Autophobic silicone copolyols in hairspray compositions

That which is claimed is:

1. An aerosol hairspray composition having improved body consisting essentially of from 0.5% to 8.0% by weight of an ethanol soluble hairspray resin dissolved in a sufficient amount of an ethanol solvent system to render the composition sprayable in aerosol form, said composition further containing an effective amount of an autophobic silicone copolyol to cause the sprayed film to contract on the hair at between 20.degree. C. to 37.degree. C. rather than to spread into an even film upon drying, said silicone copolyol consisting essentially of organosiloxy units selected from the group consisting of dimethylsiloxy units, CH.sub.3 SiO(C.sub.x H.sub.2x)(OCH.sub.2 CH.sub.2).sub.y (OCHCH.sub.3 CH.sub.2).sub.z OR, (CH.sub.3).sub.2 SiO(C.sub.x H.sub.2x)(OCH.sub.2 CH.sub.2).sub.y (OCHCH.sub.3 CH.sub.2).sub.z OR, and trimethylsiloxy units, and having a number average molecular weight of about 1500 to 6000 wherein x has a value of from 1 to 12, R is hydrogen or alkyl of 1 to 4 carbon atoms, y is greater than or equal to 1 and z is greater than or equal to 0 and the sum of y+z and the amount of dimethylsiloxy units and trimethylsiloxy units present is such that the silicone copolyol causes an ethanolic solution of the hairspray resin to contract on the hair rather to spread into an even film at 20.degree. C. to 37.degree. C. upon drying and a 0.1% by weight solution of the silicone copolyol in water has a cloud point of less than 30.degree. C. and said ethanol solvent system consists essentially of at least 70% by weight of ethanol and any remaining solvent is selected from the group consisting of water. R.sup.1 OH where R.sup.1 is an alkyl of 3 or 4 carbon atoms, and mixtures thereof.

2. The composition as claimed in claim 1 wherein the silicone copolyol is present in an amount of from about 0.02% to 0.5% by weight of the composition.

3. The composition as claimed in claim 1 wherein the silicone copolyol is composed of dimethylsiloxane units, CH.sub.3 SiO(C.sub.3 H.sub.6)(OCH.sub.2 CH.sub.2).sub.y OCH.sub.3 units endblocked with trimethylsiloxy units, has a silicon content of about 16% by weight, a number average molecular weight of about 1700, a density of 1.027 and a viscosity at 25.degree. C. of from about 70 to 130 centistokes, z is 0 and R is methyl.

4. The composition as claimed in claim 1 wherein the composition further contains a cyclic silicone fluid of the formula [(CH.sub.3).sub.2 SiO].sub.n where n has an average value of about 4 to about 5 wherein the total mount of silicone copolyol and cyclic silicone fluid is from about 0.02% to about 0.5 weight percent based on the total weight of the composition.

5. The composition as claimed in claim 1 wherein the average value of y is at least 5.

6. The composition as claimed in claim 4 wherein the silicone copolyol is composed of dimethylsiloxane units and CH.sub.3 SiO(C.sub.3 H.sub.6)(OCH.sub.2 CH.sub.2).sub.y OCH.sub.3 units endblocked with trimethylsiloxy units, has a silicon content of about 16% by weight, a number average molecular weight of about 1700, a density of 1.027 and a viscosity at 25.degree. C. of from about 70 to 130 centistokes.

7. The composition as claimed in claim 1 wherein from about 10 to 80% based on the total weight of the composition is an aerosol propellant and the resin is from 0.5% to 6% of the composition.

8. The composition as claimed in claim 1 wherein the cloud point of the silicone copolyol is no more than about 10.degree. C.

9. The composition as claimed in claim 1 wherein the composition further contains a silicone fluid of the formula (CH.sub.3).sub.3 SiO[(CH.sub.3).sub.2 SiO].sub.q Si(CH.sub.3).sub.3 where q has an average value such that the viscosity of the silicone fluid is no more than about 20 centistokes at 25.degree. C. wherein the total amount of silicone copolyol and silicone fluid is from about 0.02% to about 0.5% weight percent based on the total weight of the composition.

10. The composition as claimed in claim 9 wherein the viscosity of said silicone fluid is no more than about 10 centistokes at 25.degree. C.

