WO2000057846A1

WO2000057846A1 - Low voc hair spray compositions having enhanced styling benefits

Info

Publication number: WO2000057846A1
Application number: PCT/EP2000/001945
Authority: WO
Inventors: Natalia Nekludoff; Diane Marie Dabkowski; Tirucherai Varahan Vasudevan; Jennifer Marie Seper
Original assignee: Unilever Plc; Unilever Nv; Hindustan Lever Limited
Priority date: 1999-03-25
Filing date: 2000-03-06
Publication date: 2000-10-05
Also published as: JP2002540132A; AR023149A1; AU3164400A

Abstract

An aqueous or hydroalcoholic, aerosol or non-aerosol hair styling aid or mousse composition containing a water soluble or dispersable fixative polymer in an amount from 1 % to 40 % by weight of the composition, a neutralizing agent in an amount from 0.1 to 10 wt.%, a hydrocarbon based surfactant in an amount from 0.01 % to 5 % by weight, a salt from 0.01 % to 10 % by weight, alcohol from 10 % to 90 % by weight, a volatile ester from 0 to 90 % by weight, a volatile ketone from 0 to 90 % by weight and water from 10 % to 98 % by weight of the composition. Additionally, aerosol compositions contain a liquefied propellant gas from 5 % to 60 % by weight of the composition.

Description

LOW VOC HAIR SPRAY COMPOSITIONS HAVING ENHANCED STYLING

BENEFITS

BACKGROUND OF THE INVENTION

Regulations and laws designed to protect the environment, are leading to the production of hair care spray products which have lower volatile organic compounds (VOC) content than the current commercial products.

This invention relates to 55% VOC (and lower VOC) hair spray compositions that provide hold and feel properties similar to or better than that of the current 80% VOC hair sprays. The performance characteristics of hair sprays suffer as the VOC level is reduced from 80% to 55% in the product. Therefore, preparing 55% VOC (and lower VOC) hairspray products which have the same or better performance characteristics as 80% VOC hairspray products would be desirable .

U.S. patents in this area of technology are as follows:

U.S. Patent 5,374,420 discloses a hairspray/ hair setting composition comprising: a) 0.001-20% of a neutralizable hair fixative resin, b) 0.001-8% of a base, and c) 0.001-5% of an acid surfactant precursor in an alcohol or aqueous/alcohol carrier. U.S. Patent 5,164,177 discloses an aerosol or non-aerosol hair styling aid or mousse composition, and method, including a water-soluble or water-dispersable fixative resin in an amount of about 2% to about 40%; an electrolyte; water in an amount of about 30% to about 90%; alcohol in an amount of 0% to about 30%, and with aerosol compositions, a liquefied propellant gas such as dimethyl ether, in an amount of about 5% to about 50%.

SUMMARY OF THE INVENTION

As noted above, the performance characteristics of hair sprays generally suffer as the VOC level is reduced from 80% to 55% in the product. The purpose of this invention is to maintain and improve the performance characteristics of the 80% VOC system in the 55% VOC product.

In the present invention, the deterioration of the spray characteristics of a hydroalcoholic solution containing the hair spray resin which occurred as the VOC content was reduced from 80 to 55% was offset by incorporation of a unique combination of hydrocarbon based surfactants and an organic salt as described below. The same benefit can be obtained in aqueous systems.

The invention relates to an aqueous or hydroalcoholic, non- aerosol or aerosol hair spray composition containing a water soluble or dispersable fixative polymer in an amount from about 1% to about 40 % by weight of the composition, a neutralizing agent in an amount from about 0.1 to about 10 wt %, a hydrocarbon based surfactant in an amount from about 0.01% to about 5% by weight, a salt from about 0.01% to about 10% by weight, alcohol from about 0% to about 90%, more preferably, from about 10% to about 90% by weight, a volatile ester from about 0 to 90% by weight, more preferably about 10% to about 90% by weight; a volatile ketone from about 0 to 90% by weight, more preferably about 10% to about 90% by weight; in the case of aerosols from about 5 to about 60% by weight of liquidfied propellant gas, and water from about 10% to about 98% by weight of the composition.

As can be seen the compositions of the invention can be aqueous or hydroalcoholic.

DETAILED DESCRIPTION OF THE INVENTION

As used herein, % means weight % of the total composition unless otherwise indicated. "m N/m" means milli

Newtons/meter . Dynes/cm is the same as milli Newtons/meter .

