GB2114616A - Hair treatment process and composition - Google Patents

Abstract

A process for waving or straightening hair that leaves the hair in conditioned form which comprises treating the hair with a novel hair waving composition containing a reducing agent and certain cationic polymers followed by treating said hair with a "neutralizing" composition containing an oxidizing agent and an anionic or amphoteric detergent.

Description

SPECIFICATION (54) Hair treatment process and composition This invention relates to compositions for waving or straightening hair, and especially human hair, and to processes for effecting the same. More particularly, it concerns compositions and methods of the aforesaid character which leaves the hair in a conditioned or improved manner.

Hair waving or straightening (also often referred to as "permanent) treatment usually involves the application of an agent for reducing or cleaving the disulfide linkages of keratin in hair (hereinafter referred to as "reducing agent", and compositions containing a reducing agent hereinafter referred to as "reducing" or "waving" "composition" or "lotion"), thereby to permit hair to be shaped without any internal elasticity or other resistance, and the subsequent application of a neutralizing agent which reestablishes the keratin linkages and sets the hair in its new, desired shape. The neutralizing agent is generally an oxidizing solution, such as an aqueous solution of hydrogen peroxide and the like.

Distinguished from the waving and straightening of hair by a reducing lotion, is the so-called relaxing of hair wherein a strong alkali, usually in the form of a paste or cream is employed. The mechanism of the action of the alkali is different from the mechanism of action of the reducing agent in conventional permanent waving and straightening. While in the latter case the disulfide linkages of keratin are cleaved and remain cleaved until restored by the neutralizer, in the caustic alkaline treatment the disulfide linkages of keratin are converted to monosulfide bonds and the following "neutralization" with an acid is merely the conventional neutralization of the residual base with an acid. Hence the terms "waving" and "straightening", as used herein, do not contemplate the relaxation of hair by strong bases.

Waving or straightening of hair with reducing agents such as mercaptans, sulfites or phosphines is almost invariably accompanied by deterioration of tactile properties of hair, increased tangling and difficult combing. This is true for all types of hair and particularly bothersome for hair which, prior to waving, had been exposed to bleaching, colouring or prolonged weathering. The conventional way to ameliorate this situation is to treat the waved hair with conditioning agents such as alkyl-dimethyl benzyl halides, emulsions of mineral oil, lanolin, etc. Conditioning agents of this type are usually incorporated in the neutralizing step of the waving or the straightening process. While these conditioning compounds improve the feel of hair and allow for easier combing, their beneficial effects are only transitory and are entirely lost when the hair is shampooed.

U.S. patent No. 3,912,808 to Sokol discloses a process for waving or straightening hair which involves a waving lotion containing a reducing agent and a polydimethyldiallylammonium chloride, a cationic polymer. The teaching of this patent is employed in a commercial product which was tested and compared in connection with this application. Polydimethyldiallylammonium chloride is not being used in accordance with the present invention.

U.S. patent No. 4,175,572 to Hsiung et al. relates to a caustic alkaline hair relaxer and not to waving or straightening, which, among others, also contains polydimethyldiallylammonium chloride. The polymer can be applied also separately from the alkaline relaxer, before or after its application. It is stated that an acidic shampoo is employed after relaxing and conditioning to remove the excess alkaline solution. The last shampoo step or its composition is not specified further and it is stated not to be a part of the conditioning process. In that sense it can be equated to the commercial product based on the above-mentioned U.S. patent No. 3,912,808 in which a cationic surfactant is employed in the neutralizing composition.In contrast, in addition to not employing polydimethyldiallylammonium chloride, the present invention requires the presence specifically of an anionic surfactant to form the conditioning precipitate in the presence of hair. Furthermore, the present invention is not useful in connection with strong alkali relaxer compositions.

It has now been found that durable conditioning of hair can be obtained in a hair waving or a hair straightening process that is superior in its effects to conventional techniques and persists through repeated shampooing which comprises treating said hair with an aqueous waving composition containing an effective amount of reducing agent and at least one cationic polymer from the following group onamer, QPVAMINE, QPVP and Clairquat-1, all as defined in more detail below, and then treating said hair with an aqueous neutralizing composition containing an oxidizing agent and an anionic surfactant. As a result of the sequence of the initial reducing in the waving (or straightening) and subsequent neturalizing steps and a unique combination of ingredients, a conditioning complex, stable to repeated shampooings, is formed in the hair.

