阅读说明：本技术 包含超支化共聚物和头发定型聚合物的化妆品组合物 (Cosmetic composition comprising hyperbranched copolymer and hair styling polymer ) 是由 卡丽娜·赫克 梅兰妮·韦克尔 于 2019-08-12 设计创作，主要内容包括：本发明涉及具有特定的超支化共聚物和头发定型聚合物的化妆品组合物。已经观察到,这种化妆品组合物具有增加的头发弹性和维持卷曲头发的卷曲保持性的非常独特的组合。(The present invention relates to cosmetic compositions having specific hyperbranched copolymers and hair styling polymers. It has been observed that such cosmetic compositions have a very unique combination of increased hair elasticity and maintained curl retention of curled hair.)

1. A cosmetic composition comprising

a) Hyperbranched copolymers of the following monomers:

(i) a dodecenyl succinic anhydride, a mixture of dodecenyl succinic anhydrides,

(ii) a mixture of diisopropanolamine and a mixture of diisopropanolamine,

(iii) the amino-bis-Dimethylaminopropylamine (DMAPA),

the hyperbranched copolymer has terminal groups of the formula

And having a molecular weight Mn of from 1200 to 4000 g/mol;

and

b) a hair styling polymer which is a nonionic, anionic or amphoteric hair styling polymer or a cationic hair styling polymer selected from polyquaternium 4, polyquaternium 11, polyquaternium 16 and polyquaternium 46.

2. The composition of claim 1, wherein the hyperbranched copolymer is prepared by:

a1) polymerizing the monomers (i) and (ii) and (iii) to giveHas the formulaThe terminal dimethylamino-terminated polyester amide of (1);

a2) the dimethylamino group of the polyesteramide of step a1) is quaternized by 2-chloroacetate, in particular by sodium 2-chloroacetate.

3. Cosmetic composition according to any one of the preceding claims, characterized in that the molar ratio between the monomers (i) and (ii) is 5: 1 to 0.5: 1, in particular 4: 1 to 1: 1, preferably 3: 1 and 3: 2.

4. cosmetic composition according to any one of the preceding claims, characterized in that the molar ratio of the monomers (i) and (iii) is 5: 1 to 0.5: 1, in particular 3: 1 to 1: 1, preferably 2.5: 1 to 1.1: 1.

5. cosmetic composition according to any one of the preceding claims, characterized in that the hair-setting polymer is

-nonionic hair-setting polymers selected from homopolymers of N-vinylpyrrolidone (═ polyvinylpyrrolidone) and copolymers of N-vinylpyrrolidone and vinyl acetate;

or

-a cationic hair styling polymer selected from polyquaternium 4, polyquaternium 11, polyquaternium 16 and polyquaternium 46;

or

-an anionic hair styling polymer selected from anionic (meth) acrylate copolymers;

or

Amphoteric hair-setting polymers chosen from octylacrylamide/acrylate/butylaminoethyl methacrylate copolymers.

6. Cosmetic composition according to any one of the preceding claims, characterized in that the hair-setting polymer is an acrylic copolymer of the monomers methacrylic acid, n-butyl methacrylate, ethyl acrylate and ethyl methacrylate.

7. Cosmetic composition according to any one of the preceding claims, characterized in that the hyperbranched copolymer has a number-average molecular weight M_nFrom 1400 to 3000g/mol, preferably from 2100 to 2400 g/mol.

8. Cosmetic composition according to any one of the preceding claims, characterized in that the hyperbranched copolymer is polyquaternium-110.

9. Cosmetic composition according to any one of the preceding claims, characterized in that the weight ratio of hyperbranched copolymer and hair styling polymer is 0.1: 1 to 0.8: 1, preferably 0.2: 1 to 0.7: 1, more preferably 0.23: 1 to 0.65: 1.

10. cosmetic composition according to any one of the preceding claims, characterized in that the amount of hyperbranched copolymer in the cosmetic composition is from 0.1 to 10% by weight, preferably from 0.5 to 7% by weight, more preferably from 1 to 3% by weight.

