CA2319800A1 - Thermoplastic elastomeric copolymers and hair and skin care compositions containing the same - Google Patents
Thermoplastic elastomeric copolymers and hair and skin care compositions containing the same Download PDFInfo
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Abstract
The present invention to water or alcohol soluble or dispersible thermoplastic elastomeric copolymers and to cosmetic and pharmaceutical compositions containing these copolymers. This invention especially relates to copolymers useful for hair styling purposes, and to hair styling compositions containing these copolymers. This invention further relates to copolymers useful for providing cosmetic and pharmaceutical compositions for topical application to the skin. These tropical skin care compositions are useful for delivering and/or transdermally transporting active ingredients to or through the skin.
Description
THERMOPLASTIC ELASTOMERIC COPOLYMERS AND HAIR AND SKIN CARE
COMPOSTIONS CONTAINING THE SAME
This application has been divided out of Canadian Patent Application Serial No. 2,165,767 filed June 30, 1994.
TECHNICAL FIELD
The present invention relates to water or alcohol soluble or dispersible thermoplastic elastomeric copolymers and to cosmetic and pharmaceutical compositions containing these copolymers. These copolymers are useful for hair setting and styling purposes. A particularly useful application for these. copolymers is in hair spray and mousse compositions. This invention further relates to copolymers useful for incorporating into cosmetic and pharmaceutical compositions for topical application to the skin. Skin care compositions containing these copolymers are useful for delivering and/or transdermally transporting a wide variety of active ingredients to and/or through the skin.
BACKGROUND OF THE INVENTION
In the hair care area, the desire to have hair retain a particular style or shape is widely held. Such style retention is generally accomplished by either of two routes: permanent chemical alteration of the hair fiber or temporary alteration of hair style or shape. A
temporary alteration is one which can be removed by water or by shampooing. Temporary style alteration has generally been accomplished by application of a composition to dampened hair after shampooing and/or conditioning and prior to drying and/or styling. Products in the form of mousses, gels, lotions, or sprays are most commonly used for this purpose. Once the desired style is achieved, spray products are commonly used to help retain the style. These various hair care products utilize a variety of gums and resins for providing styling and retention. However, the gums and resins currently used tend to feel either too sticky or too stiff upon the hair. Also, these gums and resins do not wash out as easily as desired. Therefore, the need exists for improved styling and style retention materials which provide a strong, lasting, hold without being either too stiff or too sticky, and yet which are easily removed by shampooing. Furthermore, because most hair care styling compositions are water and/or alcohol based, it is necessary that these materials have good solubility or dispersibility in these bases.
Thermoplastic elastameric copolymers are well known. These copolymers combine thermoplastic properties, which give them solubility and strength, with rubber-like elastic properties, which give them flexibility and shape retention. However, despite 10 these highly desirable properties, most thermoplastic elastomeric copolymers are generally insoluble or poorly soluble in water and/or alcohol systems and would not be suitable in hair care compositions. Therefore, thermoplastic elastomeric copolymers having good water and/or alcohol solubility would be useful for developing improved hair care compositions.
In the present invention new classes of thermoplastic elastomeric copolymers have been developed which have the desired flexibility, strength, and elastic properties and yet are readily soluble and/or dispersible in water and/or alcohol systems.
20 Furthermore, these materials provide hair care compositions which leave the hair feeling natural, i.e. not stiff.
In addition to the hair care benefits provided by these copolymers, it has been found that these materials are also useful for incorporation into a wide variety of cosmetic and 25 pharmaceutical Compositions for topical application to the skin.
These copolymers provide topical coapositions which are sore easily and uniforvly spread upon the skin, which feel good upon the skin, and yet which are highly substantive. Furthermore, these copolymers are useful for enhancing the penetration of a 38 wide variety of cosuetlc and phan~aceutical actives Into the skin, or alternatively, through the skin for systemic delivery.
It is an object of the present invention to provide novel, water an4/or alcohol soluble and/or dispersible thermoplastic elastomeric copolymers.
It is another object of the present invention to provide novel thermoplastic elastomeric copolymers useful in hair care compositions.
It is another object of the present invention to provide novel hair care compositions having improved styling and/or hold properties and having improved aesthetics.
It is another object of the present invention to provide novel thermoplastic elastomeric copolymers useful in topical skin care cosmetic and pharmaceutical compositions.
It is another object of the present invention to provide novel topical cosmetic and pharmaceutical compositions useful for delivering a wide variety of cosmetic materials and pharmaceutical actives to and/or through the skin.
These and other objects will become readily apparent from the detailed description which follows.
SUMMARY OF THE INVENTION
The present invention relates to a water or alcohol soluble or dispersible thermoplastic elastomeric copolymer having a backbone and one or more polymeric side chains, said copolymer formed from the copolymerization of randomly repeating A and B units and corresponding to the formula [A]a [B]b wherein (i) A is at least one polymerizable monomer unit corresponding to the formula X - C - CR5 = CHR6 wherein X is selected from the group consisting of -OH, -OM,-OR4, -NH2, -NHR4, and -N(R4)z; M is a cation selected from the group consisting of Na+, K+, Mg++, Ca++, Zn++, NHa+, alkylammonium, dialkylammonium, trialkylammonium, and tetraalkylammonium; each R4 is selected from the group consisting of H, C~-Ca straight or branched chain alkyl, and N. N,-dimethylaminoethyl, 2-hydroxyethyl, 2-methoxyethyl, 2 ethoxyethyl; and R5 and R6 are independently selected from the group consisting of H, C~-Ca straight or branched chain alkyl, methoxy, ethoxy, and 2-hydroxyethoxy, 2-methoxyethyl, 2-ethoxyethyl;
(ii) B is at least one hydrophilic macromonomer unit copolymerizable with A corresponding to the formula RO -[-CH2CH2N-]m-CH2 C=0 CH=CH2 R' wherein R and R' are independently selected from the group consisting of H and C~-Ca straight or branched chain alkyl; and m is an integer from about 10 to about 2000; and (iii) a is an integer of about 100 or greater and b is an integer of about 2 or greater; and wherein said copolymer has a weight average molecular weight greater than about 10,000, and wherein said copolymer exhibits two distinct Tg values, said first Tg corresponding to said backbone and having a value less than about 0°C, and said second Tg corresponding to said side chains and having a value greater than about 25°C.
In further embodiments, the present invention Telates to hair care compositions, especially hair setting and styling compositions, containing these copolymers.
In further embodiments, the present invention relates to cosmetic and pharmaceutical compositions containing these copolymers for topical.application to the skin for the delivery of cosmetic materials and pharmaceutical actives onto, into and/or 10 through the skin.
All percentages and ratios used herein are by weight of the total composition and ail measurements made are at 25oC, unless otherwise designated. The invention hereof can comprise, consist of, or consist essentially of, the essential as well as optional 15 ingredients and components described herein.
DETAILED DESCRIPTION Of THE INV NTInN
The feral 'thermoplastic elastomeric copolymer' as used herein means that the copolymer has both thermoplastic and elastomeric properties. The term 'thermoplastic elastomeric copolymer' is one 20 fau,iliar to those of ordinary skill in polymer science. By 'thermoplastic' is meant that upon heating, the copolymer softens and upon cooling it rehardens; upon being subject to stress it begins to flow and upon removal of stress it stops flowing. 8y 'elastomeric' is want that the copolymer has an elastic modulus 25 such that the copolymer exhibits a resistance to deformation and has limited extensibility and retraction. In other words, the copolymer tends to recover its size and shape after deformation.
The term 'macromonomer' is one familiar to those of ordinary skill in polymer science, and is used to describe a polymeric material containing a polymerlzable moiety. A macromonomer is a macromolecular mono.er. A macromonomer is essentially a very large type of monoaer building~block~unFit which can be used in a polymerization reaction to fora polymers with itself, with other monomers, or with other macromonomsrs.
The term 'water or alcohol soluble or dispersible' as used herein means that these copolymers are either freely soluble in or dispersible (as a stable suspension) in at least one of the following solvents, or alternatively, in any combination of one of the following solvents: water, methanol, ethanol, and isopropanol.
By 'soluble' is meant that the copolymer is soluble in the solvent = or solvents at 25oC at a concentration of at least about-20 mg/ml, more preferably about 50 mg/mL, and most preferably about 100 mg/ml. By 'dispersible' is meant that the copolymer forms a 10 stable, uniform suspension (without the addition of further materials such as emulsifiers) when combined with the solvent or solvents at 25oC at a concentration of at least about 20 mg/ml, more preferably about 50 mg/ml, and most preferably about 100 mg/ml.
15 Thermoplastic Elastomeric Cooolvmers The copolymers of the present invention are characterized in having an elastomeric or flexible backbone and rigid, thermoplastic, hydrophilic side chains. This combination of both elastomeric and thermoplastic moieities in a single copolymer 20 provides the unique and useful properties of these materials. The copolymers of the present invention, can also be referred to as 'graft copolymers' because they can be prepared from the capolymeritation of monomer units and macromonmer units. In other words, the macromonomer is 'grafted' or incorporated into the 25 copolymer.
These copolymers exhibit two distinct in~iscible phases.
itithout being limited by theory, it is believed that the hydrophilic side chains of these copolymers are closely associated with each other, thereby existing in one phase, while the backbone 30 of the copolymer remains in a separate phase. A consequence of this phase ianiscibility is that these copolymers exhibit two distinct glass transition temperatures or, 'Tg's', for the backbone and the side chains. Tg is a well known ter°ei of art in polymer science used to describe the temperature at which a 35 polymer or portion thereof undergoes a transition from a solid or _. -brittle material to a liquid or rubber-like material. Glass transition temperatures can be measured using standard techniques that are well known to the polymer scientist of ordinary skill in the art. One particularly useful technique for determining glass 5 transitions is differential scanning calorimetry (also known as DSC). The glass transition phenomenon in polymers is described in Tntrnrluetier~ to Polymer Science and Technoloav: An SPE Textbook, (eds. H.S. Kxufman and J.J. Falcetta), (John wiley ~ Sons: I477).
The Tg of the backbone of the copolymers herein (i.e. that part of the copolymer not containing the side chains) should be less than about OoC. Preferably the Tg of the backbone should be from about -IOoC to about -130oC, more preferably from about -20oC
to about -125oC, and most preferably from about -55oC to about -120oC. The Tg of the side chain of the copolymers (i.e. that 15 part of the copolymer not containing the backbone) is greater than about 20oC. Preferably the Tg of the sidechain should be from about 25oC to about 200oC, more preferably from about 30oC to about 175oC, and most preferably from about 35oC to about 150oC.
Because these copolymers possess two distinct Tg's, these 20 copolymers are useful in hair styling and setting compositions.
liithout being limited by theory, it is believed that when these copolymers are subjected to temperatures above both Tg's, they are essentially liquid and can provide great flexibility during the styling process (e. g., when curling irons, blow driers, and other 25 heat sources are applied to the hair). Upon cooling of the copolymer to room temperature (e.g., when the heat source is removed from the hair) the copolymer is then at a temperature that is typically between both Tg's, and the copolymer possesses structural rigidity from the macromonomer side chains, and yet has 30 flexibility from the backbones, and can provide a strong, yet flexible, hair hold or style retention.
furthermore, at skin temperatures, these copolymers would be at a temperature which is essentially between both Tg's. these copolymers can enhance the film forming properties of skin care _8_ coiapositions, and provide benefits shuch as better and a~ore even distribution upon the skin.
