from amine and / or quaternary ammonium-substituted monomers and / or a mixture of compatible spacer monomers.

[0134] Suitable cationic polymers include, for example, cationic diallyl quaternary ammonium-containing polymers, including, for example, dimethyldiallylammonium chloride homopolymer, and copolymers of acrylamide and dimethyldiallylammonium chloride, known in the industry (CTFA) as Polyquaternium 6 and Polyquaternium 7, respectively; inorganic acid salts of amino-alkyl esters of homopolymers and copolymers of unsaturated carboxylic acids having 3 to 5 carbon atoms, as described in US Pat. No. 4,009,256 Al (NAT STARCH CHEM CORP); cationic polyacrylamides, as described in WO 95 / 22311 Al (Unilever PLC).

[0135] Other useful cationic polymers include cationic polysaccharide polymers, such as cationic cellulose derivatives, cationic starch derivatives, and cationic guar gum derivatives.

[0136] Cationic polysaccharide polymers suitable for use in the cosmetic compositions of the present invention include monomers of the formula: AO-[RN + (R1)(R2)(R3)X - ], wherein: A is an anhydroglucose residue, such as an anhydroglucose residue of starch or cellulose. R is an alkylene, oxyalkylene, polyoxyalkylene or hydroxyalkylene group or a combination thereof. R1, R2 and R3 independently represent an alkyl, aryl, alkylaryl, arylalkyl, alkoxyalkyl or alkoxyaryl group, each containing up to about 18 carbon atoms. The total number of carbon atoms in each cationic moiety (i.e., the sum of the carbon atoms in R1, R2 and R3) is preferably about 20 or less, and X - is an anionic counterion. Another type of cationic cellulose includes polymeric quaternary ammonium salts of hydroxyethyl cellulose reacted with lauryl dimethyl ammonium substituted epoxide, known in the industry (CTFA) as Polyquaternium 24. These materials are available from Amerchol Corporation, for example, under the trade name Polymer LM-200. Other suitable cationic polysaccharide polymers include quaternary nitrogen-containing cellulose ethers (such as those described in US Pat. No. 3,962,418 (L'Oréal)), and copolymers of etherified cellulose and starch (such as those described in US Pat. No. 3,958,581 (L'Oréal)).

[0137] A particularly suitable type of cationic polysaccharide polymer that can be used is a cationic guar gum derivative, such as guar hydroxypropyltrimonium chloride (commercially available from Solvay under their JAGUAR trade name series). Examples of such materials are JAGUAR C13S, JAGUAR C14, JAGUAR C15, JAGUAR C17, JAGUAR C16, JAGUAR CHT, and JAGUAR C162.

[0138] Mixtures of any of the above cationic polymers may be used.The cationic polymer may be present in the cosmetic composition in an amount of 0.01 to 5 wt%, preferably 0.05 to 1 wt%, more preferably 0.08 to 0.5 wt% of the total weight of the cationic polymer, based on the total weight of the cosmetic composition.

[0139] In at least one embodiment, the cationic polymer has a number average molecular weight of at least about 5000 g / mol, typically 10,000 g / mol to 10,000,000 g / mol, and is selected from copolymers of vinyl monomers having cationic amine or quaternary ammonium functionality and water-soluble spacer monomers such as acrylamide, methacrylamide, alkyl and dialkyl acrylamides, alkyl and dialkyl methacrylamides, alkyl acrylates, alkyl methacrylates, vinyl caprolactone, and vinyl pyrrolidone. Other suitable spacer monomers include vinyl esters, vinyl alcohol, maleic anhydride, propylene glycol, and ethylene glycol. Preferred cationic polymers are cationic cellulose, cationic starch, and cationic guar gum. Commercially available cationic guar polymers are, for example, GLUTAMATE® from Solvay

[0140] In at least one embodiment, the cosmetic composition of the present invention 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 cosmetic composition of the present invention comprises a total amount of surfactants in an amount of 0.01% to 70%, 0.1% to 40%, 1% to 30%, or 2% to 20% by weight.

[0141] In at least one embodiment, the cosmetic composition of the present invention comprises an anionic surfactant. In at least one embodiment, the anionic surfactant is selected from the group consisting of (C10-C20)-alkyl and alkylene carboxylates, alkyl ether carboxylates, fatty alcohol sulfates, fatty alcohol ether sulfates, alkylamide sulfates and sulfonates, fatty acid alkylamide polyglycol ether sulfates, alkane sulfonates and hydroxyalkane sulfonates, olefin sulfonates, acyl isethionates, α-sulfo fatty acid esters, alkylbenzene sulfonates, alkylphenol glycol ether sulfonates, sulfosuccinates, sulfosuccinic acid monoesters and diesters, fatty alcohol ether phosphates, protein / fatty acid condensation products, alkyl monoglycerol sulfates and sulfonates, alkyl glyceryl ether sulfonates, fatty acid methyl taurates, fatty acid sarcosinates, sulforicinoleates, acyl glutamates, and mixtures thereof. Anionic surfactants (and mixtures thereof) can be used in the form of their water-soluble or water-dispersible salts, examples being sodium, potassium, magnesium, ammonium, mono-, di- 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 myristeth sulfate, and mixtures thereof. Common anionic surfactants for use in the cosmetic compositions of the present invention include sodium oleyl succinate, ammonium lauryl sulfosuccinate, sodium lauryl sulfate, sodium lauryl ether sulfate, sodium lauryl ether sulfosuccinate, ammonium lauryl sulfate, ammonium lauryl ether sulfate, sodium dodecylbenzenesulfonate, triethanolamine dodecylbenzenesulfonate, sodium cocoyl isethionate, sodium lauryl isethionate, lauryl ether carboxylic acid, and sodium N-lauryl sarcosinate. Preferably, the anionic surfactant is selected from sodium lauryl sulfate, and sodium lauryl ether sulfate (n) EO, wherein n is 1 to 3; more preferably sodium lauryl ether sulfate (n) EO, wherein n is 1 to 3; most preferably sodium lauryl ether sulfate (n) EO, wherein n is 1. Preferably, the alkyl ether sulfate is present in an amount of 0.5 to 25 wt % of the total composition, more preferably 3 to 18 wt % of the total composition, and most preferably 6 to 15 wt %.

[0142] The total amount of anionic surfactants in the cosmetic composition of the present invention may range from 0.5% to 45% by weight, more preferably from 1.5% to 20% by weight.

[0143] The cosmetic compositions of the present invention may include fatty acyl isethionates, if present, preferably in an amount of 1 to 10 wt%, more preferably 2 to 8 wt%, and most preferably 2.5 to 7.5 wt%. Preferred fatty acyl isethionate products comprise fatty acyl isethionate surfactants at a level of 40 to 80 wt% of the product, and free fatty acids and / or fatty acid salts at a level of 15 to 50 wt%. Preferably, greater than 20 wt% and less than 45 wt%, more preferably greater than 25 wt% and less than 45 wt%, of the fatty acyl isethionates have a chain length greater than or equal to C16; and greater than 50 wt%, preferably greater than 60 wt%, of the free fatty acids / soaps have a chain length of C16 to C20. Additionally, the product may contain isethionates, typically present at a level of less than 5 wt%, and trace amounts (less than 2 wt%) of other impurities.

