llllllllllllllllillllllllllllllllllilllllllllllllllllllllllllilllllllllllll , US005294437A United States Patent [19] [11] Patent Number: 5,294,437 Shah et al. [45] Date of Patent: Mar. 15, 1994

[54] SPRAY ‘ [56] References Cited U.S. PATENT DOCUMENTS [75] Inventors: Snehal M. Shah, Artesia; Candelario 4,543,249 9/1985 Netson ...... , ...... 424/70 é?femndez, Jr., Torrance, both of 4,983,377 1/1991 Murphy et a1...... 424/47 Primary Examiner-Thurman K. Page [73] Assignee; Neutmgena Corporation, Los Assistant Examiner-:Jyothsna Venkat Angeles, Cal“: Attorney, Agent, or Firm-Richard R. Mybeck [57] ABSTRACT [211 App]. No.: 975,787 A composition exhibiting high curl retention, fast drying time, high rinse-out with low ?aking and [22] Filedi - NOV- 13, 1992 high shine characteristics comprised of ?xative resins, silicone plasticizers and neutralizers in a crystal clear [51] Int. Cl,5 . . _ ...... _ _, A61K 7/09; A61K 7/11 formulation which meets or exceeds the currently man [52] US. Cl...... 424/71; 424/41; dated alcohol requirements in a hand pump spray appli 424/70; 424/DIG. l; 424/DIG. 2 cation. [58] Field of Search ...... 424/47, 70, 71, DIG. l, 424/DIG. 2 1 Claim, N0 Drawings 5,294,437 1 2 the degree of neutralization of the resin, and the use of HAIR SPRAY various types of plasticizers and surfactants. The blend ing of these ingredients is important in order to obtain INTRODUCTION and maximize desired properties in the consumer prod The present invention relates generally to personal uct. care products and grooming aids and more particularly Three types of hair sprays are on the market today; to a new and novel pumpable hair spray composition pump hair sprays, hydrocarbon aerosols and carbon containing preselected resins, neutralizers and silicone dioxide aerosols. Pump hair sprays and hydrocarbon blends in a mixture with an water/alcohol solvent vehi aerosols comprise the majority of the market sales. The cle and which, when applied as a spray mist to human predominant solvent system in all three types of hair hair provides a surprisingly effective hair control prod sprays is alcohol. New regulations require the alcohol not while substantially reducing the ecological detri level to be limited to a maximum content of 80% in ment of prior art products. current and new products in an effort to reduce volatile BACKGROUND OF THE INVENTION organic compounds (VOC’s) at ground level which form ozone through a photochemical reaction with In the preparation of prior art aerosol and pump nitrogen oxides in the presence of sunlight. spray formulations, pure (100%) alcohol has, In response to consumer and environmental needs, heretofore, been the primary solvent of choice utilized we have developed three pump hair sprays that ful?ll in consumer “pump” hair sprays to deliver the product consumers high expectations in performance while onto human hair for hair control and cosmetic appear meeting strict standards for reduced air pollution. ance. Discussions of such products appear in : Active ingredients found in the prior art hair spray Science and Technology, Balsam and Sagarin, 2nd Ed., Vol. 2, 352-358, and Hair and Hair Products, Society of formulations include: a ?xative resin such as octyl Cosmetic Chemists Continuing Education Program acrylamide/acrylates copolymer octylacrylamide/ak (held in Los Angeles, Calif, Feb. 3-4, 1992) which are crylates/butylaminoethyl methacrylate copolyrner and incorporated herein by this reference hereto. the like; neutralizing agents, especially desirable when Hair spray is a styling and beautifying aid used by the ?xative resin is an acrylic acid, such as sodium hy 65% of women over thirteen. Seventy percent of these droxide, aminomethylpropanol (AMP), triethanolamine women use hair spray daily. Consumers require hair and the like; solvents including water and alcohols; sprays to perform in holding their and also to propellants such as hydrocarbons and the like for aero contribute to beautifying the appearance of their hair. sol products; plasticizers such as dirnethyl silicone, tri People who and color their hair are also con ethyl citrate and lanolin derivatives; and other optional cerned that the hair spray will not dull the color of their ingredients such as perfumes, coloring agents and pH hair or weigh down their curls. Consumers are also adjusters depending on the properties desired in a ?nal conscious of environmental issues and expect their formulation. products to comply with regulations without sacri?cing Given that silicones in a synergistic combination with