PREPARATION FOR SHAPING HAIR - RELEASED IN AEROSOL FORM

The present invention describes a cosmetic product in the form of a hair shaping hair prepa ration in aerosol form, which contains no or only very small amounts of ethanol. The use of this preparation allows the shaping of the hair; the hair shaped in this a way has a long-term hold, i.e. the hair shaping preparation according to the invention provides a long-lasting hold of the hair style.

Hair is an important part of the human body. It is present on almost all parts of the human body, except from the lips, the palms and the soles of the feet, however on most parts of the human body the hair is hardly visible. Because of the many nerve endings on the hair root, hair reacts sensitive to external influences such as wind or touch and therefore hair should not be an underestimated part of the sense of touch. However, today the most important function of human head hair is to influence the appearance of a human being in a character istic way. Similar to the skin, hair fulfills a social function, because it significantly contributes to the self-esteem of an individual by its appearance.

Hair consists of the hair shaft and the hair root. The hair root, which sticks in the skin, is the living part of the hair. The hair shaft protrudes freely from the skin, and is a keratinized (dead) section of the hair. Hair shafts represent the actual visible part of the hair, being con tinually renewed. The hair shaft consists of three parts: the medulla, the cortex, and the cuti cle. The central part, the medulla, which is also called hair marrow, is regressed in humans, often completely missing. The medulla is surrounded by the cortex being a fiber layer. This layer consists of dead horny fiber cells and determines the strength and elasticity of the hair. In this layer color pigments are also contained. The cuticle is very thin and transparent.

Assumed that there are no pathological changes, 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.

Frequently, natural hair has little volume of its own and long hair often hangs limp and straight down from the head. However, many people want their hair having more volume and be shaped (styled) in a pleasing way. This can basically be achieved in two ways, on the one hand there are methods for permanently shaping hair, for example, the perm and on the other hand non-permanent procedures that form and fix the hairstyle only for a limited time. To achieve a non-permanent hairstyle, several product forms are provided that may be used individually or in combination with one another. Examples include setting solutions, mousses, hair sprays, hair waxes, hair gels and others more. Different product forms are available, those, which are preferably applied to wet hair and others, which are applied to dry hair. For example, product forms intended for wet hair application include setting solutions and mousse. During the subsequent drying process, the hair is brought into the desired shape, for example by curlers, brushes, straighteners and other means.

Another way to get the hair shaped is to use product forms that are applied to dry hair.

Known products are hair gels, hair waxes and gel sprays, the latter being often used in Asia. After application of the above mentioned products, the dry hair is styled in the desired way, for example, by the hands, brushes or otherwise.

Hairspray products contain a fixing agent, usually a fixing polymer, which must be solubil ized. In general, said hair spray products contain a high amount of alcohol, especially etha nol. This has two advantages, on the one hand, the solubility of the fixing polymers in alcohol is very high, especially in ethanol, and on the other hand, the alcohol, especially ethanol, evaporates quickly after the spraying process, thus quickly forming a fixing film on the hair. Hair sprays, both in the form of aerosol sprays and in the form of pump sprays are thus ap plied to the already shaped and styled hair and mainly serve to fix the already styled hair.

However, the hair spray products described have disadvantages: the fixing films on the hair, formed, when conventional alcohol containing hair sprays are used, are frequently described as hard and inflexible and, in single cases, are characterized by the expression "helmet hair style". Furthermore, the fixing film on the hair may also be perceived as sticky. Due to the fast drying time of conventional hair sprays shaping the hairstyle after application of the spray is only very limited or even impossible. Because of the rapidly dried polymer film, the consumers describe the hair feel as unnatural, sticky, and rough, in sum not very pleasant.

Many consumers also complain that by frequently using hair sprays containing high amounts of alcohol, especially ethanol, the hair is getting dryer. Likewise, a sometimes stinging alco holic odor is perceived by consumers to be displeasing. In some cases, there are complaints of a tussive irritation.

Therefore, there is a need to provide a novel hair spray preparation, containing no or only a very small amount of alcohol, especially ethanol, which does not have the above mentioned disadvantages. Documents of prior art already disclosed hair sprays containing no or very little alcohol, also ethanol.

EP 25701 10 B1 describes an aerosol hair spray product, which comprises a hair styling preparation, which contains a combination of two hair styling polymers, each of which must have certain properties. This aerosol hairspray product contains less than 2% or less than 1% alcohol.

EP 2919860 A2 describes a method for styling the hair, wherein the hair styling preparation contains a water-soluble hair styling polymer and less than 2% alcohol, and wherein a certain spray rate (0.28 g / s to 0.45 g / s) has to be met and wherein the preparation is released in form of particles having an average particle distribution (Dv50) of 40 to 100 pm. Amongst others this is achieved by a valve shaped in a special way.

EP 2570192 B1 describes an aerosol hairspray product, which comprises a container and a hair styling preparation containing a hair styling polymer as well as at least 50% water and the preparation being substantially free of alcohol or ethanol and/or propanol. The container is provided with a spray head, which must meet certain characteristics.

EP 2570191 B1 discloses an aerosol hair spray product for styling and/or shaping hair com prising a hair styling preparation containing a hair styling polymer, at least 50% water and no alcohol or ethanol and/or propanol. The preparation is filled into a container having a spray nozzle characterized by certain features.

EP 25701 13 B1 also discloses an aerosol hair spray product for styling and shaping the hair. The hair styling preparation comprises a polymer blend of a hard and a soft polymer, which must have certain properties, further at least 50% water, a propellant, less than 2% or less than 1% alcohol, and less than 15% volatile organic compounds.