[0144] Preferably, a mixture of fatty fatty acids is used to prepare commercial fatty acyl isethionate surfactants. The resulting fatty acyl isethionate surfactant (e.g., produced by the reaction of an alkali metal isethionate salt with a fatty fatty acid) should preferably have greater than 20%, preferably greater than 25%, but not greater than 45%, preferably 35%, by weight (based on the fatty acyl isethionate reaction product) of fatty acyl groups having 16 or more carbon atoms to provide excellent lather and mildness to the resulting fatty acyl isethionate product. These longer chain fatty acyl isethionate surfactants and fatty acids, i.e., fatty acyl groups and fatty acids having 16 or more carbon atoms, can generally form insoluble surfactant / fatty acid crystals in water at ambient temperature.

[0145] In at least one embodiment, the cosmetic composition of the present invention comprises an acyl glycinate surfactant. In at least one embodiment, the acyl glycinate (acylglycine) surfactant conforms to formula (Y):

[0146]

[0147] in

[0148] 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 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

[0149] Q a + It is a cation.

[0150] In at least one embodiment, Q a + Selected from Li + 、Na + , K + Mg ++ , Ca ++ 、Al +++ NH4 + In at least one embodiment, the acyl glycinate (acylglycine) surfactant is selected from the group consisting of sodium cocoyl glycinate and potassium cocoyl glycinate. In at least one embodiment, the acyl glycinate (acylglycine) surfactant is selected from the group consisting of those of formula (Y), wherein R is a C12 alkyl group or a C14 alkyl group. In at least one embodiment, the acyl glycinate (acylglycine) surfactant is selected from the group consisting of those of formula (Y), wherein R is a C16 alkyl group or a C18 alkyl group.

[0151] In at least one embodiment, the cosmetic composition comprises from 0.01% to 30% by weight, or from 1% to 25% by weight, preferably from 5% to 20% by weight, more preferably from 12% to 18% by weight of anionic surfactant.

[0152] In at least one embodiment, the cosmetic composition of the present invention comprises a glutamate (glutamic acid) surfactant or a salt thereof corresponding to formula (Z):

[0153]

[0154] Where R' is HOOC-CH2-CH2- or M +- OOC-CH2-CH2- where M + is a cation; and wherein 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 a linear or branched, mono- or polyunsaturated 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 + Selected from Li + 、Na + , K + Mg ++ , Ca ++ 、Al +++ NH4 +In at least one embodiment, the surfactant is selected from the group consisting of sodium cocoyl glutamate and potassium cocoyl glutamate. In at least one embodiment, the surfactant is selected from the group consisting of sodium cocoyl glutamate and potassium cocoyl glutamate. In at least one embodiment, the surfactant is selected from the group consisting of sodium cocoyl glutamate and potassium cocoyl glutamate. In at least one embodiment, the surfactant is selected from the group consisting of sodium cocoyl glutamate and potassium cocoyl glutamate. In at least one embodiment, the surfactant is selected from the group consisting of sodium cocoyl glutamate and potassium cocoyl glutamate. In at least one embodiment, the surfactant is selected from the group consisting of sodium cocoyl glutamate and potassium cocoyl glutamate. In at least one embodiment, the surfactant is selected from the group consisting of sodium cocoyl glutamate and potassium cocoyl glutamate.

[0155] In at least one embodiment, the cosmetic compositions of the present invention include a nonionic surfactant. The nonionic surfactant may be present in the range of 0 to 5 weight percent. Nonionic surfactants that may be included in the cosmetic compositions of the present invention include condensation products of aliphatic primary or secondary linear or branched alcohols or phenols with an alkylene oxide, typically ethylene oxide and typically having 6 to 30 alkylene oxides. Alkyl ethoxylates are particularly preferred. Most preferred are alkyl ethoxylates having the formula

[0156] R-(OCH2CH2) n OH,

[0157] wherein R is a C12 to C15 alkyl chain and n is 5 to 9. Other suitable nonionic surfactants include mono- or di-alkyl alkanolamides. Examples include coconut mono- or diethanolamide and coconut monoisopropanolamide.

[0158] Another nonionic surfactant that can be included in the cosmetic composition of the present invention is an alkyl polyglycoside (APG). Generally, APGs contain an alkyl group connected (optionally via a bridge group) to a block of one or more glycosyl groups. Preferably, APGs are defined by the following formula:

[0159] RO-(G) n

[0160] wherein R is a branched or straight chain alkyl group, which may be saturated or unsaturated, and G is a saccharide group. R may represent an average alkyl chain length of about C5 to about C20. Preferably, R represents an average alkyl chain length of about C9 to about C12. G may be selected from a C5 or C6 monosaccharide residue, and is preferably a glucoside. G may be selected from glucose, xylose, lactose, fructose, mannose, and derivatives thereof. Preferably, G is glucose. The degree of polymerization, n, may have a value of about 1 to about 10 or more. Most preferably, the value of n is between about 1.3 and about 1.5. Alkyl polyglycosides suitable for use in the present invention are commercially available and include, for example, those identified as: Oramix NS10 ex Seppic; Plantaren 1200 and Plantaren 2000 ex Henkel.

[0161] Other sugar-derived nonionic surfactants that may be included in the cosmetic compositions of the present invention include fatty (e.g., C10-C18) N-alkyl (C1-C6) polyhydroxy fatty acid amides, such as C12-C18 N-methyl glucamide, for example as described in WO9206154 and US5194639, and N-alkoxy polyhydroxy fatty acid amides.

[0162] In at least one embodiment, the nonionic surfactant has an HLB (hydrophile-lipophile balance) greater than 12. Optionally, the nonionic surfactant is selected from ethoxylated or ethoxylated / propoxylated fatty alcohols having a fatty chain containing 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.

[0163] In at least one embodiment, the nonionic surfactants are selected from ethoxylated fatty alcohols, fatty acids, fatty acid glycerides or alkylphenols, in particular the products of addition of 2 to 30 mol of ethylene oxide and / or 1 to 5 mol of propylene oxide to C8- to C22-fatty alcohols, to C12- to C22-fatty acids or to alkylphenols having 8 to 15 carbon atoms in the alkyl radical, the products of addition of 1 to 30 mol of ethylene oxide to glycerol, the products of addition of 5 to 60 mol of ethylene oxide to castor oil or to hydrogenated castor oil, C12- to C22-fatty acid mono- and diesters, fatty acid sugar esters, in particular esters of sucrose and one or two C8- to C22-fatty acids. , INCI: Sucrose cocoate, sucrose dilaurate, sucrose distearate, sucrose laurate, sucrose myristate, sucrose oleate, sucrose palmitate, sucrose ricinoleate, sucrose stearate, esters of sorbitan and one, two or three C8- to C22-fatty acids and a degree of ethoxylation of 4 to 20, polyglycerol fatty acid esters, in particular polyglycerol fatty acid esters of one, two or more C8- to C22-fatty acids and polyglycerol having preferably 2 to 20 glyceryl units, alkyl glucosides, alkyl oligoglucosides and alkyl polyglucosides having C8- to C22-alkyl groups, for example decyl glucoside or lauryl glucoside, and mixtures thereof.

