FR2475393A1 - Hair setting process using compsn. contg. guanidine hydroxide - prepd. from guanidine salt and ion exchange resin hydroxide - Google Patents

Abstract

The process comprises contacting the hair in the desired arrangement with an aq. compsn. contg. a prod. prepd. by mixing in aq. medium more than 0.25 mole of at least one soluble guanidine salt and an effective amt. of at least one ion exchange resin in particle and quaternary ammonium hydroside form. The resin is chosen to have an affinity for the guanidine salt anion which is at least equal to the affinity of the resin for the hydroxide ion. After a sufficient contact, the compsn. is removed. In another embodiment the compsn. comprises guanidine hydroxide prepd. as above with at least 1 min. reaction followed by sepn. of the ion exchange resin from the soln. A compsn. for the above comprises guanidine hydroxide and at least one quaternary ammonium ion exchange resin to which is linked, at least in stoichiometric amt. based on the hydroxide, an anion as above. The process is used to frizz, relax or permanent wave the hair. The process enables in situ prepn. of guanidine hydroxide which is relatively unstable forming the carbonate in air; it also avoids disagreeable odours.

Description

 The invention relates to a method and a composition for modifying the texture of the hair so as to promote their waving or decreption. The composition in question comprises, as the main active ingredient, guanidine hydroxide and a resin. ion exchange.

 commercial products which are based on compositions containing thioglycolates, sulphites or hydroxides of an alkali metal such as sodium hydroxide, have been widely used to better permanently stiffen the wavy hair, especially to dechrean the hair frizzy negroes.

Among these products, thioglycolate compositions and sulfite-based compositions that have been widely marketed have been shown to be relatively ineffective because, in many cases, the hair returns at least partially to its original creped form. Although they are very effective in producing the desired control effect, sodium hydroxide compositions are very irritating to both the scalp and the hair; their use has resulted in many cases in irritation and / or burning of the scalp, as well as in a substantial reduction in the resistance of the treated hair and, in some cases, a significant loss of hair.

Various guanidine compounds have been tried in this field in compositions for waving or for stiffening the hair. Among them, guanidine thioglycolate has received the greatest attention from researchers. We can refer for example to: Shansky,
American Perfume and Cosmetics, Volume 78, August, 1963, 32-34; Bogaty et al, American Perfumer and Cosmetics,
Volume 78, November, 1963, pages 45-47; and Shansky, American Perfuser ana Cosmetics, Volume 78, December, 1963, pp. 29-30.

It has been found that various organic bases including guanidine accelerate the effect on the hair of calcium hydroxide suspensions. For example, Barry, "Delipatories"
Cosmetic Science and Technology, Published by Balsam and
Sagarin, 2nd Edition, Volume 2, chapter 18, pages 39, 45,
Wiley Intersoience, New York, 1972 and Barry "Depilatories" Cosmetic Science and Technology, Edited by Sagarin,
First Edition, Chapter 20, pages 461-462, Interscience Publishers, New York, 1957, and the works cited therein.

 The American patent application filed by Mario de la Guardia, under N 805 149, dated June 9, 1977, discloses that guanidine hydroxide is an effective composition for the stiffening or relaxation of human hair, as well as effective composition for their permanent setting. These compositions provide improved retention of hair resistance and a significant reduction in scalp irritation as compared to alkali metal hydroxide hair relaxation compositions. The permanent relaxation effect is as good in general as that obtained with hydroxides of an alkali metal (such as sodium hydroxide).

 U.S. Patent No. 3,157,578 of Nov. 17, 1964 discloses compositions for the permanent waving of human hair based on a solution containing, for example, thioglycolic acid and guanidine carbonate. These compositions are employed in the form of aqueous solutions having a pH of 7 to 9, guanidine serving to replace the ammonia previously used to serve as both a neutralizing agent to reduce placidity and also, in the form of ammonium carbonate, for pH adjustment.

 U.S. Patent No. 3,861,868 of January 21, 1975 mentions, in its column 1, old abandoned applications of guanidine salts for hair dyeing compositions and hair bleaching compositions.

 British Patent No. 1,274,565, issued May 17, 1972, discloses a method for stripping human hair whereby the stiffening of the hair takes place in two distinct stages. In the first stage, a known keratin weakening substance, such as an alkali hydroxide, a sulfite or a bisulfite, or a salt of the mercaptocarboxylic acid, is contacted with the hair. After complete removal of this keratin weakening component, a medium containing a swelling substance is applied to the hair. Such suitable substances include monovalent aliphatic alcohol, aromatic alcohols, aliphatic diols, ethereal alcohols, and the like. alcohols, sulfoxides, sulfones, thiocyanates, thiourea and urea, and their water-soluble derivatives.

