HAIR TREATMENT COMPOSITIONS

Abstract: A hair treatment comprising in dissolved form three essential components including at least one decomposition derivative of keratin, a cationic polymer, and at least one compound selected from organic and inorganic salts and urea having a solubility in water of over 1 g/100 g of water at 25°C. The hair treatment within the scope of the invention covers various types of treatments such as hair setting lotion, hair styling lotion, cutting lotion, brushing lotion and the like.

Description: BACKGROUND OF THE INVENTION Field of the Invention: This invention relates to the cosmetics of hair and, more particularly, to hair treatment compositions which can impart so-called steadiness and firmness to the hair and exhibit excellent touch when they are applied to the hair. Description of the Prior Art: The hair is one of the most important parts of human body, on which a diversity of beauty treatments are applied. Among the beauty treatments, permanent wave treatment is well known and is most effective in setting the hair properly. However, this treatment has the drawback that since oxidation and reduction reactions are utilized to set the hair, the hair is considerably damaged during the treatment. In recent years, there is a demand of the development of hair treatments which can effectively set the hair without resorting to any permanent wave art. Various methods have been proposed including, for example, a method of reinforcing the hair using combinations of collagen hydrolysates, quarternary ammonium salts, cationic polymers and/or harmless divalent metals (Japanese Laid-open Application No. 55-54551 and US―A―3 958 581), a method in which water-soluble salts of chitosan are used as fill-forming resin to improve the retentivity and stability of dressed hair (Japanese Laid-Open Application No. 52-156938), and a method wherein anionic polymers and cationic surface active agents and silicone derivatives are used in combination to impart high set retentivity and curl durability to hair (Japanese Laid-open Application No. 55-108811). However, although all of these methods are effective in imparting steadiness and firmness to the hair at the time of setting the hair, they have the disadvantage that the hair treated becomes stiff, considerably spoiling the inherent touch of the hair. Further, there has been proposed a method using oils which are one starting material of cosmetics but such a method is not widely applied because of the stickiness of oil. SUMMARY OF THE INVENTION It is an object of the invention to provide hair treatment compositions which can impart smoothness and softness to the hair and exhibit excellent touch on application without showing undesirable stickiness. It is another object of the invention to provide hair treatment compositions which exhibit good affinity for hair as will not be experienced in prior-art counterparts. The above objects can be achieved, according to the invention, by hair treatment compositions which comprise the following three ingredients (A), (B) and (C): (A) 0.05 to 10 wt% of at least one derivative of keratin as defined in claim 1; (B) 0.05 to 10 wt% of a cationic polymer; and (C) 0.01 to 10 wt% of urea or at least one compound having a solubility in water greater than 1 g/100 g of water at 25°C selected from inorganic ammonium, and alkali metal salts and alkali metal salts of organic acids. The derivatives of keratin of ingredient (A) used in the present invention can be prepared by oxidizing keratin materials and optionally converting them into base salts, by reducing keratin materials, chemically modifying the mercapto groups of the reduction product, and optionally converting the modified product into base salts, and by hydrolyzing keratin materials. The starting keratin materials are, for example, animal hair, human hair, feathers, nails, horns, hooves and scales, among which wool, human hair and feathers are most preferable. These keratin materials can be subjected to the oxidation or reduction reaction directly but may be cut or reduced into pieces or subjected to pretreatments such as washing and defatting, if necessary. The derivatives of keratin material can be prepared by any of the following methods. (1) Oxidation Reaction The oxidation of keratin material is effected by any of methods known per se (N. H. Leon; Textile Progress. Vol. 7, page 1 (1975)). Oxidizing agents are preferably organic or inorganic agents which are of the type that act electrophilically on the disulfide bonds (S―S bonds) in the keratin structure. Examples of the oxidizing agents include organic peracids, inorganic peroxo acids or their salts, permanganic acid or its salts, chromic acid or related compounds, halogens, peroxides and oxyacids or their salts, among which organic peracids such as peracetic acid, performic