The copolymers of the present invention are formed from the copolymerizatton of randomly repeating A and B units, preferably wherein the A units are selected from at least one polymerizable, ethylenically unsaturated monomer unit, and the B units are selected from at least- one hydrophilic macromonomer unit which contains an ethylenically unsaturated moiety which is copolymerizable with A. In typical embodiments of these copolymers, the backbone is primarily derived frog the ethylenically unsaturated portion of the A monomer unit and the ethylenically unsaturated portion of the B macromonomer unit. The side chains are derived from the non-copolymerized portions of the macromonomer. The A and B units can be selected from a wide vairety of structures as long as the limitations of the copolymer are met (e.g., solubility, Tg's, and molecular weights) The A monomer units of the copolymers of the present invention can comprise from about 40X to about 90x, more preferably from about 50x to about 85X, and most preferably from about 60X to about 80X, by weight, of the copolymers.
The hydrophilic B macromonomer units can comprise from about 10Z to about 60x, more preferably from about 15x to about 50x, and a~ost preferably frog about 20x to about 40X, by weight of the copolymers.
The copolymers of the present invention have a weight average molecular weight of at least about 10,000. There is no upper limit for molecular weight except that which limits appltcability of the invention for practical reasons, such as viscosity, processing, aesthetic characteristics, formulation compatibility, etc. In general, the weight average molecular weight is less than about 5,000,000, more generally less than about 2,500,000, and typically less than about 1,500,000. Preferably, the weight average molecular weight is froei about 10,000 to about 5,000,000, oars preferably from about T5,000 to about 1,000,000, even more _g_ preferably from about 100,000 to about 850,000, and most preferably from about 125,000 to about 750,000.
Alternatively, the copolymers of the present invention can also be represented by the formula (AJaI~Jb wherein A and B are as described herein, and where a 1s an integer of about 100 or greater, preferably a is an integer from about 100 to about 3000, more preferably from about 250 to about 2000, and most preferably from about 350 to about 1500, and b is an integer 10 of about 2 or greater, preferably from about 2 to about 50, more preferably from about 2 to about 20, and most preferably from about 2 to about 10. In this formula, it is expressly intended that even though ranges are provided for the subscripts a and b, these subscripts are not intended to strictly limit the polymers 15 herein so long as the physical propoerties of the polymers are achieved. when the copolymers herein are described by the formula disclosed in this paragraph it has been found useful to describe the copolymers by the m number average molecule weights. In _ general, the number average molecular weight is less than about 20 2,500,000, more generally less than about 1,500,000, and typically less than about 1,000,000. Preferably, the number average molecular weight is from about 15,000 to about 1,000,000, more preferably froa~ about 20,000 to about 500,000, and most preferably frog about 25,000 to about 250,000.
By appropriate selection and combination of the particular A
and B units and by the choice of specific relative ratios of the 5 units yell within the ability of one of ordinary skill in the art, the copolymers can be optimized for various physical properties such as solubility, Tg's, and the like, and for compatibility with other ingredients commonly used in hair care and skin care applications.
10 lihen the copolymers of the present invention are Incorporated into hair and/or skin care compositions, the copolymers typically comprise from about O.lx to about 25x, preferably from about 0.5%
to about 20x, more preferably from about lx to about 10%, and most preferably from about 2% to about 5X of the composition, although 15 higher or lower amounts can be used depending upon the particular application.
Monoeier 'A' Unii~
The 'A' monomer unit is selected from polymerizable monomers, preferably ethylenically unsaturated monomers. Either a single A
20 monomer or~combinations of two or more A monomers can be utilized.
For example, if two different A monomers are polymerized with a 8 macromonomer, the resulting copolymer could be described as a terpolymer. In either case, the monomers are selected to meet the requirements of the copolymer. By 'polymerizable', as used 25 herein, is meant monomers that can be polymerized using any conventional synthetic techniques. Monomers that are poiymerizable using conventional free radical initiated techniques art preferred. the term 'ethylenically unsaturated' is used herein to mean monomers that contain at least one polymeritable 30 carbon-carbon double bond (which can be ~ano~, di-, tri-, or tetra-substituted).
Ths A monomer units of the copolymers of the present invention can comprise from about 40% to about 90x, more preferably from about 50x to about 85x, and most preferably from 35 about 60'x to about 80%, by weight, of the copolymers.
The ethylenically unsaturated A monomer units preferably can be described by the following formula X - C- CRS = CHR6 S
wherein X is selected from the group consisting of -OH, -0l1, -OR4, -NH2, -NHR4, and -N(R4)Z; M is a catlon selected from the group consisting of Na+, K+, Mg++, Ca++, Zn++, HH4+, alkylammonium, dialkylammonium, trialkylanmonium, and tetralkylartenonium; each R4 10 is independently selected from the group consisting of H, C1-Cg straight or branched chain alkyl, N,N-dimethylaminoethyl, 2-hydroxyethyl, 2-methoxyethyl, and 2-ethoxyethyl; and RS and R6 are independently selected from the group consisting of H, C1-C8 straight or branched chain alkyl, methoxy, ethoxy, 15 2-hydroxyethoxy, 2-methoxyethyl, and 2-ethoxyethyl.
. Representative noniimiting examples of monomers useful herein include acrylic acid and salts, esters, and amides thereof. The salts can be derived from any of the common nontoxic metal, ammonium, or substituted ammonium counter ions. The esters can be 20 derived from C1.40 straight chain, C3-40 branched chain, or C3-40 carbocyclic alcohols; from polyhydric alcohois having from about 2 to about 8 carbon atoms and from about 2 to about 8 hydroxy groups (nonlimiting examples of which include ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, glycerin, and 25 1,2,6-hexanetriol); from amino alcohols (nonlimiting examples of which include aminoethanol, dimethylaminoethanol, and diethylaminoethanol, and their quaternized derivatives); or from alcohol ethers (nonliaiting examples of which include methoxyethanol, and ethoxy ethanol)., The asides can be 30 unsubstituted, N-alkyl or H-alkylamino mono-substituted, or N,N-dialkyl or N,H-dialkylamino di-substituted, wherein the alkyl or alkylamino group can be derived from C1-4p straight chain, C3~40 branched chain, or C3-40 carbocylic moietfes. Additionally, the alkylan~ino groups can be quaternized. Also useful as monomers 35 are substituted acrylic acids and salts, esters, and amides thereof (wherein the substituents are on the two and three carbon positions of the acrylic acid and are independently selected froo the group consisting of C1-4 alkyl, -CN, -COOH (e. g., methacrylic acid, ethacrylic acid, and 3-cyano acrylic acid). The salts, esters, and amides of these substituted acrylic acids can be defined as described above for the acrylic acid salts, esters, and amides. Other useful monomers include vinyl and aliyl esters of C1-,0 straight chain, C3-40 branched chain, or C3-40 carbocylic carboxylic acids; vinyl and allyl halides (e. g., vinyl chloride 10 and allyl chloride); vinyl and allyl substituted heterocylic compounds (e. g., vinyl pyrridine and allyl pyridine); vinylidene chloride; and hydrocarbons having at least one carbon-carbon double bond (e. g., styrene, alpha-methyistyrene, t-butylstyrene, butadiene, isoprene, cyclohexadiene, ethylene, propylene, 15 1-butane, 2-butane, lsobutylene, vinyl toluene); and mixtures thereof.
Preferred A monomers useful herein include those selected froa~ the group consisting of acrylic acid, methacrylic acid, ethacrylic acid, methyl acrylate, ethyl acrylate, Q-butyl 20 acrylat~e, ~q-butyl acrylate, ~-butyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, j,~-butyl methacrylate, ~,-butyl methacrylate, 2~ethylhexyi methacrylats, decyl methacrylate, methyl ethacrylate, ethyl ethacrylate, n-butyl ethacrytate, 25 j~-butyl ethacrylate, ~-butyl sthacrylate, 2-ethylhexyt ethacrylate, decyl ethacrylats, 2,3-dihydroxypropyl acrylate, Z,3-dihydroxypropyl methacrylate, 2-hydroxyethyi acrylate, Z-hydroxypropyl acrylate, hydroxypropyl methacrylate, glyceryl monoacrylate, giyceryl monomethacrylats, 30 acryiamide, meethacrylan~ide, ethacrylan~ide, N~methyl acrylaoida, N,H-diaiethyl acryiamide, N,N-dimethyl methacryla~aids, H-ethylacrylamide, N-isopropyl acrytamide, N-butyl acrylamide, N-~-butyl acrylamide, N,ti-di-n-butylacrylaeide, H,ti-disthylacrylamide, N-octyl acrylan~ide, N-octadecyl acrylaaide, 35 N-phenyl acrylamide, H-methyl methacrylamide, N-ethylmethacrylamide. N-dodecylmethacrylamide, N,N-dimethylaminoethyl acrylamide, quaternized N,N-dimethylaminoethyl acrylamide, N,N-dimethylaminoethyl methacrylamide, quaternized N,N-dimethylaminoethyl methacrylamide, N,N-dimethylaminoethyl acrylate, N,N-dimethylaminoethyl methacrylate, quaternized N.N-dimethylaminoethyl acrylate, quaternized N,N-dimethylaminoethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate. 2-hydroxyethyl ethacrylate, glyceryl acrylate, 2-methoxyethyl acrylate, 2-methoxyethyl methacrylate, 2-methoxyethyl ethacrylate, 2-ethoxyethyl acrylate, 2-ethoxyethyl methacrylate. 2-ethoxyethyl ethacrylate, malefic acid, malefic anhydride and its half esters, crotonic acid, itaconic acid, angelic acid, diallyldimethyl ammonium chloride, vinyl pyrrolidone methyl vinyl ether.
methyl vinyl ketone, maleimide, vinyl pyridine, vinyl imidazole, vinyl furan, styrene sulfonate, allyl alcohol, vinyl alcohol, vinyl caprolactam, and mixtures thereof.
More preferred A monomers are those selected from the group consisting of methyl acrylate, methyl methacrylate, methyl ethacrylate, ethyl acrylate, ethyl methacrylate, ethyl ethacrylate, n-butyl acrylate, n-butyl methacrylate, n-butyl ethacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, 2-ethylhexyl ethacrylate, N-octyl acrylamide, 2-methoxyethyl acrylate, 2-hydroxyethyl acrylate, N.N-dimethylaminoethyl acrylate, and mixtures thereof.
Most preferred A monomers for the embodiment of the present invention are those selected from the group consisting of n-butyl acrylate, 2-ethylhexyl acrylate, N-octyl acrylamide. 2-methoxyethyl acrylate, 2-hydroxyethyl acrylate, N,N-dimethylaminoethyl acrylate, and mixtures thereof.
Hydrophilic "B" Macromonomer Units A macromonomer is a large monomer unit, i.e. a macromolecular monomer, which can be further polymerized with itself, with other conventional monomers, or with other macromonomers. The term "macrononomer" is one that is familiar to the polymer chemist of ordinary skill in the art. The hydrophilic "B" macromonomer units of the present invention are very large monomer building blocks which can be formed from the polymerization of smaller monomer units. The 8 macromonomers encompass a wide variety of structures and are copolymerizable with the A monomer. Either a single B macromonomer or combinattons of two or more B
macromonomers can be utilized. In either case, the macromonomers are selected to meet the requirements of the copolymer.
The hydrophilic B macromonomers comprise from about lOX to about 60X, more preferably from about 15x to about 50X, and most 10 preferably from about ZOx to about 40x, by weight of the copolymers.
By the term 'copolymerizable' as used herein is meant B
macromonomers that can be reacted with the A monomer in a polymerization reaction using any conventional synthetic 15 techniques. 'Copolymerization' is a tern of art used to refer to the simultaneous polymerization of two or more different monomers.