The starting materials set forth herein are either known or can be prepared according to known methods. The compositions of the invention can be prepared either by known methods or by methods analogous to known methods.

As noted above, in the present invention, the deterioration of the spray characteristics of a hydroalcoholic solution containing the hair spray resin which occurred as the VOC content was reduced from 80 to 55% was offset by incorporation of a unique combination of hydrocarbon based surfactants and an organic salt. The same benefit can be obtained in aqueous systems.

In the present invention, the hydrocarbon surfactant may be selected from the group consisting of: sodium dioctyl sulfo succinate, sodium dodecyl sulfate, cocoamidopropyl betaine, and sodium laureth sulfate, and the like. In fact any hydrocarbon based surfactant suitable for use in hairspray compositions may be employed in the compositions of the invention. Other examples of anionic surfactants are sodium dinonyl sulfo succinate, sodium decyl sulfate, sodium alpha olefin sulfonate and the like. Nonionic and cationic surfactants may also be employed.

In the present invention, the organic salt is an organic salt which can be used in hairspray compositions and may be selected, for example, from the group consisting of: sodium benzoate, magnesium acetate, sodium acetate, sodium citrate, potassium acetate, sodium salicylate, sodium tartrate, sodium phenylsalicylate, sodium oxalate, sodium adipate, sodium butyrate, sodium caprate, sodium caproate, sodium maleate, sodium malate, sodium malonate, sodium phthalate, sodium propionate, sodium pyruvate, sodium fumarate.

In the present invention, the neutralizing agent may be selected, for example, from the group consisting of: 2- amino , 2 -methyl, 1- propanol , 2 -amino, 2 -methyl , 1,3- propanediol, dimethyl stearamine, histidine, tris (hydroxymethyl) aminomethane, triethanol amine, sodium hydroxide, and potassium hydroxide.

In the present invention, the soluble or dispersible fixative polymer may be selected from the group consisting of: vinyl and acrylic based resins and polyurethane resins. Specific resins include, but are not limited to, acrylamide copolymers, acrylate copolymers, which may or may not be modified by introduction of a quaternary ammonium group. Other fixative resins are described in copending U.S. Patent Application Serial No. 08/717,113 to Bhatt et al , filed September 20,1996. The use of resins or polymers in hairsprays is known as summarized in Grollier et al U.S. Patent No. 4,445,521. The molecular weight of the polymer has a preferred range of about 10,000 to about 1 million Daltons, a more preferred range is about 20,000 to about 500,000 Daltons and the most preferred range is about 30,000 to about 300,000.

In the present invention, the inorganic salt may be selected, for example, from the group consisting of chloride, sulfate, and nitrate salts of sodium, magnesium and ammonium.

In the present invention, the alcohol, if present, may be selected from the group consisting of: ethanol and isopropanol .

In the present invention volatile ester, if present, may be selected, for example, from the group methyl acetate, ethyl acetate, propyl acetate, butyl acetate. In the present invention volatile ketones, if present, may be, for example, acetone.

In the present invention, the propellant, if present, may be selected from the group consisting of: trichlorofluoromethane , dichlorodiflouromethane , dichlorotetraflouromethane, dimethyl ether, propane, n- butane, isobutane and mixtures thereof, and like propellants .

The compositions of the present invention may also include silicone conditioning agents such as cyclomethicone, dimethicone copolyol .

Other optional ingredients which may be included in hairspray compositions of the invention are preservatives such as benzyl alcohol, methyl paraben, propyl paraben, or imidazolidinylurea, cationic conditioners such as cetyl ammonium chloride, stearyl dimethyl benzyl ammonium chloride, coloring agents, chelating agents, such aminetetraacetic acid, plasticizers such as glycols, phthalate esters and glycerines, silicones, emollients, lubricants and penetrants such as various lanolin compounds, protein hydrosylates, and other protein derivatives ethylene adducts and polyoxyethylene cholesterol.

Aerosol and Non-Aerosol Compositions

The invention relates to an aqueous or hydroalcoholic, non- aerosol or aerosol hair spray composition containing a water soluble or dispersable fixative polymer in an amount from about 1% to about 40 % by weight of the composition, a neutralizing agent in an amount from about 0.1 to about 10 wt %, a hydrocarbon based surfactant in an amount from about 0.01% to about 5% by weight, a salt from about 0.01% to about 10% by weight, alcohol from about 0% to about 90%, more preferably 10% to about 90% by weight, a volatile ester from 0 to 90% by weight, more preferably about 10% to about 90% by weight, a volatile ketone from about 0% to about 90%, more preferably, from about 10% to about 90% by weight and water from about 10% to about 98% by weight of the composition. Additionally, in the case of aerosols, a liquefied propellant gas is present from about 5% to 60% by weight .