US Patent No. 3,865,930 of February 11, 1975 discloses a composition for permanent ripple usable in two stages, a first time during which the SS bonds of the keratin fiber are opened at an alkaline pH with the addition of a reducing agent As a thiol During the second stage, the hair is treated with an oxidizing or neutralizing agent causing the reconstitution of the SS bonds, so as to impose the desired configuration on the hair. This patent relates to a composition usable during the second time mentioned above during which the bonds
This composition is two-component, one being based on sulfite, bisulfite, metabisulfite or water-soluble thiourea, the other component being hydrogen peroxide.

 U.S. Patent Nos. 2,817,342 of December 24, 1957 and 2,840,086 of June 24, 1958, relate to compositions for permanent waving based on sulphite material. Among other described acidic sulfites is an acid solution of guanidine bisulfite obtained by bubbling sulfurous gas into an aqueous solution of guanidine carbonate.

 Japanese Patent 76-9015 discloses treatments for waving or stiffening the hair according to which the hair is treated - first with a weak alkali and then treated with a solution of a salt. chelating metal. Calcium oxide or calcium hydroxide is used as a chelator to prevent mutual interactions of the active ingredients.

 U.S. Patent No. 2,836,543, May 27, 1954 discloses the use of guanidine-as a swelling agent in a hair setting composition. This composition also contains a water-soluble sulfite or a polyfunctional aromatic addition compound such as genetistic acid which acts as an accelerator.

 U.S. Patent No. 3,642,429, February 15, 1972, relates to a composition for hair treatment based on a polycondensate of methylol compounds and a urein compound. The general formula of the resin compounds seems to contain guanidine but it is not named in this patent.

 U.S. Patent No. 3,686,296 relates to depilatories which are molecular complexes of thioglycerol based on nitrogen. The nitrogen base can be, for example, guanidine or guanidine hydrochloride.

 The invention is based on the discovery that compositions effective for the decrepitation or relaxation of human hair, or compositions for the permanent waving of human hair, based on guanidine hydroxide, can be prepared by mixing in an aqueous medium at least one water-soluble guanidine salt and at least one particulate ion exchange resin in hydroxide form, strong base, quaternary ammonium. This resin must have an affinity for the anion of the guanidine salt. which is at least equal to the affinity of the resin for the hydroxyl ion. The composition which contains the ion exchange resin is applied to the hair, left in contact therewith for a duration of action and then removed from the hair. Alternatively, when the ion exchange reaction is substantially complete, this Normally determined by the time when the free of pH is achieved, the aqueous solution of guanidine hydroxide can be separated from the ion exchange resin, applied to the hair, left in contact therewith. during a period of action and then removed from the hair.

The invention also relates to a method for the treatment of hair which results in giving them a desired configuration. The method comprises using an aqueous medium that contains an effective amount for treating guanidine hydroxide hair with at least one particulate ion exchange resin, strong base, quaternary ammonium, to which
is bound, at least in stoichiometric amount, anion on the basis of the amount of guanidine hydroxide, a compound which, when combined with the guanidine ion, produces a water-soluble salt. The resin has an affinity for the anion that is at least as great as for the hydroxyl ion.

 This method can be used for hair treatment; guanidine hydroxide causes the desired treatment. When the hair has been treated for a suitable time, the composition that remains on the hair, and which includes the ion exchange resin when present, can be easily removed. When it comes to a relatively coarse resin, just comb the hair to remove the resin beads and the rest. On the other hand, if the resin is in the finely divided state, washing or the like may be performed to remove the ion exchange resin from the hair.

 Preferably, the treated hair is finished or neutralized while it is sufficiently resistant to the desired configuration. In general, the pR of the hair is reduced to a value which is not greater than about 7 during this operation; preferably, the pH of the hair is reduced to a value of about 5 to 6.5, although higher values may be adopted if desired. Alternatively, the hair can be neutralized with a neutralizing solution such as an acid shampoo. When using such neutralizing solutions, particularly champooings, hair curlers or other means that hold the hair to the desired configuration can be removed or, if As desired, these operations can be performed while hair is held by curlers or the like, as is known in the art. Then the hair can be dried in a conventional manner, using a blowing drying apparatus, or another analog.