In the present invention, B macromonomers that are copolymerizable with A monomers using conventional free radical initiated techniques are preferred. By the term 'hydrophilic' as used 20 herein is meant B macromonomers that are soluble in or have an affinity for water and/or other polar, water-soluble solvent materials (e.g., methanol, ethanol, propanol, isopropanol and the like). "Hydrophilic' is also a tens of art used to described a substance having a strong tendency to absorb water which results 25 in the swelling, solubilization, or dispersion of the substance in water. W thout being limited by theory, the hydrophilic B
macrortanoaier units are believed to contribute to the overall water or alcohol soluble or dispersible properties of the copolymers.
B a~acromono~oers that are useful herein contain an 30 ethylenically unsaturated oioiety that is copoiyinerizable with the A mono~er. The tera 'sthylenically unsaturated" is used herein to mean B macroa~ono~ners irhat contain it least one carbon-carbon double bond (which can be mono-, dt-, tri-, or tetra-substituted).
Typically, the preferred B macromonomers are those that are 35 endcapped with the ethylenically unsaturated moiety. 8y 'endcapped' as used herein is ~oeant that the ethylenically unsaturated moiety is at or near a terminal position of the macromonomer. However, this definition of 'endcapped' is not intended to limit the macromonomer to only those macromonomers 5 which terminate in a carbon-carbon double bond (whether mono-, di-, tri-, or tetra-substituted).
The hydrophilic 8 macromonomers of the present invention can be synthesized utilizing a variety of standard synthetic procedures familiar to the polymer chemist of ordinary skill in 10 the art,. Furthermore, these macromonomers can be synthesized starting from commercially available polymers. Typically the weight average molecular weight of the macromonomer is from about 1000 to about 200,000, more preferably from 1500 to about 30,000, and most preferably from about 2000 to about 25,000.
15 For example, the hydrophilic 8 macromonomers can be synthesized by the polymerization (acid, bass, free radical, or auto-initiated)-of a hydrophilic monomer to farm a polymer which is subsequently reacted with or 'endcapped' with a structural unit E, containing the ethylenically unsaturated moiety.
20 Alternatively, the B macromonomers can be synthesized starting with commercially available hydrophilic polymers which are 'endcapped' with the structural unit E. In yet another alternative, the B macromonoa~er can be synthesized by starting with the structural unit E, and polymerizing onto it the desired 25 hydrophilic monomer units. It is to ba understood that in this third alternative, the ethylenically unsaturated moiety of the E
unit is not consumed in the synthesis but its integrity is preserved for subsequent copolymerization of tht B macromonomer with tht A monomer units. All of the synthetic alternatives are 30 merely illustrative in that any other suitable synthetic procedures can be utilized to prepare the 8 ~acromonomers and copolymers of the present invention.
The B ~nacromonomers can be described by the following formula 35 [ I jn - [ X jm - E.
X is a hydrophilic monomer unit, and m is an integer from about 10 to about 2000, preferably from about 15 to about 300, and more preferably from about 20 to about 250, so that the macromonomer meets the weight average molecular weight requirements set forth above. Preferred is when X is a hydrophilic monomer unit selected from the group consisting of oxazolines, H-alkyloxazolines, alkylene glycols, N-vinylpyrrolidones, N-allylpyrrolidones, vinylpyridines, allylpyridiens, vinylcaprolactams, allylcaprolactams, 10 vinylimidazoles, allylimidaoles, vinylfurans, allylfurans, vinyltetrahydrofurans, ailyltetrahydrofurans, and mixtures thereof. More preferred is wherein X is a monomer unit selected from the group consisting of H-alkyloxazolines, alkylene glycols, and mixtures thereof. Most preferred is wherein X is a monomer 15 unit selected from N-alkyloxazolines.
E is a structural unit containing the ethylenically unsaturated moiety or 'endcapping' group. Preferred is when E is selected from the group consisting of vinyl, allyl, acryloyl, methacryloyl, ethacryloyl, styryl, 3-vinylbenzyl, ~-vinyibenzyl, 20 3-vinylbenzoyi, 4-vinylbentoyl, I-butenyl, I-propenyi, isobutenyl, isoprenyl, cyclohexyl, cylcopentyl, and mixtures thereof. More preferred is when E is selected from the group consisting of vinyl, aliyl, acryloyl, methacryloyl, ethacryloyi, 3-vinylbenzyl, ~-vinylbenZyl, 3-vinylbenzoyl, t-vinylbenzoyl, 1-butenyl, 25 I-propenyl, isobutenyl, and mixtures thereof. !lost preferred is when E is selected from the group consisting of vinyl, ally!, acryioyl, methacryloyl, ethacryloyl, 3-vinylbenzyl, 4-vinylbenzyl, and Fixtures thereof.
I is an optionally present chemical moiety. In other words, 30 ~ is an integer selected from zero and one. Without being limited by theory, I can be derived froo a chemical initiator or solvent used in the synthesis of the B macromonomer. Honiimiting examples of such initiators from which I can be derived include hydrogen ion, hydrogen radical, hydride ion, hydroxide ion, hydroxyl 35 radical, peroxide radical, peroxide anion, C1~20 carbocations, C1-20 carbanions, CI-20 carbon radicals, C1-20 aliphatic and aromatic aikoxy anions, ammonium ion, and substituted ammonium tons (e.g., C1-20 alkyl and C1-ZO alkoxy substituted). I can be derived from any useful solvent, nonlimiting examles of which 5 inlcude water, methanol ethanol, propanol, isopropanol, acetone, hexane, dichloromethane, chlorofora, benzene, and toluene.
Nonlimiting examples of I include chemical moieties selected from the group consisting of H, CI-C6 alkyl, phenyl, 4-methyiphenyl, and benzyl; preferably H, methyl, ethyl, and phenyl; and more 10 preferably H, methyl, and ethyl.
Representative examples of classes of endcapped B
macromonomers useful herein include those selected from the group consisting of endcapped poly(N-alkyloxazolines), endcapped polyalkylene glycol monoalkyl 'ethers, endcapped 15 ~pol~y(H-vinylpyrrolidones), endcapped ,poly(N-allylpyrrolidones), endcapped polyvinyipyridines, endcapped polyallylpyridines, ~endcapped polyvinylcaprolactams, endcapped poiyallylcaprolactams, endcapped polyvinylimidazoles, endcappped polyallylimidazoles, endcapped polyvinylfurans, endcapped polyvinyltetrahydrofurans, ZO endcapped polyallylfurans, endcapped polyacrylic acids, endcapped polymethacrylic acids, endcapped polyallyltetrahdyrofur~ns, and mixtures thereof.
Preferred are eacromonomers selected froa~ the group consisting of endcapped poly(N-alkyloxazolines), endcapped 23 polyalkylene glycol monoaikyl ethers, and Aixtures thereof.
l~lore preferred ire endcapped poly(N-alkyloxazoline) macromonomers.
Exaa~ples of endcapped poly(N-alkyioxazoline) nacroaonomers are those having the following chemical formula:
R -~-NCHyCH2-j~-0-E
C~0 R' wherein R and R' are independently selected frog H or C1-8 straight or branched chain alkyl, more preferably R and R' are independently selected froo H, methyl, or ethyl; and most preferably R is methyl and R' is ethyl. E is a copolymerizable, ethylenicaily unsaturated moiety (i.e. the endcapping gaiety).
Preferred is when E is selected from the group consisting of vinyl, allyl, acryloyl, methacryloyl, ethacryloyl, styryl, 3-vinyibenzyl, ~-vinylbenzyl, 3-vinylbenzoyl, i-vinylbenzoyl, I-butenyl, I-propenyl, isobutenyl, isoprenyi, cyclohexyl, L0 cylcopentyl, and mixtures thereof. More preferred is when E is selected from the group consisting of vinyl, allyl, acryloyl, methacryloyl, ethacryloyl, 3-vinylbenzyl, 4-vinylbenzyl, 3-vinyibenzoyl, 4-vinylbenzoyl, I-butenyl, I-propenyl, isobutenyl, and mixtures thereof. Most preferred is when ~ is selected from 15 the group consisting of vinyl, allyl, acryloyl, methacryloyl, ethacryloyl, styryl, 3-vinylbenzyl, t-vinylbenzyl, and mixtures thereof. In the above structure 4 is preferably an integer from about 10 to about 2000, more preferably from about 15 to about 300, and most preferably from about 20 to about 250.
20 ~ Alternatively, other examples of endcapped poly(N-alkyloxazolint) macromonomers ire those having the following chemical formula:
R- 0 -[-CH2CH2N-I~ - CHZ
C~0 CH=CH2 R' 30 wherein R and R' are independently selected frog the group consisting of H or CI-8 straight or branched chain alkyl, more preferably R and R' are independently selected from H, methyl, or ethyl; and most preferably R is H and R' is ethyl. In the above structure m is an integer from about I0 to about 2040, more preferably from about 15 to about 300, and most preferably from about 20 to about 250.
Highly preferred examples of endcapped poly(R-alkyloxazoline) macromonomers useful herein include acryloyl endcapped 5 poly(2-ethyl oxazoline), methacryloyl endcapped poly(2-ethyl oxatoline), styryl endcapped poly(2-ethyloxazoline), acryloyl endcapped poiy(2-methyl oxazoline), methacryloyi endcapped poly(2-methyl oxazoline), 3-vlnyibenzoyl endcapped poly{2-methyloxazoline), 4-vinylbenzoyl endcapped poly(2-methyloxazoline), and mixtures thereof.
The endcapped poly(N-alkyloxazoline) macroioonomers can be synthesized using standard synthetic procedures which involve polymerizing, usually under acid-catalyzed conditions, an H-alkyloxazol.ine to yield a poiy(N~alkyloxazoline) alcohol. This 15 alcohol can then be subsequently endcapped, ea~ploying standard reaction procedures, with the desired ethylenically unsaturated moiety using a reactive or activated form of an endcapping group.
Suitable activated endcapping groups include vinyl, allyl, 1-propenyl, 3-vinylbenzyi, 4-vinylbenzyl, 3-vinylbenzoyl, and 20 4-vinylbenzoyl halides (c. g. chlorides, bromides, and iodides), and the acid chlorides and bromides derived frog acrylic acid, methacrylic acid, and ethacrylic acid. ~, e.g., S.I. Shoda et al., 'Synthesis and Surfactant Property of Copolymers Having a Poly{2-Oxazol ine) Graft Chain', Journal of Polv~ner Scien ~~ Part 25 A; Polymer Che~ni:try, vol. 30, pp. 1489-1494 (1992); T. Saegusa et al., 'Macromoiecular Engineering on the Basis of the Polymerization of 2-Oxazolines, I~la,kromol. Cheis., liacron~ol Svmn , vol. 51., pp. 1-10 (1991); S. Kobayashi et al., llacronalecylg~, vol 22, pp. 2878-2884 (1989), and U.S. Patent No. 4,011,376, to 30 T~lia et al., issued March 8, 1971; and U.S. Patent No.
3,786,116, to Milkovich et al., issued January 15, 1974.
Alternatively the poiyoxazoline macromononeers can be synthesized by polymerizing the monomers onto an appropriate endcapping group. For example, the vinyl benzyl endcapped polyoxazolines can be prepared by polymerizing Z-ethyl-Z-oxazoltne onto a mixture of 3-vinylbenzyl and 4-benzylchlorides. egg EXArIPIE III.