performance. other specially preselected ingredients is a salient fea Good holding power is perhaps the primary attribute ture of the present invention, and that silicones have a consumer looks for in a hair spray. Curl retention been employed in prior art hair sprays, it is essential to under conditions of changing humidity, especially 40 understand the diverse roles such compounds may play changes to a higher humidity, is critical to the perfor in the hair spray art. A key review of this aspect of the mance of a hair spray. Good curl retention in chemi art is found in Hair Fixatives-bene?t from the physical cally damaged hair is important since the hair ?ber is and chemical properties of silicones. Christine M. Handt, weakened by the chemical process and will be less Soap/Cosmetics Soecialties. October 1987 wherein is likely to maintain the curl. In addition, the hair spray 45 reported that different silicones, in diverse concentra must be capable of being washed out of the hair with tions can provide a variety of bene?ts to hair ?xative and it must not build up on the hair over suc I systems, including softer feel, shine and better curl re cessive use. The consumer also requires the hair spray tention. to perform as a beautifying agent. It is expected to con The “pump” hair spray products of the prior art tribute positively to the appearance of the hair. Im contain 100% alcohol as the solvent/carrier. However, proved shine and luster are some properties a consumer expects. Therefore, a careful equilibrium between ingre this can no longer be. standards require that the alcohol dients must exist to provide superior hold, be rinsable content of such products cannot exceed 80% beginning without buildup, non-?aking, and yet provide shine and Jan. 1, 1993 (See: Product Standards for Hair Sprays, manageability. 55 California Clean Air Act). Hair sprays are similar in their basic ingredient con Many researchers are engaged in the hunt for a re tent. They contain solvents, a synthetic polymeric resin, placement formulations of pump hair sprays which will a base to neutralize the resin (especially when the resin be environmentally safe and yet functionally acceptable is a carboxylic acid containing resin), plasticizers and in to the consuming public. However, problems arise some cases a surfactant and a fragrance. The resin is the 60 when water is used to either replace alcohol or to re primary ingredient responsible for the curl retention duce the alcohol to the mandated content of less than characteristics. The neutralizer contributes to the resin’s 80%. Because the products created thus far leave hair ?lm properties and also to the resin’s solubility or wash ?at and dull, require excessive drying time, promote out property. Surfactants improve the spreadability of increased tackiness and exhibit substantially weaker the resin on the hair surface. Plasticizers are added to 65 holding power for curls. provide less brittle ?lms, minimize ?aking and to maxi Obviously, the problems involved in adding rela mize shine and curl retention. Hair sprays differ from tively small amounts of water, approximately 15% of each other by the type of resin(s) and neutralizer used, the solvent system, to a pump hair spray are very signif 5,294,437 3 4 icant. The reason is that water greatly affects the physi One motivating factor leading to the present inven~ cal properties of the ?xatives. tion is the mandate requiring such products to contain The ultimate product, heretofore unattainable, should 80% or less alcohol and the determination that there provide: a hair control spray which can be delivered by was a lot more to this project than simply pouring more a pumpspray which will contain less than 80% alcohol water into the bottle. solvent; which will provide cosmetically acceptable In a preferred embodiment, the present invention curl retention; low tack and drying time; better rinse comprises, by weight percent; water in the range of 8 to out and little or no ?aking; high shine (luster); and a 23 percent, alcohol in the range of 75 to 80 percent, crystal clear formulation which yields a clear dried ?lm. ?xative resins in the range of 1.5-2 percent, potassium 10 hydroxide (KOH) neutralizer in the range of 0.2-1.72 BRIEF SUMMARY OF THE INVENTION percent, and silicone plasticizers in the range of 0.2-0.7 The present invention relates to a composition for a percent. pumpable hair spray which meets standards of alcohol The only resin found to be satisfactory was octyla content and still meets the demanding cosmetic require crylarnide/acrylates/butylaminoethyl methacrylate co ments for such a product. More particularly, the present 15 polymer (herein “OABM"). This material may be used invention is based on the remarkable discovery of a hair either alone or in combination with one other secondary spray formulation comprising a novel combination of resin, octylacrylamide/acrylates copolymer (herein water and alcohol solvent base, essential ?xative resins, “0AA"). neutralizing agents, silicone plasticizers and non-essen Potassium hydroxide (KOH) was the only neutraliz tial fragrance and coloring ingredients. 