Hair styling composition containing a non-ionic and an amphoteric polymer Technical field

The present invention belongs to the cosmetic field, and relates to a hair styling composition comprising vinyl caprolactam / VP / di-methylaminoethyl methacrylate copolymer and an amphoteric copolymer. The composition according to the present invention provides excellent styling properties upon application to human hair.

Technical background

A beautiful and attractive appearance is a desire for many people. Therefore, an essential part of the daily personal care of humans is focus on the hair of the head. Typically, the hair is first cleaned using a shampoo. Afterwards, a conditioner may be applied to provide a conditioning of the hair. Thereby, the conditioners can be formulated either as rinse-off product, which are applied to the hair and afterwards rinsed off with water, or as leave-in product, which remains in the dry or wet hair after application. After conditioning, the hair can be styled using a fixation creme, gel or spray. Alternatively, a mousse for the hair may be applied to fix the style or enhance the curling of the hair.

All the above listed products have in common that their formulations often contain polymers for various beneficial reasons. For example, polymers may be used for thickening or film building purposes, as well as to provide care or to aid as deposition enhancer in the cosmetic compositions. Hair styling compositions preferably contain polymers as styling agent wherein the polymers enhance the stiffness of the hair. Additionally, polymers used as styling agents may improve the style retention or re-styling properties of the hair. Moreover, it is desirable that the polymers used as styling agent do not make the hair feel dry upon application. Especially for aqueous or alcoholic gel sprays, which are applied to dry hair, it is beneficial if the hair feels wet and/or moist while styling.

However, polymers used in hair styling compositions are often tailored to exhibit only one or a few of the above discussed benefits. Therefore, the compositions often contain a number of different polymers to cover all the benefits needed to provide a satisfactory styling of the hair. Thereby, the combining of different polymers can be problematic as chemical reactions may occur in the composition. These chemical reactions may lead to a non-desirable agglomeration effect of the composition. Furthermore, the formulation of hair styling compositions containing a number of polymers may be expensive. Therefore, it remains desirable to provide combinations of polymers, which provide a number of benefits simultaneously. WO 2008/052886 A2 describes hair styling compositions, which provide thickening and film-forming properties, as well as a high degree of hold without the need to forego flexibility and good humidity resistance. The hair styling composition comprises at least one copolymer and at least one film-forming and/or -setting amphoteric polymer. Among others, acrylates / lauryl acrylate / stearyl acrylate / ethylamine oxide methacrylate copolymer may be chosen as amphoteric copolymer to be contained in the formulations according to WO 2008/052886 A2. However, WO 2008/052886 A2 is silent on the use of acrylates / lauryl acrylate / stearyl acrylate / ethylamine oxide methacrylate copolymer in combination with vinyl caprolactam / VP / di-methylaminoethyl methacrylate copolymer.

WO 201 1/048179 A1 discloses cosmetic compositions for shaping keratin fibers. According to the description of WO 201 1/048179 A1 , the compositions may additionally contain at least one film-forming and/or setting polymer. This polymer can be chosen from anionic, amphoteric, non-ionic, permanently cationic and temporarily cationic polymers. For each of the polymer categories listed above an extensive list of possible polymers is disclosed. Therein, polymers of the type acrylates / lauryl acrylate / stearyl acrylate / ethylamine oxide methacrylate copolymer are listed as amphoteric polymers. Vinyl caprolactam / VP / di-methylaminoethyl methacrylate copolymer can be found as one example in the category of temporarily cationic polymers. However, there is no disclosure in WO 201 1/048179 A1 teaching that it is beneficial to combine polymers of certain categories, such as amphoteric and temporarily cationic polymers. Moreover, there is no disclosure in WO 201 1/048179 A1 which suggest the combination of the present invention to provide a positive, synergetic effect on the styling properties of the hair.

WO 2013/087315 A2 discloses a powdery cosmetic composition for the temporarily shaping of keratin-containing fibers, which, according to the description, may contain at least one polymer selected from non-ionic, anionic, amphoteric and cationic polymers. Again, for each polymer category an extensive list of possible polymers is provided. Thereby, vinyl caprolactam / VP / di-methylaminoethyl methacrylate copolymer can be found in the group of non-ionic polymers. Amphoteric polymers of similar structure as in the present invention are also listed in the section describing amphoteric polymers. However, WO 2013/087315 A2 is silent about the fact whether it is beneficial to combine selected groups of polymers. Hence, in the view of WO 2013/087315 A2 it is nonobvious to add simultaneously both an amphoteric and a non-ionic polymer to the hair styling composition. Furthermore, it is even less obvious to choose within the presented groups of non-ionic and amphoteric polymers the special combination of copolymers of the present invention to provide a positive, synergetic effect on the styling properties of the hair.