Also highly useful herein are endcapped polyalkylene glycol 5 monoalkyl ether macromonomers corresponding to the following general chemical formula R'-[OCHZ-CHJp-0-E
wherein R' is selected from CI-C40 straight or branched chain alkyl, more preferably from CI-t8 straight or branched chain alkyl, most preferably from C1~C4 straight or branched chain alkyl, and most preferably methyl; R3 is selected from hydrogen, methyl, ethyl, or n-propyl, more preferably from hydrogen or 15 methyl, most preferably froa~ H. E is a copolymerizable, ethylenically unsaturated moiety (i.e. the endcapping moiety), Preferred is when E is selected fros the group consisting of vinyl, ally!, acryloyl, methacryloyl, ethacryloyl, styryl, 3-vinylbenzyl, 4-vinylbenzyl, 3-vinylbenzoyl, 4-vinylbenzoyl, ZO 1-butenyl,. 1-propenyl, isobutenyl, isoprenyl, cyclohexyl, cylcopentyl, and mixtures thereof. More preferred is when E is selected froo the group consisting of vinyl, ally!, acryioyl, methacryloyl, ethacryloyl, 3-vinylbenzyl, 4-vinylbenzyl, 3-vinytbenzoyl, 4-vinylbenzoyl, 1-butenyl, 1-propenyl, isobutenyl, 25 and ~i xtures thereof . !lost preferred i s when E i s sei ected froa~
the group consisting of vinyl, ally!, acryloyl, methacryloyl, ethacryloyl, styryl, 3-vinylbenzyl, 4-vinylbenzyl, and mixtures thereof: In the above structure, s is as described previously, wherein a~ is preferably an integer froo about 20 to about 2000, more preferably froo about 30 to about 750, and a~ost preferably frog about 40 to about 500. It is to be understood that in the above structure, that when R3 is other than hydrogen that various isoaers of the resulting a~acromonort~er ire possible depending upon the orientation of the individual glycol eoieties. Therefore, the 35 structure depicted above for these endcapped polyalkylene glycol - ~nonol kayl ethers i s a general one that i s not intended to 1 imi t these materials to any one particular isomeric structure.
Highly preferred examples of endcapped polyalkylene glycol monoalkyl ethers useful herein inlcude acryloyl endcapped polyethylene glycol monomethyl ether, 3-vinylbenzoyl endcapped polyethylene glycol monomethyl ether, 4-vinylbenzoyl endcapped polyethylene glycol monomethyl ether, methacryleyl endcapped polyethylene glycol monomethyl ether, and mixtures thereof.
The endcapped polyalkylene glycol monoalkyl ethers can be synthesized from the polyalkylene glycol monoalkyl ether and the reactive or activated form of an endcapping group employing standard reaction procedures. Suitable activated endcapping groups include vinyl, allyl, 3-vinylbenzoyl, and 4-vinylbenzoyl halides (e. g, chlorides, bromides, and iodides), and the acid chlorides and bromides derived from acrylic acid, methacrylic acid, and ethacrylic acid. The polyalkylene glycol monoalkyl ether can be synthesized from the corresponding polyalkylene glycol using any of the alkylating agents well known in the art (e. g., methyl iodide, methyl bromide, diazomethane, methyl sulfate, ethyl iodide). Polyethylene glycols of various molecular weight ranges, as well as their methyl ethers are commercially available from Aldrich Chemical Company and Union Carbide Corporation. Alternatively, the polyalkylene glycols can be synthesized from the corresponding alkylene oxides and alkylene glycois~using standard synthetic procedures (e.g., the acid or base catalyzed polymerization of ilkylene oxides).
Svn- s of the Cooolvm r In general, the copolymers can be made by free radical polymerization of the A monomers with the B macromonomers. It is not intended to necessarily exclude from this invention any copolymers made by means other than free radical polymerization, so long as the product has the desired physical properties. The copolymers herein contain randomly repeating monomer units and macromonomer uniis.
35' .22.
The general principles of free radical polymerization methods are well understood. See, for example, Odian, 'Principles of Polymerization', 2nd edition, John liiley t Sons, 1981, pp.
179-318. The desired monomers and macromonomers are all placed in a reactor, along with a sufficient amount of a mutual solvent so that when the reaction is complete the viscosity of the reaction is reasonable. Typical monomer and macromonomer loadings are from about lOx to about SOx, on a weight basis. Undesired terminators, especially oxygen, can be removed as needed. This is done by evacuation or by purging with an inert gas, such as argon or nitrogen. The initiator is introduced and the reaction brought to the temperature needed for initiation to occur, assuming thermal initiators are used. Nonlimiting examples of suitable initiators include those selected from the group consisting of azo initiators, peroxide initiators, redox initiators, a~
photochemical inittstors. The polymerization is allowed to proceed as long as needed for a high level of conversion to be achieved, typically from a few hours to a few days. The solvent is then removed, usually by evaporation or by precipitating the copolymer by addition of a nonsolvent. The copolymer can be further purified, as needed utilizing a variety of techniQues including filtration, extraction, trituration, e~embrane separation, gel permeation chromatography, and like.
There are nuuerous variations on these procedures which ire =5 entirely up to the discretion of the synthetic chemist (e. g., choice of degassing eiethod and gas, choice of initiator type, extent of conversion, reaction loading, etc). The choice of ini tiator and solvent are often deteroined by the requirements of the particular Aonomers and aiacromonoawer used, because different ,~~n and macromonomers have different solubilities and different reactivities to a specific initiator.
The copolymers of the present invt_ntion can also be synthesized by first preparing the backbone from the polyiaerization of_ suitable monomers, followed by further polymerization of the backbone with suitable hydrophilic monomers to fo no the polymeric side chains. This alternative procedure for synthesizing the copolymers herein is illustrated in EXNiPIE VIII
below.
Analysis of the copolymer reaction product and the extracted materials, and the purified copolya»r can bs per~oeired by conventional analysis techniques known in the art. Thsss include, for example, nuclear magnetic resource (WiR), infrared molecular , spectroscopies,, gel psrmsation/sizs exclusion chromatography, membrane osmometry, and atoo~ic absorption and eaission spectroscopies.
Hair Cart and Tooical Skin Carp ~..~.,~iti.....
The copolymers of the present invention can be fornulated into a wide variety of product types, including sousses, gels, lotions, tonics, sprays, shaspoos, conditioners, rinses, hand and ~y lotions, facial aaisturizers, sunscnsns, anti-acne preparations, topical analgesics, sascaras, and the tike. The carriers and additional coaiponsnts required to formulate such products vary with product type and can be routinely chosen by one skilled in the art. The following is a description of sons of ?0 these carriers and additional components.
Carriers Hair Care C_o~npositions The hair care coepositions of the present invention can comprises_ a carrier, or a efxtun of such carriers, which are suitable for application to the hair. The carriers are present at _ free abort 0.5'i to about 9g.5ii, preferably froo about 5.0~G to about 99.5it, mono preferably free :bout 10.0 to about 98.0x, of the co~position. As used herein, the phrase 'suitable for application to hair' e~eans that the carrier doss not drags or negatively affect the aesthetics of hair or cause irritation to the underlying skin.
Carriers suitable for use with hair care compositions of the pnssnt invention include, for exaapls, those used in the for~lation of hair sprays, saussea, tonics, gels, shaepoos, conditioners, and rinses. The choice of appropriate carrier will also depend on the particular copolymer to be used, and whether the product formulated is meant to be left on the surface to which 1t is applied (e. g., hair spray, mousse, tonic, or~gel) or rinsed off after use (e. q., shampoo, conditioner, rinse).
The carriers used herein can include a ride range of components conventionally used in hair care compositions. The carriers can contain a solvent to dissolve or disperse the particular copolymer being used, with water, the C1-C6 alcohols, and mixtures thereof being preferred; and water, methanol, 10 ethanol, isopropanol, and mixtures thereof being more preferred.
The carriers can also contain a wide variety of additional materials inlcuding, but not limited to acetone, hydrocarbons (such as isobutane, hexane, decene), halogenated hydrocarbons (such as Freons), linalool, esters (such as ethyl acetate, dibutyl 15 phthalate), and volatile silicon derivatives (especially siloxanes such as phenyl pentamethyl disiloxane, methoxypropyl heptamethyl cyclotetrasiloxane, chloropropyi pentamethyl disiloxane, hydroxy-propyl pentamethyl disiloxane, octamethyl cyclotetrasiloxane, decamethyl cyclopentasiloxane, cyclomethicone, and dimethicone 20 having for example, a viscosity at 25'C of about 15 centipoise or less), and mixtures thereof, when the hair care composition is a hair spray, tonic, gei, or mousse the preferred solvents include water, ethanol, volatile silicone derivatives, and mixtures thereof. The solvents used in such mixtures may be miscible or 25 i,nsiscible with each other. Mousses and aerosol hair sprays can also utilize my of the conventional propellants to deliver the material as a foam (in the case of a mousse) or as a fine, uniform spray (in the cast of an aerosol hair spray). Examples of suitable propellants include materials such as trichloro-30 fluoromethane, dichlorodifluoromethane, difluoroethane, dimethylether, propane, n-butane or isobutane. A tonic or hair spray product having a low viscosity may also utilize an emul-sifying agent. Examples of suitable emulsifying agents include nonionic, cationic, anionic surfactants, or mixtures thereof.
35 Fluorosurfactants are especially preferred, particularly if the product is a hair spray composition and most especially if it is a-spray composition having relatively low levels of volatile organic solvents, such as alcohols, and relatively high levels of water (e.g., in excess of about 10X, by reight water). If such an 5 emulsifying agent is used, it is preferably present at a level of from about O.O1X to about 7.5X of the composition. The level of propellant can be adjusted as desired but is generally from about 3X to about 30X of mousse compositions and from about 15X to about 50X of the aerosol hair spray compositions.
10 Suitable spray containers are well known in the art and include conventional, non-aerosol pump sprays i.e., 'atomizers,' aerosol containers or cans having propellant, as described above, and also pump aerosol containers utilizing compressed air as the propellant. Pump aerosol containers are disclosed, for example, 15 in U.S. Patents 4,077,441, March 7, 1978, Olofsson and 4,850,577, July 25 . 1989, TerStege, and also in Canadian Serial No. 2.129.968, Gosselin, Lund, Sojka, and Lefebvre, "Consumer Product Package Incorporating A Spray Device Utilizing Large Diameter Bubbles". Pump aerosols hair sprays using 20 compressed air are also currently marketed by The Procter & Gamble Company under their tradename UIDAL SASSOON AIRSPRAY~
hair sprays.
lihere the hair care compositions are conditioners and rinses the carrier can include a wide variety of conditioning materials.
25 y~here the hair care compositions are shampoos, the carrier can include surfactants, suspending agents, thickeners etc. Various additional components useful in hair cars compositions ire described in U.S. Patent No. 5,106,609, to Bolich, Jr. et al., issued April 21, 1992; and U.S. Patent No. 4,387,090, to Bolich, 30 Jr. issucd June 7, 1983.
Some of these additional components are described below.
Topical Skin Care Compositions The topical cosmetic and pharmaceutical compositions of the present invention can comprise a carrier. The carrier should be 35 ~cosmetlcally and/or pharmaceutically acceptable', which means that the carrier is suitable for topical application to the skin, has good aesthetic properties, is compatible with the copolymers of the present invention and any other components, and will not cause any untoward safety or toxicity concerns.
5 The carrier can be in a wide variety of forms. For exaople, emulsion carriers, including, but not lioited to, oil-in-water, water-in-oil, water-in-oil-in-water, and oil-in-water-in-silicone emulsions, ire useful herein. These emulsions can cover a broad range of viscosities, e.g, from about 100 cps to about 200,000 10 cps, These emulsions can also be delivered in the form of sprays using either mechanical pump containers or pressurized aerosol containers using conventional propellants. These carriers can also be delivered in the form of a mousse. Other suitable topical carriers include anhydrous liquid solvents such as oils, alcohois, 15 and si 1 i cones (e . g. , mi neral of 1, methanol , ethanol , i sopropanol , dimethicone, cyclomethicone, and the like); aqueous-based single phase liquid solvents (e.g., hydro-alcoholic solvent systems); and thickened versions of these anhydrous and aqueous-based single phase solvents (e. g., where the viscosity of the solvent has been 20 increased to fore a solid or semi-solid by the addition of appropriate gums, resins, waxes, polymers, salts, and the like).
