WO2025196158A1 - The use of a cosmetic composition for hair and/or skin care comprising estolide esters - Google Patents

Abstract

The present invention relates the use of a cosmetic composition for hair and/or skin care comprising estolide esters It also related to a process for preparing said 5 cosmetic composition and a method of treating the hair.

Description

THE USE OF A COSMETIC COMPOSITION FOR HAIR AND/OR SKIN CARE COMPRISING ESTOLIDE ESTERS

TECHNICAL FIELD

The present invention relates the use of a cosmetic composition for hair and/or skin care comprising estolide esters of the invention, a process for preparing a cosmetic composition and the method of treating the hair. The cosmetic compositions according to the invention are in particular for use as hair shampoo and/ or conditioning.

The present invention also relates to compositions which are effective for skincare, for example as emollients, skin repair creams, moisturizing creams and ointments, and related products.

In particular, the present invention relates to hair care compositions exhibiting both conditioning and cleansing properties for the simultaneous washing and conditioning of the hair.

TECHNICAL BACKGROUND

Human hair contains approximately 97% of the protein keratin, which needs to be protected against environmental influences to preserve hair's strength and natural look. Therefore, suitable cleaning and conditioning compositions for hair are needed. The use of simple curd soap would lead to a degeneration of the natural protective layer of the hair. Furthermore, typical hair treatments such as straightening, dyeing, permanent wave, or using hair spray can lead to damaged hair. Some results may be split ends, toneless, dry and/ or dull hair. For these reasons, improved hair care compositions are required.

Shampoo compositions are designed to provide certain benefits, including cleaning. These are usually aqueous compositions. Conditioning compositions are designed to provide some further treatment of hair. Some compositions are designed to provide both cleaning and treatment benefits. These are often referred to as 2-in- 1 (cleaning and conditioning) shampoos. Some shampoo compositions are designed to provide benefits on virgin hair and/or on damaged hair. Various compositions have been disclosed in the literature and/or have been made available to consumers. Shampoos typically comprise surfactants, usually anionic surfactants, in the form of micellar aqueous solutions. Using silicones in shampoo compositions is known. Using cationic polymers in shampoos is also known. It is believed that some silicone oil deposits onto hair to provide hair treatment. It is believed that cationic polymers can assist the deposition of silicone oil.

For example, shampoo compositions based essentially on conventional surfaceactive agents of, in particular, anionic, non-ionic and/or amphoteric type, are used for washing the hair.

These compositions are applied to wet hair and the foam generated by massaging or rubbing with the hands makes it possible, after rinsing with water, to remove dirt initially present on the hair.

Although having good washing power, these base compositions possess cosmetic properties that remain fairly weak, in particular as the relatively aggressive nature of such a cleansing treatment can result, in the long term, in more or less marked damage to the hair, damage related in particular to the gradual removal of the lipids or proteins present in or at the surface of the hair.

This is the reason why most of the hair care compositions further comprise additional cosmetic agents known as conditioners or conditioning agents, which are intended mainly to repair or limit the harmful or undesirable effects brought about by the various treatments or attacks to which keratinous materials are more or less repeatedly subjected. These conditioners can also improve the cosmetic behavior of the keratinous materials.

The most commonly used conditioning agents, especially in hair care formulations, are cationic polymers, cationic surfactants, silicones and/or silicone derivatives.

In recent times there is an increasing demand for hair care compositions with higher cosmetic performance, allowing “one shot” washing and conditioning of the hair and including safe, environment friendly and/or natural ingredients.

Several formulations have been tested in the literature, but it remains a challenge to find a formulation providing a cosmetic performance, notably in terms of softness, detanglability, shine, spreadability, along with cleansing, while being stable over time (no separation of phases). Generally speaking, the presence of relatively high amounts of cleansing agents in the hair conditioning formulations has the adverse effect of causing phase separation. Viscosity can also be affected in those cases.

This is the reason one of the major challenges when incorporating relative high amounts of cleansing agents into a hair conditioning composition is to benefit from the cleansing and conditioning properties while maintaining satisfactory softness, detanglability, shine, spreadability, along with cleansing properties and without negatively impacting viscosity and/or stability of the overall composition.

There still is a great need for improved cosmetic compositions, in particular for hair treatment, and for new hair care compositions which, based on easily available components, protect against UV light, pollution and other negative influences of the environment. Particularly in cities with higher air pollution, the hair needs to be protected over a longer period of time. The hair should remain easy to comb and should keep a good level of gloss, even for long hair, over a longer period of time. Furthermore, there is a need for providing components for cosmetic compositions that are based on natural and renewable materials or derived therefrom. There is also a need to develop cosmetic compositions that are based on biodegradable materials. Indeed, consumers are, in present times, highly conscious as to the source of the components used in such composition and these consumers feel much more comfortable using components that are derived from natural and renewable materials.

General hair treatment compositions for hair care are known, however there is still a need for compositions designed for hair care, which are based on easily available components. These compositions can improve combing and gloss properties for several hair types.

Many current skin care products such as lotions and cosmetics are waterbased. Such products are normally formulated with anti-bacterial components or preservatives to prevent the formation of bacteria which could cause infection on the skin.

Estolides are long-chain esters of the same or different (hydroxy) fatty acids or unsaturated fatty acids, made by esterification of said fatty acids by acid- catalyzed addition. One objective of the present invention is therefore to provide a stable cosmetic composition for hair and skin care products comprising components based on preferably renewable starting materials, more preferably natural renewable starting materials.

A further objective for the present invention is to provide more stable components for cosmetic compositions so that the compositions have a longer shelf life, as well as providing components that provide excellent performance in hard water areas.

It now was found that specific types of estolide ester compounds are excellent components for cosmetic compositions, in particular for hair and skin treatment.

DETAILED DESCRIPTION OF THE INVENTION

Before the use of a cosmetic composition for hair and/or skin care comprising estolide esters of the invention, a process for preparing a cosmetic composition and the method of treating the hair will be described in detail, it is to be understood that this invention is not limited to specific process conditions described herein, since such conditions may, of course, vary.

It is also to be understood that the terminology used herein is not intended to be limiting, since the scope of the present invention will be limited only by the appended claims.

As used herein, the singular forms "a", "an", and "the" include both singular and plural referents unless the context clearly dictates otherwise. By way of example, "a compound" means one compound or more than one compound.

The terms "containing", "contains" and "contained of as used herein are synonymous with "including", "includes" or " comprising", "comprises", and are inclusive or open-ended and do not exclude additional, non-recited members, elements or process steps. It will be appreciated that the terms “containing”, “contains”, "comprising", "comprises" and "comprised of as used herein comprise the terms "consisting of, "consisting essentially of", "consists" and "consists of .

Throughout this application, the term "about" is used to indicate that a value includes the standard deviation of error for the device or method being employed to determine the value. As used herein, the term “average” refers to number average unless indicated otherwise.

As used herein, the terms “% by weight”, “wt.-%”, “wt%”, “weight percentage”, or “percentage by weight” are used interchangeably. The same applies to the terms “% by volume”, “vol.- %”, “vol. percentage”, or “percentage by volume”, or “% by mol”, “mol- %”, “mol percentage”, or “percentage by mol”.

The terms "cosmetic," "cosmetic composition," and "cosmetic formulation," unless otherwise stated, shall mean any substance or preparation intended to be placed in contact with the various external parts of the human body, including the epidermis, hair system, nails, and lips. "Cosmetics" may be placed with the intended purpose of cleaning, perfuming, beautifying, changing appearance and/or correcting odors and/or protecting or keeping the contacted portions of the human body in good condition

The recitation of numerical ranges by endpoints includes all integer numbers and, where appropriate, fractions subsumed within that range (e.g. 1 to 5 can include 1, 2, 3, 4 when referring to, for example, a number of elements, and can also include 1.5, 2, 2.75 and 3.80, when referring to, for example, measurements). The recitation of end points also includes the end point values themselves (e.g. from 1.0 to 5.0 includes both 1.0 and 5.0). Any numerical range recited herein is intended to include all sub-ranges subsumed therein.

All references cited in the present specification are hereby incorporated by reference in their entirety. In particular, the teachings of all references herein specifically referred to are incorporated by reference.

Unless otherwise defined, all terms used in disclosing the invention, including technical and scientific terms, have the meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. By means of further guidance, term definitions are included to better appreciate the teaching of the present invention.

