# Patent

## Title
Low-irritating, clear cleansing compositions with relatively low pH

## Abstract

The methods and compositions of this invention relate to compositions having low irritation characteristics in combination with one or more additional characteristics, for example, relatively high clarity, relatively high foaming, and/or combinations thereof, as well as methods of making and using such compositions. These compositions have low pH values and are useful in cleansing the skin.

## Background
RELATED APPLICATIONS
This application is a CIP of Ser. No. 12/822,329, filed Jun. 24, 2010.


FIELD OF THE INVENTION
The compositions of this invention are useful in cleansing the skin and are characterized by having low irritation characteristics in combination with one or more additional beneficial characteristics, such as, relatively high clarity, relatively high foaming, and/or combinations thereof. The compositions of the present invention generally have low pH values.
BACKGROUND OF THE INVENTION
Synthetic surfactant detergents, such as cationic, anionic, amphoteric, and non-ionic surfactants, are used widely in a variety of detergent and cleansing compositions to impart cleansing properties thereto. In addition these synthetic surfactant detergents have been used in personal care compositions including shampoos and washes. In these personal care compositions, it may be desirable to use combinations and levels of surfactants sufficient to achieve relatively high levels of foam volume and/or foam stability.
However, as is recognized in the art, synthetic surfactant detergents tend to be irritating to the skin and eyes. As concentrations of such detergents increase in personal care compositions so as to impart increased cleansing and foaming properties to these compositions, the irritation associated with such compositions also tends to increase, making them undesirable for use on or near the skin and/or eyes.
Attempts to produce milder cleansing compositions have included combining relatively low amounts of anionic surfactants (which tend to be relatively high-foaming but also relatively highly irritating) with relatively lower irritating surfactants such as nonionic and/or amphoteric surfactants. See, e.g. U.S. Pat. No. 4,726,915. Another approach to producing mild cleansing compositions is to associate the anionic surfactants with amphoteric or cationic compounds in order to yield surfactant complexes. See, e.g., U.S. Pat. Nos. 4,443,362; 4,726,915; 4,186,113; and 4,110,263. Disadvantageously, mild cleansing compositions produced via both of such methods tend to suffer from relatively poor foaming and cleansing performance.
It has further been recognized that, for certain uses, consumers desire cleansing compositions to be relatively clear. In particular, clear compositions are often used advantageously to provide an aesthetic indication of purity to the consumer. However, a number of ingredients commonly used in conventional personal care compositions, including, for example, polymeric thickeners, tend to cause the compositions to become cloudy or opaque. It is not readily predictable which combinations of polymers, surfactants and other optional ingredients may be combined to create compositions that are suitable for use as cleansers and also exhibit high clarity.
Another complicating factor with respect to creating clear compositions is that certain polymeric thickeners require higher pH to maintain clarity and stability in personal care compositions.
U.S. Pat. No. 6,897,253 ('253) describes a substantially crosslinked alkali-swellable acrylate copolymer rheology modifier, water, an alkaline material, and an effective amount of surfactant so that a substantially insoluble compound is stabilized or suspended. The disclosed polymeric rheology modifiers do not start to build substantial viscosity until a pH of about 5 or 6 or higher is achieved. To formulate a composition with a lower pH is difficult but '253 discusses a “Back-Acid” thickening method to achieve clear cleansing systems with an acrylate rheology modifier and high surfactant concentrations (greater than about 9.8% actives) at low pH (about pH 4.5-5). This method involves formulating at a higher pH to obtain the appropriate viscosity and stability and then slowly lowering the pH with an organic acid.
US 2008/0113895 sets forth the use of low molecular weight acrylic polymers with the anionic surfactants sodium laureth sulfate and sodium trideceth sulfate for mild cleansing systems. Clear cleansing system are achieved, but only at pH of greater than 6.5
U.S. Pat. No. 7,803,403 describes the use of low molecular weight acrylic polymers for irritation mitigation and points out the difficulty in creating clear cleansing systems with low molecular weight hydrophobically modified polymers. While clear systems are achieved with low molecular weight acrylic polymer combined with either sodium laureth sulfate, sodium trideceth sulfate, or cocamidopropyl betaine, the pH of the compositions must be 6.5.
It is desirable to formulate skin care compositions, including cleansing compositions, to be as mild as possible to the skin and eyes. One way in which to achieve this goal is by having a composition that has pH that is compatible with the skin and eyes. In addition, there is a need for the compositions to exhibit relatively high clarity, desirable foam properties and/or other desirable aesthetic properties. Additional aspects of skin care compositions involve safety and compatible preservative systems.
The ingredients of the skin care compositions of this invention may also require certain pH parameters. For example, certain active ingredients such salicylic acid, require low pH for activity.
Some preservative systems, preservatives that function in their acidic form and not in there salt form, e.g. sodium benzoate or potassium sorbate, require a low composition pH for efficacy. The efficiency of the preservative decreases with increasing pH, dependent upon the pKa of the preservative. Therefore it is desirable to formulate at low pH to provide maximum efficiency while maintaining a pH compatible with the skin and eyes.
Additionally, it is desirable to formulate compositions to have a pH neutral to the skin, from about 5 to about 6. Cleansers having a pH below that of skin (between about 4 and about 5) may be desired in order to lower the pH of skin for enhanced enzyme function and to alter the skin microflora.
The skin care compositions of this invention have low pH yet have high clarity. The compositions have low irritation characteristics and are clear.
SUMMARY OF THE INVENTION
The compositions of this invention relate to a skin cleansing composition comprising, consisting essentially of and consisting of:
(a) a low molecular weight, non-crosslinked acrylic copolymer; and
(b) a surfactant component comprising, consisting essentially of and consisting of a surfactant selected from the group consisting of, at least one non-ethoxylated anionic surfactant and at least one amphoteric surfactant;
(c) wherein the total surfactant load of said skin cleansing composition is not greater than about 14 weight percent of the skin cleansing composition; the pH of said skin cleansing composition is about 6.2 or less; and the skin cleansing composition has a count rate of about 70 kcts/s or less in a light scattering test and has a light transmittance of greater than about 90%.