According to one embodiment of the invention, the wavy or creped hair is made stiff by bringing it into contact with an amount sufficient to cause them to stiffen the composition according to the invention and the stiffening is carried out at least for a period of time. fraction of the time during which the composition is brought into contact with the hair.On the other hand, the hair folded or corrugated by bringing them into contact with an amount sufficient for their waving and setting is at least a fraction of the time during which the composition is in contact with the hair According to the process of the invention, at least one water-soluble guanidine salt and at least one ion-exchange resin are mixed in an aqueous medium, particles, in the form of hydroquin, strong base, quaternary ammonium, which has an affinity for the anion of the guanidine salt at least equal to the affinity of the resin for the hydroxyl ion. st applied to the hair, left in contact with them for a sufficient time to be effective, then removed from the hair
According to an alternative embodiment of the invention, the aqueous guanidine oxide solution is produced by mixing in an aqueous medium at least one water-soluble guanidine salt at a concentration greater than 0.25 mol. guanidine and an effective amount of at least one ion exchange resin, partiles, hydroxide, strong base, quaternary ammonium. This resin should have an affinity for the anion of the guanidine salt which is at least equal to the affinity of the resin for the hydroxyl ion, and preferably should have a greater affinity for the anion of the guanidine salt. for the hydroxyl ion. The guanidine salt and the ion exchange resin are left in contact in the aqueous medium for at least one minute, preferably at least two minutes to give an aqueous solution of guanidine hydroxide. . The ion exchange resin is separated from the fuanidine hydroxide solution to give a guanidine hydroxide solution substantially free of ion exchange resin. The guanidine hydroxide solution thus produced is suitable for use directly on human hair, preferably after the addition of conventional products, thickeners, emulsifiers, etc.

 The ion exchange resins which are useful for the invention are ion exchange resins, in the form of hydroxide, strong base, quaternary ammonium. These resins must be in hydroxyl form to be used in accordance with the invention. It is preferable for the resin to have maximum basicity and maximum exchange capacity. It must have an exchange capacity of at least - 5 me / g, preferably at least 3 me / g, more preferably at least 3.5 me / g and still more preferably at least 4 me / g. The degree of crosslinking of the resin is not critical to the invention except to the extent that the crosslinking is likely to affect the other characteristics.

Among the commercially available ion exchange resins which can be used for the implementation of the invention include Duolite A-100 D, A-104 and A-102 D, the American Society
Diamond Shamrock Corporation, Amberlite-IRA-400, -IRA402, -IRA-420, and Amberlite CG-400 Type II and Type III, Rohm and Haas, Dowex IxI, 1x2, 1x4, at the particle size of 0.148 to 0.037 mm, from the Dow Chemical Company of the United States. With most of the abovementioned resins, 40 to 50 grams of resin is required to convert the guanidine salt to guanidine hydroxide. however, with resins having even higher exchange capacities, the amount of resin used may naturally be less than that indicated above. Normally, at least 40 grams of the resin should be used. Larger amounts of resins can be employed without any troublesome effect, from a technical point of view, but by substantially increasing the cost of the composition.

The amount of resin employed may be at least that which is required to exchange sufficient anions of the guanidine salt against hydroxyl groups, so that sufficient guanidine hydroxide is obtained to effectively apply the hair treatment as used herein. will explain later.

When it comes to resins that must be removed from the hair treated by washing or by a similar method of removal, it is preferable that the resin is at a particle size less than 0.074 mm
whereas, when the resin is to be removed from the hair by a comb or the like, then it is preferred that it be of a particle size equal to or greater than 0.25-0.35 mm.

 For the resins which are used according to the variant of the invention, in which the resin is separated from the aqueous solution of guanidine hydroxide, it is preferable for the resin to have a particle size which is at least equal and preferably greater than at 0.25 mm. . This rather large size of the resin particles facilitates the separation of this and the aqueous solution of guanidine hydroxide.

 The guanidine salt which is used in accordance with the invention should be soluble in water to such an extent that an aqueous solution of this salt can be prepared at a concentration greater than 025 moles of guanidine. A large number of guanidine salts may be used, but the salt anion and the particular ion exchange resin must be selected so that the affinity of the counterion for the resin is equal to or greater than the affinity of the resin for the hydroxide ion, so that a conversion of a substantial amount of the guanidine salt to hydroxide can occur when the aqueous solution of the guanidine salt is mixed with the ion exchange resin in the form of The most preferred guanidine salt is guanidine sulphate, but other guanidine salts that can be adopted include nitrate, tartrate, oxylate and carbonate. Less preferred, however, can be used guanidine salts including hydrochloride, sulfite, phosphate, fluoride and even, in an implementation that is even less preferable, the laurate. Guanidine acetate can be used and, in general, the guanidine salts of the alkane and alkene carboxylic acids having from 2 to 20 or more carbon atoms can be employed. Among the various organic acids, the bivalent acids are preferred. mented salts above, guanidine bicarbonate, bisulfite or bisulfate and guanidine thioglycolate and guanidine alginate can be used without preference for them. Normally, the ion exchange resin and the guanidine salt are mixed under ambient conditions although higher or lower temperatures may be expected if desired.

However, in general, the reaction temperature will not be less than 1.50 ° C. and not more than 60 ° C., since no advantage is obtained when working outside this temperature gem.

 When the two components have been mixed in an aqueous medium, the resulting solution of guanidine hydroxide must be used within about 48 hours because of the relative instability of the guanidine hydroxide solution when exposed to ambient conditions. . The guanidine hydroxide in the aqueous solution tends to be converted to guanidine carbonate as a result of its exposure to atmospheric carbon dioxide and the guanidine carbonate is inactive as a hair treatment agent according to the present invention.