11. Use of a cosmetic combination according to any of the preceding claims 1 to 10 for increasing the elasticity of hair and/or maintaining the curl retention of curly hair.

Technical Field

The invention relates to the field of cosmetics, in particular to the field of hair care.

Background

Hair care products are an important part of cosmetics. The requirements for a particular hair care product vary widely due to the varying types of hair and the manner in which the hair is styled.

However, increasing the elasticity of hair and maintaining curl retention of curly hair have been highly desirable properties in hair care and styling products, as these factors are important to prevent the hair from becoming frizzy.

"frizzy" hair is a major hair care problem for consumers, particularly those who are thick, wavy, or curly, and those who have stressed hair due to frequent chemical, mechanical, or hot ironing treatments. Frizzy hair is characterized by multiple scattered hair strands, which makes the overall style appear irregular. Frizzy hair is difficult to handle during styling and tends to lose its natural shape and/or definition of curl. This is not feasible for most consumers who desire to maintain good hair style and hair hold throughout the day.

Disclosure of Invention

The problem to be solved by the present invention is to provide a cosmetic composition having a very unique combination of increasing hair elasticity and maintaining curl retention of curled hair.

It has surprisingly been found that a cosmetic composition according to claim 1 comprising a specific hyperbranched copolymer and a hair styling polymer is able to provide a solution to this problem.

Other aspects of the invention are subject matter of further independent claims. Particularly preferred embodiments are the subject of the dependent claims.

Detailed Description

In a first aspect the present invention relates to a cosmetic composition comprising

a) Hyperbranched copolymers of the following monomers:

(i) a dodecenyl succinic anhydride, a mixture of dodecenyl succinic anhydrides,

(ii) a mixture of diisopropanolamine and a mixture of diisopropanolamine,

(iii) the amino-bis-Dimethylaminopropylamine (DMAPA),

the hyperbranched copolymer has terminal groups of the formula

And having a molecular weight Mn of from 1200 to 4000 g/mol;

and

b) a hair styling polymer which is a nonionic, anionic or amphoteric hair styling polymer or a cationic hair styling polymer selected from polyquaternium 4, polyquaternium 11, polyquaternium 16 and polyquaternium 46.

Hyperbranched copolymers

The cosmetic composition comprises a hyperbranched copolymer of the following monomers:

(i) a dodecenyl succinic anhydride, a mixture of dodecenyl succinic anhydrides,

(ii) a mixture of diisopropanolamine and a mixture of diisopropanolamine,

(iii) the amino-bis-Dimethylaminopropylamine (DMAPA),

the hyperbranched copolymer has terminal groups of the formula

And has a molecular weight Mn of from 1200 to 4000 g/mol.

The hyperbranched copolymer is preferably prepared by the following steps:

a1) polymerizing monomers (i) and (ii) and (iii) to give a monomer having formula (la)The terminal dimethylamino-terminated polyester amide of (1);

a2) the dimethylamino group of the polyesteramide of step a1) is quaternized by 2-chloroacetate, in particular by sodium 2-chloroacetate.

Related to the generation of corresponding compounds of formulaThe details of the polymerization step a1) of the dimethylamino-terminated polyesteramide of (a) are disclosed in, for example, EP 2794729B 1.

Preferably, in the polymerization step a1), the monomer (iii) is added to the mixture of monomers (ii) and (iii) with stirring and then heated.

EP 2794729B 1 also discloses details of the quaternization step a 2). Thus, the entire content of EP 2794729B 1 is incorporated herein by reference.

The term "molecular weight Mn" denotes the number average molecular weight (also commonly referred to as number average molar mass).