11. The composition as claimed in claim 1 wherein the amount of said silicone copolyol is in the range of from about 0.05% to 0.2% by weight based on the total weight of the composition.

12. The composition as claimed in claim 4 wherein the total amount of silicone copolyol and cyclic silicone fluid is about 0.1% to 0.2% of the total weight of the composition

13. The composition as claimed in claim 4 wherein the weight ratio of silicone copolyol to cyclic silicone fluid is about 1:1.

14. The composition as claimed in claim 10 wherein the total amount of silicone copolyol and the silicone fluid is about 0.1 to 0.2% of the total weight of the composition.

15. The composition as claimed in claim 10 wherein the weight ratio of silicone copolyol to silicone fluid is about 1:1.

16. The composition as claimed in claim 1 wherein the silicone copolyol has an average of about 10 dimethylsiloxy units and is endblocked with (CH.sub.3).sub.2 Si(C.sub.3 H.sub.6)(OCH.sub.2 CH.sub.2).sub.x OH units where the total value of x in the endblocking units has an average value of about 26.

17. The composition as claimed in claim 16 wherein the amount of said silicone copolyol is in the range of 0.1 to 0.2% of the total weight of the composition.

18. The composition as claimed in claim 1 wherein the silicone copolyol contains at least 10% silicon content.

19. An aerosol hairspray composition having improved body consisting essentially of from 0.5% to 8.0% by weight of an ethanol soluble hairspray resin dissolved in a sufficient amount of an ethanol solvent system to render the composition sprayable in aerosol form, said composition further containing from about 0.02 to 0.5% by weight of an autophobic silicone copolyol, said amount being sufficient to cause the sprayed film to contract on the hair at between 20.degree. C. to 37.degree. C. rather than to spread into an even film upon drying, said silicone copolyol consisting essentially of organosiloxy units selected from the group consisting of dimethylsiloxy units, CH.sub.3 SiO(C.sub.x H.sub.2x)(OCH.sub.2 CH.sub.2).sub.y OR, and trimethylsiloxy units, and having a silicon content of at least 10 percent by weight and a number average molecular weight of about 1500 to 6000 wherein x has a value of from 3 to 4, R is hydrogen or alkyl of 1 to 4 carbon atoms, y is at least 5 and the value of y and the amount of dimethylsiloxy units and trimethylsiloxy units present is such that the silicone copolyol causes an ethanolic solution of the hairspray resin to contract on the hair rather to spread into an even film at 20.degree. C. to 37.degree. C. upon drying and a 0.1% by weight solution of the silicone copolyol in water has a cloud point of less than 30.degree. C. and said ethanol solvent system consists essentially of at least 70% by weight of ethanol and any remaining solvent is selected from the group consisting of water R.sup.1 OH where R.sup.1 is an alkyl of 3 or 4 carbon atoms, and mixtures thereof.

20. The composition as claimed in claim 19 wherein the silicone copolyol has a silicon content of between about 15 and 30 percent and the cloud point is less than 10.degree. C.

21. The composition as claimed in claim 20 wherein the composition further contains a cyclic silicone fluid of the formula [(CH.sub.3).sub.2 SiO].sub.n where n has an average value of about 4 to about 5 wherein the total mount of silicone copolyol and cyclic silicone fluid is from about 0.02% to about 0.5 weight percent based on the total weight of the composition.

22. The composition as claimed in claim 21 wherein the silicone copolyol has a silicon content of about 16% by weight, a number average molecular weight of about 1700, a density of 1.027 and a viscosity at 25.degree. C. of from about 70 to 130 centistokes, and R is methyl.

23. The composition as claimed in claim 20 wherein the composition further contains a silicone fluid of the formula (CH.sub.3).sub.3 SiO[(CH.sub.3).sub.2 SiO].sub.q Si(CH.sub.3).sub.3 where q has an average value such the viscosity of the silicone fluid is no more than about 20 centistokes at 25.degree. C. wherein the total amount of silicone copolyol and silicone fluid is from about 0.02% to about 0.5% weight percent based on the total weight of the composition.

Description Submit all comments and votes

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to ethanol solvent-based hairspray compositions which employ a specific type of silicone copolyol which causes the hairspray composition to contract upon drying and thereby improve the body and hair setting properties of the hairspray composition.