acid and perbenzoic acid are most preferred. The oxidation reaction is carried out in a liquid medium using oxidizing agents in excess with respect to the disulfide bonds in keratin material, ordinarily in amounts over two equivalents or more, preferably 4 to 10 equivalents, of the sulfide bonds. The reaction may be conducted under acidic or alkaline conditions and is preferably carried out under acidic and particularly weakly acidic conditions. The conditions such as reaction temperature and pressure depend on the types of the oxidizing agent and keratin material used and are not critical. In general, room temperature is sufficient but, if necessary, heat may be applied. The pressure is a normal pressure but the reaction may be effected under reduced pressure or pressure. By this oxidation, the disulfide bonds of keratin material are converted into sulfo groups (―SO₃H). (2) Reduction and Chemical Modification Reactions Reducing agents employed for reducing keratin materials are preferably organic or inorganic reducing agents of the type which are capable of cleaving the disulfide bond in the keratin structure into a mercapto group (―SH) and act nucleophilically on the disulfide bond. Examples of the reducing agent include organic reducing agents such as 2-mercaptoethanol, thioglycollic acid, benzyl mercaptan, 1,4-dithiothreitol and tributylphosphine, and inorganic reducing agents such as sodium hydrogen sulfite, sulfides such as sodium hydrogen sulfide, metallic hydrides such as lithium aluminium hydride. The amount of the reducing agent is usually in the range of 2 to 10 equivalents of the disulfide bonds in keratin material. The reaction system has generally a pH range of 2 to 12, preferably 6 to 11. Outside the range, the undesirable hydrolysis takes place at the same time. The room temperature is sufficient but heat may be applied to shorten the reaction time. The reaction time is ordinarily in the range of 2 to 3 hours or more. Since it is necessary that the mercapto groups produced by the reaction do not undergo substantial oxidation, the reduction operation should preferably be carried out in an atmosphere of inert gas to give good results. The mercapto groups of the product obtained by the reduction of keratin material is then chemically modified to yield a derivative thereof. The derivatives of the mercapto groups are: The chemical modification of mercapto group is feasible by any techniques known per se and can be effected according to procedures known, for example, from N.H. Leon; Textile Progress, Vol. 7 (1975), "Yuuki loo Kagobutsu (Organic Sulfur Compounds)" written by Shigeru Daikyo and published by Kagaku Dojin (1968), and "Kobunshi Jikken Koza" written by Masami Oku, Vol. 12, Kyoritsu Shuppan (1957). Typical methods are described in the following. 1 Method utilizing the nucleophilic substitution reaction of SH group K - SH + R - L → K - S - R + HL (in which K represents a residue of keratin material, R represents a chemically modifying group to be introduced, and L represents a leaving atom or group such as a halogen atom or an acid residue). Compounds reacting by this method include, for example, halogen compounds such as iodoacetic acid, bromoacetic acid and chloroacetic acid. 2 Method utilizing the nucleophilic addition reaction of SH group with a double bond existing between carbon atoms (in which at least one of R₁, R₂, R₃ and R₄ represents a group having a carboxyl group or sulfo group therein and the others independently represent an alkyl group of hydrogen atom, and K has the same meaning as defined above). Compounds reacting by this method include, for example, acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, vinyl carboxymethyl sulfone, vinylsulfonic acid para-styrenesulfonic acid and 2-acrylamido-2-methylpropansulfonic acid. 3 Method using the substitution reaction between the SH group and sulfite compounds (in which K has the same meaning as defined hereinabove). (3) Hydrolysis Reaction 1 Hydrolysis with Acids Mentioned as acid are, for example, inorganic acids such as hydrochloric acid, sulfuric acid phosphoric acid, nitric acid and hydrobromic acid, and organic acids such as acetic acid, formic acid and oxalic acid. These acids are generally employed at a concentration of 3 to 85% and it is desirable that the hydrolysis reaction is at a pH below 4. The reaction temperature is preferably in the range of 40 to 100°C though it may be raised up to 160°C under pressure. The reaction time is conveniently in the range of 2 to 24 hours. The reaction product may be used directly after neutralization with bases such as sodium hydroxide, sodium carbonate and ammonia. Alternatively, it may be used after subsequent purification such as by gel filtration and ion exchange resin. The products obtained by the hydrolysis with acid involves no changes other than hydrolysis at the polypeptide chains of keratin, so that better results are obtained than those of products obtained by hydrolysis with bases. 