The amount of hyperbranched copolymer, which is a hyperbranched copolymer of the following monomers, is generally from 0.1 to 2% by weight relative to the weight of the cosmetic composition

(i) A dodecenyl succinic anhydride, a mixture of dodecenyl succinic anhydrides,

(ii) a mixture of diisopropanolamine and a mixture of diisopropanolamine,

(iii) the amino-bis-Dimethylaminopropylamine (DMAPA),

having terminal groups of the formula

And has a molecular weight Mn of from 1200 to 4000 g/mol.

Preferably, the molar ratio of monomers (i) and (ii) is 5: 1 to 0.5: 1, in particular 4: 1 to 1: 1, preferably 3: 1 and 3: 2.

further preferably, the molar ratio of monomers (i) and (iii) is 5: 1 to 0.5: 1, in particular 3: 1 to 1: 1, preferably 2.5: 1 to 1.1: 1.

number average molecular weight M of hyperbranched copolymer_nPreferably 1400 to 3000g/mol, preferably 2100 to 2400g/mol, more preferably 2100 to 2300 g/mol.

Preferably, the hyperbranched polymer is polyquaternium-110, also identified by CAS number 1323977-82-7.

Hair styling polymers

The cosmetic composition further comprises an additional polymer which is a hair styling polymer which is a nonionic, anionic or amphoteric hair styling polymer or a cationic hair styling polymer selected from polyquaternium 4, polyquaternium-11, polyquaternium-16 and polyquaternium-46. Hair styling polymers are known per se to those skilled in the art.

Non-ionicExamples of hair styling polymers are homopolymers of N-vinylpyrrolidone and copolymers of N-vinylpyrrolidone (NVP) with compatible nonionic monomers such as Vinyl Acetate (VA). Nonionic polymers comprising N-vinylpyrrolidone of various weight average molecular weights are available, for example, from Ashland. Specific examples of such materials are homopolymers of N-vinylpyrrolidone having an average molecular weight of about 630'000 sold under the name PVP K-90 and homopolymers of N-vinylpyrrolidone having an average molecular weight of about 1'000'000 sold under the name PVP K-120. For example, at 70: 30. 60: 40. 50: 50. 30: 70 of N-vinylpyrrolidone: examples of copolymers of vinyl acetate with different proportions of N-vinylpyrrolidone and vinyl acetate are commercially available. For example, they are sold by different suppliers, such as Ashland or BASF, under trade names including the identifiers VA-64 (60/40 for ratio NVP/VA) or VA-55 (50/50 for ratio NVP/VA) or VA-37 (30/70 for ratio NVP/VA) or VA-73 (70/30 for ratio NVP/VA).

Preferred nonionic hair styling polymers are PVP (polyvinylpyrrolidone) and N-vinylpyrrolidone/vinyl acetate copolymer, preferably in the ratio NVP/VA 60/40.

It is preferable thatCation(s)The hair styling polymers are polyquaternium 16 and polyquaternium 46.

It is preferable thatAmphoteric propertyA hair styling polymer. Particularly preferred are octylacrylamide/acrylate/butylaminoethyl methacrylate copolymers. Examples of such polymers are available under the trade name NouroynPolymers are commercially available.

Anion(s)Examples of hair styling polymers are: copolymers of vinyl acetate and crotonic acid; terpolymers of vinyl acetate, crotonic acid and vinyl esters of alpha-branched saturated aliphatic monocarboxylic acids, such as vinyl neodecanoate; copolymers of methyl vinyl ether and maleic anhydride (molar ratio about 1: 1), wherein the copolymers are substituted with a compound having from 1 to 4 carbon atoms50% esterification of saturated alcohol (such as ethanol or butanol); acrylic copolymers comprising acrylic acid or methacrylic acid as anionic group-containing segment with other monomers such as: esters of acrylic acid or methacrylic acid with one or more saturated alcohols having from 1 to 22 carbon atoms (e.g., methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-butyl acrylate, t-butyl methacrylate, n-hexyl acrylate, n-octyl acrylate, lauryl methacrylate, and docosyl acrylate); diols having 1 to 6 carbon atoms (e.g., hydroxypropyl methacrylate and hydroxyethyl acrylate); styrene; vinyl caprolactam; vinyl acetate; (ii) acrylamide; alkyl acrylamides and alkyl methacrylamides having 1 to 8 carbon atoms in the alkyl group (e.g., methacrylamide, t-butyl acrylamide, and n-octyl acrylamide); and other compatible unsaturated monomers.