In the following passages, different alternatives, embodiments and variants of the invention are defined in more detail. Each alternative and embodiment so defined may be combined with any other alternative and embodiment, and this for each variant unless clearly indicated to the contrary or clearly incompatible when the value range of a same parameter is disjoined. In particular, any feature indicated as being preferred or advantageous may be combined with any other feature or features indicated as being preferred or advantageous.

Furthermore, the particular features, structures or characteristics described in present description may be combined in any suitable manner, as would be apparent to a person skilled in the art from this disclosure, in one or more embodiments. Furthermore, while some embodiments described herein include some but not other features included in other embodiments, combinations of features of different embodiments are meant to be within the scope of the invention, and from different embodiments, as would be understood by those in the art.

In a first embodiment the invention relates to the use of a cosmetic composition for hair and/or skin care comprising:

A) 0.001 to 20 wt.-% of at least one component selected from at least one estolide ester compound:

Al) of formula (I) wherein Ri is selected from the group of branched or linear Ci-Ci2-alkyl or C2-Ci2-alkenyl, nl and n2 are independently between 1 and 9, ml is between 1 and 9, or

A2) of formula (II): wherein R2 is selected from the group of branched or linear Ci-Ci2-alkyl or C2-Ci2-alkenyl, n3 and n5 are independently between 1 and 10, ml is between 1 and 9, or

B) 0.001 to 20 wt.-% of an estolide ester of formula (III): wherein R2 is selected from the group of branched or linear Ci-Ci2-alkyl or C2-Ci2-alkenyl, n3 and n5 are independently between 1 and 10, ml is between 1 and 9,

Xi can be a single bond, or a double bond,

X2 can be a single bond, or a double bond, with Xi different from X2, preferably wherein in case X2 is a double bond, R2 is selected from the group of branched or linear Ci-Ci2-alkyl, and wherein the estolide ester in A) to B) is obtained by an enzymatic reaction with a lipase.

The amounts of A) to B) from 0.001 to 20 wt.-% of an estolide ester are based on the total weight of the composition.

As used herein, the term "estolide ester" means an oligomeric fatty acid ester, wherein the monomers are joined by ester linkages. The term "estolide ester" is a term known in the art (see e.g. W02013/009471). In other words, the estolide ester is the ester bond with the arrow as shown below: According to the invention, Ri and R2 are selected from the group of branched or linear Ci-Ci2-alkyl or C2-Ci2-alkenyl, preferably selected from branched or linear Ci-8-alkyl, more preferably from branched or linear Ci-3-alkyl.

Examples of alkyl and alkenyl groups include, but are not limited to, methyl; ethyls such as ethanyl, ethenyl, and ethynyl; propyls such as propan-l-yl, propan-2- yl, prop-l-en-l-yl, prop-l-en-2-yl, prop-2-en-l-yl (allyl), prop-l-yn-l-yl, prop-2-yn-l- yl, etc. ; butyls such as butan-l-yl, butan-2-yl, 2-methyl-propan-l-yl, 2- methylpropan-2-yl, but-l-en-l-yl, but-l-en-2-yl, 2-methylprop-l-en-l-yl, but-2-en-l- yl, but-2-en-2-yl, 3-methylbutan-l-ol, buta-l,3-dien-l-yl, buta-l,3-dien-2-yl, but-1- yn-l-yl, but-l-yn-3-yl, but-3-yn-l-yl, 2-ethyl-l -hexyl etc.; and the like.

In a preferred embodiment, Rl or R2 are ethyl or 2-ethyl-l -hexyl.

Component A) or B) (estolide ester) may be present in the composition in an amount of from 0.1 to 10 % by weight, preferably of from 0.1 to 8 % by weight, even more preferably of from 0.2 to 5 % by weight, in particular of from 0.2 to 3 % by weight, based on the total weight of the composition.

According to the invention, in the estolide ester as defined above, ml is from 1 to 9, preferably from 1 to 8, even more preferably from 1 to 7, even more preferably from 1 to 6. Most preferably, the ml value is a trimer (ml = 3), pentamer (ml = 4), a hexamer (ml = 5), a heptamer (ml = 6), or mixtures thereof.

In some embodiments, the compounds described herein may comprise a mixture of two or more estolide ester compounds of Formula I, II, and III. It is possible to characterize the chemical makeup of an estolide ester, a mixture of estolide esters, or a composition comprising estolide esters, by using the compound's, mixture's, or composition's measured estolide number (EN) of compound or composition which is ml in the above formula.

The EN represents the total average number of fatty acids in the molecule:

EN = ml+1 wherein ml is the number of secondary (P) fatty acids. Accordingly, a single estolide ester compound will have an EN that is a whole number, for example for dimers, trimers, and tetramers: dimer EN = 2, trimer EN = 3, tetramer EN = 4.

However, a composition comprising two or more estolide ester compounds may have an EN that is a whole number or a fraction of a whole number. For example, a composition having a 1 : 1 molar ratio of dimer and trimer would have an EN of 2.5, while a composition having a 1 : 1 molar ratio of tetramer and trimer would have an EN of 3.5.

In some embodiments, the compositions may comprise a mixture of two or more estolide esters having an EN that is an integer or fraction of an integer that is greater than 4.5, or even 5.0. In some embodiments, the EN may be an integer or fraction of an integer selected from 1.0 to 9.0.

In some embodiments, the estolide number is an integer or fraction of an integer selected from 1.2 to about 4.5. In some embodiments, the estolide number is selected from a value greater than 1.0, 1.2, 1.4, 1.6, 1.8, 2.0, 2.2, 2.4, 2.6, 2.8, 3.0,

3.2, 3.4, 3.6, 3.8, 4.0, 4.2, 4.4, 4.6, 4.8, 5.0, 5.2, 5.4, 5.6 and 5.8. In some embodiments, the estolide number is selected from a value less than 1.2, 1.4, 1.6, 1.8, 2.0, 2.2, 2.4, 2.6, 2.8, 3.0, 3.2, 3.4, 3.6, 3.8, 4.0, 4.2, 4.4, 4.6, 4.8, and 5.0, 5.2, 5.4, 5.6, 5.8, and 6.0. In some embodiments, the estolide number is selected from 1,

1.2, 1.4, 1.6, 1.8, 2.0, 2.2, 2.4, 2.6, 2.8, 3.0, 3.2, 3.4, 3.6, 3.8, 4.0, 4.2, 4.4, 4.6, 4.8, 5.0, 5.2, 5.4, 5.6, 5.8, and 6.0.

Since Ri and R2 cannot be hydrogen, then the estolide esters are not a carboxylic acid. Acids are not desired since they have the disadvantage of being prone to instability issues such as self-catalyzed hydrolysis over time. The present estolide esters in contrast provides excellent stability over time e.g. in storage. Furthermore, carboxylic acids are able to complex calcium in hard water causing them to precipitate out of solution. The present estolide ester according to the invention is an ester and provides excellent performance in hard water areas. Furthermore, due to the COO' group in negligible amount, carboxylic acids repel other negatively charged material such as keratin fibres. Consequently, the present selection of Ri and R2 provides excellent performance in a cosmetic composition suitable for application onto hair and skin since they are not repelled by the negative charges on keratin fibres.

Preferably, the cosmetic composition comprises as compound C), from 80 to 99.999 wt.-% water, more preferably from 89.0 to 99.999 wt.-% water, based on the total weight of the composition.

Preferably, the total of Xi or X2 referring to a double bond is at least 1 :1 to 10: 1 when Xi or X2 is a single bond. Thus, the ratio of XI or X2 as a double bond to XI or X2 as a single bond is at least 1 : 1 and can go up to 10: 1. Preferably, according to the present invention, the enzymatic reaction is carried out by an enzyme selected from the group consisting a Humicola lanuginosa lipase, (e.g., described in EP 258,068 and EP 305,216) a Rhizomucor miehei lipase, (e.g., as described in EP 238,023) a Candida lipase, such as a C. antarctica lipase, (e.g., the C. antarctica lipase A or B described in EP 214,761), a Pseudomonas lipase (such as a P. alcaligenes and P. pseudoalcaligenes lipase, e.g., as described in EP 218,272), a P. cepacia lipase ( e.g., as described in EP 331,376), a Bacillus lipase (e.g., a B. subtilis lipase (Dartois et al., Biochemica et Biophysica Acta 1131, pp. 253-260 (1993)), a B. stearothernophilus lipase (JP 64/744992) and a B. pumilus lipase (EP 91 00664).

Preferably, according to the present invention, the lipase is from Streptomyces sp..