[0164] In at least one embodiment, the nonionic surfactant is selected from the group consisting of 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 Fatty acid alkylolamides, (fatty acid amide polyethylene glycol), N-alkyl-, N-alkoxy polyhydroxy fatty acid amides, sucrose esters, sorbitan esters, polyglycol ethers and mixtures thereof.

[0165] In at least one embodiment, the cosmetic composition of the present invention comprises a fatty N-methyl-N-glucamide surfactant. In at least one embodiment, the fatty N-methyl-N-glucamide surfactant conforms to formula (X):

[0166]

[0167] in

[0168] R is a linear or branched alkyl or alkenyl group with 3 to 30 carbon atoms. In at least one embodiment, R is an alkyl group with 3 to 30 carbon atoms. In at least one embodiment, R is a saturated aliphatic hydrocarbon group, which can be linear or branched and can have 3 to 20 carbon atoms in a hydrocarbon chain (preferably linear or branched). Branched means that low alkyl groups such as methyl, ethyl or propyl exist as the substituent on the linear alkyl chain. In at least one embodiment, R is selected from 1-propyl, 2-propyl, 1-butyl, 2-butyl, 2-methyl-1-propyl (isobutyl), 2-methyl-2-propyl (tert-butyl), 1-pentyl, 2-pentyl, 3-pentyl, 2-methyl-1-butyl, 3-methyl-1-butyl, 2-methyl-2-butyl, 3-methyl-2-butyl, 2,2-dimethyl-1-propyl, 1-hexyl, 2-hexyl, 3-hexyl, 2-methyl-1-pentyl, 3-methyl-1-pentyl, 4-methyl-1-pentyl, 2-methyl-2-butyl, 3-methyl-2-butyl, 2,2-dimethyl-1-propyl, 1-hexyl, 2-hexyl, 3-hexyl, 2-methyl-1-pentyl, 3-methyl-1-pentyl, 4-methyl-1-pentyl, 2 1- alkyl, 1- alkyl, 1- alkyl-2- alkyl, 1- alkyl-3- alkyl, 1- alkyl-4- alkyl, 1- alkyl-5- alkyl, 1- alkyl-6- alkyl, 1- alkyl-7- alkyl, 1- alkyl-8- alkyl, 1- alkyl-9- alkyl, 1- alkyl-10- alkyl, 1- alkyl-11- alkyl, 1- alkyl-12- alkyl, 1- alkyl-13- alkyl, 1- alkyl-14- alkyl, 1- alkyl-15- alkyl, 1- alkyl-16- alkyl, 1- alkyl-17- alkyl, 1- alkyl-18- alkyl, 1- alkyl-19- alkyl, 1- alkyl-20- alkyl, 1- alkyl-21- alkyl, 1- alkyl-22- alkyl, 1- alkyl-23- alkyl, 1- alkyl-24- alkyl, 1- alkyl-25- alkyl, 1- alkyl-26- alkyl, 1- alkyl-27- alkyl, 1- alkyl-28- alkyl, 1- alkyl-29- alkyl, 1- alkyl-21- alkyl, 1- alkyl-2 In at least one embodiment, the N-methyl-N-glucamide surfactant is selected from those conforming to formula (X), wherein R is a C16 alkyl or a C18 alkyl.

[0169] In at least one embodiment, the cosmetic composition of the present invention comprises from 1% to 20%, more preferably from 2% to 10%, still more preferably from 3% to 7% by weight of a nonionic surfactant.

[0170] Amphoteric or zwitterionic surfactants may be included in the cosmetic compositions of the present invention in amounts ranging from 0.5% to about 8%, preferably from 1% to 4%, by weight of the total composition.

[0171] 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-iminodipropionate as alkali metal salts and mono-, di- and trialkylammonium salts; N-acylaminoalkyl-N,N-dimethylacetyl betaine, preferably N-(C8-C 18 )-acylaminopropyl-N,N-dimethylacetyl betaine; (C 12 -C 18 )-alkyl-dimethyl-sulfopropyl betaine; imidazoline-based amphoteric surfactant (trade name: ), preferably the sodium salt of 1-(β-carboxymethoxyethyl)-1-(carboxymethyl)-2-laurylimidazoline; amine oxides, such as (C 12 -C 18 )-alkyl-dimethylamine oxide, fatty acid amide alkyl dimethylamine oxide and mixtures thereof.

[0172] In at least one embodiment, the cosmetic composition of the present invention comprises a betaine surfactant. Optionally, the betaine surfactant is selected from C8- to C18-alkyl betaines. In at least one embodiment, the betaine surfactant is selected from cocodimethyl carboxymethyl betaine, lauryldimethyl carboxymethyl betaine, lauryldimethyl α-carboxyethyl betaine, cetyldimethyl carboxymethyl betaine, oleyldimethyl γ-carboxypropyl betaine, and laurylbis(2-hydroxypropyl)α-carboxyethyl betaine, and combinations thereof. Optionally, the betaine surfactant is selected from C8- to C18-sulfobetaines. In at least one embodiment, the betaine surfactant is selected from cocodimethyl sulfopropyl betaine, stearyldimethyl sulfopropyl betaine, lauryldimethyl sulfoethyl betaine, laurylbis(2-hydroxyethyl)sulfopropyl betaine, and combinations thereof. Optionally, the betaine surfactant is selected from carboxyl derivatives of imidazole, C8- to C18-alkyldimethylammonium acetate, C8- to C18-alkyldimethylcarbonylmethylammonium salt, and C8- to C18-fatty acid alkylamido betaines, and mixtures thereof. Optionally, the C8- to C18-fatty acid alkylamido betaines are selected from coconut fatty acid amidopropyl betaine, N-coconut fatty acid amidoethyl-N-[2-(carboxymethyloxy)ethyl]glycerol (CTFA name: cocoamphocarboxyglycinate), and mixtures thereof. A particularly preferred amphoteric or zwitterionic surfactant is cocoamphopropyl betaine. Mixtures of any of the aforementioned amphoteric or zwitterionic surfactants may also be suitable. A preferred mixture is a mixture of cocoamphopropyl betaine with another amphoteric or zwitterionic surfactant described above. A preferred other amphoteric or zwitterionic surfactant is sodium cocoamphoacetate.

[0173] In at least one embodiment, the cosmetic composition of the present invention comprises from 0.5% to 20% by weight, preferably from 1% to 10% by weight, of an amphoteric surfactant.

[0174] In at least one embodiment, the cosmetic composition of the present invention comprises a surfactant system. In at least one embodiment, the surfactant system comprises at least one surfactant selected from the group consisting of lauryl sulfate, laureth sulfate, cocamidopropyl betaine, sodium cocoyl glutamate, lauryl amphoacetate, 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.