Other suitable anionic hair styling polymers include carboxylated polyurethanes. Carboxylated polyurethane resins are linear, hydroxyl-terminated copolymers having pendant carboxyl groups. They may be ethoxylated and/or propoxylated at least at one end. The carboxyl group may be a carboxylic acid group or an ester group, wherein the alkyl segment of the ester group contains 1 to 3 carbon atoms. The carboxylated polyurethane resin may also be a copolymer of polyvinylpyrrolidone and polyurethane, under the CTFA name PVP/polycarbamoylpolyethylene glycol ester. Suitable carboxylated polyurethane resins are disclosed in EP-A-0619111 and US 5,000,955. Other suitable hydrophilic polyurethanes are disclosed in US 3,822,238; US 4,156,066; US 4,156,067; US 4,255,550 and US 4,743,673.

Preferred anionic hair styling polymers are anionic (meth) acrylate copolymers, in particular C selected from acrylic acid, methacrylic acid, acrylic acid_1-6Alkyl esters, methacrylic acid C_1-6Alkyl esters, acrylic acid C_2-10Aminoalkyl esters, C of methacrylic acid_2-10Aminoalkyl esters, C of acrylic acid_1-6C of alkylamides and methacrylic acid_1-6-copolymers of at least two monomers of alkylamides.

In a most preferred embodiment, the hair styling polymer is an anionic acrylic copolymer, particularly an acrylic copolymer of the monomers methacrylic acid, n-butyl methacrylate, ethyl acrylate and ethyl methacrylate. Preferred are acrylic copolymers such as those disclosed in WO2011/057882a 1. Details of the polymers and their production can also be found in WO2011/057882a 1. As hair styling polymers, those available under the trade name DSM Nutritional Products Ltd are particularly preferredFix A1000[CAS：1070166-98-1]Commercially available butyl methacrylate/methacrylic acid/ethyl acrylate/ethyl methacrylate copolymers.

It has been observed that the use of the above acrylic copolymers in cosmetic compositions produces particularly good and natural hair feel.

The weight ratio of hyperbranched copolymer to hair styling polymer is generally in the range of 0.1: 1 to 0.8: 1, preferably between 0.2: 1 to 0.7: 1, more preferably between 0.23: 1 to 0.65: 1.

The amount of hyperbranched copolymer in the cosmetic composition is generally from 0.1 to 10% by weight, preferably from 0.5 to 7% by weight, more preferably from 1 to 3% by weight.

Other ingredients

The cosmetic composition may comprise other ingredients mainly known to the person skilled in the art.

In particular, the cosmetic composition comprises water. The amount will depend to a large extent on the type of application and the use of the composition.

The cosmetic composition may comprise further ingredients to enhance performance and/or consumer acceptability, such as antioxidants, thickeners, emollients, antifoams, moisturizers, fragrances, cosurfactants, fillers, chelating agents, cationic, nonionic or amphoteric polymers or mixtures thereof, acidifying or basifying agents, dyes, colorants, pigments or nanopigments, pearlizing or opacifying agents, organic or inorganic particles, viscosity modifiers and natural hair nutrients, such as botanicals, fruit extracts, sugar derivatives and/or amino acids, or any other ingredient normally formulated into cosmetic compositions. The required amounts of adjuvants and additives can be easily selected by those skilled in the art based on the desired product, and will be exemplified in the examples, but not limited thereto.

In particular, the cosmetic composition may comprise other surfactants. In one embodiment, the cosmetic composition comprises a sulfate surfactant, i.e. an alkyl sulfate, an alkyl ether sulfate, an alkylamido ether sulfate, an alkylaryl polyether sulfate, or a monoglyceride sulfate.

