the composition for treating hair of the present invention either solely contains the thiol compounds or their salts formulated by formula 1 , or contain them together with other reductants . if it contains only the thiol compounds or their salts , then hair cosmetics which are superior to conventional cosmetics in terms of waving effect , odor , hair damage , texture , safety , etc ., are obtained . if it contains other reductants as well , then hair cosmetics which are superior to conventional cosmetics in terms of waving effect and texture , and as good as conventional cosmetics in terms of hair damage and such are obtained . the hair reductants from the present invention are composed of thiol compounds or their salts formulated by formula 1 . while n and m are integers from preferable if n = 2 and m = 2 or 3 . examples of the hair cosmetics of this invention include primary agents for permanent waving , pretreatment agents for hair dyeing , cosmetics for heated - type hair curling , cosmetics for hair softening and cosmetics for frizzy hair . the primary agents for permanent waving can be used as primary agents for the cold two - bath type , heated two bath type and prepared - at - use exoergic type waves , and also as primary agents for curly hair straightening agents . when blending the thiol compounds or their salts formulated by formula 1 into hair cosmetics , the blending ratio can be freely changed according to the target efficacy and effect of the hair cosmetics . for example , when they are blended as primary agents for permanents , 1 . 0 to 50 % ( weight %) is preferable , and 2 . 0 to 20 % ( weight %) is more preferable . when used together with other reductants , while the weight ratio { reductants of formula i or their salts }/{ other reductants } can be any value , the weight ratio { reductants of formula 1 or their salts }/{ other reductants } should preferably be 0 . 05 or more in order to take advantage of combined use , the preferable upper limit is 100 , above which the effect becomes the same as when only the reductants of formula 1 are used . when blending the thiol compounds or their salts formulated by formula 1 into hair cosmetics such as heated - type hair curling agents , cosmetics for hair softening , cosmetics for frizzy hair or pretreatment agents for hair dyeing , it is normally preferable to have a lower blending ratio compared to when they are blended as primary agents for permanents , and more specifically 2 . 0 % ( weight %) or less is preferable . also in this case , when used together with other reductants , the weight ratio { reductants of formula 1 or their salts }/{ other reductants } should preferably be 0 . 05 or more . when blending the thiol compounds formulated in formula 1 into cosmetics , it is normally preferable to have them in salt form as formulated by the following formula 2 , wherein n and m are the same as in the general formula ( 1 ). x -- is the an ion part of an inorganic acid such as hydrochloric acid , sulfuric acid , phosphoricacid or carbonic acid , or of an organic acid such as ethylsulfuric acid , methylsulfuric acid , citric acid , acetic acid , tartaric acid , oxalic acid , lactic acid or acidic aminoacids , as the alkali agent used to make the hair cosmetics , to which the thiol compounds or their salts formulated in formula 1 are blended , have an alkaline ph , various alkali agents can be used . for example , aqueous ammonia , ammoniumcarbonate , ammonium hydrogencarbonate , monoethanolamine , diethanolamine , morpholine , triethanolamine , aminomethylpropanol , aminomethylpropanediol , isopropanolamine , guanidine , guanidine chloride , guanidine carbonate , guanidinesulfate , l - arginine , l - lysine and inorganic alkali agents can be used . the ph of the cosmetics is preferably 3 to 11 , and more preferably 7 . 