2. Description of the Prior Art

Various types of silicone materials, and more specifically silicone copolyols such as those designated by The Cosmetic, Toiletry and Fragrance Association ("CTFA") name of "dimethicone copolyols", have been suggested for use in hairspray compositions to modify the properties of the compositions to leave the hair with various properties such as ease of brushing, to give the hair a softer feel, to reduce tackification after spraying or to impart luster to the hair.

For example, DOW CORNING.RTM. 190 and 193 Surfactants are water soluble silicone glycol copolymers which are said to be useful in hairspray products to impart luster, detackification and hold properties in hairspray compositions when used at 0.1 to 1% of the composition. DOW CORNING.RTM. Q2-5220 Resin Modifier is said to be a dimethicone copolyol as a resin modifier for hairsprays, mousses, setting lotions and styling gels which is readily compatible with ethanol and water. At a use level of 0.1 to 1.0%, the DOW CORNING Q2-5220 Resin Modifier is said to plasticize resins, making them softer, more flexible and less tacky.

European Pat. Appln. No 116,207 to Elliott et al. teaches an aerosol hairspray formulation comprising a hair-holding resin dissolved in a solvent system such as ethanol, and aerosol propellant and from 0.5 to 10% by weight of the formulation of at least one cyclic silicone such as dimethylsiloxane cyclic tetramer or dimethylsiloxane cyclic pentamer in addition to the dimethicone copolyol such as DOW CORNING 193 surfactant.

The examples in the Elliott et al. Patent indicate that the dimethylsiloxane cyclic tetramer or pentamer is used in amounts equal to or in excess of 10 parts of the tetramer or pentamer to 1 part of dimethicone copolyol. Linear and cyclic polydimethylsiloxanes are known to be hydrophobic and are therefore not compatible with water. Dimethicone copolyol such as DOW CORNING Q2-5220 resin modifier tend to form uniform films when compositions containing the silicone and a hairspray resin dissolved in an ethanol solvent system are sprayed out on a substrate such as a glass slide or the hair. Introduction of a hydrophobic silicone such as a dimethylsiloxane cyclic pentamer causes the film to contract toward the center of the substrate as the composition dries. The combination of the dimethicone copolyol and dimethylsiloxane cyclic pentamer which results in a film that contracts upon drying is thus said to impart an "autophobic" effect on the hairspray composition.

A number of hair spray compositions are commercially available and have been marketed for a number of years which contain dimethicone copolyol and also which contain dimethicone copolyol and cyclomethicone as stated on the package label of the product. For example, FINESSE pump and FINESSE Aerosol hairspray formulations sold by Helene Curtis Industries, Inc. list both dimethicone copolypol and cyclomethicone on their label. The product, when sprayed on a glass slide, was noted to have an autophobic effect in that the composition tended to contract towards the center of the glass slide upon drying. The FINESSE hairsprays were based on an ethanol solvent system.

The Elliott et al. patent application discusses the disadvantages of only using a dimethicone copolyol such as DOW CORNING 193 surfactant in hairspray compositions and suggest the use of dimethylsiloxane cyclic tetramer or pentamer in such such compositions, presumably to obtain this autophobic effect. A rather significant level of dimethylsiloxane cyclic tetramer or pentamer must be used to overcome the natural tendency of dimethicone copolyols that are water soluble to form an evenly spread film upon drying. The autophobic effect of this combination of silicone materials can be used to improve the body of hair sprayed with the hairspray resin since the hairspray resin tends to contract as it dries and thus adheres the fibers of the hair together at the points where one strand crosses another.

The use of dimethicone copolyols in cosmetic and personal care formulations is discussed in a paper by F. C. Vick in Soap/Cosmetics/Chemical Specialties for May, 1984, Vol. 60. p. 36ff entitled "Structure/property Relationships for Silicone Polyalkyleneoxide Copolymer and Their Effects or Performance in Cosmetics." The composition of the copolymers discussed very widely in molecular weight and the content and type of alkyleneoxy block present, i.e., ethyleneoxy or propyleneoxy units, present in the copolymers discussed. However, the dimethicone copolyols described in this paper have a 0.1% cloud point of at least 41.degree. C. or more which indicates that these silicone dimethicone copolyols are rather water soluble.

