CA1067411A - Hair bleaching oxidizing agent with cross linked interpolymer - Google Patents

Abstract

ABSTRACT

A hair bleaching powder for admixture with an aqueous medium such as water or aqueous hydrogen peroxide containing as essential components a hair-bleaching oxidizing agent such as peroxygen compound and, as a thickening agent, a salt of a cross-linked interpolymer of a mixture containing a polymerizable monoolefinically unsaturated carboxylic acid and a polyalkenyl polyether of a polyol containing at least 4 carbon atoms to which are attached at least 3 hydroxyl groups; the paste resulting from the admixture of such powder with an aqueous medium; methods of making and using such compositions for bleaching hair.

Description

This invention relates to hair bleaching ccmpositions, and more particularly to an ~proved powder for admixture with an aqueous medium to form a paste (including gel, cream, foam, etc.) for b1eachlr.~ (includlng lightening to any desired degree) human hair, to the paste resulting from such admixture, and to methods of making and using such composltions for bleaching human hair.
Dry bleach powders intended for admixture with water or other aqueous media including aqueous solutions of hydrogen peroxicle to form pastes for bleaching human hair, and the use of such pastes for overall or localized bleaching o~ hair as in streaking, frosting and highlighting, are well known and disclosed in the prior art. Further, it is known to include in such powders and/or pastes a thickening agent for the purpose of providing the paste wi~h the desired viscosity. As representative of such previously employed thickening agents, there may be mentioned natural gums, colloidal clay, cellulose, starch, alkali metal silicates, magnesium carbonate and/or oxide, ~atty alcohols, fatty acids and their salts (soaps), lanolin and derivatives thereof, and carboxymethyl cellulose (CMC), and the like.
Such previously known powders and pastes have however, been subject to a number of disadvantages. For example, it is often found very difficult and time-consum~lg to thoroughly and homogeneously mix the powder with the ~i 741~l aqueous medium to rorm a smooth paste because of the generally :Low wetting capacity of the powder.
On the other hand, quite often, a thickener which is so readily soluble as to promote rapid mixing, dissolution, and thickening is not sufficiently stable in the resulting paste to provlde thickening over the entire duration of the hair bleaching treatment.
Other disadvantages often reside in the incanpatibility, instability, reactivity, water dispersibility, hygroscopicity, and/or low melting or softening point o~ some of the thickening agents previously employed in formulating such powders.
Another disadvantage often attributable to the pastes obtained from such powders is a tendency to decompose and/or foam and/or release oxygen and/or dry out on the hair too rapidly, i.e. in about 15 minutes or less.
Adequate bleaching generally requires contact of the hair with the oxygen-releasing agent in moist condition for periods approximating 45 minutes or longer.
And still another common disadvantage of the previously employed pastes obtained from such powders is the tendency of the paste and/or components thereof to migrate, spread, or leach away from the situs of applicatlon on the hair during the bleaching process. This is of course particularly ob~ectionable when an isolated or restricted area of the hair is being bleached as in frosting, streaking, hi~hlighting, hair root bleaching ad~acent to the skin or scalp, etc.
It is an ob~ect of this invention to provide a hair bleach powder ~5 which will not be subJect to one or more of the above disadvantages.
Another ob~ect of the invention is the provision of such a powder which is stable in storage over relatively extended periods.
Still another ob~ect of the invention is the provision of such a powder which relatively easily and rapidly admixes with and/or disperses in an aqueous medium, especially an aqueous solution of hydrogen peroxide, '74~