 The use of higher concentrations of guanidine hydroxide in the composition prepared for hair treatment increases the risk of increased scalp irritation and hair damage. With high concentrations, the duration of treatment can generally be reduced so that, when care can be taken, as may be the case for treatments in beauty salons, high concentrations can be expected. to reduce the duration of exposure.

In general, the amount of guanidine hydroxide in the relaxation composition may vary from about 1% by weight to about 50% by weight based on the total weight of guanidine hydroxide plus water and conventional additives if there is at a, irrespective of the ion exchange resin. Concentrations of less than about 1% by weight are generally too dilute to be effective and guanidine hydroxide concentrations in the solution greater than about 50% by weight exceed the solubility limit. It is highly preferred that the concentration of guanidine hydroxide in the solution be in the range of 2 to 20% by weight based on the total weight of the composition (excluding the ion exchange resin which is present and not soluble) .It is even more appropriate to choose a concentration of guanidine hydroxide in the range of 3 to 105.0, by weight, based on the total weight of the solution, and more preferably, a concentration of guanidine hydroperoxide of between 4 and 7 by weight, based on the total weight of the solution.

Sufficient ion exchange resin should be used so that the exchange capacity of the amount of resin used is sufficient to convert enough of the guanidine salt of the solution to guanidine hydroxide in the concentration ranges mentioned above.
The mixing order of water, guanidine salt, ion exchange resin and any conventional additive is not important. Normally, however, it is simpler to prepare an aqueous solution of the guanidine salt with the other additives it must contain, and then to add this solution to the ion exchange resin. It is preferable that the guanidine salt is in the form of an aqueous solution containing at most 40% by weight of guanidine salt, preferably less than 35% by weight of this salt, and in general at least 1.2% by weight of this same salt . An increase or decrease in the concentration of one component of the composition can be compensated by appropriate adjustment of the concentration of the other ingredient, in the ratio of the two ingredients in the composition. However, the important parameter is the concentration of the resulting guanidine hydroxide in the guanidine hydroxide solution and this concentration must be within the previously specified range. When applied to the hair, the relaxing composition of the invention contains no sulfur-based keratin-breaking agent, and preferably the active components of the composition of the invention do not contain, when it is applied. In contact with the hair, no organic compound containing sulfur can be used thiourea as accelerator but this is not normally necessary and is not preferred, compounds containing sulfur may be in the initial mixture of the salt of guanidine and ion exchange resin, such as for example guanidine sulphate or guanidine sulphite or their bisulfate and bisulfite analogues However, these compounds would not be active ingredients for the treatment of hair itself, and sulphate ions and / or sulfite would be bound to the ion exchange resin to the extent of the exchange capacity thereof and, in this form, they would certainly not be an agent s active in the treatment. So, the composition. and the process of the invention is readily distinguishable from previously known compositions and methods based on thioglycolates or sulfites as active ingredients.

 The composition of the invention based on aqueous guanidine hydroxide solution which is applied to the hair according to the method of the invention must have a relatively high pH. The pH value of the guanidine hydroxide solution is generally greater than 11.8, preferably from about 12.5 to about 13.5, and most preferably about 13.5.

Normally, an excess of ion exchange resin can be used, since an excess of the guanidine salt frequently reduces the pH of the resulting mixture to such an extent that guanidine hydroxide may no longer act effectively to reduce the pH of the resulting mixture. hair treatment.
For the most ion-exchange efficient medium, the molar ratio should theoretically be 1: 1, but this condition is difficult to meet and normally the ion exchange ratio is in the range of 1: 2 - 1: 3 guanidine salt: ion exchange resin.

This ratio can be as large as 1 = 7.5 or even as high as 1 = 10 but in commercial preparations it can be expected that the ratio will be in the preferred range mentioned above.
Conventional additives may be present in the composition of the invention to provide their own functions. For example, the guanidine salt may be included in an aqueous, creamy component which may contain an enulsifier, a thickener, an emollient, and / or a humectant. Preservatives may be added to the medium and accelerators may be present, especially when low concentrations of guanidine hydroxide are expected.

 When conventional additives are added to the aqueous guanidine hydroxide solution, it is preferred that they be added to the guanidine hydroxide solution after separation from the ion exchange resin. In this way, the presence of conventional additives does not interfere with the ion exchange reaction. However, certain additives may be added to the guanidine salt prior to the ion exchange reaction or may be added to the mixture of the guanidine salt and the ion exchange resin during the time the exchange reaction occurs.