In another preferred embodiment, the cosmetic composition comprises a sulfate-free surfactant, in particular a cationic, anionic, nonionic or amphoteric surfactant. Examples of suitable anionic surfactants are alkanoyl isothionates, alkyl succinates, alkyl sulfosuccinates, alkyl ether sulfosuccinates, N-alkyl sarcosinates, alkyl phosphates, alkyl ether phosphates and alkyl ether carboxylic acids and their salts, in particular their sodium, magnesium, ammonium or monoethanolamine, diethanolamine and triethanolamine salts. The alkyl and acyl groups generally contain from 8 to 18, preferably from 10 to 16, carbon atoms and may be unsaturated. The alkyl ether sulfosuccinates, alkyl ether phosphate esters and alkyl ether carboxylic acids and salts thereof may contain from 1 to 20 ethylene oxide or propylene oxide units per molecule.

In particular, the anionic surfactant is selected from the group consisting of sodium oleyl succinate, ammonium lauryl sulphosuccinate, sodium lauryl ether sulphosuccinate, sodium cocoyl isethionate, sodium lauryl isethionate, lauryl ether carboxylic acid and sodium N-lauryl sarcosinate or mixtures thereof. Preferred anionic surfactants are sodium lauryl ether sulfosuccinate (n) EO, (where n is from 1 to 4, especially n is 3).

Examples of the nonionic surfactant include aliphatic (C)₈–C₁₈) Linear or branched primary or secondary alcohols with alkylene oxides (hetero)Often ethylene oxide, and usually having 6 to 30 ethylene oxide groups). Other representative nonionic surfactants include mono-or dialkyl alkanolamides such as coco monoethanolamide or coco diethanolamide and coco monoisopropanolamide. Other nonionic surfactants that may be included in the cosmetic compositions of the present invention are alkyl glycosides (APGs). Typically, the APG is an APG comprising an alkyl group linked (optionally via a bridging group) to one or more glycosyl blocks, e.g. Oramix^TM NS 1O ex Seppic；818UP,1200 and2000ex Cognis。

examples of amphoteric (or zwitterionic) surfactants include alkyl amine oxides, alkyl betaines, alkyl amidopropyl betaines, alkyl sultaines, alkyl glycinates, alkyl carboxyglycinates, alkyl amphoacetates, alkyl amphopropionates, alkyl amphoglycinates, alkyl amidopropyl hydroxysultaines, acyl taurates, and acyl glutamates, wherein the alkyl and acyl groups have from 8 to 19 carbon atoms. Typical amphoteric and zwitterionic surfactants used in cosmetic compositions include laurylamine oxide, coco dimethyl sulfopropyl betaine, lauryl betaine, cocamidopropyl betaine (CAPB), sodium cocoamphoacetate, and disodium cocoamphodiacetate. Particularly preferred amphoteric or zwitterionic surfactants that can be used in the cosmetic composition are cocamidopropyl betaine, cocoamphoacetate or cocoamphodiacetate, for example sodium cocoamphoacetate is most preferred.

Mixtures of any of the foregoing amphoteric or zwitterionic surfactants may also be suitable. Preferred mixtures are mixtures of cocamidopropyl betaine with other amphoteric or zwitterionic surfactants mentioned above, for example especially with sodium cocoamphoacetate or disodium cocoamphodiacetate.