2 Hydrolysis with Bases As bases, there are used inorganic bases such as sodium hydroxide, potassium hydroxide, lithium hydroxide, barium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, sodium silicate and borax. These bases are conveniently used at a concentration of 1 to 20%. Larger amounts than as required are unfavorable because the resulting hydrolysate solution becomes brown or black in color. The reaction is preferably carried out at a temperature of room temperature to 100°C for a time of 30 minutes to 24 hours. Care should be taken not to use higher temperatures and longer reaction time than necessary. As the hydrolysis reaction with bases proceeds, the hydrolysate of keratin dissolves with the attendant advantage that the extent of the reaction can be visibly observed. The reaction is completed when the reaction mixture has become homogeneous. 3 Hydrolysis with Enzymes Examples of enzymes include acidic protenases such as pepsin protease A and protease B, and neutral protenases such as papain, promeline, thermolycin, trypsin, pronase and chymotrypsin. The pH during the hydrolysis should preferably be controlled in the range of 1 to 3 for the acidic protenases such as pepsin and in the range of 5 to 8 for the neutral protenases such as papain. It is convenient to suitably adjust the pH by the use of an ammonium acetate/ammonia buffer solution. The reaction temperature is favorably in the range of 30 to 45°C and the reaction time is ordinarily in the range of 3 to 24 hours. In the hydrolysis reaction with enzymes, the molecular weight of hydrolysate is greatly influenced by the amount of enzyme, the reaction temperature and the reaction time. In order to obtain a keratin hydrolysate with an intended molecular weight, it is necessary to check by gel filtration technique the distribution of molecular weight of hydrolysate in relation to variations in amount of enzyme, reaction temperature and reaction time whereby the optimum conditions are empirically determined. The hydrolysates obtained by enzyme hydrolysis show a narrower distribution of molecular weight than hydrolysates obtained by acid, or basic hydrolysis and contain reduced amounts of free amino acids, thus being more favorable for use as cosmetics. As many as possible disulfide bonds should preferably be contained in the hydrolysates. To this end, it is necessary to use keratin materials of high purity and to effect the hydrolysis reaction under mild conditions. The products obtained by these decomposition methods should preferably have an average molecular weight of 30,000 to 100,000 for the products obtained by the method (1) or (2) and an average molecular weight of 200 to 5,000 for the product obtained by the method (3). The product obtained by the method (3) is soluble in ordinary polar solvents such as water, ethanol, methanol, ethylene glycol, propylene glycol and glycol and can be formulated in a pre-shampoo treatment of the present invention as a derivative of keratin material. In this connection, however, the products obtained by the methods (1) and (2) are insoluble in polar solvents and should be formulated after conversion into corresponding base salts. Base salts include salts of alkali metals such as sodium and potassium, ammonium salts, and salts of organic bases such as ethanolamine, diethanolamine, triethanolamine, 2-amino-2-methylpropanol, 2-amino-2-mercapto-1,3-propanediol, triisopropanolamine, glycine, histidine and arginine. These salts can be prepared separately and then added to pre-shampoo treatment compositions. Alternatively, the oxidation product or reduction derivative of keratin material and bases may be added separately to a pre-shampoo treatment composition and the salts formed in situ. Examples of the bases include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate and organic bases such as ammonia, ethanolamine, diethanolamine, triethanolamine, 2-amino-2-methyl-1-propanol, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-ethyl-1, 3-propanediol, 2-amino-1-butanol, triisopropanolamine, diisopropanol-amine, monoisopropanolamine, lysine, arginine, histidine and hydroxylysine. These bases are preferably added in an amount of 0.1 to 8 equivalents of the carboxyl or sulfo groups in the decomposition product obtained by the method (1) or (2). Among these components of (A), the base salts of the oxidation product of keratin and the derivatives of the mercapto groups of the reduction products of keratin are most preferred. The amount of the component (A) is, as having defined hereinbefore, in the range of 0.05 to 10.0 wt% (hereinafter referred to simply as %), preferably 0.1 to 2.0%, of the pre-shampoo treatment composition. The