5 to 10 . in addition to those mentioned above , there are various useful additives which can be blended into hair cosmetics . for example : urea , alkylurea , taurine , hydantoin , hydantoic acid , lithium halogenares , various solvents and polyvalent - ols as effect accelerators ; various anionic , ampholytic , cationic and nonionic surfactants as penetration assistants and wetting accelerators ; various peptides , oligopeptides , polypeptides and proteins , mink oil , lanolin and hydrocarbon oils as hair protectors ; silicone derivatives such as emulsion formulations of silicone and amodimethicone , cation modified silicone , bunte modified silicone , glycol modified silicone and trimethylcyritates of amino modified silicone , as well as various cationic polymers as hair texture improvement agents ; scent agents ; sequestering agents ; coloring agents , etc ., can be blended . in a case of a hair remover : the skin irritation relievers include glycerine , 1 - 3 butyleneglycol , sorbitol , hexyleneglycol , propyleneglycol , dipropyleneglycol , diglycerine and polyglycerine ; the skin emollient agents include various plant oils , animal oils , mineral oils , silicone and various silicone derivatives , higher alcohols , higher fatic acids and emulsifiers . it may contain various water soluble polymers , inorganic polymer perfume agents , sequestering agents , antiseptics and coloring to improve usability . also in a case of a hair dye : the solvents include benzylalcohol , n - methyl pyrolidone , ethylalcohol , isopropylalcohol , n - butylalcohol and phenylethylalcohol ; the acids include organic acids such as citric acid , acetic acid , lactic acid , tartaric acid and acidic amino acids , as well as various inorganic acids ; the acidic dyes include various tar dyes and natural dyes which dissolve in the solvents mentioned above or in water . as far as the type of agent for these cosmetics is concerned , it is obviously possible to choose , according to the intended use , such types as a transparent liquid type , an emulsion / viscous emulsion type , a transparent gel type , a cream type , or a foamy aerosol or spray type . we prepared primary agents for cold two bath type permanents with the compositions shown in table 1 , and evaluated the waving effect , hair damage , texture and odor . a hair bundle ( 12 hairs , 130 mm long ) was uniformly wrapped around a glass rod ( diameter 7 mm ), immersed in the primary agent for permanents for 10 minutes at 30 ° c ., and rinsed for 1 minute . it was then immersed in a secondary permanent agent ( 6 . 0 % nabro3 , phosphate buffer , ph 5 . 5 ) for 10 minutes at 30 ° c ., rinsed , and thus prepared as a hair coil . the hair coil diameter and hair coil length of the hair coil thus prepared were measured . for both hair coil diameter and hair coil length , smaller values indicate a stronger waving effect . permanent treatment , under the same treatment conditions as when the waving effect was measured , was conducted on a hair bundle ( 12 hairs , 60 mm long ), and the hair strength ratio of before and after the permanent treatment was measured . hair strength ratio values closer to 1 . 000 indicate less hair damage . after preparation of the primary agents for permanents they were let stand for a week at room temperature and at 40 ° c ., and then odor was evaluated by smelling ( sense ). evaluation is indicated as follows : the texture after permanent was evaluated by touch ( sense ) after permanent treatment was conducted on 5 female panelers . the permanent treatment conditions were the same as for the waving effect measurement . evaluation is indicated as follows : the results of the above - described evaluations are shown in table 1 and table 2 . in the tables , a value in parentheses () indicates the concentration ( ppm ) of hydrogen sulfide in 5 milliliters of the primary agent for permanents when it is discharged into 100 milliliters air volume . table 1__________________________________________________________________________ example example control controlcomposition ( w %) ( no . 1 ) ( no . 2 ) ( no . 3 ) ( no . 4 ) __________________________________________________________________________reductanths -- ch2ch2 -- nh -- ch2ch2 -- nh3 . cl 10 . 22hs -- ch2ch2 -- nh -- ch2ch2ch2 -- nh3 . cl 11 . 13aqueous ammonium thioglycolate ( 50 %) 12 . 00dl . cysteine . hcl . h . sub . 