It is accordingly an object of this invention to provide a process for waving or straightening hair which leaves the hair in a conditioned fashion which resists repeated shampooings.

It is also an object of the present invention to provide compositions which are useful in carrying out the aforesaid process.

Other and more detailed objects of this invention will be apparent from the following description and claims.

In the following description and the claims, wherever possible, reference is made to chemicals by their CTFA names as contained in the Cosmetic Ingredient Dictionary of The Cosmetic, Toiletry and Fragrance Association, Inc.

The cationic polymers that are useful for the purpose of the present invention are from a few specific types. Molecular weights are given on a weight average basis. A somewhat less preferred type is polyquaternium-1, a polymeric quaternized dimethylbutenylammonium chloride terminated with quaternized ethanolamine groups, sold by Onyx Chemicals Co. under the name Onamer M (hereinafter referred to as "Onamer"), and said to have the formula:

wherein n is a cardinal number which is proportional to molecular weight and the molecular weight is between 800 and 5,000 suitably between 1,000 and 3,500.

Proceeding to the more preferred cationic polymers, another type that can be employed in the present invention are polymers and copolymers of quaternized polyvinylamine prepared in a manner known per se. These are believed to be constituted from repeating units of the moiety:

where R1, R2, and R3 are either the same or different radicals and represent alkyl group having between 1 and 20 carbon atoms, and X- is a cosmetically acceptable anion such as halide (e.g.

iodide or choride) sulfate or carboxylate and n is a cardinal number that is proportional to molecular weight. The molecular weight is suitably between 3,000 and 150,000. This polymer is referred to hereinafter a "QPVAMINE". By way of example, mention can be made of trimethyl polyvinyl ammonium sulfate which is believed to be constituted of repeating units of

having an average molecular weight of about 50,000.

Another type of useful cationic material is a polymer of quaternized poly-4-vinylpyridine which is prepared in a manner known per se. This can be described by the general formula:

where R is an alkyl radical having between 1 and 20 carbon atoms and X is a cosmetically acceptable anion such as a halide, sulfate or carboxylate. This also will have a molecular weight in the range of from about 5,000 to about 500,000. This polymer is referred to hereinafter as "QPVP".

As an example of the cationic polymer of this type, the following can be mentioned:

polyvinyl methyl pyridinium idodide, e.g. having an average molecular weight of about 50,000.

Another cationic polymer which was found to produce excellent results in accordance with the present invention is poly (methacrylamidopropyltrimethylammonium chloride) which is made by polymerizing in a manner known per se the corresponding monomer sold by Texaco Chemicals under the name MAPTAC. This polymer is said to be constituted of repeating units of the moiety:

where n is a number which is proportional to molecular weight. The molecular weight is advantageously between 5,000 and 500,000. This polymer is hereafter referred to as "Clairquat-l".

As mentioned above, the particular cationic polymers described are contained in the reducing lotion employed in the process. The quantity of cationic polymer that will be present in the reducing lotion can vary somewhat depending on the results that are desired. Ordinarily, this will constitute between about 0.2% to about 10% by weight based on the total weight of the reducing lotion with the optimal range being between about 1 % to about 5% by weight thereof.

No structural or known physico-chemical features of cationic polymers can be used to predict whether a cationic polymer can be used in accordance with the present invention. Accordingly it was found that a number of cationic polymers, when substituted for those disclosed and claimed herein, will produce inadequate durable conditioning of hair. Some of these cationic polymers that were found to work insufficiently, are: quaternized poly-2-vinylpyridine adipic acid/epoxypropyl diethylenetriamine copolymer (sold by Hercules Chemical Co. under the name Delsette 101); adipic acid /dimethylaminohydroxypropyldiethylenetriamine copolymer (sold by Sandoz, Inc.

under the name Cartaretic F-4); poly (N-(3-dimethylamino)propyl)-N'-(3-(ethyleneoxyethylene dimethylamino)propyl) urea dichloride (sold under the name Mirapol Al 5 by Miranol Chemical Co., Inc.); quaternium-23, a quaternary anmmonium polymer formed by the reaction of dimethyl sulfate and a copolymer of vinyl pyrrolidone and dimethylaminoethylmethacrylate (sold by GAF Corporation under the name Gafquat 755N):: quaternium-1 9, a polymer of hydroxyethyl cellulose reacted with epichlorohydrin and then quaternized with trimethylamine (sold by Union Carbide Corp. under the name Polymer JR400); a quaternary ammonium derivative of a hydrolyzed collagen protein (sold by Croda, Inc. under the name of Crotein Q); quaternium-39, a copolymer of acrylamide and beta-methacryloxyethyl trimethyl ammonium methosulfate (sold by Hercules Chemical Co. under the name Reten 205 M); aminoethylacrylate phosphate/acrylate copolymer (sold by National Starch Co. under the name Catrex); and quaternium-41 which is a copolymer of dimethyldiallylammonium chloride with acrylamide (sold by Merck s Co., Inc. under the name Merquat-550).