component (B) of the present invention are polymers having an average molecular weight of 500 to 5,000,000 and having cationic groups in the main chain or in substituents thereof. Preferable examples are shown below. (1) Quarternarized derivatives of cellulose ethers Examples of these derivatives are those obtained by quarternarizing cellulose ethers such as hydroxyethyl cellulose, methyl cellulose, ethyl cellulose, hydroxypropyl cellulose and hydroxypropyl methyl cellulose, for example, with a cationizing agent such as glycidyltrimethylammonium chloride. Mentioned as a commercially available product is JR-400 (molecular weight 100,000 to 1,000,000; Union Carbide CO.). (2) Cyclic cationic group-containing polymers 1 Diallyl quarternary ammonium homopolymers of the recurring units of the formula (I) or (II) in which R₅ and R₆ are the same or different and represent hydrogen or an alkyl group having 1 to 18 carbon atoms, preferably 1 to 4 carbon atoms, R₇ and R₈ are the same or different and independently represent hydrogen, an alkyl group having 1 to 3 carbon atoms, or phenyl group, X⁻ represents an anion, i.e. a halogen ion such as chlorine or bromine, an anion of an inorganic acid such as sulfuric acid or nitric acid, an anion of an organic acid such as methylsulfuric acid, or a hydroxycarboxylic acid, and n is a value sufficient to give a molecular weight of 10,000 ∼ 1,000,000. 2 Polymers of recurring units of the formula (III) or (IV) (in which m₁ and m₂ are values sufficient to give a molecular weight of 10,000 to 1,000,000, and R₅, R₆, R₇ and R₈ have the same meanings as defined above, respectively). 3 Polymers of the formula (V) (in which R₉ and R₁₀ are the same or different and independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms, or a phenyl group and n and X⁻ have the same meanings as defined hereinbefore, respectively). Among these cyclic cationic group-containing polymers, preferable polymers are a homopolymer of dimethyldiallyl-ammonium chloride commercially sold as MERQUAT 100 (MERCK Inc.) and a copolymer of dimethyldiallylammonium chloride and acrylamide commercially available as MERQUAT 550 (MERCK Inc.). (3) Quarternarized derivatives of copolymers of N-vinylpyrrolidone/vinyl monomer Quarternarized derivatives of copolymers of N-vinylpyrrolidone/vinyl monomer of the formula (VI) (in which 1, p and q are values which are such that the monomer units in the respective brackets are, respectively, 20 to 99 mole%, 1 to 80 mole% and 0 to 50 mole%, y is 1 or 0, R₁₁ represents a hydrogen atom or methyl group, R₁₂ represents or (CH₂ (wherein K is a value of 2 to 18), R₁₃ represents an alkyl group having 1 to 4 carbon atoms and preferably ―CH₃, ―C₂H₅ or t-butyl group, R₁₄ represents Z represents chlorine, bromine, iodine, SO₄, HSO₄ or CH₃SO₃, and M represents a monomer unit of a copolymerizable vinyl monomer). This quarternarized copolymer can be prepared by copolymerizing N-vinylpyrrolidone, a dialkyl(lower)aminoalkyl (or hydroxyalyl)acrylate (or methacrylate) and other arbitary copolymerizable vinyl monomer. The proportions by mole% of the unit monomers are as follows: the vinylpyrrolidone unit is 20 to 99%, the dialkyl(lower)aminoalkyl(or hydroxyalkyl)acrylate(or methacrylate) unit is 1 to 80%, and the other copolymerizable vinyl monomer unit is in the range of 0 to 50%. The molecular weight of this terpolymer is generally in the range of 15,000 to 1,000,000, preferably 50,000 to 500,000. Mentioned as commercially available products are GAFQUAT® 734 (average molecular weight of about 100.000 GAF Co., Ltd.) and GAFQUAT® 755 (average molecular weight of about 1,000,000, GAF Co. Ltd.). The content of the component (B) in the air treatment composition is in the range of 0.05 to 10%, preferably 0.1 to 2%, as defined hereinbefore. The component (C) used in the present invention is urea or ammonium, and alkali metal salts at least one member selected from inorganic and alkali metal salts of organic acids having a solubility in water greater than 1 g/100g of water at 25°C (hereinafter referred to generically as water-soluble salt). The inorganic or organic salts should preferably have a solubility in water of 10 to 100 g/100 g of water at 25°C. Examples of these inorganic or organic salts include potassium phosphate, potassium hydrogen phosphate, potassium thiocyanate, sodium chloride, lithium chloride, ammonium bicarbonate, ammonium nitrate, sodium sulfate, sodium lactate, sodium benzoate and sodium citrate. Of these, preferable salts are sodium chloride, potassium thiocyanate, sodium sulfate, potassium hydrogen phosphate, sodium lactate, sodium benzoate, and sodium citrate. This component (C) is an essential one for achieving the purpose of the present invention and when this component is substituted with a known adjuvant such as, for example, ethanol, glycerine