DE19853215A1 - Hair treatment products - Google Patents

Description

FIELD OF THE INVENTION

The invention relates to hair treatment agents, in particular special hair styling agent, the precursors of natural hair Ceramides included, and the use of the means to climb tion of physical properties of the hair fiber, in particular special shine smoothness, manageability, softness and full Continuity of the cuticle.

BACKGROUND OF THE INVENTION

Lipids are important components of the hair structure, being for the cuticular or corticular Cell-cell liability are responsible.

The lipids are on the surface of the fiber Surface membrane bound and in the cell membrane complex before and it is believed that it is to shine, smoothness, Manageability, softness, protection, lubricity and contribute to the completeness of the cuticle of the hair fiber.

Lipids go down due to physical and fiber chemical damage, including washing, rough Hairdressing treatment and weather influence is caused, ver loren. This in turn reduces the natural ability of the Resist fiber structure, mechanical damage, and increases the potential for further damage to the hair, the cause is that it is dull, lifeless and brittle and eventually breakage and formation of split hair ends.

Ceramides are believed to be particularly important Represent components in the hair's lipid profile, and them  have already been proposed for use in hair treatment agents beat.

EP-A-278 505 (Estee Lauder) describes a hair protective agents, such as a shampoo or a conditioning agent tel, which contains a ceramide and a cholesterol derivative.

EP-A-739 625 (L'Oreal) describes cleaning and Treatment of hair an agent, the anionic surfactant, am contains photic surfactant, cationic polymer and ceramide.

JP-A-63/243 016 (Kanebo) lists ceramide-containing ones oily hair tonic and scalp treatment formulations.

WO-A1-97 / 15274 (L'Oreal) describes cosmetic agents containing hair fixative polymer and ceramide. It will communicated that the agents should protect the hair against breakage len, a well-known problem that is encountered when having hair fixing polymer is styled due to the unraveling and styling polymer-coated hair fibers again force required by brushing / combing.

Exogenous application of free ceramids via hair hand Solvent, as described above, has some detections split up. First, there are costs for the extraction of the Materials from natural sources or through chemical syn thesis. Then ceramides as a class of molecules are highly hydrophobic and have an occlusive effect and are therefore difficult to handle formulation products. Furthermore, exogenous trains introduced ceramides as opposed to natural ceramides that extractable from the fiber only by alkaline hydrolysis are not becoming one and loosely bound to the hair fiber.

We have now found cultured hair follicles Natural hair ceramides can synthesize when using certain specific amino acid nutrients that the Represent precursors for ceramide biosynthesis become.

Amino acids are known for the nutrition of the Hair root and hair growth of importance in humans. GB-A-1 401 089 describes hair treatment compositions which are natural contain amino acids or protein hydrolyzates. Especially preferred are glycine, glutamic acid, aspartic acid, lysine, Serine and alanine, since you can find these amino acids in nature  Form of polypeptides in collagen and keratin, the as structural components of skin and hair in humans occur, combined finds. A shampoo is used wrote, the protein hydrolyzate from the complete Hy drolysis of collagen was added.

EP-A-0 186 025 discloses cosmetic preparations for the care of skin and hair with a hydrolyzate from almond protein. Almond protein is acidic due to a high percentage and basic amino acids and contains 40-50 Weight percent glutamic acid, aspartic acid and arginine.

WO-A-97/01322 also describes hair care components at least one "conditioning agent" selected from egg one or more specific amino acids (including Se rin, tyrosine and lysine). It is said that the "Kondi tioning agent "penetrates into the treated hair and the Hair structure stabilizes, especially if the hair is damaged was damaged.

Numerous publications describe the use formation of a number of amino acids, often in a "cocktail" form, in lotions or in tonic form for topical use for the Treatment of baldness and other skin disorders, Scalp and hair. Examples of such revelations are JP 59/007111 - the publication relates to a hair cosmetic with dandruff-preventing properties, the vitamin E Ace tat and contains methionine, CA-A-888 689 - this publication describes preparations for hair and scalp to normal the excretions of the scalp and to promote the Hair growth, which includes cysteine and methionine in egg basis, the bergamot oil and nonionic emulsifier contains, may contain, and WO-A-92/00720, these Document describes an agent that L-leucine, L-isoleucine and contains L-valine, which is reported to be the Growth and regeneration of hair and fingernails sti mulated.