In addition to the cationic polymer, the waving or reducing lotion employed in this invention can also contain other conventional ingredients commonly employed in such waving lotion.

Thus, the vehicle for the lotion is an aqueous vehicle which has incorporated therein one or more reducing agents. A variety of reducing agents are known in the prior art which are useful in waving or straightening hair. By way of example, we can mention thioglycollic acid, cysteine, thiolactic acid, sodium-, potassium-, and ammonium sulfites and bisulfites, tris(hydroxyethyl phosphine). Although the present invention can be employed with all waving and straightening compositions, in the preferred form of this invention the reducing agents that will be employed are thioglycollic acid and alkali metal salts e.g. sodium salts of sulfurous acids (e.g. sulfites and bisulfites).

The quantity of reducing agent contained in the waving lotion will also vary somewhat depending on the agent selected and the results desired. Usually, however, the waving lotion will contain from about 0.5% to about 20% by weight of reducing agent based on the total weight of the waving lotion. Optimal results are obtained when the reducing agent comprises from about 2% to about 10% by weight based on the total weight of the lotion. The term "effective amount", as used throughout the specification and the claims with respect of any ingredient of the composition, means an amount effective to achieve the intended purpose.

Generally there is no criticality in any given range of concentration and the invention does not reside in any particular concentration, but rather in the components themselves. The amount that is most effective can be determined by routine experimentation.

In addition, the waving lotion can also contain fragrances, alkalizing agents and other conventional waving lotion ingredients. Most often the lotion has pH in the range of from about 5 to about 10.

The second essential component of the present conditioning system are amphoteric or anionic detergents which will constitute part of the neutralizing lotion. There are a number of amphoteric detergents that are suitable for use in the present invention. However, two classes of detergents have been found to be especially effective. The first class can be defined by the formula:

in which R is a long chain fatty radical containing from 10 to 1 8 carbon atoms. A typical example of such a compound or compounds is the case in which R represents coconut fatty radicals. A material of this character is known as amphoteric-2 and is sold under the trade name Miranol C2MSF.

A second variety of amphoteric detergents that is particularly effective for the purposes of the present invention can be defined by the formula: R-NH-CH2-CH2-COOH wherein R is a long chain fatty alkyl group having from 10 to 1 8 carbon atoms. In an example of such a detergent the R in the formula is a mixture of lauryl and myristyl fatty alkyl groups.

This material is known as lauraminopropionic acid and is sold under the trade name Deriphat 170C.

Not all amphoteric surfactants were found to be suitable. None of a number of betaines worked in accordance with the present invention. Since betaines are zwitterionic compounds, it could be expected that some zwitterionic surfactants may not work as well, although we found zwitterionic surfactants that are acceptable. As used throughout the specification and the claims, the term "amphoteric surfactant product" denotes that the amphoteric surfactant will work in accordance with the invention. Whether any amphoteric surfactant is an amphoteric surfactant product can be simply and routinely determined by adding an aqueous solution of the surfactant to an alkaline pH solution of one of the claimed cationic polymers and if a precipitate is formed, then the amphoteric surfactant is an ampohteric surfactant product. Since amphoteric surfactants become anionic above their pKa value, the term "anionic surfactant" as used throughout the specification and the claims encompasses both anionic surfactants and amphoteric surfactant products.

All anionic detergents that were tested have been found useful in this invention; thus, salts of alkyl sulfonates, alkyl sulfates, sulfonated and sulfated alkyl ethers as well as long chain carboxylic acids (where the chain length is at least C,O) exhibit formation of conditioning complexes. By way of specifically illustrating the anionic detergents that are useful herein, the following may be mentioned: sodium lauryl sulfate, sodium lauryl ether sulfate, TEA lauryl sulfate, sodium stearate, etc.

The quantity of amphoteric or anionic detergent which will be contained in the neutralizing lotion of this invention will vary somewhat again depending on the economics and the results sought. However, usually this will be in the range of from about 0.2 to about 50% by weight and ideally, in the range of from about 0.5% to about 20% by weight based on the total weight of the neutralizing lotion.

