and Use Thereof

Technical field

The invention relates to a cosmetic preparation, in particular a hair styling composition, com prising at least one nonionic fixing polymer and at least one cationic film-forming polymer, preferably one nonionic fixing polymer and a combination of two or more cationic film-forming polymers, and evening primrose oil. The application of cosmetic preparation results in long lasting hair styling together with an improvement of the physical-optical properties of hair, es pecially referring to moisturizing the hair. The invention also relates to the use of the cos metic preparation.

Background Art

The entire human body, with the exception of the lips, the palms of the hands and the soles of the feet, is covered with hair, albeit for a large part barely visible. Because of the many nerve endings at the hair root, hair reacts sensitively to external influences such as wind or touch and is therefore a part of the sense of touch that should not be underestimated. How ever, nowadays, the most important function of human head hair lies in helping to create the appearance of the person in a characteristic manner. Similarly to the skin, it fulfils a social function because it contributes considerably to interpersonal relations and to the self-esteem of an individual via its outward appearance.

Hair is consisting of hair shaft and hair root. Hair shaft protrudes freely from the skin, and is a keratinized (dead) section of the hair. Hair shaft represents the actual visible part of the hair, which is continually renewed. Hair root which sticks in the skin is the living part of the hair. Hair shaft consists of three layers: the central part, which is called hair marrow (medulla), is regressed in humans, often completely missing; then there is the marrow, also called cortex; and cuticle as the outermost layer, comprising up to ten horny layers.

Human hair in its freshly grown condition is virtually impossible to improve. The part of the hair in the vicinity of the scalp accordingly has a virtually closed horny layer. In particular, the horny layer, being the external sheath of the hair, and also the inner region below the cuticle are subjected to particular stress by environmental influences. Sunlight, mechanical stress by intensive combing or brushing, hair treatments, such as hair colorations, bleaching and permanent waving, and also hair shaping using a hair dryer or other tools can cause damage to hair.

Moisturizing hair is connected with the idea of delivering water and/or natural oils to hair. The outmost structure of hair is the cuticula, which is arranged in form of shingles. If the cuticula is intact and compact, for example water and natural moisturizing factors cannot escape from the cortex of hair. The hair looks healthy and resembles hair in a freshly grown condition. If the cuticula is damaged for various reasons, water and natural moisturizing factors can es cape from the cortex causing a dry condition of hair. In order to moisturize hair water binding components and natural oils can be delivered to hair helping to restore the cuticula and pro vide the cortex with water binding components. If the cuticula is restored, water and natural moisturizing factors can be inclosed again.

In general, compositions intended to be applied to hair for different purposes should help to retain the natural state of freshly grown hair. Natural healthy hair has a silky shine look, low porosity and a pleasant, smooth feel.

One aim of a hair styling compositions is to provide a means to form a desired hair style and keep the hair style over a couple of hours, at best for the whole day. To achieve this aim, hair styling composition generally contains one or more hair fixing agents. These hair fixing agents should be easily brushed and/or washed out, leaving the hair in a non-dry, non-dam- aged and pleasant condition. On the other hand the hair styling composition should provide the hair with care. Especially moisturizing of the hair helps the hair to look very natural and healthy.

Evening primrose oil, the INCI name being Oenthera biennis (Evening primrose) oil, is pro duced from the seeds of Oenothera biennis. The plant Oenothera biennis belonging to the family of Onagraceae is indigenous to North America, where the American Indians used the plant as food and medicine for hundreds of years.

Evening primrose oil is characterized by a high content of essential fatty acids. An analysis of the composition of the fatty acids of evening primrose is shown in the table below:

Essential fatty acids, namely cis-y-linolenic acid and linoleic acid, are contained in relatively high amounts in evening primrose oil.

In medicine, evening primrose oil is used to treat eczema, premenstrual syndrome, poly arthritis, multiple sclerosis, and menopausal symptoms.

In the cosmetic field, the use of evening primrose oil in skin care compositions is known.