to yield a smooth, homogeneous paste.
Yet another ob~ect o~ the invention is the provision of such a powder which ls capable Or yielding an aqueous hair bleach paste which is relatively stable and/or is of relatively increased resistance to drying out and/or migrating when in situ on the hair.
Further ob~ects of the invention are the provislons of aqueous pastes using such powders, and of methods for ~making and using such composltions for bleaching hair.
Other objects and advantages will ~ppear as the description proceeds.
The attainment of one or more of the above objects is made possible by this invention which includes the provision of a powder for admixture ~ith an aqueous m~dium to form a paste for bleaching human hair, said powder containing as essential components and in solid, particulate fo~m, a hair-bleach~ng oxldizing agent and, as a thickening agent, about 0.1 to about 10% of a monovalent alkali metal, ammonium or amine salt of a water insoluble, highly water swellable cross-linked interpolymer of a monomerlc mixture containing as essential ingredients (1) at least about 40% of a monamerlc, polymerizable monoolefinically unsaturated lower allphatic carboxyllc acid, (2) fron 0 to about 60% of a different olefinically unsatur~ted monomer copolymerlzable with said unsaturated acid, and (3) fram about 0.1 to about 10~ of a polyether of a polyol containing a~ least 4 carb~n atoms to which are attached at least 3 hydroxyl groups, the hydroxyl grouPs of said polyol which are modifled being etherlfied with alkenyl grouPs, said polyether containing an average of at least two aIkenyl groups per molecule.
The above-defined cross-linked interpolymers are hereinafter referred to as "Carbomers" or ~arbomer polymers." The materials, conditions and methods employed ~or their production and neutralization 2re well known ~nd fully descr~bed in U.S. Patent 2,798,053. Carbomer pol~mers ~0t~'7411 and their salts operative herein are ornmercially available, for example those marketed under the Carbopol tradenark (B. ~. Goodrich) such as Carbopols 934,940 and 941.
Monomeric, polymerizable monoolefinically unsaturated lower aliphatic (e.g. less than about 8 carbon atoms) carboxylic acids (ingredient (1) ) operative in making these ¢arbomers are amply illustrated in the portions from column 2, line 20 to column 3, line 45 of said patent.
Those preferred are of the alpha-beta unsaturated type, especially acrylic acid. The polyol polyalkenyl polyethers (ingredient (3) ) operative in making these Carbomers, and methods for their production, are amply illustrated in the portions from column 3, line 46 to column 4, line 44, and Example 1 of said patent. The preferred polyols are those selected from the group consisting of oligosaccharides, reduced derivatives thereof in which the carbonyl group is converted to an alcohol group, and pentaerythritol, especially sucrose. The preferred alkenyl group is allyl, and the number thereof in the polyether is preferably about 5.0 to about 6.o8.
Other different olefinically unsaturated monomers (ingredient (2) ) copolymerizable with said unsaturated acid and which are operative in making these Carbomers are amply illustrated in the portions from column 5, line 25 to column 6, line 12.
Said monomeric mixture is polyrnerized in known manner, as illustrated in the portions from lines 13 to 57 in colu~n 6, and the examples of said patent, preferably in an inert diluent and in the presence of a free-radical catalyst. For high water swellable, water sensitive properties, it is preferred to employ an interpolymer of a monomeric mixture consisting essentially of about 96 to 99.9% of ingredient (1), preferably acrylic acid, and about 0.1 to about 4.0% more preferably about 0.20 to about 2.5%
especially about 1% of ingredient (3), preferably a polyallyl ether of sucrose containing an average of about 5.0 to 6.08, especially about 5.6 to about 5.8, allyl groups per sucrose molecule, and to form the corresponding iVf~74~
monovalent alkall metal (preferably sodium), ammonium, or amlne (having no more than 1 prinEry or secondary amino group, mono--, di-, or trlethanolamine~
salt of the interpolymer by neutralization as disc:Losed for example in column 7, lines 4-17 of said patent, preferably to the extent of about 50 to 90% especially about 75% neutralization.
These Carbomer polymers, employed in the powders of this invention in an effective thickening amount, generally about 0.1 to about 10%, preferably about 0.5 to about 5.0%, especially about 1.0 to about 3.0%, of the po~der, generally have a molecular weight in the range of about 200,000 to 2,000,000, especially about 1,000,000, relatively highly viscous aqueous dispersions being produced therewith.
The solid, particulate, hair bleaching oxidizing component of the powders of this invention is preferably water soluble and may consist of any of the known oxygen-releasing oxidlzing hair bleaching compounds or any mixtures thereof. Preferably, this oxidlzing agent comprises at least one per compound selected from the group consisting of urea peroxide, guanidine alkaline earth metal peroxide, melamine peroxide, and the alkali metal~ ammonium and amine peroxides,peroxysulfates (mono- and di-), peroxyphosphates (mono~ and di-), perborates, percarbonates, carbonate peroxides, and persilicates, preferably the sodiwn, potassium and/or ammonium sa].ts. When employed as the sole oxidizing component in the resulting paste, as when the powder is admixed with water or other non-oxidizing aqueous medium, this oxidizing component may comprise about 90 to 99.9% of the powder, although ranges of about 30 to about 90%
are preferred to allow for the inclusion of the known additives such as acti~ators, alkalizers, fillers, anti-caking agents, hair conditioners, sur~ace active wetting, dispersing and emulsifying agents, bu~ers, perfumes, dyes, and sequestering agents.
When the powder is intended for use as a booster for admixture wlth an aqueous solution of hydrogen peroxide, said oxidizing component preferably comprlses about 30 to about 60% of the powder, and in turn about 30 to 60%
of the oxidizing component is preferably employed in the form of ammonium ;741~