As can be seen, the compositions of the invention can be aqueous or hydroalcoholic.

Preferred ranges of a water soluble or dispersible fixative polymer are about 1 to about 40% by weight of the composition, more preferably about 2 to about 20%, and most preferably about 3 to about 10%.

Preferred ranges of a neutralizing agent are about 0.1 to about 10% by weight of the composition, more preferably about 0.25% to about 5%, and most preferably about 0.5% to about 2.5%.

Preferred ranges of a hydrocarbon based surfactant are about 0.01% to about 5% by weight of the composition, more preferably about 0.05% to about 2.5%, and most preferably about 0.1% to about 1.0%. Preferred ranges of the salt are about 0.01 to about 10% by weight of the composition, more preferably about 0.05% to about 5%, and most preferably about 0.1% to about 1%.

Preferred ranges of silicone conditioning agents are 0.001 to about 10% by weight of the composition, preferably from 0.01 to about 5%.

Also preferred are compositions of the invention in which the polymer is a ethyl acrylate, methyl methacrylate and methacrylic acid copolymer in the molecular weight range of about 10 to about 1000 Kilo Daltons, preferably about 20 to 500 Kilo Daltons, and most preferably about 50 to about 300 Kilo Daltons. Also preferred are compositions of the invention in which the polymer is a terpolymer of ethyl acrylate, t-butyl acrylate and methacrylic acid in the molecular weight range about 10 to about 1000 Kilo Daltons, preferably about 20 to 500 Kilo Daltons, and most preferably about 50 to about 300 Kilo Daltons. Also preferred are compositions of the invention in which the polymer is a octyl acrylamide, acrylates and butylaminoethyl methacrylate copolymer in the molecular weight range of about 10 to about 1000 Kilo Daltons, preferably about 20 to 500 Kilo Daltons, and most preferably about 50 to about 300 Kilo Daltons. Also preferred are compositions of the invention in which the polymer is a methacrylic acid, n- butyl acrylate and methyl methacrylate copolymer in the molecular weight range about 10 to about 1000 Kilo Daltons, preferably about 20 to 500 Kilo Daltons, and most preferably about 50 to about 300 Kilo Daltons. Also preferred are compositions of the invention in which the polymer is a methacrylic acid, n-butyl acrylate and ethyl methacrylate copolymer in the molecular weight range about 10 to about 1000 Kilo Daltons, preferably about 20 to 500 Kilo Daltons, and most preferably about 50 to about 300 Kilo Daltons. Also preferred are compositions of the invention in which the polymer is a butyl acrylate, methyl methacrylate, hydroxyethyl methacrylate and methacrylic acid copolymer in the molecular weight range of about 10 to about 1000 Kilo Daltons, preferably about 20 to 500 Kilo Daltons, and most preferably about 50 to about 300 Kilo Daltons. Also preferred are compositions of the invention in which the polymer is a vinyl acetate, crotonates and vinyl neodecanoate copolymer in the molecular weight range of about 10 to about 1000 Kilo Daltons, preferably about 20 to 500 Kilo Daltons, and most preferably about 50 to about 300 Kilo Daltons.

Also preferred are compositions of the invention in which the polymer is a butyl ester of vinyl methyl ether and maleic anhydride copolymer in the molecular weight range about 10 to about 1000 Kilo Daltons, preferably about 20 to 500 Kilo Daltons, and most preferably about 50 to about 300 Kilo Daltons. Also preferred are compositions of the invention in which the polymer is an ethyl ester of vinyl methyl ether and maleic anhydride copolymer in the molecular weight range about 10 to about 1000 Kilo Daltons, preferably about 20 to 500 Kilo Daltons, and most preferably about 50 to about 300 Kilo Daltons. Also preferred are compositions of the invention in which the polymer consists of polystyrene sulfonate monomers in the molecular weight range of about 10 to about 1000 Kilo Daltons, preferably about 20 to 500 Kilo Daltons, and most preferably about 50 to about 300 Kilo Daltons. Also preferred are compositions of the invention in which the polymer consists of 1 -vinyl -2- pyrrolidone monomers in the molecular weight range of about 10 to about 1000 Kilo Daltons, preferably about 20 to 500 Kilo Daltons, and most preferably about 50 to about 300 Kilo Daltons. Also preferred are compositions of the invention in which the polymer is a vinyl acetate and vinylpyrrolidone copolymer in the molecular weight range of about 10 to about 1000 Kilo Daltons, preferably about 20 to 500 Kilo

