USOO6537532B1 (12) United States Patent (10) Patent No.: US 6,537,532 B1 Torgerson et al. (45) Date of Patent: *Mar. 25, 2003 (54) SILICONE GRAFTED THERMOPLASTIC (52) U.S. Cl. ................ 424/70.12; 424/70.1; 424/70.11; ELASTOMERIC COPOLYMERS AND HAIR 424/70.15; 424/70.16; 424/78.08; 424/78.17; AND SKIN CARE COMPOSITIONS 424/78.24 CONTAINING THE SAME (58) Field of Search ............................. 424/70.12, 70.1, 424/70.11, 70.15, 70.16, 78.08, 78.17, 78.24 (75) Inventors: Peter Marte Torgerson, Washington Court House, OH (US); Sanjeev (56) References Cited Midha, Blue Ash, OH (US) U.S. PATENT DOCUMENTS (73) Assignee: The Procter & Gamble Company, 4.011,376 A 3/1977 Tomalia et al. ............. 528/392 Cincinnati, OH (US) 4,988,506 A * 1/1991 Mitra et al. ............ 424/70.122 5,106,609 A * 4/1992 Bolich, Jr. et al............. 424/70 (*) Notice: Subject to any disclaimer, the term of this 5,916,547 A * 6/1999 Torgerson et al. ....... 424/70.12 patent is extended or adjusted under 35 5,919,439 A * 7/1999 Torgenson et al. ..... 424/70.122 U.S.C. 154(b) by 0 days. * cited by examiner This patent is Subiect to a terminal dis- Primary Examiner Thurman- K. Page p ASSistant Examiner-Liliana Di Nola-Baron claimer. (74) Attorney, Agent, or Firm-Brent M. Peebles (21) Appl. No.: 09/342,726 (57) ABSTRACT (22) Filed: Jun. 29, 1999 The present invention relates to water or alcohol soluble or dispersible Silicone grafted thermoplastic elastomeric Related U.S. Application Data copolymers and to cosmetic and pharmaceutical composi tions containing these copolymers. This invention especially (63) Continuation of application No. 08/748,705, filed on Nov. relates to copolymers useful for hair Styling purposes, and to application13, 1996, now No. Pat.08/446,189, No. 5,916,547, filed on which May is19, a division1995, now of hairstvliaIrSly IIng composiuOnSiti containingtaining lineseth copolymerS.1 ThIn IS abandoned, which is a continuation of application No. invention further relates to copolymers useful for providing 08/257,961, filed on Jun. 16, 1994, now abandoned, which cosmetic and pharmaceutical compositions for topical appli is a continuation-in-part R Esties 08/236,881, filed cation to the skin. These topical Skin care compositions are on Apr. 29, 1994, now abandoned, which is a continuation ful for deliveri d t d IV t ti abandoned.E.R.E.E.S.E.R.S.E SYS activeuseful ingredientsfor delivering to or and/orthorugh transdermallythe skin. transporting (51) Int. Cl." ............................. A61K 7/06; A61K 7/11 10 Claims, No Drawings US 6,537,532 B1 1 2 SILICONE GRAFTED THERMOPLASTIC tend to have a low Surface energy and provide unique ELASTOMERIC COPOLYMERS AND HAIR aesthetic and formulation advantages not usually obtained AND SKIN CARE COMPOSITIONS from non-Silicon grafted polymers. However, Silicon grafted CONTAINING THE SAME thermoplastic elastomeric copolymers are heretofore unknown. This is a continuation of application Ser. No. 08/748,705, In the present invention new classes of thermoplastic now U.S. Pat. No. 5,916,547, filed on Nov. 13, 1996, which elastomeric copolymers have been developed which have is a divisional of application Ser. No. 08/446,189, filed on the desired flexibility, Strength, and elastic properties and yet May 19, 1995, now abandoned, which is a continuation of are readily Soluble and/or dispersible in water and/or alcohol application Ser. No. 08/257,961, filed on Jun. 16, 1994, now Systems. These copolymerS also incorporate polysiloxane abandoned, which is a continuation-in-part of application Side chains which further modify their Surface properties to Ser. No. 08/236,881, filed on Apr. 29, 1994, now abandoned, give them a Smooth, Slick feel, and make them easier to which is a continuation of Ser. No. 08/110,592, filed on Aug. formulate into a wide variety of vehicles. Furthermore, these 23, 1993 now abandoned. materials provide hair care compositions which leave the 15 TECHNICAL FIELD hair feeling natural, i.e. not very Stiff or Sticky. In addition to the hair care benefits provided by silicon The present invention relates to water or alcohol soluble containing thermoplastic elastomeric copolymers, it has or dispersible Silicone grafted thermoplastic elastomeric been found that these materials are also useful for incorpo copolymers and to cosmetic and pharmaceutical composi ration into a wide variety of cosmetic and pharmaceutical tions containing these copolymers. These copolymers are compositions for topical application to the skin. These useful for hair Setting and Styling purposes. A particularly copolymers provide topical compositions which are more useful application for these copolymers is in hair Spray and easily and uniformly spread upon the skin, which feel good mousse compositions. This invention further relates to upon the Skin, and yet which are highly Substantive. copolymers useful for incorporating into cosmetic and phar Furthermore, these copolymers are useful for enhancing the maceutical compositions for topical application to the skin. 25 penetration of a wide variety