[0175] In at least one embodiment, the cosmetic composition of the present invention contains an organosilicon compound as an additional component. The cosmetic composition may contain up to 5% by weight (e.g., 0.1 to 5% by weight) of the organosilicon compound. Suitable organosilicon compounds include polyalkyl or polyaryl siloxanes. Preferred organosilicon compounds are polydimethylsiloxanes, polydiethylsiloxanes, and polymethylphenylsiloxanes, such as those available from Wacker (Germany) or Dow Corning, such as Xiameter PMX DC 200. The organosilicon compound can be obtained as an organosilicon oil or emulsion. The organosilicon compound can be additionally incorporated into the composition of the present invention in the form of an emulsion, wherein the emulsion is preformed and added to the formulation, or is prepared by mechanical stirring during the formulation process, with or without the aid of an additional surfactant selected from anionic surfactants, nonionic surfactants, cationic surfactants, and mixtures thereof.

[0176] In at least one embodiment, the cosmetic composition of the present invention contains a silicone conditioning agent. Preferably, they are emulsified droplets of silicone conditioning agents. They are used to enhance conditioning performance.

[0177] Suitable silicones include polydiorganosiloxanes, in particular polydimethylsiloxanes, which have the CTFA name dimethicone. Also suitable for use in the cosmetic compositions of the present invention are polydimethylsiloxanes having hydroxyl end groups, which have the CTFA name dimethiconol. Also suitable for use in the cosmetic compositions of the present invention are slightly cross-linked silicone rubbers, such as described in WO 96 / 31188. The viscosity of the emulsified silicone itself (not the emulsion or the final composition) is typically at least 10,000 cSt at 25°C. The viscosity of the silicone itself is preferably at least 60,000 cSt, most preferably at least 500,000 cSt, ideally at least 1,000,000 cSt. Preferably, the viscosity does not exceed 1 x 10 9 cSt for ease of formulation. The emulsified silicone used in the cosmetic compositions of the present invention will typically have an average silicone droplet size in the composition of less than 30, preferably less than 20, more preferably less than 10 microns, ideally 0.01 to 1 micron. Silicone emulsions having an average silicone droplet size of less than 0.15 microns are generally referred to as microemulsions.

[0178] Silicone particle size can be measured by laser scattering techniques, for example using a 2600D Particle Sizer from Malvern Instruments. Examples of suitable pre-formed emulsions include Xiameter MEM 1785 and microemulsion DC2-1865 available from Dow Corning. These are emulsions / microemulsions of dimethiconol. Cross-linked silicone rubbers are also available in pre-emulsified form, which is advantageous for ease of formulation. Another preferred type of silicone for inclusion in the cosmetic composition of the present invention is amino-functional silicone. "Amino-functional silicone" means a silicone containing at least one primary, secondary, or tertiary amine group, or a quaternary ammonium group. Examples of suitable amino-functional silicones include polysiloxanes having the CTFA designation "amodimethicone." Specific examples of aminofunctional silicones suitable for use in the cosmetic compositions of the present invention are aminosilicone oils DC2-8220, DC2-8166 and DC2-8566 (all available from Dow Corning). Suitable quaternary silicone polymers are described in EP-A-0 530 974. A preferred quaternary silicone polymer is K3474 available from Goldschmidt.

[0179] Also suitable are emulsions of amino-functional silicone oils with nonionic and / or cationic surfactants. Preformed emulsions of amino-functional silicones can also be obtained from suppliers of silicone oils such as Dow Corning and General Electric. Specific examples include DC939 cationic emulsion and nonionic emulsions DC2-7224, DC2-8467, DC2-8177, and DC2-8154 (all available from Dow Corning).

[0180] Combinations of amino and non-amino functional silicones may also be used.

[0181] The total amount of silicone is preferably from 0.01 to 10 wt %, more preferably from 0.1 to 5 wt %, most preferably from 0.5 to 3 wt % of the total composition.

[0182] In at least one embodiment, the cosmetic composition of the present invention comprises a preservative or preservative system. Examples of suitable preservatives include benzyl alcohol, phenoxyethanol, parabens, benzoic acid / sodium benzoate, sorbic acid / potassium sorbate, and other organic acids used to provide antimicrobial protection. In at least one embodiment, the cosmetic composition comprises 0.01 to 5% by weight, particularly preferably 0.05 to 1% by weight, of at least one preservative. Suitable preservatives are substances listed as having a "preservative" function in the International Cosmetic Ingredient Dictionary and Handbook, 9th edition. In at least one embodiment, the preservative is selected from phenoxyethanol, benzyl paraben, butyl paraben, ethyl paraben, isobutyl paraben, isopropyl paraben, methyl paraben, propyl paraben, iodopropynyl butylcarbamate, methyldibromoglutaronitrile, DMDM hydantoin, and combinations thereof. In at least one embodiment, the cosmetic composition comprises a preservative selected from the group consisting of cetyltrimethylammonium chloride, cetylpyridinium hydrochloride, benzethonium chloride, diisobutylethoxyethyldimethylbenzyl ammonium chloride, sodium N-lauryl sarcosinate, sodium N-palmitylmethyl sarcosinate, lauroyl sarcosine, N-myristoyl glycine, potassium N-lauryl sarcosinate, trimethylammonium chloride, sodium aluminum chlorohydroxyacetate, triethyl citrate, tricetylmethylammonium chloride, 2,4,4'-trichloro-2'-hydroxydiphenyl ether, phenoxyethanol, 3,4,4'-trichloro-N-carbanilide (Triclocarban), diaminoalkylamides , L-lysine hexadecylamide, heavy metal salts of citric acid, zinc salts, phenol zinc sulfate, farnesol, naftifone, terbinafine, selenium disulfide, methylchloroisothiazolinone, methylisothiazolinone, methyldibromoglutaronitrile, AgCl, chloroxylenol, sodium salt of diethylhexyl sulfosuccinate, sodium benzoate, phenoxyethanol, benzyl alcohol, phenoxyisopropanol, parabens such as butyl, ethyl, methyl and propyl paraben, and their salts, sorbic acid, benzoic acid, lactic acid, imidazolidinyl urea, diimidazolidinyl urea, dimethyloldimethylhydantoin (DMDMH), sodium salt of hydroxymethylglycinate, hydroxyethylglycine of sorbic acid, and combinations thereof. In at least one embodiment, the preservative is selected from the group consisting of phenoxyethanol, benzyl paraben, butyl paraben, ethyl paraben, isobutyl paraben, isopropyl paraben, methyl paraben, propyl paraben, iodopropynyl butylcarbamate, methyldibromoglutaronitrile, DMDM hydantoin, and combinations thereof. In at least one embodiment, the cosmetic composition of the present invention is substantially free of parabens.

[0183] The cosmetic compositions of the present invention may also contain a dispersed, non-volatile, water-insoluble oily conditioning agent. "Insoluble" means that the material is not soluble in water (distilled or equivalent) at a concentration of 0.1% (w / w) at 25°C.