Daltons, and most preferably about 50 to about 300 Kilo Daltons. Also preferred are compositions of the invention in which the polymer is a vinylcaprolactam homopolymer in the molecular weight range of about 10 to about 1000 Kilo Daltons, preferably about 20 to 500 Kilo Daltons, and most preferably about 50 to about 300 Kilo Daltons. Also preferred are compositions of the invention in which the polymer is a quaternary ammonium polymer formed by the reaction of diethyl sulfate and a copolymer of vinyl pyrrolidone and dimethyl aminoethylmethacrylate in the molecular weight range of about 10 to about 1000 Kilo Daltons, preferably about 20 to 500 Kilo Daltons, and most preferably about 50 to about 300 Kilo Daltons. Also preferred are compositions of the invention in which the polymer is a modified or an unmodified polyurethane as described in U.S. Patent 6,007,793 issued to Bhatt et al .

Also preferred are compositions of the invention in which the hydrocarbon surfactant is an anionic surfactant. Also preferred are compositions of the invention in which the anionic surfactant is sodium dioctyl sulfosuccinate or its acid form. Also preferred are compositions of the invention in which the anionic surfactant is magnesium dioctyl sulfosuccinate or its acid form. Also preferred are compositions of the invention in which the anionic surfactant is ammonium dioctyl sulfosuccinate or its acid form. Also preferred are compositions of the invention in which the anionic surfactant is sodium dodecyl sulfate or its acid form. Also preferred are compositions of the invention in which the anionic surfactant is magnesium dodecyl sulfate or its acid form. Also preferred are compositions of the invention in which the anionic surfactant is ammonium dodecyl sulfate or its acid form. Also preferred are compositions of the invention in which the anionic surfactant is sodium laureth sulfate or its acid form.

Also preferred are compositions of the invention in which the anionic surfactant is magnesium laureth sulfate or its acid form. Also preferred are compositions of the invention in which the anionic surfactant is ammonium laureth sulfate or its acid form.

Also preferred are compositions of the invention in which the hydrocarbon based surfactant is a zwitterionic surfactant. Also preferred are compositions of the invention in which the zwitterionic surfactant is cocoamidopropyl betaine .

Also preferred are compositions of the invention in which the salt is an organic salt. Also preferred are compositions of the invention in which the organic salt is sodium benzoate. Also preferred are compositions of the invention in which the organic salt is magnesium benzoate. Also preferred are compositions of the invention in which the organic salt is sodium acetate. Also preferred are compositions of the invention in which the organic salt is magnesium acetate.

Also preferred are compositions of the invention in which the salt is an inorganic salt. Also preferred are compositions of the invention in which the inorganic salt is sodium chloride. Also preferred are compositions of the invention in which the inorganic salt is magnesium chloride.

Also preferred are compositions of the invention in which the alcohol is ethanol .

Also preferred are compositions of the invention in which the alcohol is isopropanol .

Also preferred are compositions of the invention further including silicone based surfactants in an amount from 0.01% to 5% by weight of the composition. Also preferred are compositions of the invention in which the silicone based surfactant is dimethicone copolyol . Also preferred are compositions of the invention in which the silicone based surfactant is cyclomethicone .

Also preferred are compositions of the invention in which the neutralizing agent is 2 -amino, 2 -methyl , 1-propanol . Also preferred are compositions of the invention in which the neutralizing agent is dimethyl stearamine . Also preferred are compositions of the invention in which the neutralizing agent is sodium hydroxide. Also preferred are compositions of the invention in which the neutralizing agent is potassium hydroxide.

Also preferred are aerosol compositions of the invention in which the liquefied propellant gas is dimethyl ether. Also preferred are aerosol compositions of the invention in which the liquified propellant gas is a mixture of propane and butane as well as mixtures of dimethyl ether, propane and butane .

Hair spray compositions of the invention can be in the form of hair sprays, spritzes, mousses etc.

The invention also relate to a method of treating or styling hair which comprises contacting said hair with the hairspray compositions of the invention. After hair spray compositions are applied to the hair, said hair can be styled, etc in various ways which are known in the art.

What follows are non-limiting examples of hair spray compositions of the invention.

The materials, definitions, and performance criteria, for low VOC Compositions of the invention having enhanced styling benefits are set forth just below.