Further documents which comprise at least one of the components of the present invention addressing the styling of the hair are for example DE 10201 1089578 A1 , WO 2006/044193 A2 and WO 1997/004796 A1 . None of the documents cited discloses any guidance to the present invention.

Summary

The present invention is to provide a combination of polymers with improved styling properties for human hair. It has surprisingly been found out that a hair styling composition comprising a vinyl caprolactam / VP / di-methylaminoethyl methacrylate copolymer and one or more amphoteric copolymers, which are specified in the following, shows excellent styling properties upon application to human hair. In particular, it was unexpected that the inventive combination of polymers showed a synergistic improvement of the styling properties when application to human hair.

Accordingly, the first object of the present invention is a hair styling composition for human hair comprising vinyl caprolactam / VP / di-methylaminoethyl methacrylate copolymer and one or more amphoteric copolymer, polymerized from

• at least one monomer (M01 ) selected from acrylic acid, methacrylic acid, acrylic acid alkyl esters and methacrylic acid alkyl ester, and

• at least one monomer (M02) selected from a monomer according to formula (I)

wherein Ri is a Hydrogen or a CH3 group, n is an integer in the range from 1 to 4, p is an integer in the range from 1 to 10 and q is an integer in the range from 1 to 10,

and a monomer according to formula (I I)

1 '2t+1 , wherein R2 is a Hydrogen or a CH3 group, r is an integer in the range from 1 to 4, s is an integer in the range from 1 to 10, t is an integer in the range from 1 to 10 and u is an integer in the range from 1 to 4.

A further object of the present invention is the use of the composition of the present invention to temporarily shape human hair.

The hair styling composition of the present invention comprises vinyl caprolactam / VP / di-methylaminoethyl methacrylate copolymer. Vinyl caprolactam / VP / di-methylaminoethyl methacrylate copolymer is a non-ionic polymer formed by the monomers N-vinylpyrrolidone (VP), n-vinylcaprolactam and 2-(Dimethylamino)ethyl methacrylate (DMAEMA).

The total concentration of vinyl caprolactam / VP / di-methylaminoethyl methacrylate copolymer in the composition of the present invention is in the range from 0.1 % to 10%, preferably 0.5% to 5% and most preferably 1 % to 4% by weight calculated to the total composition.

Generally, vinyl caprolactam / VP / di-methylaminoethyl methacrylate copolymer is supplied in an alcoholic and/or aqueous solution. In the solution vinyl caprolactam / VP / di- methylaminoethyl methacrylate copolymer can either be suspended and/or dissolved.

The hair styling composition of the present invention is preferably prepared by adding the vinyl caprolactam / VP / di-methylaminoethyl methacrylate copolymer to the composition as alcoholic and/or aqueous suspension, wherein the solid content is about 10% to 50%, preferably 28% to 40% by weight calculated to the total weight of the alcoholic suspension.

An alcoholic suspension containing vinyl caprolactam / VP / di-methylaminoethyl methacrylate copolymer is commercially available under the trade name Gaffix™ VC-713 polymer from the Fa. Ashland. Aqueous solutions containing vinyl caprolactam / VP / di- methylaminoethyl methacrylate copolymer can be purchased under the trade name Advantage S Solution polymer from the Fa. Ashland.

The hair styling composition of the present invention comprises one or more amphoteric copolymers, polymerized from at least one monomer (M01 ) selected from acrylic acid, methacrylic acid, acrylic acid alkyl esters and methacrylic acid alkyl ester, and at least one monomer (M02) selected from a monomer according to formula (I) and formula (II).

The alkyl-groups of acrylic acid alkyl esters and methacrylic acid alkyl ester can contain up to 24 C-atoms.

