accordingly , there is still a need for hair cosmetic preparations which are distinguished by a reduction in unwanted damage to the hair . it has now surprisingly been found that hair cosmetic preparations containing a cationically derivatized protein hydrolyzate ( a ) and a carbohydrate ( b ) and / or a cationic , anionic or ampholytic polymer ( c ) have a far less unfavorable influence on the hair . the use of these combinations of active substances increases the tensile strength of hair and also provides for better style retention and improved volume . in addition , no maillard reaction occurs in the combinations ( a )+( b ) and ( a )+( b )+( c ). accordingly , the present invention relates to preparations containing typical constituents for the washing and care of hair , characterized in that they contain a combination of active substances consisting of ( a ) a cationically derivatized protein hydrolyzate and ( b ) a carbohydrate and / or ( c ) a cationic , anionic or ampholytic polymer . cationically derivatized protein hydrolyzates ( a ) are mixtures of substances which may be obtained , for example , by reaction of alkali -, acid - or enzyme - hydrolyzed proteins with glycidyl trialkyl ammonium salts or 3 - halo - 2 - hydroxypropyl trialkyl ammonium salts . proteins used as starting materials for the protein hydrolyzates may be of both animal and vegetable origin . typical starting materials are , for example , keratin , collagen , elastin , soya protein , milk protein , wheat protein , silk protein and almond protein . mixtures having molecular weights in the range from about 100 to about 50 , 000 daltons are formed by the hydrolysis . typical average molecular weights are in the range from about 500 to about 1000 dalton . further particulars of cationic derivatization can be found inter alia in japanese patent application 77 / 73485 ( chemical abstracts , abstract 90 : 174508v ). the cationically derivatized protein hydrolyzates advantageously contain one or two long alkyl chains containing 8 to 22 carbon atoms and , accordingly , two or one short alkyl chain containing 1 to 4 carbon atoms . compounds containing one long alkyl chain are preferred . preferred compounds ( a ) correspond to formula ( i ): ## str1 ## in which r represents the side chains of the amino acids of the protein , r 1 and r 2 independently of one another represent alkyl chains containing 1 to 4 carbon atoms and r 3 represents an alkyl chain containing 8 to 22 carbon atoms . a commercially available product is lamequat ® l ( chemische fabrik grtinau ). it has the following structure : ## str2 ## in which r represents the side chains of the amino acids of collagen . its ctfa name is lauryldimonium hydroxypropylamino hydrolyzed animal protein . this product is a particularly preferred component ( a ). according to the invention , both monosacchafides and oligosacchafides , such as for example cane sugar , lactose and raffinose , may be used as the carbohydrates ( b ). the use of monosaccharides is preferred . preferred monosacchafides are compounds containing 5 or 6 carbon atoms . suitable pentoses and hexoses are , for example , ribose , arabinose , xylose , lyxose , allose , altrose , glucose , mannose , gulose , idose , galactose , talose and fructose . arabinose , glucose , galactose and fructose are preferred carbohydrates , glucose being particularly preferred . in addition , derivatives of these pentoses and hexoses , such as the corresponding onic and uronic acids ( sugar acids ), sugar alcohols and glycosides , may also be used in accordance with the invention . preferred sugar acids are gluconic acid , glucuronic acid , sugar acid , mannosugar acid and mucic acid . preferred sugar alcohols are sorbitol , mannitol and dulcitol . preferred glycosides are the methyl glucosides . quatemized carbohydrates may also be used as component ( b ) in accordance with the invention . the commercial product glucquat ® 100 ( ctfa name : lauryl methyl gluceth - 10 hydroxypropyl dimonium chloride ) is a preferred quaternized carbohydrate . since the carbohydrates used are normally obtained from natural raw materials , such as starch , the carbohydrates generally have the configurations corresponding to these raw materials ( for example d - glucose , d - fructose and d - galactose ). the following are examples or cationic polymers ( c ) suitable for use in accordance with the invention : quatemized cellulose derivatives of the type commercially available under the names of celquat ® and polymer jr ®. the compounds celquat h 100 , celquat l 200 and polymer jr ® 400 are preferred quatemized cellulose derivatives . copolymers of vinyl pyrrolidone with quaternized derivatives of dialkyl aminoacrylate and