2 o 11 . 45ethylenediaminetetraacetic acid - 4 sodium 0 . 1 0 . 1 0 . 1 0 . 1polyoxyethylene ( 20 e . o .) cetylether 0 . 1 0 . 1 0 . 1 0 . 1monoethanolamine suitable suitable suitable suitable amount amount amount amountpurified water balance balance balance balancetotal 100 100 100 100__________________________________________________________________________ for each primary agent preparation , the ph at 25 ° c . was 8 . 5 ± 0 . 1 , and the reductant level was 0 . 652n . table 2__________________________________________________________________________ example example control controlevaluation ( item ) ( no . 1 ) ( no . 2 ) ( no . 3 ) ( no . 4 ) __________________________________________________________________________wave effect ( mm ) hair coil 9 . 5 10 . 3 17 . 3 26 . 2 diameter hair coil 19 . 7 23 . 6 40 . 8 55 . 4 lengthhair damage hair strength 0 . 875 0 . 888 0 . 754 0 . 912 ratiotexture after touch ( sense ) ⊚ ⊚ x ◯ permanent very good very good poor goododor of primary let stand for ⊚ ⊚ x δagent for 1 week at room ( o ) ( o ) ( 416 ) ( 73 ) permanents temperature ( smelling : sense ) let stand for ⊚ ⊚ xx xx 1 week ( 0 ) ( 0 ) ( 830 ) ( 1650 ) at 40 ° c . __________________________________________________________________________ the comparison shows that examples no . 1 and no . 2 are superior to controls no . 3 ( containing ammonium thioglycolate ) and no . 4 ( containing cysteine ) in terms of waving effect , texture and odor . it is also shown that they are superior to the control ( no . 3 ) in terms of hair damage , as well . according to the 12 - hour open patch test on 5 panelers , faint red spots were observed on two panelers in control no . 3 , but no faint red spots nor any other irritations were observed on any of the panelers in the examples . we prepared primary agents for cold two bath type permanents with the compositions shown in table 3 , and evaluated the waving effect , hair damage and texture . this embodiment shows examples in which other reductants as well as the thiol compounds formulated in formula 1 contained . the results of the measurements are shown in table 4 . table 3__________________________________________________________________________ example example control controlcomposition ( w %) ( no . 5 ) ( no . 6 ) ( no . 7 ) ( no . 8 ) __________________________________________________________________________reductanths -- ch2ch2 -- nh -- ch2ch2 -- nh3 . cl 2 . 0 2 . 0aqueous ammonium thioglycolate ( 50 %) 10 . 0 14 . 0dl - cysteine 5 . 0 6 . 5ethylenediaminetetraacetic acid - 4 sodium 0 . 1 0 . 1 0 . 1 0 . 1polyoxyethylene ( 20 e . o .) cetylether 0 . 1 0 . 1 0 . 1 0 . 1monoethanolamine suitable suitable suitable suitable amount amount amount amountpurified water balance balance balance balancetotal 100 100 100 100__________________________________________________________________________ for each primary agent preparation , the ph at 25 ° c . was 8 . 5 ± 0 . 1 . reductant : 7 . 0 w / w % table 4__________________________________________________________________________ example example control controlevaluation ( item ) ( no . 5 ) ( no . 6 ) ( no . 7 ) ( no . 8 ) __________________________________________________________________________wave effect ( mm ) hair coil 9 . 8 10 . 9 12 . 8 28 . 4 diameter hair coil 23 . 5 27 . 8 36 . 3 63 . 9 lengthhair damage hair strength 0 . 899 0 . 891 0 . 701 0 . 955 ratiotexture after touch ( sense ) ⊚ ⊚ x ◯ permanent__________________________________________________________________________ the methods for evaluating waving effect and hair damage for all but the hair used were the same as for example 1 . in terms of waving effect and texture after permanent , it is shown that example no . 5 is superior to control no . 7 , and example no . 6 is superior to control no . 8 . in terms of hair damage , example no . 5 is superior to control no . 7 , and both example no . 6 and control no . 8 show good results . we prepared cosmetics for heated - type hair curling with the compositions shown in table 5 , and evaluated the curling effect , hair damage and texture , the results are also shown in table 5 . table 5______________________________________ example controlcomposition ( w %) ( no . 