CA1111769A - Thioglycolic acid, ammonia and carbonate for permanent waving - Google Patents

Abstract

Title : PERMANENT WAVING COMPOSITIONS AND METHOD

ABSTRACT
The waving composition of this invention com-prises about 0.03 to about 0.06 mole of thioglycolic acid, about 0.06 to about 0.12 mole of total ammonia, about 0.01 to about 0.06 mole of free ammonia and about 0.01 to about 0.06 mole of a carbonate per 100 ml of the composition and has a pH of about 7.4 to about 8.0 at 25°C.
The method of this invention comprises applying the permanent waving composition to the hair at room temperature before, during and/or after winding the hair, treating the hair for about 5 to about 30 minutes in an atmosphere having a temperature of about 40 to about 60°C
and over-saturated with moisture, and hardening the hair by oxidation.
This invention gives uniform wavings without causing over-waving and damage to the hair and skin.

Description

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PERMANENT WAVING COMPOSITIONS AND METHOD

This invention relates to permaner1t waving compositions and method, and more particularly to com-positions and method for tepid permanent wavlng.
The main method of permanent waving has been so~called "cold waving'~ which uses a waving composition containing a reducing agent such as alkaline thioglycolic acid and which is most distlnctly featured by the use of the waving composition at room temperature. To practice this methodg the hair is sectioned and wound on a curler with application o~ the waving composition. The wound hair is then saturated with the composition and held in contact therewith for about`lQ to about 30 minutes.
During this periodg the hair is so~tened with its disul-~lde linkages broken with the reduclng agent and re-arranged by the force externally applied by winding.
The hair is thereafter hardened with another composltion ' containing an oxidizing agent or neutralizer and thereby permanently waved. The cold waving composition, which 19 ~lntended to produce wQv9s at room temperature~ contains the reduclng agent in a high conoentration and has a hlgh alkalinlty and a high pH to permlt the reducing agent to act e~fectively~ Consequently there arises a difference between a section wound at first and another ..
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~ 2 section thereafter wound ln the processing time during which the waving composition ls held in contact wlth the hairg with the possible result that the hair wlll not be uni~ormly waved ln its entirety. Additionally the waving compositiong when allowed to stand for more than a specified time after application9 causes overwaving~
fails to produce uniform waves over the entlre length o~ the hair or causes damage to the hair~ possibly breaking the hairO The hair must therefore be wound quickly by more than one person. The highly alkaline composition is likely to cause ~amage to the hand skin of the hairdresser or to the scalp o~ the customer.
Heat waving is also known by which the hair is treated with a waving composition comprislng an alkali agent such as non-volatile alkanolamine or volatile ammonia and a reducing agent such as thioglycolic acid and is thereafter heated with lnfrared raysg hot steam, hot curler or the like to permanently wave the hair.
This method merely contemplates a reduction in the processing time simply with the application of heat.
Accordingly the alkali agent contained in the composition is ln no way weaker than that contained in the cold waving composition. The heat-waving composition there-fore has dif~iculty ln uniform1y waving the whole hair, is prone to overwaving3 fails to produce uniform waves .
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over the entire length of the hair and causes damage to the hand skin of the hairdresser or to the hair and scalp of the customer. When containing volatile ammonia as an alkali agent9 the composition has another drawback that the ammonia gives off a marked dlsagreeable odor on heating although overwaving is avoidable owing to the volatilization of the ammonia which reduces the alkalinity and pH of the composition.
An ob~ect of this invention is to provide a mild permanent waving composition with whlch the forego-ing drawbacks have been eliminated or substantially overcome and a method of permanent waving with use of the composition.
Another ob~ect of this inventlon is to provide ~5 a composition for and a method of permanently waving the ' hair unlformly in its entirety.
Another obJect of thls lnventlon is to provide a compositlon for and a method of permanently waving the hair substantlally uniformly over the entire length thereof without causing overwav~ng or damage to the hair.
Another ob~ect of this lnventlon is to provide .
~ a composition for and a method of permanent waving : -~ ~ substantially without chapp~ing the hand of the halr-:
~ ~ dresser or causlng damage to the scalp of the customer.
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~ 25 These and other ob~ects of the invention will :