DETAILED DESCRIPTION OF THE INVENTION
Applicants have discovered that the skin cleansing compositions of this invention exhibit a unique and unexpected combination of properties including relatively low irritation and relatively high clarity at a lower than expected pH, a pH that is compatible with skin. This makes the compositions of this invention ideal for skin care, including baby and infant skin, cosmetic or cleansing compositions. The compositions include a low molecular weight, non-crosslinked, acrylic copolymer and a surfactant component, which includes at least one non-ethoxylated anionic surfactant and at least one amphoteric surfactant. Surprisingly, using a select group of surfactants to bind with the low molecular weight, non-crosslinked, acrylic copolymer, results in a composition that is clear at a pH lower than previously thought would be possible.
The term “total surfactant load” means the total weight percentage of all surfactants, including both anionic and amphoteric surfactants as well as additional surfactants which may be present in the compositions of this invention. Such additional surfactants may include nonionic surfactants, for example. In accordance with the present invention, the total surfactant load of said skin cleansing composition is not greater than about 14 weight percent of the skin cleansing composition
As used herein, the term “low pH” shall include pH measurements of less than or equal to about 6.2 as determined by ASTM method E70-07 Standard Test Method for pH of Aqueous Solutions With the Glass Electrode. In a preferred embodiment, the pH range is between about 3.5 and about 6.2. In a more preferred embodiment, the pH range is between about 4 and about 6. In a most preferred embodiment, the pH range is between about 4.5 and about 5. It was previously known that pH also affects certain preservative systems. For example, a high pH reduces the efficacy of preservative system. As detailed below, an organic acid preservative system may become ineffective if the appropriate pH is not maintained.
As used herein, the terminology “relatively high clarity” and/or “clear composition” may be used interchangeably and shall mean that the composition shall have a light transmittance of greater than about 90%, more preferably greater than about 90.5%, and most preferably greater than about 95% as determined by the Clarity Test as defined in the methods section. As used herein, the term “clear composition” shall mean that the composition shall have a count rate of less than about 70 kcts/s, more preferably less than about 50 kcts/s kcts/s, and most preferably less than about 40 kcts/s, as determined by the Light Scattering Test as defined in the methods section.
Polymeric Material
As used herein the term “low molecular weight” polymer refers to a polymer having a number average molecular weight (Mn) of about 100,000 or less as measured by gel permeation chromatography (GPC) calibrated with a poly(methyl methacrylate) (PMMA) standard. In certain preferred embodiments, low-molecular weight polymers are those having molecular weight ranges of from about 5,000 to about 80,000 Mn, more preferably from about 10,000 to about 50,000 Mn, and more preferably between about 15,000 and 40,000 Mn.
The polymeric material useful in the composition of this invention is preferably a polymeric material suitable for associating anionic and/or amphoteric surfactant thereto and is preferably a non-crosslinked, linear acrylic copolymer that mitigates the impaired dermal barrier damage typically associated with surfactant systems without substantially increasing viscosity build. The non-crosslinked, linear polymers are preferably of low molecular weight having a number average molecular weight of 100,000 or less as measured by gel permeation chromatography (GPC) calibrated with a poly(methyl methacrylate) (PMMA) standard (as used herein, unless otherwise specified, all number average molecular weights (Mn) refer to molecular weight measured in such manner). Thus, the polymeric material functions as a copolymeric mitigant. The copolymeric mitigant is polymerized from at least two monomeric components. The first monomeric component is selected from one or more α,β-ethylenically unsaturated monomers containing at least one carboxylic acid group. This acid group can be derived from monoacids or diacids, anhydrides of dicarboxylic acids, monoesters of diacids, and salts thereof. The second monomeric component is hydrophobically modified (relative to the first monomeric component) and is selected from one or more α,β-ethylenically unsaturated non-acid monomers containing a C1 to C9 alkyl group, including linear and branched C1 to C9 alkyl esters of (meth)acrylic acid, vinyl esters of linear and branched C1 to C10 carboxylic acids, and mixtures thereof. In one aspect of the invention the second monomeric component is represented by the formula:

CH2═CRX

wherein R is hydrogen or methyl; X is —C(O)OR1 or —OC(O)R2; R1 is linear or branched C1 to C9 alkyl; and R2 is hydrogen or linear or branched C1 to C9 alkyl. In another aspect of the invention R1 and R2 is linear or branched C1 to C8 alkyl and in a further aspect R1 and R2 are linear or branched C2 to C5 alkyl.

Exemplary first monomeric components include (meth)acrylic acid, itaconic acid, citraconic acid, maleic acid, fumaric acid, crotonic acid, aconitic acid, and mixtures thereof. Exemplary second monomeric components include ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, vinyl formate, vinyl acetate, 1-methylvinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, vinyl pivalate, vinyl neodecanoate, and mixtures thereof. As used herein, the term “(meth)acrylic” acid and “(meth)acrylate” are meant to include the corresponding methyl derivatives of acrylic acid and the corresponding alkyl acrylate For example, “(meth)acrylic” acid refers to acrylic acid and/or methacrylic acid and “(meth)acrylate” refers to alkyl acrylate and/or alkyl methacrylate.
More preferably, said first monomeric component is selected from the group consisting of (meth)acrylic acid and said second monomeric component is selected from the group consisting of at least one C1 to C9 alkyl (meth)acrylate.
The non-crosslinked, linear acrylic copolymer mitigants of the invention can be synthesized via free radical polymerization techniques known in the art. In one aspect of the invention, the amount of the first monomeric component to the second monomeric component utilized ranges from about 20:80 wt. % to about 50:50 wt. %, based on the total weight of all of the monomers in the polymerization medium. In another aspect the weight ratio of the first monomeric component to the second monomeric component is about 35:65 wt. %, and in a further aspect the weight ratio of first monomeric component to second monomeric component is about 25:75 wt. %, all based on the total weight of all monomers in the polymerization medium.
In another aspect emulsion polymerization techniques can be used to synthesize the non-crosslinked, linear acrylic copolymer mitigants of the invention. In a typical emulsion polymerization, a mixture of the disclosed monomers is added with mixing agitation to a solution of emulsifying surfactant, such as, for example, an anionic surfactant (e.g., fatty alcohol sulfates or alkyl sulfonates), in a suitable amount of water, in a suitable reactor, to prepare a monomer emulsion. The emulsion is deoxygenated by any convenient method, such as by sparging with nitrogen, and then a polymerization reaction is initiated by adding a polymerization catalyst (initiator) such as sodium persulfate, or any other suitable addition polymerization catalyst, as is well known in the emulsion polymerization art. The polymerization medium is agitated until the polymerization is complete, typically for a time in the range of about 4 to about 16 hours. The monomer emulsion can be heated to a temperature in the range of about 70 to about 95° C. prior to addition of the initiator, if desired. Unreacted monomer can be eliminated by addition of more catalyst, as is well known in the emulsion polymerization art. The resulting polymer emulsion product can then be discharged from the reactor and packaged for storage or use. Optionally, the pH or other physical and chemical characteristics of the emulsion can be adjusted prior to discharge from the reactor. Typically, the product emulsion has a total solids content in the range of about 10 to about 50 wt. %. Typically, the total polymer content (polymer solids) of the product emulsion is in the range of about 15 to about 45 wt. %, generally not more than about 35 wt. %.
In one aspect, the number average molecular weight (Mn) of the linear copolymeric mitigants of this invention as measured by gel permeation chromatography (GPC) calibrated with a poly(methyl methacrylate) (PMMA) standard is 100,000 or less. In another aspect of the invention, the molecular weight ranges between about 5,000 and about 80,000 Mn, in a further aspect between about 10,000 and 50,000 Mn, and in a still further aspect between about 15,000 and 40,000 Mn.
In one aspect of the invention, the linear copolymeric mitigants have a viscosity of 500 mPa·s or less (Brookfield RVT, 20 rpm, spindle no. 1) at a 5 wt. % polymer solids concentration in deionized water and neutralized to pH 7 with an 18 wt. % NaOH solution. The viscosity can range from about 1 to about 500 mPa·s in another aspect, from about 10 to about 250 mPa·s in a further aspect, and from about 15 to about 150 mPa·s in a still further aspect.
Preferably, the low molecular weight, non-crosslinked linear acrylic copolymer is potassium acrylates copolymer.
Any of a variety of non-ethoxylated anionic surfactants may be combined with a polymeric material of this invention to form a cleansing composition according to preferred embodiments of the present invention. Non-ethoxylated anionic surfactants are surfactants that have a negative charge and do not contain any ethoxylated segments, that is to say there are no —(C—C—O)v segments on the surfactants. According to certain embodiments, suitable non-ethoxylated anionic surfactants include those selected from the following classes of surfactants: alkyl sulfates, alkyl sulfonates, alkyl monoglyceride sulfonates, alkylaryl sulfonates, alkyl sulfosuccinates, alkyl sulfosuccinamates, alkyl carboxylates, fatty alkyl sulfoacetates, alkyl phosphates, acylglutamates, sarcosinates, taurates, and mixtures of two or more thereof. Examples of certain preferred anionic surfactants include:
alkyl sulfates of the formula

R′—CH2OSO3X′;

alkyl monoglyceride sulfates of the formula




alkyl monoglyceride sulfonates of the formula




alkyl sulfonates of the formula

R′—SO3X′;

alkylaryl sulfonates of the formula




alkyl sulfosuccinates of the formula:




alkyl phosphates
wherein

    
    
        R′ is an alkyl group having from about 7 to about 22, and preferably from about 7 to about 16 carbon atoms,
        R′1 is an alkyl group having from about 1 to about 18, and preferably from about 8 to about 14 carbon atoms,
        R′2 is a substituent of a natural or synthetic I-amino acid,
        X′ is selected from the group consisting of alkali metal ions, alkaline earth metal ions, ammonium ions, and ammonium ions substituted with from about 1 to about 3 substituents, each of the substituents may be the same or different and are selected from the group consisting of alkyl groups having from 1 to 4 carbon atoms and hydroxyalkyl groups having from about 2 to about 4 carbon atoms and
        
            w is an integer from 0 to 20;

and mixtures thereof.