The lipase can form the "estolide ester", i.e an oligomeric fatty acid ester, wherein the monomers are joined by ester linkages. In other words, the estolide ester is the ester bond with the arrow as shown below:

Preferably, according to the present invention, the lipase comprises the amino acid sequence SEQ ID NO. 1 as follows:

ATATAATPAAEATSRGWNDYSCKPSAAHPRPWLVHGTFGNSIDNWLVL

APYLVNRGYCVFSLDYGQLPGVPFFHGLGPIDKSAEQLDVFVDKVLDATG

APKADLVGHSQGGMMPNYYLKFLGGADKVNALVGIAPDNHGTTLLGLT KLLPFFPGVEKFISDNTPGLADQVAGSPFITKLTAGGDTVPGVRYTVIATK YDQVVTPYRTQYLDGPNVRNVLLQDLCPVDLSEHVAIGTIDRIAFHEVAN ALDPARATPTTCASVIG or a sequence having at least 75% identity, preferably at least 80% identity, in particular at least 85% identity, for example at least 90% identity, with the sequence SEQ ID NO. 1.

Preferably, according to the present invention, the compound A2) is wherein R2 is selected from the group of branched or linear Ci-Ci2-alkyl or C2-Ci2-alkenyl, n is between 1 and 9. In a preferred embodiment, R2 is ethyl or 2- ethyl-1 -hexyl.

Preferably, according to the present invention, the compound Al) is wherein Ri is selected from the group of branched or linear Ci-Ci2-alkyl or C2-Ci2-alkenyl, n is between 1 and 9. In a preferred embodiment, Ri is ethyl or 2- ethyl-1 -hexyl.

Preferably, according to the present invention, the compound B) is wherein R2 is selected from the group of branched or linear Ci-Ci2-alkyl or C2-Ci2-alkenyl n is between 1 and 9,

Xi can be a single bond, or a double bond

X2 can be a single bond, or a double bond, with Xi different from X2, preferably wherein in case X2 is a double bond, R2 is selected from the group of branched or linear Ci-Ci2-alkyl.

Preferably, according to the present invention, the compound B) is wherein R2 is selected from the group of branched or linear Ci-Ci2-alkyl or C2-Ci2-alkenyl n is between 1 and 9,

Xi can be a single bond, or a double bond

X2 can be a single bond, or a double bond, with Xi different from X2, preferably wherein in case X2 is a double bond, R2 is selected from ethyl or 2-ethyl- 1 -hexyl.

In a preferred embodiment of the invention, Ri and/or R2 is ethyl or 2-ethyl- 1 -hexyl.

Preferably, according to the present invention, the composition may further comprise:

C) 0.0001 to 95 wt.-% water

D) 0.01 to 5 wt.-% solubilizer

E) 0.01 to 2.5 wt.-% surfactant

F) 0.01 to 2.5 wt.-% foaming agent

G) 0.01 to 2.5 wt.-% thickener

H) 0.00 to 2.5 wt.-% guar gum

I) 0.00 to 2.5 wt.-% amphoteric surfactant

J) 0.00 to 2.5 wt.-% anionic surfactant

K) 0.00 to 2.5 wt.-% preservative, wherein the total of A) to K) is 100 %.

The compositions of the invention may contain one or more silicone oils, or can be silicone oil free compositions. Preferably, the compositions of the invention are free of silicone oil. In terms of the invention, silicone oil free compositions contain less than 0,001% by weight of silicone oil, based on the total weight of the composition. More preferably, the compositions contain less than 0,0005%, less than 0,0001%, less than 0,00005%, less than 0,00001%, less than 0,000005%, or less than 0,000001% or silicone oil, based on the total mass of the composition. Preferably the compositions contain less than 5 ppm, less than 1 ppm, less than 0,05 ppm, less than 0,01 ppm, or less than 0,001 ppm of silicone oil, based on the total weight of the composition.

The cosmetic compositions of the invention can be used in different cosmetic applications, in particular haircare and skincare.

For example, the compositions of the present invention are useful for skincare applications, such as emollient compositions, skin moisturizing compositions and other skincare applications.

For example, the cosmetic composition of the invention may be a topical composition which can be formulated as a suspension (e.g., a liposomal suspension), emulsion, nano-emulsion, hydrogel, multiphase solution, liposomal dispersion, lotion, cream, gel, essence, foam, liquid, cake, ointment, paste, serum, spray, aerosol, conditioner, shampoo, mask, cleanser, tonic, makeup (e.g., lipstick, foundation, bronzer, rouge, eyeshadow), patch, pencil, powder, towelette, soap, cleanser, stick, mousse, elixir, concentrate and/or after-shave.

A skincare composition can be formulated within a wide range of pH levels. In one embodiment, the pH of the topical composition ranges from 1.0 to 13.0. In some embodiments, the pH of the topical composition ranges from 2.0 to 12.0. Other pH ranges suitable for the subject composition include from 3.5 to 7.0, or from 7.0 to 10.5. Suitable pH adjusters such as sodium hydroxide, citric acid and triethanolamine may be added to bring the pH within the desired range.

Preferably, a cosmetic skincare composition may comprise additional cosmetic ingredients. These components may be considered active ingredients or inactive ingredients and can be categorized by the benefit they provide or by their postulated mode of action; however, it is to be understood that the additional components can in some instances provide more than one benefit or operate via more than one mode of action. Therefore, classifications herein are made for the sake of convenience and are not intended to limit the agent to that particular application or applications listed. Examples of such cosmetic ingredient classes include: organic solvents, silicones, pH adjusters, chelating agents, gelling agents, proteins, vitamins, emollients, oils, hydroxy acids, exfoliants, retinoids, viscosity modifiers, polymers, minerals, insect repellents, lubricants, preservatives, botanicals, clarifying agents, humectants, non-biological surfactants, antioxidants, thickeners, softeners, sunscreens, moisturizers, dyes, colorants, fragrances, abrasives, absorbents, aesthetic components such as essential oils, skin sensates, astringents, anti-acne agents, anti-caking agents, antifoaming agents, antimicrobial agents, depigmenting agents, anti-inflammatory agents, advanced glycation end-product (AGE) inhibitors, steroids, binders, biological additives, buffering agents, bulking agents, chelating agents, chemical additives, denaturants, external analgesics, keratolytic agents, desquamating agents, keratinocyte proliferation enhancers, collagenase inhibitors, elastase inhibitors, film formers or materials, opacifying agents, propellants, reducing agents, enzymes, sequestrants, skin bleaching and lightening agents, skin-conditioning agents, skin soothing and/or healing agents, thickeners, minerals, vitamins and derivatives thereof.

Details with respect to these and other suitable cosmetic ingredients can be found in the “International Cosmetic Ingredient Dictionary and Handbook,” 10^th Edition (2004), published by the Cosmetic, Toiletry, and Fragrance Association (CTFA), at pp. 2177-2299, which is herein incorporated by reference in its entirety.

For example, the compositions of the present invention can be used in personal care products. For example, the compositions can be used by applying the cosmetic composition to an area of skin on a body; washing the area of skin on the body; and rinsing the area of skin on the body.

For example, a topical cosmetic composition can be formulated as, for example, a suspension, emulsion, nanoemulsion, hydrogel, multiphase solution, liposomal dispersion, lotion, cream, gel, foam, ointment, paste, spray, conditioner, shampoo, mask, cleanser, micellar water, tonic, makeup (e.g., lipstick, foundation, bronzer, rouge, eyeshadow), and/or after-shave.

For example, the cosmetic composition of the invention can be used for improving the health and/or appearance of skin wherein a topical cosmetic composition according to embodiments of the present invention is applied directly to an area of the subject’s skin in need thereof. Moreover, the compositions of the invention are preferably used in hair conditioning compositions, preferably wherein said use is for increasing hair hydrophobicity.

Ammonium lauryl ether sulfate and coconut di ethanol ami de (DEA) are exemplary surfactants for use in shampoos.