The prior art discussed above speaks not the biosynthesis of natural hair ceramides in hair follies cry out.  

SUMMARY OF THE INVENTION

In a first aspect, the present invention provides a hair styling formulation for delivering precursors of natural hair ceramides to the hair follicle, comprising:

• (i) a ceramide precursor, namely an amino acid, selected from serine and analogs and / or derivatives thereof, the precursor in amounts of 0.01 to 20 percent by weight, based on the total weight of the agent, and 20 to 100 Weight percent, based on the total weight of the Amino acids present
• (ii) 0.5% to 10% of a hair styling resin;
• (iii) a cosmetically acceptable solvent or a cosmetically acceptable carrier;
• (iv) 0% to 50% of an aerosol propellant; and
• (v) at least one auxiliary lipid component selected from the group consisting of phospholipids, free fatty acid and mixtures thereof.

In a second aspect, the invention provides ver use of an amino acid selected from serine and analogs and / or derivatives thereof, as a ceramide precursor in a hair treatment agent, preferably a hair styling agent, for Increase at least one of the properties below the hair surface: gloss, smoothness, manageability, softness and completeness of the cuticle, ready. Preferably the amino acid in connection with at least one auxiliary pid component as defined above.

PRECISE DESCRIPTION Amino acid ceramide precursor

L-serine is the most preferred amino acid (i) for agents according to the invention. Without being tied to a theory To be wanted, this is believed to be the most direct Precursor for ceramide synthesis in the hair follicle provides, forming the backbone of the ceramide molecule. Some biochemical pathways have been found in the literature proposed, but not all of them have yet been elucidated been.  

Simple derivatives of amino acid (i) can be used like salts and hydrosalts. It is also possible to use other derivatives such as acyl, ester and peptide derivatives. These can also be used as salts or hydrosalts be used.

Examples are N-alkanoyl derivatives, in which the Alka noyl residue an alkyl chain length of 3 to 20 carbon atoms Men, preferably has 4 to 10 carbon atoms for example N-butanoyl, N-hexanoyl and N-octanoyl derivatives, N-alkyl or COO alkyl derivatives in which the alkyl group is ge is wheel-chain and has 1 to 20 carbon atoms, preferably 1 has up to 4 carbon atoms, for example methyl, ethyl and n-propyl, and peptide derivatives in which the peptide residue 2 comprises up to 8 amino acid residues or sub is constituted.

Mixtures of amino acids can be used for example those obtained from protein hydrolyzate that can. However, such a mixture must be carefully considered be selected to ensure that 20 to 100 Weight percent, based on the total weight of the amino acid, in the agent obtained from one or a mixture the specific amino acids (i).

Preferably there are 90 to 100 percent by weight preferred to the total weight of the agent obtained lying amino acids, from one or a mixture of the spe specific amino acids (i).

The total amount of amino acid (i) in the Invention modern means is in the range of 0.01% to 20% by weight of the agent, preferably 0.02% to 5%, most preferred 0.05% to 2%.

Hair styling resin

Those used in the agents according to the invention Hair styling resins should be able to form a film and that Hair of the user after the volatile components have evaporated can keep out of the hair styling.

Hair styling resins are well-known commercial items and numerous of these resinous polymers that contain residues  which are cationic, anionic, amphoteric or Giving non-ionic properties are customary in the trade. To provide optimal sprayability in form Spray-type formulations such as hair sprays, pump sprays and mousses ses, the polymers used are generally in one number average molecular weight range from 5000 to 100,000, with 10,000 to 50,000 being more preferred. For use in the pump spray hair styling resins are generally in number average molecular weight range 10,000 to 50,000 used.

The amount of resin can range from 0.5 to 10%, preferably 1.5 to 6 percent by weight of the hair styling agent lie gene.