9 ) ( no . 10 ) ______________________________________reductanths -- ch2ch2 -- nh -- ch2ch2 -- nh3 . cl 1 . 0sodium pyrosulfite 4 . 0 4 . 0ethylenediaminetetraacetic acid - 4 sodium 0 . 1 0 . 1polyoxyethylene ( 20 e . o .) cetylether 0 . 1 0 . 1monoethanolamine suitable suitable amount amountpurified water balance balancetotal 100 100evaluation resultscurling effect hair coil diameter 10 . 0 24 . 0 ( mm ) hair coil length 30 . 2 66 . 6hair damage hair strength ratio 0 . 953 0 . 960texture touch ( sense ) ⊚ ⊚ ______________________________________ the curling agents were prepared to have a ph of 8 . 5 at 25 ° c . the evaluation method was almost the same as for examplem 1 , except that the curling agent treatment was conducted for 20 minutes at 40 ° c . it is shown that example no . 9 has a degree of texture and hair damage equivalent to control no . 10 , but that it is superior to control no . 10 in terms of curling effect . we prepared cold two bath type permanent agents with the following compositions : ______________________________________ ( w %) ______________________________________primary agent for permanents1 . hs -- ch2ch2 -- nh -- ch2ch2 -- nh3 . cl 6 . 02 . aqueous ammonium thioglycolate ( 50 %) 2 . 03 . monoethanolamine 1 . 54 . ammonium hydrogen - carbonate 2 . 55 . l - arginine 0 . 56 . amodimethicone emulsion * 2 . 07 . stearyl - trimethyl ammonium chloride 0 . 18 . polyoxyethylene ( 20 e . o .) cetylether 0 . 59 . keratin hydrolysis product ** 1 . 010 . perfume 0 . 111 . ethylenediaminetetraacetic acid 4 - sodium 0 . 112 . purified water 83 . 7secondary agent for permanents1 . sodium bromate 6 . 02 . purified water 94 . 0______________________________________ * toray silicone sm8702c , manufactured by toray dowcorning silicone , ltd . ** promois wkh , manufactured by seiwa supply , ltd . using 80 ml of the primary agent for permanents and 100 ml of the secondary agent for permanents , treatment with conventional methods was performed on women with medium length hair . very resilient waves were obtained without a residual odor after the permanents , and smooth and shiny hair styles resulted . we prepared a hair cosmetic for frizzy hair with the following composition : ______________________________________ ( w %) ______________________________________1 . hs -- ch2ch2 -- nh -- ch2ch2 -- nh3 . cl 2 . 02 . sodium pyrosulfite 5 . 03 . merquat 100 *** 1 . 04 . monoethanolamine suitable amount5 . aqueous ammonia ( guaranteed reagent ) 2 . 06 . cetanol 1 . 07 . stearyl - trimethyl ammonium chloride 0 . 28 . polyoxyethylene ( 20 e . o .) cetylether 0 . 19 . perfume 0 . 110 . purified water balance total 100 . 0 % ( w %) ______________________________________ the ph was adjusted to 8 . 5 using monoethanolamine . *** a cation polymer manufactured by merck , ltd . using 80 ml of this liquid agent , heating with a hair dryer was conducted with a conventional method for 20 minutes at 50 ° c . the rods were then removed after adequate rinsing , resulting in resilient curls with good hair texture . after shampooing in a bath tub , 10 ml of this liquid agent was applied , then rinsed off after letting stand for approximately 5 minutes . after repeating this treatment for approximately a week , the relatively stiff and somewhat frizzy hair of the woman became easier to manage , and soft and flowing . we prepared a pretreatment agent for hair dyeing with the following composition : ______________________________________ ( w %) ______________________________________1 . hs -- ch2ch2 -- nh -- ch2ch2 -- nh3 . cl 1 . 02 . n - acetyl - l - cysteine 1 . 03 . sodium carbonate suitable amount ( ph 8 . 0 ) 4 . polyoxyethylene ( 20 e . o .) cetylether 0 . 15 . purified water balance total 100 . 