or propylene glycol, the above purpose cannot be attained. It is essential to incorporate a sufficient amount of the component (C) in the hair treatment composition to dissolve the anionic material or component (A) and the cationic material or component (B). Therefore, the amount of component (C) should be in the range of 0.01 to 10%, preferably 0.1 to 3%, as defined hereinbefore. The hair treatment composition according to the invention is prepared by mixing these three components by a usual method whereby various types of compositions such as hair setting lotions, hair styling lotions, cutting lotions, brushing lotions, hair sprays, permanent wave lotions, hair dyes, decolorants, shampoos, hair conditioners, and hair rinses can be obtained. As a matter of course, the hair treatment composition according to the invention may further include various arbitrary ingredients including, for example, surface active agents such as alkyl sulfates, fatty acid salts, polyoxyethylene alkylamidosulfates, α-olefinsulfates, alkyltrimethylammonium salts, alkyldimethylammonium salts. N-alkylbetaines, N-alkylamidobetaines, alkylmidazolines, polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylenesorbitane fatty acid esters and glycol fatty acid esters, oils such as hydrocarbons, silicones, lanolin derivatives, olive oil, hardened castor oil and esters, solvents such as ethanol, ethylene glycol, 1,3-butyleneglycol, propylene glycol, glycerine and polyethylene glycol, bacericides, preservatives, colorants and thickeners. The present invention is described in more detail by way of examples and synthetic examples, which should not be construed as limiting the present invention thereto. Synthetic Example 1 Preparation of Derivatives by oxidation of Keratin Material: (a) Ten grams of wool fibers were oxidised by immersing them in 700 g of an aqueous 8% peracetic acid solution at room temperature for 1 day. The resulting oxidized wool fibers were filtered, washed with water and immersed in 700 g of a 0.1 N aqueous ammonia at room temperature for 1 day, about 90% of the wool dissolved in the ammoniacal solution. About 1 g of the insoluble material was removed by filtration and the aqueous ammoniacal solution of keratose (oxidized product of the wool keratin) was admixed with 2N hydrochloric acid to adjust the pH to 4.0, whereupon α-keratose precipitated. This precipitate was filtered, washed with acetone and dried to obtain 5.4 g of α-keratose. (b) Wool fibers were heated under pressure in an autoclave by the use of a saturated stream of 6 kg/cm² for 6 minutes and were abruptly released into the air to obtain a porous puffed product. Ten grams of the purified product which had been reduced into pieces were immersed in 250 g of formic acid and 50 g of 30% aqueous hydrogen peroxide solution in a 500 ml three neck flask and left to stand at room temperature for 1 day, whereupon no powder was found in the solution but foam-like masses floated in the upper layer. This reaction mixture was filtered and the filtrate was poured into 1.5 liters of water, followed by adding hydrochloric acid to adjust the pH to 4. The resulting precipitate was collected by filtration and washed with 500 ml of water to yield 4.5 g of α-keratose. The insoluble material from which the reaction product had been removed by filtration was immersed in 350 ml of water and then a ammoniacal solution to adjust the pH to 11, the mixture was allowed to stand at room temperature for 1 day. The mixture was filtered and hydrochloric acid was added to the filtrate to adjust the pH to 4. The resulting precipitate was collected by filtration to yield 0.7 g of α-keratose. The insoluble material (1.4 g) was found to be primarily β-keratose. Synthetic Example 2 Preparation of Reduced Derivatives of Keratin Materials: (a) Ten grams of wool fibers were immersed in 600 ml of an aqueous solution of 8M urea and 0.01 M tris buffer, to which was added 6 ml of 2-mercaptoethanol, followed by adjusting the pH to 10 by means of a 5N aqueous potassium hydroxide. The reduction reaction was carried out in a stream of nitrogen at room temperature. About 3 hours after commencement of the reaction, about 85% of the wool dissolved in the reaction solution. While adjusting the pH of the reaction mixture with a 5N potassium hydroxide solution so that the pH was not below 7, 16.5 g of iodoacetic acid was gradually added and the pH of the system was finally adjusted to 8.5 and the carboxymethylation reaction was carried out at room temperature for 2 hours. The reaction solution was filtered to remove insoluble material therefrom and the resultant filtrate was charged into a cellulose tube wherein it was dialyzed against ion-exchanged water to remove low molecular weight impurities including urea. As the urea was dialyzed, the content in the cellulose tube