Examples of topical carrier systems useful in the present invention are described in the following four references:
'Sun 25 Products Formulary' ~osmetic~ il Toiletries, vol. 105, pp. 122-139 (December 1990); 'Sun Products Formulary', ~,Qseretics 8 Toiletries, vol. 102, pp. 117-136 (March 1987); U.S. Patent No. 4,960,764 to Figueroa et al., issued October 2, 1990; and U.S. Patent No.
COMPOSTIONS CONTAINING THE SAME
This application has been divided out of Canadian Patent Application Serial No. 2,165,767 filed June 30, 1994.
TECHNICAL FIELD
The present invention relates to water or alcohol soluble or dispersible thermoplastic elastomeric copolymers and to cosmetic and pharmaceutical compositions containing these copolymers. These copolymers are useful for hair setting and styling purposes. A particularly useful application for these. copolymers is in hair spray and mousse compositions. This invention further relates to copolymers useful for incorporating into cosmetic and pharmaceutical compositions for topical application to the skin. Skin care compositions containing these copolymers are useful for delivering and/or transdermally transporting a wide variety of active ingredients to and/or through the skin.
BACKGROUND OF THE INVENTION
In the hair care area, the desire to have hair retain a particular style or shape is widely held. Such style retention is generally accomplished by either of two routes: permanent chemical alteration of the hair fiber or temporary alteration of hair style or shape. A
temporary alteration is one which can be removed by water or by shampooing. Temporary style alteration has generally been accomplished by application of a composition to dampened hair after shampooing and/or conditioning and prior to drying and/or styling. Products in the form of mousses, gels, lotions, or sprays are most commonly used for this purpose. Once the desired style is achieved, spray products are commonly used to help retain the style. These various hair care products utilize a variety of gums and resins for providing styling and retention. However, the gums and resins currently used tend to feel either too sticky or too stiff upon the hair. Also, these gums and resins do not wash out as easily as desired. Therefore, the need exists for improved styling and style retention materials which provide a strong, lasting, hold without being either too stiff or too sticky, and yet which are easily removed by shampooing. Furthermore, because most hair care styling compositions are water and/or alcohol based, it is necessary that these materials have good solubility or dispersibility in these bases.
Thermoplastic elastameric copolymers are well known. These copolymers combine thermoplastic properties, which give them solubility and strength, with rubber-like elastic properties, which give them flexibility and shape retention. However, despite 10 these highly desirable properties, most thermoplastic elastomeric copolymers are generally insoluble or poorly soluble in water and/or alcohol systems and would not be suitable in hair care compositions. Therefore, thermoplastic elastomeric copolymers having good water and/or alcohol solubility would be useful for developing improved hair care compositions.
In the present invention new classes of thermoplastic elastomeric copolymers have been developed which have the desired flexibility, strength, and elastic properties and yet are readily soluble and/or dispersible in water and/or alcohol systems.
20 Furthermore, these materials provide hair care compositions which leave the hair feeling natural, i.e. not stiff.
In addition to the hair care benefits provided by these copolymers, it has been found that these materials are also useful for incorporation into a wide variety of cosmetic and 25 pharmaceutical Compositions for topical application to the skin.
These copolymers provide topical coapositions which are sore easily and uniforvly spread upon the skin, which feel good upon the skin, and yet which are highly substantive. Furthermore, these copolymers are useful for enhancing the penetration of a 38 wide variety of cosuetlc and phan~aceutical actives Into the skin, or alternatively, through the skin for systemic delivery.
It is an object of the present invention to provide novel, water an4/or alcohol soluble and/or dispersible thermoplastic elastomeric copolymers.
It is another object of the present invention to provide novel thermoplastic elastomeric copolymers useful in hair care compositions.
It is another object of the present invention to provide novel hair care compositions having improved styling and/or hold properties and having improved aesthetics.
It is another object of the present invention to provide novel thermoplastic elastomeric copolymers useful in topical skin care cosmetic and pharmaceutical compositions.
It is another object of the present invention to provide novel topical cosmetic and pharmaceutical compositions useful for delivering a wide variety of cosmetic materials and pharmaceutical actives to and/or through the skin.
These and other objects will become readily apparent from the detailed description which follows.
SUMMARY OF THE INVENTION
The present invention relates to a water or alcohol soluble or dispersible thermoplastic elastomeric copolymer having a backbone and one or more polymeric side chains, said copolymer formed from the copolymerization of randomly repeating A and B units and corresponding to the formula [A]a [B]b wherein (i) A is at least one polymerizable monomer unit corresponding to the formula X - C - CR5 = CHR6 wherein X is selected from the group consisting of -OH, -OM,-OR4, -NH2, -NHR4, and -N(R4)z; M is a cation selected from the group consisting of Na+, K+, Mg++, Ca++, Zn++, NHa+, alkylammonium, dialkylammonium, trialkylammonium, and tetraalkylammonium; each R4 is selected from the group consisting of H, C~-Ca straight or branched chain alkyl, and N. N,-dimethylaminoethyl, 2-hydroxyethyl, 2-methoxyethyl, 2 ethoxyethyl; and R5 and R6 are independently selected from the group consisting of H, C~-Ca straight or branched chain alkyl, methoxy, ethoxy, and 2-hydroxyethoxy, 2-methoxyethyl, 2-ethoxyethyl;
(ii) B is at least one hydrophilic macromonomer unit copolymerizable with A corresponding to the formula RO -[-CH2CH2N-]m-CH2 C=0 CH=CH2 R' wherein R and R' are independently selected from the group consisting of H and C~-Ca straight or branched chain alkyl; and m is an integer from about 10 to about 2000; and (iii) a is an integer of about 100 or greater and b is an integer of about 2 or greater; and wherein said copolymer has a weight average molecular weight greater than about 10,000, and wherein said copolymer exhibits two distinct Tg values, said first Tg corresponding to said backbone and having a value less than about 0°C, and said second Tg corresponding to said side chains and having a value greater than about 25°C.
In further embodiments, the present invention Telates to hair care compositions, especially hair setting and styling compositions, containing these copolymers.
In further embodiments, the present invention relates to cosmetic and pharmaceutical compositions containing these copolymers for topical.application to the skin for the delivery of cosmetic materials and pharmaceutical actives onto, into and/or 10 through the skin.
All percentages and ratios used herein are by weight of the total composition and ail measurements made are at 25oC, unless otherwise designated. The invention hereof can comprise, consist of, or consist essentially of, the essential as well as optional 15 ingredients and components described herein.
DETAILED DESCRIPTION Of THE INV NTInN
The feral 'thermoplastic elastomeric copolymer' as used herein means that the copolymer has both thermoplastic and elastomeric properties. The term 'thermoplastic elastomeric copolymer' is one 20 fau,iliar to those of ordinary skill in polymer science. By 'thermoplastic' is meant that upon heating, the copolymer softens and upon cooling it rehardens; upon being subject to stress it begins to flow and upon removal of stress it stops flowing. 8y 'elastomeric' is want that the copolymer has an elastic modulus 25 such that the copolymer exhibits a resistance to deformation and has limited extensibility and retraction. In other words, the copolymer tends to recover its size and shape after deformation.
The term 'macromonomer' is one familiar to those of ordinary skill in polymer science, and is used to describe a polymeric material containing a polymerlzable moiety. A macromonomer is a macromolecular mono.er. A macromonomer is essentially a very large type of monoaer building~block~unFit which can be used in a polymerization reaction to fora polymers with itself, with other monomers, or with other macromonomsrs.
The term 'water or alcohol soluble or dispersible' as used herein means that these copolymers are either freely soluble in or dispersible (as a stable suspension) in at least one of the following solvents, or alternatively, in any combination of one of the following solvents: water, methanol, ethanol, and isopropanol.
By 'soluble' is meant that the copolymer is soluble in the solvent = or solvents at 25oC at a concentration of at least about-20 mg/ml, more preferably about 50 mg/mL, and most preferably about 100 mg/ml. By 'dispersible' is meant that the copolymer forms a 10 stable, uniform suspension (without the addition of further materials such as emulsifiers) when combined with the solvent or solvents at 25oC at a concentration of at least about 20 mg/ml, more preferably about 50 mg/ml, and most preferably about 100 mg/ml.
15 Thermoplastic Elastomeric Cooolvmers The copolymers of the present invention are characterized in having an elastomeric or flexible backbone and rigid, thermoplastic, hydrophilic side chains. This combination of both elastomeric and thermoplastic moieities in a single copolymer 20 provides the unique and useful properties of these materials. The copolymers of the present invention, can also be referred to as 'graft copolymers' because they can be prepared from the capolymeritation of monomer units and macromonmer units. In other words, the macromonomer is 'grafted' or incorporated into the 25 copolymer.
These copolymers exhibit two distinct in~iscible phases.
itithout being limited by theory, it is believed that the hydrophilic side chains of these copolymers are closely associated with each other, thereby existing in one phase, while the backbone 30 of the copolymer remains in a separate phase. A consequence of this phase ianiscibility is that these copolymers exhibit two distinct glass transition temperatures or, 'Tg's', for the backbone and the side chains. Tg is a well known ter°ei of art in polymer science used to describe the temperature at which a 35 polymer or portion thereof undergoes a transition from a solid or _. -brittle material to a liquid or rubber-like material. Glass transition temperatures can be measured using standard techniques that are well known to the polymer scientist of ordinary skill in the art. One particularly useful technique for determining glass 5 transitions is differential scanning calorimetry (also known as DSC). The glass transition phenomenon in polymers is described in Tntrnrluetier~ to Polymer Science and Technoloav: An SPE Textbook, (eds. H.S. Kxufman and J.J. Falcetta), (John wiley ~ Sons: I477).
The Tg of the backbone of the copolymers herein (i.e. that part of the copolymer not containing the side chains) should be less than about OoC. Preferably the Tg of the backbone should be from about -IOoC to about -130oC, more preferably from about -20oC
to about -125oC, and most preferably from about -55oC to about -120oC. The Tg of the side chain of the copolymers (i.e. that 15 part of the copolymer not containing the backbone) is greater than about 20oC. Preferably the Tg of the sidechain should be from about 25oC to about 200oC, more preferably from about 30oC to about 175oC, and most preferably from about 35oC to about 150oC.
Because these copolymers possess two distinct Tg's, these 20 copolymers are useful in hair styling and setting compositions.
liithout being limited by theory, it is believed that when these copolymers are subjected to temperatures above both Tg's, they are essentially liquid and can provide great flexibility during the styling process (e. g., when curling irons, blow driers, and other 25 heat sources are applied to the hair). Upon cooling of the copolymer to room temperature (e.g., when the heat source is removed from the hair) the copolymer is then at a temperature that is typically between both Tg's, and the copolymer possesses structural rigidity from the macromonomer side chains, and yet has 30 flexibility from the backbones, and can provide a strong, yet flexible, hair hold or style retention.
furthermore, at skin temperatures, these copolymers would be at a temperature which is essentially between both Tg's. these copolymers can enhance the film forming properties of skin care _8_ coiapositions, and provide benefits shuch as better and a~ore even distribution upon the skin.