According to the invention the acrylic acid alkyl ester can preferably be selected from acrylic acid methyl ester, acrylic acid ethyl ester, acrylic acid propyl ester, acrylic acid isopropyl ester, acrylic acid butyl ester, acrylic acid isobutyl ester, acrylic acid hexyl ester, acrylic acid octyl ester, acrylic acid decyl ester, acrylic acid lauryl ester, acrylic acid myristyl ester, acrylic acid cetyl ester and/or acrylic acid stearyl ester.

Furthermore, the methacrylic acid alkyl ester can preferably be selected from methacrylic acid methyl ester, methacrylic acid ethyl ester, methacrylic acid propyl ester, methacrylic acid isopropyl ester, methacrylic acid butyl ester, methacrylic acid isobutyl ester, methacrylic acid hexyl ester, methacrylic acid octyl ester, methacrylic acid decyl ester, methacrylic acid lauryl ester, methacrylic acid myristyl ester, methacrylic acid cetyl ester and/or methacrylic acid stearyl ester.

The total concentration of the one or more amphoteric copolymers in the hair styling composition of the present invention is preferably in the range from 0.1 % to 10%, more preferably 0.5% to 5% and most preferably 0.75% to 3% by weight calculated to the total composition.

Furthermore, in one embodiment of the present invention the ratio of the one or more amphoteric copolymers to vinyl caprolactam / VP / di-methylaminoethyl methacrylate copolymer is 2:1 to 1 :3 by weight, preferably 1 :1.8 to 1 :2.2 by weight. Surprisingly, it was found that especially at a ratio of 1 :1 .8 to 1 :2.2 by weight a synergetic effect of both polymers was found for the moisture feeling of the hair directly after application, the stiffness and the style retention of the hair after drying under room condition and the restyling properties of the hair 4h after application.

In one preferred embodiment of the present invention the hair styling composition contains only one amphoteric polymer, wherein the amphoteric copolymer is polymerized from

• at least two monomers (M01 ), wherein one of the monomers is selected from acrylic acid, acrylic acid methyl ester, acrylic acid ethyl ester, acrylic acid propyl ester, acrylic acid isopropyl ester, methacrylic acid methyl ester, methacrylic acid ethyl ester, methacrylic acid propyl ester and methacrylic acid isopropyl ester and the second monomer is selected from acrylic acid stearyl ester and methacrylic acid stearyl ester, and

• a monomer (M02) of the structure

u ' '2q+1 wherein Ri is a CH3 group, n is an integer in the range from 1 to 4, p is an integer in the range from 1 to 2 and q is an integer in the range from 1 to 2.

A preferred amphoteric copolymer fulfilling the above described requirements is acrylates / stearyl acrylate / ethylamine oxide methacrylate copolymer. This copolymer is commercially available under the trade name Diaformer Z-632 and Diaformer Z-772. Both products can be purchased from the Fa. Mitsubishi Chemical.

In another preferred embodiment of the present invention the hair styling composition contains only one amphoteric copolymer, wherein the amphoteric copolymer is polymerized from

• at least two monomers (M01 ), wherein the monomers are selected from acrylic acid, acrylic acid methyl ester, acrylic acid ethyl ester, acrylic acid propyl ester, acrylic acid isopropyl ester, methacrylic acid methyl ester, methacrylic acid ethyl ester, methacrylic acid propyl ester and methacrylic acid isopropyl ester, and

• a monomer (M02) of the structure CH ₂ O C _s H _2s†1 O 58

I I I

R, C C O CH ; ^■ N CH, - C— O ^" (II)

u

t i i _{2t+ i} wherein R2 is a CH3 group, r is an integer in the range from 1 to 4, s is an integer in the range from 1 to 2, t is an integer in the range from 1 to 2 and u is equal to 1.

A preferred amphoteric polymer fulfilling the requirements described above is methacryloyi ethyl betaine / acrylates copolymer, which is commercially available under the trade name Yukaformer. Yukaformer type copolymers can be purchased from the Fa. Mitsubishi Chemical.