20 ing agent found to be effective to neutralize the acid Accordingly, a principal object of the present inven effects of the resins, provided it was blended with the tion is to provide a novel and unique hair spray product other essential ingredients of this invention. Potassium which meets all of the requirements of current clean air hydroxide was found to be responsible for lowering the legislation without sacri?cing those physical properties drying time and stickiness time. This helped our inven which today’s consumer demands in such products. 25 tion by countering the negative effects of the addition of Another object of the present invention is to provide water to the formulation. Addition of water makes hair a novel hair spray which is dispensable from a hand spray tackier and over plasticized which results in a pump container. sticky hair feel and slower drying time. See data below A still further object of the present invention is to (Prepared by Meczka Marketing Research, March provide a novel and unique hair spray which provides 30 1992)

Salon Testing Results TEST Natural Hold Super Hold Intense Hold Vidal Sassoon Paul Mitchell PANEL: Prototype 20 Prototype 19 Prototype 21 Extra 20 Freeze 8t Shine 40 Drying time versus usual brand used by panelist Better 55% 32% 62% 60% 60% Same 35% 47% 33% 30% 28% Worse 10% 2l% 5% 10% 22% equal or better curl retention than that previously ob Two speci?c silicone materials are required, these tainable with sprays having essentially a 100% alcohol being a blend of polyphenylmethylsiloxane and dime solvent system. thicone/ glycol copolymer. Still another object of the present invention is to Although none of these essential ingredients of this provide a novel and unique pumpable hair spray con 45 composition is unique per se, the combination of ingre taining less than 80% alcohol but which provides equal dients in the speci?c ranges described herein and set or better tack and drying time than that heretofore forth below, yields a performance that either matches obtainable with sprays having essentially a l00% alco or exceeds the prior art l00% alcohol based formula hol solvent system. tions and provide unexpected and surprising results. A still further objective of the present invention is to 50 The composition of the hair spray of the present provide a new and unique hair spray formulation con invention, in weight percent is: taining approximately 15% water as solvent while ob taining equal or better rinse-out without ?aking, and INGREDIENT Range in weight % equal or better shine than heretofore obtainable with Alcohol’ 75% to 80% sprays having a 95-100% alcohol solvent system. 55 Water 8% to 23% These and still further objects, as shall hereinafter OABM 1.9% to 9% appear, are readily ful?lled by the present invention in 0AA 0% to 3% a remarkably unexpected manner as will be readily Potassium Hydroxide 0.2% to 1.72% Polyphenylmethylsiloxane 0.1% to 0.3% discerned from the following detailed description of an Dimethicone Glycol copolymer 0.1% to 0.3% exemplary embodiment thereof. Other ingredients in a quantity suf?cient to make 100%. ‘In practice. the alcohol is added u 190 proof. that is, 95% alcohol with 5% water DESCRIPTION OF THE PREFERRED by volume. EMBODIMENT The present invention comprises a unique mixture of In the practice of the present invention, three formu ingredients which yields a remarkably effective and 65 lations providing varying degrees of “hold” power cosmetically pleasing hair spray which is applied from a have been accomplished. The compositions hereof con pump sprayer and based in an environmentally accept tain the following ingredients in the following ranges able solvent system. (expressed in weight percent); 5,294,437 5 6 Results of the testing performed on the various sam ples appear in TABLE I-TABLE IV. In weight Ercent Intensive Super Regular TABLE I Ingredient Hold Hold Hold Curl Retention of Permed Hair at 90% Humidity Water 8% to 