The copolymers of the present invention are formed from the copolymerizatton of randomly repeating A and B units, preferably wherein the A units are selected from at least one polymerizable, ethylenically unsaturated monomer unit, and the B units are selected from at least- one hydrophilic macromonomer unit which contains an ethylenically unsaturated moiety which is copolymerizable with A. In typical embodiments of these copolymers, the backbone is primarily derived frog the ethylenically unsaturated portion of the A monomer unit and the ethylenically unsaturated portion of the B macromonomer unit. The side chains are derived from the non-copolymerized portions of the macromonomer. The A and B units can be selected from a wide vairety of structures as long as the limitations of the copolymer are met (e.g., solubility, Tg's, and molecular weights) The A monomer units of the copolymers of the present invention can comprise from about 40X to about 90x, more preferably from about 50x to about 85X, and most preferably from about 60X to about 80X, by weight, of the copolymers.
The hydrophilic B macromonomer units can comprise from about 10Z to about 60x, more preferably from about 15x to about 50x, and a~ost preferably frog about 20x to about 40X, by weight of the copolymers.
The copolymers of the present invention have a weight average molecular weight of at least about 10,000. There is no upper limit for molecular weight except that which limits appltcability of the invention for practical reasons, such as viscosity, processing, aesthetic characteristics, formulation compatibility, etc. In general, the weight average molecular weight is less than about 5,000,000, more generally less than about 2,500,000, and typically less than about 1,500,000. Preferably, the weight average molecular weight is froei about 10,000 to about 5,000,000, oars preferably from about T5,000 to about 1,000,000, even more _g_ preferably from about 100,000 to about 850,000, and most preferably from about 125,000 to about 750,000.
Alternatively, the copolymers of the present invention can also be represented by the formula (AJaI~Jb wherein A and B are as described herein, and where a 1s an integer of about 100 or greater, preferably a is an integer from about 100 to about 3000, more preferably from about 250 to about 2000, and most preferably from about 350 to about 1500, and b is an integer 10 of about 2 or greater, preferably from about 2 to about 50, more preferably from about 2 to about 20, and most preferably from about 2 to about 10. In this formula, it is expressly intended that even though ranges are provided for the subscripts a and b, these subscripts are not intended to strictly limit the polymers 15 herein so long as the physical propoerties of the polymers are achieved. when the copolymers herein are described by the formula disclosed in this paragraph it has been found useful to describe the copolymers by the m number average molecule weights. In _ general, the number average molecular weight is less than about 20 2,500,000, more generally less than about 1,500,000, and typically less than about 1,000,000. Preferably, the number average molecular weight is from about 15,000 to about 1,000,000, more preferably froa~ about 20,000 to about 500,000, and most preferably frog about 25,000 to about 250,000.
By appropriate selection and combination of the particular A
and B units and by the choice of specific relative ratios of the 5 units yell within the ability of one of ordinary skill in the art, the copolymers can be optimized for various physical properties such as solubility, Tg's, and the like, and for compatibility with other ingredients commonly used in hair care and skin care applications.
10 lihen the copolymers of the present invention are Incorporated into hair and/or skin care compositions, the copolymers typically comprise from about O.lx to about 25x, preferably from about 0.5%
to about 20x, more preferably from about lx to about 10%, and most preferably from about 2% to about 5X of the composition, although 15 higher or lower amounts can be used depending upon the particular application.
Monoeier 'A' Unii~
The 'A' monomer unit is selected from polymerizable monomers, preferably ethylenically unsaturated monomers. Either a single A
20 monomer or~combinations of two or more A monomers can be utilized.
For example, if two different A monomers are polymerized with a 8 macromonomer, the resulting copolymer could be described as a terpolymer. In either case, the monomers are selected to meet the requirements of the copolymer. By 'polymerizable', as used 25 herein, is meant monomers that can be polymerized using any conventional synthetic techniques. Monomers that are poiymerizable using conventional free radical initiated techniques art preferred. the term 'ethylenically unsaturated' is used herein to mean monomers that contain at least one polymeritable 30 carbon-carbon double bond (which can be ~ano~, di-, tri-, or tetra-substituted).
Ths A monomer units of the copolymers of the present invention can comprise from about 40% to about 90x, more preferably from about 50x to about 85x, and most preferably from 35 about 60'x to about 80%, by weight, of the copolymers.
The ethylenically unsaturated A monomer units preferably can be described by the following formula X - C- CRS = CHR6 S
wherein X is selected from the group consisting of -OH, -0l1, -OR4, -NH2, -NHR4, and -N(R4)Z; M is a catlon selected from the group consisting of Na+, K+, Mg++, Ca++, Zn++, HH4+, alkylammonium, dialkylammonium, trialkylanmonium, and tetralkylartenonium; each R4 10 is independently selected from the group consisting of H, C1-Cg straight or branched chain alkyl, N,N-dimethylaminoethyl, 2-hydroxyethyl, 2-methoxyethyl, and 2-ethoxyethyl; and RS and R6 are independently selected from the group consisting of H, C1-C8 straight or branched chain alkyl, methoxy, ethoxy, 15 2-hydroxyethoxy, 2-methoxyethyl, and 2-ethoxyethyl.
. Representative noniimiting examples of monomers useful herein include acrylic acid and salts, esters, and amides thereof. The salts can be derived from any of the common nontoxic metal, ammonium, or substituted ammonium counter ions. The esters can be 20 derived from C1.40 straight chain, C3-40 branched chain, or C3-40 carbocyclic alcohols; from polyhydric alcohois having from about 2 to about 8 carbon atoms and from about 2 to about 8 hydroxy groups (nonlimiting examples of which include ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, glycerin, and 25 1,2,6-hexanetriol); from amino alcohols (nonlimiting examples of which include aminoethanol, dimethylaminoethanol, and diethylaminoethanol, and their quaternized derivatives); or from alcohol ethers (nonliaiting examples of which include methoxyethanol, and ethoxy ethanol)., The asides can be 30 unsubstituted, N-alkyl or H-alkylamino mono-substituted, or N,N-dialkyl or N,H-dialkylamino di-substituted, wherein the alkyl or alkylamino group can be derived from C1-4p straight chain, C3~40 branched chain, or C3-40 carbocylic moietfes. Additionally, the alkylan~ino groups can be quaternized. Also useful as monomers 35 are substituted acrylic acids and salts, esters, and amides thereof (wherein the substituents are on the two and three carbon positions of the acrylic acid and are independently selected froo the group consisting of C1-4 alkyl, -CN, -COOH (e. g., methacrylic acid, ethacrylic acid, and 3-cyano acrylic acid). The salts, esters, and amides of these substituted acrylic acids can be defined as described above for the acrylic acid salts, esters, and amides. Other useful monomers include vinyl and aliyl esters of C1-,0 straight chain, C3-40 branched chain, or C3-40 carbocylic carboxylic acids; vinyl and allyl halides (e. g., vinyl chloride 10 and allyl chloride); vinyl and allyl substituted heterocylic compounds (e. g., vinyl pyrridine and allyl pyridine); vinylidene chloride; and hydrocarbons having at least one carbon-carbon double bond (e. g., styrene, alpha-methyistyrene, t-butylstyrene, butadiene, isoprene, cyclohexadiene, ethylene, propylene, 15 1-butane, 2-butane, lsobutylene, vinyl toluene); and mixtures thereof.
Preferred A monomers useful herein include those selected froa~ the group consisting of acrylic acid, methacrylic acid, ethacrylic acid, methyl acrylate, ethyl acrylate, Q-butyl 20 acrylat~e, ~q-butyl acrylate, ~-butyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, j,~-butyl methacrylate, ~,-butyl methacrylate, 2~ethylhexyi methacrylats, decyl methacrylate, methyl ethacrylate, ethyl ethacrylate, n-butyl ethacrytate, 25 j~-butyl ethacrylate, ~-butyl sthacrylate, 2-ethylhexyt ethacrylate, decyl ethacrylats, 2,3-dihydroxypropyl acrylate, Z,3-dihydroxypropyl methacrylate, 2-hydroxyethyi acrylate, Z-hydroxypropyl acrylate, hydroxypropyl methacrylate, glyceryl monoacrylate, giyceryl monomethacrylats, 30 acryiamide, meethacrylan~ide, ethacrylan~ide, N~methyl acrylaoida, N,H-diaiethyl acryiamide, N,N-dimethyl methacryla~aids, H-ethylacrylamide, N-isopropyl acrytamide, N-butyl acrylamide, N-~-butyl acrylamide, N,ti-di-n-butylacrylaeide, H,ti-disthylacrylamide, N-octyl acrylan~ide, N-octadecyl acrylaaide, 35 N-phenyl acrylamide, H-methyl methacrylamide, N-ethylmethacrylamide. N-dodecylmethacrylamide, N,N-dimethylaminoethyl acrylamide, quaternized N,N-dimethylaminoethyl acrylamide, N,N-dimethylaminoethyl methacrylamide, quaternized N,N-dimethylaminoethyl methacrylamide, N,N-dimethylaminoethyl acrylate, N,N-dimethylaminoethyl methacrylate, quaternized N.N-dimethylaminoethyl acrylate, quaternized N,N-dimethylaminoethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate. 2-hydroxyethyl ethacrylate, glyceryl acrylate, 2-methoxyethyl acrylate, 2-methoxyethyl methacrylate, 2-methoxyethyl ethacrylate, 2-ethoxyethyl acrylate, 2-ethoxyethyl methacrylate. 2-ethoxyethyl ethacrylate, malefic acid, malefic anhydride and its half esters, crotonic acid, itaconic acid, angelic acid, diallyldimethyl ammonium chloride, vinyl pyrrolidone methyl vinyl ether.
methyl vinyl ketone, maleimide, vinyl pyridine, vinyl imidazole, vinyl furan, styrene sulfonate, allyl alcohol, vinyl alcohol, vinyl caprolactam, and mixtures thereof.
More preferred A monomers are those selected from the group consisting of methyl acrylate, methyl methacrylate, methyl ethacrylate, ethyl acrylate, ethyl methacrylate, ethyl ethacrylate, n-butyl acrylate, n-butyl methacrylate, n-butyl ethacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, 2-ethylhexyl ethacrylate, N-octyl acrylamide, 2-methoxyethyl acrylate, 2-hydroxyethyl acrylate, N.N-dimethylaminoethyl acrylate, and mixtures thereof.
Most preferred A monomers for the embodiment of the present invention are those selected from the group consisting of n-butyl acrylate, 2-ethylhexyl acrylate, N-octyl acrylamide. 2-methoxyethyl acrylate, 2-hydroxyethyl acrylate, N,N-dimethylaminoethyl acrylate, and mixtures thereof.
Hydrophilic "B" Macromonomer Units A macromonomer is a large monomer unit, i.e. a macromolecular monomer, which can be further polymerized with itself, with other conventional monomers, or with other macromonomers. The term "macrononomer" is one that is familiar to the polymer chemist of ordinary skill in the art. The hydrophilic "B" macromonomer units of the present invention are very large monomer building blocks which can be formed from the polymerization of smaller monomer units. The 8 macromonomers encompass a wide variety of structures and are copolymerizable with the A monomer. Either a single B macromonomer or combinattons of two or more B
macromonomers can be utilized. In either case, the macromonomers are selected to meet the requirements of the copolymer.
The hydrophilic B macromonomers comprise from about lOX to about 60X, more preferably from about 15x to about 50X, and most 10 preferably from about ZOx to about 40x, by weight of the copolymers.
By the term 'copolymerizable' as used herein is meant B
macromonomers that can be reacted with the A monomer in a polymerization reaction using any conventional synthetic 15 techniques. 'Copolymerization' is a tern of art used to refer to the simultaneous polymerization of two or more different monomers.
In the present invention, B macromonomers that are copolymerizable with A monomers using conventional free radical initiated techniques are preferred. By the term 'hydrophilic' as used 20 herein is meant B macromonomers that are soluble in or have an affinity for water and/or other polar, water-soluble solvent materials (e.g., methanol, ethanol, propanol, isopropanol and the like). "Hydrophilic' is also a tens of art used to described a substance having a strong tendency to absorb water which results 25 in the swelling, solubilization, or dispersion of the substance in water. W thout being limited by theory, the hydrophilic B
macrortanoaier units are believed to contribute to the overall water or alcohol soluble or dispersible properties of the copolymers.