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become apparent from the following description.
'rhe present inventlon provides a permanent wavlng composition comprislng about 0.03 to about 0. o6 mole of thioglycolic acid, about o.o6 to about 0.12 mole of total ammonia9 about 0.01 to about oOo6 mole of free ammonia and about 0.01 to about 0. o6 mole of a carbonate per lO0 ml of the composition and having a pH of about 7.4 to about 8.0 at 25C.
The invention also provides a method of tepid permanent waving comprising the steps of applying the permanent waving composition of this invention to the hair at room temperature beforel during and/or after winding the hairg treating the hair for about 5 to about 30 minu~es in an atmosphere having a temperature of about 40 to about 60C and over-saturated with moIsture and hardenlng the treated halr by oxidation.
In the specification and appended claims, the term "total ammonia" refers to the ammonia contained in any form whatever in the waving composition, and the 20 ~term "free ammonia" refers to the ammonia which is con- ~
` tained in the total ammonia and which can be liberated ¦
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~ on heating,~or the ammonia portion of the compound whIch ~ .
; liberates ammonia on heating, the term usually meaning the ammonIa which is not combined with thIo~lyco1-ic acId.
~urther the term "carbonate'l re~ers to the carbon dioxide ., : ~ :
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Our research has revealed that a waving com-position prepared from an aqueous solution of thioglycolic acid by incorporating specified amounts of ammonia and a carbonate into the solution and ad~usting the resulting mlxture to a specified pH exhibits very unique pH
variations when heated under given conditions. Stated more speci~ically the waving composition remains stable at room temperatureg retaining the specified pH without substantially permitting the escape o~ the carbonate and ammonia components there~rom in the form of a gas.
~hen heated to about llo to about 60C~ howeverg the com-. .
position starts to release carbon dioxide and ammonia :
gas, with carbon dioxide volatilizing at a higher veloclty in the initial stage to result in a higher pH
value. Wlth further heating, volatillzation of ammonia~
~in turn mainly takesplace, conversely reducing the pH~
Thus while not heated, the waving composition of this ¦
invenkion remains very mild wlth its pH maintained at a low~value of about 7.4 to about 8.o and is almost unlikely to chap the hand during wlnding. Unlike con-ventional waving compos~itions adJusted to a high pH
value~ the composltion of this lnvention ha~ little or ~ ~ ; : .
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no ability to form waves at room temperature, so that even when there is a difference between a section of the hair wound at f'irst and another section therea~ter wound in the duration of contact between the composition and the hair9 the hair will not be unevenly waved locally. When the waving composition is heated to about 40 to about 60Cg the volatilization of'carbon dioxide first elevates the pH to a value of at least about 8.2 at which the composition is fully capable of forming waves. After a specified period of time which is usually about 5 to about 30 minutes, preferably about 8 to about 15 minutes, the volatilization of ammonia in turn pre-dominates~ lowering the pH and waving ability as the quantity of alkali reduces. Consequently even lf allowed to stand for more than the specified period of time, the composition will not cause overwaving or damage to the ' hair and scalp. Additionally the proximal portion of A the hair which is positioned outside in a wound state is ;
subjected to the processing heat more intensely than the inside distal end (which is usually easier to wave)~
with the result that a uniform wave is formed over the entire length of the hair.
These outstanding effects of this invention :`
can be'achieved only when the waving compositlons contains the specified quantities of the ingredients ~ .

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, 'g and has a pH of about 7.4 to about 8~o. In fact, the desi.red effects contemplated will not be available if the pH is outslde the speci~ied range or when the ingredients are used in amounts other than those specified aboveg as when an organic amine, ~or example, is slngly used instead of the conjoint use of carbonate and ammoniaa when ammonia is used singly or when less than about 0.01 mole of ~ree ammonia is present in 100 ml of the com-position. :
The waving composition of this invention con-tains thioglycolic acid (HSCH2COOH, molecular weight 92.12) in a concentration o~ about 0.03 to about o~o6 mole tabout 2.8 to about 5.5 w/v %), preferably about 0.04 to about 0.055 mole (about 3.68 to about 5.0 w/v %), .
per 100 ml of the composition. When containing less than 0.03 mole of thioglycolic acid, the.composition 1s likely to have a low waving ability and produce a poor result with a processing time of 5 to 30 minutesO With more than 0.06 mole o~ the acid present~ the composition is liable to cause damage to the hair or flush, swell, itoh or otherwise irritate the scalp.
The waving composition contains as ammonla (NH3, molecular weight 17.03~ about o.o6 to about 0.12 . . mole:~about 1.0 to about 2.0 w/v %) of total ammonia and .
~5 about 0.01 to about 0. o6 mole, preferably about 0.02 to .
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about 0.05 mole (about 0.34 to about o.85 w/v %)~ of free ammonia per 100 ml of the composltion. When more than about 0. o6 mole of free ammonia i5 present, the composition will have an increased pH, exhibiting a waving ability even at room temperature, resulting in the tendency that the hair will be waved unevenly locally and giving off an ammonia odor. With less than about 0.01 mole of free ammonia present~ the composition may still be able to wave damaged hair or easy-to-wave hair but fails to satisfactorily wave the normal hair.
The waving composition contains a carbonate (C02, molecular weight 44.01) in a concentration of about 0.01 ko about 0.06 mole (about ~ to about 2.6 w/~ %), preferably about 0.02 to about 0~05 mole (about 0.88 to about 2.2~w/v ~) per 100 ml of the composition. If the carbonate concentration is less than abouk 0.01 mole, a hlgher pH will result, affording a waving ability even at room temperature and rendering the composition unable to wave the hair uniformly in its entirety. Carbonate concentrations higher than about 0. o6 mole permit escape of carbon dioxide with ease especlally at higher tem- ¦
peratures, posing problems during preservation such as break oP-khe container.
The~waving composition of this invention can be adapte~ to wave the hair suitably as desired by the :. : `