 A total mixture of the ingredients of the medium is strongly recommended especially when using a creme or emulsion. The ion exchange reaction between the resin and the guanidine salt generally occurs quite rapidly as soon as the proper mixture is made and normally is substantially complete within a few minutes. In some circumstances the ion exchange reaction is substantially complete in one minute or slightly different and with the preferred composition the exchange reaction is completed in two minutes or a little different time. in some cases additional time may be observed for the exchange reaction to occur and times as long as 5 or even 10 minutes may be required with some variations of the coating including particular ion exchange resins and particular salts of guanidine. The coarse indication of the time required can be obtained by measuring the time for a given composition to reach the pH equilibrium. Such a balance is noticeable when the pH of the medium remains substantially constant for several minutes. The time at which this pH is reached first can be easily determined by the use of a pH electrode and the time it took for this value to be reached can be considered as the time of establishment of the pH balance.

 It is preferable to use a medium that reaches pH balance within one to two minutes after mixing, so that the ion exchange reaction is substantially complete. However, the presence of the resin on the hair at the time of application of the composition allows the exchange reaction to continue on the hair itself so that, in the spirit of the invention, the composition can be brought into contact with the hair before the ion exchange reaction is substantially complete.

 Although creams or emulsions may be used under certain circumstances, with certain guanidine salts, such as guanidine alginate, the salt itself may have sufficient thickening effect for other thickeners or emulsifiers are not necessary.

 The duration of the hair treatment performed in accordance with the invention, with the composition of the invention, is normally in the range of 5 to 45 minutes, this duration starting with the first contact of the composition with the hair . Normally, this treatment time is at least 10 minutes and there is no actual upper limit of how long the composition may remain in contact with the hair but the above-mentioned 45 minute duration is generally the most great that is acceptable to those who undergo the treatment. It is greatly preferable to observe a treatment time which does not exceed about 30 minutes and which is preferably less than about 25 minutes. It is preferable, still more, that the duration of the treatment is of the order 20 minutes or very little different.

 As the above-indicated duration of treatment has elapsed, the remaining composition must be removed from the hair to prevent further reduction in the strength maintained by the treated hair. The largest portion of the guanidine hydroxide and any resin used can be removed from the hair by thorough rinsing.

This rinsing operation may be preceded by a combing operation when relatively large particle ion exchange resins which are in the hair have been used. It is preferred that the rinsing operation be followed by a neutralization operation with any suitable neutralizing agent.

A buffered neutralizing shampoo has been found to be effective, but any conventional neutralizing method or composition well known in the art can be used.

For example, citric acid can be added to a conventional shampoo until the pH of the acidified shampoo is reduced to about 5 to become an effective neutralizing shampoo. Preferably, the hair is neutralized by reducing its pH to a value not greater than about 7 and preferably to about 5 to about 6%. While lower pH values may be retained, it is generally preferable to maintain the pH of the treated hair in a range of about 7 to about 7.

 In general the composition is contacted with the hair at room temperature but the composition could have a temperature of 1.5 to 600C if desired. No advantage is gained when working outside this temperature range.

 Commercially available hair setting compositions are based on ammonium thioglycolate or sodium sulfite and / or ammonium sulfite. These compositions give rise to an indisputably unpleasant odor of mercaptans, ammonia and / or sulfurous gas. In addition to the advantages explained above, another decisive advantage of the invention when used for setting or rippling operations is that it is free of these unpleasant odors.

 We will now give, without limiting intention, the description of several examples of implementation of the invention.

- MPLE 1 -
Duolite At 104, ion exchange resin-benzyltriethylammonium chloride manufactured by
Diamond Shamrock, having a theoretical capacity to cut a salt of 3.5 me / g was placed in a beaker of 1 1 equipped with a magnetic stirrer. Approximately 600 g of resin was washed with 1N hydrochloric acid, collected by filtration, rinsed several times with deionized water and then washed with 1N sodium hydroxide solution for ion conversion. chloride of the resin in hydroxide ions. The contents of the beaker were allowed to settle and the degree of conversion was checked by adding silver nitrate to the settled product (a precipitate indicates that chloride ions are still to be removed from the resin). When the ion exchange reaction was complete, the contents of the beaker were allowed to settle and the resin was washed with deionized water.
A solution of guanidine hydrochloride having a pH of about 7 was formed by dissolving 23.21 grams of guanidine hydrochloride in 500 ml of deionized water. 300 ml of the ion exchange resin prepared above was taken, having a bulk density of 700-750 g per liter, it was placed in a beaker and covered with a solution of guanidine hydrochloride. After stirring for 30 minutes at room temperature (to ensure complete exchange of the ions), the product which has been decanted in the beaker was checked for the presence of chloride ions and the presence of any of the these latter.