[0184] Suitable oiliness or fatty material are selected from hydrocarbon oil, fatty ester and its mixture.Straight chain hydrocarbon oil will preferably contain about 12 to about 30 carbon atoms.Also be suitable for the polymeric hydrocarbon of olefinic monomer for example C2-C6 olefinic monomer.The specific example of suitable hydrocarbon oil comprises paraffin oil, mineral oil, saturated and unsaturated 12 carbon hydrocarbons (dodecane), saturated and unsaturated 13 carbon hydrocarbons (tridecane), saturated and unsaturated 14 carbon hydrocarbons (tetradecane), saturated and unsaturated 15 carbon hydrocarbons (pentadecane), saturated and unsaturated 16 carbon hydrocarbons (hexadecane) and its mixture.Can also use the branched isomer of these compounds and the hydrocarbon of chain length longer.

[0185] Suitable fatty esters are characterized in that they have at least 10 carbon atoms and include esters with a hydrocarbyl chain derived from a fatty acid or alcohol. Monocarboxylic acid esters include alcohols and / or acid esters of the formula R'COOR, wherein R' and R independently represent an alkyl or alkenyl group and the sum of carbon atoms in R' and R is at least 10, preferably at least 20. Di- and tri-alkyl and alkenyl esters of carboxylic acids can also be used. Particularly preferred fatty esters are mono-, di- and tri-glycerides, more particularly glycerol and long-chain carboxylic acids such as mono-, di- and tri-esters of C8-C22 carboxylic acids. Preferred materials include cocoa butter, palm stearin, sunflower oil, soybean oil and coconut oil.

[0186] The oily or fatty material may be present in an amount of 0.05 to 10 wt%, preferably 0.2 to 5 wt%, more preferably 0.5 to 3 wt%, based on the total weight of the cosmetic composition.

[0187] In a particularly preferred embodiment, the composition of the present invention is a shampoo composition.

[0188] In at least one embodiment, the shampoo composition comprises 1 to 99% by weight, preferably 5 to 95% by weight, more preferably 10 to 90% by weight of water, based on the total composition, and 0.1 to 99% by weight, preferably 1 to 95% by weight, more preferably 5 to 90% by weight, and often 5 to 25% by weight of a cleansing surfactant, based on the total composition. Suitable cleansing surfactants are typically anionic, amphoteric, betaine, or zwitterionic surfactants. For example, the anionic surfactant is an alkyl ether or alkyl ether sulfate, such as sodium lauryl sulfate, or other compounds described above.

[0189] In at least one embodiment, the shampoo composition comprises one or more additional cosmetically acceptable components (F), which may be present in an amount of at least 0.5% by weight, or from 0.5 to 20% by weight, based on the total weight of the shampoo composition. Preferably, component (F) is selected from cleansing ingredients, acidity regulators, colorants, conditioners, emulsifiers, film formers, fragrances, glossing agents, humectants, lubricants, moisturizers, pigments, preservatives, transdermal absorption enhancers, scalp actives, stabilizers, surfactants, thickeners, and viscosity regulators, and combinations thereof. More preferably, component (F) is selected from surfactants, viscosity regulating polymers, and conditioning ingredients. In at least one embodiment, the shampoo composition comprises 0.05% to 5% by weight (preferably 0.1% to 2.0% by weight, more preferably 0.1% to 1.0% by weight, particularly preferably 0.1% to 0.5% by weight) of piroctone and at least 0.5% by weight of one or more additional components (F) selected from surfactants, polymers, conditioners, actives, acid regulators, lubricants, moisturizers, oils, preservatives, chelating agents, strengtheners, sunscreens, and combinations thereof.

[0190] In at least one embodiment, the shampoo composition comprises a cleansing ingredient as an additional cosmetically acceptable component (F). In at least one embodiment, the shampoo composition comprises 0.05 to 20% by weight of the cleansing ingredient, based on the total weight of the shampoo composition. In at least one embodiment, the cleansing ingredient is present in an amount of 1 to 20% by weight, preferably 5 to 18%, more preferably 8 to 16%, based on the total weight of the shampoo composition. In at least one embodiment, the cleansing ingredient is selected from non-polymeric surfactants, saponins, polymeric surfactants, and combinations thereof. Preferably, the cleansing ingredient comprises or consists of a surfactant.

[0191] In at least one embodiment, the shampoo composition comprises 0.05% to 5% by weight (preferably 0.1% to 2.0% by weight, more preferably 0.1% to 1.0% by weight, particularly preferably 0.1% to 0.5% by weight) of piroctone, and at least 0.5% by weight of a surfactant, preferably a cleansing anionic or nonionic surfactant, such as sodium laureth sulfate, sodium lauryl sulfate, ammonium laureth sulfate, ammonium lauryl sulfate, olefin sulfonates, olefin sulfates. ), Laureth-3 or -4, Cocamide DEA, Glucoside, Cocamidopropyl Betaine, Coco-Betaine, Cocoamphodipropionate, Sodium Methyl 2-Sulfolaurate and other Laurates, Sulfoacetates, Sulfosuccinates, Lactates, Sulfobetaine, Caprylate / Caprate, Isethionates, Glutamate, Taurate, Sarcosinate, Glucosamide, and combinations thereof.

[0192] In at least one embodiment, the shampoo composition is free of silicone. In at least one embodiment, the shampoo composition is free of sulfate. In at least one embodiment, the shampoo composition is free of silicone and free of sulfate.

[0193] In at least one embodiment, the shampoo composition comprises, based on the total weight of the shampoo composition:

[0194] (i) 0.05 to 5% by weight, preferably 0.1 to 2.0% by weight, more preferably 0.1 to 1.0% by weight, particularly preferably 0.1 to 0.5% by weight, of piroctone;

[0195] (ii) 5% to 20% by weight of one or more anionic surfactants;

[0196] (iii) at least 50% by weight water; and

[0197] (iv) at least one additional cosmetically acceptable component (F) selected from silicones, cationic polymers, rheology modifiers and amphoteric or zwitterionic surfactants.

[0198] In at least one embodiment, the shampoo composition comprises the following, based on the total weight of the shampoo composition:

[0199] (i) 0.05 to 5% by weight, preferably 0.1 to 2.0% by weight, more preferably 0.1 to 1.0% by weight, particularly preferably 0.1 to 0.5% by weight, of piroctone;

[0200] (ii) 5% to 20% by weight of one or more anionic surfactants;

[0201] (iii) at least 50% by weight of water;

[0202] (iv) at least one additional component selected from silicones, cationic polymers, rheology modifiers, and amphoteric or zwitterionic surfactants; and

[0203] (v) at least one further cosmetically acceptable component (F).