became cloudy since water-insoluble HGT (component with high contents of glycerine and tyrosine) precipitated. After completion of the dialysis, HGT was centrifugally removed and S-carboxymethyl keratin (SCMKA) was obtained from the neutral transparent solution by the isoelectric precipitation. That is, 1N hydrochloric acid was added to the system to adjust its pH to 4.4 which precipitated the SCMKA. This precipitate was filtered, washed with ethanol and dried to yield 4.2 g of SCMKA. (b) The procedure of Synthetic Example 2 (a) was repeated except that there was used instead of wool fibers feathers which were heated for 6 minutes in an autoclave by means of a superheated steam at 6 kg/cm² and 240°C and then abruptly released into the air to obtain a porous puffed product and that 1.75 g of maleic acid was used instead of iodoacetic acid thereby yielding 5.3 g of S-(1,2-dicarboxyethyl)-keratin. (c) The procedure of Synthetic Example 2 (a) was repeated using powdered horse's hooves instead of wool fibers and 11 g of acrylic acid instead of iodoacetic acid, thereby yielding 4.2 g of S-(2-carboxyethyl)-keratin. (d) The procedure of Synthetic Example 2 (a) was repeated using 28 g of p-styrenesulfonic acid instead of iodoacetic acid thereby obtaining 4.8 g of S-(p-sulfophenylvinyl)-keratin. (e) Eight grams of wool fibers were dispersed in 300 ml of n-propanol and 300 ml of a 0.1N tris buffer solution. After replacing the air with nitrogen, 3.2 ml of tri-n-butylphosphine was added, followed by agitating at room temperature for 24 hours. The solution was subjected to filtration and to the resulting insoluble material were added 400 ml of water, 9.28 g of maleic acid and about 30 ml of 5N potassium hydroxide to adjust the pH to 8.0, followed by agitating at room temperature for 6 hours. To the reaction mixture was added about 20 ml of a 28% aqueous ammonia to adjust the pH to 11.5, after which it was agitated for further 18 hours at room temperature. The reaction solution was filtered to remove insoluble material therefrom and the resultant filtrate was placed into a cellulose tube in which it was dialyzed against ion-exchanged water to remove low molecular weight impurities therefrom. After completion of the dialysis, the insoluble material in the cellulose tube was removed by centrifugal separation and the resulting neutral transparent aqueous solution was adjusted in pH to 4.4 by addition of about 5.5 ml 1N hydrochloric acid and the resulting precipitate was collected by filtration, washed with ethanol and dried to yield 3.9 g of S-(1,2-dicarboxyethyl)-keratin. (f) The procedure of Synthetic Example 2 (e) was repeated except that there was used instead of wool fibers a powdered porous puffed product which has been obtained by heating wool in an autoclave by means of a saturated steam at 6 kg/cm² for 6 minutes and abruptly releasing the heated wool into the air and that 16.5 g of 2-acrylamido-2-methylpropanesulfonic acid was used instead of maleic acid, thereby obtaining 4.5 g of S-[2-(1,1-dimethyl-2-sulfoethylcarbamoyl)ethyl]-keratin. Synthetic Example 3 Preparation of Hydrolysis Derivatives of Keratin Materials: (a) Ten grams of wool fibers were immersed in 300 g of a 1 % aqueous sodium hydrogen sulfite, whose pH was adjusted to 6.7 by the use of a 5N aqueous caustic soda solution. Thereafter, 0.2 g of papain was added to the reaction mixture and the hydrolysis reaction was carried out at 60°C for 15 hours, by which about 80% of the wool dissolved. Insoluble material was removed by filtration and the sulfite in the resulting filtrate was removed by the ultrafiltration technique using a membrane with a fractional molecular weight of 500. The aqueous solution of the hydrolysate was concentrated and freeze dried to yield 7.7 g of the hydrolysate having a molecular weight of 500 to 2,000. (b) Ten grams of wool fibers were immersed in 300 g of 75% aqueous phosphoric acid and the hydrolysis reaction was carried out at 120 to 130°C for 5 hours. The reaction mixture was cooled and filtered to remove insoluble material therefrom, to which was added 4 ∼ 5 times the volume of the filtrate of water to further remove insoluble material. Then, calcium carbonate or barium hydroxide was added to the filtrate to adjust its pH to 6.7, after which the resulting precipitate was collected by filtration and dried to yield 8.0 g of a hydrolysate having a molecular weight of 500 to 2,000. Note: The amount of S―S bonds in the hydrolysate obtained by the procedure of Synthetic Example 3 (a) or 3 (b) was 50 moles per 10⁵ g of the hydrolysate, revealing that little or no cystine was destroyed during the course of the hydrolysis. (c) One hundreds grams of feathers were heated under pressure in an autoclave for 6 minutes by the use of a superheated steam at 6 kg/cm² and 240°C and then abruptly released into