23% % Curl Retention and standard deviation Potassium Hydroxide 0.2% to 1.72% Product 15 min 1.5 hours 2.5 hours 20 hours Alcohol 75% to 80% Octylacrylamide/Acrylates/Butyl- 1.9% to 9% NGNA 97:4 87:6 84:6 85:6 aminoethyl methacrylate copolymer _ Natural NGNA 96:5 89:5 86:8 84:7 Octylacrylamide/Acrylates 0% to 3% 10 Copolymer super Polyphenylmethylsiloxane 0.1% to 0.4% NGNA 96:4 90:6 89:6 93:7 Dimethicone/glycol copolymer 0.1% to 0.3% Intense Triethyl citrate 0.05% to 0.2% Paul 92:6 80:4 79:5 77:6 Other ingreidents quantity sufficient to make 100% Mitchell AquaNet 93:4 89:4 86:7 85:6 15 Ultimate Extensive laboratory testing was performed to evalu Vidal 92:2 84:3 83:3 80:5 ate the efficacy and performance of the present inven Sassoon tion. The products were evaluated for hold and curl Extra I Pantene 89:3 78:4 72:6 71:9 retention, rinsability/buildup, and hair shine. In addi Natural tion consumer and independent marketing survey test 20 FinalNet 85:5 72:8 63:12 61:6 ing evaluated other factors including feel, ?aky residue, Regular drying time, and consumer impression. The modes of AquaNet 90:6 :8 71:11 73:5 Super investigation used include in-vitro, quantitative labora Rave 84:7 :6 73:6 70:10 tory studies, in-vivo half head studies and an indepen Super dently conducted consumer test. Laboratory test results 25 Rave 84:10 73_8 64:12 65:11 are summarized below, describing the performance of Ultra the current invention compared to currently available Control- 79 : 8 70 : 9 68 : 11 63 : l2 Untreated consumer products where applicable. Hair Curl Retention-An in-vitro laboratory curl reten tion study was done to evaluate the effectiveness of three embodiments of the present invention; Intense TABLE II Hold, Super Hold, and Natural Hold in retaining curl in Curl Retention of Permed Hair at 50% Humidity permed and water set hair at 50% and 90% humidity. % Curl Retention and standard deviation Leading competitive brands were evaluated for com Product 30 min 1.5 hours 2.5 hours 18 hours parison. 35 NGNA 98:2 97:3 96:2 95:2 Swatches of European virgin light brown hair were Natural subjected to the methods which included; 1) washing NGNA 97:3 96:2 94:3 93:4 with 1 ml. of Shampoo for Permed and Super Color Treated Hair and then rinsed under warm tap NGNA 98:3 97:3 97:3 97:4 40 Intense water, 2) air dried at 40% humidity and 25° C., 3) Paul 99:2 95:2 95:5 94:5 trimmed to uniform length, 4) measured for length to Mitchell 0.1 cm., 5) measurements recorded as Ls, and 6) AquaNet 99:1 97:3 94:4 93:4 combed. The swatch was then secured at the bottom of Ultimate a pegboard and subjected to 40% humidity-25° C. Vidal 97:4 97:4 93:4 90:5 Sassoon (40/25) environment for 24 hours. One hour prior to 45 Extra testing they were removed from the board and laid ?at. Control- 96 : 4 92 : 4 90 : 4 87 : 3 Samples to be tested for curl retention of permed hair Untreated were treated with a commercial alkaline perm solution Hair and allowed to dry, laying ?at, at the 40/25 environ 50 ment for 24 hours. TABLE III Five sample swatches were used for each product tested and ?ve additional for control. Testing was per Curl Retention of Wet Set Virgin Hair at 90% Humidity formed by spraying each swatch with the selected prod % Curl retention and standard deviation uct, dried (1 hr.), and measured for length (L0). The Product 1 Hour 3 hours 6 hours 24 hours environment was maintained at 40/25 throughout the NGNA 34:4 40:9 32:4 32:5 testing period. The swatches were then suspended verti Natural , NGNA 50:6 43:9 46:10 43:6 cally in a humidity chamber at either 50% or 90%. Super Measurements of the length of the sample were then NGNA 39:6 36:8 35:6 37:7 made at various times throughout a 24 hour period. Intense Curl retention was calculated using the equation: 60 Paul 38:11 23:3 25:3 21:3 Mitchell AquaNet 21:6 17_3 16:4 15:6 . _ Ls ~ Ll Ultimate % Curl Retention - —-——LS__ L0 X 100 Vidal 31:7 27:6 26:6 27:5 Sassoon Where 65 Extra FinalNet 13:4 7:4 5:3 5:3 Ls=initia1 length after trimming Regular Lo=length after curling & spraying Control- 4 : 4 0 3 + 0.7 0 O Lt=length at various times in chamber Untreated 5,294,437 7 8 and then hung to dry overnight at 40% RH and 22' C. TABLE Ill-continued When completely dry and at constant weight the Curl Retention of Wet Set Virgin Hair at 90% Humidity swatches’ weight was recorded and the weight of any % Curl retention and standard deviation residue calculated as a percent of the amount of product Product 1 Hour 3 hours 6 hours 24 hours 5 applied. To determine if buildup would occur, the Hair swatches