[0204] In at least one embodiment, the shampoo composition consists of the following, based on the total weight of the shampoo composition:

[0205] (i) 0.05 to 5% by weight, preferably 0.1 to 2.0% by weight, more preferably 0.1 to 1.0% by weight, particularly preferably 0.1 to 0.5% by weight, of piroctone;

[0206] (ii) 5% to 20% by weight of one or more anionic surfactants;

[0207] (iii) at least 50% by weight of water;

[0208] (iv) at least one additional component selected from silicones, cationic polymers, rheology modifiers, and amphoteric or zwitterionic surfactants; and

[0209] (v) at least one additional cosmetically acceptable component (F) selected from conditioning agents such as panthenol, panthenyl ethyl ether, proteins, hydrolyzed proteins (preferably of vegetable or animal origin, such as hydrolyzed collagen or hydrolyzed keratin), nutrients; antioxidants such as vitamin E; emollients such as PPG-3 myristyl ether, trimethylpentyl hydroxyethyl ether; hair styling polymers such as amphoteric styling polymers, cationic styling polymers, anionic styling polymers, nonionic styling polymers and silicone graft copolymers; preservatives such as benzyl alcohol, methylparaben, propylparaben and imidazolidinyl urea; pH adjusting agents such as citric acid, sodium citrate, succinic acid, phosphoric acid, sodium hydroxide, sodium carbonate; salts, typically such as potassium acetate and sodium chloride; colorants; hair oxidizing (bleaching) agents such as hydrogen peroxide, perborates and persulfates; hair reducing agents such as thioglycolates; fragrances; and chelating agents such as disodium EDTA.

[0210] Cosmetic composition of the present invention can be manufactured by methods known in the art. For example, cosmetic composition of the present invention can be manufactured by mixing its ingredients. For example, piroctone can be mixed with other ingredients of cosmetic composition of the present invention.

[0211] The present invention also relates to the use of the crystallized or precipitated piroctone obtained by the process of the present invention or the piroctone granules according to the present invention as an antidandruff agent or as a preservative. In a preferred embodiment, the present invention relates to the use of the crystallized or precipitated piroctone obtained by the process of the present invention or the piroctone granules according to the present invention as an antidandruff agent. In a preferred embodiment, the present invention relates to the use of the crystallized or precipitated piroctone obtained by the process of the present invention or the piroctone granules according to the present invention as a preservative.

[0212] Particularly preferably, piroctone is incorporated into a cosmetic composition. Preferably, the cosmetic composition is a shampoo composition or a conditioner composition. More preferably, the cosmetic composition is a shampoo composition, particularly preferably an anti-dandruff shampoo composition. Even more preferably, the cosmetic composition of the present invention is a conditioner composition.

[0213] Preferably, dandruff is caused by dandruff-causing microorganisms, more preferably of the genus Malassezia, even more preferably Malassezia and / or Malassezia, particularly preferably Malassezia, yet particularly preferably Malassezia.

[0214] The present invention also relates to a method of treating the hair and / or scalp comprising:

[0215] a) applying a shampoo composition and / or conditioner composition described herein (preferably a shampoo composition) to wet hair and / or scalp and then

[0216] b) removing the shampoo composition and / or conditioner composition (preferably the shampoo composition) from the hair and / or scalp.

[0217] The present invention also relates to a method for preparing piroctone olamine salt, comprising the following steps:

[0218] i) reacting pure piroctone with monoethanolamine in a solvent to obtain a solution containing piroctone olamine salt; and

[0219] ii) crystallizing or precipitating piroctone olamine salt from the solution containing piroctone olamine salt obtained in step i).

[0220] In one embodiment, pure piroctone preferably refers to piroctone having a purity of at least 90% by weight, more preferably at least 92% by weight, more preferably at least 94% by weight, still more preferably at least 96% by weight, still more preferably at least 97% by weight, particularly preferably at least 98% by weight, based on the total weight of pure piroctone.

[0221] In one embodiment, pure piroctone preferably refers to piroctone containing not more than 10% by weight, more preferably not more than 8% by weight, more preferably not more than 6% by weight, still more preferably not more than 4% by weight, still more preferably not more than 3% by weight, and particularly preferably not more than 2% by weight of impurities, based on the total weight of pure piroctone.

[0222] Advantageously, the use of pure piroctone in such a process results in higher yields and higher purity of the piroctone olamine salt.

[0223] According to step i), pure piroctone is reacted with monoethanolamine in a solvent to obtain a solution containing piroctone ethanolamine salt.

[0224] Preferably, the solvent in step i) is selected from the group consisting of heptane, hexane, cyclohexane, methylcyclohexane, dimethylcyclohexane, toluene, benzene, dichloromethane, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, tert-amyl alcohol, dimethylformamide, dimethyl sulfoxide, tetrahydrofuran, acetonitrile, 2-aminopyridine, ethyl acetate, methyl tert-butyl ether, dibutyl ether, diisopropyl ether, water and mixtures thereof.

[0225] More preferably, the solvent in step i) is selected from heptane, hexane, cyclohexane, methylcyclohexane, dimethylcyclohexane, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, ethyl acetate, methyl tert-butyl ether, dibutyl ether, diisopropyl ether and mixtures thereof.

[0226] Still more preferably, the solvent in step i) is selected from heptane, isopropanol, ethyl acetate, methyl tert-butyl ether and mixtures thereof. Particularly preferably, the solvent in step i) is selected from heptane, isopropanol, methyl tert-butyl ether and mixtures thereof.

[0227] In a preferred embodiment, step i) is carried out at a temperature in the range of 30 to 100°C, preferably 50 to 90°C, more preferably 60 to 85°C, particularly preferably 70 to 80°C.

[0228] Preferably, the molar ratio of pure piroctone to monoethanolamine is from 1.0:1.0 to 1.0 to 1.5, more preferably from 1.0:1.0 to 1.0:1.2, still more preferably from 1.0:1.0 to 1.0:1.1, particularly preferably from 1.0:1.0 to 1.0:1.05.

[0229] According to step ii), piroctone olamine salt is crystallized or precipitated from the piroctone olamine salt-containing solution obtained in step i).

[0230] In a preferred embodiment, in step ii), the piroctone olamine salt is crystallized or precipitated by cooling the solution containing the piroctone olamine salt to a temperature in the range of -5 to 50° C., preferably 0 to 35° C., more preferably 0 to 25° C., particularly preferably 0 to 20° C. In a preferred embodiment, in step ii), the piroctone olamine salt is crystallized or precipitated by cooling the solution containing the piroctone olamine salt to a temperature in the range of -5 to 20° C., preferably 0 to 15° C., more preferably 0 to 10° C., particularly preferably 0 to 5° C. In a preferred embodiment, in step ii), the piroctone olamine salt is crystallized or precipitated by cooling the solution containing the piroctone olamine salt to a temperature in the range of 0 to 35° C., preferably 5 to 30° C., more preferably 10 to 25° C., particularly preferably 15 to 20° C.

[0231] In a preferred embodiment, the crystallized or precipitated piroctone is isolated by filtration. After filtration, it can be washed with a solvent (preferably the solvent used in step i)) and dried.

