Abstract:
The aqueous hair fixing composition is in the form of a highly viscous sprayable gel and contains 0.1 to 50 percent by weight of one or more disaccharides or a mixture of 2 to 37 percent by weight of one or more disaccharides and 63 to 98 percent by weight of one or more oligosaccharides, 0.05 to 30 percent by weight of one or more cationic polymers, and 0.05 to 10 percent by weight of at least one thickener selected from the group consisting of honopolymers of acrylic acid, acrylic acid/acrylamides copolymers and sclerotium gum, The composition of the invention necessarily does hot contain monovalent aliphatic alcohols having 1 to 4 carbon atoms and no inorganic salts of alkali metals or inorganic salts of bivalent or trivalent metals. Either the composition is sprayed with the aid of a mechanical spray device or, alternatively, a gaseous propellant is included in it and the composition and propellant is included under pressure in a dispensing container.

Description:
This application is a continuation under 35 U.S.C. 371 of PCT/EP94/01422, filed May 4, 1994. 
    
    
     This application is a continuation under 35 U.S.C. 371 of PCT/EP94/01422, filed May 4, 1994. 
     BACKGROUND OF THE INVENTION 
     The subject of the present invention is an aqueous composition for fixing hair in the form of a highly viscous sprayable gel which contains a combination of at least one disaccharide or a disaccharide and an oligosaccharide with a cationic polymer and a thickener and has no monovalent aliphatic alcohols with 1 to 4 carbon atoms and determined salts. 
     At present, along with the conditioning and cleaning of hair, increasing importance is placed on shaping or hairstyling. In this respect, a distinction must be drawn between permanent and temporary hair-shaping. 
     Permanent shaping involves chemical action in the structure of the hair with the use of permanent wave compositions, whereas in temporary shaping, compositions whose essential constituents are film-forming polymers are used for fixing hair. 
     Film-forming polymers are conventionally used in alcoholic or aqueous-alcoholic solution in hair fixing compositions, foam fixing compositions, hair sprays and fixing gels. 
     The greatest disadvantages of known gel formulations are the poor proportioning and distributing properties of these gels, which are normally dispensed from tubes, and the intensive loading of hair associated with these gels. 
     This poses the problem of finding a hair fixing composition in gel form which provides good fixing of the hair and is easy to proportion and distribute in the hair. 
     SUMMARY OF THE INVENTION 
     Surprisingly, it has now been found that this problem is solved in an outstanding manner by an aqueous composition for fixing hair in the form of a highly viscous sprayable gel which contains a combination of a disaccharide or a mixture of a disaccharide and an oligosaccharide with a cationic polymer and a thickener and is free of monovalent aliphatic alcohols with 1 to 4 carbon atoms and certain inorganic salts. 
     Therefore, the subject of the present invention is an aqueous hair fixing composition in the form of a highly viscous sprayable gel containing 
     a) 0.1 to 50 percent by weight of at least one disaccharide or a mixture of 2 to 37 percent by weight of at least one disaccharide and 63 to 98 percent by weight of at least one oligosaccharide, 
     b) 0.05 to 30 percent by weight of at least one cationic polymer and 
     c) 0.05 to 10 percent by weight of at least one thickener and which contains 
     d) no monovalent aliphatic alcohols with 1 to 4 carbon atoms and 
     e) no inorganic salts of alkali metals or inorganic salts of bivalent or trivalent metals. 
     The highly viscous sprayable gel according to the invention preferably has a viscosity of 200 to 10,000 m Pa.s (milli-pascal seconds), in particular preferably 500 to 6,000 m Pa.s. The viscosity of the gel according to the invention was measured by a Haake viscosimeter VT 501 at 25° C. and a SV-DIN shear rate of 12.9 s -1  (row B, position 5). 
     Although it takes the form of a high-viscosity gel, the composition according to the invention can be sprayed with a conventional mechanical spraying device (e.g., a spray pump) or with a propellant from a conventional aerosol pressurized container with a conventional spray head as a finely distributed gel. 
     Since it may be sprayed, the composition according to the invention can be proportioned precisely and distributed uniformly in hair. The polymer film produced on the hair by the composition according to the invention is resilient and resistant to moisture in the air. 