methacrylate , for example vinyl pyrrolidone / dimethyl aminomethacrylate copolymers quaternized with diethyl sulfate . compounds such as these are commercially available under the names of gafquat ® 734 and gafquat ® 755 . vinyl pyrrolidone / methoimidazolinium chloride copolymers of the type commercially available under the name of luviquat ®. polymeric dimethyl diallyl ammonium salts and copolymers thereof with esters and amides of acrylic acid and methacrylic acid . the products commercially available under the names of merquat ® 100 { poly ( dimethyl diallyl ammonium chloride )} and merquat ® 550 ( dimethyl diallyl ammonium chloride / acrylamide copolymer ) are examples of such cationic polymers . polyacrylic and polymethacrylic acids , salts thereof , copolymers thereof with esters and amides of ( meth ) acrylic acid and derivatives thereof obtained by crosslinking with polyfunctional agents . compounds of this type are commercially available , for example , under the names of carbopol ® 934 , carbopol ® 934p , carbopol ® 940 , carbopol ® 950 , carbopol ® 980 and hostacerin ® pn 73 . polyoxycarboxylic acids , such as polyketocarboxylic and polyaldehydocarboxylic acids and salts thereof , such as for example poc ® hs 5060 and poc ® as 5060 . polymers and copolymers of crotonic acid with esters and amides of ( meth ) acrylic acid , such as vinyl acetate / crotonic acid and vinyl acetate / vinyl propionate / crotonic acid copolymers . compounds of this type are commercially available as luviset ® ca - 66 and luviset ® cap . in the context of the invention , ampholytic polymers are understood to be amphoteric polymers , i . e . polymers which contain both free amino groups and free -- cooh or so 3 h groups in the molecule and which are capable of forming inner salts , zwitterionic polymers containing quaternary ammonium groups and -- coo -- or -- so 3 -- groups in the molecule and polymers containing -- cooh or so 3 h groups and quaternary ammonium groups . one example of an ampholytic polymer suitable for use in accordance with the invention is the acrylic resin commercially available as amphomer ® which is a copolymer of tert - butyl aminoethyl methacrylate , n -( 1 , 1 , 3 , 3 - tetramethylbutyl )- acrylamide and two or more monomers from the group consisting of acrylic acid , methacrylic acid and simple esters thereof . other ampholytic polymers suitable for use in accordance with the invention are the compounds mentioned in gb - a - 2 , 104 , 091 , ep - a47 714 , ep - a - 217 274 , ep - a - 283 817 and de - a - 28 17 369 . ( a ) monomers containing quaternary ammonium groups corresponding to general formula ( ii ): in which r 4 and r 5 independently of one another represent hydrogen or a methyl group and r 6 , r 7 and r s independently of one another represent c 1 - 4 alkyl groups , z is an nh group or an oxygen atom , n is an integer of 2 to 5 and a . sup . (-) is the anion of an organic or inorganic acid ; and in which r 9 and r 10 independently of one another represent hydrogen or methyl groups . these compounds may be used in accordance with the invention both directly and in salt form , i . e . after neutralization of the polymers , for example with an alkali metal hydroxide . full particulars of the production of these polymers can be found in de - a - 39 29 973 . polymers in which monomers of type ( a ), where r 6 , r 7 and r 8 are methyl groups , z is an nh group and a . sup . (-) is a halide , methoxysulfate or ethoxysulfate ion , are most particularly preferred . acrylamidopropyl trimethyl ammonium chloride is a particularly preferred monomer ( a ). acrylic acid is preferably used as monomer ( b ) for the polymers mentioned . the active substances ( a ) are present in a quantity of 0 . 1 to 10 % by weight , based on the preparation as a whole . concentrations of 0 . 5 to 5 % by weight are preferred . the active substances ( b ) are also present in a quantity of 0 . 1 to 10 % by weight , based on the preparation as a whole . concentrations of 0 . 5 to 5 % by weight are preferred . it has been found that a particularly advantageous effect is obtained when compounds ( a ) and ( b ) are present in a ratio by weight of 0 . 5 : 1 to 2 : 1 . preparations in which components ( a ) and ( b ) are present in substantially equal parts by weight are particularly preferred . the active substances ( c ) are preferably present in the preparations according to the invention in a quantity of 0 . 1 to 5 % by weight and , more preferably , in a quantity of 0 . 