WO2014059676A1

WO2014059676A1 - Composition comprising an oxydized ester modified starch

Info

Publication number: WO2014059676A1
Application number: PCT/CN2012/083246
Authority: WO
Inventors: Yuchao CHEN; Xinrong Lin; Baiwei CHEN; Jerome Senee; Jian Zhou
Original assignee: L'oreal
Priority date: 2012-10-19
Filing date: 2012-10-19
Publication date: 2014-04-24
Also published as: CN104717959A; CN104717959B

Abstract

The invention relates to a cleansing composition comprising at least one surfactant and an acetylated oxidized starch, and a process for producing the same The cleansing composition according to the present invention is useful in cosmetic and personal care applications.

Description

COMPOSITION COMPRISING AN OXYDIZED ESTER MODIFIED STARCH

Field of the invention

[ 0001 ] The present invention relates to compositions and, in particular, cleansing compositions comprising an oxidized ester modified starch, preferably an oxidized acetylated modified starch that are useful in cosmetic and personal care applications.

Background of the invention

[ 0002 ] Formulations for personal care are conventionally known and have been used for a very long time. Products such as shampoo, cleanser, and soap are well-established products belonging to this category. Generally, such products are formulated so as to have an attractive smell, a sufficient foaming quality, and at least agreeable rinsing ability to the consumers.

[ 0003 ] Conventional cleansing compositions, especially facial cleansing compositions typically contain surfactants, and polymers. EP2042216 claims a body and hair cleansing product comprising water, substance from E list which comprises starch acetate under the code 1451 , and sodium stearoyl lactylate at the pH 4-8.

[ 0004 ] However, the conventional compositions do not have sufficient foaming quantity during application. Besides, the rinsing ability of conventional cleansing compositions is not quick enough. Lastly, conventional cleansing compositions do not bring expected skin finish, i.e., moisturizing or softening.

[ 0005 ] Thus, there remains a need for products with improved foaming properties, rinseabilities, and better skin finish in the market.

Summary of the Invention

[ 0006 ] In one respect, the present invention relates to a composition comprising at least one surfactant and an oxidized ester modified starch, preferably oxidized acetylated modified starch.

[ 0007 ] In another respect, the present invention relates to a method for treating keratin material especially skin comprising applying to the keratinous material the composition according to the present invention.

[ 0008 ] In another respect, the present invention relates to a use of an oxidized ester modified starch, preferably oxidized acetylated modified starch in producing a cleansing composition. [0009] The composition according to the present application has advantages by virtue of improved foaming properties, rinsing abilities, and better skin finishing as compared with compositions in the prior art, and can be widely used as facial cleanser.

Brief Description of the Drawing

[0010] While the specification concludes with claims distinctly pointing out the subject matter that applicant regards as his invention, it is believed that the invention will be better understood when taken in connection with the accompanying drawing in which:

[0011] Figs.1 -6 are plots showing Performance of foam produced by different level of surfactant and Acetylated Oxidized Starch, wherein

[0012] Fig .1 illustrating the volume of the foam, rinseability level, and skin finish of the invention formulas 01 to 04.

[0013] Fig. 2 illustrating the volume of the foam, rinseability level, and skin finish of the invention formulas 05 to 08.

[0014] Fig. 3 illustrating the volume of the foam, rinseability level, and skin finish of the invention formulas 09 to 12.

[0015] Fig. 4 illustrating the volume of the foam, rinseability level, and skin finish of the invention formulas 13 to 16.

[0016] Fig. 5 illustrating the volume of the foam, rinseability level, and skin finish of the invention formulas 17 to 20.

[0017] Fig. 6 illustrating the volume of the foam, rinseability level, and skin finish of the invention formulas 21 to 24.

Detailed Description of the Invention

[0018] According to the present invention, there is provided a composition comprising at least one surfactant and an oxidized ester modified starch, preferably oxidized acetylated modified starch.

[0019] According to some embodiments of the present invention, the composition optionally comprises one or more cosmetically acceptable adjuvants.

[0020] According to some embodiments of the present invention, there is provided a composition comprising 1 -20% by weight of at least one surfactant and 1 - 10% by weight of an oxidized ester modified starch, preferably oxidized acetylated modified starch, based on the total weight of the composition. [ 0021 ] Preferably, the oxidized ester modified starch, preferably oxidized acetylated modified starch represents from about 1 % to about 10% of the total weight of the composition, more preferably from about 1 % to about 5% of the total weight of the composition, and most preferably from about 2.5% to about 3.5% of the total weight of the composition, including all ranges and subranges therebetween.

[ 0022 ] According to some embodiments of the present invention, there is provided a composition comprising 1 -20% by weight of at least one surfactant; 1 - 10% by weight of an oxidized ester modified starch, preferably oxidized acetylated modified starch; and optically one or more cosmetic acceptable adjuvants, based on the total weight of the composition.

[ 0023 ] According to the present invention, there is provided a method for treating keratin material especially skin comprising applying to the keratinous material the composition.

[ 0024 ] According to some embodiments, the method for treating keratin material comprises cleansing the keratinous substrate.

[ 0025 ] According to the present invention, there is provided a use of an oxidized ester modified starch, preferably oxidized acetylated modified starch in producing a cleansing composition.

[ 0026 ] As used herein, the expression "at least one" means one or more and thus includes individual components as well as mixtures/combinations.

[ 0027 ] As used herein, the expression "oxidized" means that at least one hydroxy group of the starch has been oxidized especially in position 6 of the glucose unit of the starch: the groups -CH₂-OH for becoming an aldehyde group -C(O)-H or carboxy -C(O)-OH.