     The composition according to the invention has a very good fixing action and may be washed out of hair easily. Surprisingly, in spite of the saccharide content in the composition according to the invention, hair which has been treated with the composition according to the invention does not have a sticky feel. Moreover, the composition according to the invention has none of the monovalent aliphatic alcohols with 1 to 4 carbon atoms which are contained in conventional compositions for fixing hair. 
     Saccharide-containing hair treatment compositions are known, for example, from DE-OS 34 04 627. The described compositions preferably take the form of lotions and necessarily contain salts. DE-OS 34 04 627 does not suggest providing a hair fixing composition in the form of a highly viscous sprayable gel which can be favorably proportioned and distributed easily and uniformly. 
     In the present invention, oligosaccharides are understood as saccharides with 3 to 6 monosaccharides connected in the manner of acetal compounds. 
     DESCRIPTION OF THE PREFERRED EMBODIMENTS 
     The disaccharide/oligosaccharide mixtures which can be contained in the composition according to the invention as component a) are preferably mixtures of glucose disaccharides and glucose oligosaccharides such as those sold by Cerestar, Krefeld, Germany, under the trade name C-Pur®. In particular, the composition according to the invention preferably contains, as component a), maltose or the glucose disaccharide/glucose oligosaccharide mixture sold by Cerestar, Krefeld, Germany, under the trade name C-Pur® 01924. 
     The composition according to the invention preferably contains 1 to 25 percent by weight of component a). 
     The cationic polymers contained in the composition according to the invention as component b) are preferably polyvinylpyrrolidone/dimethylaminoethyl methacrylate polymers. In a particularly preferred embodiment, the composition according to the invention contains the polyvinylpyrrolidone/dimethylaminoethyl methacrylate copolymer sold by Gaf Co., New York, U.S.A., under the trade name Gafquat® 755N. Other examples of cationic polymers are the copolymer of polyvinylpyrrolidone and imidazoliminmethochioride sold by BASF AG, Ludwigshafen, Germany, under the trade name Luviquat® H11 550, the terpolymer of dimethyl diallyl ammonium chloride, sodium acrylate and acrylamide sold by Calgon, Pittsburgh, U.S.A., under the trade name Merquat® Plus 3330, the terpolymer of vinylpyrrolidone, dimethylaminoethyl methacrylate and vinylcaprolactum sold by ISP, U.S.A., under the trade name Gaffix® VC 713, the quaternary ammonium salt of hydroxyethylcellulose and a trimethylammonium-substituted epoxide sold by Amerchol, Edison, U.S.A., under the trade name Polymer IR®, the vinylpyrrolidone/methacrylamidopropyltrimethyl ammonium chloride copolymer sold by Gaf Co., New York, U.S.A. under the trade name Gafquat® HS 100 and the diquaternary polydimethylsiloxane sold by Goldschmidt, Essen, Germany, under the trade name Abil® Quat 3272. 
     The composition according to the invention preferably contains 0.05 to 10 percent by weight of component b). 
     Preferred thickeners contained in the composition according to the invention as component c) are homopolymers of acrylic acid with a molecular weight of 2,000,000 to 6,000,000 such as those sold by B.F. Goodrich, Cleveland, U.S.A., under the trade name Carbopol®. In particular, the composition according to the invention preferably contains an acrylic acid homopolymer with a molecular weight of 4,000,000 such as that sold by B.F. Goodrich under the trade name Carbopol® 940. Other thickeners are, e.g., the acrylic acid homopolymers sold by B.F. Goodrich under the trade name Carbopol® ETD 2001 or by Protex, France, under the trade name Modarez V 600 PX, the polymer of acrylic acid and acrylamide (sodium salt) with a molecular weight of 2,000,000 to 6,000,000 sold by Hoechst, Germany, under the trade name Hostacerin PN 73® and the sclerotium gum sold under the trade name Amigel® by Alban Muller, Montreuil, France. 
     The composition according to the invention preferably contains 0.1 to 5 percent by weight of component c). 
     In addition, the composition according to the invention can contain 0.1 to 15 percent by weight, preferably 0.1 to 7 percent by weight, of at least one nonionic polymer. Preferred nonionic polymers which may be contained in the composition according to the invention are polyvinylpyrrolidone polymers such as those sold by BASF AG, Ludwigshafen, Germany, under the trade name Luviskol®. A particularly preferred polyvinylpyrrolidone polymer contained in the composition according to the invention is that sold by BASF AG under the trade name Luviskol® VA 64. 
     A naturally occurring nonionic polymer is hydroxypropyl chitosan, for example. 