The cosmetic composition may further comprise a suspending agent. Suitable suspending agents are selected from the group consisting of polyacrylic acids, crosslinked polymers of acrylic acid, copolymers of acrylic acid with hydrophobic monomers, copolymers of carboxylic acid-containing monomers with acrylic esters, crosslinked copolymers of acrylic acid with acrylic esters, heteropolysaccharide gums and crystalline long chain acyl derivatives. The long chain acyl derivative is desirably selected from the group consisting of ethylene glycol stearate, alkanolamides of fatty acids having from 16 to 22 carbon atoms, and mixtures thereof. Ethylene glycol distearate and polyethylene glycol 3 distearate are preferred long chain acyl derivatives because they impart pearlescence (pearlescence) to the compositions. Polyacrylic acid can be used as420、488 or493 are commercially available. Acrylic polymers crosslinked with polyfunctional agents may also be used; they can be used as910、934、941、980 andultrez 10Polymer is commercially available. Examples of suitable copolymers of carboxylic acid-containing monomers and acrylic esters are1342、Ultrez 20 orUltrez 21, Pemulen TR1 or Pemulen TR 2. All ofOrThe material may be obtained from Lubrizol.

A suitable heteropolysaccharide gum is xanthan gum, for example from KelcoIs of type ortype-Vanzan NF from RT Vanderbilt Inc. or from Rhodia-type (II).

Mixtures of any of the foregoing suspending agents may be used. Preferred are mixtures of crosslinked polymers of acrylic acid and crystalline long chain acyl derivatives.

The cosmetic composition may further comprise a neutralizing agent, particularly aminomethyl propanol, such as AMP-Ultra PC, commercially available from ANGS Chemical Company.

The cosmetic composition as described above is in particular a hair gel, a cream or a gel.

It is preferred that the cosmetic composition is left on the hair after application and not washed off immediately (within 30 minutes of application). Such products are known as "leave-on" formulations. Preferred product forms are leave-on formulations such as gels, mousses, sprays and aerosols. The pH of the composition at 30 ℃ is preferably from 2.5 to 9, more preferably above 4, most preferably from 5 to 8. The cosmetic compositions of the present invention may comprise a carrier or mixture of carriers, particularly suitable for use with hair. The carrier preferably comprises from 0.5% to 99.5%, more preferably from 5.0% to 99.5%, even more preferably from 10.0% to 98.0% of the composition. As used herein, the phrase "suitable for use with hair" means that the carrier does not harm or negatively affect the aesthetics of the hair or cause irritation to the underlying skin. Preferably, the cosmetic composition comprises a buffering agent or a pH adjusting agent. Preferred buffers or pH adjusters include weak acids and bases such as glycine/sodium hydroxide, citric acid, lactic acid, succinic acid, acetic acid and salts thereof. Mixtures of buffer systems are generally used, such as sodium citrate and citric acid. Suitable carriers for use in cosmetic compositions include, for example, those used in the formulation of hair sprays, mousses, hair tonics (hair tonics), lotions, creams, shampoos, conditioners, and lotions. The selection of a suitable carrier will depend on the particular product being formulated. The carrier used herein may include various components conventionally used in cosmetic compositions. Mousses and aerosol sprays can also deliver the material in the form of a foam (in the case of mousses) or as a fine and uniform spray (in the case of aerosol sprays) using any conventional propellant. Examples of suitable propellants include materials such as trichlorofluoromethane, dichlorodifluoromethane, difluoroethane, dimethyl ether, propane, n-butane or isobutane. The level of propellant can be adjusted as desired, but is generally from about 3% to about 30% by weight based on the total weight of the mousse composition and from about 15% to about 50% by weight based on the total weight of the aerosol hairspray composition.

Hair styling creams or gels typically also contain a structuring or thickening agent, typically in an amount of from 0.01% to 10% by weight. Suitable aerosol containers are well known in the art and include conventional non-aerosol pump sprayers, i.e., "atomizers," aerosol containers or canisters with propellant, and aerosol containers that utilize compressed air as a propellant.

The cosmetic product may include conditioning materials such as surfactants, cationic hair conditioning agents, quaternary silicone polymers, silicone-based conditioning agents and emulsions thereof, and amino-functional silicones and emulsions thereof. Other conventional ingredients suitable for use in cosmetic compositions include carboxylic acid polymer thickeners for hair shampoo and conditioner compositions.