Materials

Polymers Amphomer 28-4910 : Octylacrylamide, acrylates and butyl aminoethyl methacrylate copolymer with a molecular weight range of 165 to 225 Kilo Daltons from National Starch and Chemicals Co. of NJ, USA.

Amphomer LV-71 : Octylacrylamide, acrylates and butyl aminoethyl methacrylate copolymer with a molecular weight range of 120 to 165 Kilo Daltons from National Starch and Chemicals Co. of NJ, USA.

HC 7801 : Methacrylic acid, n-butyl acrylate and ethyl methacrylate copolymer with a molecular weight range of 50 to 100 kilo Daltons.

Resyn 28-2930 : Vinyl acetate, crotonates, vinyl neodecanoate copolymer with a molecular weight range of 70 to 110 kilo Daltons from National Starch and Chemicals Co. of NJ, USA..

Neutralizer

2-amino, 2-methyl, 1-propanol from Angus Chemical Company, LA, USA.

Silicone surfactants

Dimethicone copolyol : Silwet L-720 from Witco Corp., WV, USA

Cyclomethicone : DC 245 from Dow Corning, MI, USA Hydrocarbon surfactants

Sodium dioctyl sulfo succinate : Monawet MO 75 -E from Uniqema, NJ, USA

Sodium dodecyl sulfate : Obtained from BDH Laboratory supplies, Poole, England

Cocoamidopropyl betaine : Tegobetaine from GoldSchmidt Industries

Sodium laureth sulfate (2 moles EO) : Empicol ESB 3/AQ from Albright & Wilson, IL, USA

Organic salts:

Sodium benzoate : Boric chemical, IL USA

Magnesium acetate : Aldrich, WI , USA

Propellant

Dimethyl ether : Dymel DME from DuPont Chemical Co., Wilmington, DE USA

Definitions

Dynamic Surface Tension A test liquid in a typical surface tension experiment is static and any surface active material would be in equilibrium. In reality, spraying and subsequent wet out on hair are both dynamic processes and are affected by the surface tension of the formulation. Any materials that are surface active need time to migrate to and organize themselves at the air- liquid interface in order to effectively lower the surface tension. Any difference in perceived static versus dynamic surface tension could result in less than optimum performance. As described below, the faster the surface tension of a composition equilibrates, the better are its hairspray characteristics.

The dynamic surface tension experiment is typically conducted using a maximum bubble pressure method. This method is based on recording the pressure required to form bubbles at a given rate/ frequency in a test liquid. The surface tension is then calculated based on the measured pressure. The results are typically expressed in terms of dynamic surface tension against the surface age. Surface age is the time elapsed between the bubble formation and detachment of the bubble.

A surface age of about 10 msec is the time frame of interest for drop formation in spray process. The liquids used in hair spray applications generally reach equilibrium within 1000 msec (surface age of 1 sec.) . To obtain good spray properties, the difference between the surface tension obtained at very short time scales (ex: 10 msec) and the equilibrium surface tension (obtained for example at 1000 sec or higher) should be as small as possible. The difference in surface tension obtained at a surface age of about 10 msec and that obtained at a surface age of about 1500 msec (Δ ₁₀ - 1500) was chosen as the criterion for comparing the performance of different hair spray solutions.

An absolute surface tension value at about 11 msec was chosen as a criterion for comparing the performance of different hair spray solutions.

Preparation of 55% VOC Non-Aerosol and Aerosol Hairspray Solutions

Equipment

Fawcett Co, Model 103 -A Mixer Mettler Toledo PG5002-S balance medium sized stir bar (optional) beaker transfer pipets

USA Standard Testing Sieve #100, WS Tyler Unc . 150micrometer

Procedure

1. Add item#l, SD Alcohol 40-B into a suitably sized container.

2. Begin moderate agitation using an overhead mixer or a stir bar. 3. Add item#2, neutralizer. Increase agitation to high setting until a vortex is created. - I i

4. Add item#3, polymer, slowly directly into the vortex. Reduce mixing speed to moderate setting. Continue mixing until solution is clear.

5. Add item#4, surfactant, followed item#5, Silicone surfactant, and item#6, fragrance.

6. Add item#7, water followed by item#8, salt.

7. Continue mixing until solution is clear.

8. Conduct an alcohol correction for any alcohol which might have evaporated during the mixing process . 9. Filter solution through a 150 micron mesh filter.

10. Fill an aerosol can with the filter solution and add an appropriate level of propellant, under pressurized conditions (for aerosol only) .