[0232] Unless otherwise indicated, all percentages are by weight (w / w) of the total composition. Unless otherwise indicated, all ratios are by weight. "% by weight" means percentage by weight. "QS" or "QSP" means sufficient for 100% or for 100 g. Unless otherwise indicated, "molecular weight" or "M.Wt." or "MW" and grammatical equivalents mean number average molecular weight.

[0233] The present invention is further illustrated by the following examples without limiting the invention thereby. Example

[0234] As used herein, piroctone is also known as 1-hydroxy-4-methyl-6-(2,4,4-trimethylpentyl)-2(1H)-pyridone and refers to the compound of the formula:

[0235]

[0236] As used herein, Pyron is also known as 1-hydroxy-4-methyl-6-(2,4,4-trimethylpentyl)-2(1H)-pyrone and refers to the compound of the formula:

[0237]

[0238] Piroctone olamine salt used herein is also referred to as piroctone olamine. The chemical name of piroctone olamine salt is the monoethanolamine salt of 1-hydroxy-4-methyl-6-(2,4,4-trimethylpentyl)-2(1H)-pyridone. Therefore, piroctone olamine salt is the monoethanolamine salt of piroctone.

[0239] Examples 1 to 4

[0240] Crude piroctone was prepared as follows:

[0241] 1 molar equivalent of pyron (50 g) was reacted with 1.44 molar equivalents of hydroxylamine sulfate in toluene (50 ml) and water (1% of the batch) in the presence of 1.44 molar equivalents of sodium carbonate. The reaction mixture was heated gradually to control the reaction temperature, i.e., the reaction mixture was slowly heated to 65-70° C. (observation: exotherm) and maintained for 3 h, then heated to 80° C. (observation: endotherm), then heated to 90-95° C. and maintained for 12 h. The reaction mixture was cooled to 70-75° C. and quenched with water, the organic layer was separated and the solvent was completely distilled off until the water content was no more than 0.8% to obtain crude piroctone (as a residue).

[0242] Example 1: Crude piroctone (residue, 50 g) was dissolved in heptane (1 V, 50 mL) at 70-75°C, cooled to 0-5°C, filtered, and the wet cake was washed with heptane (2 V, 100 mL) and dried.

[0243] Example 2: Crude piroctone (residue, 50 g) was dissolved in heptane (3 V, 150 mL) at 70-75° C., cooled to 15-20° C., filtered, and the wet cake was washed with heptane (1 V, 50 mL) and dried.

[0244] Example 3: Crude piroctone (residue, 25 g) was dissolved in heptane (5 V, 125 mL) at 70-75° C., cooled to 15-20° C., filtered, and the wet cake was washed with heptane (1 V, 25 mL) and dried.

[0245] Example 4: Crude piroctone (residue, 50 g) was dissolved in heptane (5V, 250 mL) at 70-75°C, cooled to 15-20°C, filtered, the wet cake was washed with heptane (1V, 50 mL) and dried.

[0246] The results are provided in the table below:

[0247]

[0248] Note: ND = Not Determined

[0249] The particle size distribution (PSD) is determined as follows:

[0250] PSD instrument: Malvern Mastersizer 3000.

[0251] Sample preparation and PSD measurement: The required amount of about 1 g is placed into the sample hopper device and the measurement is started with an obscuration of 0.5% to 1.5%.

[0252] PSD measurements: Each sample was analyzed twice. The values provided in the table above are the average of the two measurements.

[0253] The solubility tests of the piroctone of Examples 1 to 4 are as follows:

[0254] 0.5g piroctone is dispersed in about 10g water (demineralized).In the next step, add about 45g Genapol LRO Liquid (it is surfactant) and solution is stirred under about 300rpm.Visual inspection sample, and measure time until solution is clear and all solids dissolve.

[0255] Dissolution times are provided in the table below:

[0256] Example Dissolution time (min) 1 30-35 2 30-35 3 20-25 4 20-25

[0257] These examples show that piroctone of the present invention is soluble in formulations containing surfactants. A dissolution time of 30-35 min in such formulations is a good result for piroctone. A dissolution time of 20-25 min is even better.

[0258] Example composition

[0259] Example 5

[0260] Cosmetic composition (ingredients are provided in wt %)

[0261]

[0262]

[0263] Example 6

[0264] Cosmetic composition (ingredients are provided in wt %)

[0265]

[0266]

[0267]

[0268]

[0269] Example 7

[0270] Cosmetic composition (ingredients are provided in wt %)

[0271]

[0272]

[0273] Example 8

[0274] Conditioner composition

[0275]

[0276]

[0277] Example 9

[0278] Conditioner composition

[0279]

[0280] Life: Clariant, INCI = Polyquaternium-116 and Butylene Glycol

[0281] Repair: Clariant, INCI = Quaternium-98

[0282] Hydra: Clariant, INCI = Lauryl / Myristyl Polyricinoleate and Glycerin

[0283] Example 10

[0284] Conditioner composition

[0285]

[0286]

[0287] Life: Clariant, INCI = Polyquaternium-116 and Butylene Glycol

[0288] Repair: Clariant, INCI = Quaternium-98

[0289] Hydra: Clariant, INCI = Lauryl / Myristyl Polyricinoleate and Glycerin

[0290] Example 11

[0291] Shampoo composition

[0292]

[0293]

[0294] Example 12

[0295] Shampoo composition

[0296]

[0297]

[0298] Example 13

[0299] Shampoo composition

[0300]

[0301] Example 14

[0302] Shampoo composition

[0303]

[0304] Example 15

[0305] Shampoo composition

[0306]

[0307]

[0308] Example 16

[0309] Shampoo composition

[0310]

[0311]

[0312] Example 17

[0313] Shampoo composition

[0314]

[0315]

[0316] Example 18

[0317] Shampoo composition

[0318]

[0319] Example 19

[0320] Shampoo composition

[0321]

[0322]

[0323] Example 20 Shampoo composition

[0324]

[0325]

[0326] Example 21 Shampoo composition

[0327]

[0328] Example 22 Shampoo composition

[0329]

[0330]

[0331] Example 23 Shampoo composition

[0332]

[0333] Example 24 Shampoo composition

[0334]

[0335] Example 25 Shampoo Soap

[0336]

[0337]

[0338] Examples 26 to 29

[0339] 1 molar equivalent of pyron (50 g) was reacted with 1.44 molar equivalents of hydroxylamine sulfate in toluene (50 ml) and water (1% of the batch) in the presence of 1.44 molar equivalents of sodium carbonate. The reaction mixture was heated gradually to control the reaction temperature, i.e., the reaction mixture was slowly heated to 65-70° C. (observation: exotherm) and maintained for 3 h, then heated to 80° C. (observation: endotherm), then heated to 90-95° C. and maintained for 12 h. The reaction mixture was cooled to 70-75° C. and quenched with water, the organic layer was separated and the solvent was completely distilled off until the water content was no more than 0.8%, to obtain crude piroctone (as a residue).