were again treated with the respective test product and the same procedure followed. TABLE IV The hair spray test products were: ® Ulti mate hold, Neutrogena® Natural hold (506,-66AV), Curl Retention of Wet Set Virgin Hair at 50% Humidity 10 Neutrogena @ Super hold ( 506-65AV), Neutrogena ® Curl retention and standard deviation Intense hold (506-72), Paul Mitchell ® Freeze and Product 1 Hour 2 Hours 18 Hours Shine and Vidal Sassoon ® Extra hold. NGNA 54 i 7 51 t 8 46 i 7 TABLE V, below, shows the results from the in vitro Natural NGNA 70:7 68:7 63i8 quantitative laboratory study. The data is presented as Super the per cent of hair spray residue remaining on the hair NGNA 75 i 8 72 i 10 71 t 9 after washing with shampoo. All of the products tested Intense Paul 68 :t 8 66 i 6 64 i 6 were removed over 90 percent. Natural hold, Super Mitchell hold and Intense hold hair sprays were over 95% re Aqua Net 46 -_+- 15 42 :2: 15 35 i 13 moved with one shampoo, therefore leaving virtually Ultimate 20 Vidal 60 1t 7 53 i 6 48 t 6 no residue. Sassoon TABLE V Extra Control- 31 i 6 26 i 5 20 i 6 Laboratory Rinsability/Buildup Results Untreated % Hairspray residue left on hair after shamroing Hair 25 % Residue & SD’ % Residue an SD' PRODUCT 1 Treatment 2 Treatments Swatches were prepared using 25:0.05 g European NGNA Natural 2.5 i 2.1 —0.5 1- 0.8 virgin dark brown hair (De Meo Bros. New York, New NGNA Super 3.9 1' 3.3 1.4 i’ 2.2 NGNA Intense 1.7 i 0.9 0.08 i 1.2 York) allowing use of 20 cm. of the hair. The swatches 30 Paul Mitchell 7.7 i 2.5 3.7 i 1.3 were prewashed with 1 ml. of Neutrogena shampoo for Aqua Net Ultimate 6.9 i 3.8 7.6 i 1.8 penned and color treated hair, rinsed for 1 min. with Vidal Sassoon Extra 3.7 I 5.9 1.1 i 4.2 warm tap water (38° C.) and dried in a controlled hu ‘SD is standard deviation midity and temperature environment of 40%i5% RH and 20° C.i2' C. for a minimum of 24 hours or until at From the foregoing it is apparent that a hair spray has constant weight. Any loose were pulled from the been herein described and illustrated which ful?lls all of swatches and then they were weighed on an analytical the aforestated objectives in a remarkably unexpected balance to the nearest 0.0001 gram and the weight re fashion. It is of course understood that such modi?ca corded. The temperature and humidity of the room tions, alterations and adaptations as may readily occur were recorded at each weighing. The swatches were to the artisan confronted with this disclosure are in divided into groups of ?ve per test product and two tended within the spirit of this disclosure which is lim untreated control groups. An environmental control ited only by the scope of the claims appended herein. group was used to monitor and correct for any changes Accordingly, what is claimed is: in humidity which would affect the weight of the hair. l. A crystal clear hand pumpable hair spray composi A second control group was used to monitor any 45 tion comprising, in weight percent: from about 75 to change in weight as a result of the wash procedure. about 80 percent of alcohol; from about eight to about One milliliter of the test product was applied to each 23 percent water; from about 1.9 to about 9 percent of swatch in the respective test group with a 1 ml. dispos able syringe. The hair spray was applied evenly and a fixative resin selected from the group consisting of carefully along the length of the swatch so as not to let octylacrylamide/acrylates/butylaminoethyl methacry any product drip off the swatch. The treated swatches 50 late copolymer, octylacrylamide/acrylates copolymer were hung vertically to dry at 40% RH and 22° C. or a mixture thereof; from about 0.2 to about 0.7 percent When completely dry they were weighed and the of silicone plasticizer; in which said silicone plasticizer weight recorded. When at constant weight the consist of a blend of polyphenymethyl siloxane and swatches were wetted with warm tap water (38' C.) diomethicone/glycol copolymer in a ratio of about 1:3 55 until the hair was saturated and then washed with 2 ml. to about 4:1 respectively; from about 0.2 to about 1.72 of Neutrogena R Shampoo for Permed and Color percent of potassium hydroxide neutralizer, said resin, Treated hair for 1 minute and then rinsed for another said silicone plasticizer and said potassium hydroxide minute under tap water at 38° C. and 2000-2500 being dispsered throughout said water and said alcohol. cc./min. Each swatch was washed in the same manner 0 0 t it i

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