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g cuskomer and in accordance with khe properties of the halr by altering the concentration Or l;he free ammonia, thioglycolic acid or carbonate contained in the composition wikhin the speci~ied range to appropriately adJust khe pH of the composition. For instance, when wavlng the hair which has been impaired by dyeing or which is easy to wave, or when waving the hair moderately, the wavlng composition may be used with its ~ree ammonia concentration reduced to a Iower level so that the pH will not greatly exceed about 8.2 when the composit~on is heated.
The permanent waving composition of this inven-tion may be prepared by adding to purified water a specif~ed amount of thioglycolic acid, ammonia and carbon dioxide as they are. They may be added each in the form of an aqueous solution. For the ease of preparation, howeverg it is desirable that ammonium thioglycolake, ammonium carbonate, ammonium hydrogencarbonate and like salts, which give the above-mentioned components on dis-sociation an~/or on heating, be mixed together in a suitable combination.
In order to impart the desired properties and enhanced usefulness to the wav1ng composition of the invention comprising the foregoing essential components, the composition may further incorporate additives, such as other alkali agenks, emulsi~iers, wetting agents, :

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hair conditioning agents,coloring agents, perfumes and the like, which are usually used in the art. Examples of useful alkali agents are alkanolamines~ basic amino acids, hydroxides of alkali metals, etc. which are used ln quantities which will not fully neutralize thioglycolic acid. Examples of useful emulsifiers are non-ionic surfactants such as polyoxyethylene sorbitan fat~y acid esters and polyoxyethylene alkyl ethers, anionic surfactants such as alkyl sulfates and alkyl phosphates, ampho]ytic sur~ac~ants, ~atty acids, etcO Examples of useful wetting agents are glycols, glycerinsg sorbitol, etc. Examples of useful hair conditionlng agents are alkyl-trimethylammonium chloride, alkyl-pyridinium chloride and like cationic surfactants 3 amino acids, polypeptides, vegetable oils9 lanolin, higher aliphatic alcohols, etc. Other useful additives include isopropanol, ethanol and like solvents, ethylenediaminetetraacetic acid disodium salt and like metal ion sequestering agent, glycyrrhizinate and like anti-inflammatory agents~ sodium alginate, polyvinyl alcohol and like thickener, etc.
The permanent waving composition prepared from the~oregoing ingredients must essentially have a pH of I about 7~4 to about 8.o. With a pH of less than 7.4, the composition will have difflculty in e~hibiting a pH of at least about 8.2 when heated, failing to produce ,.

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satis~actory waves although the result ls dependent on the curler diameter~ heatlng conditions, etc. With a pH somewhat exceeding 8.o, the composition may have some waving ability even at room temperature depending on the processing conditions and will have difficulty in waving the hair uniformly in its entirety~ hence objection~
able.
The hair treated with the waving composition of this invention is thereafter treated with an oxidizing agent, which serves to neutralize an excess of` the waving composition and also to harden the hair softened with the waving composition. The disulfide linkages are made permanent by the hardening step as rearranged in the hair.
The oxidizing agent useful in this invention are not particularly llmited, any of vaPious known oxidizing agent heretofore used in the art is usable. Thus various commercial oxidlzing agents can be used. Examples of useful agents are potassium bromate, sodium bromate and 11ke bromates, sodium perborate and like perborates, hydrogen~peroxide~ urea peroxide and like peroxides, sodium percarbonate, etc. These oxidizing agents are .
used slngly or in admixture. The concentration of the oxidizing agent is not limitative but is variable in .
~accordance with the hardening conditions such as tem-~ 25 ~perature and~ime. Usually the oxidizing agent i used :: :: ;: : ~
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in a concentration of about 3.5 to about 16 w/v %
calculated as sodium bromate. Stated more specifically in connectlon with the hardening conditions~ desirable concentrations o~ the oxidizing agent calculated as sodium bromate are about 4 w/v % for treatment at 50C
for 10 minutes, about ll w/v % for treatment at room tem-perature for 20 minutes and about 12 w/v % for treatment at room temperaturefor 10 minutes. The oxidizing agent :Ls usable conjointly with known additives.
According to this invention, the hair is per-manently waved with the present composition by the ~ollow-ing method. First, the hair is wound on a curler with application of the waving composition at room temperature.
Preferably this step is performed by wetting the hair with a portion of the specified quantity of the waving composition first~ then winding the hair on the curler, and appl~ing the remainder Or the composition to the wound hair immediately thereafter. However, the applica-tion of the waving composition is not limited to a particular method; the whole quantity of the composition is applicable to the hair before, during andior after winding. In any case 9 the waves formed will not differ from section to section since the waving composition of this inventlon has no waving ability at room temperature.
~ ~his ~ellminates the need for quick winding or the :: : : ' . .. : , . - : .
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necessity of more than one person for winding. The amount of the waving composltion to be used is suitably determined in accordance with the pH of the composition, -the type of the hair, etc. Usually the composition is used ln such an amount as to fully saturate the hair.
Any of known curling devices are usable which include3 for example, splral rods, cro~uignol curlers, etc. The curler diameterg one of the factors determining the quality-of wave produced, is suitably selected in accordance with the wave form desired, type of the hairg etc.
The hair wound with application of the waving composition as above is then sub~ected to a reducing process in an atmosphere having a temperature of about 40 to about 60C and over-saturated with moisture~
usually for about 5 to about 30 minutes. Preferably the processing time is 8 to 15 minutes in view of efficiency and waving ability. Temperatures lower than 4QC are very like1y to take a prolon~ged processing time, while temperatures above 60C are liable to damage the hair or produce locally uneven waves. If the humidity is less than over-saturation, the waving composition will partly condense on the surface of the hair, possibly causing - , - ~ damage to the hair. The processing temperature and ~ , ~ ~ 25 humidity may be controlled accurately as desired by the :