EP 32601 10 A1 also describes an aerosol hair spray product for styling and shaping the hair. The hair styling formulation contains at least 50% water, a hair styling polymer, which is se lected from a group of polymers, namely Acrylates Copolymer, obtainable from two or more monomers of (meth) acrylic acid or one of its simple esters; Octylacrylamide/acrylates/butyla- minoethyl methacrylate copolymers; Acrylates/hydroxyesters Acrylates Copolymers obtaina ble from butyl acrylate, methyl methacrylate, methacrylic acid, ethyl acrylate and hydroxy- ethyl methacrylate; Polyurethane-14/AMP-Acrylates polymer blend and combinations thereof, further a propellant, less than 2% alcohol or no alcohol, and less than 54% volatile organic compounds.

However, there is still a need to improve or simplify the mentioned products. On the one hand, the spray devices have to meet certain criteria in order to obtain a sufficiently fine spray pattern and to allow a sufficiently quick drying of the droplets of the hair spray prepara tion generated during the process of spraying (see EP 2919860 A2, EP 2570192 B1 ,

EP 2570191 B1 ). On the other hand, it is necessary to combine two different types of special fixing polymers in order to achieve a sufficient fixation of the hairstyle. If the preparation is aimed at providing good fixing properties, a stable film on the hair usually forms rapidly after the application of such a preparation. Shaping a hairstyle is not or hardly not possible.

Moreover, it is desirable, if only one product satisfies different needs in relation to hair styling, such as providing volume to the hair, definition of curls, straightening hair, counteracting hair frizz, and providing styling products for men. In particular, it is desirable to make available product forms, which enable a uniform and economical use of the hair shaping and fixing preparation.

Furthermore, it is advantageous, if the shaping preparation does not have to be applied with the hands, as is the case with hair gels and hair waxes. When using the said product forms, the preparations must first be distributed in the hands and is then applied to the hair. The hands get sticky and greasy and product remains are left on the hands. Consumers often perceive this as unpleasant. In addition, a uniform distribution of said products on the hair is often difficult.

Therefore, there was a need to provide a hair shaping and fixing preparation that allows both processes in one step, namely a shaping and fixing of the hairstyle. During shaping a variety of hair styles are feasible (volume, curl definition, hair straightening, anti-frizz, styles for men), which then are long-lasting. It is intended to generate a fixing film on the hair, which allows styling and shaping the hair after applying the preparation and before the film is dried. The hairstyle should be characterized by a flexible and natural grip. In addition, the prepara tion should leave a hardly noticeable film on the hair, which is perceived as non-sticky and gives a pleasant hair feel. Also, if hands are used to shape the hairstyle, they should not be left with excessive sticky product residues. Furthermore, even a mild odor should character ize the preparation, which is not interfered by an alcoholic odor, which is perceived as sting ing. A simple, economical and uniform application of the preparation is also desirable. The above objects are achieved by a preparation for shaping hair, released in aerosol form, containing

a setting polymer selected from Acrylates Copolymers, in particular dispersible in an emulsion,

one or more emulsifier(s),

one or more preservatives,

> 55% by weight of water, in relation to the total weight of the preparation,

£ 0.1 % by weight of ethanol, in particular 0% by weight or 0.0001 to 0.01% by weight, in relation to the total weight of the preparation, and

25 to 50% by weight of a propellant, in relation to the total weight of the preparation; wherein the preparation for shaping hair is contained in an aerosol packaging device, wherein the aerosol packaging device comprises a dispenser,

the dispenser having a valve characterized by a stem having a tapered bore (7) having an inner diameter of 0.25 to 0.7 mm and a body having at least two bores, wherein one of the bores is gas phase bore (4) having an inner diameter of 0.4 to 0.8 mm.

In the context of the present invention the term hair refers to human hair, in particular head hair.

In the hair shaping preparation of the present invention water is contained in an amount of 55% by weight or more; preferably 60 to 70% by weight, more preferably 63 to 66% by weight, in relation to the total weight of the preparation.

The setting polymer is selected from the Acrylates Copolymers. Acrylates Copolymers are characterized in that the synthesis is carried out from monomers comprising acrylic acid, methacrylic acid and branched and/or unbranched C1 to C4 esters of acrylic acid and/or methacrylic acid. For example, the properties of the particular Acrylates Copolymers may be influenced by the ratio of the anionic monomers (for example acrylic acid and methacrylic acid) to the nonionic monomers (branched and / or unbranched C1 to C4 esters of acrylic acid and/or methacrylic acid), the degree of crosslinking and the particular conditions during synthesis.

The Acrylates Copolymer may be characterized by a specific charge density. According to the invention it is preferred, if the anionic charge density of the Acrylates Copolymer is 1 to 2 meq/g, in particular 1.3 to 1 .8 meq/g. The charge density may be determined with the fol lowing method: Apparatus and Reagents:

Analytical Balance (±0.001 g)

Erlenmeyer Flasks - 250 ml

Burette - 50 ml (0.1 ml gradation)

Sodium Hydroxide, Aqueous solution, 0.100 N, Standardized

Phenolphthalein Indicator (1% in anhydrous ethanol, SDA-40-2 quality).

Procedure:

1 ) Weigh 0.8 - 1.0 g (determine weight to 0.001 g) of the respective polymer into a 250 ml wide-mouth Erlenmeyer Flask.

2) Add 50 ml of anhydrous ethanol, SDA-40-2 quality and swirl gently until solution is

completed. The flask should be stoppered to minimize the evaporation of solvent.

3) Add 3 drops of Phenolphthalein Indicator solution and titrate with standardized 0.100 N NaOH to the first persistent (30 seconds) pink end-point.

4) Determine the Free-Acidity of the respective polymer in duplicate.

5) Determine a blank titration on 50 ml of anhydrous ethanol, SDA-40-2 quality.