[ 0028 ] As used, the expression "ester" means that at least one hydroxy group of the glucose unit A of the starch is esterified by a (thio)carboxylic acid, especially (Ci-C8)(thio)carboxylic acid, and preferably an acetyl acid for obtaining an ester B, C or D with C and D corresponding respectively to the end or the beginning of the starch, Ra, Rb, Rc, Rd, and Re representing a hydrogen atom or a alkyl(thio)carbonyl group such as (Ci-C₈)alkyl-C(O)- or (CrC₈)alkyl-C(S)-, being understood that at least one of the radical chosen from Ra, Rb, Rc, Rd, and Re represents a alkyl(thio)carbonyl group in at least one unit of the starch :

A B c D

[ 0029 ] Therefore "oxidized ester" means that at least one hydroxy group of the starch is "oxidized" as defined herein before, and at least on other hydroxy group of the starch is "esterified" as defined herein before.

[ 0030 ] According to some embodiments, the composition of the current invention comprises as a oxidized ester modified starch, a starch which contains at least a linear polymer of glucose i.e. an amylose derivative of formula (I) and/or at least a branched polymer of glucose i.e. an amylopectine derivative of formula (II), their anomers, preferably alpha (a) anomer, their cosmetically acceptable salts, and their solvates such as hydrates :

(I)

(II)

Formula (I) and (II) wherein :

• R¹, R², R³, R⁴, and R⁵, identical or different, represent a hydroxymethyl group -CH₂-OH or an oxidized form such as -CH₂-C(O)-H, or -C(O)-OH, being understood that at least one of radical R¹, R², R³, R⁴, or R⁵ represents an oxidized form, especially -C(O)-OH, and more preferably R⁴ is in oxidized form and R¹ , R², R³ and R⁵ represent a hydroxymethyl group ;

• R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, and R¹⁶, identical or different, and

represent an hydroxy group or an (Ci-C₈)alkylcarbonyloxy group, or an (C Csjalkylthiocarbonyloxy group, preferably hydroxy group or an (Ci- C6)alkylcarbonyloxy group such as acetyl group, being understood that at least one of radical R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, or R¹⁶ ;

represents an (d-C₈)alkylcarbonyloxy group, or an (C

Csjalkylthiocarbonyloxy group, preferably (Ci-C6)alkylcarbonyloxy group such as acetyl group,

more preferably R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹³, R¹⁴, R¹⁵, and R¹⁶ represent hydroxy group and R¹² represents an (CrC₈)alkylcarbonyloxy group, or an (Ci- Csjalkylthiocarbonyloxy group, preferably (Ci-C6)alkylcarbonyloxy group such as acetyl group

• n represents an integer, especially comprized between 50 and 300 000,

especially between 100 to 200 000, more specifically between 200 to 100 000, preferably between 400 to 100 000 and more particularly between 470 to 95 000.

[0031] Average molecular masses of amylopectin modified molecules of formula (II) are at least 10⁷ and may be as large as 10⁹.

[0032] According to a preferred embodiment of the invention, the oxidized ester modified starch contains a mixture linear and branched polymer of glucose i.e. a mixture of amylose and amylopectine derivatives and more particularly in an amount between 10 and 40 % of amylose and between 60 and 90 % of amylopectine; more preferably between 15 and 20 % of amylose and between 80 and 85 % of amylopectine.

[0033] According to another embodiment of the invention the oxidized ester modified starch contains a majority of amylose derivative, more specifically between 60 to 100%, such as between 80 to 85 %.

[0034] According to an embodiment of the invention the oxidized ester modified starch, preferably oxidized acetylated modified starch is constituted of amylose derivatives of formula (I) with an average molecular masses of amyloses from different commercial starches are in the 10⁴ to 10⁷ range , more particularly 10⁵— 10⁶ range, which means that they have average degrees of polymerization (DP, number of glucosyl units per molecule) of is preferably comprised between 50 and 20000, especially between 100 and 10000 more particularly between 600 and 6000. According to some embodiments, the oxidized ester modified starch, preferably oxidized acetylated modified starch of the current invention derives from any of the natural starch that is commonly found in the plants.

[ 0035 ] Such natural starch can be found, for example, in arrowroot, tapioca, potato, sweet potato, bean (fave, lentil, and pea), buckwheat, banana, barley, cassava, corn, kudzu, oca, rice, sago, sorghum, taro, wheat, yarns, and a mixture thereof. Advantageously, tapioca, potato and wheat starch are used to produce the acetylated oxidized starch of the current invention.

[ 0036 ] According to some embodiments the oxidized ester modified starch is a acetylated modified starch. More preferably "Acetylated modified starch" as used herein is a white powder widely used in food industry with INS Number of E 1451 , and with C.A.S. number 68187-08-6.

[ 0037 ] For the purpose of the current invention, the viscosity of the oxidized ester modified starch, especially the acetylated modified starch is in the ranges from 10cP to 2000cP, preferably from 18cP to 1500cP, more preferably from 18cP to 1400cP under the temperature of at least 25 °C, preferably under the temperature of at least 45 °C, more preferably under the temperature of 85 °C. The viscosity of the the oxidized ester modified starch especially the acetylated modified starch is tested using the equipment Brookfield Visco-Meter, NDJ-1 . the ester value of the said modified starch is above 0.05.

[ 0038 ] According to a preferred embodiment, the content of the ester such as (CrC₈)alkylcarbonyloxy group, or an (CrC₈)alkylthiocarbonyloxy group, preferably (Ci-C6)alkylcarbonyloxy group such as acetyl group in particular acetyl group, of the oxidized ester modified starch, especially the acetylated modified starch is in the ranges between 0.1 % and 2.5%, preferably between 0.5% and 1 %. Being understood that the percentage correspond to the number of hydroxy group on starch have been esterified compared to the molecular weight of the modified starch.