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use of any of kno-wn devices, preferable examples of which are disclosed in Published Unexamined ~apanese Patent Applications No.77749/1978~ No.82569/1978, No .82570/1978 and No. 82568/1978, Published Unexamlned Japanese Utility Model Application No.152787/1978, etc.
These devices are adapted for the accurate control of temperature and quantity of moisture with use of a micro-computer.
The hair thus processed by reduction is then hardened by oxidation with an oxidizing agent. The hardening treatment may be conducked at room temperature or under the same temperature and humidity conditlons as employed for the reduction process describedO The oxidizing agent is used in an amount sufficient to . , neutralize the waving composltion and to set the rearranged disulfide linkages permanent. Usually the amount is '~
about 1.2 to about 2 times the quantity o~ the waving ,.
composition ueed. The oxidation treatment is c~nducted usually for about 10 to 20 minutes at room temperature or for about 8 to about 16 minutes at elevated temperature .
and humidityl although the treating time may be variable with the concentration o~ the oxidizing agent~ etc.
; ~ ~ Flnally the hardened hair is released from the curler, rinsed~with water preferably at about 30 to 40C
and dried.

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According to this lnvention, the hair can be unlformly waved in its en-tirety without overwaving or hair breakage or damage. Additionally the hair can be waved uniformly over the entire length from its proximal to distal end. The present composition is usable sub-stantially without chapping ~he hand of the hairdresser, causing damage to the scalp or entailing other problems.
The ~eatures o~ this invention will be described below in greater detail with reference to experiments, comparison experiments, examples and comparison examples.
Fig. 1 shows variations with tlme at 50C in the pH (Curve 1), free alkali concentration (Curve 2) and carbonate concentration (Curve 3) of a waving com-positlon (Formulation 1) according to this invention, Figs. 2 and 3 show variatlons w1th time at 50C in the pH (indicated at 1) and free alkali concen-tration (indicated at 2) of comparison waving compositions (Comparison Formulations 1 and 2~ respectively);
Fig. 4 shows variations with time at 50C in :
the pH (Curve 1), free alkali concentration (Curve 2) and carbonate concentration ~Curve 3) of another wavlng composition (Formulatlon 2).according to this inventlon;
Flgs. 5 a and b each show a tress of halr processed with~the waving composition ~Formulation 1) ;o~ this invention and thereafter treated with a ~nown :
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oxidizing agent to illustrate the inrluence of temperature, E~'ig. 5 a showing the result achieved at 50C, and Fig.5 b the result at 25C;
Fig. 6 showstresses of hair processed with the waving composition (Formulation 1) of this inventlon and therearter treated with the knownoxidlzing agent at 50C to illustrate changes taking place with lapse of time~
Figs. 7 and 8 show tresses of hair processed lU with the comparison waving compositions (Comparison Formulations 1 and 2, respectively) and thereafter treated with the known oxidizing agent to illustrate the influence of temperature, Figs. 7 a and 8 a showing the results achieved at 50C, and Figs. 7 b and 8 b showing the results achieved at 25C;
Figs. 9 and 10 show tresses of hair processed :
with the comparison waving compositions (Comparison ~Formulations 1 and 2, respectively) and thereafter treated with the known oxidizing agent at 50C to illustrate changes taking place with lapse o~ time;
Fig. 11 shows the result of a test conducted on tresses of hair with use of another waving composition, , (Formulation 3) of the invention;
Figs. 12 to 15 show the results of tests con-~: :
~ 25 ducted on tresses with the use of comparison waving com-`:
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posltions (Comparison Formulations 3 to 6); and ~ ig. 16 shows increases in the weight of the hair due to absorption of water to indicate the degree of damage to the hair which varies with the procèssing time.
xperiment 1 A permanent waving composition of the invention is prepared according to Formulation 1 given below.
The composition is heated and checked for pH, free alkali concentration and carbonate concentration.
(1) Preparation of the waving composition Formulation 1 w/v %
Aqueous solution o~ ammonium thloglycolate 10.00 (containing 50% of thioglycolic acid~