Examples of anionic hair styling resins are the copolymers of vinyl acetate and crotonic acid, terpolymers of vinyl acetate, Crotonic acid and vinyl ester of an α-branched, saturated, aliphatic monocarboxylic acid such as vinyl neodecanoate; Copolymers of methyl vinyl ether and maleic anhydride (Molar ratio about 1: 1), such copolymers with egg saturated alcohol containing 1 to 4 carbon atoms holds, like ethanol or butanol, 50% esterified; and Acrylic copolymers, terpolymers etc., the acrylic acid or meth acrylic acid as the portion containing the anionic residue ent hold, and esters of acrylic or methacrylic acid with one or several saturated alcohols with 1 to 22 carbon atoms such as methyl methacrylate, ethyl acrylate, Methyl methacrylate, n-butyl acrylate, acrylic acid re-t-butyl ester, methacrylic acid t-butyl ester, methacrylic acid re-n-butyl ester, n-hexyl acrylic acid, n-octyl acrylic acid esters, lauryl methacrylate and behenyl acrylate, Glycols with 1 to 6 carbon atoms, such as hydroxypropyl meth acrylate and hydroxyethyl acrylate, styrene, vinyl caprolactam, Vinyl acetate, acrylamide, alkyl acrylamides and methacrylamides with 1 to 8 carbon atoms in the alkyl group, such as tert-butylacrylamide and n-octylacrylamide and other compatible ones unsaturated monomers. A specific example is that emulsion-polymerized terpolymer of methacrylic acid, n-butyl acrylate and ethyl acrylate (e.g.  in a weight ratio of 31: 42: 27). Another spe The target example is Ultrahold® 8 (name of the CTFA-Cosmetic, Toiletries and Fragrance Association for Acrylate / acrylamide copolymer).

Amphoteric polymers derived from monomers cationic groups such as methacrylic acid t-butylaminoethyl esters, and carboxyl groups derived from monomers, such as Acrylic acid or methacrylic acid, may contain can also be used in the present invention. A is a specific example of an amphoteric hair styling resin Amphomer®, available from National Starch and Chemical Cor poration.

Examples of non-ionic hair styling resins are Ho copolymers of N-vinylpyrrolidone, homopolymers of N-vinyl formamide and copolymers of N-vinylpyrrolidone with Kompägli Chen nonionic monomers such as vinyl acetate and terpoly mers of ethyl acrylate, butyl methacrylate and Methyl methacrylate. Nonionic polymers that N-vinylpyrrolidone in various weight average molecules Lar weights included, are commercially available from ISP Corporation Lich how homopolymers of N-vinylpyrrolidone with a mean ler molecular weight of about 630,000 sold by ISP (formerly GAF Corporation) under the trade name PVP K-90, and those with an average molecular weight of about 1,000,000, sold under the trademark PVP K-120.

Examples of cationic hair styling resins are copo polymers of acrylate monomers with amino functionality, such as Lower alkylamino alkyl esters, or methacrylate monomers re, such as dimethylaminoethyl methacrylate, with compatible Chen monomers, such as N-vinyl pyrrolidone, vinyl caprolactam, or Alkyl methacrylates, such as methyl methacrylate and Methyl methacrylate, and alkyl acrylate, such as Acrylic acid ethyl ester and acrylic acid n-butyl ester. Cationic Polymers containing N-vinyl pyrrolidone are commercially available from ISP Corporation, such as those under the trademarks Copolymer 845 and Copolymer 937 are sold (copolymers of N-vinyl pyrrolidone and methacrylic acid t-butylaminoethyl esters with an average molecular weight of about 1,000,000) and  Gafquat® 755 and 755N (quaternary ammonium polymers, herge represents by reaction of dimethyl sulfate and a copolymer of N-vinylpyrrolidone and methacrylic acid dimethylaminoethyl esters with an average molecular weight of about 1,000,000).

Certain of these resins may require it be to neutralize some acidic groups to make them soluble speed / to promote the dispersibility. Examples of more suitable Neutralizers include 2-amino-2-methyl-1,3-propane diol (AMPD); 2-amino-2-ethyl-1,3-propanediol (AEPD); 2-Ami no-2-methyl-1-propanol (AMP); 2-amino-1-butanol (AB); Monoetha nolamine (MEA); Diethanolamine (DEA); Triethanolamine (TEA); Mon noisopropanolamine (MIPA); Diisopropanolamine (DIPA); Triiso propanolamine (TIPA); Dimethylstearamine (DMS). If that Hair styling resin containing carboxyl groups can neutralize tion a long chain amine such as lauramidopropyldimethylamine, can be used, such as in US-A-4,874,604 wrote. The amounts of neutralizing agents are in the Range from about 0.001 to about 10 weight percent of the co tels.

Solvent or carrier

The agents according to the invention comprise a cosmetic compatible solvent or a cosmetically compatible Chen carrier, which is preferably in an amount of 0.1% to 99 percent by weight of the agent is present. The term kosme table compatible solvent or cosmetically compatible The carrier is used herein to be a vehicle write that on the desired surface, namely that Hair, components of the agent to be applied or wearing.