        
        
    
    


According to certain embodiments, the anionic surfactant of this invention is preferably a non-ethoxylated SOx anionic surfactant conforming to the structure below




Where SO3− is the anionic hydrophilic group, M+ is a monovalent cation (such as NH4+, Na+, K+, (HOCH2CH2)3N+, etc.), and R comprises any of a broad range of hydrophobic groups and optionally, a) functional groups to link the hydrophilic and hydrophobic moieties and/or b) additional hydrophilic groups. Examples include:

    
    
        Alkyl sulfonates, where R equals C6-C20 alkyl, (linear or branched, saturated or unsaturated), preferably C10-C18, and most preferably C12-C17. Specific examples include Sodium C13-C17 Alkane Sulfonate (R=C13-C17 alkyl, M+=Na+) and Sodium C14-C17 Alkyl Sec Sulfonate (R=s-C13-C17 alkyl, M+=Na+)
        Alpha olefin sulfonates, where R equals a mixture of
    
    






and





where R1=C4-C16 alkyl or mixtures thereof, preferably C6-C12, more preferably C8-C12, and most preferably C10-C12. Specific examples include Sodium C12-14 Olefin Sulfonate (R1=C8-C10 alkyl, M+=Na+) and Sodium C14-16 Olefin Sulfonate (R1=C10-C12 alkyl, M+=Na+).

    
    
        Alkyl sulfate esters, where R1=C6-C20,
    
    






(linear or branched, saturated or unsaturated), preferably C12-C18, more preferably C12-C16, and most preferably C12-C14. Specific examples include Ammonium Lauryl Sulfate (R1=lauryl, C12H25, M+=NH4+), Sodium Lauryl Sulfate (R1=lauryl, C12H25, M+=Na+), and Sodium Cocosulfate (R1=coco alkyl, M+=Na+).

As used herein, the term “amphoteric” shall mean: 1) molecules that contain both acidic and basic sites such as, for example, an amino acid containing both amino (basic) and acid (e.g., carboxylic acid, acidic) functional groups; or 2) zwitterionic molecules which possess both positive and negative charges within the same molecule. The charges of the latter may be either dependent on or independent of the pH of the composition. Examples of zwitterionic materials include, but are not limited to, alkyl betaines and amidoalkyl betaines. The amphoteric surfactants are disclosed herein without a counter ion. One skilled in the art would readily recognize that under the pH conditions of the compositions of this invention, the amphoteric surfactants are either electrically neutral by virtue of having balancing positive and negative charges, or they have counter ions such as alkali metal, alkaline earth, or ammonium counter ions.
Examples of amphoteric surfactants suitable for use in this invention include, but are not limited to, amphocarboxylates such as alkylamphoacetates (mono or di); alkyl betaines; amidoalkyl betaines; alkyl sultaines; amidoalkyl sultaines; amphophosphates; phosphorylated imidazolines such as phosphobetaines and pyrophosphobetaines; carboxyalkyl alkyl polyamines; alkylimino-dipropionates; alkylamphoglycinates (mono or di); alkylamphoproprionates (mono or di),); N-alkyl β-aminoproprionic acids; alkylpolyamino carboxylates; and mixtures thereof.
Examples of suitable amphocarboxylate compounds include those of the formula:

A-CONH(CH2)xN+R5R6R7 

    
    
        wherein
        A is an alkyl or alkenyl group having from about 7 to about 21, e.g. from about 10 to about 16 carbon atoms;
        x is an integer of from about 2 to about 6;
        R5 is hydrogen or a carboxyalkyl group containing from about 2 to about 3 carbon atoms;
        R6 is a hydroxyalkyl group containing from about 2 to about 3 carbon atoms or is a group of the formula:

R8—O—(CH2)nCO2−
        
            wherein
            R8 is an alkylene group having from about 2 to about 3 carbon atoms and n is 1 or 2; and
        
        
        R7 is a carboxyalkyl group containing from about 2 to about 3 carbon atoms;
    
    


Examples of suitable alkyl betaines include those compounds of the formula:

B—N+R9R10(CH2)PCO2−

    
    
        wherein
        
            B is an alkyl or alkenyl group having from about 8 to about 22, e.g., from about 8 to about 16 carbon atoms;
            R9 and R10 are each independently an alkyl or hydroxyalkyl group having from about 1 to about 4 carbon atoms; and
            p is 1 or 2.
        
        
    
    


A preferred betaine for use in this invention is lauryl betaine, available commercially from Albright & Wilson, Ltd. of West Midlands, United Kingdom as “Empigen BB/J.”
Examples of suitable amidoalkyl betaines include those compounds of the formula:

D-CO—NH(CH2)q—N+R11R12(CH2)mCO2−

    
    
        wherein
        
            D is an alkyl or alkenyl group having from about 7 to about 21, e.g. from about 7 to about 15 carbon atoms;
        
        
        R11 and R12 are each independently an alkyl or
        Hydroxyalkyl group having from about 1 to about 4 carbon atoms;
        q is an integer from about 2 to about 6; and m is 1 or 2.
    
    


One amidoalkyl betaine is cocamidopropyl betaine, available commercially from Goldschmidt Chemical Corporation of Hopewell, Va. under the tradename, “Tegobetaine L7.”
Examples of suitable amidoalkyl sultaines include those compounds of the formula




    
    
        wherein
        
            E is an alkyl or alkenyl group having from about 7 to about 21, e.g. from about 7 to about 15 carbon atoms;
            R14 and R15 are each independently an alkyl, or hydroxyalkyl group having from about 1 to about 4 carbon atoms;
            r is an integer from about 2 to about 6; and
            R13 is an alkylene or hydroxyalkylene group having from
            about 2 to about 3 carbon atoms;
        
        
    
    


In one embodiment, the amidoalkyl sultaine is cocamidopropyl hydroxysultaine, available commercially from Rhone-Poulenc Inc. of Cranbury, N.J. under the tradename, “Mirataine CBS.”
Examples of suitable amphophosphate compounds include those of the formula:




    
    
        wherein
        
            G is an alkyl or alkenyl group having about 7 to about 21, e.g. from about 7 to about 15 carbon atoms;
            
                s is an integer from about 2 to about 6;
                R16 is hydrogen or a carboxyalkyl group containing from about 2 to about 3 carbon atoms;
                R17 is a hydroxyalkyl group containing from about 2 to about 3 carbon atoms or a group of the formula:

R19—O—(CH2)t—CO2−
                
                    wherein R19 is an alkylene or hydroxyalkylene group having from about 2 to about 3 carbon atoms and t is 1 or 2; and
                
                
                R18 is an alkylene or hydroxyalkylene group having from about 2 to about 3 carbon atoms.
            
            
        
        
    
    


In one embodiment, the amphophosphate compounds are sodium lauroampho PG-acetate phosphate, available commercially from Mona Industries of Paterson, N.J. under the tradename, “Monateric 1023,” and those disclosed in U.S. Pat. No. 4,380,637, which is incorporated herein by reference.
Examples of suitable phosphobetaines include those compounds of the formula:




wherein E, r, R1, R2 and R3, are as defined above. In one embodiment, the phosphobetaine compounds are those disclosed in U.S. Pat. Nos. 4,215,064, 4,617,414, and 4,233,192, which are all incorporated herein by reference.