B a~acromono~oers that are useful herein contain an 30 ethylenically unsaturated oioiety that is copoiyinerizable with the A mono~er. The tera 'sthylenically unsaturated" is used herein to mean B macroa~ono~ners irhat contain it least one carbon-carbon double bond (which can be mono-, dt-, tri-, or tetra-substituted).
Typically, the preferred B macromonomers are those that are 35 endcapped with the ethylenically unsaturated moiety. 8y 'endcapped' as used herein is ~oeant that the ethylenically unsaturated moiety is at or near a terminal position of the macromonomer. However, this definition of 'endcapped' is not intended to limit the macromonomer to only those macromonomers 5 which terminate in a carbon-carbon double bond (whether mono-, di-, tri-, or tetra-substituted).
The hydrophilic 8 macromonomers of the present invention can be synthesized utilizing a variety of standard synthetic procedures familiar to the polymer chemist of ordinary skill in 10 the art,. Furthermore, these macromonomers can be synthesized starting from commercially available polymers. Typically the weight average molecular weight of the macromonomer is from about 1000 to about 200,000, more preferably from 1500 to about 30,000, and most preferably from about 2000 to about 25,000.
15 For example, the hydrophilic 8 macromonomers can be synthesized by the polymerization (acid, bass, free radical, or auto-initiated)-of a hydrophilic monomer to farm a polymer which is subsequently reacted with or 'endcapped' with a structural unit E, containing the ethylenically unsaturated moiety.
20 Alternatively, the B macromonomers can be synthesized starting with commercially available hydrophilic polymers which are 'endcapped' with the structural unit E. In yet another alternative, the B macromonoa~er can be synthesized by starting with the structural unit E, and polymerizing onto it the desired 25 hydrophilic monomer units. It is to ba understood that in this third alternative, the ethylenically unsaturated moiety of the E
unit is not consumed in the synthesis but its integrity is preserved for subsequent copolymerization of tht B macromonomer with tht A monomer units. All of the synthetic alternatives are 30 merely illustrative in that any other suitable synthetic procedures can be utilized to prepare the 8 ~acromonomers and copolymers of the present invention.
The B ~nacromonomers can be described by the following formula 35 [ I jn - [ X jm - E.
X is a hydrophilic monomer unit, and m is an integer from about 10 to about 2000, preferably from about 15 to about 300, and more preferably from about 20 to about 250, so that the macromonomer meets the weight average molecular weight requirements set forth above. Preferred is when X is a hydrophilic monomer unit selected from the group consisting of oxazolines, H-alkyloxazolines, alkylene glycols, N-vinylpyrrolidones, N-allylpyrrolidones, vinylpyridines, allylpyridiens, vinylcaprolactams, allylcaprolactams, 10 vinylimidazoles, allylimidaoles, vinylfurans, allylfurans, vinyltetrahydrofurans, ailyltetrahydrofurans, and mixtures thereof. More preferred is wherein X is a monomer unit selected from the group consisting of H-alkyloxazolines, alkylene glycols, and mixtures thereof. Most preferred is wherein X is a monomer 15 unit selected from N-alkyloxazolines.
E is a structural unit containing the ethylenically unsaturated moiety or 'endcapping' group. Preferred is when E is selected from the group consisting of vinyl, allyl, acryloyl, methacryloyl, ethacryloyl, styryl, 3-vinylbenzyl, ~-vinyibenzyl, 20 3-vinylbenzoyi, 4-vinylbentoyl, I-butenyl, I-propenyi, isobutenyl, isoprenyl, cyclohexyl, cylcopentyl, and mixtures thereof. More preferred is when E is selected from the group consisting of vinyl, aliyl, acryloyl, methacryloyl, ethacryloyi, 3-vinylbenzyl, ~-vinylbenZyl, 3-vinylbenzoyl, t-vinylbenzoyl, 1-butenyl, 25 I-propenyl, isobutenyl, and mixtures thereof. !lost preferred is when E is selected from the group consisting of vinyl, ally!, acryioyl, methacryloyl, ethacryloyl, 3-vinylbenzyl, 4-vinylbenzyl, and Fixtures thereof.
I is an optionally present chemical moiety. In other words, 30 ~ is an integer selected from zero and one. Without being limited by theory, I can be derived froo a chemical initiator or solvent used in the synthesis of the B macromonomer. Honiimiting examples of such initiators from which I can be derived include hydrogen ion, hydrogen radical, hydride ion, hydroxide ion, hydroxyl 35 radical, peroxide radical, peroxide anion, C1~20 carbocations, C1-20 carbanions, CI-20 carbon radicals, C1-20 aliphatic and aromatic aikoxy anions, ammonium ion, and substituted ammonium tons (e.g., C1-20 alkyl and C1-ZO alkoxy substituted). I can be derived from any useful solvent, nonlimiting examles of which 5 inlcude water, methanol ethanol, propanol, isopropanol, acetone, hexane, dichloromethane, chlorofora, benzene, and toluene.
Nonlimiting examples of I include chemical moieties selected from the group consisting of H, CI-C6 alkyl, phenyl, 4-methyiphenyl, and benzyl; preferably H, methyl, ethyl, and phenyl; and more 10 preferably H, methyl, and ethyl.
Representative examples of classes of endcapped B
macromonomers useful herein include those selected from the group consisting of endcapped poly(N-alkyloxazolines), endcapped polyalkylene glycol monoalkyl 'ethers, endcapped 15 ~pol~y(H-vinylpyrrolidones), endcapped ,poly(N-allylpyrrolidones), endcapped polyvinyipyridines, endcapped polyallylpyridines, ~endcapped polyvinylcaprolactams, endcapped poiyallylcaprolactams, endcapped polyvinylimidazoles, endcappped polyallylimidazoles, endcapped polyvinylfurans, endcapped polyvinyltetrahydrofurans, ZO endcapped polyallylfurans, endcapped polyacrylic acids, endcapped polymethacrylic acids, endcapped polyallyltetrahdyrofur~ns, and mixtures thereof.
Preferred are eacromonomers selected froa~ the group consisting of endcapped poly(N-alkyloxazolines), endcapped 23 polyalkylene glycol monoaikyl ethers, and Aixtures thereof.
l~lore preferred ire endcapped poly(N-alkyloxazoline) macromonomers.
Exaa~ples of endcapped poly(N-alkyioxazoline) nacroaonomers are those having the following chemical formula:
R -~-NCHyCH2-j~-0-E
C~0 R' wherein R and R' are independently selected frog H or C1-8 straight or branched chain alkyl, more preferably R and R' are independently selected froo H, methyl, or ethyl; and most preferably R is methyl and R' is ethyl. E is a copolymerizable, ethylenicaily unsaturated moiety (i.e. the endcapping gaiety).
Preferred is when E is selected from the group consisting of vinyl, allyl, acryloyl, methacryloyl, ethacryloyl, styryl, 3-vinyibenzyl, ~-vinylbenzyl, 3-vinylbenzoyl, i-vinylbenzoyl, I-butenyl, I-propenyl, isobutenyl, isoprenyi, cyclohexyl, L0 cylcopentyl, and mixtures thereof. More preferred is when E is selected from the group consisting of vinyl, allyl, acryloyl, methacryloyl, ethacryloyl, 3-vinylbenzyl, 4-vinylbenzyl, 3-vinyibenzoyl, 4-vinylbenzoyl, I-butenyl, I-propenyl, isobutenyl, and mixtures thereof. Most preferred is when ~ is selected from 15 the group consisting of vinyl, allyl, acryloyl, methacryloyl, ethacryloyl, styryl, 3-vinylbenzyl, t-vinylbenzyl, and mixtures thereof. In the above structure 4 is preferably an integer from about 10 to about 2000, more preferably from about 15 to about 300, and most preferably from about 20 to about 250.
20 ~ Alternatively, other examples of endcapped poly(N-alkyloxazolint) macromonomers ire those having the following chemical formula:
R- 0 -[-CH2CH2N-I~ - CHZ
C~0 CH=CH2 R' 30 wherein R and R' are independently selected frog the group consisting of H or CI-8 straight or branched chain alkyl, more preferably R and R' are independently selected from H, methyl, or ethyl; and most preferably R is H and R' is ethyl. In the above structure m is an integer from about I0 to about 2040, more preferably from about 15 to about 300, and most preferably from about 20 to about 250.
Highly preferred examples of endcapped poly(R-alkyloxazoline) macromonomers useful herein include acryloyl endcapped 5 poly(2-ethyl oxazoline), methacryloyl endcapped poly(2-ethyl oxatoline), styryl endcapped poly(2-ethyloxazoline), acryloyl endcapped poiy(2-methyl oxazoline), methacryloyi endcapped poly(2-methyl oxazoline), 3-vlnyibenzoyl endcapped poly{2-methyloxazoline), 4-vinylbenzoyl endcapped poly(2-methyloxazoline), and mixtures thereof.
The endcapped poly(N-alkyloxazoline) macroioonomers can be synthesized using standard synthetic procedures which involve polymerizing, usually under acid-catalyzed conditions, an H-alkyloxazol.ine to yield a poiy(N~alkyloxazoline) alcohol. This 15 alcohol can then be subsequently endcapped, ea~ploying standard reaction procedures, with the desired ethylenically unsaturated moiety using a reactive or activated form of an endcapping group.
Suitable activated endcapping groups include vinyl, allyl, 1-propenyl, 3-vinylbenzyi, 4-vinylbenzyl, 3-vinylbenzoyl, and 20 4-vinylbenzoyl halides (c. g. chlorides, bromides, and iodides), and the acid chlorides and bromides derived frog acrylic acid, methacrylic acid, and ethacrylic acid. ~, e.g., S.I. Shoda et al., 'Synthesis and Surfactant Property of Copolymers Having a Poly{2-Oxazol ine) Graft Chain', Journal of Polv~ner Scien ~~ Part 25 A; Polymer Che~ni:try, vol. 30, pp. 1489-1494 (1992); T. Saegusa et al., 'Macromoiecular Engineering on the Basis of the Polymerization of 2-Oxazolines, I~la,kromol. Cheis., liacron~ol Svmn , vol. 51., pp. 1-10 (1991); S. Kobayashi et al., llacronalecylg~, vol 22, pp. 2878-2884 (1989), and U.S. Patent No. 4,011,376, to 30 T~lia et al., issued March 8, 1971; and U.S. Patent No.
3,786,116, to Milkovich et al., issued January 15, 1974.
Alternatively the poiyoxazoline macromononeers can be synthesized by polymerizing the monomers onto an appropriate endcapping group. For example, the vinyl benzyl endcapped polyoxazolines can be prepared by polymerizing Z-ethyl-Z-oxazoltne onto a mixture of 3-vinylbenzyl and 4-benzylchlorides. egg EXArIPIE III.