     In addition, the composition according to the invention can contain 0.1 to 15 percent by weight, preferably 0.1 to 7 percent by weight, of at least one anionic polymer. In particular, anionic polymers preferably contained in the composition according to the invention are the sodium polystyrene sulfonate sold under the trade name Flexan® 130 by National Starch, Braunston, Great Britain, and the copolymer of methacrylic acid and methacrylate sold under the trade name Diahold® A 503 by Sandoz, Basel, Switzerland. Other anionic polymers include the terpolymer of polyvinylpyrrolidone, ethylmethacrylate and methacrylic acid sold by Stepan, Northfield, U.S.A., under the trade name Stepanhold® R-1 and the copolymer of methacryloyl ethyl betaine and methacrylate sold by Sandoz under the trade name Diaformer® Z 301 and shellac, e.g., Schellack MHP 210 available from Pennig, Germany. 
     The composition according to the invention preferably contains no organic solvents. 
     The composition according to the invention contains 20 to 98 percent by weight, preferably 50 to 96 percent by weight, water. The composition according to the invention has a pH of 4 to 9, preferably 6 to 8. 
     Of course, in addition to the ingredients mentioned above, the composition according to the invention can also contain conventional cosmetic additives such as perfume oils in quantities of approximately 0.1 to 5.0 percent by weight, opacifiers such as ethylene glycol distearate in quantities of approximately 0.5 to 5.0 percent by weight, pearlescing agents such as a mixture of fatty acid monoalkylolamide and ethylene glycol distearate in quantities of approximately 0.01 to 10.0 percent by weight, amines or alkanolamines suitable for neutralizing, e.g., 2-amino-2-methylpropanol, wetting agents or emulsifiers from the classes of anionic, cationic, amphoteric or nonionic surface-active substances such as fatty alcohol sulfates, ethoxylated fatty alcohol sulfates, alkyl sulfonates, alkyl benzene sulfonates, alkyl trimethylammonium salts, alkyl betaines, ethoxylated fatty alcohols, ethoxylated nonylphenols, fatty acid alkanolamides, glyceride alkoxylates, e.g., fatty acid esters of hydrated castor oil with ethoxylated glycerol in quantities of 0.01 to 15 percent by weight, as well as dyes such as fluorescein sodium salt in quantities of approximately 0.1 to 1.0 percent by weight, hair nurturing additives such as pantothenic acid in quantities of approximately 0.01 to 10 percent by weight, hair moisteners such as 1,2-propanediol and glycerol, dyes, lightfastness agents, antioxidants, brighteners such as sorbitol and preservatives such as p-hydroxybenzoic acid ester, sorbic acid, salicylic acid, mandelic acid or formic acid in quantities of 0.01 to 10 percent by weight. 
     If desired, the hair fixing composition according to the invention can be used to dye or tint hair at the same time when it contains cosmetic dyes. Such preparations are known commercially, for example, as dye fixing compositions or tint fixing compositions. They contain, in addition, conventional dyes which are absorbed directly in the hair, e.g. aromatic nitro dyes such as 1,4-diamnino-2-nitrobenzene, picramic acid, 1-N-hydroxyethylamino-4-methyl-2-nitrobenzene, 1-hydroxy-2-amino-4-nitrobenzene and 1,4-bis(2-hydroxyethyl)amino-2-nitro-5-chlorobenzene, azo dyes such as Acid Brown 4 (C.I. 14,805), anthraquinone dyes such as Disperse Violet 4 (C.I. 61,105) and triphenylmethane dyes such as Basic Violet I (C.I. 42,535), Basic Violet 14 (C.I. 42,510), Basic Red 76 (C.I. 12,245) or Basic Blue 7 (C.I. 42,595:1). Depending on their substituents, these dyes can have an acidic, nonionic or alkaline character. The total concentration of such dyes in the composition according to the invention is generally approximately 0.01 to 2.0 percent by weight. 
     The hair fixing composition according to the invention is preferably sprayed by a propellant or with the aid of a mechanically operated spraying device. 
     Lower alkanes such as n-butane, i-butane and propane, or mixtures of lower alkanes with dimethyl ether and other gaseous propellants, e.g. N 2 , N 2  O and CO 2 , at the appropriate pressures, as well as mixtures of the aforementioned propellants are suitable for use as propellants. 
     In particular, the hair fixing composition according to the invention is preferably sprayed with the aid of a mechanically operated spraying device. 
     By mechanically operated spraying device is meant devices which spray liquids without the use of propellants. For example, a suitable mechanical spraying device can be a spray pump or a flexible container which is provided with a spray valve and contains the cosmetic composition according to the invention under pressure. This flexible container expands and the composition can be dispensed in a continuous manner from this container due to the contraction of the flexible container by opening the spray valve. 
     The hair fixing composition according to the invention provides excellent fixing without a sticky feel and can be brushed out and washed out of hair easily. Since it can be sprayed by mechanical spraying devices or with the use of propellants, it is easy to proportion and distributed in the hair. 
    