The following compositions 1 through 23 of the invention were made, while compositions 24 through 45 could be made by processes described herein and by processes known to those skilled in the art.

Table 1

55% VOC Non-Aerosol Hair Spray Compositions

Test Solution # 10 11 12

Component CONTROL wt%

Ethanol 53.0 55.0 55.0 55.0 55.0 55.0 55.0 55.0 55.0 55.0 55.0 55.0

Isopropanol 2.0

2 -amino, 2 -methyl, 1-propanol 0.91 0.82 0.82 0.82 0.82 0.82 0.82 0.82 0.82 0.82 0.82 0.41

Amphomer 28-4910 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 3.0

Dimethicone copolyol 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3

Cyclomethicone 0.13 0.13 0.13

Sodium dodecyl sulfate 0.2

Sodium dioctyl sulfosuccinate 0.2 0.2 0.2 0.2 0.05 0.2

Sodium lauryl ether sulfate 0.2

Cocoamidopropyl betaine 0.2

I r

Sodium benzoate 0.0 0.144 0.3 0.3 0.07 0.3

Magnesium acetate 0.3 0.3 0.3 0.3 0.3

Fragrance 0.12 0.12 0.12 0.12 0.12 0.12 0.12 0.12 0.12 0.12 0.12 0.12

Water to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100to 100

Table 2

55% VOC Non-Aerosol Hair Spray Compositions

Test Solution # 13 14 15 16 17 18 19 20 21 22 23

Component wt^!

Ethanol 55.0 55.0 55.0 55.0 55.0 55.0 55.0 55.0 55.0 55.0 55.0 I

2 -amino, 2 -methyl, 1-propanol 0.84 0.84 0.74 0.74 0.74 0.74 0.74 0.74 0.74 0.74 0.37

HC 7801 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 3.0

Dimethicone copolyol 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3

Cyclomethicone 0.13 0.13 0.13 0.13 0.13

Sodium dodecyl sulfate 0.2

Sodium dioctyl sulfosuccinate 0.2 0.4 0.2 0.2 0.05 0.2

Sodium lauryl ether sulfate 0.2

Cocoamidopropyl betaine 0.2

Sodium benzoate 0.144 0.144 0.144 0.07 0.3

Magnesium acetate 0.144 0.144 0.144 0.1440.3

Fragrance 0.12 0.12 - 0.12 0.12 0.12 0.12 0.12 0.12 0.12 0.12

Water to 100 100 100 100 100 100 100 100 100 100 100

Table 3

55% VOC Aerosol Hair Spray Compositions

Test Solution # 24 25 26 27 28 29 30 31 32 33 34

Component wt%

Ethanol 22.0 22.0 22.0 22.0 22.0 22.0 22.0 22.0 22.0 22.0 22.0

2 -amino, 2 -methyl , to 1-propanol 0.56 0.56 0.56 0.56 0.56 0.56 0.56 0.56 0.56 0.56 0.29

Resyn 28-2930 5.7 5.7 5.7 5.7 5.7 5.7 5.7 5.7 5.7 5.7 3.0

Dimethicone copolyol 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3

Cyclomethicone 0.13 0.13 0.13

Sodium dodecyl sulfate 0.2

Sodium dioctyl sulfosuccinate 0.2 - - 0.2 0.2 - - - 0.05 - 0.2

Sodium lauryl ether sulfate - - - - - - 0.2 -

Cocoamidopropyl betaine - - - - - 0.2 -

Sodium benzoate 0.0 0.144 0.3 0.3 - - - - - 0.07 0.3

Magnesium acetate - - - - 0.3 0.3 0.3 0.3 0.3 ro

Fragrance 0.12 0.12 0.12 0.12 0.12 0.12 0.12 0.12 0.12 0.12 0.12

Dimethyl ether 33.0 33.0 33.0 33.0 33.0 33.0 33.0 33.0 33.0 33.0 33.0

Water to 100 100 100 100 100 100 100 100 100 100 100

Table 4

55% VOC Aerosol Hair Spray Compositions

Test Solution # 35 36 37 38 39 40 41 42 43 44 45

Component wt%

Ethanol 22.0 22.0 22.0 22.0 22.0 22.0 22.0 22.0 22.0 22.0 22.0

2 -amino, 2 -methyl , 1-propanol 0.74 0.74 0.74 0.74 0.74 0.74 0.74 0.74 0.74 0.74 0.37