In a more preferred embodiment of the present invention the hair styling composition contains only one amphoteric polymer, wherein the amphoteric copolymer is polymerized from

• at least three monomers (M01 ), wherein one of the monomers is selected from acrylic acid, acrylic acid methyl ester, acrylic acid ethyl ester, acrylic acid propyl ester, acrylic acid isopropyl ester, methacrylic acid methyl ester, methacrylic acid ethyl ester, methacrylic acid propyl ester and methacrylic acid isopropyl ester, the second monomer is selected from acrylic acid stearyl ester and methacrylic acid stearyl ester, and the third monomer is selected from acrylic acid lauryl ester and methacrylic acid lauryl ester, and

• a monomer (M02) of the structure

w _q i i _{2q+ 1} wherein Ri is a CH3 group, n is an integer in the range from 1 to 4, p is an integer in the range from 1 to 2 and q is an integer in the range from 1 to 2.

A preferred amphoteric polymer fulfilling the above described requirements is acrylates / lauryl acrylate / stearyl acrylate / ethylamine oxide methacrylate copolymer. This polymer is commercially available under the trade name Diaformer Z-631 and Diaformer Z-651 . Both products can be purchased from the Fa. Mitsubishi Chemical.

Generally, acrylates / lauryl acrylate / stearyl acrylate / ethylamine oxide methacrylate copolymer is supplied in an aqueous and/or alcoholic solution. In this solution acrylates / lauryl acrylate / stearyl acrylate / ethylamine oxide methacrylate copolymer can either be suspended and/or dissolved.

It is preferred to add the acrylates / lauryl acrylate / stearyl acrylate / ethylamine oxide methacrylate copolymer to the composition as an aqueous and alcoholic solution, wherein the aqueous and alcoholic solution contains preferably

• 20% to 40% by weight acrylates / lauryl acrylate / stearyl acrylate / ethylamine oxide methacrylate copolymer,

• 50% to 70% by weight ethanol,

• 1 % to 20% by weight water, more preferably

• 28% to 32% by weight acrylates / lauryl acrylate / stearyl acrylate / ethylamine oxide methacrylate copolymer,

• 61 % to 65% by weight ethanol,

• 5% to 9% by weight water, calculated to the total weight of the aqueous and alcoholic solution.

Furthermore, it is preferred if the aqueous and alcoholic solution, containing acrylates / lauryl acrylate / stearyl acrylate / ethylamine oxide methacrylate copolymer, ethanol and water, is characterized in that the aqueous and alcoholic solution has a viscosity in the range from 600 mPa-s to 1300 mPa-s, preferably 800 mPa-s to 1 100 mPa-s, more preferably 900 mPa-s to 1000 mPa-s measured at a temperature of 20°C. It was surprisingly found out that by preparing the inventive composition with an aqueous and alcoholic solution with a viscosity as described above, the hair styling properties of the hair styling composition of the present are found to be improved. Such an aqueous and alcoholic solution containing acrylates / lauryl acrylate / stearyl acrylate / ethylamine oxide methacrylate copolymer, ethanol and water is commercially available under the trade name Diaformer Z-631 from the Fa. Mitsubishi Chemical. The viscosity of Diaformer Z-631 was determined to be 930 mPa-s at 20°C, using the measurement described below.

In another preferred embodiment of the present invention two or more amphoteric copolymers can be included in the hair styling composition of the present invention, whereby these amphoteric copolymers are selected from acrylates / lauryl acrylate / stearyl acrylate / ethylamine oxide methacrylate copolymer, methacryloyl ethyl betaine / acrylates copolymer and acrylates / stearyl acrylate / ethylamine oxide methacrylate copolymer. By combining two or more of these copolymers the composition of the present invention provides excellent styling properties to human hair.

Additionally, in one embodiment of the invention the hair styling composition of the present invention preferably comprises water. Preferably the concentration of water in the composition of the present invention exceeds 80% by weight, more preferably 90% by weight calculated to the total weight of the composition.

In another embodiment of the invention the hair styling composition of the present invention preferably comprises ethanol. Preferably the concentration of ethanol in the composition of the present invention exceeds 80% by weight, more preferably 90% by weight calculated to the total weight of the composition.

The hair styling composition of the present invention preferably contains one or more water-soluble solvents. Preferred water-soluble solvents are glycerol, ethylene glycol and propylene glycol. The concentration of the one or more water-soluble solvents in total is in the range of preferably 0.1 % to 5%, more preferably 0.25% to 3% and most preferably 0.5% to 2% by weight calculated to the total composition.