of cosmetic and pharmaceuti Skin care compositions containing these copolymers are cal actives into the skin, or alternatively, through the skin for useful for delivering and/or transdermally transporting a Systemic delivery. wide variety of active ingredients to and/or through the skin. It is an object of the present invention to provide novel, BACKGROUND OF THE INVENTION water and/or alcohol Soluble and/or dispersible Silicone In the hair care area, the desire to have hair retain a grafted thermoplastic elastomeric copolymers. particular Style or shape is widely held. Such style retention It is another object of the present invention to provide is generally accomplished by either of two routes: perma novel Silicone grafted thermoplastic elastomeric copolymers nent chemical alteration of the hair fiber or temporary useful in hair care compositions. alteration of hair Style or shape. A temporary alteration is 35 It is another object of the present invention to provide one which can be removed by water or by Shampooing. novel hair care compositions having improved Styling and/or Temporary Style alteration has generally been accomplished hold properties and having improved aesthetics. by application of a composition to dampened hair after It is another object of the present invention to provide Shampooing and/or conditioning and prior to drying and/or novel Silicone grafted thermoplastic elastomeric copolymers Styling. Products in the form of mousses, gels, lotions, or 40 useful in topical skin care cosmetic and pharmaceutical Sprays are most commonly used for this purpose. Once the compositions. desired Style is achieved, Spray products are commonly used It is another object of the present invention to provide to help retain the Style. These various hair care products novel topical cosmetic and pharmaceutical compositions utilize a variety of gums and resins for providing Styling and useful for delivering a wide variety of cosmetic materials retention. However, the gums and resins currently used tend 45 and pharmaceutical actives to and/or through the skin. to feel either too Sticky or too Stiff upon the hair. Also, these These and other objects will become readily apparent gums and resins do not wash out as easily as desired. from the detailed description which follows. Therefore, the need exists for improved Styling and Style retention materials which provide a strong, lasting, hold SUMMARY OF THE INVENTION without being either too stiff or too Sticky, and yet which are 50 The present invention relates to a water or alcohol soluble easily removed by Shampooing. Furthermore, because most or dispersible thermoplastic elastomeric copolymer having a hair care Styling compositions are water and/or alcohol backbone and two or more hydrophilic polymeric Side based, it is necessary that these materials have good Solu chains and one or more polysiloxane Side chains, Said bility or dispersibility in these bases. copolymer formed from the copolymerization of randomly Thermoplastic elastomeric copolymers are well known. 55 repeating A, B, and C units wherein Said copolymer com These copolymers combine thermoplastic properties, which prises: give them Solubility and Strength, with rubber-like elastic (i) from about 20% to about 89.9% by weight of said A properties, which give them flexibility and shape retention. units, wherein Said A units are monomer units copoly However, despite these highly desirable properties, most merizable with said B and C units; thermoplastic elastomeric copolymers are generally 60 (ii) from about 10% to about 60% by weight of said B insoluble or poorly Soluble in water and/or alcohol Systems units, wherein Said Bunits are hydrophilic macromono and would not be Suitable in hair care compositions. mer units having a polymeric portion and a moiety Therefore, thermoplastic elastomeric copolymers having copolymerizable with Said A and C units, and good water and/or alcohol solubility would be useful for (iii) from about 0.1 to about 20% by weight of said C developing improved hair care compositions. 65 units, wherein Said C units are polysiloxane mac It is also known that polymers can be modified by the romonomer units having a polymeric portion and a incorporation or grafting of Silicon. Silicon grafted polymers moiety copolymerizable with Said A and B units, US 6,537,532 B1 3 4 wherein Said A units, in conjunction with Said copolymeri and is pendant from Said backbone after polymerization; n is able moieties of Said B units and Said C units, forms said 0 or 1; t is an integer from 1 to 3; and c is an integer of about backbone; wherein Said polymeric portion of Said B units 1 or greater. forms Said hydrophilic side chains, wherein Said polymeric In further embodiments, B is at least one hydrophilic portion of Said C units forms Said polysiloxane Side chains, macromonomer unit copolymerizable with A and C corre wherein Said copolymer has a weight average molecular sponding to the formula weight greater than about 10,000, and wherein Said copoly mer exhibits at least two distinct T, values, said first T.