Calculation:

The Free-Acidity of the respective polymer is expressed as milli equivalents/gram (meq/g)

A = ml NaOH required for blank,

B = ml NaOH required for the respective polymer sample,

W = weight of the respective polymer in g,

N = normality of NaOH solution.

As can be seen from the information on the charge density, the Acrylates Copolymer of the present invention is an acidic polymer. In order that the necessary properties of the polymer, namely the fixing properties, come into effect, it is necessary to neutralize the polymer. Ad vantageously, 2-amino-2-methyl-1 -propanol (AMP), 2-amino-2-methyl-1 ,3-propanediol (AMPD), mono-isopropanolamine, triisopropananolamine, and inorganic bases, such as so dium hydroxide and potassium hydroxide may be used as neutralizing agents. In particular, 2-amino-2-methyl-1 -propanol (AMP) is preferred. A degree of neutralization of 95 to 1 10% of the Acrylates Copolymer is advantageous. To approximately determine how much of the neutralizing agent is required to achieve the desired degree of neutralization, the following formula may be used:

W = Part by weight (g) of the respective polymer,

A = Acidity (meq/g) of the respective polymer,

N = % neutralization required (decimal),

E = Equivalent weight of base used,

S = percentage solids (expressed as a decimal) of the respective polymer,

Y = Parts by weight (g) of base required.

Moreover, it is advantageous, if the Acrylates Copolymer is dispersible in an emulsion. The dispersibility in an emulsion enables a simple form of incorporation of said polymer into an aqueous preparation, especially into the hair shaping preparation. Thus, it is advantageous, if the Acrylates Copolymer is provided as a raw material, which is in the form of an emulsion, in which the Acrylates Copolymer is contained. It is preferred, if an anionic surfactant is con tained in said raw material emulsion.

According to the present invention it is advantageous, if an Acrylates Copolymer is con tained, which for example is obtainable from AkzoNobel under the trade name BALANCE ^® CR Polymer.

In the preparation according to the present invention the setting polymer selected from Acry lates Copolymers is contained in an amount of 1.0 to 7.5 % by weight, preferably 2.5 to 7.5 % by weight, more preferably 3.5 to 4.4 % by weight, in relation to the total weight of the preparation and in relation to the active content of the Acrylates Copolymer. Alcohols are derivatives of unsubstituted, aliphatic or alicyclic hydrocarbons having hydroxyl groups. According to the number of hydroxyl groups one molecule has, monohydric, dihydric, and polyhydric alcohols may be differentiated. If the hydroxyl group is on a primary carbon atom, these alcohols may be called primary alcohols. Monohydric, primary alcohols having 1 to 3 carbon atoms are very fluid liquids that can be mixed with water at any rate. Monohydric, primary alcohols having 4 to 12 carbon atoms are oily liquids, which are only water-miscible in certain proportions.

In the meaning of the present invention, alcohols are understood to mean only monohydric primary alcohols having 1 to 12 C atoms.

The preparation according to the invention advantageously contains little, in particular 0.0001 to 0.01 % by weight of alcohol, in relation to the total weight of the preparation, or no alcohol, with the proviso that said ranges are not referring to ethanol. Nevertheless, in different em bodiments, the incorporation of higher content of alcohol may be desirable; in this case it is advantageous, if the amount of alcohol does not exceed 5.0% by weight, in particular does not more exceed 2.0% by weight, in relation to the total weight of the preparation, with the proviso that said ranges are not referring to ethanol.

The preparation according to the invention contains £ 0.1% by weight of ethanol, in particular 0% by weight or 0.0001 to 0.01% by weight of ethanol, in relation to the total weight of the preparation.

However, there are advantageous embodiments containing ethanol in an amount of 2.4 to 5.4 % by weight, in relation to the total weight of the preparation. These embodiments are described as:

Preparation for shaping hair released in aerosol form containing

a setting polymer selected from Acrylates Copolymers, in particular dispersible in an emul sion,

one or more emulsifier(s),

one or more preservative(s),

> 55% by weight of water, in relation to the total weight of the preparation,

2.4 to 5.5% by weight of ethanol, in relation to the total weight of the preparation, and 25 to 50% by weight of a propellant, in relation to the total weight of the preparation, wherein the preparation for shaping hair is contained in an aerosol packaging device, wherein the aerosol packaging unit comprises a dispenser, the dispenser having a valve characterized by a stem having a tapered bore (7) having an inner diameter of 0.25 to 0.7 mm and a body having at least two bores, wherein one of the bores is gas phase bore (4) having an inner diameter of 0.4 to 0.8 mm.

The preparation according to the invention contains a propellant. The propellant consists of one or more propellant gas/gases, which may be selected from hydrocarbon gases, fluori- nated gases, fluorocarbon gases, dimethyl ether, nitrogen, air or carbon dioxide or mixtures thereof. Preferably the propellant is dimethyl ether having a gas pressure rating of 4.2 bar.

In the context of the present invention it is advantageous, if the propellant is contained in an amount of 25.0 to 50.0% by weight, in particular 27.5 to 40.0% by weight, in relation to the total weight of the preparation for shaping hair.

According to the invention, the preparation for shaping hair does not contain any or only very small amounts of ethanol. Ethanol is known to have a function as a germicidal agent, i.e. eth anol may be used as a preservative. Furthermore, ethanol is a good solvent for both hydro philic and lipophilic substances. By not or hardly not using ethanol, a good preservative and a good solvent is not contained in the preparation for hair shaping any longer. Hence, a dif ferent way of preservation and different types of solubilizer have to be used in the hair shap ing preparation according to the invention.

One or more emulsifier(s), being effective as solubilizers, are contained in the hair shaping preparation according to the invention.