DE 102007037678 A1 describes the use of primrose oil and grape seed oil in different kinds of emulsions, which are applied to the skin.

EP 2303222 B1 discloses means to protect body-care and household products from photo- lytic and oxidative degradation. Specific lactone derivatives are shown to be suitable for said product protection. Amongst others the effect is shown using evening primrose oil.

The possible use of evening primrose oil is mentioned in several prior art documents refer ring to hair treatment, for instance EP 1792607 B1 , EP 2258337 B1 , EP 2184052 A1 , EP 1908456 A1 , EP 1212038 B1 , WO 2010/026009 A1 . Evening primrose oil is always men tioned in a list together with other oils. No specific effect resulting from evening primrose oil is described.

The Mintel Database also discloses several products showing styling properties and contain ing evening primrose oil, for instance Mintel numbers 2759569, 1253789, and 1 186185, Fast Form Cream Gels, all available from John Paul Mitchell Systems (USA), and Mintel number 2290617 Style Guru Styling Cream, available from Sasi Group. All these products contain evening primrose oil amongst other oils. No specific effect is attributed to evening primrose oil.

Products according to Mintel numbers 4333887, Ritual Curl Nutri-Activating Cream, Pierre Fabre; 1538570, Blow Dry Fluid, L’Oreal; 151 1714, Potion9 Styling Treatment, Procter & Gamble; 661807 and 573472, Week Straighter smoothing cream, HM Mane Solutions;

10153093, Thermal Designing Foam, Shiseido contain evening primrose oil and either a fix ing polymer or a film-forming polymer or a combination of fixing and film-forming polymers, which is not according to the invention.

None of the mentioned documents explicitly shows any effect of evening primrose oil con cerning the improvement of hair, especially dry hair, with respect to elasticity, curl retention, moisture and non-greasiness provided by hair styling compositions.

Furthermore, prior art hair styling compositions also suffer from the following disadvantages: Frequent perming and dying damages the hair. Curl revive creams are frequently used to re pair the damaged hair and to hold the curl shape. These revive creams often contain sili cones, sometimes in considerable amounts. The silicones tend to deposit on the hair. These deposits are hardly to remove. The hair looks greasy and becomes more and more dry over the time.

The present invention is made to overcome the above mentioned disadvantages of the prior art hair styling compositions. The aim of the present invention is to provide a styling composi tion for the application on the hair and thereby providing healthy and natural looking hair, be ing moisturized and well styled.

Preferably, the styling composition of the present invention should help to style the hair in the desired way and provide a good and elastic hold of the styled hair together with a care of the hair by natural oils, especially evening primrose oil.

Summary of the invention

Inventors of the present invention found out that a styling composition containing evening primrose oil in a concentration of 0.01 to 10.0% by weight is able to style the hair and im prove the physical-optical properties of hair. In a first aspect, the present invention provides a hair styling composition, comprising at least one nonionic fixing polymer and at least one film-forming polymer and evening primrose oil in an amount of 0.01 to 10.0 % by weight.

In a further aspect, the composition comprises preferably 0.05 to 7.5 % by weight, more pref erably 0.1 to 6.0 % by weight, most preferably 1.0-6.0% by weight of evening primrose oil.

Furthermore, the composition can optionally comprise at least one auxiliary component as listed in the part of“detailed description of the invention”. The at least one auxiliary compo nent is selected from further conditioning components, emulsifiers, preservatives, antioxi dants, and mixtures thereof.

In addition to the above components and the auxiliary components, the composition com prises a balance amount of water, so that all the components amount to 100% by weight.

In another aspect the composition of the invention is free from silicones. In the meaning of the present invention“free from” means less than 0.1 % by weight, preferably 0.01 % by weight, and more preferably 0% by weight of silicone, referring to the total content of the composition. In the meaning of the present invention a silicone is a compound containing si- loxane units. Said siloxane units are chains of alternating silicon atoms and oxygen atoms.