Union Carbide Corporation also markets a series of dimethicone copolyols under the trademark SILWET. The Union Carbide Data Sheet No. F-44773 12/80-5M entitled "SILWET.RTM. Surface Active Copolymers", 1980. page 13 suggests the use of SILWET copolymers L-720, L-7600 and L-7002 for use in personal care products, specifically for hair care products. Nothing is mentioned concerning the use of SILWET.RTM. L-7602 in hair care applications. A 1987 Union Carbide Data Sheet entitled "SILWET.RTM. SURFACTANTS FOR USE IN PERSONAL CARE PRODUCTS" lists SILWET L-7602 among 5 others for personal care use, some of which included improving hair sheen and soft feel. The recommended starting use level is 1.0% by weight of the total formulation.

U.S. Pat. No. 3,928,558 to Cheesman et al. teaches that certain polydimethylsiloxane-polyoxyalkylene block copolymers can be incorporated into hairspray compositions comprising a film forming resin in a cosmetic vehicle. These polymers have a ,silicon content of 15 to 25%, a molecular weight of from,1,200 to 5,000 and a viscosity at 25.degree. C. of 3 to 10 poises and their inclusion makes the resin easier to brush out from the hair. Cheesman et al. teach that all three variables are critical in obtaining the proper polydimethylsiloxane-polyoxyalkylene block copolymers which can be used in their invention. Cheeseman et al. teaches nothing concerning the presence or absence of an autophobic character to the block copolymers employed in their invention.

U.S. Pat. No. 4,423,041 to Clum et al. teaches detackifying compositions for use in emulsion-type personal care compositions which comprise a mixture of a silicone fluid which can be a dimethylsiloxane cyclic tetramer or pentamer (CTFA name "Cyclomethicone") and a silicone wax in a ratio of from about 9:1 to 1:3. The silicone wax can be a dimethicone copolyol having a molecular weight of about 1,600 to about 2.000. but is required to be a solid or semi-solid at body temperature and must be insoluble in water and insoluble or only slightly soluble in cosmetic oils. Nothing is taught concerning the use of this combination of materials in a hairspray composition.

SUMMARY OF THE INVENTION

What the prior art has failed to recognize is that SILWET.RTM. L-7602 surfactant--which contains a relatively high amount of hydrophobic dimethylsiloxane units relative to the siloxane units containing the hydrophilic polyethyleneoxide units--imparts autophobic properties to ethanolic solvent system hairspray compositions without a necessity for the use of large amounts of hydrophobic silicone compounds or polymers as will be further described below. The unique properties of the class of autophobic silicone copolyols to which SILWET.RTM. L-7602 belongs provide significant advantages when such compounds are incorporated into hairspray compositions based on ethanol solvent systems.

The present invention provides a hairspray composition--in the form of a pump spray or a self-pressurized aerosol composition--having improved body by virtue of the presence of a sufficient, but small, amount of an autophobic silicone copolyol surfactant to cause the hairspray film to contract on the hair at between 20.degree. C. and 37.degree. C. rather than to spread into an even film upon drying.

These compositions possess improved hair body properties through the use of a single silicone copolyol surfactant which is a specific type of dimethicone copolyol which is used in an amount which is effective to impart autophobic properties to a hairspray composition using an ethanol soluble hairspray resin dissolved in an ethanol solvent system which can optionally further contain an aerosol propellant. Generally, the autophobic silicone copolyol is used in an amount of 0.02% to about 0.5% weight percent based on the total weight of the hairspray composition with the objective being to use the minimum level needed to achieve the desired body and other properties on the hair sprayed with the composition. More preferably, the amount of autophobic silicone copolyol employed is about 0.05% to 0.2% of the hairspray composition.