Preferred emulsifiers are O/W-emulsifiers. O/W-emulsifiers are characterized by HLB values of 8 to 15. HLB values can be determined according to the following formula:

HLB = 20 x (1 -Mii _pophiie /M), wherein M^ _hii represents the molecular weight of the lipophilic portion of the emulsifier and M represents the molecular weight of the entire emulsifier.

In general, emulsifiers having an HLB value up to about 8 are considered as W/O-emulsifi- ers. By contrast, O/W-emulsifiers have HLB values of greater than 8 to 15.

The following emulsifiers may act as O/W-emulsifiers: Glyceryl stearate in admixture with ceteareth-20, ceteareth-25, ceteareth-6 in admixture with stearyl alcohol, cetylstearyl alcohol in admixture with PEG-40 castor oil and sodium cetyl stearyl sulphate, triceteareth-4 phosphate, sodium cetylstearyl sulphate, lecithin trilaureth-4 phosphate, laureth-4 phosphate, Stearic acid, propylene glycol stearate SE, PEG-25 hydro genated castor oil, PEG-54 hydrogenated castor oil, PEG 6 caprylic acid / capric acid glycer ides, glyceryl oleate admixed with propylene glycol, ceteth-2, ceteth-20, polysorbate 60, glyc eryl stearate in admixture with PEG-100 stearate , Laureth-4, ceteareth-3, isostearyl glyceryl ether, cetyl stearyl alcohol in admixture with sodium cetylstearyl sulfate, laureth-23, steareth- 2, glyceryl stearate in admixture with PEG-30 stearate, PEG-40 stearate, glycol distearate, PEG-22 dodecyl glycol Copolymer, polyglyceryl-2-PEG-4 stearate, ceteareth-20, methyl glu cose sesquistearate, steareth-10, PEG-20 stearate, steareth-2 in admixture with PEG-8 dis tearate, steareth-21 , steareth-20, isosteareth-20 , P EG-45 / dodecylglycol copolymer, meth- oxy-PEG-22 / dodecyl glycol copolymer, PEG-20 glyceryl stearate, PEG-20 glyceryl stearate, PEG-8 beeswax, polyglyceryl-2-laurate, isostearyl diglyceryl succinate, stearamidopropyl PG-dimonium chloride phosphate, Glyceryl stearate SE, ceteth-20, triethyl citrate, PEG-20 methyl glucose sesquistearate, ceteareth-12, glyceryl stearate citrate, cetyl phosphate, tri- ceteareth-4-phosphate, trilaureth-4-phosphate, polyglycerylmethyl glucose distearate, potas sium cetyl phosphate, isosteareth-10, polyglyceryl-2-sesquiisostearate, ceteth - 10, oleth-20, isoceteth-20, glyceryl stearate in admixture with ceteareth-20, ceteareth-12, cetylstearyl alco hol and cetyl palmitate, cetylstearyl alcohol in admixture with PEG-20 stearate, PEG-30 stea rate, PEG-40 stearate, PEG- 100 stearate.

Preferred are those O/W-emulsifiers, which are characterized in that they are ethoxylated fatty alcohols or that they contain ethoxylated fatty alcohols in admixture with another emulsi fier. More preferred are those ethoxylated fatty alcohols, whose alkyl residues are predomi nantly lauryl residues or only lauryl residues. Even more preference is given to the com pounds Laureth-4, Laureth-5, Laureth-7, Laureth-9, Laureth-10 and Lauerth-12. Further even more preference is given to the emulsifier Laureth-4, which for example may be obtained from Sasol under the trade name Marlosol PK 9040.

In the preparation according to the invention the one emulsifier or more emulsifiers i s/are contained in a total amount of 0.05 to 1% by weight, preferably 0.1 to 0.8% by weight, in rela tion to the total weight of the preparation and in relation to the active content of the emulsi fier.

The hair shaping preparation of the invention contains one or more preservatives. Preserva tives, which may be used, are all preservatives, which are in accordance with the Cosmetics Regulation, with the proviso that ethanol is contained only with an amount < 0.1% by weight in relation to the total weight of the preparation or as otherwise specified in the present inven tion. Preference is given to a preservation with phenoxyethanol and/or parabens. It is particu larly preferred, if phenoxyethanol is contained as a preservative. It is further particularly pre ferred, if a combination of phenoxyethanol and ethylhexyl glycerol is contained in the prepa ration of the present invention. Although ethylhexyl glycerol is not included in the list of pre servatives that are allowed to be used in cosmetics, it is known that ethylhexyl glycerol may support the effect of certain preservatives, what may be described that ethylhexyl glycerol acts as a preservative booster.

The respective preservatives may be used individually or in combination. Advantageously, the total amount of one or more preservatives i s/are in a range of 0.01 to 1.0 % by weight, preferably 0.1 to 0.8 % by weight, in relation to the total weight of the preparation and in rela tion to the active content of the respective preservative.

If for preservation a combination of phenoxyethanol and ethylhexylglycerol is contained, the amount of phenoxyethanol ranges from 0.3 to 0.7 % by weight, in relation to the total weight of the preparation and the active content of phenoxyethanol and the amount of ethylhexyl glycerol is in the range of 0.1 to 0.5 % by weight, in relation to the total weight of the prepara tion and the active content of ethylhexyl glycerol.

In an advantageous embodiment, additionally selected perfume raw materials are contained in the hair shaping preparation according to the invention. The incorporation of selected per fume raw materials has several advantages.

On the one hand, the hair shaping preparation itself may be perfumed in an appealing man ner. This is important because the decision to buy a product and also to buy it again is not only determined by the actual product properties, which are often recognized and appreci ated by the consumer only after prolonged use of a product, but also by an appealing per fume. Whether a perfume is liked, is determined by using a product tester in the store right at the moment of purchase.