[ 0039 ] According to another preferred embodiment, the oxidized ester modified starch, preferably oxidized acetylated modified starch of the current invention comprises, comparing to the total weight of the modified starch, from 0.3 % to 5% of the carboxyl group, preferably from 0.35% to 0.4% of the carboxyl group, more preferably from 0.37% to 0.4% of the carboxyl group.

[0040 ] Advantageously, the oxidized ester modified starch, preferably oxidized acetylated modified starch of the current invention is an acetylated oxidized tapioca starch with a viscosity of 1400cP under the temperature of 25 °C. It contains 0.4% of carboxyl group, and having a content of acetyl group of 0.76%.

[0041 ] In a preferred embodiment, in the oxidized ester modified starch, preferably oxidized acetylated modified starch contains at least one polymer of glucose of formula (I) and/or at least a branched polymer of glucose i.e. an amylopectine derivative of formula (II) as defined herein before wherein n is between 470 and 95 000 and

- R¹ , R², R³ and R⁵ represent a hydroxymethyl group ;

- R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹³, R¹⁴, R¹⁵, and R¹⁶, represent a hydroxy group and;

- R⁴ represents a carboxy group -C(O)-OH or it salt; and

- R¹² represents a (CrC6)alkylcarbonyloxy group such as acetyl group.

[0042 ] Such a starch also commercially available, for example, "Acetylated

Oxidized Starch" from Zhucheng Xingmao Corn Developing Co., Ltd. , "OXC-10" from Suzhou Gaofeng Starch Technology Co., Ltd. and "MS#6100" from Asia Modified Starch Co., Ltd, etc.

[0043] Acetylated modified starch can be easily produced in a known manner in the art. For example, the manufacturing process includes two reaction steps oxidization and esterification. Step 1 oxidization: disperse the native starch into water and take place the oxidization by sodium hydroxide and sodium hypochlorite. Add sodium metabisulfite to stop the reaction then neutralize by hydrochloric acid. Step 2 Esterification: esterify the oxidized starch obtained by step 1 by acetic anhydride and then neutralize by hydrochloric acid.

[0044 ] "Surfactant" of the current invention can be anionic surfactants, non- ionic surfactants, zwitterionic surfactants, or a mixture thereof, preferably anionic surfactants, zwitterionic surfactants, or a mixture thereof. According to an embodiment of the invention the at least surfactant is chosen from the anionic surfactant or "surface-active agent".

[0045] Anionic surfactant is understood to mean an amphiphilic compound in which the hydrophobic part carries an anionic hydrophilic group with a cationic counterion which is generally metallic (alkali metal, such as Na or K) or ammonium; the hydrophilic group is thus polar and capable of dissociating to give anions in aqueous solution.

[0046] More particularly the anionic part of the anionic surfactant is belonging to the group chosen from :

-C(O)-OH, -C(O)-O^", -SO3H, -S(O)₂O^", -OS(O)₂-OH, -OS(O)₂-O^", -P(O)(OH)₂, P(O)₂-O^",-P(O)-O₂ ^", -P(OH)₂, =P(O)-OH, -P(OH)O^", =P(O)-O^", =P-OH, =PO-, the anionic part comprising a cationic counter anion such as alkali or alkaline earth metal or organic cationic counter anion such as ammonium. Mention may be made, as anionic surface-active agents, of surface-active agents comprising carboxylate, sulfate, sulfonate, sulfoacetate, sulfosuccinate, phosphate, phosphonates, isethionate, sarcosinate, glutamate, lactylate or taurate anionic groups, salts of fatty acids, salts of galactosiduronic acids, salts of ether carboxylic acids and their mixtures, preferably sulfates, sulfonates, sulfosuccinates, phosphates, carboxylates, isethionates,, phosphonates, and a mixture.

[0047 ] More particularly, the anionic surface-active agent or agents according to the invention are chosen from:

• C₆-C₃o)alkyl sulfates, (C₆-C₃o)alkyl ether sulfates, (C₆-C₃o)alkylannido ether sulfates, alkylaryl polyether sulfates or monoglyceride sulfates;

• (C6-C3o)alkyl sulfonates, (C6-C3o)alkylamidesulfonates, (C6-C30)alkylaryl sulfonates, α-olefin sulfonates, paraffin sulfonates;

• (C6-C3o)akyl phosphates;

• (C₆-C₃o)alkyl sulfosuccinates, (C₆-C₃o)alkyl ether sulfosuccinates or (C₆- C3o)alkylamido sulfosuccinates;

• (C6-C3o)alkyl sulfoacetates;

• (C6-C₂₄)acylsarcosinates;

• (C₆-C₂₄)acylglutamates;

• (C6-C3o)alkylpolyglycoside carboxylic ethers;

• (C6-C3o)alkylpolyglycoside sulfosuccinates;

• (C6-C3o)alkyl sulfosuccinamates;

• (C6-C₂₄)acyl isethionates;

• N-[(C₆-C₂₄)acyl] taurates;

• salts of fatty acids; • R-C(O)-N(H)-CH₂-CH2-N[CH2-C(O)-O^"]-CH2-CH2-O-CH₂-C(O)-O^", (Q⁺)₂ with R-C(O)- representing a fatty acid especially the ones derived from coconut oil, and Q⁺, identical or different, representing an cationic counterion such as alkali metal for eg. sodium;

• (Cs-C2o)acyl lactylates;

• salts of (C₆-C₃o)alkyl-D-galactosiduronic acids;

• salts of (C6-C3o)alkyl polyoxyalkylenated ether carboxylic acids, of (Ce- C₃o)alkylaryl polyoxyalkylenated ether carboxylic acids or of (C₆-C₃o)- alkylamido polyoxyalkylenated ether carboxylic acids;

• and their mixtures.

[0048 ] These anionic surface-active agents are advantageously found in the form of salts in the composition according to the invention, in particular of salts of alkali metals, such as sodium; of alkaline earth metals, such as, for example, magnesium; of ammonium salts; of amine salts; or of aminoalcohol salts.