Amphomer LV-71 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 1.25

Resyn 28-2930 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 1.25

Dimethicone copolyol 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3

Cyclomethicone 0.13 0.13 0.13 0.13 0.13

Sodium dodecyl sulfate 0.2

Sodium dioctyl sulfosuccinate 0.2 0.4 - 0.2 0.2 - - - 0.05 - 0.2

Sodium lauryl ether sulfate - - - - - - 0.2 -

Cocoamidopropyl betaine - - - - - 0.2 -

Sodium benzoate 0.144 0.144 - 0.144 - - - - - 0.07 0.3 ,

Magnesium acetate - - 0.144 0.144 0.144 0.144 0.3 - - K

Fragrance 0.12 0.12 - 0.12 0.12 0.12 0.12 0.12 0.12 0.12 0.12

Dimethyl ether 33.0 33.0 33.0 33.0 33.0 33.0 33.0 33.0 33.0 33.0 33.0

Water to 100 100 100 100 100 100 100 100 100 100 100

As used in this specification, test solutions of a certain number refer to the test solutions in the tables just above. Thus, test solution #1 is the first solution in the above table 1 and test solution #16 is the sixteenth solution which appears in table 2.

Example 1

Comparison of Dynamic Surface Tension of 55% VOC Test Hair Spray Solutions with Commercial Hair Sprays

A combination of an organic salt (sodium benzoate) and a hydrocarbon surfactant is required to bring the surface tension difference of the 55% VOC test solution down to that of 80% VOC commercial product . A Test solution in which only a hydrocarbon based surfactant is used, a Test solution in which a combination of silicone and hydrocarbon surfactants is present, or test solutions in which a combination of an organic salt and a silicone based surfactant is present do not bring the surface tension difference to that of the 80% VOC product.

Example 2

Comparison of Sodium Benzoate and Magnesium Acetate

Using the Dynamic Surface Tension measurement described herein (units of measurement are mN/m) it was shown in test solutions (that is, compositions of the invention) that both sodium benzoate and magnesium acetate brings the surface tension difference of the 55% VOC test solution closer to that of the commercial product .

Example 3

Effect of Different Surfactants on Dynamic Surface Tension

Using the Dynamic Surface Tension measurement described herein (units of measurement are mN/m) it was shown in test solutions containing Amphomer 28-4910 (that is, compositions of the invention) that hydrocarbon surfactants tested bring down the surface tension difference closer to that of a commercial product .

Example 4

Comparison of Effect of Silicone Versus Hydrocarbon Based Surfactant and Organic Salt on Dynamic Surface Tension

Using the Dynamic Surface Tension measurement described herein (units of measurement are mN/m) it was shown in test solutions (that is, compositions of the invention) that a combination of hydrocarbon surfactant and an organic salt brings down the surface tension difference down to that of commercial product, also with HC 7801 styling resin. In the absence of hydrocarbon surfactant and an organic salt the surface tension difference remains high (> 11) . Example 5

Comparison of Sodium Benzoate and Magnesium Acetate

Using the Dynamic Surface Tension measurement described herein (units of measurement are mN/m) it was shown it was shown in test solutions (that is, compositions of the invention) that both sodium benzoate and magnesium acetate bring the surface tension difference of the 55% VOC test solution closer to that of the commercial product , also with HC 7801 styling resin.

Example 6

Effect of Different Surfactants on Dynamic Surface Tension

Using the Dynamic Surface Tension measurement described herein (units of measurement are mN/m) it was shown (that is, compositions of the invention) that hydrocarbon surfactants tested bring down the surface tension difference closer to that of commercial product, also with HC 7801 styling resin.

Example 7

Effect of Different Levels of Polymers and Surfactants on Dynamic Surface Tension

Using the Dynamic Surface Tension measurement described herein (units of measurement are mN/m) it was shown (that is, compositions of the invention) that the combination of organic salt and the hydrocarbon based surfactant shows synergy at low polymer level of 3.0% and also low dioctyl sulfosuccinate level of 0.05 wt%.

Example 7a

Comparison of Composition of Test Solution of the invention with a Commercial Product Rave in a Consumer Test of Spray Characteristics

Sequential monadic testing of consumers with a composition of the invention (that is, a composition wherein the surface tension difference of the 55% VOC test solution is reduced to about 10.0) shows that it performs as well as the 80% VOC commercial product.