On the other hand, perfume raw materials may be contained, which have comparatively low volatility, and therefore provide fragrance to the shaped hair.

The following perfume components are only a very small selection from the wide variety of perfume raw materials that may be incorporated into the hair styling formulation: coumarin, benzyl acetate, benzyl alcohol, benzyl benzoate, cinnamic aldehyde, cinnamyl alcohol, citral, citronellol, eugenol, geraniol, limonene, linalyl acetate, methyl benzoate and terpineol. This selection should only serve for illustration and by no means be limiting. Further examples of fragrances can be found, for example, in the book by S. Arctander "Perfume and Flavor Chemicals, Vol. I and II, Montclair, N.J., 1969 or later editions or other books of comparable content or patent literature in the field of scent science. Said literature is known to the person skilled in the art, who is involved in perfuming cosmetic products. The perfume raw materials may be divided into different groups, the person skilled in the art would address top notes, middle notes and base notes. Such a classification takes into account, for example, the vola tility of the individual components. Perfume raw materials that may be assigned to the top notes are characterized by a greater volatility than those associated with the base notes. Re ferring to the components of the above selection, methyl benzoate, limonene and benzyl ace tate may be classified as top notes, while coumarin, cinnamaldehyde and cinnamyl alcohol may be classified as base notes.

In addition to the volatility, the odor impression of the respective perfume raw materials also plays an important role and must be considered when creating a perfume mixture. A perfume mixture should always convey a well-balanced overall odor.

In the hair shaping preparation the perfume raw materials are contained as perfume mixtures and advantageously, the perfume mixtures being contained in an amount of 0.1 to 0.5 % by weight, in particular 0.14 to 0.28 % by weight, in relation to the total weight of the preparation for hair shaping.

In a further advantageous embodiment, components providing care are additionally con tained in the hair shaping preparation according to the invention. In the meaning of the pre sent invention components providing care are all substances that achieve a caring effect on the hair and/or the scalp. In the broadest sense a caring effect contributes to an improvement of the surface and/or structure of hair and/or scalp. The caring effect is limited to a cosmetic effect and is not a dermatological one. Since the preparation for hair shaping remains on the hair and is not immediately removed, the components providing care stay on the hair and/or scalp for a longer period of time, thus helping to improve hair and/or scalp.

In the context of the present invention, a variety of substances may act as components providing care, a selection of which is described below, namely lanolin, substances of the vit amins of the B group and/or the vitamin B complex, silicone compounds, polar oils and/or hu- mectants. According to the present invention is advantageous, if lanolin alcohol is used. Lanolin alcohol may additionally be contained in the preparation according to the invention. Lanolin alcohol is the unsaponifiable part of wool wax, comprising a mixture of alcohols having an average mo lecular weight of about 370 Da. Typical ingredients include cholesterol, lanosterol, agnosterol and their dihydro derivatives, as well as straight and branched chain aliphatic alcohols.

It is particularly preferred, if lanolin alcohol known under the trade name Eucerit ^® is con tained. Eucerit ^® comprises a mixture of aliphatic alcohols, especially alkanols with chain lengths of C18 to C20, diols with chain lengths of C16 to C26 and sterols.The cholesterol content is at least 30% by weight of the raw material.

In the preparation according to the present invention lanolin alcohol is contained in an amount of 0.005 % by weight to 5 % by weight, preferably 0.05 % by weight to 2 % by weight, more preferably 0.01 % by weight to 1.0 % by weight, in relation to the total weight of the preparation for hair shaping.

According to the present invention, it is also advantageous, if additionally one or more sub stances of the vitamins of the B group and/or of the vitamin B complex are contained. Sub stances of the vitamin B group and/or of the vitamin B complex are usually water-soluble and have an important function in the cell metabolism of plants and animals.

According to the invention, examples of substances of the vitamins of the B group and/or of the vitamin B complex include thiamine (vitamin B1 ), riboflavin (vitamin B2), nicotinic acid (vitamin B3), nicotinamide (niacinamide), pantothenic acid (vitamin B5), panthenol (Provita min B5), panthenol triacetate, panthenol monoethyl ether, pantolactone, pyridoxine and pyri- doxal. It is preferred, if panthenol is contained in the preparation according to the invention.

For example, panthenol may be obtained from the company BASF under the trade name D-panthenol 75 W as a 77% solution in water.

Likewise it is preferred, if niacinamide is contained in the hair shaping preparation according to the invention. For example, niacinamide may be obtained from the company Lonza.

According to the invention, one or more substances of the vitamins of the B group and/or of the vitamin B complex is/are contained in an amount of 0.005% by weight to 5% by weight, preferably 0.05% by weight to 2% by weight, particularly preferably 0, 01 % by weight to 1.0 % by weight, in relation to the total weight of the preparation and in relation of the active content of the respective substance contained in the preparation of the present invention.

According to the invention it is also advantageous, if one or more silicone compounds are additionally contained in the preparation according to the invention. Silicones are also known as poly (organo) siloxanes, being a group of synthetic polymers, in which silicon atoms are linked by oxygen atoms. Silicones consist of individual siloxane units. The terms silicone compound, silicone, poly (organo) siloxane and polysiloxane compound are used synonymously.

Silicones may be represented by the general formula R _n SiO ₍ 4- _n ) / 2 (n = 0, 1 , 2, 3), illustrating that a siloxane unit may have one to four further substituents.

Siloxane units are therefore mono-, di-, tri- and tetrafunctional. In a symbolic notation the following letters represent:

M (mono), M corresponds to R ₃ S1O _1/2 ,

D (di), D corresponds to R2S1O2/2,

T (tri), T corresponds to RS1O _3/2 and

Q (quatro), Q corresponds to Si0 _4/2 .