Water is in the agents according to the invention useful solvent or carrier, ent neither alone nor mixed with other solvents or carriers. The solvent or carrier can be found in Ab depending on the intended product form different vis have degrees of viscosity and can be aqueous or non-aqueous include serige carriers, which may be a ge  is added to an aqueous or to get non-aqueous gel.

In formulations in which the solvent or carrier comprises an aqueous gel, suitable gelling agents include:
Carboxyvinyl polymers such as those available from BF Goodrich Chemical Company under the tradename CARBOPOL;
Sodium magnesium silicate (available under the trade name LAPONITE from Laporte Industries);
gel-forming gums such as xanthan gum, guar gum, carrageenan gum, carob tree gum and cellulose gum.

Other suitable carriers are volatile silicones, such as Cyclomethicone, and short chain alcohols such as ethanol.

Product form

Hair styling agents according to the invention can be used as a spray be formulated in aerosol or non-aerosol form and can be made from containers containing aero-propellant represent sol containers, or alternatively from pump spray containers tern, which are operated without any propellant become. Alternatively, styling gel or styling moussepro duct shapes can be used.

When the hair styling agent is under pressure aerosol container must be dispensed, an aerosol propellant medium to be included in the medium. That means is for the ejection of the other materials from the container and responsible for the formation of the hairspray or mousse character Lich.

The propellant can be any liquefiable gas that is commonly used for aerosol containers. The density of the blowing agent or a mixture is preferably some of them less than that of the hair styling concentrate, so that no pure propellant is released from the container. Examples of suitable blowing agents include dimethyl ether, Propane, n-butane and isobutane, individually or in admixture used one. Other examples of blowing agents are Nitrogen, carbon dioxide and compressed air.  

The amount of propellant is determined by normal factors, which are known in the field of aerosol technology. For hair styling agents, the amount of blowing agent is generally about 3 to about 50%, preferably about 5 to about 45%, optimally about 35 to 45% of the total agent.

Auxiliary lipid component

Agents according to the invention close as a stock some also selected at least one auxiliary lipid component from phospholipids, free fatty acids and mixtures thereof, on. In this way, the hair fiber can be locally exogenous Lipid, which comes from the agent, can be supplemented, thus the natural effect of the ceramide precursor in the agent, which, as we noted, via biosynthetic pathways in the Hair follicle is built up to natural hair ceramides the root is added.

Particularly preferred auxiliary lipid components include:
natural phospholipids such as lecithin;
biomimetic phospholipids such as PHOSPHOLIPID EFA (linoleic amidopropylphosphatidyl PG dimonium chloride) and PHOSPHOLIPID PTC (cocamidopropylphosphatidyl PG dimonium chloride), both from Mona Industries, Inc .;
Mixtures of phospholipids, such as CERAMAX material, sold by Quest.

Suitable examples of free fatty acids include branched chain fatty acids such as 18-methyleicosanoic acid and other homologues of this series, straight chain fatty acids, such as Stearic, myristic and palmitic acids, and unsaturated Fatty acids such as oleic acid, linoleic acid, linolenic acid and arachi donic acid, a. Particularly preferred are those fatty acids that in natural form as essential, integral components the hair fiber occur and therefore due to fiber damage and replenishment may be needed. The fatty acids can be used individually, as mixtures or in the form of Mixtures derived from extracts from, for example, lano lin, can be added. Most preferred are straight chain fatty acids stearic acid, myristic acid, oleic acid and  Palmitic acid. These were found to be Haarfa give it good protection against damage. A very before preferred branched chain fatty acid is 18-methyleicosanoic acid, those in maintaining fiber condition and completeness cuticle is involved.

Mixtures of any of the auxiliary materials mentioned above pid components can also be used. Such Components are generally sold individually in an amount of 0.001% to 10%, preferably 0.005% to 5%, by weight of the agent used.

Possibly existing components

Agents according to the invention can normally be further Contain ingredients used in hair styling formulations These other components can be emulsifiers, such as ionic or nonionic surfactants, silicones, viscosity mo differentiating agents, preservatives, colorants, che latifying agents such as EDTA, antioxidants, fragrances, include antimicrobials and sunscreens. Each of these components lies in one to effect its Before effective amount. In general, these are ge any ingredients present individually in an amount up to about 5 percent by weight of the total agent used.