Examples of suitable pyrophosphobetaines include those compounds of the formula:




wherein E, r, R1, R2 and R3, are as defined above. In one embodiment, the pyrophosphobetaine compounds are those disclosed in U.S. Pat. Nos. 4,382,036, 4,372,869, and 4,617,414, which are all incorporated herein by reference.
Examples of suitable carboxyalkyl alkylpolyamines include those of the formula:




    
    
        wherein
        
            I is an alkyl or alkenyl group containing from about 8 to about 22, e.g. from about 8 to about 16 carbon atoms;
            R22 is a carboxyalkyl group having from about 2 to about 3 carbon atoms;
            R21 is an alkylene group having from about 2 to about 3 carbon atoms and
            u is an integer from about 1 to about 4.
        
        
    
    


Any suitable amounts of polymeric material and surfactants may be used in accord with the compositions and methods of this invention. In certain preferred embodiments, the compositions of this invention comprise, consist essentially of and consist of from greater than zero to about 6 weight percent of polymeric material (based on active amount of polymeric material in the total weight of composition). In certain more preferred embodiments, the compositions comprise, consist essentially of and consist of from about 0.1 to about 4.5 weight percent of polymeric material, more preferably from about 0.1 to about 3.5 weight percent of polymeric material, and even more preferably from about 0.2 to about 2.5 weight percent of polymeric material.
In certain preferred embodiments, the compositions of this invention comprise, consist essentially of and consist of from greater than about 2 to less than about 14 weight percent of surfactants based on total active amount of surfactant(s) in the total weight of composition. In certain more preferred embodiments, the compositions comprise, consist essentially of and consist of from about 2 to about 12 weight percent of total surfactants. Preferred embodiment formulas have from about 2 to about 9 weight percent total surfactants. Preferred embodiments have from about 2 to about 7 weight percent total surfactants.
When formulating the compositions of the present invention, when the ratio of non-ethoxylated anionic surfactant to amphoteric surfactant is less than 0.5, the pH of the composition should be between 4.8 and about 6.2. When the ratio of non-ethoxylated anionic surfactant to amphoteric surfactant is greater than 0.5, the pH of the composition can be less than or equal to 6.2, preferably between 2.5 and 6.2.
The non-crosslinked, linear acrylic copolymers useful in the compositions of this invention can be synthesized via free radical polymerization techniques known in the art. In one aspect of the invention, the amount of the first monomeric component to the second monomeric component utilized ranges from about 20:80 wt. % to about 50:50 wt. %, based on the total weight of all of the monomers in the polymerization medium. In another aspect the weight ratio of the first monomeric component to the second monomeric component is about 35:65 wt. %, and in a further aspect the weight ratio of first monomeric component to second monomeric component is about 25:75 wt. %, all based on the total weight of all monomers in the polymerization medium.
The cleansing compositions produced, as well as any of the compositions containing polymeric material and a surfactant component having at least one non-ethoxylated anionic surfactant and at least one amphoteric surfactant that are combined in the combining step according to the methods of this invention may further contain any of a variety of other components nonexclusively including additives which enhance the appearance, feel and fragrance of the compositions, such as colorants, fragrances, preservatives, pH adjusting agents and the like.
Any of a variety of nonionic surfactants are suitable for use in the compositions of this invention, keeping in mind that total surfactant load should not exceed about 14 weight percent of the compositions set forth herein. Examples of suitable nonionic surfactants include, but are not limited to, fatty alcohol acid or amide ethoxylates, monoglyceride ethoxylates, sorbitan ester ethoxylates, alkyl polyglucosides, polyglyceryl esters, mixtures thereof, and the like. Certain preferred nonionic surfactants include alkyl polyglucosides, such as but not limited to coco-glucoside and decyl-glucoside, and polyglyceryl esters, such as but not limited to polyglyceryl-10 laurate and polyglyceryl-10 oleate.
Any of a variety of commercially available secondary conditioners, such as volatile silicones, which impart additional attributes, such as gloss to the hair are suitable for use in this invention. In one embodiment, the volatile silicone conditioning agent has an atmospheric pressure boiling point less than about 220° C. The volatile silicone conditioner may be present in an amount of from about 0 percent to about 3 percent, e.g. from about 0.25 percent to about 2.5 percent or from about 0.5 percent to about 1.0 percent, based on the overall weight of the composition. Examples of suitable volatile silicones nonexclusively include polydimethylsiloxane, polydimethylcyclosiloxane, hexamethyldisiloxane, cyclomethicone fluids such as polydimethylcyclosiloxane available commercially from Dow Corning Corporation of Midland, Mich. under the tradename, “DC-345” and mixtures thereof, and preferably include cyclomethicone fluids.
Any of a variety of commercially available humectants, which are capable of providing moisturization and conditioning properties to the personal cleansing composition, are suitable for use in this invention. The humectant may be present in an amount of from about 0 percent to about 10 percent, e.g. from about 0.5 percent to about 5 percent or from about 0.5 percent to about 3 percent, based on the overall weight of the composition. Examples of suitable humectants nonexclusively include 1) water soluble liquid polyols selected from the group comprising glycerine, propylene glycol, hexylene glycol, butylene glycol, dipropylene glycol, and mixtures thereof; 2) polyalkylene glycol of the formula: HO—(R′′O)b—H, wherein R′′ is an alkylene group having from about 2 to about 3 carbon atoms and b is an integer of from about 2 to about 10; 3) polyethylene glycol ether of methyl glucose of formula CH3—C6H10O5—(OCH2CH2)c—OH, wherein c is an integer from about 5 to about 25; 4) urea; and 5) mixtures thereof, with glycerine being the preferred humectant.
Examples of suitable chelating agents include those which are capable of protecting and preserving the compositions of this invention. Preferably, the chelating agent is ethylenediamine tetracetic acid (“EDTA”), and more preferably is tetrasodium EDTA, available commercially from Dow Chemical Company of Midland, Mich. under the tradename, “Versene 100XL” and is present in an amount, based upon the total weight of the composition, from about 0 to about 0.5 percent or from about 0.05 percent to about 0.25 percent.
Suitable preservatives include organic acid preservatives may include benzoic acid and alkali metal and ammonium salts thereof (e.g. sodium benzoate), sorbic acid and alkali metal and ammonium salts thereof (e.g. potassium sorbate), p-Anisic acid and alkali metal and ammonium salts thereof, and salicylic acid and alkali metal and ammonium salts thereof. The pH of the composition may be adjusted to the appropriate acidic value using any cosmetically acceptable organic or inorganic acid, such as citric acid, acetic acid, glycolic acid, lactic acid, malic acid, tartaric acid, or hydrochloric acid.
In one embodiment of the composition, sodium benzoate is present in the composition in an amount, based upon the total weight of the composition, from about 0 to about 0.5 percent. In another embodiment, potassium sorbate is present in the composition in an amount, based upon the total weight of the composition, from about 0 to about 0.6 percent, more preferably from about 0.3 to about 0.5 percent.
The methods of this invention may further comprise, consist essentially of and consist of any of a variety of steps for mixing or introducing one or more of the optional components described hereinabove with or into a composition comprising a polymeric material before, after, or simultaneously with the combining step described above. While in certain embodiments, the order of mixing is not critical, it is preferable, in other embodiments, to pre-blend certain components, such as the fragrance and the nonionic surfactant before adding such components into a composition comprising a polymeric material and/or an anionic surfactant.
The cleansing methods of this invention may further include any of a variety of additional, optional steps associated conventionally with cleansing hair and skin including, for example, lathering, rinsing steps, and the like.
Although applicants do not wish to be bound by or to any particular theory of operation, it is believed that surfactant associated with the low molecular weight hydrophobically-modified polymer (hm-polymer) is more stable than surfactants that exist as a micelle. Thus, surfactant contained in a micelle structure more readily disperses out of the micelle than it does when associated with low molecular weight hydrophobically-modified polymer.
The foregoing information regarding low molecular weight hydrophobically-modified polymers as well as compositions that may be useful in the methods of this invention are set forth in 7803403, US2006/0257348, and US20070111910, all of which are hereby incorporated herein by reference.
The methods and compositions of this invention illustratively disclosed herein suitably may be practiced in the absence of any component, ingredient, or step which is not specifically disclosed herein. Several examples are set forth below to further illustrate the nature of the invention and the manner of carrying it out. However, the invention should not be considered as being limited to the details thereof.
Methods
Clarity Test:
The clarity of each sample was measured via the Clarity Test, the procedure for which involves preparing a 1 cm cell sample of the composition to be measured and measuring the % light transmittance associated with such sample using an Agilent 8453 UV-Visible Spectrophotometer with a 1 cm cell at a wavelength of 800 nm. The clarity was determined for each cleansing composition without dilution. The results are reported as % T, the % transmittance through cleansing composition in the 1 cm cell.
Light Scattering Test:
The clarity of a cleanser is determined by colloidal assembles that scatter light. A cleanser that is clearer typically will have only small colloidal assemblies. Larger colloidal assemblies, on the order of 1⁄3 the wavelength of light, will scatter light and produce a hazy or turbid solution.
The cleanser samples were analyzed using a Zetasizer Nano ZS DLS instrument (Malvern Instruments, Inc., Southborough, Mass.) operating at 25.0° C. The instrument was integrated with the Malvern Dispersion Technology Software. The unfiltered sample solutions was diluted to 3% and dispensed into cuvettes (12 mm Square Polystyrene Cuvettes, DTS0012) to the 10 mm mark, and covered. The measurements were done at attenuation 7, with a 4 mW He—Ne, 633 nm laser at position 4.65 mm. The temperature was kept constant at 25 degrees Celsius. Measurements were done in 3 repetitions and 11 runs each.
The laser (at 633 nm) is incident on the cleansing composition and scatters from colloidal assemblies back to the detector. A hazy cleansing solution will have more and larger colloidal particles therefore producing more scattering to the detector and a higher count rate.
Example 1
Comparatives C1-C4
Preparation of Cleansing Compositions
The cleansing compositions of C1-C4 were prepared according to the materials and amounts listed in Table