Specific examples of other suitable (anionic) surfactants includes sodium lauryl sulfate, sodium lauryl ether sulfate, ammonium lauryl sulfate, triethanolamine lauryl sulfate, sodium Ci4 -Ci6 olefin sulfonate, ammonium C12 - C15 pareth sulfate, sodium myristyl ether sulfate, di sodium monooleamidosulfosuccinate, ammonium lauryl sulfosuccinate, sodium dodecylbenzene sulfonate, triethanolamine dodecylbenzenesulfonate, and sodium N-lauryol sarcosinate. Examples of amphoteric surfactants include cocoamphocarboxyglycinate, cocoamphocarboxypropionate, cocobetaine, N- cocamidopropyldimethylglycine, N-lauryl-N-carboxymethyl-N-(2- hydroxyethyl)ethylenediamine; betaines such as alpha- (tetradecy 1 dimethyl ammoni o)acetate, b eta (hexadecyl di ethyl ammoni o)propi onate, and gamma- (dodecyldimethylammonio)butyrate; and sultaines such as 3- (dodecyldimethylammonio)- propane- 1 -sulfonate, and 3- (tetradecyldimethylammonio)ethane-l -sulfonate. Examples of nonionic surfactants suitable for use may include fatty acid di ethanol ami des such as isostearic acid DEA, lauric acid DEA, capric acid DEA, linoleic acid DEA, myristic acid DEA, oleic acid DEA, and stearic acid DEA; fatty acid monoethanolamides such as coconut fatty acid monoethanolamide; fatty acid monisopropanolamides such as oleic acid monoisopropanolamide and lauric acid monoisopropanolamide; alkyl amine oxides such as N-cocodimethylamine oxide, N-lauryl dimethylamine oxide, N-myristyl dimethylamine oxide, and N-stearyl dimethylamine oxide; N-acyl amine oxides such as N-cocoamidopropyl dimethylamine oxide and N-tallowamidopropyl dimethylamine oxide; N-alkoxyalkyl amine oxides such as bi s(2-hydroxy ethyl) C12 -Cl 5 alkoxy-propylamine oxide; and polyoxyethylene sorbitol fatty acid esters (e.g., polysorbates 20 and 80). Examples of zwitterionic surfactants which may be used include 4-[N,N-di(2-hydroxyethyl)-N-octadecylammonio]butane-l- carboxylate, 5-[S-3-hydroxypropyl-S-hexadecylsulfonio]-3-hydroxypentane-l - sulfate, 3- [P,P-diethyl-P-3, 6, 9-trioxatetradexocylphosphonio]-2-hydroxypropane- 1 -phosphate, 3-[N,N- dipropyl-N-3-dodecoxy-2-hydroxypropylammonio]- propane-l-phosphonate , 3-(N,N- dimethyl-N-hexadecylammonio)-propane-l - sulfonate, 3-(N,N-dimethyl-N- hexadecylammonio)-2-hydroxypropane-l - sulfonate, 4-[N,N-di(2-hydroxyethyl)-N-(2- hydroxydodecyl)ammonio] -butane- 1 -carboxylate, 3-[S-ethyl-S-(3-dodecoxy-2- hydroxypropyl)sulfonio]propane-l - phosphate, 3-[P,P-dimethyl-P-dodecylphosphonio]- propane-l-phosphonate, and 5- [N,N-di(3-hydroxypropyl)-N-hexadecylammonio]-2- hydroxypentane- 1 -sulfate.

Preferably, according to the invention, the composition used in a hair shampoo and/or conditioning composition, is sulfated or sulfated-free.

The use of the estolide esters described herein may have improved properties which render them useful personal care and cosmetic formulations. Exemplary personal care and cosmetic products include but are not limited to a shampoo, conditioner, hair lotion, tonic, hair spray, hair mousse, hair gel, hair dyes, moisturizer, suntan lotion, color cosmetic, body lotion, hand cream, baby skin-care product, facial cream, lipstick, lip balm, mascara, blush, eyeliner, nail products, baby shampoo, baby moisturizer, baby lotion, shower gel, soap, shaving product, deodorant, bath cream, body wash, serum, cream, solid, gel, lubricant, gelly, balm, tooth paste, whitening gel, disposable towel, disposable wipe or ointment.

In certain embodiments, the estolide esters described herein provide a level of control over viscosity and consistency factors in many aqueous- and oil-based systems where control over the rheology is a concern. Embodiments may include cosmetic and personal care applications including hair styling, hair conditioners, shampoos, bath preparations, cosmetic creams, gels, lotions, ointments, deodorants, powders, skin cleansers, skin conditioners, skin emollients, skin moisturizers, skin wipes, sunscreens, shaving preparations, and fabric softeners, wherein the estolide ester compounds may help to provide desirable gel strength and shear thinning characteristics, and versatile viscometric properties and synergistic interactions with added agents to adjust their rheology profile to optimize properties such as sedimentation, flow and leveling, sagging, and spattering.

Preferably, the use of the cosmetic composition according to the invention is for or in hair care compositions, preferably in hair conditioning compositions; preferably wherein said use is for increasing hair hydrophobicity.

In a further embodiment, the invention relates to a process for preparing the cosmetic composition that may be used for hair and/or skin care, in particular a hair shampoo and/ or conditioning composition, comprising: the step of mixing at least one estolide ester of formula (I), (II) or (III) and water, and at least one further component B or D, and optionally further components G and/ or E.

In a further embodiment, the invention relates to a method of treating the hair, comprising the steps of applying a hair shampoo and/ or conditioning composition onto wet hair, lathering and removing said shampoo and/ or conditioning composition from the hair, characterized in that the hair shampoo and/ or conditioning composition comprises at least one estolide ester of formula (I), (II) or (III) as described above, optionally a surfactant component E), optionally a thickener component G), optionally a solubilizer D), and optionally a further component J), different to components A) to K), with the proviso that the shampoo and/ or conditioning composition contains at least one component E) or at least one component D).

Preferably, the invention relates to a method of treating the hair, comprising the following steps: a) applying a hair shampoo composition onto the hair; b) washing the hair with the hair shampoo composition; c) removing the hair shampoo composition from the hair; d) applying a conditioning composition onto wet hair.

The hair shampoo and/or conditioning composition of the present invention can comprise water in an amount of from 0.0001 to 95 wt.-% water, preferably 5 to 90 % by weight relative to the total weight of the composition. It may comprise for instance at least 25 %, for instance at least 50 %, for instance at least 60 % of water, relative to the total weight of the composition.

In one embodiment, the cosmetically acceptable aqueous medium can be composed solely of water. For example, the composition of the invention may further comprise at least one water-miscible organic solvent and its salts. Preferably, the cosmetically acceptable aqueous medium can be composed of a mixture of water and of a cosmetically acceptable solvent, such as a lower C1-C4 alcohols or such as alkylene glycols. The lower C1-C4 alcohols are preferably chosen from ethanol, isopropanol, tert-butanol, and n-butanol. The alkylene glycols are preferably chosen from propylene glycol and glycol ethers.

The composition of the invention may further comprise additional optional ingredients which may bring specific benefits for the intended use. Such optional ingredients may include colorants, pearlescent agents, hydrating agents, preservatives and pH adjusters. The skilled person is able to select according to general knowledge in the art of formulating cosmetic compositions, such as creams, ointments, hair shampoos and conditioners, appropriate such optional ingredients for application purposes.

Preferably, the composition of the present invention comprises a benefit agent selected from insoluble or partially insoluble ingredients such as conditioners, hair coloring agents, anti-UV agents, fragrances or essential oils, anti-dandruff agents, and provides enhanced deposition of such benefit agent on the hair.

Preferably, the personal care composition of the present invention further comprises from about 0.1 to about 50 % by weight, more typically from about 0.3 to about 25 % by weight, and still more typically from about 0.5 to 10 % by weight, of one or more benefit agents.

In general, hair care compositions may optionally comprise, based on 100 % by weight of the personal care composition and independently for each such ingredient, up to about 10%, preferably from 0.5 % to about 5.0 %, of such other ingredients, depending on the desired properties of the hair care composition.

Preferably, the composition according to the present invention further comprises a fragrance material or perfume.

Preferably, a “fragrance material or perfume” means any organic substance or composition which has a desired olfactory property and is essentially non-toxic. Such substances or compositions include all fragrance material and perfumes that are commonly used in perfumery or personal care compositions. The compounds involved may be natural, semi-synthetic or synthetic in origin. For example, the composition may comprise from 0.01 to 10 % by weight of the fragrance material or perfume based on the total weight of the composition. In another example, the composition may comprise from 0.1 to 5 % by weight of the fragrance material or perfume based on the total weight of the composition. In still another embodiment, the composition comprises from 0.2 to 2 % by weight of the fragrance material or perfume based on the total weight of the composition.

A hair care composition provided by the present invention is used in a manner known in the art, for example by application of the composition to the hair and optionally rinsing the composition off of the hair with water.

Preferably, the composition of the invention may have a pH comprised between 4 and 11, for instance between 4 and 6.