    
     The following examples explain the subject matter of the invention in more detail. 
     EXAMPLES 
     Example 1 
     Gel spray with normal fixing 
     
         ______________________________________6.00 g  maltose0.06 g  polyvinylpyrrolidone/dimethylaminoethyl methacrylate   copolymer (Gafquat ® 755 N, Gaf Co., U.S.A.)0.20 g  homopolymer of acrylic acid with a molecular weight of   4,000,000 (Carbopol ® 940, B. F. Goodrich, U.S.A.)0.23 g  2-amino-2-methylpropanol0.10 g  perfume oil93.41 g water100.00 g______________________________________ 
    
     Example 2 
     Gel spray with intensive fixing 
     
         ______________________________________8.00 g   mixture of glucose disaccharide and glucose    oligosaccharide (C-Pur ® 01924, Cerestar, Germany)0.08 g   polyvinylpyrrolidone/dimethylaminoethyl methacrylate    copolymer (Gafquat ® 755 N, Gaf Co., U.S.A.)0.22 g   homopolymer of acrylic acid with a molecular weight of    4,000,000 (Carbopol ® 940, B. F. Goodrich, U.S.A.)0.26 g   2-amino-2-methylpropanol0.15 g   perfume oil91.29 g  water100.00 g______________________________________ 
    
     Example 3 
     Gel spray with extra-intensive fixing 
     
         ______________________________________10.00 g mixture of glucose disaccharide and glucose   oligosaccharide (C-Pur ® 01924, Cerestar, Germany)0.50 g  dimethyl diallyl ammonium chloride/sodium acrylate/   acrylamide terpolymer (Merquat ® Plus 3 330, Calgon,   U.S.A.)0.25 g  copolymer of acrylic acid and acrylamide sodium salt   (Hostacerin PN 73 ®, Hoechst, Germany) and3.00 g  polyvinylpyrrolidone (Luviskol ® VA 64, BASF AG,   Germany)0.20 g  nonylphenol ethoxylated with 14 moles ethylene oxide0.20 g  p-hydroxybenzoic acid methyl ester0.10 g  perfume oil85.75 g water100.00 g______________________________________ 
    
     Example 4 
     Gel spray with normal fixing 
     
         ______________________________________5.00 g   mixture of glucose disaccharide and glucose    oligosaccharide (C-Pur ® 01924, Cerestar, Germany)0.50 g   diquaternary polydimethylsiloxane (Abil ® Quat 3272,    Goldschmidt, Germany)1.00 g   sclerotium gum (Amigel ®, Alban Muller)0.20 g   nonylphenol ethoxylated with 14 moles ethylene oxide0.20 g   p-hydroxybenzoic acid methyl ester0.10 g   perfume oil93.00 g  water100.00 g______________________________________ 
    
     Example 5 
     Gel spray with normal fixing 
     
         ______________________________________3.00 g   maltose0.50 g   polyvinylpyrrolidone/imidazoliminmethochloride    (Luviquat ® HM 550, BASF AG, Germany)0.20 g   homopolymer of acrylic acid with a molecular weight of    4,000,000 (Carbopol ® 980, B. F. Goodrich, U.S.A.)0.25 g   ammonia, 25-percent aqueous solution0.50 g   shellac0.20 g   nonylphenol ethoxylated with 14 moles ethylene oxide0.20 g   p-hydroxybenzoic acid methyl ester0.10 g   perfume oil95.05 g  water100.00 g______________________________________ 
    