2 to 2 % by weight , based on the preparation as a whole . although the combinations of active substance ( a ) and active substance ( b ) or active substance ( a ) and active substance ( c ) have a surprisingly strong effect on the structure and properties of the hair , it has been found that a further unexpectedly marked increase in effect occurs where all three active substances are combined . in one preferred embodiment , therefore , the preparations according to the invention contain both active substance ( b ) and active substance ( c ) in addition to active substance ( a ). combinations of ( a ), ( b ) and ( c ), in which ( c ) is an ampholytic polymer , are most particularly preferred . the preparations according to the invention may be used both in hair treatment processes in which the preparation is rinsed out from the hair after use and in hair treatment processes where the preparation remains in the hair . preparations which are normally rinsed from the hair after use are , for example , shampoos , wave preparations and coloring preparations . products which normally remain in the hair are , for example , hair setting preparations , hair tonics and blow - wave preparations . in addition to the compulsory components , any other auxiliaries and additives typical of the application in question may be present , depending on the type and preparation . in the case of shampoos , such auxiliaries and additives besides water as the base are anionic , nonionic and zwitterionic surfactants , pearlescers , perfumes , ph regulators , dyes , preservatives , optionally alkoxylated fatty acids and fatty alcohols and viscosity regulators . hair rinses , which are also water - based in most cases , generally contain quaternary ammonium compounds , lower alcohols , solubilizers , active principles , such as panthenol for example , nonionic polymers , viscosity regulators and perfume oils . in addition to water , hair setting preparations generally contain lower alcohols , surfactants , preferably nonionic surfactants , stabilizers , cationic and / or anionic polymers , ph regulators and -- in the case of setting foams -- propellants . hair coloring preparations normally contain substantive dyes and / or oxidation dye precursors ( modifiers , developer components ), surfactants , fatty alcohols and ph regulators . in addition to a reducing agent ( thioglycolic acid , thiolactic acid ), wave preparations generally contain ph regulators , surfactants , complexing agents , solubilizers , fatty alcohols and perfume oils . the corresponding fixing solutions contain oxidizing agents , such as hydrogen peroxide and potassium bromate , instead of the reducing agent . four shampoos were tested , their compositions being set out in table 1 below . alkinco type 6621 hair tresses ( tress length : 12 cm ) were used for the measurements . the tresses were treated for 20 minutes with the test shampoo , then rinsed for about 30 seconds and dried with a blow dryer for about 1 . 5 hours at 38 ° c . the tresses were then ultrableached for 20 minutes ( composition of the ultrableach : 6 % by weight of hydrogen peroxide , 15 % by weight of ammonium peroxydisulfate , conc . ammonia ad ph 9 . 4 , remainder water ) and rinsed with water for about 1 minute . the wet tresses were then shampooed , rinsed and dried as described above . the tresses were then cold - waved ( wave solution : 7 % by weight thioglycolic acid , conc . ammonia ad ph 9 . 0 , remainder water ), rinsed with water ( 38 ° c .) for about 1 minute and treated with a fixing solution ( 2 % by weight hydrogen peroxide , citric acid ad ph 4 . 0 , remainder water ), shampooed , rinsed and dried as described above . the cycle of ultrableaching , rinsing , shampooing , rinsing , drying , cold waving , rinsing , fixing , rinsing , table 1______________________________________test shampooscomponent 1 2 3 4______________________________________texapon ® n25 . sup . 1 43 43 43 43dehyton ® k - is . sup . 2 10 10 10 10euperlan ® pk 810 is . sup . 3 5 5 5 5akypo ® rlm 100 nv . sup . 4 5 5 5 5edenor ® kpk c12 - 18 + 9 . 2 eo . sup . 5 1 1 1 1preservative 0 . 3 0 . 3 0 . 3 0 . 3sodium chloride 1 . 2 0 . 25 0 . 19 0 . 19perfume oil , dyes 1 . 1 1 . 1 1 . 1 1 . 1lamequat ® l . sup . 6 -- 3 3 3d glucose -- 3 3 3polymer jr ® 400 . sup . 7 -- -- 0 . 2 -- polymer p1 acc . to de 39 29 973 . sup . 8 -- -- -- 1citric acid ad ph 7 . 2 7 . 2 7 . 2 7 . 0water ← ad 100 → viscosity [ mpas ] 9300 9700 8500 9200______________________________________ . sup . 1 sodium lauryl ether sulfate ; ctfa name : sodium laureth sulfate ( about 28 % active substance in water ) ( henkel ) . sup . 2 fatty acid amide derivative , betaine structure , corresponding to the formula rconh ( ch . sub . 2 ). sub . 3n . sup .+ ( ch . sub . 3 ). sub . 2ch . sub . 2coo . sup . ; cfta name : cocoamidopropyl betaine ( about 30 % active substance in water ( henkel ) . sup . 