Preferably, the composition of the invention may be prepared using a concentrated flowable composition.

The invention is also directed toward concentrates that are suitable to prepare a composition of the invention.

Concentrates including a mixture of surfactants and/or conditioning agents and/or solubilizer are advantageous as their use would reduce the need to transport a plurality of individual components.

Personal care compositions are usually prepared by mixing individual surfactants, solubilizers and conditioning agents. These components may be supplied as concentrated solutions which are diluted and/or and combined in appropriate ratios by the formulator. The invention covers any concentrate to be used as component ingredient to prepare a composition of the invention, and especially to concentrates containing limited levels of water (more advantageous from a cost and environmental perspective).

Furthermore, the present invention also covers any concentrate that can be used to prepare a composition of the invention.

The viscosity of the composition of the invention is satisfactory per se.

Furthermore, a composition of the invention may further comprise a thickener. Moreover, a composition of the invention may comprise less than 5 % by weight of an additional thickener. In particular, a composition of the invention may comprise less than 5 % by weight of polymeric thickener(s), relative to the total weight of composition, for instance less than 3 % by weight, for instance less than 2 % by weight, for instance less than 1 % by weight.

Further, a composition of the invention may comprise substantially no polymeric thickener, i.e. from 0 to less than 0.1 % by weight of polymeric thickener per 100 % by weight of the composition, for instance no polymeric thickener, i.e. 0 % by weight of polymeric thickener per 100 % by weight of the composition.

A particularly preferable formulation based on the cosmetic composition according to the invention comprises the following ingredients: A further example of a cosmetic formulation in the form of an emulsion is as follows:

MATERIALS AND METHODS

The current section is structured in the following manner. Section 1 presents information on the components used in the examples. That includes the actives of interest (with potential conditioning action) and the surfactants or other components employed in the surfactant chassis of a particular active. In section 2 the experimental protocols are described, employed to prepare the formulations, perform the in vitro (wet and dry combing) and in vivo evaluations.

1. Materials. Table 2 presents the composition of surfactant chassis of the formulation used in the examples. Table 1. Components used to prepare the formulations: Table 2. Composition of surfactant chassis of the formulation, oil-infused shampoo.

2. Methods The current section is organized in the following manner. Section 2.1 presents the protocols for the preparation of the exemplified formulation. Section 2.2 explains the protocol for production of home bleached tresses, starting from virgin tresses. In sections 2.3-2.5 the protocols for characterization of the formulation are described: transmittance, viscosity and stability, respectively. In sections 2.6 and 2.7, the procedure for evaluation of the systems in combing test - wet and dry mode, respectively is described. Section 2.8 presents the procedure, used for evaluation of the humidity of the tresses. In 2.8, the protocol for measurement of contact angle of water on hair fibers is described. Finally, in section 2.10, it is explained how the products are evaluated in sensorial panels.

2.1. Protocol for preparation of the formulation.

Protocol for preparation of the formulation.

Formulation A was prepared via the following procedure.

1. In a main beaker, charge water, start heating at 65°C and add Mackamide CPA and Alkamuls S6000.

2. Stir for at 150 rpm until full dissolution.

3. Add required amount of water to fill water loss during the heating step. Re-homogenize.

4. When the mixture was liquid and homogenous, progressively add Mackam CAB 818 and after RHOD APEX ESB 30HA1.

5. Stir for 10 minutes at 150 rpm.

6. Add the active.

7. Add the Jaguar® EXCEL at constant stirring.

8. Stir for 10 minutes at 150 rpm.

9. Add the phenoxyethanol.

10. Adjust pH to the target value of 5 b adding solution of citric acid at small steps.

11. Add NaCl to achieve viscosity with a target value between 8000 and 12000 mPa.s.

2.2. Preparation of bleached tresses.

In the majority of the in vitro experiments, Caucasian tresses, Damaged, Level 2 are used. These tresses are mass produced and suitable for experiments like wet combing. However, for the evaluation of the effect of the actives on the wettability of the hair fibers, home bleached tress was needed. Preliminary tests show that the variation of the results (contact angle) with home bleached tresses was significantly lower compared to commercially available tresses.

The procedure for bleaching of virgin hair tresses was described below. Tresses: 25 of 4 g virgin medium brown DA 450 163 8300.

Commercial products for bleaching:

■ « Oxydant creme 30% volume », L’Oreal Professionnel Paris lot 44H304 ■ « Poudre decol orante Plastifiz Precision », L’Oreal Professionnel Paris lot 44J200

Equipement:

1 Beak in PET capacity 600 ml

1 Tripour beak capacity 400 ml

1 Small Plastic spatule

1 Special hair bleached brush

2 Aluminium sheets

1 red bulk filled up hot water

2 sinks available to rinse

Protocol:

1. Prepare the mixture based on following: mMixTURE (/g of hair)=4.75g weigh first powder with a mask and premix with a spatule and use the add oxidant cream on top in a 600ml mixer when adding water slowly in 4 beak minutes.

2. Drop half of the mixture on aluminium sheet and spread with the special hair bleached-brush

3. Start the timer

4. Deposit the tresses and put the last part of mixture on tresses and spread with the brush

5. First step: mass fast each tress with the mixture (15s/tress). Insist on roots and tips.

6. Second step: mass again each strand more deeply (25s/tress from the top to the bottom). The application time must not exceed 20 min to stay significantly lower than the exposition time. 7. Let them stand until 180 minutes elapsed well covered by a aluminum sheet.

8. Stop oxidation: remove a big part of bleaching cream and dip all the tresses in the same bulk of water to remove at least all of the bleaching product (less than one minute)

9. Rinsing step.

2.3. Measurement of the optical transmittance of the studied systems.

The transmittance of the formulations was measured via the following procedure.

(1) Fill ³/4 of the cuvette (over the line) with a formulation sample.

(2) Ensure the formulation does not contain any air bubbles and remove any dust on the cuvette, for an accurate measurement. If the sample was viscous and air bubbles are present, allow the formulation to rest in the cuvette for at least 6 hours or overnight before measurement.

(3) Select the wavelength programmed - Lambda 40Bio Shampoo Transparency at 600 nm.

(4) Calibrate the spectrophotometer’ s transparency of 99 to 100% with DI water as the reference.

(5) Place the sample cuvette into the spectrometer, with the clear sides of the cuvette parallel to the light source/monochromator and detector.

(6) Close the lid and run the transmittance measurement.

2.4. Measurement of the viscosity of the studied systems.

The viscosity of the formulations was measured via the following procedure.

• Formulation was filled (90%) into a 100 mL glass bottle.

• Attach the selected spindle to the Brookfield instrument and place the spindle into the glass bottle of formulation.

• Run the selected program for 1 minute for viscosity measurement.

• For high accuracy/effective measurement: - Keep the spindle in the center of the bottle

- Ensure the spindle does not touch the bottom and the wall of the bottle

The midline of the spindle was fully submerged in the formulation

- Ensure that the selected spindle and speed (rpm) provides a good range of viscosity (e.g.: spindle 4 and 10 rpm read a max of 20 000 cP)

Torque percentage between 10 to 100%

2.5. Tests of the storage stability of the formulation.

The samples were put into glass bottles of 100 ml and stored at three different temperatures: 4 °C, room temperature, 40 °C. On a monthly basis the samples, stored at 4/40 °C, was taken out of the fridge/climate chamber, thermo stated for 24 hours and their transmittance, pH and viscosity are measured.

2.6. Procedure for wet combing and data interpretation.

The wet combing was performed via a combing instrument, produced by Diastron. Tresses of Caucasian hair were used, damaged level 2, 4 grams, length 17 mm.

The hair of the tress was held together by a plastic part, which is attached to the (force) sensor of the instrument. The comb moves down the tress with a constant speed (300 mm/min). The comb has relatively wide teeth (6.9 teeth per centimeter). During this movement the instrument records the force exerted on the sensor. Typical result (force vs. distance) is presented in Figure 5.

The results presented in Figure 5 can be processed to quantify the softness of the tress, and therefore the effectiveness of the active as a conditioning agent. The following parameters can be utilized:

• Force in the plateau, Fp.

• Thermodynamic work for combing in the plateau, Wp.

• Thermodynamic work for combing for the entire pass of the comb, W.

• Maximum force, FM.