In another aspect, the present invention refers to use of the composition of the present inven tion for styling and caring hair, especially to moisturize the hair, resulting in hair that is not weighed down, but looks natural and healthy. In another aspect the use of the compositions of the present invention are providing a strong hold of the styled hair without generating it stiff. The styled hair remains elastic.

By using the composition of the present invention, the disadvantages of the prior art styling compositions are overcome. The styling composition of the present invention leads to signifi cantly improved qualities of the hair referring to moisture and non-greasiness, shown by the parameters of moisture and weightlessness, together with good hold of the styled hair, shown by the parameters of hardness and curl retention, without leaving the hair stiff, shown by the parameter of elasticity.

Detailed description of the invention Evening primrose oil is obtained from the seeds of Oenothera biennis. For example, evening primrose oil is commercially available as life’GLA’10’n-6 Oil from DSM Nutritional Products Europe.

The use of evening primrose oil is essential for the present invention.

According to the invention at least one nonionic fixing polymer and at least one film-forming polymer is contained in the composition according to the invention.

Fixing polymers can build up very small bridges between single hairs or hair tresses thereby fixing the hair. Fixing polymers are known in prior art. They may be classified as anionic, nonionic and cationic polymers.

According to the invention nonionic fixing polymers have to be contained in the composition according to the invention. Nonionic fixing polymers may be homopolymers of vinyl pyrrolidone, N -vinylformamides or N-vinylcarprolactam. Suitable are also copolymers of vinylpyrrolidone and vinylacetate or vinylpyrrolidone and dimethylaminoethylmethacrylat, terpolymers of vinylpyrrolidone, vinylacetate and propionate or vinylcaprolactam,

vinylpyrrolidone and dimethylaminomethacrylate. According to the present invention it is preferred to use coplymers of vinyl pyrrolidone and vinylacetate, known as VP/VA polymers, which may be purchased as PVP/VA W-735 from Ashland Specialty Ingredients.

The at least one nonionic fixing polymer is used preferably in an amount of 0.1 to 7.5 % by weight, more preferably 0.5 to 5.0 % by weight, relative to the total weight of the composition. The values are referring to the active content of the fixing polymers. The content is referring to the total content of fixing polymers in the respective composition.

As the fixing polymers according to the present invention interact with the surface of the hair to build the brigdes between single hairs or hair tresses, said polymers may also show film- formimg properties. Often it is difficult, even impossible, to asign a single attribute to a class of polymers. The properties are overlapping and the respective polymers often show more than one property. Film-forming polymers are characterized by their adherence to the surface of the hair. This may be achieved by polymers having positively charged groups. The positively charged resi dues are able to interact with the partially negatively charged cystine residues, which are fre quently present in the keratin fibers of the hair. Polymers having positively charged groups are known as cationic polymers.

Cationic polymers are either of natural origin, namely animal or plant derived, or of synthetic origin. The polymers are composed of monomers, either identical ones, resulting in homopol ymers, or different ones, resulting in co- or terpolymers.

The cationic groups of the cationic polymers are preferably derived from nitrogen atoms, which are more preferably present in form of primary, secondary, tertiary or quaternary amine groups. The primary, secondary, and tertiary amine groups may be positively charged depending on the pH value. Quaternary amine groups, also called ammonium groups, are permanently positively charged groups, independent of the pH value.

The film-forming polymers according to the present invention are cationic polymers. Advanta geously, the cationic polymers of natural origin are plant derived, preferably based on the cellulose molecule which is modified in such a way that cationic substituents are introduced or substituents are introduced which are cationic at specific pH values, specifically at those pH values of the hair conditioning compositions. A preferred example of the modified cellu lose molecules is Polyquaternium-10, which may be purchased from Dow Chemical as Ucare Polymer JR 400.

Another preferred example of naturally based cationic polymers is Polyquaternium-4, which is a polymeric quaternary salt of hydroxyethylcellulose quaternized with diallyl-dime- thylammonium chloride. Polyquaternium-4 may be purchased from Akzo Nobel as Celquat L- 200 (28-6829).