The neutralizing lotion can also contain other ingredients usually employed in such neutralizing lotions that are utilized in hair waving or hair straightening prodcedures. Again, the vehicle will ordinarily be an aqueous vehicle which will contain an oxidizing agent that will serve to "neutralize" the action of the reducing agent contained in the waving lotion after the latter has been applied to the head. A number of oxidizing agents are known to those skilled in this art which will accomplish this purpose. These include hydrogen peroxide, sodium and potassium bromates, sodium perborate, etc.

The quantity of oxidizing agent that will be contained in the neutralizing lotion can also vary somewhat; again, depending on the agent selected and the results desired. For the most part, this will comprise between about 0.2% to about 20% by weight of the neutralizing lotion based on the total weight of said neutralizing lotion. In a preferred form of the invention, the oxidizing agent will constitute about 1 % to about 10% by weight based on the total weight of the neutralizing lotion.

In addition to the above, among the other ingredients that can be contained in the neutralizing lotion. Mention can be made of such materials as organic and inorganic acids (e.g.

phosphoric, citric acid, etc.). The pH of the neutralizing lotion will usually be in the range of from about 2 to about 10, except when an amphoteric surfactant is employed in which case the pH would be more on the basic side.

The term "anionic surfactant", as used throughout the specification and the claims, includes amphoteric surfactant products when the pH of the neutralizing composition is above the pKa value of the amphoteric surfactant product, since at such basic pH levels the amphoteric has anionic character.

Conveniently the compositions of the present invention can be sold in a package containing two containers, one containing the waving lotion including at least one of the enumerated cationic polymers and the reducing agent, and-the other containing the reducing solution which contains the reducing agent and the anionic surfactant.

The following specific examples are intended to illustrate more fully the nature of the present invention without limiting its scope.

EXAMPLE 1 Waving Lotion-A hair waving lotion was prepared having the following composition: By Wt.

ammonium thioglycollate 7.0 monoethanolamine 3.5 fragrance 0.1 Clairquat-1 3.0 water to 100.0 Neutralizing Lotion-This was prepared having the following composition: By Wt.

amonium lauryl sulfate 3.0 hydrogen peroxide 1.4 phosphoric acid 0.1 water to 100.0 In addition to the above samples, both the waving lotion and the neutralizer have also been prepared without the cationic polymer and the anionic detergent respectively.

Four sets of intact caucasian hair tresses were treated under identical conditions of time and temperature followed by rinsing and neutralization. The tresses were wound on 1/2 inch rods and two of them saturated with the waving lotion containing the polymer while the other two were saturated with the waving lotion without that cationic polymer. All tresses were then wrapped in Saran Wrap and placed for 20 minutes in an oven kept at 35"C. After this time, the waving lotion was rinsed off and the tresses, while still on rods, were treated for 5 minutes with the neutralizing solutions. The neutralizing solution containing ammonium lauryl sulfate was applied to two waved tresses (one waved with and one without the polymer) while the other two were exposed to the neutralizer in which there was no ammonium lauryl sulfate present.

It was found that only in the case of the waved hair tress where the waving solution employed contained the polymer and where the neutralizer contained the anionic detergent, was it soft, lustrous and conditioned. The effect was found to be durable by being resistant to at least four shampoos.

In Example 2 below, the embodiments of the invention are directly compared with the products available now on the market. In one of the products (Product I) a cationic polymer i.e.

a high molecular weight polydimethyldiallyammonium chloride is present in the waving solution and a cationic conditioner is used in the neutralizing step, the product being sold under the trade name Toni Lightwave and made in accordance with U.S. patent No. 3,912,808. The other product, Product II, contains no polymer in the waving lotion but claims that a conditioner is present in the neutralizing solution.

EXAMPLE 2 Waving Lotion-A hair waving lotion was prepared having the following composition: By Wt.

amnioniuni suifite 3.0 sodium sulfite 2.0 onamer 5.0 c,ysteine HCI 0.2 water to 100.0 Neutralizing Lotion-This was prepared having the following composition: By Wt.

sodium bromate 6.0 amonium laureth sulfate 6.0 preservative 0.1 fragrance 0.1 water to 100.0 The procedures utilized for each product are briefly described as follows: Product I Procedure: Clean (shampooed), damp tresses are wound on rods, using end papers. The activator and stabilizer of Product I are poured into the shaping lotion. After shaking well for 30 seconds, the lotion is applied to the pre-wrapped tresses until the hair is well saturated. The tresses are then placed in a 35 oven for 35 minutes. Tresses are rinsed under tap water for 2 minutes. After the rinse, hair is removed from the rods and treated with Product I conditioner (optional step), working it well into the hair. After 1 minute, the hair is throughly rinsed.