TABLE 1







Cl
C2
C3
C4


Trade Name
INCI name
w/w %
w/w %
w/w %
w/w %




















Cedepal TD-403
Sodium Trideceth 
2.70
2.70
2.70
2.70


(30%)
Sulfate






Tegobetaine 
Cocamidopropyl 
2.70
2.70
2.70
2.70


L-7V (30%)
Betaine






Merquat S
Polyquaternium-7
0.01
0.01
0.01
0.01


Versene 100 XL
Tetrasodium 
0.10
0.10
0.10
0.10



EDTA






Aqua SF-1 
Acrylates 
—
1.80
—
—


(30%)
Copolymer






Ex-968 (30%)
Potassium 
—
—
1.80
—



Acrylates







Copolymer






Inutec SP-1
Inulin Lauryl 
—
—
—
1.80



Carbamate






20% NaOH
Sodium Hydroxide
qs
qs
qs
qs


Deionized water
Water
qs
qs
qs
qs





*expressed in % w/w actives






Each of the compositions of Table 1 was independently prepared as follows: Water (50.0 parts) was added to a beaker. The following ingredients were then added thereto independently with mixing until each respective resulting mixture was homogenous: the hm-polymer (Ex. 968, Aqua SF-1, Inutec SP-1, etc. depending on the example), Cedepal TD403MF-D, Tegobetaine L7-V, Merquat S, Versene 100XL, and Nipasept. The pH of the resulting solution was then adjusted with a 20% solution of Citric Acid or Sodium hydroxide solution until the final desired pH was obtained. The remainder of the water was then added thereto. Formulas with the same components, but different pH's were all made independently.
Example 2
Clarity Results for Samples C1-C4 at Different pH's
The clarity of compositions of C1-C4 determined according to the Clarity test.











TABLE 2







hydrophobically-modified

Clarity


Ex
Base
Polymer added
pH
(% T)







C1
—
No polymer
6.3-6.6
99.1


C2
—
Acrylates copolymer
6.3-6.6
88.3


C3
—
Potassium Acrylates Copolymer
6.3-6.6
98.8


C4
—
Inulin Lauryl Carbamate
6.3-6.6
37.1


C2
—
Acrylates copolymer
4.0
18.0


C3
—
Potassium Acrylates Copolymer
4.0
24.1


C4
—
Inulin Lauryl Carbamate
4.0
36.4



JBS
Potassium Acrylates Copolymer
6.5
95.3



JBS
Potassium Acrylates Copolymer
4.8
27.5



HTT
Potassium Acrylates Copolymer
6.5
93.9



HTT
Potassium Acrylates Copolymer
4.8
17.7









Table 2 shows the results of the clarity test of a series of cleansing compositions (C1-C4) containing a series of low molecular weight hydrophobically-modified polymers and a combination of ethoxylated anionic surfactant and amphoteric surfactant, Sodium Trideceth Sulfate and Cocamidopropyl Betaine, respectively as described in Table 1. While the clarity of the cleansing compositions are clear (i.e. have a % Transmittance as measured by the Clarity test greater than about 90%) at high pH, around about 6.3, the clarity is much lower at lower pH. Six grams of the low molecular weight hydrophobically-modified polymer potassium acrylates copolymer were added to 94 grams samples of each of the commercial products JBS (Johnson's Baby Shampoo which contains the ingredients as listed on the label (Water, Cocamidopropyl Betaine, PEG-80 Sorbitan Laurate, Sodium Trideceth Sulfate, PEG-150 Distearate, Fragrance, Tetrasodium EDTA, Polyquaternium-10, Quaternium-15, Sodium Hydroxide, Citric Acid, D&C Yellow 10, D&C Orange 4) and HTT (Johnson's Head-to-Toe Body Baby Wash which contains the ingredients as listed on the label (Water, Cocamidopropyl Betaine, PEG-80 Sorbitan Laurate, Sodium Laureth Sulfate, PEG-150 Distearate, Tetrasodium EDTA, Sodium Chloride, Polyquaternium-10, Fragrance, Quaternium-15, Citric Acid). The new clarity of the new compositions was measured by the Clarity test. The clarity of the cleansing compositions is greater than about 90% (clear) at high pH, around about 6.3, and the clarity is lower at lower pH. In US, 7803403 cleansing systems containing sodium trideceth sulfate or sodium laureth sulfate and commercial products JBS and HTT were evaluated. While U.S. Pat. No. 7,803,403 shows clear cleansing systems with a low molecular weight linear acrylic polymer and these surfactants, when these systems are prepared at lower pH (below about a pH of 6.2) the cleansing systems lose clarity and become hazy and translucent.
Example 3
Comparatives C5-C11
Preparation of Cleansing Compositions
The cleansing compositions of C5-C11 were prepared according to the materials and amounts listed in Table 3.














TABLE 3






C5
C6
C7
C8
C9
C10
C11


INCI name
w/w %
w/w %
w/w %
w/w %
w/w %
w/w %
w/w %






















Sodium Benzoate
0.50
0.50
0.50
0.50
0.50
0.50
0.50


Potassium Acrylates Copolymer
1.80
1.80
1.80
1.80
1.80
1.80
1.80


Cocamidopropyl hydroxysultaine
—
3.40
—
—
—
—
—


Decyl Glucoside
—
—
3.70
—
—
—
—


Cocamidopropyl betaine
—
—
—
2.1
4.4
—
—


Disodium lauroamphodiacetate
—
—
—
—

2.5
5.3


Sodium hydroxide
q.s.
q.s.
q.s.
q.s.
q.s.
q.s.
q.s.


Water
q.s.
q.s.
q.s.
q.s.
q.s.
q.s.
q.s.