The force and the work for combing are a function of the following properties/parameters (at the same speed):

• Distance between the teeth of the comb. The narrower the teeth are the greater the resistance is to the motion of the comb. When comparing a range of systems one needs to use the same comb. • Inherent softness of the tress, all of the experiments were performed with the same type of tress (Caucasian hair, damaged level 2, 4 g). The quality and properties of these tresses were to a significant extend standardized. However, the inherent softness of the tresses (before treatment with shampoo) can vary significantly.

• Effectiveness of the conditioning active, deposited on the tress. The conditioning active deposited on the hair can change the softness, which results in lower resistance of the tress to the combing.

One of the ways to compare the softness of different systems is to compare the total work for combing, W. The lower this value is, the more efficient the respective active is in bringing conditioning to the hair. However, W does not account for the inherent softness of the tress. The efficiency of the active should be judged by the change in the softness of the tress (before and after treatment with the active), and not by the absolute value of the thermodynamic work. That is why in the current description, the parameter PPis scaled in the following manner:

PPDL = [(PFBEFORE-PFAFTER)/PFBEFORE] X 100 (1)

The parameters in the equation above have the following meaning:

• PFBEFORE - work for combing of the tress after pretreatment (see text below for explanation).

• PFAFTER - work for combing of the tress after treatment with formulation (see text below for explanation).

• PFDL - reduction of the work for combing, as a result of the treatment with shampoo, scaled with the initial work for combing. The multiplication by 100 is done in order to present the results in percent.

In this representation the higher the value of PFDL is, the more efficient the respective active is. It is also possible to use the difference (PFAFTER - PPBEFORE), which by default is negative. In this case, the lower this number is, the more efficient the active is. The practical procedure on how to perform the wet combing test is presented below.

The procedure consists of three steps: (1) Tress pre-treatment; (2) Treatment of the tress with shampoo; (3) Combing test. Below each of these steps are described.

2. Pretreatment of the tress. • Wash for 1 minute the tress with water with temperature 36-37 °C (water temperature was automatically regulated). Water volume rate 60-70 ml/second.

• Add 2 ml solution of 14 wt. % SLES to the tress.

• Massage for 1 minute.

• Rinse for 1 minute.

• Add solution 2 ml of 14 wt. % SLES to the tress.

• Massage for 1 minute.

• Rinse for 1 minute.

(2) Treatment of tress with shampoo.

• Homogenize the formulation via an overhead stirrer (20 min, 300 rpm).

• Pretreat the tress.

• Weight out 0.8 grams of shampoo (0.2 g of shampoo per one gram of hair tress).

• Massage for 45 seconds.

• Rinse for 30 seconds. Water volume rate 60-70 ml/second.

• Re-apply shampoo once.

(3) Combing test.

• Dip in the water.

• Comb, speed of combing 300 mm/min.

• Remove the excess water.

• Comb, speed of combing 300 mm/min.

• Perform combing test.

• Repeat the step 15 times.

2.7. Procedure for dry combing and data interpretation.

In order to evaluate the conditioning performance of the studied actives the following procedure was used:

The hair tresses were washed with solution of SLES (concentration 14 %; pH = 6).

The tresses were dried in climatic room at controlled conditions: relative humidity = 57 %; Temperature = 20 °C.

The tresses were subjected to a coming test (speed of combing 300 mm/min) via a comb with narrow teeth (11 teeth per centimeter). At least 10 passes were applied. The average initial total work for combing was calculated (PFBEFORE).

The tress was than treated with shampoo formulation, as described in the previous section.

The tress again dried at the same conditions (relative humidity = 57 %; Temperature = 20 °C).

The tresses were subjected to a coming test (speed of combing 300 mm/min) via a comb with narrow teeth (11 teeth per centimeter). At least 10 passes were applied. The average total work for combing was calculated (JTAFTER). The dimensionless work reduction was calculated, PFDL, via equation (1).

The water content of the tress was measured via the procedure described in the next section.

2.8. Measurement of the water content in hair tresses.

Information on the water content of the hair tresses is of essential importance for the interpretation of the experimental results. That is why it is measured via the following procedure.

(1) 2 g grams of hair fibers was taken from the bottom part of the tress.

(2) The hair fibers were put in a thermo gravimetric balance (producer: Mettler Toledo; model: HX204). This equipment allows real-time measurement of the mass of a sample during heating.

(3) The sample was heated at 105°C for a period of time, which is automatically determined by the equipment. The heating was stopped when there was no measurable change in the humidity.

(4) From the information of the initial and final mass of the tresses, the initial water content of the tress was calculated.

2.9. Measurement of the contact angle on hair fiber.

In the following the principle of the measurement of contact angle on hair fiber is described. The measurement protocol is described in detail in Appendix A. The contact angle on treated hair fibers was measured via tensiometer Kruss K14. The tresses used in this case are home bleached. As shown in ref. 6 the home bleached tresses allow for better reproducibility and therefore clearer evaluation of the experimental trends. The fiber was cut 5 cm from the root. The radius of the fiber was measured via a micrometer. The fiber was dipped in water container with the cuticles directed toward the end of the tip of the fiber placed in the container The instrument measures the downward force, F, exerted on the fiber via a sensitive force sensor, and calculates the contact angle from the following expression:

F = Zycos(0A) (2)

Here F is the force exerted by the capillary force on the fiber; L is the perimeter of the wetted hair fiber, calculated form the radius R of the hair fiber; 0A is advancing contact angle. This measurement was performed for 10 hair fibers. The outliers of the measurement are removed via the following procedure in Microsoft Excel:

1. The values of the first, QI and third, Q3 quartiles of the data are calculated.

2. After that the interquartile value was calculated IQV = Q3-Q1.

3. The lower and upper acceptable values are calculated via the following formulas:

LAV = Q1-1.5*IQV

UAV = Q1+1.5*IQV

If a specific value of the contact angle is outside the range LAV-UAV, it is discarded.

Quartile is a type of quantile which divides the number of data points into four parts, or quarters, of more-or-less equal size. The data must be ordered from smallest to largest to compute quartiles; as such, quartiles are a form of order statistic. The three main quartiles are as follows: The first quartile (QI) is defined as the middle number between the smallest number (minimum) and the value that falls between the 25^th and 75^th percentiles of the sample (which cuts off the first quarter of all the samples). It is also known as the lower quartile, as 25% of the data is below this point. The second quartile (Q2) is the median of a data set; thus 50% of the data lies below this point. The third quartile (Q3) is the middle value between the value that cuts off the last quarter of samples and the highest value (maximum) of the data set. It is known as the upper quartile, as 75% of the data lies below this point.

2.10. Sensorial panels in hairdresser’s saloon (shampoo formulations).

The sensorial tests of the shampoo formulations were performed via the following procedure.

(1) The hair of the model was washed for 1 min.

(2) The shampoo was applied on the hair for 1.5 minutes. The system of interest was applied to the left, while the benchmark was applied to the right, 6 grams of product each. In some cases, more shampoo was applied (10 g), this was done for longer and/or thicker hairs. During this process, the properties of foam were assessed in terms of:

• Flash foam (ease of foam generation).

• Foam amount.

• Feeling of the foam.

• Appearance (brightness) of the foam.

• Appearance of the bubbles (size, size distribution).

(3) The shampoo was rinsed off from the hair in the following sequence: (1) 30 seconds, right side; (2) 30 seconds, left side; (3) 45 seconds, right side; (4) 45 seconds, left side. During this step, the sensorial perception of the hair was evaluated with respect to the following parameters:

• Ease of rinsing.

• Sensorial perception of the hair.

(4) The hair was combed and the time for combing of each side was measured.

(5) The sensorial properties of the hair in wet state were evaluated, namely:

• Ease of detangling.

• Softness (roots and lengths).

• Softness (tips).

• Cleanliness.

• Lightness.

(6) The hair was dried, and the time for drying was measured.

(7) The sensorial properties of the hair in dry state were evaluated, namely:

• Speed of drying.

• Manageability.

• Cleanliness.

• Shine.

• Softness (roots and lengths).

• Softness (tips).

• Homogeneity of treatment.

• Anti-electrostatic.

• Hair vitality.

• Untied effect.

• Lightness. In the end of the panel the hairdresser makes a preference regarding the product with better performance and explains the rationale of her/his choice. In these tests models with Caucasian hair with damaged hair level 3-5 were employed.

Appendix A

Protocol for the measurement of the contact angle of hair fibers:

Hair treatment

Materials:

- Tresses

- Pre-treatment solution 14% pH: 6

- Gloves

- Syringe 2 ml

- Comb

- Stopwatch

- Thermometer

- Metronome

- Test tube 21

Pre-treatment:

- Leave the wicks to soak for 15 minutes in the water.