Based on the fact that different siloxane units can be linked together in the molecule, a multitude of silicone compounds may be formed. Following the system atics of organic polymers, several groups may be differentiated:

* Cyclic polysiloxanes are ring-shaped of difunctional siloxane units, Dn.

* Linear polysiloxanes are built as MD _n M, or R ₃ SiO[R ₂ SiO] _n SiR ₃ , for example polydime- thylsiloxane may be mentioned.

* Crosslinked polysiloxanes are chain- or ring-shaped molecules linked in flat or three- dimensional networks of tri- and tetrafunctional siloxane units. The formation of high molecular weight silicones is achieved by forming chains and crosslinking.

The elements effecting the branching of polysiloxanes are the trifunctional or tetrafunctional siloxane units, M _n D _m T _n . The branching points are found either in a polysiloxane chain or a ring. Various substituents may be bound to the silicon atoms of the silicones, the substituents be ing very often methyl groups; accordingly linear, branched or crosslinked polydimethylsilox- anes may be differentiated. Depending on the length and degree of crosslinking different sized and complex molecules may be formed. In the case of liquid or free-flowing polydime- thylsiloxanes, a characterization of which is given by using the appropriate viscosity values issued by the manufacturer or supplier.

In addition to the methyl groups as substituents, there are a variety of other substituents. In order to improve the solubility of the polysiloxanes and thus achieve a better incorporation into aqueous cosmetic preparations, alkoxy residues, in particular ethylene oxide residues, may be introduced into the polysiloxanes. Ethylene oxide residues are also referred to as polyethylene glycol residues, abbreviated to PEG.

According to the invention, it is advantageous, if polysiloxanes, which have 8 to 20 ethylene oxide residues, preferably 10 to 18 ethylene oxide residues, are used. A preferred example of such a polysiloxane compound is PEG-12 dimethicone, which for example may be pur chased from Dow Corning under the trade name Xiameter OFX-0193 Fluid.

Advantageously, in the hair shaping preparation one or more polysiloxane compound(s) comprising 8 to 20 ethylene oxide residues, preferably 10 to 18 ethylene oxide residues, i s/are contained in a total amount of 0.01 to 3% by weight, preferably 0.05 to 1.0% by weight, in relation to the total weight of the preparation and in relation to the active content of said polysiloxane compound(s).

According to the invention, it is advantageous, if additionally one or more oils are contained in the preparation according to the invention. The oils may be selected from the group of po lar oils, for example from the group of lecithins and fatty acid triglycerides, namely the triglyc erol esters of saturated and/or un saturated, branched and/or unbranched alkane carboxylic acids having a chain length of 8 to 24, in particular 12 to 18 C atoms. The fatty acid triglycer ides may be selected, for example, advantageously from the group of synthetic, semi-syn thetic and natural oils, such as coco glyceride, olive oil, sunflower oil, soybean oil, peanut oil, rapeseed oil, almond oil, palm oil, coconut oil, castor oil, wheat germ oil, grapeseed oil, this tle oil, evening primrose oil, macadamia nut oil and the like.

It is also advantageous, if squalene, a polyunsaturated organic compound from the group of triterpenes is contained in the preparation of the present invention. In the context of the present invention, further advantageous polar oil components may be chosen from the group of esters of saturated and/or unsaturated, branched and/or un branched alkane carboxylic acids having a chain length of from 3 to 30 carbon atoms and saturated and/or unsaturated, branched and/or unbranched alcohols having a chain length of 3 to 30 carbon atoms and from the group of esters of aromatic carboxylic acids and saturated and/or unsaturated, branched and/or unbranched alcohols having a chain length of 3 to 30 carbon atoms. Particularly advantageously, such ester oils may be selected from the group of octyl palmitate, octyl cocoate, octyl isostearate, octyl dodecyl myristate, cetearyl isonona- noate, isopropyl myristate, isopropyl palmitate, isopropyl stearate, isopropyl oleate, n-butyl stearate, n-hexyl laurate, n-decyl oleate, isooctyl stearate, isononyl stearate, isononyl isonon- anoate, ethylhexyl palmitate, 2-ethylhexyl laurate, 2-hexyldecyl stearate, 2-octyl dodecyl pal mitate, stearyl heptanoate, oleyl oleate, oleyl erucate, erucyl oleate, erucyl erucate, tridecyl stearate, tridecyl trimellitate, as well as synthetic, semi-synthetic and natural mixtures of such esters, e.g. jojoba oil.

Furthermore, advantageously one or more oils may be selected from the group of dialkyl ethers and dialkyl carbonates, examples being dicaprylyl ether (available under the trade- name Cetiol OE) and/or or dicaprylyl carbonate (available under the trade name Cetiol CC).

Advantageously, any mixtures of said oil components may be contained in the preparations of the present invention.

Sunflower oil, castor oil, soybean oil, jojoba oil and macadamia oil are particularly preferred, they may be referred to as caring oils.

Advantageously, the oil or oils i s/are contained in a total amount of 0.01 to 1.0% by weight, preferably 0.003 to 0.1% by weight, in relation to the total weight of the preparation.

According to the invention additionally one or more humectants may be contained in the preparation according to the invention. Humectants may impart moisture to the hair and/or scalp and/or help prevent the loss of moisture from hair and/or scalp. Humectants are hygro scopic substances capable of binding water. This water binding capacity is due to hydrophilic groups, mainly hydroxyl groups, but amine groups and carboxyl groups are also of im portance. For example, humectants are propylene glycol, hexylene glycol, butylene glycol, glyceryl triacetate, glycerin, sorbitol, xylitol, maltitol, polydextrose, urea, aloe vera gel, honey and alpha hydroxy acids such as lactic acid. It is preferred, if propylene glycol and/or glycerol i s/are contained in the preparation according to the invention. In the preparation of the present invention the one humectant or more humectants i s/are con tained in a total amount of 0.01 to 1 % by weight, preferably 0.1 to 0.8 % by weight, in rela tion to the total weight of the preparation.