     Example 6 
     Wet gel 
     
         ______________________________________3.00 g   mixture of glucose disaccharide and glucose    oligosaccharide (C-Pur ® 01924, Cerestar, Germany)0.50 g   vinylpyrrolidone/dimethylaminoethyl methacrylate/    vinylcaprolactum terpolymer (Gaffix ® VC 713, ISP,    U.S.A.)0.25 g   homopolymer of acrylic acid with a molecular weight of    6,000,000 (Modarez ® V 600 PX, Protex, France)0.20 g   2-amino-2-methylpropanol0.20 g   nonylphenol ethoxylated with 14 moles ethylene oxide0.10 g   perfume oil95.75 g  water100.00 g______________________________________ 
    
     Example 7 
     Gel spray with intensive fixing 
     
         ______________________________________3.00 g   maltose0.50 g   vinylpyrrolidone/methacrylamidopropyl    trimethylammonium chloride copolymer (Gafquat ® HS    100, Gaf Co., U.S.A.)0.20 g   homopolymer of acrylic acid with a molecular weight of    4,000,000 (Carbopol ® 980, B. F. Goodrich, U.S.A.)1.00 g   methacrylic acid/methacrylate copolymer (Diahold ®    A 503, Sandoz, Switzerland)0.50 g   hydroxypropyl chitosan0.20 g   nonylphenol ethoxylated with 14 moles ethylene oxide0.10 g   perfume oil94.50 g  water100.00 g______________________________________ 
    
     The pH of the composition is adjusted to 7.0 with aqueous sodium hydroxide solution. 
     Example 8 
     
         ______________________________________ 7.000 g  mixture of glucose disaccharide and glucose oligosaccharide  (C-Pur ® 01924, Cerestar, Germany) 0.500 g  polyvinylpyrrolidone/dimethylaminoethyl methacrylate  copolymer (Gafquat ® 755 N, Gaf Co., U.S.A.) 0.250 g  homopolymer of acrylic acid with a molecular weight of  4,000,000 (Carbopol ® 980, B. F. Goodrich, U.S.A.) 0.290 g  2-amino-2-methylpropanol 0.200 g  hydrated castor oil ethoxylated with 45 moles ethylene oxide 0.200 g  cetyl/stearyl alcohol alkoxylated with 9 moles ethylene oxide  and 2 moles propylene oxide 1.800 g  p-hydroxybenzoic acid methyl ester 0.180 g  Basic Red 76 (C.I. 12,245) 0.015 g  Basic Violet 14 (C.I. 42,510) 0.230 g  1-N-hydroxyethylamino-4-methyl-2-nitrobenzene 0.300 g  1,4-bis(2-hydroxyethyl)amino-2-nitro-5-chlorobenzene 0.200 g  perfume oil 88.835 g  water100.00 g______________________________________ 
    
     Example 9: 
     
         ______________________________________7.0000 g mixture of glucose disaccharide and glucose    oligosaccharide (C-Pur ® 01924, Cerestar, Germany)0.5000 g polyvinylpyrrolidone/dimethylaminoethyl methacrylate    copolymer (Gafquat ® 755 N, Gaf Co., U.S.A.)0.2500 g homopolymer of acrylic acid with a molecular weight of    4,000,000 (Carbopol ® 980, B. F. Goodrich, U.S.A.)0.2900 g 2-amino-2-methylpropanol0.2000 g hydrated castor oil ethoxylated with 45 moles ethylene    oxide0.2000 g cetyl/stearyl alcohol alkoxylated with 9 moles ethylene    oxide and 2 moles propylene oxide1.8000 g p-hydroxybenzoic acid methyl ester0.0300 g 1-N-hydroxyethylamino-4-methyl-2-nitrobenzene0.0035 g 1,4-bis(2-hydroxyethyl)amino-2-nitro-5-chlorobenzene0.2000 g perfume oil89.5265 g    water100.00 g______________________________________ 
    
     All percentages indicated in the present Application represent percent by weight.