Ammonium hydrogencarbonate 3.80 Water-soluble polypeptide 1.00 Water-soluble lanolin 0.40 Ethylenediaminetetraacetic acid 0.10 disodlum salt :
Cetyl alcohol 0.20 Polyoxyethylene sorbitan monooleic acid ester 0.07 (20 EØ) .
Polyoxyethylene cetyl ether (6 EØ) 0O03 ~ ; 25 Stearic acid 0.04 :, .: , :

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.. _ Polyoxyethylene lauryl ether (20 E.O.) 0.10 Puri~ied water q.s. 100 ml pH (at 25C) 7.82

(2) Procedure of the experlment --1. Preparation o~ specimens A glass dish 9 cm in diameter is placed on a hot water bath adjusted to 50C and heated. Accurately 800 ml of the waving composition is placed dropwise on the dlsh, and the dish is removed from the bath upon lapse of a predetermined time. The composition is washed off the dish with 40 ml of purified water~
The resulting mixture is used as a specimen.
2~ Measurement of pH
The specimen is checked for pH wlth use of a glass electrode pH meter. -~

3. Measurement of free alkali Ten ml of lN H~l is added to the specimen to cause the specimen to fully evolve carbon dloxide, and the specimen is therea~ter back-titrated with 0.2N NaOH to the end point of pH 6.5.

4. Measurement of carbonate A 20 ml quan~ity of lN H2S04 is added to the speclmen, and the amount of the resulting carbon .
dioxide is measured by a gas burette.
The results are shown~in Fig. 1, which indicates , :
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that the wavlng composit:lon of Formulatlon 1 ha~ a low pH
while not heated. It is seen that when the composition is heated to 50Cg the pH rises for the first period of about 15 minutes but thereafter lowers.
Comparison Experiment6 1 and 2 Comparison permanent waving compositions are prepared according to Comparison Formulations 1 and 2 given below and are checked for pH and alkalinity at an elevated temperature in the same manner as in Experiment 1. The specimens are titrated with O.lN HCl to the end .
point of pH 6.5 for the determ~nation of free alkali.
Comparison Formulation 1 w/v %
Aqueous solution of ammonium thioglycolate 10.00 (contalning 50% of thioglycolic acid) 28% Ammonia aqueous solution 2.00 Water-soluble polypeptide 1.00 Water-soluble lanolin 0.40 .
: Ekhylenediaminetetraacetic acid 0.10 : 20 disodium salt :
Cetyl:alcohol 0.20 ,. .
Polyoxyethylene sorbitan monooleic acid ester 0.07 : (20 EØ) . ~ : .. -: ; :: : Polyoxyethylene cekyl ether ~6 EØ) 0.03 25 ~ Stearic acid 0.04 .

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Polyoxyethylene lauryl ether (20 EØ) 0.10 Puri.~ied water q.s. 100 ml pH (at 25C) 9.27 Comparison Formulation 2 w/v %
Aqueous solution of monoethanolamine 10.00 thioglycolate (containing 50% of thioglycolic acid) Monoethanolamine 1.40 Water-soluble polypeptide 1.00 Water-soluble lanolin 0.40 Ethylenediaminetetraacetic acid disodium salt 0.10 : Cetyl alcohol 0.20 Polyoxyethylene sorbitan monooleic acid ester 0.07 : 15 (20 E.O.) : Polyoxyethylene cetyl ether (6 E.O.j 0.03 : ~ Stearic acid 0.04 Polyo~yethylene lauryl ether ~20 E.O~) OolO
Purified water q.s. 100 ml 2P : pH (at 25C) 9.20 Flgs. 2 and 3 show the results achieved with the use `of Comparison Formulations 1 and 2.
Fig. 2 indicates t~hat the composition of Com-parison Formula~ion 1 in which ammonia alone in used as an. alkali agent releases ammonia-due to heating~ with a .

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.- 21 -marked reduction in pH, consequently exhibiting little or no waving ability Ll to 5 minutes after the start of heating.
Fig. 3 reveals that the composition of Comparison Formulation 2 in which monoethanolamine alone is ùsed as an alka'Li agent is likely to cause damage to the hair when allowed to stand ~or more than a given period of tirne after application since monoethanolamine does not '' volatilige despite heating~
' Experiment' 2 A permanent waving composition is prepared according to Formulation 2 of this invention given below for processing damaged hair and easy-to-wave hair. The compositlon is checked for pH and alkalinity a~ an elevated temperature in the same manner as in Experiment 1.
~ormulation 2 w/v %
A~ueous solution of ammonium thlo~lycolate 10.0 (containing 50% of thioglycolic acid) Ammonium hydrogencarbonate ~ 2.00 20 Water-soluble p~lypeptide 1.00 Water-soluble~lanolin 0.40 Ethylenediaminetetraacetic acid 0.10 disodium sait -Cetyl alcohol 0.20 25 Polyoxyethylene sorbitan monooleic acid ester 0.07 (20 E. O.) . .