*expressed in w/w % actives






Each of the compositions of Table 3 was independently prepared as follows: Water (50.0 parts) was added to a beaker. The following ingredients were then added thereto independently with mixing until each respective resulting mixture was homogenous: the hydrophobically-modified polymer Potassium Acrylates Copolymer (Ex. 968, Lubrizol, Brecksville, Ohio), then the surfactant Cocamidopropyl hydroxysultaine, Decyl Glucoside, Cocamidopropyl betaine, or Disodium lauroamphodiacetate as called for. The pH of the resulting solution was then adjusted with a 20% solution of Sodium hydroxide or citric acid until the final desired pH was obtained. The remainder of the water was then added thereto. Formulas with the same components, but different pH's were all made independently.
Example 4
Clarity Results for Samples C5-C11 at Different pH's
The clarity of compositions of C5-C11 determined according to the Clarity test.












TABLE 4








Surfactant

Clarity


Ex
Surfactant Type
Surfactant
(w/w %)
pH
(% T)




















C5
—
No surfactant:
0
4.0
3.8




hydrophobically-







modified polymer at







1.8%





C6
Amphoteric
Cocamidopropyl
3.4
5.0
86.9




hydroxysultaine





C6
Amphoteric
Cocamidopropyl
3.4
6.0
84.2




hydroxysultaine





C7
Non-ionic
Decyl Glucoside
3.7
5.0
86.7


C7
Non-ionic
Decyl Glucoside
3.7
6.0
83.4


C8
Amphoteric Cocamidopropyl betaine
2.1
4.0
Separated



C9
Amphoteric Cocamidopropyl betaine
4.4
4.0
Separated



 C10
Amphoteric
Disodium
2.5
4.0
Separated




lauroamphoacetate





 C11
Amphoteric
Disodium
5.3
4.0 
Separated




lauroamphoacetate












As shown in Table 4, the low Mw hydrophobically-modified polymer without surfactant, C5, at a low pH of 4.0 has a low clarity. As shown in Table 2, clear cleansing compositions are readily made at moderate pH's (pH between about 6.3-6.6) with the low molecular weight linear acrylic polymer, Potassium Acrylates Copolymer, and a number of different types of surfactant systems. Table 4 shows cleansing compositions that are not clear (% T less than about 90%) at low pH: the low molecular weight linear acrylic polymer, Potassium Acrylates Copolymer, and the amphoteric and non-ionic surfactants, Cocamidopropyl hydroxysultaine and Decyl Glucoside respectively. Table 4 also shows cleansing compositions that phase separate and form a white precipitate at low pH, Cocamidopropyl betaine and Disodium lauroamphodiacetate, respectively. This phase separation was present at low and high surfactant concentrations.
Example 5
Comparatives C12-C18
Preparation of Cleansing Compositions
The cleansing compositions of C12-C18 were prepared according to the materials and amounts listed in Table 5.














TABLE 5






C12
C13
C14
C15
C16
C17
C18


INCI name
w/w %
w/w %
w/w %
w/w %
w/w %
w/w %
w/w %






















Sodium Benzoate
0.50
0.50
0.50
0.5
0.5
0.50
0.50


Potassium Acrylates Copolymer
1.80
1.80
1.80
1.8
1.80
1.80
1.80


Sodium Trideceth Sulfate
2.70
—
—
—
—
—
—


Sodium Laureth Sulfate
—
0.80
4.60
—
—
—
—


Sodium Alpha Olefin Sulfonate
—
—
—
2.00
3.90
—
—


Sodium Coco Sulfate
—
—
—
—
—
1.80
3.70


Sodium hydroxide
q.s.
q.s.
q.s.
q.s.
q.s.
q.s.
q.s.


Water
q.s.
q.s.
q.s.
q.s.
q.s.
q.s.
q.s.





*expressed in w/w % actives






Each of the compositions of Table 5 was independently prepared as follows: Water (50.0 parts) was added to a beaker. The following ingredients were then added thereto independently with mixing until each respective resulting mixture was homogenous: the hydrophobically-modified polymer, Potassium Acrylates Copolymer (Ex. 968, Lubrizol, Brecksville, Ohio), then the surfactant Sodium Trideceth Sulfate, Sodium Laureth Sulfate, Sodium Alpha Olefin Sulfonate, or Sodium Coco Sulfate was added as called for. The pH of the resulting solution was then adjusted with a 20% solution Sodium hydroxide or Citric acid until the final desired pH was obtained. The remainder of the water was then added thereto. Formulas with the same components, but different pH's were all made independently.
Example 6
Clarity Results for Samples C12-C18 at Different pH's
The clarity of compositions of C12-C18 was determined according to the Clarity test.












TABLE 6








Surfactant

Clarity


Ex
Surfactant Type
Surfactant
(w/w %)
pH
(% T)




















C12
Ethoxylated
Sodium Trideceth
2.7
4.0
81.9




Sulfate





C13
Ethoxylated
Sodium Laureth Sulfate
0.8
4.0
78.8


C14
Ethoxylated
Sodium Laureth Sulfate
4.6
4.0
88.7


C15
Anionic non-EO Sodium Alpha Olefin
2.0
4.0
86.1





Sulfonate





C16
Anionic non-EO
Sodium Alpha Olefin
3.9
4.0
95.7




Sulfonate





C17
Anionic non-EO
Sodium Coco Sulfate
1.8
4.0
83.7


C18
Anionic non-EO
Sodium Coco Sulfate
3.7
4.0
99.6









As shown in Table 2, clear cleansing compositions are readily made at moderate pH's (pH between about 6.3 and about 6.6) with the low molecular weight linear acrylic polymer, Potassium Acrylates Copolymer, and a number of different types of surfactant systems. However in Table 2, when these cleansing compositions are taken to low pH (below a pH of about 6.2), they lose clarity. Furthermore, the lower pH cleansing compositions C12-C14 contain a range of ethoxylated anionic surfactants over a range of levels, none of which achieve clear systems at low pH.
Cleansing compositions with the low molecular weight linear acrylic polymer, Potassium Acrylates Copolymer, and a low amount of non-ethoxylated anionic surfactant, Sodium Alpha Olefin Sulfonate and Sodium Coco Sulfate, C15 and C17, respectively, also have low clarity. However, cleansing systems with the low molecular weight linear acrylic polymer, Potassium Acrylates Copolymer, and non-ethoxylated anionic surfactant can achieve high clarity, C16 and C18. A sufficient amount of anionic surfactant, more than about 2.0% actives, is requirement to achieve a sufficiently clear formula.
Example 7
Comparative Examples C19-25
Non-Ethoxylated Anionic Surfactant Cleansing Compositions and Clarity
The cleansing compositions of C19-25 were prepared according to the materials and amounts listed in Table 7.














TABLE 7






C19
C20
C21
C22
C23
C24
C25


INCI name
w/w %
w/w %
w/w %
w/w %
w/w %
w/w %
w/w %






















Sodium Benzoate
0.5
0.5
0.5
0.50
0.50
0.50
0.5


Potassium Acrylates
1.80
1.80
1.80
1.80
1.80 1.80
1.80



Copolymer









Ammonium Lauryl
3.4
—
—
—
—
—
—


Sulfate









Sodium Dodecyl
—
8.40
16.8
—
—
—
—


Benzene Sulfonate









Sodium Lauryl Sulfate
—
—
—
12.0
—
—
—


Sodium Tridecyl
—
—
—
—
3.4
—
—


Sulfate 303









Sodium Tridecyl
—
—
—
—
—
3.4
—


Sulfate 203









Sodium Tridecyl
—
—
—
—
—
—
3.4


Sulfate Agt









Sodium Hydroxide
q.s
q.s.
q.s.
q.s.
q.s.
q.s.
q.s.


Water
q.s
q.s.
q.s.
q.s.
q.s.
q.s.
q.s.