It has been found that cosmetic compositions as detailed above have a very unique combination of increasing hair elasticity and maintaining curl retention of curled hair.

Hair elasticity describes the ability of a hair swatch (hair swatch) to return to its original shape after mechanical deformation, for example how a curled swatch returns to its shape after stretching, or how a straight swatch returns to its shape after curling. Hair elasticity is usually evaluated by measuring hair strands by a mechanical bending test.

The pre-washed hair swatches were treated with the product of the present invention, combed 5 times, and dried in an oven at 45 ℃ for 40 minutes. After storage overnight at controlled humidity and temperature (21 ℃, 65% rH (═ rH)), the bending force measurements were performed 3 consecutive times. The first bending force determines the maximum bending force required to break the "hold/retain" membrane. The "hysteresis" bending force was measured by bending once, returning to the original starting point and bending again (up to 2 times) to assess the retained flexibility. Detailed information can be found in "underftating Claims for Hair Care Products", M.Brandt et al, SOFW 2016,142, 17-24.

Curl retention describes the retention of curls when exposed to high humidity for extended periods of time. In this method, curls are made by treating a pre-washed sample of hair with the product of the invention, combing 5 times and rolling it on a curler. When the samples were dried (40 minutes, 45 ℃) and stored overnight under controlled humidity and temperature (21 ℃, 65% rH), the curlers were carefully removed and the curled samples were placed in a climatic chamber of relatively high humidity (21 ℃, 90% rH). Then, the length of curls was measured for a set period of time up to 6 hours, and Curl Retention (CR) was calculated from the original length of curls. Detailed information can be found in "underftating Claims for Hair Care Products", M.Brandt et al, SOFW 2016,142, 17-24.

The cosmetic composition can maintain Curl Retention (CR). The term "maintain" as used in this document means that the curl retention is not less than 45%, preferably not less than 50%, more preferably not less than 55%, after 360 minutes in a climatic chamber as measured using the method described above.

Thus, in another aspect, the present invention relates to the use of a cosmetic composition as described above for increasing the elasticity of hair and/or for maintaining the Curl Retention (CR) of curly hair.

Examples

The invention is further illustrated by the following experiments. These examples are illustrative only and are not intended to limit the scope of the present invention in any way.

Preparation of hyperbranched copolymer (HBC1)

Hyperbranched copolymer of the monomers dodecenyl succinic anhydride and diisopropanolamine and bisdimethylaminopropylamine HBC1 was prepared according to example 3 in EP 2794729B 1 using 237.59g of N, N-bis (N 'N' -dimethylaminopropyl) amine and 112.6 g of diisopropanolamine and 426.89 g of dodecenyl succinic anhydride. After heating and vacuum, the residual carboxylic acid content was < 0.3meq/g (by tridose analysis), AV 9.8mg KOH/g, the amine content 2.99meq/g (by tridose analysis), and the molecular weight Mn 2240 Da. This product was reacted with sodium chloroacetate in water and stirred at 80 ℃ until complete conversion of the chloroacetate salt was indicated by 1H-NMR analysis, giving a hyperbranched copolymer HBC1 having end groups of the formula and a molecular weight Mn of 2.3kDa

In the following experiments, the hyperbranched copolymer HBC1 was used as a 45% aqueous solution.

Composition comprising a metal oxide and a metal oxide

For the experiments, compositions 1, 2, 3 and ref.1 (without HBC1) have been prepared, respectively, according to the amounts given in table 1.

TABLE 1 compositions

¹Aminomethyl propanol, available from ANGS Chemical Company.

²From DSM Nutritional Products Ltd.

³The polymer content was 45% by weight

Elasticity assessment

Elasticity or stiffness was evaluated by performing a three-point bending stiffness test.

Five hair swatches were used per test product (Kerling Art.826200 European hair, weight: 0.7g +/-0.05g, length 12cm, Euro Natur, colour 6/0). The bending stiffness of each hair sample was measured 3 times in succession.