In a further advantageous embodiment, additionally one or more sunscreen filters are con tained in the hair shaping preparation according to the invention. By using UV filters in the inventive preparation the UV filters come into contact with the hair and may be deposited on the hair, where the UV filters absorb UV rays. This is how the damaging effect of UV rays for the hair itself, but also for hair colors, as used in the permanent, semi-permanent and/or tem porary hair dyeing compositions, may be reduced.

In the context of the present invention it is advantageous, if the UV filters are sulfonated and water-soluble, examples are:

• Phenylene-1 ,4-bis (2-benzimidazyl) -3,3'-5,5'-tetrasulfonic acid and its salts, especially the corresponding sodium, potassium or triethanolammonium salts, especially the phe- nylene-1 ,4 bis (2-benzimidazyl) -3,3'-5,5'-tetrasulfonic acid bis-sodium salt having the INCI name bisimidazylate (CAS No .: 180898-37-7), which is available, for example, under the trade name Neo Heliopan AP is available from Haarmann & Reimer;

• Salts of 2-phenylbenzimidazole-5-sulfonic acid, such as its sodium, potassium or its tri ethanolammonium salt, and the sulfonic acid itself with the INCI name phenylbenzimid- azole sulfonic acid (CAS No. 27503-81 -7), which, for example sold under the trade name Eusolex 232 by Merck or under Neo Heliopan Hydro by Haarmann & Reimer;

• 1 ,4-di (2-oxo-10-sulfo-3-bomylidenemethyl) benzene (also: 3,3 '- (1 ,4-phenylenedi- methylene) bis- (7,7-dimethyl-2-) oxo-bicyclo [2.2.1 ] hept-1 -yl methane sulfonic acid) and its salts (especially the corresponding 10-sulfato compounds, in particular the cor responding sodium, potassium or triethanolammonium salt), which is also known as benzene 1 ,4-di (2-oxo-3-bornylidenemethyl-10-sulfonic acid) Benzene-1 ,4-di (2-oxo-3- boronylidenemethyl-10-sulfonic acid) having the INCI name Terephtalidene Dicampher Sulfonic acid (CAS No .: 90457-82-2) and is available, for example, under the trade name Mexoryl SX from Chimex;

• sulfonic acid derivatives of 3-Benzylidencamphers, such as. B. 4- (2-oxo-3-bornyli- denme-methyl) benzenesulfonic acid, 2-methyl-5- (2-oxo-3-bomylidenemethyl) sulfonic acid and salts thereof.

Certain UV filters, which are readily soluble in organic solvents may also be contained in the preparation according to the present invention. For example, ethylhexyl methoxycinnamate (octinoxate), being available under the trade name Escalol 557 from Ashland Specialty Ingre dients, is particularly suitable.

5-benzoyl-4-hydroxy-2-methoxybenzenesulfonic acid (benzophenone-4), which may be ob tained, for example, under the trade name Uvinul MS 40 from BASF, is an example of a par ticularly suitable UV filter.

In the preparation of the present invention the UV filter(s) i s/are contained in a total amount of 0.05 to 2% by weight, preferably 0.1 to 1.0% by weight, in relation to the total weight of the preparation.

In a further advantageous embodiment, one or more antioxidants are additionally contained in the hair shaping preparation according to the invention. Antioxidants are molecules that prevent other molecules from being oxidized. Oxidation reactions can cause free radicals, which in turn damage or destroy other molecules. For example, the free radicals can be ren dered harmless by antioxidants. The antioxidants may comprise various molecules of natural or synthetic origin. Among the synthetic molecules, compounds such as butylhydroanisole (BHA), butylhydroxytoluene (BHT) and pentaerythrityl tetra-di-t-butyl-hydroxyhydrocinnamate may be mentioned, butylhydroxytoluene being preferred according to the invention. g-Oryzanol, being a suitable example of an antioxidant of natural origin, may be contained in the preparation according to the present invention. g-Oryzanoi is an ester of ferulic acid and phytosterols.

Advantageously, the at least one antioxidant may be contained in a total amount of 0.01 to 1 .0% by weight, preferably of 0.02 to 0.7% by weight, in relation to the total weight of hair shaping preparation and in relation to the active content of the respective antioxidant (s).

In further advantageous embodiments, one or more perfume raw materials, one or more components providing care, preferably chosen from the various groups of components providing care, namely lanolin alcohol, substances of the vitamins of the B group and/or the vitamin B complex, silicone compounds, polar oils and/or humectants, one or more UV filters and/or one or more antioxidants are contained in the hair shaping preparation of the present invention. The preparation for shaping hair is contained in an aerosol packaging device. This aerosol packaging device is a compressed gas container having a can and a dispenser. The aerosol packaging device is under pressure by the propellant.

The dispenser comprises a valve having a dip tube (6), a stem with a tapered bore (7) and body with one or more bore(s), and furthermore, the dispenser has an actuator, which is shown in part form in Fig. 2.

According to the invention, the can may essentially be a cylindrical vessel made of metal (aluminum, tinplate, content <1000 ml). For selecting the suitable can compression and frac ture strength, corrosion resistance, easy filling, etc., but also aesthetic considerations, handi ness, printability, etc. are important. The maximum permissible operating pressure of metal spray cans is 12 bar at 50°C and the maximum filling volume at this temperature is approx. 90% of the total volume.

According to the present invention it is advantageous, if the cans are made of tinplate or alu minum. In case the cans are made of aluminum, a protective lacquer, preferably a polyamide protective layer, is required, which is applied to the inner surface.