 To the contents of the beaker was added 10% by weight as an emulsifier of a cetomacrogol wax and 2.5% by weight as a thickener of cetyl alcohol, after which the contents of the beaker were applied to light brown hair having a structure from medium to fine. Ten hairs were wrapped on a 5 mm diameter glass rod and held on the rod with rubber bands and ribbons. The contents of the beaker were brought into contact with the coiled hair using a spatula. The composition was left in contact with the hair for 15 minutes and then rinsed off with hot tap water for 2 minutes. The treated hair was neutralized to a pH of 6.4 to 6.5, rinsed again with hot tap water and dried for 5 minutes using an air dryer. the hair of the glass stem by cutting them to prevent opening of the loops and left at room temperature for 18 hours after which the diameter of the loops and the length of the hair were measured. The treated hair had a smaller loop diameter and shorter length than control hair that had been treated with thickened deionized water.

- EXEEPIE 2
Guan turkey hydroxide was prepared by following the general procedure of Example 1 by performing all operations under nitrogen blanket to exclude carbon dioxide. A solution containing 5% by weight of guanidine hydroxide was obtained in the beaker. Titration of the contents of the beaker showed that no carbonate was present.

About 25 to 35 medium-textured, black frizzy hair was stiffly attached to a glass stem and then dipped
at room temperature in the beaker which contained the guanidine hydroxide solution and the ion exchange resin. Two tests were carried out with immersion times of 20 and 30 minutes.

Guanidine hydroxide and ion exchange resin were rinsed off the hair with hot tap water for 2 minutes and the rinsed hair was neutralized to pH 6.4 to 6. , 5, rinsed again and blow-dried. After removal of the fixation means, there was a noticeable increase in the stiffening effect obtained in each of the tests compared to a control test in which the hair was immersed in deionized water. EXPRES 3-15 -
These examples relate to the production of guanidine hydroxide by ion exchange with several different salts of guanidine. The ion exchange resin used for these examples was Duolite A-104 having a theoretical exchange capacity of 3, 5 m / g and a useful measured exchange capacity of 3.1 m / g. The
Duolite A-104 had a particle size of 1 mm to 0.29 mm.

In these examples, the guanidine salts listed are used in an amount corresponding to 0.00oc8 mole of guanidine. The appropriate amount of guanidine salt was dissolved in 10 ml of water (with the exception that guanidine laurate used 15 ml of water) and the resulting solution of guanidine salt was added to the solution. Duolite A-104 resin to which 10 ml of water had also been added before adding the guanidine salt solution. The quantity of resin was that which was necessary to produce the equivalent molar ratios indicated. Before pouring the solutions of guanidine salts into the resin, they were titrated to a fold of 8 to give them equal values of the resin. were titrated either with guanidine hydroxide when their pH was below 8, or with an acid corresponding to the anion of guanidine salt when the pH was greater than 8. In this case, only With the exception of guanidine alginate (which gave a gel), the resin-guanidine salt mixture was stirred. The following Table gives the results of the preparation of the guanidine hydroxide compositions according to these examples.

Example Guanidine salt Molar ratio Final pH Time for reaching
equivalent salt: resin measured in the equilibrium
pH (minutes) 3 Sulfate 1: 6.6 13.50 2 4 Carbonate 1: 5.6 12.95 2 Hydrochloride 1: 7.7 13.30 1 6 Nitrate 1: 6.6 13.30 2 7 Tartrate 1: 6.3 13.30 1 8 Sulphite 1: 6.5 13.25 1 9 Laurate 1: 6.6 12.80 8 10 Phosphate 1: 7.6 13.10 3 11 Fluoride 1: 7.5 12 , 95 2 12 Oxalate 1: 6.5 13.30 1 13 Trioglycolate 1: 7.2 12.95 5 14 Acetate 1: 7.2 12.85 2 15 Alginate 1: 6.8 12.58 2
All of the ion exchange products obtained from the above exchange reaction effectively stiffened or relaxed black hair, consistent with the process described in Example 2.

 In the above examples the composition of the invention was brought into contact with the hair by immersion of it in the composition. For the normal application to the users, the composition of the invention can be brought into contact with the hair by various means depending, for example, on the viscosity of the composition. This can be applied using a spatula, poured on hair holding devices, passed on the hair with a sponge, etc.

 The process and the composition of the invention can be used for setting the hair, but the results obtained so far suggest that the most advantageous use of the invention is the stiffening or relaxation of the frizzy hair of the individuals of the hair. Negroid type.

- EXAMPLE 16
Duolite A-104 ion exchange resin-benzyltrimethylammonium chloride- manufactured by Diamond Shamrock, having a theoretical breaking capacity of a salt of 3.5 m.sup.2 / g was placed in a one-liter beaker provided with a magnetic agitator. Approximately 600 g of resin was washed with 1N hydrochloric acid, collected by filtration, rinsed several times with deionized water and then washed with 1 N sodium hydroxide solution for ion conversion. chloride of the resin in hydroxide ions.