The hair styling composition of the present invention can further comprise at least one vitamin, provitamin or derivatives thereof to provide additional care to the hair and/or the skin. This vitamin, provitamin or derivative thereof can be selected from all substances assigned to the groups of vitamin A, vitamin B, vitamin C, vitamin E, vitamin F and vitamin H. Preferred are the vitamins, provitamins and derivatives thereof which are assigned to the vitamin B group. More preferred vitamins which can be contained in the composition of the present invention are panthenol and/or nicotinic acid amide. The vitamins, provitamins and derivatives thereof are preferably used in a total concentration of 0.05% to 1 % by weight calculated to the total composition.

In a preferred embodiment of the invention only panthenol and/or nicotinic acid amide are included as vitamins, provitamins and derivatives thereof in the composition of the present invention.

The hair styling composition of the present invention preferably comprises one or more emulsifiers. These emulsifiers can be selected from anionic, cationic, amphoteric and non- ionic emulsifier. Most preferred are non-ionic emulsifiers.

Non-ionic emulsifier can preferably be selected from polyalkyleneglycol ether of fatty acid glycerides or partial glycerides containing 4 to 500 polyalkylene units. Suitable, but not limited, examples of those are PEG-30 hydrogenated castor oil, PEG-35 hydrogenated castor oil, PEG-40 hydrogenated castor oil, PEG-45 hydrogenated castor oil, PEG-50 hydrogenated castor oil, PEG-55 hydrogenated castor oil, PEG-60 hydrogenated castor oil, PEG-65 hydrogenated castor oil, PEG-70 hydrogenated castor oil, PEG-75 hydrogenated castor oil, PEG-80 hydrogenated castor oil, PEG-100 hydrogenated castor oil, PEG-150 hydrogenated castor oil, PEG-200 hydrogenated castor oil.

Further, polyalkyleneglycol ether of fatty acid glycerides or partial glycerides are preferably defined by the following formula (III)

CH ₂ 0(CH ₂ CH ₂ 0) _y R ₃

CH ₂ 0(CH ₂ CH ₂ 0) _w R ₄ (IN)

CH ₂ 0(CH ₂ CH ₂ 0) _x R ₅

wherein R3, R ₄ and R5 are independently selected from a hydrogen or a linear or branched, saturated and/or unsaturated acyl radical comprising 6 to 22 carbon atoms, and wherein v, w and x are an integer in the range from 0 to 500, wherein sum of the integer v, w and x has to be equal to 3 or larger. Suitable examples are PEG-6 caprylic/capric glycerides, PEG-8 caprylic/capric glycerides, PEG-6 glyceryl caprate, PEG-3 glyceryl cocoate, PEG-7 glyceryl cocoate, PEG-30 glyceryl cocoate, PEG-40 glyceryl cocoate, PEG-80 glyceryl cocoate, PEG-15 glyceryl diisostearate, PEG-30 glyceryl diisostearate, PEG-12 glyceryl distearate, PEG-8 glyceryl laurate, PEG-20 glyceryl laurate, PEG-20 glyceryl stearate and PEG-30 glyceryl stearate. The most preferred non-ionic emulsifiers are PEG-40 hydrogenated castor oil, PEG-6 caprylic/capric glycerides and mixtures thereof.

The total concentration of one or more non-ionic emulsifiers in the hair styling composition of the present invention is preferably in the range from 0.05% to 5% by weight, more preferably in the range from 0.1 % to 0.5% by weight calculated to the total composition.

In a preferred embodiment of the present invention only PEG-40 hydrogenated castor oil and PEG-6 caprylic/capric glycerides are contained as non-ionic emulsifier, whereby the total concentration of both emulsifiers in the composition of the present invention is in the range from 0.1 % to 0.5% by weight calculated to the total composition.

The hair styling composition of the present invention may further comprise one or more preservatives. Preservatives are substances which prevent the decomposition of a cosmetic composition by microbial growth or undesirable chemical changes.

Preferred preservatives to be comprised in the composition of the present invention are phenoxyethanol, ethylhexyglycerin, methylparaben, ethylparaben, butylparaben, methylisothiazolinone, chlormethylisothiazolinone, DMDM-hydantoin (1 ,3- Bis(hydroxymethyl)-5,5-dimethylhydantoine) and/or mixtures thereof.

The total concentration of the one or more preservatives in the hair styling composition of the present invention is in the range from 0.1 % to 3%, preferably 0.2% to 0.8% by weight calculated to the total composition.