Cationic polymers of synthetic origin are composed of monomers, of which at least one kind of monomer is one with a cationic function. A preferred cationic polymer is Polyquaternium- 37, which is a polymeric quaternary ammonium salt the monomers of which conform gener ally to the following formula wherein Ri is -CH ₃ , A is -(CH ₂ )2, and R ₂ , R3 _a nd R ₄ are each -CH ₃ . X- corresponds to Cl-.

Polyquaternium-37 may be purchased from BASF as COSMEDIA CTH (E).

The cationic function of cationic polymers of synthetic origin may be contributed by different monomers exhibiting a cationic function. A suitable cationic monomer is dimethyl diallyl am monium chloride. This monomer is present in the homopolymer Polyquaternium-6 and the copolymer Polyquaternium-7, both of which are suitable cationic polymers.

Polyquaternium-1 1 is a further suitable cationic polymer resulting from the reaction of diethyl sulfate and a copolymer of vinylpyrrolidone and dimethyl aminoethylmethacrylate.

Still another suitable cationic polymer is Polyquaternium 16, a copolymer of methyl vinylimid- azolium chloride and vinylpyrrolidone.

It is even more preferred, if Polyquaternium-37 is contained in the composition according to the present invention.

According to the present invention the at least one film-forming polymer, being a cationic pol ymer, is contained in a total amount of 0.01 to 5.0 % by weight, preferably 0.5 to 3.0% by weight, relative to the total weight of the composition and referring to the active content.

In a preferred embodiment a combination of two or more cationic polymers is contained, more preferred a combination of three different cationic polymers. It is still more preferred, if the combination contains naturally based and synthetic cationic polymers. It is even still more preferred, if the weight ratio of the naturally based polymers to the synthetic polymer is from 0.05:1 to 4:1 , especially from 0.5:1 to 1 :1 . It is further even still more preferred, if the combi nation consists of two naturally based cationic polymers and one synthetic cationic polymer.

It is most preferred, if the combination consists of Polyquaternium-4, Polyquaternium-10 and Polyquaternium-37.

Due to the interaction of cationic polymers and the resulting film on the surface of the hair the film-forming polymers of the present invention also have conditioning and fixing properties. However, according to the present invention the fixing polymers are nonionic polymers and the film-forming polymers are cationic polymers.

In another preferred embodiment the at least one nonionic fixing polymer, preferably at least one VP/VA polymers and the at least one cationic film-forming polymer, preferably the com bination of Polyquaternium-4, Polyquaternium-10 and Polyquaternium-37, are contained in a selected weight ratio, namely the at least one nonionic fixing polymer: at least one cationic film-forming polymer from 0.5:1.0 to 5.0:1.0, more preferably from 1 .0:1.0 to 3.0:1.0.

According to the invention, additional conditioning components may be comprised in the composition supporting the effect of evening primrose oil.

These components may be selected from C12-15 alkyl benzoate, Paraffinum Liquidum and PEG90M + silica. Each of these components can be used alone or in combination with each other.

C12-15 alkyl benzoate is a mixture of benzoic acid esters from of benzoic acid and alcohols that have a carbon chain length from 12 to 15. C12-15 alkyl benzoate may be purchased from Evonik Industries as Tegosoft TN B.

In the composition according to the invention, C12-15 alkyl benzoate is contained in an amount of 0.1 to 8.0 % by weight, preferably 0.5 to 3.0 % by weight, relative to the total weight of the composition.

Paraffinum Liquidum consists of hydrocarbon molecules which are saturated, unbranched or branched. They can be obtained synthetically or refined from petroleum. For example, Paraf finum liquidum can be obtained from H & R ChemPharm with the trade name Pionier 2076. Paraffinum Liquidum can be used in an amount of 0.1 to 10.0 % by weight, preferably 0.5 to 6.0 % by weight, relative to the total weight of the composition.

PEG90M + silica is also advantageously contained in the compositions according to the pre sent invention. The abbreviation PEG stands for polyethylene glycols, consisting of numer ous molecules of ethylene oxide. 90M indicates that 90,000 molecules of ethylene oxide are contained. M is the abbreviation for thousand.