Claims

WHAT IS CLAIMED IS:

1. An aqueous or hydroalcoholic hair styling aid composition selected from the group consisting of:

I. an aqueous or hydroalcoholic non-aerosol hair styling aid composition comprising a water soluble or dispersable fixative polymer in an amount from 1% to 40 % by weight of the composition, a neutralizing agent in an amount from 0.1 to 10 wt%, a hydrocarbon based surfactant in an amount from 0.01% to 5% by weight, a salt from 0.01% to 10% by weight, alcohol from 0% to 90% by weight, and water from 10% to 98% by weight of the composition; and

II. an aqueous or hydroalcoholic aerosol hair styling aid composition containing a water soluble or dispersable fixative polymer in an amount from 1% to 40 % by weight of the composition, a neutralizing agent in an amount from 0.1 to 10 wt%, a hydrocarbon based surfactant in an amount from 0.01% to 5% by weight, a salt from 0.01% to 10% by weight, alcohol from 0% to 90% by weight, and water from 10% to 98% by weight of the composition and a liquified propellant gas from 5% to 60% by weight.

2. A composition according to claim 1 wherein the polymer is in the molecular weight range of about 10 to about 1000 Kilo Daltons.

3. A composition according to claim 1 in which the polymer is a polymer selected from the group consisting of ethyl acrylate, methyl methacrylate and methacrylic acid copolymer; ethyl acrylate, t-butyl acrylate and methacrylic acid terpolymer; octyl acrylamide, acrylates and butylaminoethyl methacrylate copolymer; methacrylic acid, n-butyl acrylate and methyl methacrylate copolymer; methacrylic acid, n-butyl acrylate and ethyl methacrylate copolymer; butyl acrylate, methyl methacrylate, hydroxyethyl methacrylate and methacrylic acid copolymer; vinyl acetate, crotonates and vinyl neodecanoate copolymer; a butyl ester of vinyl methyl ether and maleic anhydride copolymer; an ethyl ester of vinyl methyl ether and maleic anhydride copolymer; a polymer which consists of polystyrene sulfonate monomers; a polymer consists of 1-vinyl -2 -pyrrolidone ; vinyl acetate and vinylpyrrolidone copolymer; vinylcaprolactam homopolymer; a quaternary ammonium polymer formed by the reaction of diethyl sulfate and a copolymer of vinyl pyrrolidone and dimethyl aminoethylmethacrylate; and mixtures thereof; modified or unmodified polyurethanes .

4. A composition according to claim 1 in which the hydrocarbon surfactant is an anionic surfactant selected from the group consisting of sodium dioctyl sulfosuccinate or its acid form; magnesium dioctyl sulfosuccinate or its acid form; ammonium dioctyl sulfosuccinate or its acid form; sodium dodecyl sulfate or its acid form; magnesium dodecyl sulfate or its acid form; ammonium dodecyl sulfate or its acid form; sodium laureth sulfate or its acid form; magnesium laureth sulfate or its acid form; and ammonium laureth sulfate or its acid form.

5. A composition according to claim 1 in which the hydrocarbon surfactant is the zwitterionic surfactant cocoamidopropyl betaine .

6. The composition according to claim 1 wherein the salt is an organic salt selected from the group consisting of sodium benzoate; magnesium benzoate; sodium acetate; and magnesium acetate.

7. The composition according to claim 1 wherein the salt is an inorganic salt selected from the group consisting of sodium chloride and magnesium chloride.

8. The composition according to claim 1 wherein the alcohol is selected from the group consisting of ethanol and isopropanol.

9. A composition according to claim 1 which further

, comprises silicone based surfactants in an amount from 0.01% to 5% by weight of the composition.

10. The compositions in claim 9 in which the silicone based surfactant is selected from the group consisting of dimethicone copolyol and cyclomethicone.

11. The composition in claim 1 in which the neutralizing agent is selected from the group consisting of 2- amino, 2 -methyl , 1-propanol; dimethyl stearamine; sodium hydroxide; and potassium hydroxide.

12. The composition in accordance with claim 1 wherein the liquified propellant gas is selected from the group consisting of dimethyl ether, a mixture of propane and butane, and a mixture of dimethyl ether, propane and butane .

13. The composition according to claim 1 in which the volatile ester is methyl acetate, ethyl acetate, propyl acetate or butyl acetate

14. The composition according to claim 1 in which the volatile ketone is acetone.

15. A method for treating hair which comprises contacting said hair with a composition according to claim 1.

16. A composition according to claim 1 which further comprises a volatile ketone from about 10% to about 90^; by weight .

7. A composition according to claim 1 which further comprises a volatile ester from about 10% to about 90% by weight .