3 mixture of fatty alcohol ether sulfates with pearlescing substances ; ctfa name : glycol distearate ( and ) sodium laureth sulfate ( and ) cocoamide mea ( and ) laureth9 ( about 37 % active substance , including about 13 % anionic surfactant , in water ) ( henkel ) . sup . 4 c . sub . 12 - 14 fatty alcohol + 10 eo acetic acid sodium salt ; ctfa name : sodium laureth11 carboxylate ( 22 % active substance ) ( chemy ) . sup . 5 coconut palm kemel oil fatty acid ( c . sub . 12 - 18 ) + 9 . 2 ethylene oxide ( henkel ) . sup . 6 cationic protein hydrolyzate corresponding to the formula : ## str3 ##- - ( r = side chains of the aminoacids of collagen ); ctfa name : lauryldimoniu hydroxypropylamino hydrolyzed animal protein ( about 35 % dry matter ) ( chemische fabrik grunau ) . sup . 7 quaternized hydroxyethyl cellulose ( union carbide ) . sup . 8 polymer of acrylamidopropyl trimethyl ammonium chloride and acryli acid in a molar ratio of 3 : 1 , neutralized with naoh ( 20 % active substance in water ). shampooing , rinsing and drying was then repeated another two times . for the dry measurement , the tresses were heated in air at 38 ° c . for the wet measurements , the tresses were stored in water until . just before the measurement . 15 % elongation value ( tensile force at which the hair is elongated by 15 %) particulars of the measuring process can be found in the literature ( arztl . kosmetologie 15 , 347 - 355 ( 1985 ) and parf umerie & amp ; kosmetik 72 , 74 - 81 ( 1991 )). brittleness is determined as the percentage of hairs which show a break at 20 % elongation and less . ______________________________________ shampoo 1 2 3 4______________________________________wet measurementmaximum breaking stress [ mn ] 380 462 390 51115 % elongation value [ mn ] 268 307 290 304dry measurementmaximum breaking stress [ mn ] 477 446 461 50115 % elongation value [ mn ] 432 401 403 418breaking elongation [%] 21 28 28 42brittleness [%] 68 52 52 30______________________________________ the dry combing work was determined on brown hair ( alkinco 6634 , tress length 12 cm , tress weight 1 g ) in the form of a comparison of paired mean values . to determine the zero value , the tresses were rinsed with water ( 1 l / min , 38 ° c .) for 1 . 5 minutes and combed out . the tresses were then dried with a blow dryer for 40 minutes at 45 ° c . after conditioning for 12 hours at 30 ° c ./ 40 % relative air humidity , the combing work was determined . the tresses were then treated with 100 g of the formulation for 5 minutes and then rinsed , dried and conditioned as described above . the dry combing work was then determined . particulars of the measuring process can be found in the literature ( arztl . kosmetologie 20 , 498 - 502 ( 1990 )). ______________________________________ dry combing work , mjshampoo before after b / a , % ______________________________________1 6 . 5 6 . 5 1002 5 . 1 7 . 6 1503 5 . 5 9 . 7 1754 7 . 6 10 . 9 144______________________________________ ______________________________________ % by weight______________________________________a ) hair setting foameumulgin ® 0 . 5luviset ® 4 . 5amp ® 0 . 4gafquat ® 0 . 5d glucose 0 . 2lamequat ® l 0 . 2ammonia ( 25 % solution ) 0 . 1perfume oil 0 . 13ethanol 5 . 0drivosol ® 3 . 5 . sup . 13 7 . 0water ad 100b ) rinsecremophor ® rh 40 . sup . 14 1 . 5dehyquart ® sp . sup . 15 1 . 0luviskol ® k 30 . sup . 16 1 . 0panthenol 1 . 0d glucose 2 . 0lamequat ® l 1 . 0polymer pl acc . to de 39 29 973 3 . 0hydroxyethyl cellulose 1 . 8ethanol ( 96 %) 12 . 0water ad 100______________________________________ . sup . 9 oleyl alcohol + 5 ethylene oxide ; ctfa name : oleth5 ( henkel ) . sup . 10 vinyl acetate / crotonic acid copolymer ( 90 : 10 ) ( basf ) . sup . 11 2amino - 2 - methyl propanol ( 95 % active substance , remainder water ) ( angus chemie ) . sup . 12 dimethylaminoethyl methacrylate / vinyl pyrrolidone copolymer quaternized with diethyl sulfate ; ctfa name : polyquaternium 11 ( about 19 % active substance in water ) ( gaf ) . sup . 13 propane / isobutane / butane / dimethyl ether mixture ( 24 : 72 : 3 : 1 ) ( h uls ) . sup . 14 hydrogenated castor oil reacted with 45 moles of ethylene oxide per mole of castor oil ( basf ) . sup . 15 oxyethyl alkylammonium phosphate ; ctfa name : quaternium52 ( 50 % active substance in water ) ( henkel ) . sup . 16 polyvinyl pyrrolidone ( 95 % active substance , remainder water ) ( basf ).
the invention concerns the use of combinations of active substances , consisting of a cationic derivative of a protein hydrolyzate and a carbohydrate and / or a cationic , anionic or ampholytic polymer , in hair - cleaning and hair - care agents , thus improving the qualities of the hair , in particular its brittleness and its ease of combing when dry .