0 w % ______________________________________ this agent was applied to the approximately 50 % gray hair ( side ) of a male by using absorbent cotton soaked with approximately 5 ml of the agent , and the hair was let stand for 10 minutes . then , after cleaning with a wet towel the area where this agent was applied , a commercial hair dyeing agent was applied , and the hair was let stand for 10 minutes . after rinsing and drying , the gray hair was nicely dyed and substantially less prominent . the effect was found to continue for approximately 2 weeks . ______________________________________1 . hs -- ch2ch2 -- nh -- ch2ch2 -- nh3 . cl 1 . 02 . erythrocin ( red no . 3 ) 0 . 13 . indigo carmine ( blue no . 2 ) 0 . 14 . quinoline yellow ws ( yellow no . 203 ) 0 . 15 . benzyl alcohol 10 . 06 . ethyl alcohol 10 . 07 . citric acid 1 . 08 . xanthenegum 1 . 09 . purified water balance total 100 % ______________________________________ approximately 80 ml of this agent was applied on the entire head of hair of a man with 50 % gray hair . after letting stand for 10 minutes , the agent was thoroughly rinsed off with water . the hair was then washed with normal shampoo , wiped with a towel , and dried with a hair drier . the gray hair became significantly less conspicuous , and the entire head of hair changed to natural looking black hair . the color held for approximately 2 weeks . ______________________________________1 . hs -- ch2ch2 -- nh -- ch2ch2 -- nh3 . cl 1 . 02 . sodium hydroxide appropriate quantity ( ph 10 ) 3 . stearyl alcohol 3 . 04 . cetyl alcohol 3 . 05 . vaseline 15 . 06 . liquid paraffin 10 . 07 . polyoxyethylene ( 50 eo ) oleyl other 4 . 08 . polyoxyethylene ( 8 eo ) oleyl ether 1 . 79 . urea 2 . 010 . perfume appropriate quantity11 . purified water balance total 100 . 0 ( wt %) ______________________________________ approximately 10 g of this product was uniformly applied on a portion ( 10 cm × 4 cm ) of an arm with unwanted hair ( body hair ) and , after letting stand for 5 minutes , the area was thoroughly rinsed with warm water and wiped with a towel to remove excess moisture . the unwanted hair was removed clean . there was no skin irritation nor redness observed during or after use . the composition of the invention for hair reductants can be contained in hair cosmetics . when contained alone , superior results are obtained compared to conventional cosmetics in terms of waving effect , odor , hair damage , texture and safety . when contained together with other reductants , superior results are obtained compared to conventional cosmetics in terms of waving effect and texture , and equivalent results are obtained compared to conventional cosmetics in terms of hair damage and such . when the cosmetics are heated - type hair curling cosmetics , the curling effect is much superior to that of conventional cosmetics while hair damage and texture results are more or less equivalent . when the cosmetics are cosmetics for frizzy hair and cosmetics for hair softening , they are superior to conventional cosmetics in terms of their frizzy hair correction effect and their hair softening effect . when the cosmetics are pretreatment agents for hair dyeing , they are almost equivalent to conventional cosmetics in terms of hair damage and texture , and much improved in terms of their dyeing effect with acidic hair dyeing agents . when the cosmetics are human hair remover they are superior to conventional cosmetics in terms of their odor and safety in hair removing effect .
a composition for treating hair comprised of a thiol compound that is a superior hair reductant and hair cosmetic , especially in terms of waving effect , odor , hair damage , texture and safety and where the thiol compound has the formula hs -- n -- nh --- m - nh2 and the n and the m are integers from 1 to 4 . the composition may include the salts of the compound . the composition is useful for a method of treating hair by applying the composition to the hair ; leaving the composition on the hair for a sufficient period of time , depending on the desired effect ; and then removing the composition . the invention , in particular , relates to hair reductants as well as primary agents for permanent waving , pretreatment agents for hair dyeing , cosmetics for heated hair curling , cosmetics for frizzy hair and cosmetics for human hair removing .