In general, polyethylene glycols consisting of from about 1000 to about 500M ethylene oxide can be used according to the present invention.

Said polyethylene glycols, especially PEG 90M + silica, can be used in an amount of 0.01 to 5.0 % by weight, preferably 0.05 to 2.0 % by weight, relative to the total weight of the compo sition.

The hair styling compositions of the present invention preferably contain humectants. Hu- mectants are hygroscopic substances which bind water and therefore provide moisture. The hygroscopic quality is due to hydrophilic substituents of the molecule, in many cases hy droxyl groups, but other functional groups as amine or carboxyl groups can fulfill the same function. Examples of humectants are propylene glycol, hexylene glycol, and butylene glycol, glyceryl triacetate, glycerol, sorbitol, xylitol, maltitol, polydextrose, urea, Aloe vera gel, alpha hydroxy acids such as lactic acid, honey. Preferred humectants are lactic acid and propylene glycol.

One or more humectants can be used according to the present invention. However it is pre ferred that at least two different humectants are present in the compositions according to the invention. The one or more humectant(s) is/are used preferably in an amount of 0.1 to 7.5 % by weight, more preferably 1.0 to 5.0 % by weight, relative to the total weight of the composi tion. The values are referring to the active content of the humectant.

According to the present invention, the compositions may comprise preservatives, which are allowed and suitable for cosmetic preparations. However, it is preferred, if Methylparaben, Ethylparaben, Phenoxyethanol, Benzethonium Chloride, or mixtures thereof are contained. The preferred preservatives may be used alone or in combination. The total amount of pre servative, referring as well to one single preservative as to a combination of preservatives, is from 0.01 to 2.0 % by weight, preferably 0.05 to 1 .0 % by weight, relative to the total weight of the composition. The values are referring to the active content of the preservatives.

According to the present invention the hair styling composition may contain at least one emulsifier. In general, emulsifiers are substances, which are stabilizing emulsions. They may be classified as ionic and non-ionic emulsifiers, the last ones being preferred. According to the present invention especially preferred are sorbitans which are esterified with fatty acids and ethoxylated. Polysorbate 60 is an example of this class of emulsifiers. Polysorbate 60 may be obtained from Croda Chemical Co., Ltd with the trade name SP Tween 60 MBAL- SS-(SG).

According to the invention the at least one nonionic emulsifier, in particular Polysorbat 60, is contained in an amount of 0.1 to 7.5 % by weight, more preferably 0.5 to 3.0 % by weight, relative to the total weight of the composition.

According to the present invention antioxidants may be used in the hair styling compositions. In general antioxidants are molecules which prevent other molecules from being oxidized. Oxidation processes can produce free radicals which are damaging or destroying other mole cules. When these other molecules are part of living cells these cells may be damaged.

There are several molecules which are able to function as radical scavenger. These mole cules are also called antioxidants. The antioxidants may be of natural origin as for example vitamin C, gluthathione, lipoic acid, carotenes, vitamin E and coenzyme Q. But there are also synthetic antioxidants as butylhydroanisol (BHA), butylhydroxytoluol (BHT) and pentaeryth- rityl tetra-di-t-butyl-hydroxyhydrocinnamate. According to the invention it is preferred to use antioxidants of synthetic origin.

The at least one antioxidant is used in an amount of 0.001 to 0.1 % by weight, preferably 0.01 to 0.07 % by weight, relative to the total weight of the composition. The values are refer ring to the active content of the antioxidants.

Preparation method

The composition of the present invention may be prepared by any technique known or effec tive to prepare a hair styling composition. The hair styling compositions may be prepared as pump creams, pump sprays or mousses. However, it is preferred to prepare the composi tions of the present invention as pump sprays. The process to prepare the composition of the present invention comprises conventional formulating and mixing techniques.