The contents of the beaker were allowed to settle and the degree of conversion was checked by adding silver nitrate to the settled product (a precipitate indicates that chloride ions are still to be removed from the resin). When the exchange reaction was complete, the contents of the beaker were allowed to settle and the resin was washed with deionized water.

 A solution of guanidine hydrochloride having a pH of about 7 was formed by dissolving 23.21 g of guanidine hydrochloride in 500 ml of deionized water. Approximately 300 ml of the ion exchange resin prepared above having a bulk density of 720 to 750 g per liter was placed in a beaker and covered with guanidine hydrochloride solution. After stirring for 30 minutes at room temperature, the contents of the beaker were allowed to settle, the decant product having a pE of 12.7 to 12.8. This product was tested for the presence of chloride ions and none of these ions were found.

 To the decant product was added 10% by weight cetomacrogol wax emulsifier and 2.5% by weight cetyl alcohol thickener in an aqueous solution of guanidine hydroxide, and the resulting composition was applied to light brown hair of medium to fine texture. 10 hairs were wound on a glass rod 5 mm in diameter and retained on this rod with a ribbon and rubber bands. The composition was applied using a spatula with coiled hair. It was left in contact with them for 15 minutes and then was rinsed out with hot tap water for 2 minutes. The treated hair was neutralized to a 6E4 to 6X fold. , 5, rinsed again with hot tap water and dried for 5 minutes with a blower. The hair was removed from the glass stem by cutting to prevent opening of the loops and left in the ambient conditions for 18 hours after which the loop diameter and the hair length were measured. had a smaller loop diameter and shorter length than control hair that had been treated with thickened deionized water.

- EXAMPLE 17
Guanidine hydroxide was prepared by following the general procedure described in Example 16 to obtain an aqueous solution containing 5% by weight of guanidine hydroxide.
Twenty to twenty-five medium-textured frizzy hairs were fixed to the elongate state on a glass rod and then immersed in a beaker containing the guanidine hydroxide solution at room temperature. parts Two tests were performed with immersion times of 20 and 30 minutes. The hair was rinsed with hot tap water for 2 minutes to remove the guanidine hydroxide and then neutralized to pH 6.4 to 6.5, rinsed again and After removal of the fixation means, a significant increase in the stiffening effect was obtained during each of the tests compared to a control test in which the hair was immersed. in deionized water.

- EXAMPLES 18 TO 30
These examples relate to the preparation of guanidine hydroxide by ion exchange with several different salts of guanidine. The ion exchange resin used for these examples was Duolite
A-104 having a theoretical exchange capacity of 3.5 m 2 / g and a real exchange capacity measured of 3.1 m 2 / g. The
Duolite A-104 had a particle size of 0.350 mm.

In these examples, the guanidine salts listed below were used in an amount corresponding to 0.00348 moles of guanidine. The appropriate amount of the guanidine salt was dissolved in 10 ml of water. the exception of guanidine laurate for which 15 ml of water was used) and the resulting solution of the guanidine salt was added to the Duolite A-104 resin, to which was also added 10 ml of water before adding of the guanidine salt solution. The amount of resin used was that which was necessary to provide the indicated equivalent molar ratios. Before adding the solutions of the guanidine salt to its resin were titrated to a fold of 8 so that the starting pH values were equal. The resins were titled with either guanidine hydroxide when their pH was lower at 8 or with the acid corresponding to the anion of the guanidine salt when the pH was greater than 8. In each case, with the exception of that of the sodium alginate (which gave a gel) the resin mixture The guanidine salt was stirred.

 The following table gives the results obtained by the preparation of guanidine hydroxide solutions according to these examples.

Example Guanidine salt Mole ratio equivalent final pH Time to reach
salt / resin measured pH balance
(minutes) 18 Sulfates 1: 6.6 13.50 2 19 Carbonate 1: 5.6 12.95 2 Hydrochloride 1: 7.7 13.30 1 21 Nitrate 1: 6.6 13.30 2 22 Tartrate 1 : 6.3 13.30 1 23 Sulphite 1: 6.5 13.25 1 24 Laurate 1: 6.6 12.80 8 25 Phosphate 1: 7.6 13.10 3 26 Fluoride 1: 7.5 12, 95 2 27 Oxalate 1: 6.5 13.30 1 28 Thioglycolate 1: 7.2 12.95 5 29 Acetate 1: 7.2 12.85 2 30 Alginate 1: 6.8 12.58 2
All guanidine hydroxide solutions obtained by the above ion exchange reactions were found to be effective in producing the stiffening or relaxation of black frizzy hair in accordance with the procedure of Example 17.