Depending on the purpose and the physical nature of the content the internal structure of the cans and the valve design may vary, for instance being a one-, two- or three-phase system. For suitable embodiments, reference is made to the "Aerosol Technology Handbook of Aero sol Packaging" (Wolfgang Tauscher, Melcher Verlag GmbH Heidelberg / Munich, 1996).

Valves may or may not have a dip tube. The elements, which form a valve may consist of the following materials:

CUD: tinplate: bright, gold or clear lacquered, foil-laminated (PE, PP or PET)

Aluminum: bright, silver or gold lacquered, different lacquer variants, Stoner-Mudge-version.

Gasket: natural or synthetic elastomers or thermoplastic inner and outer seals (sleeve-gas kets, foil-laminated by PE or PP), for instance made from Perbunan, Buna, neoprene, butyl, CLB, LDPE, Viton, EPDM, chlorobutyl, bromobutyl and/or various other compounds.

Stem: polyamide (PA), polyoxymethylene (POM), brass and various special materials, standard bores (for example 0.25 to 0.70 mm or 2 x 0.45 to 2 x 1.00 mm),

different shaft diameters. Spring: metal, more preferably V2A, stainless steel; plastic and as well elastomer.

Body: standard and impact

VPH holes, RPT holes or slotted for overhead applications

Materials: e.g. polyacetal, PA, PE, POM and the like.

Dip tube: plastic (polymer resin), e.g. PE, PP, PA or polycarbonate.

An example of an advantageous valve according to the invention (FIG. 1 ), an actuator ad vantageous according to the invention (FIG. 2) and a nozzle (FIG. 3) which is advantageous according to the invention are shown in the respective figures. The reference numerals in the respective figures have the following meaning:

1 = stem gasket

2 = cup gasket

3 = cup

4 = gas phase bore

5 = body

6 = dip tube

7 = tapered bore

8 = stem

9 = nozzle bore

10 = front plate

1 1 = spring

12 a = central bore

12 = nozzle tap

13 = nozzle channel

14 = nozzle channel contact surface

15 = nozzle.

An example of an inventively advantageous valve is shown in part in Fig. 1. The valve is characterized by a cup (3), a stem gasket (1 ), a cup gasket (2), a spring (1 1 ) and a body (5), having a gas phase bore (4) with an inner diameter of 0,4 to 0.8 mm, preferably 0.4 to 0.45 mm. The valve stem (8) has a central bore (12a) with an inner diameter of 1 x 0.5 to 1 x 0.7 mmm. Furthermore, the valve stem has a tapered bore (RTP) with an inner diameter of 0.25 to 0.7 mm, preferably 0.32 to 0.5 mmm, more preferably 0.4 to 0.5 mm. Through the gas phase bore, additional propellant from the propellant phase in the container can enter the interior of the body and come into contact with the mixture of the preparation for shaping hair and propellant already being in the housing. By this way, the portion of pro pellant fed to the preparation for shaping hair gets larger, which in turn influences the droplet size. Droplets with a smaller mean diameter are formed, when released from the exit of the spray nozzle.

An actuator, which is in accordance with the invention, is shown in part in fig. 2. The actuator has a nozzle (15), which has nozzle channels (13) arranged in a characteristic way. The ar rangement of the nozzle channels (shown in fig. 3) ensures that the mixture of preparation for shaping hair and the propellant is swirled. This again affects the droplet size; the spray jet being released from the nozzle contains droplets with a smaller mean droplet diameter.

According to the invention, suitable actuators and suitable valves may be purchased from the company Aptar, especially suitable is a combination of the valve Ariane M and the actuator 3813.

For products in spray form, in particular aerosol products, the spray characteristic is of rele vance. An important feature is the droplet size. For hair spray products, droplet size distribu tions with a small mean diameter are preferred, because the solvent of the droplets must evaporate quickly to achieve short drying times. In relation to the present invention, if the dry ing time is too long, the hair will get wet and sticky. Small mean droplet diameters, being as sociated with short drying times of the solvent, are even more important for hair styling and shaping preparation in spray form, which contain no or only very small amounts of ethanol, but instead a large amount of water. If the drying time of such a preparation is too long, the feeling, that the hair is wet gets more pronounced and the stickiness and/or sticking of the hair increases.

Due to the choice of the valve and the nozzle, both according to the present invention, a droplet size distribution is achieved, having a sufficient amount of small droplets, so that the preparation for shaping hair is finely distributed. The solvent water is just as long present as to get the hair properly shaped before the solvent has largely evaporated.

It is advantageous, if the a spray rate is 0.25 to 0.55 g/s, wherein the spray rate refers to the amount of a preparation emerging from the nozzle opening of an aerosol packaging device per time unit. For example the spray rate may be determined according to the ASTM D 3069-94 standard (determination of the spray power of spraying cans). In order to evaluate the droplet size and distribution, a spray jet produced by a product ac cording to the invention consisting of the preparation for shaping hair and the aerosol pack aging device according to claim 1 can be examined with the Spraytec device from Malvern Instruments. In the meaning of the present invention, the terms droplets and particles are meaning the same subject. The particle distribution of a typical spray pattern obtained by a product according to the present invention is shown in fig. 4. It becomes obvious that a Dv(50)-value of 39.35 pm is achieved. The Dv(50)-value indicates the mean particle size by volume; i.e. 50% of the particles are smaller than the specified value.

In order for a preparation to be suitable for shaping hair Dv(50)-values should be in the range of 30 to 100 pm, in particular Dv(50)-values of 35 to 75 pm.

Examples:

The following examples are intended to illustrate the invention without limiting it. The amounts refer to the respective active content. The amounts are given in % by weight.

Summary of INCI names and raw materials: