CA1112174A

CA1112174A - 2-acrylamido-2-methylpropane sulfonic acid salt polymer as lubricant in personal care product

Info

Publication number: CA1112174A
Application number: CA289,851A
Authority: CA
Inventors: Larry D. Lundmark; Allan L. Melby; Ho-Ming Chun
Original assignee: Henkel Corp
Current assignee: Henkel Corp
Priority date: 1977-02-16
Filing date: 1977-10-31
Publication date: 1981-11-10
Also published as: ATA893577A; NL7714042A; US4065422A; BE863465A; GB1581621A; CH628242A5; FR2381097B1; AT371995B; FR2381097A1; IT1091692B; DE2805130A1; DE2805130C2

Abstract

ABSTRACT OF THE DISCLOSURE
This invention relates to compositions which may be used on keratin-ous substrates such as skin or hair or upon mucous membranes to impart a high-ly lubricated feel thereon. Such compositions contain a homopolymeric salt of 2-acrylamido-2-methylpropane sulfonic acid and have utility in diverse personal care products as hand and body creams, soap bars, suntan lotion, preelectric shave skin conditioners, after shave lotions, lip balms, cold creams, bubble baths, cleansing and lotion pads, and household cleaning pro-ducts as well as many other similar compositions.

Description

~AC~GROUND OF THE INVENTION

1. Field of the Invention The present invention relates to aleohol based personal eare produets whieh impart a feeling of lubrieity to the eontacted substrate.

2. Description of the Art Aleohol based personal care products are widely marketed. Such aleoholic formulations are ordinarily prepared such that the alcohol is a carrier or solvent for the remainder of the composition or in the case of higher moleeular weight aleohols such as cetyl or stearyl alcohol to provide not only a earrier but also to give an emollient effect upon the skin.
In addition to emolliency it is desireable that alcoholie personal eare f'ormulations be able to impart a feeling of lubrieity or silkiness to the skin or hair. Aside from the general "good" feeling such eompositions also provide sheen and manageability to the hair. --It is now been found useful to incorporate into aleoholie personal care formulations high moleeular weight polymerie salts of 2-acrylamido-2-methylpropane sulfonie aeid to provide a lubrieated feel.
Previous uses of 2-aerylamido-2-methylpropane sulfonie aeid polymers have been for non-personal care produets. For instance, German OLS 2,153,292 laid open for inspeetion May 4, 1972 suggests the use of similar polymers to thicken water-based hydraulie fluids eontaining glyeols or ether derivatives. Sueh polymers have also been known as deseribed in U.S. Patent 3,931,089 issued January 6, 1976 to Karl as thiekeners for aeid solutions having a pH value of about 2 or below.
Related but strueturally dissimilar polymers have stated uses as emulsifiers, thickeners, adhesives, dye ~., ~
r~
- : . ' . :

equalizers, and color printing agents as described in Italian Patent 404,109 issued May 21J 1943.
Interpolymers of acrylamido-aklylsulfonates are described in United States Patent 3,332,904 issued July 25, 1967 to La Combe et al for use as detergents and flexible films. In the United States Patent 3,275,561 to Pye et al issued September 27, 1966 compositions are described containing acrylamides to improve the lubricity of shaving soaps. Thickened salt solu-tions containing alcohols and vinyl aromatic sulfonate polymers are described in United States Patent 3,238,141 issued to Gatza on March 1, 1966.
While certain homopolymers and copolymers of 2-acrylamido-2--methylpropane sulfonic acid are known it has not been previously suggested to incorporate such materials into alcoholic personal care products to pro-vide a high degree of lubricity.
SUMMARY OF THE INVENTION
According to one aspect of the present invention there is pro-vided a personal care composition which imparts lubricity having a pH of from about 3 to about 10 and comprising:
(a) from about 0.01% to about 50% by weight of a homopolymeric salt of 2-acrylamido-2-methylpropane sulfonic acid - CH2 - CH _ 1=o . .
NH
I

_ _ x wherein x has a value such that the molecular weight of the anionic portion of the polymer is from about 1,000,000 to about 5,000,000; and ~ b) from about 1% to about 99.99% by weight of a monohydric alco-hol.
In another aspect the invention provides a method of imparting lubricity to a substrate including contacting the substrate with the personal r~ ' `~ ~$~;~174 care composition described above.
The above composition may be varied to provide a -3a-,f~ `.
~l .

- ' . . ~ ' ' high viscosity aqueous formulation by including as component (c) from about 1% to about 90% by weight water.
Throughout the specification and claims, percentages and ratios are by weight and temperatures are in degrees Celsius unless otherwise indicated.
DETAILED DESCRIPTION OF THL INV~NTION
The materials which have been found to lubricate keratinousness substrates such as skin or hair are polymers of 2-acrylamido-2-methylpropane sulfonate. The preparation of such polymers is described in Canadian Patent 864,433 issued February 23, 1971 and in German OLS 2,153,292 laid open ~ay 4, 1972.
The lubricating polymer of the present invention has the repeating linkage shown in the summary of the invention and is prepared from O

CH2'CH-lNH-C (CH3)2-CH2S03H
of a salt thereof. The polymerization reaction may be accomplished by solution,emulsion or suspension polymerization processes. The medium for the polymerization is conveniently water, the monohydric alcohol, or a mixture thereof. The choiceof the medium is best dictated by the requirements of the final personal care product to be formulated.
The polymerization reaction is described as temperature, pH, and catalyst sensitive. In addition it is desirable to exclude oxygen from the reaction vessel used to form the polymer as that material inhibits the polymerization process. The catalysts which are included to enhance the rate of polymerization are materials such .../4 i74 as ammonium bisulfi~e, ferrous sulfate, hydrogen peroxide, sodium metabisulfite, or other redox catalysts.
The polymer may be varied in molecular weight by controlling the amount of the catalyst, the pH, or the rate of addition of the monomer to the reaction vessel. The polymerization may be facilitated by converting the monomer ~ -rom its acid form to a salt which is water-soluble. This step is quite desirable in any event as the application of the personal care product of the skin requires that the pH
of the personal care product be non-irritating. That is, the in use pH of the personal care product should be from about 3 to about 10, preferably about 4.5 to about 9.0 and most preferably from about 5 to about 8. Thus within the foregoing ranges some of the polymer may be in the acid form.
The salts of the polymer preferably contain as cations, sodium, potassium, ammonium, monoethanolamine, diethanolamine, triethanolamine and 2-amino-2-methyl-1-propanol as well as mixtures thereof. The foregoing list is merely exemplary of water-soluble salts which may be used. Also within the scope of the present invention are water-insoluble salts where the personal care product is not adversely affected by percipitation of the polymer. Such products where water-insoluble salts of the polymer may be utilized are soap-bars, or substantially non-aqueous products such as bodv lotions. Examples of suitable water-insoluble salts are calcium and magnesium.
As was previously mentioned the molecular weight of the polymer may be controlled by the pH, the rate of addition of the monomer or the judicious use of the catalyst. It has been found desirable to utilize the aforedescribed polymers having a molecular weight of from about 1,000,000 to about 5,000,000 more preferably from about 2,500,000 to about 4,500,000 to increase the asthetics of the personal care '.

~$1~174 compositions. That is, it has been found that extremely high molecular wei~ht polymers of the type described may result in a pituitive or stringy consistency of the end product. It has therefore been found desirable to limit the pituitivness by selecting the preferred molecular weight range. To this end any common chain transfer agent such as mercaptosuccinic acid may be used to limit the molecular weight of the polymer.
It is noted that the terminal groups on the polymer have little bearing on the desired properties of the personal care products and are thus not specified. In the interest of complete disclosure it is noted that the terminal groups are most often hydrogen, but may also be hydroxyl, sulfate, sulfonate or .. , ll -CH=CH_c_NH2 The monohydric alcohol component of the present invention is preferably limited to those alcohols (Cl-C24) which are non-irritating to the skin or hair such as methanol, ethanol, isopropanol, propyl, lauryl, myristyl, cetyl, and stearyl as well as mixtures thereof. The choice of the alcohol to be utilized with the particular polymer of the present invention will ordinarily be dictated by product asthetics and physical form of the composition. For instance, where liquid compositions are desired the lower alcohols are preferably utilized while solid or cream compositions within the scope of the present invention will normally require the higher alcohols. Where the personal care formulations of the present invention contain ingredients other than the polymer or the alcohol in substantial amounts the choice of the particular alcohol becomes less important. For example, if the personal care product is to be an abrasive hand cleaning product then a large proportion of the product will ~:~1;2i74 be surface active agents and an abrasive such as pumice or sand thereby giving wide latitude to the choice of the particular alcohol.
When it is desired the personal care products of the present invention may be substantially non-aqueous. An importa-lt variable which has been discovered is that the polymers contrary to expectation are highly soluble in monohydric alcohols. That is, it was highly unexpected that the polymers of the present invention would be soluble to any degree in alcohol considering the molecular weight of the polymer and the fact that acrylamide polymers of similar weight are considerably less soluble in alcohols. It is not necessary, however, that the polymer be soluble in the alcohol as long as it is dispersible.
Therefore in the present invention the polymer is ordinarily present at from about 0.01% to about 50% by -weight, preferably from about 0.1% by weight to about 10%
by weight most preferably from about 0.5% by weight to about 5% by weight. The amount of the ~hydric alcohol used is from about 1% to about 99.99% preferably from about 2% to about 40%, most preferably from about 3% to about 30% by weight.
A desirable variable of the present invention is the incorporation of water to a mixture of the polymer and the monohydric alcohol with a resultant increase in viscosity over that which would be expected based on the viscosity of the polymer and the monohydric alcohol alone thus giving wide latitude in formaulating the personal care products.
The particular weight ratios at which the desirable increase in viscosity occurs for mixtures of the polymer, monohydric ..
alcohol and water are respectively from about 1:5:80 to about 1:80:5. Preferably this ratio is in the range of from about 1:10:40 to about 1:40:10. Within the aforementioned range highly viscous personal care compositions are obtained with low solids content. Such compositions are desirable in that they allow compositions such as suntan or body lotions to be formulated in a thickened state providing greater ease of application.
The personal care products of the present lnvention as previously indicated may be formulated into such diverse products as soap bars, dishwashing compositions, douches, hand and body lotions, suntan lotion, cold creams, preshave and after shave products as well as cleansing or lotion pads and wound dressings and many other personal care products.
Listed below are materials which may be included in such personal care products.
Hand and body lotions frequently contain emollients such as stearic acid, glycerol monostearate, mineral oil, glycerine, sesame oil, beeswax, lauryl, myristyl, cetyl or stearyl alcohols, lanolin, lecithin, sterols, isopropyl-myristate, and as well any other art recognized emollients.
; Emollients are typically~used in the present invention at levels of from about 1% to about 50% by weight.
Astringents and antiseptics may be incorporated into the compositions of the present invention. A preferred astringent material is zinc phenolsulfonate. The foregoing material exhibits not only astringent but also antiseptic qualities and is of particular use in preshave formulations to make the beard "stand up". Humictants such as propylene glycol are also desirable ingredients for inclusion in personal care products to prevent drying of the skin.
Allantoin is included in such compositions for its perported soothing and healing affects upon injured skin.
The soap bar, dishwashing products and shampoos of the present invention may contain all manner of anionic non-ionic, zwitterionic, ampholytic or cationic surfactants.
Typically the surfactant will be present at from about 1%

._ .~,'4 to about 70%, preferably about 3% to about 35% by weight.
Most preferably the dishwashing compositions of the present invention contain anionic surfactants which for example include alkylether sulfates, olefin sulfonates, alkyl and alkenyl sulfates, alkyl sulfonates, and alkylbenzene sulfonates. A particularily useful discovery is that the polymer when used with a surface active agent enhances and prolongs suds life. That is, consumers using dishwashing products often tend to overuse the composition when the suds disappear from the surface of the dishpan. Thus in the surfactant formulations of the present invention the presence of the polymer maintains the suds level thus avoiding inadvertent overuse of the product by the consumer.
The soap bars of the present invention may either contain real soap, combinations of soap and synthetic surfactants or may be formulated solely with synthetic surfactants such as alkylbenzene sulfonates. A more particular d~sclosure of components which are ordinarily found either as surfactants or additives in dishwashing compositions are more fully described in U.S. Patent

3,963,649 issued June 15, 1976 to Spadini et al. The general method of pro-ducing soap or detergent bars which may be formu~lated in accordance with the present invention is described in U.S. Patent 3,899,566 issued August 12, 1975 to Murray. Shampoo formulations which may be prepared according to the present invention are described in U.S. Patent 3,897,348 issued July 29, 1975 to Atkinson. Also within the scope of the present invention is the use of the polymer and monohydric alcohol as a drilling mud and for fracturing oil and gas wells. The following are examples of the present invention.

7 g EXAMPLE I

- C~ -C~i--A polymer of 2 1 C=O
the structural NH
formula l fH2 SO- .
Na+

having a molecular weight of about 4,500,000 is prepared in the following manner:
A solution of 90.1 parts (0.437 mole) of 2-acryamido-2-methylpropanesulfonic acid in 100 parts of water is blanketed with nitrogen. 231 parts (0.437 mole) Na2CO3 is added with stirring. After about 5 minutes of stirring at room temperature the solution becomes very viscous and an exothermic reaction is observed. After 10 minutes the reaction is complete and the product is a clear gel.

EXAMPLE II

A polymer is prepared having the formula described in Example I in the following manner:
45.2 grams of the monomer are neutralized with NaOH in 50 ml H2O. The resultant salt is placed in a resin flask and 0.5 gram sodium lauryl sulfate is added. The mixture is stirred and purged with nitrogen. 0.001 gram each of ammonium persulfate and sodium metabisulfite are added with stirring. 500 grams of benzene are added and the flask is heated to 50C. Following polymerization, the polymer is washed with dimethyl ketone and dried at 65C.
The molecular weight of the polymer is determined by its inherent viscosity to be 3,100,000. In similar fashion polymers are prepared having molecular weights of 3,300,000;
3,500,000, and 4,000,000.

~, .

~$1~4 EXAMPLE III
A portion of the polymer prepared in Example II
having a molecular weight of 3,100,000 is incorporated into a soap bar containing:
90 parts sodium stearate 9 parts cetyl alcohol 1 part polymer When used as a hand soap the composition provides the skin with a silky feel. Similar results are obtained when the sodium stearate is replaced by sodium dodecyl benzene sulfonate.

EXAMPLE IV

A hand and body lotion is prepared containing: --1.5% stearic acid 1.5 glycerol monostearate mineral oil - 10 lauryl alcohol sesame oil ~9 3 Generol 122 tsoYa sterol) 1 triethanolamine 1 polymer balance water, preservatives, perfumes and minors The above product when applied to the skin provides a lubricated feel and emollient properties.

EXAMPLE V

Suntan lotions are prepared using each of the polymers in turn of Example I and Example II in the following formulation:
e ~1~rl( .

20% mineral oil 7~ cetyl alcohol 1.5% Amyl-para-dimethylaminobenzoate (sunscreen) S 3.3% Generol 122 E16 (a soya sterol condensed with 16 moles of ethylene oxide per mole of sterol) 0 2% allantoin 2.0% ethanol 0.5% polymer balance water, perfume and minors The above compositions are effective suntan lotions which provide a high degree of lubricity when applied to the skin.

EXAMPLE VI
A cold cream base is prepared containing:
50% mineral oil 15% Beeswax

4% Generol -122 20% polymer (of Example II having a molecular weight of about 4,000,000 neutralized with 2-amino-2-methyl-1-propanol) 10% cetyl alcohol 1% sodium borate This composition imparts a silky feel to the skin when used as a cold cream.

EXAMPLE VII
A cleansing douche is prepared using the polymer of Example I in the following product:

0.5% polymer (neutralized to pH 6 with triethanolamine)

5.0% cetyl alcohol 2.0% sodium dodecylhexethoxysulfate balance water, perfume, colorant The product cleans effectively while providing lubrication to the mucous membranes.

EXAMPLE VIII
A preshave lotion is prepared containing a polymer as described in Example II having a molecular weight of about 3,~00,000 comprising:
15% isopropyl myristate 0.3% polymer balance ethanol The preshave product provides a high degree of lubricity to the skin during shaving with an electric razor thereby lessening razor drag. Substantially similar results are obtained when the ethanol is replaced by isopropanol or the isopropyl myristate is varied between 10-25% and the polymer is at from 0.1 to 1.6%.

EXAMPLE IX
An astringent preshave lotion product is prepared with poIymer descrlbed in Example VIII comprising:
2% dodecyltetraethoxylated alcohol 0.05% menthol 1.0% zinc phenolsulfonate 1.0% polymer 49.0% ethanol balance water, perfumes and miscellaneous.

The polymer was introduced into the preshave product as a premix by dispersing it in the ethanol. The product is thus stable and the zinc salt does not cause the polymer to precipitate out of the product. The product is a milky lotion having a viscosity of about 1000 cps on a Brookfield viscometer spindle number 2. When compared to a similar product not containing the polymer it is found that the ~inc sal~ does not crystallize on the skin upon evaporation of the solvent thus the skin becomes evenly taut and the beard is easily removed by an electric or safety razor~ Again skin drag is reduced by the polymer.
EXAMPLE X
An a~ter shave personal care product is prepared using a polymer having an approximate molecular weight of 3,100,000 prepared in accordance with Example II. The formulation is as follows:
2% Fragrance, Albert Verley #CS-19611 10% Premix of ethanol containing 1 part acid polymer per 50 parts alcohol 3% propylene glycol 70% ethanol 5% isopropyl myristate q.s. triethanolamine to pH 4-5 balance water The after shave containing the polymer and humictant (propylene glycol) provides the skin with a silky non-dry feeling following shaving.
EXAMPLE XI
A personal care pad is prepared by applying a mixture containing 2 parts of the polymer of Example I and 98 parts ethanol to cheesecloth substrate. If desired some of the alcohol may be evaporated off the substrate.
A small amount of surfactant such as triethanolamine lauryl sulfate may be added to the pad if cleansing action is desired. Medication may also be added to the pad for use as a bandage which is easily removable.
EXAMPLE XII
A detergent composition useful for washing dishes ~ T~de nhrK

. . ~

1~1;2174 and tableware is prepared containing the polymer of Example II having a molecular weight of about 3,500,000 comprising:
0.5% polymer 3% ethanol S 20% sodium hexaethoxylaurylsulfate balance water The composition cleans the dishware and tableware effectively while imparting a silky feel to the skin. The composition sudses well initially and maintains suds through-out the wash.

~ - - - . ,_. _ .
'~' ' .. . .

Claims

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

1. A personal care composition which imparts lubricity having a pH
of from about 3 to about 10 and comprising:
(a) from about 0.01% to about 50% by weight of a homopolymeric salt of 2-acrylamido-2-methylpropane sulfonic acid wherein x has a value such that the molecular weight of the anionic portion of the polymer is from about 1,000,000 to about 5,000,000; and (b) from about 1% to about 99.99% by weight of a monohydric alcohol.

2. The composition of claim 1 wherein the monohydric alcohol is se-lected from the group consisting of methyl, ethyl, isopropyl, propyl, lauryl, myristyl, cetyl, and stearyl alcohol and mixtures thereof.

3. The composition of claim 1 wherein the molecular weight of the polymer is from about 2,500,000 to about 4,500,000.

4. The composition of claim 1 additionally comprising water in a weight ratio of (a):(b):water of from about 1:5:80 to about 1:80:5.

5. The composition of claim 1 additionally comprising a member se-lected from the group consisting of anionic, nonionic, zwitterionic, ampho-lytic, and cationic surfactants at from about 1% to about 70% by weight.

6. The composition of claim 1 additionally comprising an emollient at from about 1% to about 50% by weight.

7. The composition of claim 1 wherein the cation of the polymer is selected from the group consisting of sodium, potassium, ammonium, mono-ethanolamine, diethanolamine, triethanolamine, and 2-amino-2-methyl-1-propan-ol and mixtures thereof.

8. A method of imparting lubricity to a substrate including contact-ing the substrate with a personal care composition having a pH in the range from about 3 to about 10 comprising:
(a) from about 0.01% to about 50% by weight of a homopolymeric salt of 2-acrylamido-2-methyl propane sulfonic acid wherein x has a value such that the molecular weight of the anionic portion of the polymer is from about 1,000,000 to about 5,000,000; and (b) from about 1% to about 99.99% by weight of a monohydric alcohol.

9. The method of claim 8 wherein the monohydric alcohol is selected from the group consisting of methyl, ethyl, isopropyl, propyl, lauryl, myris-tyl, cetyl, and stearyl alcohol and mixtures thereof.

10. The method of claim 8 wherein the molecular weight of the polymer is from about 2,500,000 to about 4,500,000.

11. The method of claim 8 wherein the personal care product addition-ally comprises water in a weight ratio of (a):(b):water of from about 1:5:80 to about 1:80:5.

12. The method of claim 8 wherein the personal care product additionally comprises a member selected from the group consisting of anionic, nonionic, zwitterionic, ampholytic, and cationic surfactants at from about 1%
to about 70% by weight.

13. The method of claim 8 wherein the personal care product addition-ally comprises an emollient at from about 1% to about 50% by weight.

14. The method of claim 8 wherein the cation of the polymer is se-lected from the group consisting of sodium, potassium, ammonium, monoethanol-amine, diethanolamine, triethanolamine, and 2-amino-2-methyl-1-propanol and mixtures thereof.

15. The method of claim 8 wherein the substrate is skin, hair or mu-cous membrane.