The hair styling composition of the present invention may further contain one or more additional film-forming or hair-strengthening polymers which can be selected from the group of anionic polymers, cationic polymer, non-ionic polymers and/or amphoteric polymers.

Film-forming polymers are understood to be polymers which when used in a concentration of 0.01 % to 20% by weight in an aqueous, alcoholic or aqueous-alcoholic composition are capable of depositing a polymer film on the hair, wherein the concentration is calculated to the total composition. Hair-strengthening polymers are understood to be polymers which are used to shape and fix the hair. All polymers are understood to be hair-strengthening polymers which increase the strength of a hair, measured in a commonly used curl retention test. A description of the curl-retention measurement can for example be found in US 5089253 A.

However, as the hair styling composition of the present invention solely provides surprisingly good styling properties, it is preferred that the composition of the present invention is free from further film-forming or hair-strengthening polymers.

In the sense of the present invention silicone containing polymers are explicitly not considered as film-forming or hair-strengthening polymers. Hence, the hair styling composition of the present invention may further contain one or more silicone containing substances to provide an effective conditioning of the hair. These substances may be silicone oils or silicon containing polymers, such as Silicone Quaternium-18 or other quaternary ammonium groups and silicon containing polymers.

However, as silicone compounds often lead to hair being weighed down, it is preferred that the hair styling composition of the present invention is free from silicone containing polymers.

Another category of conditioning agents which may optionally be added to the hair styling composition of the present invention are protein and polyprotein hydrolysates, such as hydrolyzed silk, hydrolyzed wheat protein and/or hydrolyzed collagen.

The hair styling composition of the present invention may further comprise pearlescent pigments, mica and/or effect pigments to prepare visually attractive compositions.

The hair styling composition according to the invention may also comprise substances such as UV-filter, dyes, ubiquinone such as coenzyme Q10, plant extracts, antioxidants such as oryzanol, and fragrances.

The hair styling composition according to the present invention may preferably be a mousse for the hair, an aerosol hair spray, a non-aerosol gel spray, a gel and/or a wax. Most preferred is a non-aerosol gel spray, which has a viscosity of 0.2 to 200 mPa-s at a temperature of 20°C, and is contained in a pump spray.

The viscosity of the inventive composition and of the raw material was measured using a Brookfield RVT (Brookfield Engineering). The measurements were performed at a temperature of 20°C. The stirring unit used for the measurements was an RV-4 spindle. The rotation speed was set to 20 min ^"1 .

In the sense of the present invention the term "directly after" means a time scale of up to one minute, the term "free from" means that the total concentration of the named substance in the hair styling composition of the present invention does not exceed 0.1 % by weight calculated to the total composition, and the term "room condition" is defined as 20°C and 1013 mbar.

Examples

The following examples should illustrate the hair styling composition of this invention, without, however, intending to limit the invention to these examples. The numerical values in the examples are percentages by weight, based on the total weight of the compositions. The compositions are prepared by mixing the individual components in water.

Examples 1 -4: Aqueous hair spray

Type: Aqueous hair spray Ex.1 Ex.2 Ex.3 Ex.4

Ingredient Inv Inv Inv Inv

Vinyl caprolactam/VP/ dimethylaminoethyl 1 1.5 2 2 methacrylate Copolymer ¹

Acrylates/ lauryl acrylates/ stearyl 2 1.5 1

acrylates/ethylamine oxide methacrylate

copolymer ²

Acrylates / stearyl acrylates / ethylamine oxide 1 methacrylate copolymer ³

Propylene glycol 1 1 1 1

Panthenol 0.1 0.1 0.1 0.1

DMDM Hydantoin 0.28 0.28 0.28 0.28

Methylisothiazolinone 0.0003 0.0003 0.0003 0.0003

Methylchloroisothiazolinone 0.0009 0.0009 0.0009 0.0009 PEG-40 Hydrogenated Castor Oil 0.1 0.1 0.1 0.1