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Polyoxyethylene cetyl ether (6 E.0~) 0.03 Stearic acid -4 Polyoxyethylene lauryl ether (20 EØ) 0.10 Purified water q.s. 100 ml pH (at 25C) The resulks are shown in Fig. 4, which indicates that the composition exhibits similar variations in pH
and alkalinity to the composition of Formulation 1.
Example 1 10. The same permanent waving composition (Forrnula-tion 1) of this invention as used in Experiment 1 and an aqueous solution of oxidizing agent of the formula given below are tested for hair waving ability.
~: ~ Formula w/v %
.
Sodium bromate 5.oo Cetyl trimethyl ammonium saccharinate 0.60 Oleyl alcohol - . 0.60 Coconut oil '1.20 20; Polyoxyethylene lauryl ether (20 EØ) 0.50 : Polyethylene glycol monostearic acid ester 0.80 Purified water -q.s. 100 ml :
(I) Effect of tempera~ure on waving ~ ; :

Two ~resses of normal hair of the same person, . ~25 each we~ghing 2 g and about 18 cm in length, are washed : : :
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-: : . . -76g with a 5.5% aqueous solution of sodium laurylsulfate and spontaneously dried at room temperature to prepare speci~
mens. Each of the spec:lmens is wound on a plastics curler, 10.0 mm in diameter, and 3 ml of the waving com-position (Formulation 1~ of this invention is applied tothe specimen. One of the specimens is then allowed to stand at room temperature (25C) for 10 minutes and rinsed with water. A 3 ml quantity of the aqueous solution of oxidizing agent is applied to the specimen, which is thereafter allowed to stand for 10 m~nutes. The other specimen is allowed to stand for 10 minutes in an atmo-sphere having a temperature of 50C and over-saturated with moisture and rinsed with water. A 3 ml quantity of the aqueous oxidizing solution is then applied to the speoimen, and the specimen is allowed to stand in the same atmosphere for a further lO minutes. The above heatlng and humidifying procedure for the latter specimen - ls performed with use o~ a device (trade mark "SYOSS Hair Controller YH 1000," product of SYOSS CORPORATION, Japan) whlch is adapted to accurately control temperature and .
humidity with use of a microcomputer.

Plg. 5 a shows the result achieved at 50C, .
and Fig. 5 b ~he result at 25C. It is seen that the waving composition of this invention, although having .:
little or no waving ability at 25C, waves the hair .. . . , . ,. . ' : ' , : .-' ' ~ :: -,. . . ~ . . : ....................... .. , ~ . .:
- ~ : . ., , ., , '. ' ' , ' ' ., ;: :. ~ ' . ' ' : ' ' -uniformly from proximal to distal end at 50C.
(II) Effect of heating time on waving Each of five tresses of hair prepared in the same manner as above is wound on a plastics curler, 10.0 rnm in diameter, and 3 ml of the waving composltion (Formulation 1) of this invention is applied to the spec~men. The flve specimens are thereafter allowed to stand in an atmosphere having a temperature of 50C
and over-saturated with moisture for 5, 10, 15, 20 and 30 minutes respectively. The specimens are subsequently rinsed with water9 and 3 ml portions of the~same oxidizing solution as used in (I) are applied to the specimens respectively. Each of the specimens is then allowed to stand in the same atmosphere as above for 10 minutes, removed from the curlerg rinsed with running water thoroughly and dried spontaneously. The-above heating and humidifying procedure is conducted with use of the same device as used ln (I). Fig. 6 shows the results obtained at 5, 10, 15, 20 and 30 minutes as indicated respectively by 1, 2, 3, 4 and 5. It is seen that the hair can be waved satis~actorily from its proximal to distal end in about 10 minutes, with no noticeable changes subsequently observed in the waving process.
It is clear that the-hair is free of over-waving even in 30 minutes.
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Comparison Examples 1 and 2 The same waving compositions as used in Com-parison Experiments 1 and 2 according to Comparison Formulations 1 and 2 (Comparison Examples 1 and 2, res-pectively) are tested for waving abilit;y in the samemanner as in Example 1. The results are as follows.
(I) Effect of temperature on waving Figs. 7 b and 8 b reveal that both Comparison Formulations 1 and 2 afford a waving ability even at room temperature (25~C).
(II) Effect of heating time on waving Fig. 9 shows the results obtained at 5~ 10, 15, 20 and 30 minutes as indicated respectively by 1, 2, 3, 4 and 5. It is observed that Comparison Formulation 1~