- Check the flow rate (1100ml +/- 40ml for 10s), the water temperature (36.5°C +/- 1°C) and the water hardness if not done (set point: Ix/week).

- Remove the wick from the soaking tank and hang it on the rack. Wring out the wick roughly.

- Use the syringe to withdraw 2ml of washing solution for one wick. Apply the solution to the entire length of the wick.

- Massage for 1 minute (30s per side) at a metronome pace (108 bips/min).

- Rinse for 1 minute under water (30s per side) with fingertips, following the metronome rhythm (58 bips/min).

- Comb through until you get an easy comb through (wide gap).

Repeat all these steps a second time.

Treatment of the tresses:

- Draw up 0.8 ml of shampoo with the syringe. Apply the solution to the entire length of the strand.

- Massage for 45 seconds at a metronome pace (108bips/min). - Rinse for 30 seconds under water (15s per side) with fingertips, respecting the metronome rhythm (58bips/min).

- Wring out the strand in 1 pass

- Comb through until the comb passes easily (wide gap).

Repeat all these steps a second time

Contact angle measurement

Materials:

- Scissors

- Pliers

- Aluminum foil

- Crystallizer (25ml)

- Micrometer

To measure the contact angle of the hair fibres it is important to always measure the surface tension of the water in which the fibres will be soaked. This step is very important in order to verify that the water is completely free of impurities which could distort the results.

- Measurement of the surface tension of (distilled) water

Clean the crystallizer with DECON90 and rinse with tap water and distilled water. Allow to dry on a clean surface.

- Fill the crystallizer with distilled water.

- Place the crystallizer on the balance platform.

- Then hang the rod on the scale.

- Close the scale doors and turn on the scale.

- To measure the surface tension of the water you will then need the platinum blade and a small hook

- Heat the platinum blade twice with the Bunsen burner.

- Hang the hook, then the turntable blade on the hook and raise the platform using the knob on the right of the scale until the water level was flush with the blade without touching it.

Surface and Interfacial Tension was measured using the KRUSS Laboratory Desktop 3.2 application.

- Measure as many times as necessary to obtain a tension of 72.5 mN/m. If the tension was too low, either the crystallizer was not clean or the water temperature was above 20°C.

Hair selection - Select a fiber and place it on paper: root to top of the stem

- Using a ruler, cut about 5 cm from the root and 5 cm from the tip

- Measure the diameter of the fiber: using the pliers, grab the fiber and position it in the micrometer.

- Place the fibre on the small sticky tip and cut so that % mm of hair remains above the tip

- Check that the fibre is positioned straight

Measurement of the hair contact angle

Place the small tip where the hair is attached on the rod and place the rod on the scale

- Raise the platform until the water level is flush with the hair

- Make sure that the hair is straight, if not, straighten it without damaging it with the small pliers

Appendix B

Protocol of the measurement with LC/MS (Liquid chromatography-mass spectrometry), GC (Gas chromatography).

SAMPLE PREPARATION:

- Remove approximately 400 mg of hair from a 16-ml falcon tube and pack the hair into the bottom of the falcon.

- Add approximately 4.5ml extraction solvent (CELCh-MeOH 50/50)

- Vortex for lh30.

- Remove the liquid part and perform a second extraction 4.5ml extraction solvent then vortex for lh30

- Melt the liquid fractions and evaporate to dryness on a GreenHouse Blowdown Evaporator (Radleys).

- Perform L/L extraction by adding 3 mL H2O and 3 mL CH2C12

- Remove the aqueous phase

- Evaporate again to dryness with the evaporator

- Resume in 5g BuOH to make the assay solutions

- Filter the solution obtained

EXAMPLES

OCDE 301F - Ready Biodegradability assessment using emulsion procedure

Biodegradability of estolide esters was determined using the standardized manometric assay OECD 301F test, using OxiTop®-IDS sensor available from Xylem Analytics (France). The inoculum used in this experiment was composed of a washed activated sludge sampled from La Courly, a wastewater treatment plant from Pierre-Benite (France. The inoculum was sampled and was aerated under agitation overnight to decrease organic carbon content and consequently endogenous respiration as preconized by the OECD 301 guideline using an emulsion procedure.

After overnight incubation, a final sample preparation was performed to remove the remaining excessive organic carbon. To do this, three successive centrifugation steps (9250 rpm, 15 min at room temperature) were done to remove the liquid content and resuspend the inoculum at 5 g L'¹ of MLSS (mixed liquor suspended solids) in the mineral medium of the biodegradation assay. The composition of the medium of the biodegradation assay was 85 mg L ¹ KH2PO4, 217.5 mg L ¹ K2HPO4, 334 mg L ¹ Na₂HPO₄, 27.5 mg L ¹ CaCl₂, 11.5 mg L ¹ MgSCh and 0.100 mg L ¹ FeCh. The pH of the medium was adjusted to 7.2 by the addition of a 1 M aqueous solution of HC1.

Estolide esters are poorly soluble in water or ZW medium (<1 g.L-1), in this case a emulsion was prepared before the biodegradation test OECD 301F assessment. The emulsion protocol consists at the preparation of a stock solution at 2 g/L in a non-biodegradable surfactant solution (Symperonic PE 105 at 1 g.L-1), then, this stock solution was diluted by 2 with silicone oil and an emulsion was formed, using an ultra-turax. The emulsion maintained under constant agitation was introduced directly into the test bottle which already contains the mineral medium.

A biodegradation assay was performed by incubating the washed inoculum at a final concentration of 28.38 mg MLSS L'¹ in the presence of the sample at approximatively 140 mg O2 L'¹ consumed to mineralize the totality of the sample expressed in ThOD. Biodegradation was assessment in BOD flasks incubated at 20 °C using the TS608/4i incubation chambers (Xylem Analytics; France). Biodegradation measurements are based on the variation of the atmospheric pressure, which was registered daily with the use of the OxiTop®-IDS sensors. Biodegradability was then expressed in percentage according to the quantity of oxygen required to mineralize the sample. Additional testing conditions were carried out using a reference substance used in the assay to conclude both on the functionality of the inoculum and about a non-relevant or low toxicity of the sample. To confirm the functionality of the inoculum, biodegradability of starch was followed at a final concentration of 52 mg O2 L'¹ ThOD as the reference control. Finally, to confirm the non-toxicity of the sample both starch and the item were added at the initial concentration, in an assay and the biodegradability of the mixture was assessed as the toxicity control.

Biodegradability of the sample was assessed in an enhanced ready biodegradability test, meaning that the biodegradation was followed for more than 28 days and less than 60 days. During the procedure, a set of four quality criteria were assessed to status on the quality of the biodegradation assessment. The Reference control highlighted an adequate functionality of the inoculum which degraded more than 60% (ThOD) of the starch in less than 14 days. The sample appeared as non-toxic as the toxicity control at day 14 was higher than 25% (ThOD). The repeatability of the replicates was below 10% which was in accordance with the guideline as well as the respiration of the sludge without any carbon sources was lower than 60 mg O2 L'¹ at the end of the incubation period of 28 days as needed for a valid assay. The results are shown in the Table 5 below.

According to these results estolide esters which passed the 60% biodegradation after 28 days and before 60 days can be considered as inherently biodegradable chemicals (according to the OECD guidelines) or enhanced readily biodegradable chemicals (according to the ECETOC proposal).

Example A: Preparation of Lipase from Streptomyces sp.

Streptomyces sp. Lipase gene was cloned into the pET26-b(+) expression vector from Novagen (Merck Biosciences subdivision of Merck KgaA (Darmstadt, Germany)) and then this vector was integrated into Escherichia coli host cells. (BL21 (DE3)) from Novagen. The cells were cultured in the autoinducer medium (Overnight Express Instant TB Express Medium obtained from Merck Chemicals Ltd subdivision of Merck KgaA (Darmstadt, Germany)) in the presence of kanamycin (60 pg/mL). The medium was seeded from a glycerol stock. The culture was incubated for 2 hours at 37°C then for 23 hours at 25°C (until Odeoonm = 11). After centrifugation, the cell pellets were collected and then freeze-dried. In the following examples, the quantities of lipase (El) used are expressed in milligrams of lyophilized cells

Example B

Starting materials:

Ricinoleic acid 12-HSA

Example for the Product:

Table 3

Ratio of unsaturated (RAC) and saturated (12-1) monomers.