[0049] They might also, according to the conditions, occur in their acid form. It should be noted that the alkyl or acyl radicals of these various compounds preferably comprise from 12 to 20 carbon atoms. Preferably, the aryl radical denotes a phenyl or benzyl group. Furthermore, the polyoxyalkylenated anionic surface- active agents preferably comprise from 2 to 50 alkylene oxide groups, in particular ethylene oxide groups. In accordance with a preferred embodiment of the invention, the anionic surface-active agent is chosen from salts of fatty acids.

[0050 ] These anionic surface-active agents are advantageously found in the form of salts in the composition according to the invention, in particular of salts of alkali metals, such as sodium; of alkaline earth metals, such as, for example, magnesium; of ammonium salts; of amine salts; or of aminoalcohol salts.

[0051 ] They might also, according to the conditions, occur in their acid form.lt should be noted that the alkyl or acyl radicals of these various compounds preferably comprise from 12 to 20 carbon atoms. Preferably, the aryl radical denotes a phenyl or benzyl group. Furthermore, the polyoxyalkylenated anionic surface- active agents preferably comprise from 2 to 50 alkylene oxide groups, in particular ethylene oxide groups. In accordance with a preferred embodiment of the invention, the anionic surface-active agent is chosen from salts of fatty acids. [ 0052 ] Preferred anionic surfactants suitable for the current invention are chosen from salt of laureth sulfate, salt of lauryl sulfate, salt of laureth sulfosuccinate, and salt of cocoamphodiacetate, and a mixture thereof. More specifically, the anionic surfactants that can be used in the current invention can be found in the market. Non-limiting examples of such commercialized anionic surfactants are TEXAPON^® N 702 from COGNIS, TEXAPON^® LS 30 from COGNIS, TEXAPON^® SB 3 UNKONS from COGNIS, MIRANOL^® C2M CONC NP from RHODIA, and a mixture thereof. In some embodiments, the current invention comprises non-ionic surfactants.

[ 0053 ] Among the nonionic surfactants according to the invention, mention may be made, alone or as mixtures, of fatty alcohols, a-diols and alkylphenols, these three types of compound being polyethoxylated, polypropoxylated and/or polyglycerolated and containing a fatty chain comprising, for example, 8 to 40 carbon atoms, the number of ethylene oxide or propylene oxide groups possibly ranging especially from 2 to 50 and the number of glycerol groups possibly ranging especially from 2 to 30. Mention may also be made of copolymers of ethylene oxide and propylene oxide, condensates of ethylene oxide and of propylene oxide with fatty alcohols; polyethoxylated fatty amides preferably having from 2 to 30 mol of ethylene oxide, polyglycerolated fatty amides containing on average 1 to 5, and in particular 1 .5 to 4 glycerol groups, ethoxylated fatty acid esters of sorbitan containing from 2 to 30 mol of ethylene oxide, fatty acid esters of sucrose, fatty acid esters of polyethylene glycol, alkylpolyglycosides, N-alkylglucamine derivatives, amine oxides such as (Cio-Ci )alkylamine oxides or N-acylaminopropylmorpholine oxides.

Preferably the nonionic surfactant is chosen from:

• (poly)ethoxylated fatty alcohols;

• glycerolated fatty alcohols;

• alkylpolyglycosides.

[ 0054 ] The term "fatty chain" means a linear or branched, saturated or unsaturated hydrocarbon-based chain comprising from 6 to 30 carbon atoms and preferably from 8 to 30 carbon atoms.

[ 0055 ] As regards the alkyl polyglycosides or APGs, these compounds are well known to a person skilled in the art (see, for example, Kirk-Othmer's Encyclopedia:

http://onlinelibrary.wiley.eom/doi/10.1002/0471238961 .1921 180612251414.a01 .pub2 /pdf or Ullmann's Encyclopedia of Industrial Chemistry http://onlinelibrary.wiley.com/doi/10.1002/14356007.a25_747/pdf).

[ 0056 ] These compounds are represented more particularly by the following general formula:

R¹⁷O-(R¹⁸O)t (G)v (Ma)

in which formula (I la):

R¹⁷ represents a linear or branched alkyl and/or alkenyl radical comprising approximately from 8 to 24 carbon atoms or an alkylphenyl radical, the linear or branched alkyl radical of which comprises from 8 to 24 carbon atoms;

R¹⁸ represents an alkylene radical comprising approximately from 2 to 4 carbon atoms;

G represents a sugar unit comprising from 5 to 6 carbon atoms;

t denotes a value ranging from 0 to 10 and preferably from 0 to 4, and v denotes a value ranging from 1 to 15.

[ 0057 ] Preferred alkyl polyglycosides according to the present invention are compounds of formula (I la) in which R¹⁷ more particularly denotes a saturated or unsaturated and linear or branched alkyl radical comprising from 8 to 18 carbon atoms, t denotes a value ranging from 0 to 3 and more particularly still equal to 0, and G can denote glucose, fructose or galactose, preferably glucose.

The degree of polymerization, i.e. the value of v in the formula (I la), can range from 1 to 15 and preferably from 1 to 4. The average degree of polymerization is more particularly between 1 and 2 and even more preferentially from 1 .1 to 1 .5.

The glycoside bonds between the sugar units are of 1 -6 or 1 -4 type and preferably of 1 -4 type.

[ 0058 ] Compounds of formula (I la) are represented in particular by the products sold by Cognis under the names Plantaren^® (600 CS/U, 1200 and 2000) or Plantacare^® (818, 1200 and 2000). Use may also be made of the products sold by Seppic under the names Triton CG 1 10 (or Oramix CG 1 10) and Triton CG 312 (or Oramix^® NS 10), the products sold by BASF under the name Lutensol GD 70 or the products sold by Chem Y under the name AG10 LK.