: . .
although ~orming a wave in 5 minutes if not satisfactory, subsequently effects little or no~changes in the waving process, consequently producing only a weak wave in 30 minutes. Fig.~10 shows the results obtained at 5, lOg 15, 20 and 30 minutes as indicated respectively by 1, 2, 3, 4 . . .
; 20 and 5. lt is revealed that Comparison Formulation 2 effects waving with increasing tightness with time3 produc-ing a very~strong wave in 20 to 30 minutes wlth à curled-up distal end.
Example~2 :
~ 25~ A waving composition is prepared according to i9 Formulation 3 of this lnvention.
ormulation 3 w/v %
Aqueous solution of ammonium thloglycolate 8.00 (containing 50% thioglycolic acid) Ammonium hydrogencarbonate 3.80 Water-soluble polypeptide1.00 Water-soluble lanolin 0.40 Rthylenediaminetetraacetic acid 0.10 disodium salt Cetyl alcohol 0.20 Polyoxyethylene sorbitan monooleic acid ester 0.07 (20 EØ) Polyoxyethylene cetyl ether (6 EØ)0.03 Stearic acid 0.04 Polyoxyethylene lauryl ether (20 EØ) 0.10 Purified water q.s. 100 ml :
pH (at 25C) 7.85 Thioglycolic acid concentration 0.043 mole/100 ml Free ammonla concentration o.o48 mole/100 ml The above waving composition is tested for I
: waving ability in the same manner as in Example 1, (I) : except that the reducing process is carried out for 12 minutes in an atmospher having a temperature of 50C ~nd :over-saturated ~ith moisture. m e result ls given in - , . : .,: .. . . - . . : -.

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Fig. 11, which shows that the hair has been waved uniformly ~rom its proxlmal end to distal end.
Comparison Examples 3 to 6 Waving compositions according to Comparison Formulations 3 and 4 given below are tested in the same manner as in Example 29 with the results shown in Figs.
12 and 13. Further waving compositions according to Comparison Formulations 5 and 6 given below are tested in the same manner as in Example 2 except that the reduc-lng process is conducted at a temperature of 25C for 10 minutes. Figs. 14 and 15 show the results.
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Fig. 12 shows that the waving composition con~
taining less than 0.03 mole/100 ml of thioglycolic acid produces a wave which is weaker than thak produced in Example 2.
Fig. 13 reveals khat the composition having a free ammonia concentration of less than 0.01 mole/100 ml also forms a wave which is weaker than that obtained ln Example 2.
~hen having a free ammonia concentration of above o.o6 mole/100 ml (Fig. 14)~ or when having a carbonate concentration of less than 0.01 mole/100 ml (Fig. 15)~
the composition has a waving ability even at 25C. Thus when winding takes a prolonged kime, ik is likely that the hair will not be waved uniformly in its entirety or overwaving will result.
Examp~le 3 Degree of damage caused by wavlng to the hair The hair processed with the waving composition of Formulatlon 1 is tested for water absorption to 2Q determine khe degree of damage caused by the composition.
The normal hair flber has a scale-like cuticle surface layer including an epicuticle which is the outermost membrane and has a khickness of about 100 A. The epicutlcle prevents the passage of excessive water~
However when the hair is damaged by chemical treatmenk .

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as with a reducing agent~ oxidizing agent or alkali agent, the epicuticle layer is broken, perm:Ltting the passage of excessive water with ease. Thus the greater the absorp-tion of water, the greater is the degree of damage to S the hair.
(l) Preparation of specimens Tresses of the hair of the same person are washed and dried at room temperature to prepare speclmens in the same manner as in Example l, (I).
(2) Experimental procedure Each of the specimens is wound on a plastics curler, lO.0 mm in diameter, and 3 ml of the waving com-position of Formulation l of the invention is applied.
The specimens are allowed to stand at 50C for 5, ~0, 15, lS 20 and 30 minutes respectively and then rinsed wlth water.
A 3 ml quan~ity of the same aqueous oxidizing solution as used in Example l is applied to each of the specimens.
The specimen is then allowed to stand at 50C ~or lO
minutes, remo~ed ~rom the curler, thoroughly rinsed with 20~ running water and spontaneously dried.
The specimen thus treated is dried to a constant weight in a desiccator containing 60% H2S04, then lmmersed in water for lO minutes and therearter centrifuged. The resulting irlcrease t%) in the weight of the specimen is determined.

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Fig. 16 shows the result (Curve A).
' C'ompari's'o'n Ex'ampl'es' 7'and 8 The same procedure as in Example 3 is repeated except that comparison waving compositions according to Comparison Formulation 1 (Comparison E~ample 7) and Comparison Formulation 2 (Comparison Example 8) are used in place of the waving composition of this invention to test the composition for hair damage in terms of absorp-tion of water.
The results are shown in Fig. 16, in which Curve B represents the result ach'ieved by Comparison Formulation 1~ and Curve C the result by Comparison Formulation 2. Apparently the use o~ the comparison cornpositions has entailed greater increase in the weight of the hair, namely higher degrees of damage, than the composition o~ Example 3. ~; ~
' xamp'l'es 4 and 5~''and Co'mparison Ex'amples 9 and 10 : : : .
Chapping test ~ -~ The~waving compos~ition o~ this invention is'applled to the whole~ hair o~ a person, and the ' hair is wound on curlers, 10.0 mm in dlameter, with the bare hands and then allowed to stand for 10 minutes n~an atmosph;ere having a temperature o;f 50C and over-saturated with moisture. The hair is therea~ter ' ~ treated in the same atmosphere with the same aqueous .