*expressed in % w/w actives






Each of the compositions of Table 7 was independently prepared as follows: Water (50.0 parts) was added to a beaker. The following ingredients were then added thereto independently with mixing until each respective resulting mixture was homogenous: the hydrophobically-modified polymer, Potassium Acrylates Copolymer (Ex. 968, Lubrizol, Brecksville, Ohio), then the surfactant Ammonium Lauryl Sulfate, Sodium Dodecyl Benzene Sulfonate, Sodium Lauryl Sulfate, or Sodium Tridecyl Sulfate as called for. The pH of the resulting solution was then adjusted with a 20% solution Sodium hydroxide or Citric acid until the final desired pH was obtained. The remainder of the water was then added thereto. Formulas with the same components, but different pH's were all made independently.
Example 8
Clarity Results for Comparative Examples C16, 18-25 at Different pH's
The clarity of compositions of C16, 18-25 was determined according to the Clarity test.













TABLE 8








Sur-


Count





factant


rate



Surfactant

(w/w

Clarity
(@7)


Ex
Type
Surfactant
%)
pH
(% T)
kcts/s





















C16
Anionic
Sodium Alpha
3.9
4.0
95.7
—



non-EO
Olefin Sulfonate 






C16
Anionic
Sodium Alpha
3.9
5.0
99.4
—



non-EO
Olefin Sulfonate






C16
Anionic
Sodium Alpha
3.9
6.5
99.4
—



non-EO
Olefin Sulfonate






C18
Anionic
Sodium Coco
3.7
4.0
99.6
—



non-EO
Sulfate






C18
Anionic
Sodium Coco
3.7
5.0
99.9
—



non-EO
Sulfate






C18
Anionic
Sodium Coco
3.7
6.5
99.6
—



non-EO
Sulfate






C19
Anionic
Ammonium 
3.4
4.0
100.0
36.7



non-EO
Lauryl Sulfate






C19
Anionic
Ammonium 
3.4
5.0
100.0
—



non-EO
Lauryl Sulfate






C19
Anionic
Ammonium 
3.4
6.5
100.0




non-EO
Lauryl Sulfate






C20
Anionic
Sodium dodecyl
8.4
4.0
90.6
—



non-EO
benzene sulfonate






C21
Anionic
Sodium dodecyl
16.8
4.0
98.2
18.8



non-EO
benzene sulfonate






C21
Anionic
Sodium dodecyl
16.8
5.0
99.7
—



non-EO
benzene sulfonate






C22
Anionic
Sodium Lauryl
12.0
5.0
99.8
10.1



non-EO
Sulfate






C22
Anionic
Sodium Lauryl
12.0
6.5
97.9
—



non-EO
Sulfate






C23
Anionic
Sodium Tridecyl
3.4
4.5
98.9
—



non-EO
Sulfate 303






C23
Anionic
Sodium Tridecyl 
3.4
6.5
100
—



non-EO
303 Sulfate 






C24
Anionic
Sodium Tridecyl
3.4
4.5
99.4
—



non-EO
Sulfate 203






C24
Anionic
Sodium Tridecyl
3.4
6.5
99.9




non-EO
Sulfate 203






C25
Anionic
Sodium Tridecyl
3.4
4.5
97.4
—



non-EO
Sulfate Agt






C25
Anionic
Sodium Tridecyl
3.4
6.5
98.3
—



non-EO
Sulfate Agt













All of the cleansing compositions in Table 8, C16, 18-25, contain the low Mw hydrophobically-modified polymer, Potassium Acrylates copolymer, and a range of non-ethoxylated anionic surfactants at levels above 2.0% actives, and all of these cleansing compositions have high clarity as measured by the Clarity test and or the Light Scattering test (clarity when the count rate is less than about 70 kcts/s). In cleansing compositions with low MW hydrophobically-modified polymer and non-ethoxylated anionic surfactants, at levels between about 9.0 wt % actives and about 2.0 wt % actives, the clarity of the compositions was high even at low pH.
Example 9
Inventive Examples E1-6
Non-Ethoxylated Anionic Surfactant-Amphoteric Surfactant Cleansing Compositions
The cleansing compositions of E1-6 were prepared according to the materials and amounts listed in Table 9.













TABLE 9






E1
E2
E3
E4
E5
E6


INCI Name
w/w %
w/w %
w/w %
w/w %
w/w %
w/w %





















Glycerin
0.50
0.50
0.50
0.50
0.50
0.50


Sodium Coco-Sulfate
1.66







Sodium Lauryl Sulfoacetate
1.30







Sodium Lauryl Sulfosuccinate




3.00



Sodium C14-16 Olefin Sulfonate





2.82


Ammonium Lauryl Sulfate

1.82
0.91





Sodium Isotridecyl Alcohol Sulfate



2.78
1.26



Cocamidopropyl Betaine
6.30
4.38
2.19
4.38
2.92
0.70


Cocamidopropyl Hydroxysultaine
3.36







Polyglyceryl-10 Laurate
1.00







hydrophobically-modified polymer Potassium
0.30
0.30
0.30
0.60
0.30
0.90


Acrylates Copolymer








Polyquaternium-7
0.08







Sodium Benzoate




0.50
0.50


Potassium Sorbate

0.50
0.50





Dowicil 200



0.05




Phenoxyethanol; Ethylhexylglycerin (Euxyl
0.80







PE9010)








Fragrance
0.20
0.20
0.20
0.20
0.20
0.20


Sodium Hydroxide
QS
QS
QS
QS
QS
QS


Citric Acid
QS
QS
QS
QS
QS
QS


Water
QS
QS
QS
QS
QS
QS





*expressed in % w/w actives






Each of the compositions of Table 9 was prepared as follows: Water (50.0 parts) was added to a beaker. The following ingredients were then added thereto independently with mixing and/or heating until each respective resulting mixture was homogenous: Polyglyceryl-10 Laurate and Sodium Lauryl Sulfoacetate with heat to 70° C. Then the heat was removed and the mixture was allowed to cool while the following ingredients were added: glycerin, then the surfactants, Sodium Lauryl Sulfosuccinate, Sodium C14-16 Olefin Sulfonate, Ammonium Lauryl Sulfate, Sodium Isotridecyl Alcohol Sulfate, Sodium Coco-Sulfate, Cocamidopropyl Betaine, and/or Cocamidopropyl Hydroxysultaine, and then Polyquaternium-7 where required, then the hydrophobically-modified polymer, Potassium Acrylates Copolymer (Ex. 968, Lubrizol, Brecksville, Ohio), and then the preservative and fragrance as called for. The pH of the resulting solution after the addition of hydrophobically-modified polymer, Potassium Acrylates Copolymer, (Ex. 968, Lubrizol, Brecksville, Ohio), was adjusted with a 20% solution of sodium hydroxide to a pH greater than 7.0. After the addition of preservative and fragrance, the pH of the resulting solution was adjusted with 20% solution of citric acid until the final desired pH was obtained. The remainder of the water was then added thereto. Formulas with the same components, but different pH were made from the same batch and samples were taken at different pH levels.
Example 10
Clarity Results for Inventive Examples E1-6 at Different pH
The clarity of compositions of E1-6 was determined according to the Clarity test and the Light Scattering test.