Product 11 Procedure Waving lotion applied to clean (shampooed), damp tresses, and wound on rods, using end papers. Hair resaturated with lotion, wrapped in plastic wrap and placed in 35 oven for 1 hour.

Tress then rinsed under tap water for 3 minutes. Excess water blotted with paper towel and tress saturated with neutralizer. After 10 minutes at 35 , tress removed from rod, neutralizer worked through the hair, and hair then rinsed throughly. Hair combed and hung to air dry.

Procedure for Present Invention: The procedure was as that described above in connection with Product II up to after the water rinse but for 2 minutes after 1 hour treatment. After rinse, hair was removed from rod and treated with 1 cc. of the the bromate neutralizer, the latter was worked into a lather and left on hair for 5 minutes, followed by thorough rinsing.

Each of the above procedures was performed on six tresses of both virgin and three-times dyed tresses.

The waved tresses were evaluated for wet and dry combability utilizing the technique for these measurements as described by Garcia and Diaz (J. Soc. Cosmet. Chem. 27, 379, 1976). The test essentially involves passing of hair tress through a comb attached to a strain gauge which in turn is connected to a recording device. Work is expended to accomplish the passage of the hair tress through the comb, and this work, read off the integrator, is the objective measure of combing ease/difficulty. The greater the values, the harder it is to comb the hair and thus the less conditioned the hair is. The data for both virgin and dyed hair tresses are given in Table I.

TABLE I Wet and Dry Combability of Waved Hair Work of Combing (gcm) Virgin Hair Dyed Hair Product Wet Dry Wet Dry Control 337 277 2567 3606 (no waving) Product I 363 225 1979 2392 Product Il 682 273 3060 1392 Present Invention 142 217 260 361 There was no significant change in conditioning ranking of these products after as many as six repeated applications.

Although the invention has been described with reference to specific forms thereof, it will be understood that many changes and modifications may be made without departing from the ambit of this invention.

Claims (7)

1. A process for waving or straightening hair which leaves the hair in a conditioned form which conditioning persists through repeated shampooing, which comprises: (a) treating said hair with an aqueous waving composition containing an effective amount of reducing agent and at least one cationic polymer from the following group: onamer, QPVAM INE, QPVP and Clairquat-1: and then, (b) treating said hair with an aqueous neutralizing composition containing an oxidizing agent and an anionic surfactant.

2. A process according to claim 1 in which the waving composition contains, based on the weight of said waving composition, from about 0.5% to about 20% by weight of said reducing agent and from about 0.2% to about 10% by weight of said cationic polymer, and said nuetralizing composition contains, based on the weight of said neutralizing composition, from about 0.2% to about 20% by weight of oxidizing agent and from about 0.2% to about 50% by weight of said surfactant.

3. A process according to claim 1 or 2 in which: (a) said reducing agent is thioglycollic acid or an alkali metal salt of sulfurous acid; (b) said cationic polymer is Onamer M having a molecular weight between 1,000 and about 3,500; or Clairquat-1 having a molecular weight between about 5,000 and about 500,000; (c) said oxidizing agent is hydrogen peroxide or sodium or potassium bromate; and (d) said detergent is sodium or ammonium lauryl sulfate.

4. An aqueous hair waving composition useful in the waving or straightening of hair containing, based on the weight of the waving composition: (a) from about 0.5% to about 20% by weight of a reducing agent; and (b) from about 0.2% to about 10% by weight of at least one cationic polymer from the following group: onamer, QPVAMINE, QPVP and Clairquat-1.

5. A two part package for use in waving or straightening of hair, said package containing two containers, one of said containers comprising waving lotion which is an aqueous solution of a reducing agent, and at least one cationic polymer of the group onamer, QPVAMINE, QPVP and Clairquat-1, and the other container comprising a neutralizing lotion which is an aqueous solution of a neutralizing agent and an anionic surfactant.

6. A process according to claim 1, substantially as described in the foregoing Examples section.

7. A composition according to claim 6, substantially as described in the foregoing Examples section.