salts to provide ~nonia as an activator for the release of oxygen from the hydrogen peroxide.
The approximately 70% to 40% remainder of the oxidizing agent, other thc~n the aEorementioned ammoni~ per compounds are preferably alkali metal per compounds, especially sodium and potassium per compounds and mixtures thereof, preferably in proportions of about 1:1. The mixture of per compounds preferably employed as the oxidizing agent are preferably salts of the same per compound, especially the peroxysulfates.
As stated above, the powder of the present invention preferably contains known additives and may even contain other known thickening agents. An optional but particularly desirable additive is an alkali metal, preferably sodium, metasilicate, employed in proportions of about 10 to about 35% of the powder, and providing combined functions of alkalizer, thickener, diluent~ and as an assis~ant in releasing activating ammonia from the aforementioned ammonium per compounds, for which purpose it is generally employed in weight proportions relative to such compounds, e.g. ammonium peroxysulfate, of from about 0.5:1 to 1:1. This metasilicate usually constitutes about 20 to 25% of the powders of this invention.
These powders also preferably contain about 10 to 30%, preferably about 20%, of other known additi~es or diluents. For example, the use of about 5 to 18~, preferably about 10 to 15%, of one or a mixture of nonionic, amphoteric, and/or preferably anionic surface active agents is highly beneficial in providing improved wetting, dispersing, emulsifying, detersive and/or stabilizing functions. These surface active agents likewise permit quick and thorough removal of the bleach paste from the hair when the desired degree of bleaching is reached. ~5 illustrative of suitablb anionic surface active agents, there may be mentioned the alkali metal (e.g. sodium, potassium) ammonium, and amine ~e.g. mono-, di- or tri-ethanolamine) salts of higher fatty acids such as lauric, myristic, stearic and oleic acids, alkyl aryl sulfonic acids including C10 20 alkyl ~0~'74i~
(e.g. dodecyl~ benzene sulfonic aci~s, C10 25 olefin sulfonic acids, C10 20 paraffin sulfonic acids, higher (C10 20) acyl sarcosinates, taurides and isethionates such as lauroyl and oleoylsarcosLnates and ~sethionates and lauroyl N-methyl tauride, C8 20 alkyl sulfates such as lauryl sulfate, tallow alcohol sulfate and alpha- or omega- methoxyoctRdecyl sulfate, C8 18 alkanoyl (such as coconut oil fatty acid) mono- and diglyceride sulfates and sulfonates, bis-tC5 10 alhyl) sulfosuccinates, sulfate esters of nonionic surfactants, i.e. the reaction products of about 1 to 20 moles of a C2 4 alkylene oxide, preferably ethylene oxide, with 1 mole of a C8 24 reactive hydrogen-containing compound including aliphatic and alicyclic alcohols such as lauryl, tallow, Oxotridecyl, coconu~ oil~
and abietyl alcohols, aliphatic dihydric alcohols such as polyoxy-propylenated ethylene and propylene glycols, diamines, and dithiols, aliphatic and alicylic acids such as stearic acid and abietic acid, aliphatic mercaptans such as dodecyl mercaptan, aliphatic and alicyclic amines such as stearyl amine and rosin amine, aliphatic amides such as hydroxylated aromatie compounds such as stearyl amide, and~allyl phenols ~n~luding nonyl and dinonyl phenol, and the corTesponding phosphates and phosphonates.
Suitable nonionic surface active agents include the above-described nonionic surfactants (precursors of the corresponding sulfate esters~.
A particularly preferred mixture of surface active agents is one containing, approximately by weight of the powder, 6 to 10% of alkali metal C8 16 alkanoyl isethionates, 3 to 7% of alkali metal C12 1~ alkanoates, and 0.5 to 1.5% of alkali metal bis (C6 10 alkyl) sulfosuccinates.
Other desirable additives include about 3 to 10% of an anti-caking agent such as silica, and about 0.5 to 2.5% of a heavy metal se~uestrant such as the alkali metal salts of ethylene diamine tetraacetic acid (EDTA).
If desired, still other additives known in the art may be included in the powders and compositions of this ;nvention. Thus, there may be ad~ed emollient and hair conclitioners such as propylene glycol, glycerine, fatty acids and fatty alcohols, buffers to malntain an alkaline pH such as carbonates, ortho-, meta- and tripolyphosphates, particularly 1:1 mixtures of disodium hydrogen phosphate and trisodi~ phosphate, dessicant-stabilizers such as sodium sulfite, humect:ant-coolants such as urea, drabbing agents such as blue metal complex azo dyes, bleach accelerating, activating, catalytic and/or enhancing agents as disclosed for example in U.S. Patents 2,283,350, 2,955,905, 3,177,148, 3,338,839, 3,816,614, 3,823,231 and 3,836,636, the P-containing hair-protective I0 agents disclosed in U.S. Patents 3,202,579 and 3,542,918, and the like.
The aqueous medium with vhich the pastes of this invention are admixed prior to treatment of hair therewith may be water, optionally containing known additives such as surface active agents, etc., but is preferably an aqueous solution containing about 1.5 to 18%, preferably about 2 to 10~9 and more preferably about 3 to 6% of hydrogen peroxide. This solution may if desired contain the usual stabilizers such as about 0.02 to 1~ of ph~nacetin, acetanilide, p-hydroxy-benzoates, stannic hydroxide, sodium stannate, EDTAa and the like. British Patent 827,331 is of interest in this respect in disclosing aqueous hydrogen peroxide compositions stabilized if desired with phenacetin or salts of EDTA and thickened with salts of interpolymers of the type employed in the powders and compositi~ns of this invention.
In employing the powders of this in~ention, they are thoroughly mixed or pasted with the aqueous medium, desirably containing hydrogen peroxide, i~mediately prior to use for bleaching (including lightening) hair. It will be understood that only enough aqueous medium is employed as will yield a paste, i.e. cream, gel, etc. of suf~icient viscosity to prevent spreading, migration, bleeding, leaching, etc. in situ on the hair. Generally, this involves the use of approximately by weight, 1 to 3, preferably about 2, parts of the aque~ls medium per part of the powder.
The paste generally has an alkaline pH e.g. About 9.5 to 11.5 and pre:~erably about 10 to 11.

~0~i7411 When the paste is intended for application on or in contact with the scalp, as when intended for bleaching hair roots, it may be desirable to thoroughly admix therein a small amount oE a skin protectant or conditioner, for example about 0.25 to 1 part by weight per part of the powder employed. The protectant may be for example a fatty alcohol or fatty acid or any other skin protectant, if desired first dispersed or emulsified in the form of an emollient lotion.
The resulting paste is then simply applied locally or overall on the hair as desired and permitted to remain in situ until the desired degree of bleaching is reached, after which the paste is readily, quickly and thoroughly removed from the hair by washing or rinsing.
The following examples are only illustrative of preerred embodiments of this invention. All amounts and proportions referred to herein arè by weight unless otherwise indicated.

A free-flowing bleach powder is prepared by thoroughly mixing together the following formulation:
Bleach Powder Formulation ~ Parts sodium met~silicate 23.0 ammonium peroxysulfate 24.0 sodium peroxysulfate 15.5 potassium peroxysulfate 15.5 fumed silica 5.0 disodium EDTA 1.5 sodium stearate 5.0 dioctylsodiums~lfosuccinate 0.8 sodium lauroylisethionate 8.2 sodium Carbomer * 1.5 * water soluble sodium salt of a carboxylic interpolymer of a monomeric mixture contaimng about 99% acrylic acid and about 1~ of a polyallyl ether of sucrose analyzed as having an average of about 5.8 allyl groups per sucrose molecule, prepared by the process of Example 2 of U.S. 2,798,053 and 75% neutralized with caustic.

63 parts o~ t~e above powder and 1~0 parts of a 6~ aqueous solution of h~drogen peroxide stabilized with 0.055~ ~henacetin are thoroughly mixed to thick paste form by stirring in a bowl immediately prior to use ~or o.~f-the-scalp bleaching (including lightening) such as ~or ~rosting, streaking, hairpainting~ etc.
The paste is readily washed or rinsed with water from the hair after about 45 minutes when the desired localized degree of bleaching is attained.

Similar results are obtained when the procedure o~ Example 1 is repeated but substituting for the sodium Carbomer an equivalent amount of the corresponding ammonium Carbomer produced by 75~
neutralization o~ the SQme carboxylic interpolymer with an equiva-lent amount of ammonium hydroxide as disclosed for example itl Column 7, lines 4 through 17 o~ U.S. Patent 2,798,053.

Similar results are obtained when the procedure o~ Example 1 is repeated but substituting for the sodium Carbomer an equivalent amount of the corresponding lithium Carbomer produced by 75~
neutralization of the SQme carboxylic interpolymer with an equiva-lent amount of lithium hydroxlde as disclosed for example in Column 7, lines 4 through 17 of U.S. Patent 2,798,053.

A free ~lowing bleach powder is prepared by thoroughly mixing together the following formulation:

Bleach Powder ~ormulation P~rts sodium metasilicate 23.0 ammonium peroxysul~ate 24.0 sodium peroxysulfate 15.2 potass ium pe roxysulfate 15.2 ~umed sillca 4,9 dis~odium EDTA 1.5 sodium stearate 5.0 dioctylsodiumsul~osuccinate o~8 sodium lauroylisethionate 8.0 sodium Carbomer * 2.4 * As in Example 1 7~

63 parts o~ the above powder are thorou~hly mixed with 120 parts oP a stabili~ed 6~ aqueous solution o~ hydrogen peroxide as in Example 1 to form a paste. 25 parts of a lotion containing about 91~ of oleic acid, 4.5~ of 28~ ammonium hydroxide ~aqueous) and 4.5~ o~ ethanol are then added and thoroughly mixed into the paste, all immediately prior to use for on-the-scalp bleaching. The paste is readily washed or rinsed with water ~rom the hair and scalp after about 45 minutes when the desired localized de~ree of bleaching is attained.
EXAMpLE 5 Similar results are obtained when the procedure of Example 4 is repeated but substi~uting for the sodium Carbomer an equiva-lent amount Or the ammonium Carbomer employed in Example 2.

.
Similar results are obtained when the procedure of Example 4 is repeated but substituting for the sodium Carbomer an equiva-lent amount of the lithium Car~omer employed in Example 3 This invention has been disclosed with respect to preferred embodiments, and it will be understood that modifications and variations thereof will become obvious to those skilled in the art and are to be included within the splrit and purview of this application and the scope of the appended cla~ms.

Claims (20)

WHAT IS CLAIMED IS:

1. As a composition of matter, a powder for admixture with an aqueous medium to form a paste for bleaching human hair, said powder containing as essential components and in solid, particulate form, a hair-bleaching oxidizing agent and, as a thickening agent, about 0.1 to about 10% of a monovalent alkali. metal, ammonium or amine salt of a water insoluble, highly water swellable cross-linked interpolymer of a monomeric mixture containing as essential ingredients (1) at least about 40% of a monomeric, polymerizable monoolefinically-unsaturated lower aliphatic carboxylic acid, (2) from 0 to about 60% of a different olefinically unsaturated monomer copolymerizable with said unsaturated acid, and (3) from about 0.1 to about 10% of a polyether of a polyol containing at least 4 carbon atoms to which are attached at least 3 hydroxyl groups, the hydroxyl groups of said polyol which are modified being etherified with alkenyl groups, said polyether containing an average of at least two alkenyl groups per molecule.

2. A composition as defined in claim 1 wherein said carboxylic acid is alpha-beta monoolefinically unsaturated and said polyol is selected from the group consisting of oligosaccharides, reduced derivatives thereof in which the carbonyl group is converted to an alcohol group, and pentaerythritol.

3. A composition as defined in claim 2 wherein said carboxylic acid is acrylic acid and said polyol is sucrose.

4. A composition as defined in claim 3 wherein said monomeric mixture contains about 96 to 99.9% of monomeric acrylic acid and about 0.1 to about 4.0% of a polyallyl ether of sucrose containing an average of about 5.0 to 6.08 groups per molecule.

5. A composition as defined in claim 4 wherein said aqueous medium is an aqueous solution of hydrogen peroxide.

6. A composition as defined in claim 5 wherein said oxidizing agent com-prises at least one per compound selected from the group consisting of urea peroxide, guanidine peroxide, melamine peroxide, and the alkali metal, alkaline earth metal, ammonium, and amine peroxides, peroxysul-fates, perborates, percarbonates, carbonate peroxides, and persilicates.

7. A composition as defined in claim 6 wherein said powder contains about 10 to about 35% of an alkali metal metasilicate.

8. A composition as defined in claim 1 wherein said aqueous medium is an aqueous solution of hydrogen peroxide.

9. A composition as defined in claim 1 wherein said oxidizing agent comprises at least one per compound selected from the group consisting of urea peroxide, guanidine peroxide, melamine peroxide, and the alkali metal, alkaline earth metal, ammonium and amine peroxides, peroxysulfates, per-oxyphosphates, perborates, percarbonates, carbonate peroxides and persilicates.

10. A composition as defined in claim 1 wherein said powder contains about 10 to about 35% of an alkali metal metasilicate.

11. A hair-bleaching paste comprising an admixture of a powder as defined in claim 1 with an aqueous medium.

12. A paste as defined in claim 11 wherein said aqueous medium is an aqueous solution of hydrogen peroxide.

13. A hair bleaching paste comprising an admixture of a powder as defined in claim 7 with an aqueous medium.

14. A paste as defined in claim 13 wherein said aqueous medium is an aqueous solution of hydrogen peroxide.

15. A method of bleaching human hair comprising treating the same with a paste as defined in claim 11.

16. A method of bleaching human hair comprising treating the same with a paste as defined in claim 14.

17. A method comprising admixing a powder as defined in claim 1 with an aqueous medium to form a paste, and applying such paste to human hair for a time sufficient to achieve the desired degree of bleaching thereof.

18. A method is defined in claim 17 wherein said aqueous medium is an aqueous solution of hydrogen peroxide.

19. A method comprising admixing a powder as defined in claim 7 with an aqueous medium to form a paste, and applying such paste to human hair for a time sufficient to achieve the desired degree of bleaching thereof.

20. A method as defined in claim 19 wherein said aqueous medium is an aqueous solution of hydrogen peroxide.