PEG-6 Caprylic/Capric Glycerides 0.1 0.1 0.1 0.1

Fragrance 0.1 0.1 0.1 0.1

Aqua ad 100 ad 100 ad 100 ad 100

Inv = Inventive example, according to the invention

¹ Gaffix™ VC-713 polymer from Ashland, active content 37% by weight

² DIAFORMER Z-631 from Mitsubishi Chemical, active content 30% by weight

³ DIAFORMER Z-632 from Mitsubishi Chemical, active content 30% by weight

Examples 5-8: Aqueous hair spray

Inv = Inventive example, according to the invention

¹ Gaffix™ VC-713 polymer from Ashland, active content 37% by weight ² DIAFORMER Z-631 from Mitsubishi Chemical, active content 30% by weight

³ DIAFORMER Z-632 from Mitsubishi Chemical, active content 30% by weight

4YUKAFORMER SM from Mitsubishi Chemical, active content 30% by weight

Examples 9-13: Aqueous solution

The following test was carried out to show that by use of the inventive composition a solution for the problem introduced above is provided. The test performed was a hair tresses test. The assessment was carried out by trained hairdressers. Asian black hair (10 g per test) was used for the test presented herein.

The following compositions were assessed in the hair tresses test:

Com = Comparative example, not according to the invention

Inv = Inventive example, according to the invention

¹ Gaffix™ VC-713 polymer from Ashland, active content 37% by weight

² DIAFORMER Z-631 from Mitsubishi Chemical, active content 30% by weight

The styling of human hair is dependent on a number of parameters. According to the invention the styling properties of a composition to be applied to human hair correspond to the moisture feeling of the hair directly after application, the stiffness and the style retention of the hair, which are evaluated after drying the hair under room condition, as well as the restyling properties of the hair, wetted with water (0.5 g water per 10 g hair) 4 hours after application of the hair styling composition. In order to value the styling properties of the compositions all the following parameters were assessed by the hair dressers: the moisture feeling of the hair tresses directly after application, the stiffness and the style retention after the hair tresses were dry under room condition, and the re-styling properties of the hair 4 hours after application. The detailed test procedure was as follows:

The hair tresses were washed using a shampoo composition which was free of any conditioning agent. For that purpose the hair tresses were wetted with warm water, then shampoo was applied and spread through the hair for 10 seconds. For each sample the same amount of shampoo was applied. Afterwards the shampoo composition was rinsed off the hair with warm water until no shampoo remained. Before applying the example compositions to be tested, the hair tresses were dried.

In order to assess the styling properties, 2.2 g of the styling composition were sprayed on the dry hair tresses. Then the hair dresser evaluated the moisture feeling of the hair by spreading through the hair tresses with the hands. Afterwards, it was waited at room condition until the hair was fully dried. To evaluate the stiffness of the hair, the hair dresser analyzed the force which needed to be applied to bend the hair tresses with the fingers. At this stage, also the style retention was assessed by analyzing the retention of the hair tresses after touching them. The re-styling properties were analyzed 4 hours after application of the composition. For that purpose, 0.5 g of water was sprayed on the hair and the hair was formed again using the hands. The re-styling properties were rated according to the fact whether it was possible restyle the hair.

Each parameter was rated with a score value between 1 and 7, whereby 1 means bad and 7 corresponds to good. Here, it should be noted that a score of 7 for the moisture feeling means that the hair felt moist after application of the spray. A score of 7 for the stiffness means that the hair was stiff. A score of 7 for style retention means the style of the retained well after application. A score of 7 for re-styling after 4 hours means that 4 hours after application of the composition it was possible to re-style the hair.

As all the parameters listed contribute to the styling properties of the compositions, the scores achieved for the parameters were summed to value the total styling properties of the compositions.

All the results are presented in the following Table:

Hair tresses test Ex.9 Ex.10 Ex.11 Ex.12 Ex.13

Moisture feeling 5.0 5.3 5.6 5.8 5.1 Stiffness 5.8 6.0 6.2 6.5 6.0

Style retention 5.8 6.2 6.0 6.5 6.3

Re-styling after 4 hours 5.8 6.2 6.0 6.2 5.6

Styling properties 22.4 23.7 23.8 25 23

In the above Table showing the results of the tests the worst styling properties were determined for the composition Ex.9 and Ex.13, which only contained one of the substances needed for the invention and are therefore not according to the present invention. For all inventive compositions, which are Ex.10, Ex.1 1 and Ex.12, show improved styling properties in comparison to the non-inventive samples. As the total concentration of the polymers in all compositions tested was 3% a synergistic effect has been determined for the inventive compositions.