[ 0059 ] Use may also be made, for example, of C8-C16 alkyl 1 ,4- polyglucoside as a 53% aqueous solution, sold by Cognis under the reference Plantacare^® 818 UP, or PLANTACARE^® 2000 UP from COGNIS. [ 0060 ] As regards the mono- or polyglycerolated surfactants, they preferably comprise on average from 1 to 30 glycerol groups, more particularly from 1 to 10 glycerol groups and in particular from 1 .5 to 5.

[ 0061 ] The monoglycerolated or polyglycerolated surfactants are preferably chosen from the compounds of the following formulae:

RO[CH₂CH(CH₂OH)O]_mH,

RO[CH₂CH(OH)CH₂O]_mH or

R'O[CH(CH₂OH)CH₂O]_mH;

in which formulae:

• R' represents a saturated or unsaturated, linear or branched hydrocarbon- based radical comprising from 8 to 40 carbon atoms and preferably from 10 to 30 carbon atoms;

• m is an integer between 1 and 30, preferably between 1 to 10 and more particularly from 1 .5 to 6; R may optionally comprise heteroatoms, for instance oxygen and nitrogen.

[ 0062 ] In particular, R' may optionally comprise one or more hydroxyl and/or ether and/or amide groups. R' preferably denotes optionally mono- or polyhydroxylated C10-C20 alkyl and/or alkenyl radicals.

[ 0063 ] Use may be made, for example, of the polyglycerolated (3.5 mol) hydroxylauryl ether sold under the name Chimexane^® NF from Chimex.

[ 0064 ] The (poly)ethoxylated fatty alcohols that are suitable for performing the invention are chosen more particularly from alcohols containing from 8 to 30 carbon atoms, and preferably from 12 to 22 carbon atoms.

[ 0065 ] The (poly)ethoxylated fatty alcohols more particularly contain one or more linear or branched, saturated or unsaturated hydrocarbon-based groups, comprising 8 to 30 carbon atoms, which are optionally substituted, in particular with one or more (in particular 1 to 4) hydroxyl groups. If they are unsaturated, these compounds may comprise one to three conjugated or non-conjugated carbon-carbon double bonds.

[ 0066 ] The (poly)ethoxylated fatty alcohol(s) preferably have the following formula:

Rf-[O-CH₂-CH₂]_n<-OH

with - Rf representing a linear or branched Cs-C₄o alkyl or linear or branched Cs-C₄o and preferably C₈-C₃o alkenyl group, optionally substituted with one or more hydroxyl groups, and

- n' is an integer between 1 and 200 inclusive, preferentially between 2 and 50 and more particularly between 8 and 30, such as 20.

[ 0067 ] The (poly)ethoxylated fatty alcohols are more particularly fatty alcohols comprising from 8 to 22 carbon atoms, oxyethylenated with 1 to 30 mol of ethylene oxide (1 to 30 OE). Among these, mention may be made more particularly of lauryl alcohol 2 OE, lauryl alcohol 3 OE, decyl alcohol 3 OE, decyl alcohol 5 OE and oleyl alcohol 20 OE.

[ 0068 ] Mixtures of these (poly)oxyethylenated fatty alcohols may also be used.

[ 0069 ] Among the nonionic surfactants, use is preferably made of C6-C2₄ alkyl polyglucosides and (poly)ethoxylated fatty alcohols, and C₈-Ci₆ alkyl polyglucosides are more particularly used.

[ 0070 ] Non-limiting examples of the non-ionic surfactants that can be used in the current invention comprise fatty alcohol, alkyl glucoside, polyoxyalkylene glycol ether, sorbitan alkyl ester, ethanolamine and its derivatives, alkylamide oxide, block copolymer, polyethoxylated tallow amine, and a mixture thereof. Preferred examples of the non-ionic surfactants as used in the current invention comprises coco- glucoside, decyl glucoside, cocamide MEA, dodecyldimethylamine oxide , and a mixture thereof.

[ 0071 ] Zwitterionic surfactant means a neutral surfactant having cationic and anionic charges in equilibrium; wherein the charges are generally on non adjacent atoms.

[ 0072 ] Amphoteric surfactant means also a surfactant having central equilibrated cationic and anionic charges which can be anionic in alkaline media, cationic in acid medium and non-ionic at neutral pH.

[ 0073 ] The amphoteric or zwitterionic surfactant(s) that may be used in the present invention may especially be optionally quaternized secondary or tertiary aliphatic amine derivatives containing at least one anionic group, for instance a carboxylate, sulfonate, sulfate, phosphate or phosphonate group, and in which the aliphatic group or at least one of the aliphatic groups is a linear or branched chain comprising from 8 to 22 carbon atoms. [ 0074 ] The zwitterionic or amphoteric surfactants, whose nature is not a critical factor in the context of the present invention, can in particular be (non- restrictive list) derivatives of aliphatic secondary or tertiary amines, wherein the aliphatic radical is a linear or branched chain containing 8 to 22 atoms of carbon and containing at least one water-solubilising anionic group (for example carboxylate, sulphonate, sulphate, phosphate or phosphonate); the (C₈-C₂o) alkyl betaines, sulphobetaines, (C8-C20) alkyl amido(Ci -Ce) alkyl betaines or (C8-C20) alkyl amido(Ci-C6) alkyl sulphobetaines may also be cited.

[ 0075 ] Examples of amphoteric or zwitterionic surfactants that may be used include alkylbetaines, N-alkylamidobetaines and derivatives thereof, sultaines, alkylpolyaminocarboxylat.es (APAC) and alkyl amphoacetates, and mixtures thereof.