Another advantage of the use of such an autophobic silicone copolyol surfactant is that only a small amount of such a surfactant is necessary to obtain a hairspray composition which is autophobic upon drying. This has the advantage of minimizing the use of silicone surfactants in the composition while permitting the properties of the silicone such as softer hair feel and reduced stickiness of the sprayed hair to be observed. There is no need to employ a rather large amount of hydrophobic silicone material such as decamethyl cyclopentasiloxane relative to the dimethicone copolyol to overcome the film spreading nature of the latter and thereby obtain a hairspray composition which is autophobic upon drying

The use of small amounts of silicone additives is also advantageous from an economic standpoint since silicone materials are rather expensive. It is also well known that use of an excess of silicone additive can result in loss of adhesion and hold in the hair. Furthermore, use of an excess amount of silicone additive can result in a hairspray composition that is too easy to brush out and is thus subject to loss of "body". For the purposes of this invention, the term "body" means "flexible hold" which is the ability of the hair to retain its styled appearance despite the effects of the wind or motion of the head on the hair.

The autophobic effect on the hairspray composition as it is drying on the hair causes large droplets of the composition to form and thus larger juncture points between hair fibers are produced. The result is stronger bonds and greater hold. This development is at the cost of less uniform coating of the hair by the hairspray resin. The effect of a non-uniform coating is that the hair fiber between the juncture points is more flexible and the styled hair feels softer to the touch. The end result is softer hair that holds better and thus has improved body. Another advantage of the use of small amounts of such autophobic silicone copolyols is that wicking forces are reduced which result in less matting of adjacent hair fibers. The benefits outweight the minor detrimental effects caused by such silicones: slower drying hairspray compositions and a slightly rougher hair surface that combs more raspy than a hairspray composition that leaves a more uniform film of resin on the hair.

In an alternative embodiment, the hairspray compositions of the present invention can additionally include further amounts of a hydrophobic silicone compound or polymer such as dimethylsiloxane cyclic pentamer, dimethylsiloxane cyclic tetramer or a low viscosity polydimethylsiloxane fluid of about 20, and preferably no more than about 10, centistokes in viscosity at 25.degree. C., and mixtures thereof in an amount of about 0.02% to 0.5% by weight of the total hairspray composition. More preferably, the ratio of the autophobic silicone copolyol used herein and such hydrophobic silicone compound or polymer is 1:1 and the total of both additives is about 0.1% to 0.2% by weight of the hairspray composition.

DETAILED DESCRIPTION OF PRESENT INVENTION

These and other advantages of the present invention are provided by an aerosol hairspray composition having improved hold consisting essentially of from 0.5% to 8.0% by weight of an ethanol soluble hairspray resin dissolved in a sufficient amount of an ethanol solvent system to render the composition sprayable in aerosol form, said composition further containing an effective amount of an autophobic silicone copolyol to cause the sprayed film to contract on the hair at between 20.degree. C. to 37.degree. C. rather than to spread into an even film upon drying, said silicone copolyol surfactant consisting essentially of organosiloxy units selected from the group consisting of dimethylsiloxy units, CH.sub.3 SiO(C.sub.X H.sub.2x)(OCH.sub.2 CH.sub.2).sub.y (OCHCH.sub.3 CH.sub.2).sub.z OR, (CH.sub.3).sub.2 SiO(C.sub.x H.sub.2x) (OCH.sub.2 CH.sub.2).sub.y (OCHCH.sub.3 CH.sub.2).sub.z OR. and trimethylsiloxy units, and having a number average molecular weight of about 1500 to 6000 wherein x has a value of from 1 to 12, R is hydrogen or alkyl of 1 to 4 carbon atoms, y is greater than or equal to 1 and z is greater than or equal to 0 and the sum of y+z and the amount of dimethylsiloxy units and trimethylsiloxy units present is such that the silicone copolyol causes an ethanolic solution of the hairspray resin to contract on the hair rather to spread into an even film at 20.degree. C. to 37.degree. C. upon drying and a 1% by weight solution of the silicone copolyol in water has a cloud point of less than 30.degree. C. and said ethanol solvent system consists essentially of a least 70% by weight of ethanol and any remaining solvent is selected from the group consisting of water, R.sup.1 OH where R.sup.1 is an alkyl of 3 or 4 carbon atoms, and mixtures thereof.

"Ethanol soluble hairspray resin" as used herein and in the attached claims is intended to mean a film-forming polymer which is soluble in an ethanol solvent system which is composed of at least 70% by weight of ethanol with any remaining solvent being selected from water, alcohols of the formula R.sup.1 OH where R.sup.1 is an alkyl of 3 or