Type of capping agent: ethanol (Et.) or 2-ethyl-l -hexanol (2EtH). Number of monomers in the chain (estolide number (EN)). The capping agent is R2 or Ri. EN is the estolide number.

It is worth noting that end capping with ethanol may present a significant advantage in terms of the ease of production. Ethanol being a volatile raw material, it may be more easily removed from the crude reaction mixture through evaporation whereas this is much more difficult to do for ethylhexanol due to its boiling point. Thus, the downstream processing could be made significantly easier by using an end capping agent as ethanol. Physical Parameters

Table 4 In table 4, the pH-value of the formulations was 5. The formulations can be used for skin and/or hair care.

For a commercial product, a surfactant chassis is needed, which ensures a formulation which is: (1) Clear, high transmittance; (2) Stable on storage; (3) High enough viscosity. The inventive estolide esters fulfill these properties.

Table 5 - Biodegradability

Different results are presented in the figures by implementing the compositions according to the invention shown in the tables above. Each figure is detailed below.

The Figure 2 shows the impact of type of tresses on the improvement of the combing.

The left column in the Fig. 2 relates to bleached hair, the right to double bleached hair. While there was no clear differentiation of the systems with bleached hair, the differentiation of the estolide esters was more pronounced with Double Bleached tresses. The results show that the estolide esters as a product in hair care are relevant for damaged hair with a significant improvement in combing.

The formula for the test was as follows: In Fig. 3 the impact of the nature of the estolide esters was illustrated (wet combing double bleached). These results showed that the estolide esters according to the invention make it possible to obtain better results than with the negative benchmark. Different amounts in the shampoo formulation (chassis A) are illustrated.

Fig. 4 illustrates the results at the different concentrations (wet combing double bleached) for

- Ricinoleic acid 100 means the estolide ester of C in table 3 or 5 in table 4.

12 HSA 100 means: the estolide ester of B in table 3 or 4 in table 4 etc.

These results show that higher performances are obtained at higher concentration of estolide ester. In addition, similar trends are obtained with saturated and unsaturated molecules.

A plateau in the performance at 0.50 wt-.% was reached. All the tests are performed with Chassis A. WW inoculum” etc. means here wastewater treatment plant inoculum.

Fig. 6 shows a testing of a haircare composition according to the invention in a sensorial panel. Two hair conditioning compositions were prepared using the same formulations which only differed in the following ingredient:

A: 1% by weight amodimethicone (silicone oil) (Comparative example)

B: 01% by weight Estolide ricinoleic acid 100 according to the invention (corresponding to estolide ester of C in table 3 or 5 in table 4).

Upon testing in sensorial panels, even if the performances are close between the two formulations, the combination in test composition B was preferred by all the sensorial panels with respect to several properties, in particular easy to comb, glide, softness, shine, as can be seen from Fig.6. As silicone oils have poor biodegradability, the cosmetic composition according to the present invention make it possible to replace them in personal care products while having the same performances.

Claims

C L A I M S

1. The use of a cosmetic composition for hair and/or skin care comprising:

A) 0.001 to 20 wt.-% of at least one component selected from at least one estolide ester compound

Al) of formula (I) wherein Ri is selected from the group of branched or linear Ci-Ci2-alkyl or C2-Ci2-alkenyl, nl and n2 are independently between 1 and 9, ml is between 1 and 9, or

A2) of formula (II) wherein R2 is selected from the group of branched or linear Ci-Ci2-alkyl or C2- Ci2-alkenyl, n3 and n5 are independently between 1 and 10, ml is between 1 and 9, or

B) 0.001 to 20 wt.-% of an estolide ester of formula (III): wherein R2 is selected from the group of branched or linear Ci-Ci2-alkyl or C2- Ci2-alkenyl, n3 and n5 are independently between 1 and 10, ml is between 1 and 9,

Xi can be a single bond, or a double bond,

X2 can be a single bond, or a double bond, with Xi different from X2, preferably wherein in case X2 is a double bond, R2 is selected from the group of branched or linear Ci-Ci2-alkyl, and wherein the estolide ester in A) to B) is obtained by an enzymatic reaction with a lipase.

2. The use according to claim 1, wherein the cosmetic composition comprises as compound C), 80 to 99.999 wt.-% water, based on the total weight of the composition.

3. The use according to claim 1 or 2, wherein the total of Xi or X2 referring to a double bond is at least 1 :1 to 10: 1 when Xi or X2 is a single bond.

4. The use according to any of the claims 1 to 3, wherein the enzymatic reaction is carried out by an enzyme selected from the group consisting a Humicola lanuginosa lipase , a Rhizomucor miehei lipase, a Candida lipase, such as a C. antarctica lipase, a Pseudomonas lipase such as a P. alcaligenes and P. pseudoalcaligenes lipase, a P. cepacia lipase, a Bacillus lipase, a B. stearothernophilus lipase and a B. pumilus lipase.

5. The use according to any of the claims 1 to 4, wherein the lipase is from Streptomyces sp..

6. The use according to any of the claims 1 to 5, wherein the lipase having the amino acid sequence SEQ ID NO. 1 next:

ATATAATPAAEATSRGWNDYSCKPSAAHPRPVVLVHGTFGNSIDNWLVL APYLVNRGYCVFSLDYGQLPGVPFFHGLGPIDKSAEQLDVFVDKVLDATG APKADLVGHSQGGMMPNYYLKFLGGADKVNALVGIAPDNHGTTLLGLT KLLPFFPGVEKFISDNTPGLADQVAGSPFITKLTAGGDTVPGVRYTVIATK YDQVVTPYRTQYLDGPNVRNVLLQDLCPVDLSEHVAIGTIDRIAFHEVAN ALDPARATPTTCASVIG, or a sequence having at least 75% identity with the sequence SEQ ID NO. 1.

7. The use according any of the claims 1 to 6, wherein compound A2) is wherein R2 is selected from the group of branched or linear Ci-Ci2-alkyl or C2-Ci2-alkenyl, n is between 1 and 9.

8. The use according any of the claims 1 to 7, wherein compound Al) is wherein Ri is selected from the group of branched or linear Ci-Ci2-alkyl or C2-Ci2-alkenyl, n is between 1 and 9.

9. The use according to any of the claims 1 to 8, wherein compound B) is wherein R2 is selected from the group of branched or linear Ci-Ci2-alkyl or C2-Ci2-alkenyl n is between 1 and 9,

Xi can be a single bond, or a double bond

X2 can be a single bond, or a double bond, wherein in case X2 is a double bond, R2 is selected from the group of branched or linear Ci-Ci2-alkyl.

10. The use according to any of the claims 1 to 9, wherein Ri and/or R2 is ethyl or 2-ethyl-l -hexyl.

11. The use according to any of the claims 1 to 10, wherein the composition further comprises:

C) 0.0001 to 95 wt.-% water

D) 0.01 to 5 wt.-% solubilizer

E) 0.01 to 2.5 wt.-% surfactant

F) 0.01 to 2.5 wt.-% foaming agent

G) 0.01 to 2.5 wt.-% thickener

H) 0.00 to 2.5 wt.-% guar gum

I) 0.00 to 2.5 wt.-% amphoteric surfactant

J) 0.00 to 2.5 wt.-% anionic surfactant

K) 0.00 to 2.5 wt.-% preservative, wherein the total of A) to K) is 100 %.

12. The use according any of the claims 1 to 11 in a hair shampoo and/or conditioning composition that is sulfated or sulfated-free.

13. The use of the cosmetic composition according any of the claims 1 to 12 in hair care compositions, preferably in hair conditioning compositions, preferably wherein said use is for increasing hair hydrophobicity.

14. A process for preparing a cosmetic composition use for hair and/or skin care according to claims 1 to 13, in particular a hair shampoo and/ or conditioning composition, comprising: the step of mixing at least one estolide ester of formula (I), (II) or (III) according to one or more of claims 1 to 10 and water, and at least one further component B or D, and optionally further components G and/ or E.

15. A method of treating the hair, comprising the steps of applying a hair shampoo and/ or conditioning composition onto wet hair, lathering and removing said shampoo and/ or conditioning composition from the hair, characterized in that the hair shampoo and/ or conditioning composition comprises at least one estolide ester of formula (I), (II) or (III) as described in any of claims 1 to 10, optionally a surfactant component E), optionally a thickener component G), optionally a solubilizer D), and optionally a further component J), different to components A) to K), with the proviso that the shampoo and/ or conditioning composition contains at least one component E) or at least one component D).