Specifically, compositions of the present invention and a comparative composition are prefer ably produced with the following procedure (Table 1 shows the detailed composition of the examples, and table 3 shows the corresponding trade names and INCI names of the compo nents):

• Heat oily phase to 80°C (emulsifier; additional conditioning component, for instance C12-15 Alkyl Benzoate; preservative, for instance Phenoxyethanol);

• heat water phase to 75-80°C (water; naturally based cationic polymer(s), for instance Polyquaternium-10 and/or Polyquaternium-4);

• combine both phases whilst stirring, then homogenize the batch until the appearance is homogeneous;

• add synthetic cationic polymer (for instance: Polyquaternium-37), stir continuously and homogenize;

• Cool down to 45°C;

• add fixing polymer (for instance VP/VA polymer), fragrance, Evening primrose Oil and optionally other additives;

• stir continuously and cool to room temperature.

Test method

In order to show that the addition of evening primrose oil into the inventive compositions has an effect and contributes to the solution of the above-mentioned problem, a halfhead test is conducted. The test is carried out through the following procedure:

Compositions comprising evening primrose oil at different concentrations ranging from 0.5 to 4.0 % by weight (Examples 1 -5) are prepared as samples of the present invention, and as well as a comparative sample (Comparative Example), which does not comprise any evening primrose oil at all. Respective test samples are filled in syringes, not revealing any details of the composition therein. Depending on the length of the hair, the sample use amount will be 3-5 ml.

Wash the subject’s hair with a base blank shampoo. Towel the hair to remove the spare wa ter and separate subject’s hair from the middle of head. Put each sample in one hand. Spread each sample on one side of the hair.

Use a hair dryer to gently dry the hair from hair tip to root until the two half sides are in the same state. The two sides of the head are kept separated by using a wind shield. Evaluate the following attributes in dry hair directly: Hardness, curl retention, moisture and weightless.

The evaluation is done based on a 10-point system,“1 point” corresponds to“bad”, and“10 points” corresponds to“good”. A value of 5 points is a medium value, corresponding to suffi cient qualities. The values of 9 to 6 points give descending values, making it possible to dif ferentiate stepwise between good and sufficient. Correspondingly, the values of 4 to 2 points give descending values, making it possible to differentiate stepwise between sufficient and bad.

The test and evaluation results are shown in Table 2, wherein the average score based on the 8 evaluation scores is recorded for each sample.

It can clearly be seen from table 2, comparing the inventive examples to the compara tive example, that the addition of evening primrose oil to the composition influences the condition of the hair.

Hair treated with compositions containing evening primrose oil in increasing amounts is evaluated better referring to“Curl Retention” in all cases than hair treated with the com parative composition. The parameter of“Curl Retention” indicates the strong the hold of the styled hair. Even though evening primrose oil is primarily not a fixing agent, it sup ports the styling of the hair.

Referring to the evaluation of moisture, it is obvious, that the addition of evening prim rose oil improves the moisture content of hair, very good evaluations are given for hair treated with compositions containing evening primrose in concentration of 1 % by weight or more.

The addition of evening primrose oil to hair styling compositions does not lead to a worse evaluation referring to the weighing down of hair. The hair treated with composi tions containing evening primrose oil is nearly equally well evaluated compared to hair treated with composition containing no evening primrose oil.

Even though the hair treated with compositions containing evening primrose oil is eval uated to be harder than hair treated with compositions without evening primrose oil, it is apparent that the increase is only slightly and varying. Compositions according to ex ample 4 have a value of hardness of 6.5 that means only 6.6 % differing from the value for hair treated with compositions without evening primrose oil. The increase of hard ness is only very small and shows that the addition of evening primrose oil to hair styl ing compositions does not lead to stiff hair.

It can be seen, that primrose oil positively influences the moisture of hair without weigh ing hair down or exerting a negative influence on the styling properties.

The above examples of the present invention are provided only for illustrative purposes, and are not intended to limit the invention in any aspect. One skilled in the art should know that, changes and modifications may be carried out to technical solutions of the present invention within the spirit and scope of the present invention.