Claims (24)

 1) A method of treating the hair to give them and to keep them in a desired configuration, according to which the hair is brought into contact while they are at the desired configuration with an effective amount of an aqueous composition, characterized in that this composition contains the product which is prepared by mixing in an aqueous medium at least one water-soluble guanidine salt in solution in this aqueous medium in an amount greater than 0.25 moles of guanidine and an effective amount of at least one particulate ion exchange resin in the form of hydroxide, strong base, quaternary ammonium, this resin being chosen to have an affinity with the anion of the guanidine salt which is at least equal to the affinity of the resin for the hydroxyl ion, this composition is then removed from the hair after a sufficient duration of contact.  2) Process according to claim 1 characterized in that an ion exchange resin is used in finely divided form.  3) Process according to claim 2 characterized in that a resin is used having a size not less than 0.037 min.  4) Process according to claim 1 characterized in that a resin having a salt breaking capacity of at least 3.0 m / g is used.  5) Process according to claim 1 characterized in that a resin having a salt-cutting capacity of at least 3.5 m 2 / g is used.  6) Method according to claim 5 characterized in that at least 40 g of resin for the treatment of an adult hair.  7) Method according to claim 6 characterized in that one uses at least 50 grams of resin for the treatment of the hair of an adult.  8) Process according to claim 1, characterized in that the guanidine salt is selected from the group comprising: guanidine sulphate, guanidine hydrochloride, guanidine nitrate, guanidine tartrate, guanidine sulphite and guanidine iloxalate.  9) Process according to claim 1, characterized in that the guanidine salt and the ion exchange resin are mixed together at a temperature of between approximately 50 ° C. and approximately 950 ° C.  10) A composition for the treatment of hair in order to give them and to keep them a desired configuration, intended to be brought into contact with the hair to be treated, characterized in that this composition comprises an aqueous medium containing an effective amount for the treatment of guanidine hydroxide and at least one particulate ion exchange resin, strong base, quaternary ammonium, to which at least a stoichiometric amount is attached, based on the amount of guanidine hydroxide, an anion which when combined with the guanidine ion produces a water-soluble salt, which resin has an affinity for said anion which is at least as great as its affinity for the hydroxyl ion.  11) Composition according to claim 10 characterized in that the resin has a size that is not less than 0.037 mm.  12) Composition according to claim 10 characterized in that the anion is selected from the group comprising the following: sulfate, nitrate, tartrate, oxolate, hydrochloride, sulfite.  13) A method according to claim 1 characterized in that the salt selects guanidine dance group comprising the following salts: sulfate, carbonate, hydrochloride, nitrate, sulfite, phosphate, fluoride, ocalate, thioglycolate, alginate and acid salts carboxylic acids of alkane and alkene carboxylic acids having from 2 up to about 20 carbon atoms.  14) A method for treating the hair to give it and to maintain a desired configuration in which it is brought into contact for an effective period with an effective amount of an aqueous composition which is then removed hair, characterized in that that this composition comprises guanidine hydroxide as the main active ingredient which is thus prepared: a) at least one water-soluble guanidine salt is mixed in an aqueous medium at a concentration greater than 0.25 mole of guanidine; and a sufficient amount of at least one hydroxide, granular, strong base, quaternary ammonium ion exchange resin having an affinity for the anion of the guanidine salt which is at least equal to its affinity for the hydroxide ion ,  b) allowing the guanidine salt and the resin in contact in this aqueous medium for at least 1 minute to obtain an aqueous solution of guanidine hydroxide,  c) separating the ion exchange resin from the guanidine hydroxide solution to obtain a guanidine hydroxide solution substantially free of ion exchange resin.  15) Process according to Claim 14, characterized in that the guanidine salt is selected from the group comprising the following guanidine salts: sulphate, carbonate, hydrochloride, nitrate, sulphite, phos phate, fluoride, oxalate, thioglycolate, alginate and the carboxylic acid salts of guanidine carboxylic acids alkane and awl having from 2 to about 20 carbon atoms.  16) Method according to claim 14, characterized in that the hair is put in the state of stiffening during their treatment with the composition.  17) The method of claim 16 characterized in that using an ion exchange resin having a size of 0.25 mm or more.  18) Process according to claim 17 characterized in that a resin having a salt breaking capacity of at least 3 m / g is used.  19) The method of claim 17 characterized in that a resin having a salt breaking capacity of at least 3.5 me / g is used.  20) Method according to claim 18, characterized in that at least 40 grams of resin is used to treat the hair of an adult.  21) Method according to claim 20, characterized in that at least 50 grams of resin is used to treat the hair of an adult.  22) Process according to claim 20, characterized in that the guandine salt is selected from the group comprising the following guanidine salts: sulfate, hydrochloride, nitrate, tartrate, sulfite, oxalate.  23. Process according to claim 14, characterized in that the guanidine salt and the ion exchange resin are mixed at a temperature of between approximately 50 and approximately 95 ° C.  240) Method according to claim 14 characterized in that the guanidine salt and the ion exchange resin are left in contact in the aqueous medium for at least 2 minutes.