[0340] Solvent (as specified in the table above) (2V, 100 mL) was charged to the crude piroctone and stirred at 70-75°C (observation: clear solution). The reaction mixture was slowly cooled to room temperature, then to 15-20°C and maintained at 15-20°C for 2 h. The solid was filtered and washed with cold solvent (1V, 50 mL) (as specified in the table above) and dried.

[0341]

[0342]

[0343] Examples 30 to 32

[0344] Preparation of piroctone ethanolamine salt from pure piroctone

[0345] Example 30:

[0346] Dissolve pure piroctone in heptane at 70-80°C.

[0347] Add monoethanolamine dropwise at 70-80°C,

[0348] Keep at 70-80℃ for 2 hours,

[0349] Cool to room temperature (RT),

[0350] Cool to 0-5°C and filter the material at 0-5°C.

[0351] raw material quantity Moore Molar equivalent Pure piroctone 50g 0.21 1.0 heptane 150mL Monoethanolamine 12.87g 0.2109 1.004

[0352] Example 31:

[0353] The reaction was also carried out using methyl tert-butyl ether (MTBE) as solvent. In this case, pure piroctone was dissolved in MTBE at room temperature.

[0354] Example 32:

[0355] The reaction was also carried out using isopropyl alcohol (IPA) as solvent. In this case, pure piroctone was dissolved in IPA at room temperature.

[0356]

[0357]

Claims

1. A method for crystallizing or precipitating piroctone, comprising the steps of: a) dissolving the piroctone-containing product in a solvent; b) cooling the solution; and c) isolating the crystallized or precipitated piroctone.

2. The process according to claim 1 , wherein the solvent in step a) is selected from the group consisting of heptane, hexane, cyclohexane, methylcyclohexane, dimethylcyclohexane, toluene, benzene, dichloromethane, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, tert-amyl alcohol, dimethylformamide, dimethyl sulfoxide, tetrahydrofuran, acetonitrile, 2-aminopyridine, methyl tert-butyl ether, dibutyl ether, diisopropyl ether, water, and mixtures thereof.

3. The process according to claim 1 , wherein in step a) at least 50 ml, preferably at least 100 ml, more preferably at least 300 ml, particularly preferably at least 500 ml of solvent are used per 100 g of piroctone-containing product.

4. The process according to claim 1 , wherein in step a) the piroctone-containing product is dissolved in a solvent at a temperature in the range of 30 to 100° C., preferably 40 to 90° C., more preferably 50 to 80° C., particularly preferably 60 to 80° C.

5. The process according to any one of claims 1 to 4, wherein in step b) the solution is cooled to a temperature in the range of -5 to 50°C, preferably 0 to 35°C, more preferably 0 to 25°C, particularly preferably 0 to 20°C.

6. The process according to claim 1, wherein the piroctone-containing product used in step a) is prepared by reacting pyron with hydroxylamine or a hydroxylammonium compound, preferably a hydroxylammonium compound.

7. The method according to claim 1 , wherein the crystallized or precipitated piroctone has a d value of 250 μm or less, preferably 200 μm or less, more preferably 150 μm or less, particularly preferably 100 μm or less. 90 .

8. The method according to any one of claims 1 to 7, wherein the crystallized or precipitated piroctone has a d of 90 μm or less, preferably 80 μm or less, more preferably 75 μm or less, particularly preferably 70 μm or less. 50 .

9. Piroctone particles having a d of 250 μm or less 90 .

10. The piroctone granules according to claim 9, wherein the piroctone granules have a d of 200 μm or less, preferably 150 μm or less, particularly preferably 100 μm or less. 90 .

11. The piroctone granules according to claim 9 or 10, wherein the piroctone granules have a d of 90 μm or less, preferably 80 μm or less, more preferably 75 μm or less, particularly preferably 70 μm or less. 50 .

12. A method for preparing piroctone, comprising the steps of: 1) reacting pyron with hydroxylamine or a hydroxylammonium compound in solvent S1; and 2) crystallizing or precipitating piroctone from solvent S2, The prerequisite is that if the solvent S2 used in step 2) is heptane, the solvent S1 used in step 1) is not heptane.

13. The method according to claim 12, wherein the solvent S1 in step 1) is selected from the group consisting of heptane, hexane, cyclohexane, methylcyclohexane, dimethylcyclohexane, toluene, benzene, dichloromethane, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, tert-amyl alcohol, dimethylformamide, dimethyl sulfoxide, tetrahydrofuran, acetonitrile, 2-aminopyridine, methyl tert-butyl ether, dibutyl ether, diisopropyl ether, water, and mixtures thereof.

14. The method according to claim 12 or 13, wherein the solvent S2 in step 2) is selected from the group consisting of heptane, hexane, cyclohexane, methylcyclohexane, dimethylcyclohexane, toluene, benzene, dichloromethane, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, tert-amyl alcohol, dimethylformamide, dimethyl sulfoxide, tetrahydrofuran, acetonitrile, 2-aminopyridine, methyl tert-butyl ether, dibutyl ether, diisopropyl ether, water, and mixtures thereof.

15. Use of the crystallized or precipitated piroctone obtained by the method defined in any one of claims 1 to 8 or 12 to 14 or the piroctone particles defined in any one of claims 9 to 11 for the manufacture of a cosmetic composition, wherein the cosmetic composition is preferably selected from shampoo, conditioner, hair tonic, hair lotion, shower gel, bubble bath, bath oil, facial cleanser, cleansing mask, cleansing milk, micellar water, makeup remover, cleansing wipes, perfume, soap, shaving soap, shaving foam, cleansing foam, facial mask, facial cream, hand cream and body lotion.

16. Use of crystallized or precipitated piroctone obtained by the process defined in any one of claims 1 to 8 or 12 to 14 or piroctone granules defined in any one of claims 9 to 11 as an antidandruff agent or as a preservative.

17. A method for preparing piroctone olamine salt, comprising the steps of: i) reacting pure piroctone with monoethanolamine in a solvent to obtain a solution containing piroctone olamine salt; and ii) crystallizing or precipitating piroctone olamine salt from the solution containing piroctone olamine salt obtained in step i).

18. The method according to claim 17, wherein the solvent in step i) is selected from the group consisting of heptane, hexane, cyclohexane, methylcyclohexane, dimethylcyclohexane, toluene, benzene, dichloromethane, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, tert-amyl alcohol, dimethylformamide, dimethyl sulfoxide, tetrahydrofuran, acetonitrile, 2-aminopyridine, ethyl acetate, methyl tert-butyl ether, dibutyl ether, diisopropyl ether, water, and mixtures thereof.

19. The process according to claim 17 or 18, wherein step i) is carried out at a temperature in the range of 30 to 100°C, preferably 50 to 90°C, more preferably 60 to 85°C, particularly preferably 70 to 80°C.

20. The process according to any one of claims 17 to 19, wherein the piroctone olamine salt is crystallized or precipitated in step ii) by cooling the solution containing the piroctone olamine salt to a temperature in the range of -5 to 50°C, preferably 0 to 35°C, more preferably 0 to 25°C, particularly preferably 0 to 20°C.

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