[ 0076 ] Examples of alkylbetaines that may be mentioned include cocobetaine, for instance the product sold under the name Dehyton AB-30^® by the company Cognis; laurylbetaine, for instance the product sold under the name Genagen KB^® by the company Clariant; oxyethylenated (10 EO) laurylbetaine, for instance the product sold under the name Lauryl Ether (10 OE) Betaine^® by the company Shin Nihon Rica; oxyethylenated (10 EO) stearylbetaine, for instance the product sold under the name Stearyl Ether (10 OE) Betaine^® by the company Shin Nihon Rica. Preferably cocobetaine sold under the name Dehyton AB-30^® by the company Cognis is used in the current invention.

[ 0077 ] Among the N-alkylamidobetaines and derivatives thereof that may be mentioned, for example, are the cocamidopropylbetaine sold under the name Lebon 2000 HG^® by the company Sanyo, under the name Empigen BB^® by the company Albright & Wilson, or under the name DEHYTON® PK 45 by the company COGNIS; the lauramidopropylbetaine sold under the name Rewoteric AMB12P^® by the company Witco. Preferably cocamidopropylbetaine sold under the name DEHYTON^® PK 45 from COGNIS is used in the current invention.

[ 0078 ] A sultaine that may be mentioned is the cocoyl- amidopropylhydroxysulfobetaine sold under the name Crosultaine C-50^® by the company Croda.

[ 0079 ] Alkylpolyaminocarboxylat.es (APAC) that may be mentioned include the sodium cocoylpolyaminocarboxylate sold under the name Ampholak 7 CX/C^® and Ampholak 7 CX^® by the company Akzo Nobel; the sodium stearylpolyamino- carboxylate sold under the name Ampholak 7 TX C^® by the company Akzo Nobel; the sodium carboxymethyloleylpolypropylamine sold under the name Ampholak XO7/C^® by the company Akzo Nobel.

[0080] Examples of alkylamphoacetates that may be mentioned include N- disodium N-cocoyl-N-carboxymethoxyethyl-N-carboxymethylethylenediamine (CTFA name: disodium cocamphodiacetate), for instance the product sold under the name Miranol C2M Concentrate NP^® by the company Rhodia Chimie; and N-sodium N- cocoyl-N-hydroxyethyl-N-carboxymethylethylenediamine (CTFA name: sodium cocamphoacetate).

[0081] Among the amphoteric or zwitterionic surfactants that will be used more particularly are:

- cocobetaine such as the commercial products Dehyton AB-30^® sold by the company Cognis,

- cocamidopropylbetaine such as the commercial products DEHYTON^® PK 45 sold by the company COGNIS,

or mixtures thereof.

[0082] Preferably, the at least one surfactant represents from 1 % to 20% of the total weight of the composition, more preferably from 5% to 16% of the total weight of the composition, and most preferably from 9% to 1 1 % of the total weight of the composition, including all ranges and subranges therebetween.

[0083] In a known manner, the composition of the invention may also contain adjuvants that are common in cosmetics and/or dermatology, such as active agents, preserving agents, antioxidants, complexing agents, pH modifiers (acidic or basic), fragrances, fillers, bactericides, odour absorbers, colorants (pigments and dyes), film-forming polymers, thickeners and/or gelling agents, and solvents like glycols ( glycerine, propylene glycol and butylenes glycol) The amounts of these various adjuvants are those conventionally used in the field under consideration, for example from 0.1 % to 10% of the total weight of the composition. Depending on their nature, these adjuvants may be introduced into the fatty phase, into the aqueous phase and/or into the lipid vesicles.

[0084] Needless to say, a person skilled in the art will take care to select this or these optional additional compound(s), and/or the amount thereof, such that the make up removing/oily residue removing properties of the composition according to the invention are not, or are not substantially, adversely affected by the envisaged addition. [ 0085 ] In the patent application, unless specifically mentioned otherwise, the contents are expressed on a weight basis relative to the total weight of the composition.

[ 0086 ] The examples that follow are aimed at illustrating the compositions and processes according to this invention, but are not in any way a limitation of the scope of the invention. All the parts and percentages in the examples are given on a weight basis and all the measurements were obtained at about 25°C, unless otherwise mentioned.

[ 0087 ] According to preferred embodiments of the present invention, compositions of the present invention can comprise water. Preferably, cleansing compositions of the present invention comprise from 50% to 95% water, more preferably from 70% to 90% water, and more preferably from 80% to 86% water by weight with respect to the total weight of the composition, including all ranges and subranges there between.

[ 0088 ] "Foaming property" as used herein refers to volume of foam, being obtained at the end of rubbing hands, which is evaluated visually after collecting all of the foam in one hand; foam density, the compactness of foam quality, which is evaluated tactilely by pressing the foam between two palms at the end of rubbing hands. The more the foam is pressed, the less dense the foam is.

[ 0089 ] "Rinseability" as used herein refers to quickness of the strongest squeaky feeling of whole face occurs. Rinsing ability is evaluated tactilely during several rinsing movements, when fingers "rub" face from top to bottom of cheeks.

[ 0090 ] "Skin finish" as used herein refers to dry skin, astate of dehydration or relative deficiency of water, is evaluated visually by lifting cheeks by fingers, and observing conditions of dehydration lines on face; tight skin, tugging sensation, is evaluated by feeling absence or presence of tugging of skin when making facial expressions.

[ 0091 ] Unless otherwise indicated, all numbers expressing quantities of ingredients, reaction conditions, and so forth used in the specification and claims are to be understood as being modified in all instances by the term "about." Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained by the present invention. [ 0092 ] Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contain certain errors necessarily resulting from the standard deviation found in their respective measurements. The following examples are intended to illustrate the invention without limiting the scope as a result. The percentages are given on a weight basis.