TABLE 10











Count




Surfactant
Anionic:

Clarity
Rate (@7)


Ex
Surfactants
(w/w %)
Amphoteric
pH
(% T)
kcts/s





















E1
Sodium Coco-Sulfate
13.6
0.3
6.0
90.2




Sodium Lauryl








Sulfoacetate








Cocamidopropyl








Hydroxysultaine







E2
Ammonium Lauryl
6.2
0.4
6.0
98.5




Sulfate








Cocamidopropyl








Betaine







E2
Ammonium Lauryl
6.2
0.4
4.8
77.9




Sulfate








Cocamidopropyl








Betaine







E3
Ammonium Lauryl
3.1
0.4
6.0
99.1
15.7



Sulfate








Cocamidopropyl








Betaine







E3
Ammonium Lauryl
3.1
0.4
4.8
44.9
91.7



Sulfate








Cocamidopropyl








Betaine







E4
Sodium Isotridecyl
7.2
0.6
4.8
99.3




Alcohol Sulfate








Cocamidopropyl








Betaine







E5
Sodium Isotridecyl
7.2
1.5
4.8
98.7




Alcohol Sulfate








Disodium Lauryl








Sulfosuccinate








Cocamidopropyl








Betaine







E6
Alpha Olefin
3.5
4.0
5.5
95.4
32.7



Sulfonate








Cocamidopropyl








Betaine







E6
Alpha Olefin
3.5
4.0
4.8 94.8
36.7




Sulfonate








Cocamidopropyl








Betaine









The previous cleansing compositions, C1-C4 and C6-C10, shown, have contained amphoteric, nonionic and/or ethoyxlated anionic surfactants. All of these cleansing compositions, at lower pH (i.e., below about 6.2), have demonstrated low clarity. All of the cleansing compositions in Table 8, C16, 18-25, contain the low Mw hydrophobically-modified polymer, Potassium Acrylates copolymer, and a range of non-ethoxylated anionic surfactants at levels above 2.0% actives, and all of these cleansing compositions have had high clarity.
Surprisingly, combining low Mw hydrophobically-modified polymer, Potassium Acrylates copolymer, and non-ethoxylated anionic surfactants with amphoteric surfactants produces cleansing compositions that are clear below pH about 6.2 (E1-6 from Table 10). In low Mw hydrophobically-modified polymer, Potassium Acrylates copolymer, and non-ethoxylated anionic surfactant blends with amphoteric surfactant, the ratio of anionic:amphoteric surfactant is critical for achieving clarity at low pH. When the anionic:amphoteric surfactant ratio is less than about 0.5, clarity is achieved at pH less than about 6.2 but is not achieved at lower pH, i.e., less than about 4.8. The effect of anionic:amphoteric surfactant ratio on cleansing composition clarity is independent of total surfactant concentration. Surprisingly, in cleansing compositions with anionic:amphoteric surfactant ratio less than about 0.5, the concentration of non-ethoxylated anionic surfactant was less than about 2% actives and the cleansing compositions are clear at less than about 6.2 and greater than about 4.8.
When the anionic:amphoteric surfactant is greater than about 0.5, clarity is achieved at pH less than about 6.2. Clarity at low pH for anionic-amphoteric surfactant cleansing compositions with low Mw hydrophobically-modified polymer, Potassium Acrylates copolymer, is achieved for non-ethoxylated anionic surfactants blended with amphoteric surfactants but is not achieved for low Mw hydrophobically-modified polymer, Potassium Acrylates copolymer, and ethoxylated anionic surfactants blended with amphoteric surfactants.

## Claims

1. A skin cleansing composition comprising:
(a) a low molecular weight, non-crosslinked, linear acrylic copolymer derived from at least one first monomeric component selected from the group consisting of (meth)acrylic acid and at least one second monomeric component selected from the group consisting of one or more C1 to C9 alkyl (meth)acrylates, wherein the low molecular weight copolymer has a number average molecular weight of about 100,000 or less; and
(b) a surfactant component comprising at least one non-ethoxylated anionic surfactant and at least one amphoteric surfactant; wherein the total surfactant load of said skin cleansing composition is not greater than about 14 weight percent of the skin cleansing composition; the pH of said skin cleansing composition is about 6.2 or less; and the skin cleansing composition has a count rate of about 70 kcts/s or less in a light scattering test.

2. A skin cleansing composition comprising:
(a) a low molecular weight, non-crosslinked, linear acrylic copolymer derived from at least one first monomeric component selected from the group consisting of (meth)acrylic acid and at least one second monomeric component selected from the group consisting of one or more C1 to C9 alkyl (meth)acrylates, wherein the low molecular weight copolymer has a number average molecular weight of about 100,000 or less; and
(b) a surfactant component comprising at least one non-ethoxylated anionic surfactant and at least one amphoteric surfactant; wherein the total surfactant component of said skin cleansing composition is not greater than about 14 weight percent of the skin cleansing composition; the pH of said skin cleansing composition is about 6.2 or less; and the skin cleansing composition has a light transmittance of greater than about 90%.

3. A skin cleansing composition according to claim 1 wherein the at least one non-ethoxylated anionic surfactant and the at least one amphoteric surfactant are present in a ratio of less than 0.5 and the pH is from about 4.8 to about 6.2.

4. A skin cleansing composition according to claim 1 wherein the at least one non-ethoxylated anionic surfactant and the at least one amphoteric surfactant are present in a ratio of greater than 0.5 and the pH is less than about 6.2.

5. A skin cleansing composition according to claim 1 wherein said surfactant component comprises (a) at least one non-ethoxylated anionic surfactant and (b) at least one amphoteric surfactant.

6. A skin cleansing composition according to claim 5 wherein the ratio between surfactant (a) and surfactant (b) is less than about 0.5 and the pH of said composition is from about 4.8 to about 6.2.

7. A skin cleansing composition according to claim 5 wherein the ratio between surfactant (a) and surfactant (b) is greater than about 0.5 and the pH of said composition is less than about 6.2.

8. A skin cleansing composition according to claim 1 wherein said at least one non-ethoxylated anionic surfactant is selected from the group consisting of alkyl sulfates and sulfonates.

9. A skin cleansing composition according to claim 1 wherein said amphoteric surfactants are selected from the group consisting of betaines, sultaines monoamphoacetates and amphoacetates (mono or di).

10. A skin cleansing composition according to claim 1 wherein said a low molecular weight, non-crosslinked, linear copolymer is a non-crosslinked, linear acrylic polymer.

11. A skin cleansing composition according to claim 1 wherein said composition further comprises a nonionic surfactant.

12. A skin cleansing composition comprising:
(a) a low molecular weight, non-crosslinked, linear acrylic copolymer derived from at least one first monomeric component selected from the group consisting of (meth)acrylic acid and at least one second monomeric component selected from the group consisting of one or more C1 to C9 alkyl (meth)acrylates, wherein the low molecular weight copolymer has a number average molecular weight of about 100,000 or less; and
(b) a surfactant component comprising at least one non-ethoxylated anionic surfactant and at least one amphoteric surfactant and at least one nonionic surfactant; wherein the total surfactant load of said skin cleansing composition is not greater than about 14 weight percent of the skin cleansing composition; the pH of said skin cleansing composition is about 6.2 or less; and the skin cleansing composition has a count rate of about 70 kcts/s or less in a light scattering test.

13. A skin cleansing composition comprising:
(a) a low molecular weight, non-crosslinked, linear acrylic copolymer derived from at least one first monomeric component selected from the group consisting of (meth)acrylic acid and at least one second monomeric component selected from the group consisting of one or more C1 to C9 alkyl (meth)acrylates, wherein the low molecular weight copolymer has a number average molecular weight of about 100,000 or less; and
b) a surfactant component comprising at least one non-ethoxylated anionic surfactant and at least one amphoteric surfactant and further comprises a nonionic surfactant; wherein the total surfactant component of said skin cleansing composition is not greater than about 14 weight percent of the skin cleansing composition; the pH of said skin cleansing composition is about 6.2 or less; and the skin cleansing composition has a light transmittance of greater than about 90%.

14. A skin cleansing composition according to claim 13 wherein said nonionic surfactant is selected from the group consisting of fatty alcohol acid, fatty alcohol amide ethoxylates, monoglyceride ethoxylates, sorbitan ester ethoxylates, alkyl polyglucosides, polyglyceryl esters and mixtures thereof.

15. A method of cleansing the skin comprising applying to the skin the composition according to claim 1.