The agents according to the invention preferably contain also auxiliaries that are suitable for hair care. In general, such components are individually in one Amount up to 2%, preferably up to 1% by weight of the entire means used.

Suitable hair care aids include:

• (i) natural hair root nutrients such as amino acids and sugar. Examples of suitable amino acids include Argi nin, cysteine, glutamine, glutamic acid, isoleucine, leucine, Me thionine, serine and valine and / or precursors and derivatives there from a. The amino acids can be used individually, in mixtures or in Form of peptides, for example di- and tripeptides will give. The amino acids can also be in the form of a pro teinhydrolysats, such as keratin or collagen hydrolyzate will give. Suitable sugars are glucose, dextrose and  Fructose. These can be used individually or in the form of example wise fruit extracts are added. One especially before preferred combination of natural hair root nutrients for Use in the agents according to the invention is isoleucine and Glucose. A particularly preferred amino acid nutrient is Arginine.
• (ii) The hair fiber benefit agent. Examples are:
  Ceramides to keep the fiber moist and to keep the cuticle complete. Ceramides are available by extraction from natural sources or as synthetic ceramides and pseudoceramides. A preferred cera mid is Ceramid II from Quest. Mixtures of ceramides may also be suitable, such as Ceramid LS from Laboratoires Se robiologiques.

Use form

The agents according to the invention are mainly for topical application to the hair and / or scalp of a People to increase the surface properties of the Hair fiber, such as smoothness, softness, manageability, complete the cuticle and especially gloss.

Accordingly, the present invention also provides Use of an amino acid selected from serine and analo gene and / or derivatives thereof as a ceramide precursor in one Hair treatment agent, preferably a hair styling agent, ready to increase at least one of the below Surface properties of the hair: gloss, smoothness, handling Availability, softness and completeness of the cuticle.

Preferably the ceramide precursor is in the agent in connection with one or more as above auxiliary lipid components used.

The invention will now be described with reference to the following non-limiting examples are explained.  

EXAMPLE 1 Illustration of the in vitro incorporation of serine in cera mide through human hair follicles

Human hair follicles were removed according to the method of Philpott et al. (1990, J. Cell. Sci. 97: 463-470) isolated and grown in the presence of radiolabeled serine. The follicles were incubated for 2 days at 37 ° C, 5% CO ₂ in air and <95% humidity.

At the end of the entire incubation period, the Lipid portion of the follicles extracted and analyzed.

The results clearly showed that the majority of the labeled species were ceramides and monoglycerides. To determine the amount of the radiolabeling incorporated in ceramide, the monoglycerides were hydrolyzed to fatty acids and the ceramides were isolated using mini columns with bound NH ₂ functionalities.

The bound lipid from the hair was also ex trailed, separated and analyzed. The ceramides from the Hair fibers were also labeled with radiolabeled serine.  

Examples 2 and 3

The following examples illustrate hairspray formulations according to the invention

Examples 4 and 5

The following examples illustrate hair styling gel formulations according to the invention

Examples 6 and 7

The following examples illustrate hair styling spray gel formulations according to the invention

Examples 8 and 9

The following examples illustrate hair styling mousse formulations according to the invention

Claims (4)

1. A hair styling formulation for delivering precursors of natural hair ceramides to the hair follicle, comprising:

• (i) a ceramide precursor, namely an amino acid selected from serine and analogs and / or derivatives thereof, the precursor in amounts of 0.01 to 20 percent by weight, based on the total weight of the agent, and 20 to 100 percent by weight, based on the Total weight of the amino acids present in the agent;
• (ii) 0.5% to 10% of a hair styling resin;
• (iii) a cosmetically acceptable solvent or carrier;
• (iv) 0% to 50% of an aerosol propellant; and
• (v) at least one auxiliary lipid component selected from phospholipids, free fatty acids and mixtures thereof.

2. Composition according to claim 1, wherein the auxiliary lipid component nente is selected from stearic acid, myristic acid, oil acid, palmitic acid, 18-methyleicosanoic acid and mixtures there from. 3. Use of an amino acid selected from serine and analogs and / or derivatives thereof as a ceramide precursor in a hair treatment agent, preferably a hair styling medium, to increase at least one of the following eggs Properties of the hair surface: gloss, smoothness, manageable ity, softness and completeness of the cuticle. 4. Use according to claim 3, wherein the hair hand at least one auxiliary lipid component according to claim 1.