[ 0093 ] The examples that follow are aimed at illustrating the compositions and processes according to this invention, but are not in any way a limitation of the scope of the invention. All the parts and percentages in the examples are given on a weight basis and all the measurements were obtained at about 25°C, unless otherwise mentioned.

EXEMPLES

Example 1

[ 0094 ] A cleansing composition was prepared containing the following ingredients:

SODIUM CHLORIDE from Morton Salt)

CITRIC ACID (CITRIC ACID

MONOHYDRATE FINE GRANULAR from

E CITRIQUE BELGE) 0.20

METHYLISOTHIAZOLINONE (NEOLONE™

950 PRESERVATIVE from Rohm and Haas,

F DOW Chemical) 0.01

WATER Qsp to 100

[0095] Procedure for preparation of the cleansing composition: disperse phase A in water, heat to 75 °C to dissolve the mixture, add phase B, C and D in order, cool down the temperature to 40 °C to add phase E and F, finish the procedure at 28 °C.

Example 2

[0096] cleansing compositions were prepared containing the following ingredients in the same manner as that in example 1 :

Formula of 1% Total Surfactant

Formula of 20% Total Surfactant

of the raw material)

Invention formula number 05 06 07 08

SODIUM LAURETH SULFATE

2 2 2 2 (TEXAPON® N 702 from Cognis BASF)

COCO-BETAINE (MIRATAINE® BB/FLA

18 18 18 18 from RHODIA)

ACETYLATED OXIDIZED STARCH (OXC-

0 1 5 10 10 from Suzhou Gaofeng 1 1 )

METHYLISOTHIAZOLINONE

(NEOLONE™ 950 PRESERVATIVE from 0.01 0.01 0.01 0.01 Rohm and Haas, DOW Chemical)

WATER 79.99 78.99 74.99 69.99

Formula of 5% Total Surfactant

PERCENTAGE OF INGREDIENTS (% by weight of the raw material)

Invention formula number 09 10 1 1 12

COCO-BETAINE (MIRATAINE® BB/FLA

1 1 1 1 from RHODIA)

DECYL-GLUCOSIDE (PLANTACARE®

4 4 4 4 2000 UP from BASF)

ACETYLATED OXIDIZED STARCH (OXC-

0 1 5 10 10 from Suzhou Gaofeng)

METHYLISOTHIAZOLINONE

WATER 94.99 93.99 89.99 84.99

Formula of 16% Total Surfactant

PERCENTAGE OF INGREDIENTS (% by weight of the raw material) Invention formula number 13 14 15 16

SODIUM LAURETH SULFATE

4.5 4.5 4.5 4.5 (TEXAPON® N 702 from Cognis BASF)

COCO-BETAINE (MIRATAINE® BB/FLA

6 6 6 6 from RHODIA)

DECYL-GLUCOSIDE (PLANTACARE®

1 1 1 1 2000 UP from BASF)

DISODIUM LAURETH SULFOSUCCINATE

(TEXAPON® SB 3 UNKONS from COGNIS 4.5 4.5 4.5 4.5

BASF)

ACETYLATED OXIDIZED STARCH (OXC-

0 1 5 10 10 from Suzhou Gaofeng)

METHYLISOTHIAZOLINONE

WATER 83.99 82.99 78.99 73.99

Formula of 9% Total Surfactant

(NEOLONE™ 950 PRESERVATIVE from

Rohm and Haas, DOW Chemical)

WATER 90.99 89.99 85.99 80.99

Formula of 11% Total Surfactant

[0097] The performance of cleansing compositions obtained in examples 1 and 2 are subject to evaluation of washing the skin and the skin with makeup by five expert panelists. Foaming property, rinseability and skin finish were evaluated according to the following methods and average values of evaluation scores by five panelists were calculated. The results obtained are showed in Figs. 1 -6.

[0098] Evaluation of the foaming property (volume of foam)

[0099] Score: 5: very large; 4:slightly large; 3:common; 2: slightly small; 1 :small.

[00100] Evaluation of rinseability

[00101] Score: 5: makeup is removed; 4: makeup is slightly removed; 3: common; 2: makeup is less removed; 1 : makeup is not removed. [00102] Evaluation of skin finish

[00103] Score: 5: very good; 4: good; 3: fair; 2: slightly bad; 1 : bad.

[00104] It can be seen from Figs.1 -6 that the acetylated modified starch improves the performance of foam in terms of the enhancement of foaming property, rinse ability and skin finish at level of 1 %, 5%, 10%, compared with the score from the products without the starch as such. This is same case when the invention formulas contain different levels of surfactants (1 %, 5%, 9%, 1 1 %, 16% and 20%). In this experiment, three categories of surfactant— anionic surfactants (SLS, DISODIUM LAURETH SULFOSUCCINATE), zwitterionic or amphoteric surfactants (coco betaine) and nonionic surfactants (APG) are used in different combination. As it can be observed from the results, the composition according to the invention containing at least one oxidized ester modified starch and at least one surfactant significantly improves the foam in surfactant base gel cleanser.

[00105] While the present invention has been discussed in connection with preferred embodiments, those skilled in the art will recognize or be able to ascertain using no more than routine experiments, numerous equivalents to the specific compositions described herein. Such equivalents are considered to be within the scope of the present invention and are covered by the following claims.

Claims

WHAT IS CLAIMED IS:

1 . A composition comprising at least one surfactant and at least one oxidized ester modified starch, preferably oxidized acetylated modified starch.