The hair swatches have been pre-washed twice with a standard cleansing shampoo: 0.25ml/g hair, 30 seconds of foaming, rinsing with 38 ℃ warm water at 5l/min for 30 seconds, and then drying overnight in a thermostatic chamber at 21 ℃/65% relative humidity.

Each sample was treated with 0.3g of the corresponding composition of table 1. The product was applied evenly from root to tip using a syringe, combed 5 times, dried at 45 ℃ for 40 minutes and stored at 21 ℃/65% relative humidity for at least 12 hours.

Elasticity or stiffness was then evaluated by a three-point bending stiffness test performed on a texture analyzer (TA XTplus). Monitoring the applied force and initiating distance (d) for bending distance₀) And drawing is carried out. The first correlation point is at distance (d)_max) At the measured maximum force (F)_max). This force is related to the breaking of the polymer film. The force is now released by reducing the bending distance. In a further step, the bending distance is increased again to the distance (d)_max) And measuring the force (F)₁). The force is now released again by reducing the bending distance. Finally, the bending distance is increased again to the distance (d)_max) And measuring the force (F)₂)。

In table 2, the measured forces are summarized.

	Ref.1	1	2	3
					Fmax[g]	137.5	142.8	144.9	149.4
F1[g]	107.7	96.7	86.3	74.9
					F2[g]	99.4	82.9	71.0	65.7

TABLE 23 Point bending stiffness test

Figure 1 is a graphical representation of these values. The results given in Table 2 and FIG. 1 show, on the one hand, that compositions 1 and 2 and 3 have a relatively high force F_maxRespectively, a better retention and a better "style retention" than the reference composition ref.1. On the other hand, compositions 1, 2 and 3 have a significantly lower force (F) compared to the reference composition ref.1₁) Force of harmony (F)₂) This indicates better elasticity.

It further shows that these advantages are increased by the addition of hyperbranched polymers of monomers (i), (ii) and (iii).

Evaluation of curl Retention

Three hair swatches (Kerling Art.826500, KT length, length 23 cm, free hair 21 cm, Euro Natur, color 6/0) were used per test product.

The hair swatches were pre-washed with a standard shampoo (10 sec wet, shampooed for 30 sec, 30 sec rinse), combed 5 times, and dried under defined conditions (21. + -. 1 ℃ C., 65% rH) overnight.

Each sample was then treated with 0.5ml of the composition ref.1 or 3 of table 1. The product was applied evenly from root to tip with a syringe and combed 5 times. The hair samples were wound on a curler (12 mm diameter, plastic wire) and dried in an oven at 45 ℃ for 40 minutes. .

After conditioning overnight at 21 ℃ and 65% rH, the hair swatches were removed from the curler and suspended for up to 6 hours in a special climatic chamber (21 ℃, 90% rH). The length of the crimp is taken from the beginning as the original length (L) of the crimp₀) Measurements were taken. The length of crimp height (L) was monitored over time under these conditions_t) And last for a maximum of 360 minutes. Curl retention has been calculated as a function of time (═ CR ═ L)_t/L₀) And is shown in table 3 and fig. 2. The higher the value, the better the curl retention.

Crimp Retention (CR) [% ]]	Ref.1	3
			After 0 minute	100	100
After 15 minutes	97.0	93.9
			After 30 minutes	93.1	90.9
After 45 minutes	86.2	83.8
			After 60 minutes	83.2	77.8
After 90 minutes	78.2	72.7
			After 120 minutes	74.3	68.7
After 240 minutes	68.3	62.6
			After 360 minutes	62.4	56.6

TABLE 3 values for curl Retention

The results given in table 3 and fig. 2 show that the composition comprising the styling polymer (ref.1) maintains excellent curl retention when composition (3) additionally comprises hyperbranched copolymers of monomers (i) and (ii) and (iii).

Thus, excellent curl retention of curled hair is observed, in combination with excellent elasticity.