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' ' solution of oxidizing agent as used in Example 1. 'rhe same procedure as above is repeated fo:r four other persons.
Furthermore the same procedure is repeated wlth the waving composition replaced by comparison waving com-positions of Comparison Formulations 1 and 2, f'or fivepersons with each composition. The treatment with each composition for five persons is conducted by the same operator and takes about 8 hours. The operators' hands are checked for the state of the skin, with the results 10 listed in Table 1.
Table 1 ' Fo'rmulat'ion''' ''' ' Re'sult Example 4 Formulatlon 1 A
Example 5 Formulation 2 A
Comp. Ex. 9 Comparison Formulation 1 C
Comp. Ex. 10 Comparison Formulation 2 B
Note: A: No changes.~ ~
B: Finger tips flushed with irritation.
~ C: Finger tips flushed with intense '~ 20 ~ irritation.
' Ex'ample 6 The waving composition of Formulation 1 accord-lng~to the inventlon (80 ml) is~applied~to the normal hair~,~up to abou~ 12 cm in length, of each of three ~persons, and the hair is wound on 70 rods (trade mark : ~ ~

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- .. .. ~ . . - . . :, : , , : -~ : . . . ~.,,. , . : ,, ::, "NEW EVER ROD No.6, 1I product of Yasumoto Kasei Co., Ltd., Japan), 10 mm in diameter and 86 mm In length, over a perlod of about 25 m:inutes. The hair is then allowed to stand in an atmosphere at a temperature of 50C and humidity o~ at least 100% with use of a device ("SYOSS
Hair Controller YH 1000") for accurately controlling temperature and humidity with a microcomputer. The hair is thereafter rinsed with water, and 120 ml of the same aqueous solution of oxidizing agent as used in Example 1 is applied to the hair. The hair is subsequently treated for 10 minutes under the same conditions as above with the use of the same device, then rlnsed with water and dried.
The characteristics of the waves obtained are listed in Table 2.
~x'ample 7 The same procedure as in Example 6 is repeated with the use of the waving composition of Formulation 2 according to the invention. Formulation 2 contains a les~ser amount of alkali and is adapted to produce waves with reduced tightness.
Table 2 shows the characteristics of the waves formed.
' Compa`ri's'on Examples''ll'an~''l2 ~ 25 The~same procedure~as ln Example 6 is repeated : :
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with the use of the compositions of Comparison Formula-tions 1 and 2 (Comparison Examples 11 and 12, respecti~ely).

Table 2 shows the characteristics o~ the waves obtained.

Table 2 Tightness of Uniformity over Uniformity of wave entire hair - whole hair ~ le'ngth ' ''''' ' _ _ Example 6 High Uniform Uniform Example 7 Low Uniform Uniform Comp.Ex. 11 Slightly Uneven 1) Slightly tight uneven Comp.Ex. 12 High Uneven 2~ Uneven 3) 15Note: 1) The distal end only is tightly waved.

2) The distal end is tightly waved or curled up.

3) Sections wound;earlier tend to tightly wa~e.

Table 2 reveals that the use of the compositions ~:
~of the invention (Formulations 1 and 2~ produces waves ~, with the desired tightness and uniformity~
Example 8 Table 3 shows other waving compositions of this i~vention which have substantially the same advantages as Formulations 1, 2 and 3 of the invention.

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Claims (8)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE PROPERTY
OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A permanent waving composition comprising about 0.03 to about 0.06 mole of thioglycolic acid, about 0.06 to about 0.12 mole of total ammonia, about 0.01 to about 0.06 mole of free ammonia and about 0.01 to about 0.06 mole of a carbonate per 100 ml of the composition and having a pH of about 7.4 to about 8.0 at 25°C.

2. A permanent waving composition as defined in claim 1 wherein the thioglycolic acid concentration is about 0.04 to about 0.055 mole per 100 ml of the composition.

3. A permanent waving composition as defined in claim 1 wherein the free ammonia concentration is about 0.02 to about 0.05 mole per 100 ml of the composition.

4. A permanent waving composition as defined in claim 1 wherein the carbonate concentration is about 0.02 to about 0.05 mole per 100 ml of the composition.

5. A method of permanent waving comprising the steps of applying a permanent waving composition to the hair at room temperature before, during and/or after winding the hair, the waving composition comprising about 0.03 to about 0.06 mole of thioglycolic acid, about 0.06 to about 0.12 mole of total ammonia, about 0.01 to about 0.06 mole of free ammonia and about 0.01 to about 0.06 mole of a carbonate per 100 ml of the composition and having a pH of about 7.4 to about 8.0 at 25°C, treating the hair for about 5 to about 30 minutes in an atmosphere having a temperature of about 40 to about 60°C and over-saturated with moisture, and hardening the hair by oxidation.

6. A method of permanent waving as defined in claim 5 wherein the hair is processed with the waving composition for about 8 to about 15 minutes.

7. A method of permanent waving as defined in claim 5 wherein the hair is hardened by oxidation for about 8 to about 16 minutes in the atmosphere.

8. A method of permanent waving as defined in claim 5 wherein the hair is hardened by oxidation at room temperature for about 10 to about 20 minutes.