2. A composition according to claim 1 , wherein the oxidized ester modified starch contains i) at least a linear polymer of glucose i.e. an amylose derivative of formula (I) and/or ii) at least a branched polymer of glucose i.e. an amylopectine derivative of formula (II), their anomers, preferably alpha (a) anomer, their cosmetically acceptable salts, and their solvates such as hydrates :

(II)

formula (I) and (II) wherein :

represent an hydroxy group or an (Ci-Csjalkylcarbonyloxy group, or an (Ci- Csjalkylthiocarbonyloxy group, preferably hydroxy group or an (Ci- C₆)alkylcarbonyloxy group such as acetyl group, being understood that at least one of radical R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, or R¹⁶ ;

represents an (Ci-Csjalkylcarbonyloxy group, or an (Ci- Csjalkylthiocarbonyloxy group, preferably (Ci-C6)alkylcarbonyloxy group such as acetyl group,

more preferably R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹³, R¹⁴, R¹⁵, and R¹⁶ represent hydroxy group and R¹² represents an (Ci-Csjalkylcarbonyloxy group, or an (Ci- Csjalkylthiocarbonyloxy group, preferably (Ci-C6)alkylcarbonyloxy group such as acetyl group

• n represents an integer, especially comprized between 50 and 300 000,

especially between 100 to 200 000, more specifically between 200 to 100 000, preferably between 400 to 100 000 and more particularly between 470 to

95 000 ;

• average of molecular masses of amylopectin derivative molecules of formula (II) is at least 10⁷ and may be as large as 10⁹.

3. A composition according to any of the preceding claims, wherein the oxidized ester modified starch contains a mixture of linear and branched polymer of glucose i.e. a mixture of amylose and amylopectine derivatives and more particularly in an amount between 10 and 40 % of amylose and between 60 and 90 % of amylopectine; more preferably between 15 and 20 % of amylose and between 80 and 85 % of amylopectine.

4. A composition according to the claims 1 or 2, wherein the oxidized ester modified starch contains a majority of amylose derivative, more specifically between 60 to 100%, such as between 80 to 85 %.

5. A composition according to any of the preceding claims, wherein the oxidized ester modified starch contains amylose derivatives of formula (I) with an average molecular masses of amyloses in the 10⁴ to 10⁷ range, more particularly 10⁵— 10⁶ range, and/or have average degrees of polymerization comprised between 50 and 20000, especially between 100 and 10000 more particularly between 600 and 6000.

6. A composition according to any of the preceding claims, wherein the oxidized ester modified starch comprises, based on the total weight of the starch, from 0.3 to 5%, preferably from 0.35% to 0.4%, more preferably from 0.37% to 0.4%, of carboxyl group -C(O)OH or its salt.

7. A composition according to any of the preceding claims, wherein the surfactant is selected from the group consisting of anionic surfactants, nonionic surfactants, zwitterionic or amphoteric surfactants, and a mixture thereof, preferably anionic surfactants and/or zwitterionic or amphoteric surfactants, and the mixtures thereof.

8. A composition of any of the preceding claims, wherein the surfactant is selected from the group consisting of sulfates, sulfonates, sulfosuccinates, phosphates, carboxylates, isethionates, and phosphonates, fatty alcohol, alkyl glucoside, alkylbetaines, polyoxyalkylene glycol ether, sorbitan alkyl ester ofmonoethanolamine (MEA), alkylamide of monoethanolamine and its dirivatives, alkylamide oxide, block copolymer, polyethoxylated tallow amine, and a mixture thereof, and preferably sulfates such as laureth sulfate, sulfosuccinates such as laureth sulfosuccinate, alkylgucoside such as decyl glucoside and alkylbetaines such as coco-betaines and a mixture thereof.

9. A composition of the any one of the preceding claims, wherein the surfactant is selected from the group consisting of salt of laureth sulfate especially of alkaline metal such sodium, salt of lauryl sulfate especially of alkaline metal such sodium, salt of laureth sulfosuccinate especially of alkaline metal such sodiumsalt of cocoamphodiacetate, especially of alkaline metal such sodium, coco-glucoside, decyl glucoside, cocamide MEA, dodecyldimethylamine oxide, coco-betaine, cocamidopropyl betaine, and a mixture thereof.

10. A composition of any of the preceding claims, wherein the surfactant is present in the composition ranging from 1 % to 20%, preferably from 5% to 16%, more preferably from 9% to 1 1 % by total weight of the composition.

1 1 . A composition of any of the preceding claims, wherein the modified starch is present in the composition ranging from 1 % to 10%, preferably from 1 % to 5%, more preferably from 2.5% to 3.5% by total weight of the composition.

12. A composition of any of the preceding claims, further comprising one or more cosmetic acceptably adjuvants selected from the group fillers, emulsifiers, colorants, fragrance agent, thickener, preservative, pH regulator, active agents, antioxidants, complexing agents, bactericides, odour absorbers, film-forming polymers, thickeners, gelling agents, solvents, and mixtures thereof.

13. A cleansing composition of any of the preceding claims, wherein the filler is selected from the group consisting of aluminum hydroxide, aluminum silicate, bentonite, calcium carbonate, calcium chloride, kaolin, magnesium aluminum silicate, magnesium carbonate, magnesium oxide, mica, montmorillonite, perlite, pumice, silica, sodium metasilicate, sodium potassium, aluminum silicate, sodium silicate, hetorite, talc, and a mixture thereof.

14. A method for treating keratin material especially skin comprising applying to the keratinous material the composition of any one of claims 1 to 13.

15. The method of the preceding claim, wherein said method for treating keratin material comprises cleansing the keratinous substrate.

16. A use of an oxidized ester modified starch, preferably oxidized acetylated modified starch, for cosmetic purpose, especially for cleansing keratin material wherein said oxidized ester modified starch contains i) at least a linear polymer of glucose i.e. an amylose derivative of formula (I) and/or ii) at least a branched polymer of glucose i.e. an amylopectine derivative of formula (II), their anomers, preferably alpha (a) anomer, their cosmetically acceptable salts, and their solvates such as hydrates, wherein (I) and (II) are as defined in any of the preceding claims 2 to 6.