the air to obtain a porous puffed product. This product was reduced into pieces, and 3 l of 0.3N caustic soda was added. The hydrolysis reaction was carried out at 60°C for 18 hours, followed by neutralizing with 1n hydrochloric acid and filtering the reaction mixture. The sodium chloride in the resulting filtrate was removed by the ultrafiltration method using a membrane with a fractional molecular weight of 500. The aqueous solution of the hydrolysate of keratin was concentrated and freeze dried to yield 7.2 g of the hydrolysate of the keratin. The molecular weight of the hydrolysate was found to be 1,800 when determined by gel filtration. (d) 100 g of pieces of horse's hoof with a uniform size of 0.25 to 1 mm which were defatted with a 50% methanol and 50% chloroform solution and then treated with a 1 % ammonia solution to remove soluble proteins therefrom, were then placed in a three neck flask, 20 g of sodium hydroxide and 400 g of ion-exchanged water were added and the hydrolysis reaction was carried out at 90°C for 4 hours while agitating. After cooling, hydrochloric acid was added to adjust the pH to 8 and the reaction mixture was filtered. The sodium chloride in the filtrate was removed, followed by repeating the procedure of Synthetic Example 3 (c) to yield 68 g of a hydrolysate of the keratin. This hydrolysate had a molecular weight of 2,500 when determined by gel filtration. Example 1 Hair treatment compositions (setting lotions) of the following formulations were prepared and the texture of the hair treated therewith and the set retention effect were checked. The result are as shown in Table 1. Formulation Tests (1) Texture of Treated Hair A hair tress having a length of 20 cm and a weight of 20 g and from Japanese female hair was treated completely with 2 g of each hair treatment compositions and then rinsed with running water at 40°C for 1 minute, after which the rinsed hair was organoleptically evaluated. The organoleptic evaluation was conducted by the paired comparison technique using as reference hair which was treated with a commercially available hair rinse comprised mainly of a quarternary ammonium salt and hydrocarbons according to the following evaluation standard. (In the table, average values of 20 expert panel members are indicated.) (2) Set Retention Effect A hair tress of Japanese female hair and having a length of 20 cm and a weight of 5 g was treated with each hair treatment composition and then rinsed with running water at 40°C for 1 minute, followed by absorbing excess water on the hair with a filter paper. The tress was wound about a glass tube of 1.5 cm in diameter having a winding width of 5 cm and then fixed at opposite sides thereof. The wound tube was allowed to stand under conditions of 65 R.H.% and 20°C for 24 hours for curling, followed by removing the curled tress after 24 hours and vertically suspending it to measure length of the suspended tress. The degree of the curling was calculated according to the following equation: Degree of Curling (%) = A - (B - A) A × 100 A: Length of the tress immediately after removal B: Length of the tress 12 hours after removal (3) Measurement of Combing Force in Wet State After evaluation of the texture of the hair tress, it was set in a strain gauge, and was combed with a nylon comb twenty times to measure resisting forces. The average of the measured forces were determined as a combing force. (4) Measurement of Combing Force in Dry State After evaluation of the texture and measurement of the combing force in wet state, the hair tress was air dried and evaluated according to the procedures of (1) and (3). Example 2 Hair treatment compositions of the following formulations were prepared to check their stability and set retentivity. The stabilizing effect was determined by storing each composition at 25°C for 1 month after preparation and judging the state of the stored composition according to the following standard. The set retentivity was determined in the same manner as in Example 1. The results are shown in Table 2 below. Formulation Example 3 Shampoo Composition: The following ingredients were mixed to give a shampoo composition. The shampoo composition exhibited excellent texture, set retentivity and stability. Example 4 Hair Rinse Composition: The following ingredients were mixed to obtain a hair rinse composition. The composition showed an excellent rinsing effect to give firmness and stiffness to the hair and its stability was good. Example 5 Hair Treatment Composition: The following ingredients were mixed to obtain a hair treatment composition. The composition exhibited excellent texture when applied to hair and imparted firmness and stiffness to hair. Example 6 Hair setting Lotion: The following ingredients were mixed to give a hair setting lotion, exhibiting an excellent setting effect.

Claims: 1. A hair treatment composition comprising the following three ingredients (A), (B) and (C): (A) 0.05 to 10 wt.-% of at least one derivative of keratin selected from hydrolysates of keratin, products obtained by the oxidation of keratin materials and derivatives of the mercapto group of the products obtained by the reduction of keratin materials, wherein said derivatives are selected from the group (B) 0.05 to 10 wt.-% of a cationic polymer; and (C) 0.01 to 10 wt.-% in urea or at least one compound having a solubility in water greater than 1g/100 g of water at 25°C selected from inorganic ammonium and alkali metal salts and alkali metal salts of organic acids. 2. A hair treatment composition according to Claim 1, wherein the amount of the ingredient (A) is 0.1 to 2% by weight of the composition. 3. A hair treatment composition according to Claim 1, wherein the cationic polymer has a molecular weight of 500 to 5,000,000 and has cationic groups in the main chain or in substituents thereof. 4. A hair treatment composition according to Claim 1 or 3, wherein the cationic polymer is a member selected from quarternarized derivatives of cellulose ethers, diallyl quarternary ammonium homopolymers of the recurring units of the formulas (I) and (II) in which R₅ and R₆ are the same or different and represent hydrogen or an alkyl group having 1 to 18 carbon atoms, R₇ and R₈ are the same or different and independently represent hydrogen, an alkyl group having 1 to 3 carbon atoms, or phenyl group, X⁻ represents a halide ion, an anion of an inorganic acid, or an anion of an organic acid and n is a value sufficient to give a molecular weight of 10,000 to 1,000,000 polymers of the recurring units of the formulas (III) and (IV). (in which m₁ and m₂ are values sufficient to give a molecular weight of 10,000 to 1,000,000, and R₅, R₆, R₇ and R₈ have the same meanings as defined above, respectively), polymers of the formula (V) (in which R₉ and R₁₀ are the same or different and independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, and n and X⁻ have the same meanings as defined hereinbefore, respectively), and quarternarized derivatives of compolymers of N-vinyl-pyrrolidone/vinyl monomer of the formula (VI). (in which 1, p and q are values which are determined such that the monomer units in the respective brackets are, respectively, 20 to 99 mole%, 1 to 80 mole% and 0 to 50 mole%, y is 1 or 0, R₁₁ represents a hydrogen atom or methyl group, R₁₂, represents or (CH₂ (wherein K is a value of 2 to 18), R₁₃, represents an alkyl group having 1 to 4 carbon atoms and preferably ―CH₃, ―C₂H₅ or t-butyl group, R₁₄ represents -CH₃, -C₂H₅ or Z represents chlorine, bromine, iodine, SO₄, HSO₄ or CH₃SO₃, and M represents a monomer unit of a copolymerizable vinyl monomer). 5. A hair treatment composition according to Claim 4, wherein the amount of ingredient (B) is 0.1 to 2% by weight of the composition. 6. A hair treatment composition according to Claim 1, wherein the amount of the ingredient (C) is 0.1 ∼ 3% by weight of the composition. 7. A hair treatment composition according to Claim 1, wherein the inorganic ammonium, and alkali metal salts and alkali metal salts of organic acids have a solubility in water of 10 to 100 g/100 g of water at 25°C. 8. A hair treatment composition according to Claim 1, wherein the inorganic ammonium, and alkali metal salts and the alkali metal salts of organic acids are selected from sodium chloride, potassium thiocyanate, sodium sulfate, potassium hydrogen phosphate, sodium lactate, sodium benzoate and sodium citrate.

Inventors: ABE, YOSHIAKI, TSUSHIMA, RIKIO, WATANABE, HIROSHO
Applicants: KAO SOAP COMPANY, LTD.
Application year: 1982
Main classification: A61K7
IPC codes: A61K8, A61Q5