Also highly useful herein are endcapped polyalkylene glycol 5 monoalkyl ether macromonomers corresponding to the following general chemical formula R'-[OCHZ-CHJp-0-E
wherein R' is selected from CI-C40 straight or branched chain alkyl, more preferably from CI-t8 straight or branched chain alkyl, most preferably from C1~C4 straight or branched chain alkyl, and most preferably methyl; R3 is selected from hydrogen, methyl, ethyl, or n-propyl, more preferably from hydrogen or 15 methyl, most preferably froa~ H. E is a copolymerizable, ethylenically unsaturated moiety (i.e. the endcapping moiety), Preferred is when E is selected fros the group consisting of vinyl, ally!, acryloyl, methacryloyl, ethacryloyl, styryl, 3-vinylbenzyl, 4-vinylbenzyl, 3-vinylbenzoyl, 4-vinylbenzoyl, ZO 1-butenyl,. 1-propenyl, isobutenyl, isoprenyl, cyclohexyl, cylcopentyl, and mixtures thereof. More preferred is when E is selected froo the group consisting of vinyl, ally!, acryioyl, methacryloyl, ethacryloyl, 3-vinylbenzyl, 4-vinylbenzyl, 3-vinytbenzoyl, 4-vinylbenzoyl, 1-butenyl, 1-propenyl, isobutenyl, 25 and ~i xtures thereof . !lost preferred i s when E i s sei ected froa~
the group consisting of vinyl, ally!, acryloyl, methacryloyl, ethacryloyl, styryl, 3-vinylbenzyl, 4-vinylbenzyl, and mixtures thereof: In the above structure, s is as described previously, wherein a~ is preferably an integer froo about 20 to about 2000, more preferably froo about 30 to about 750, and a~ost preferably frog about 40 to about 500. It is to be understood that in the above structure, that when R3 is other than hydrogen that various isoaers of the resulting a~acromonort~er ire possible depending upon the orientation of the individual glycol eoieties. Therefore, the 35 structure depicted above for these endcapped polyalkylene glycol - ~nonol kayl ethers i s a general one that i s not intended to 1 imi t these materials to any one particular isomeric structure.
Highly preferred examples of endcapped polyalkylene glycol monoalkyl ethers useful herein inlcude acryloyl endcapped polyethylene glycol monomethyl ether, 3-vinylbenzoyl endcapped polyethylene glycol monomethyl ether, 4-vinylbenzoyl endcapped polyethylene glycol monomethyl ether, methacryleyl endcapped polyethylene glycol monomethyl ether, and mixtures thereof.
The endcapped polyalkylene glycol monoalkyl ethers can be synthesized from the polyalkylene glycol monoalkyl ether and the reactive or activated form of an endcapping group employing standard reaction procedures. Suitable activated endcapping groups include vinyl, allyl, 3-vinylbenzoyl, and 4-vinylbenzoyl halides (e. g, chlorides, bromides, and iodides), and the acid chlorides and bromides derived from acrylic acid, methacrylic acid, and ethacrylic acid. The polyalkylene glycol monoalkyl ether can be synthesized from the corresponding polyalkylene glycol using any of the alkylating agents well known in the art (e. g., methyl iodide, methyl bromide, diazomethane, methyl sulfate, ethyl iodide). Polyethylene glycols of various molecular weight ranges, as well as their methyl ethers are commercially available from Aldrich Chemical Company and Union Carbide Corporation. Alternatively, the polyalkylene glycols can be synthesized from the corresponding alkylene oxides and alkylene glycois~using standard synthetic procedures (e.g., the acid or base catalyzed polymerization of ilkylene oxides).
Svn- s of the Cooolvm r In general, the copolymers can be made by free radical polymerization of the A monomers with the B macromonomers. It is not intended to necessarily exclude from this invention any copolymers made by means other than free radical polymerization, so long as the product has the desired physical properties. The copolymers herein contain randomly repeating monomer units and macromonomer uniis.
35' .22.
The general principles of free radical polymerization methods are well understood. See, for example, Odian, 'Principles of Polymerization', 2nd edition, John liiley t Sons, 1981, pp.
179-318. The desired monomers and macromonomers are all placed in a reactor, along with a sufficient amount of a mutual solvent so that when the reaction is complete the viscosity of the reaction is reasonable. Typical monomer and macromonomer loadings are from about lOx to about SOx, on a weight basis. Undesired terminators, especially oxygen, can be removed as needed. This is done by evacuation or by purging with an inert gas, such as argon or nitrogen. The initiator is introduced and the reaction brought to the temperature needed for initiation to occur, assuming thermal initiators are used. Nonlimiting examples of suitable initiators include those selected from the group consisting of azo initiators, peroxide initiators, redox initiators, a~
photochemical inittstors. The polymerization is allowed to proceed as long as needed for a high level of conversion to be achieved, typically from a few hours to a few days. The solvent is then removed, usually by evaporation or by precipitating the copolymer by addition of a nonsolvent. The copolymer can be further purified, as needed utilizing a variety of techniQues including filtration, extraction, trituration, e~embrane separation, gel permeation chromatography, and like.
There are nuuerous variations on these procedures which ire =5 entirely up to the discretion of the synthetic chemist (e. g., choice of degassing eiethod and gas, choice of initiator type, extent of conversion, reaction loading, etc). The choice of ini tiator and solvent are often deteroined by the requirements of the particular Aonomers and aiacromonoawer used, because different ,~~n and macromonomers have different solubilities and different reactivities to a specific initiator.
The copolymers of the present invt_ntion can also be synthesized by first preparing the backbone from the polyiaerization of_ suitable monomers, followed by further polymerization of the backbone with suitable hydrophilic monomers to fo no the polymeric side chains. This alternative procedure for synthesizing the copolymers herein is illustrated in EXNiPIE VIII
below.
Analysis of the copolymer reaction product and the extracted materials, and the purified copolya»r can bs per~oeired by conventional analysis techniques known in the art. Thsss include, for example, nuclear magnetic resource (WiR), infrared molecular , spectroscopies,, gel psrmsation/sizs exclusion chromatography, membrane osmometry, and atoo~ic absorption and eaission spectroscopies.
Hair Cart and Tooical Skin Carp ~..~.,~iti.....
The copolymers of the present invention can be fornulated into a wide variety of product types, including sousses, gels, lotions, tonics, sprays, shaspoos, conditioners, rinses, hand and ~y lotions, facial aaisturizers, sunscnsns, anti-acne preparations, topical analgesics, sascaras, and the tike. The carriers and additional coaiponsnts required to formulate such products vary with product type and can be routinely chosen by one skilled in the art. The following is a description of sons of ?0 these carriers and additional components.
Carriers Hair Care C_o~npositions The hair care coepositions of the present invention can comprises_ a carrier, or a efxtun of such carriers, which are suitable for application to the hair. The carriers are present at _ free abort 0.5'i to about 9g.5ii, preferably froo about 5.0~G to about 99.5it, mono preferably free :bout 10.0 to about 98.0x, of the co~position. As used herein, the phrase 'suitable for application to hair' e~eans that the carrier doss not drags or negatively affect the aesthetics of hair or cause irritation to the underlying skin.
Carriers suitable for use with hair care compositions of the pnssnt invention include, for exaapls, those used in the for~lation of hair sprays, saussea, tonics, gels, shaepoos, conditioners, and rinses. The choice of appropriate carrier will also depend on the particular copolymer to be used, and whether the product formulated is meant to be left on the surface to which 1t is applied (e. g., hair spray, mousse, tonic, or~gel) or rinsed off after use (e. q., shampoo, conditioner, rinse).
The carriers used herein can include a ride range of components conventionally used in hair care compositions. The carriers can contain a solvent to dissolve or disperse the particular copolymer being used, with water, the C1-C6 alcohols, and mixtures thereof being preferred; and water, methanol, 10 ethanol, isopropanol, and mixtures thereof being more preferred.
The carriers can also contain a wide variety of additional materials inlcuding, but not limited to acetone, hydrocarbons (such as isobutane, hexane, decene), halogenated hydrocarbons (such as Freons), linalool, esters (such as ethyl acetate, dibutyl 15 phthalate), and volatile silicon derivatives (especially siloxanes such as phenyl pentamethyl disiloxane, methoxypropyl heptamethyl cyclotetrasiloxane, chloropropyi pentamethyl disiloxane, hydroxy-propyl pentamethyl disiloxane, octamethyl cyclotetrasiloxane, decamethyl cyclopentasiloxane, cyclomethicone, and dimethicone 20 having for example, a viscosity at 25'C of about 15 centipoise or less), and mixtures thereof, when the hair care composition is a hair spray, tonic, gei, or mousse the preferred solvents include water, ethanol, volatile silicone derivatives, and mixtures thereof. The solvents used in such mixtures may be miscible or 25 i,nsiscible with each other. Mousses and aerosol hair sprays can also utilize my of the conventional propellants to deliver the material as a foam (in the case of a mousse) or as a fine, uniform spray (in the cast of an aerosol hair spray). Examples of suitable propellants include materials such as trichloro-30 fluoromethane, dichlorodifluoromethane, difluoroethane, dimethylether, propane, n-butane or isobutane. A tonic or hair spray product having a low viscosity may also utilize an emul-sifying agent. Examples of suitable emulsifying agents include nonionic, cationic, anionic surfactants, or mixtures thereof.
35 Fluorosurfactants are especially preferred, particularly if the product is a hair spray composition and most especially if it is a-spray composition having relatively low levels of volatile organic solvents, such as alcohols, and relatively high levels of water (e.g., in excess of about 10X, by reight water). If such an 5 emulsifying agent is used, it is preferably present at a level of from about O.O1X to about 7.5X of the composition. The level of propellant can be adjusted as desired but is generally from about 3X to about 30X of mousse compositions and from about 15X to about 50X of the aerosol hair spray compositions.
10 Suitable spray containers are well known in the art and include conventional, non-aerosol pump sprays i.e., 'atomizers,' aerosol containers or cans having propellant, as described above, and also pump aerosol containers utilizing compressed air as the propellant. Pump aerosol containers are disclosed, for example, 15 in U.S. Patents 4,077,441, March 7, 1978, Olofsson and 4,850,577, July 25 . 1989, TerStege, and also in Canadian Serial No. 2.129.968, Gosselin, Lund, Sojka, and Lefebvre, "Consumer Product Package Incorporating A Spray Device Utilizing Large Diameter Bubbles". Pump aerosols hair sprays using 20 compressed air are also currently marketed by The Procter & Gamble Company under their tradename UIDAL SASSOON AIRSPRAY~
hair sprays.
lihere the hair care compositions are conditioners and rinses the carrier can include a wide variety of conditioning materials.
25 y~here the hair care compositions are shampoos, the carrier can include surfactants, suspending agents, thickeners etc. Various additional components useful in hair cars compositions ire described in U.S. Patent No. 5,106,609, to Bolich, Jr. et al., issued April 21, 1992; and U.S. Patent No. 4,387,090, to Bolich, 30 Jr. issucd June 7, 1983.
Some of these additional components are described below.
Topical Skin Care Compositions The topical cosmetic and pharmaceutical compositions of the present invention can comprise a carrier. The carrier should be 35 ~cosmetlcally and/or pharmaceutically acceptable', which means that the carrier is suitable for topical application to the skin, has good aesthetic properties, is compatible with the copolymers of the present invention and any other components, and will not cause any untoward safety or toxicity concerns.
5 The carrier can be in a wide variety of forms. For exaople, emulsion carriers, including, but not lioited to, oil-in-water, water-in-oil, water-in-oil-in-water, and oil-in-water-in-silicone emulsions, ire useful herein. These emulsions can cover a broad range of viscosities, e.g, from about 100 cps to about 200,000 10 cps, These emulsions can also be delivered in the form of sprays using either mechanical pump containers or pressurized aerosol containers using conventional propellants. These carriers can also be delivered in the form of a mousse. Other suitable topical carriers include anhydrous liquid solvents such as oils, alcohois, 15 and si 1 i cones (e . g. , mi neral of 1, methanol , ethanol , i sopropanol , dimethicone, cyclomethicone, and the like); aqueous-based single phase liquid solvents (e.g., hydro-alcoholic solvent systems); and thickened versions of these anhydrous and aqueous-based single phase solvents (e. g., where the viscosity of the solvent has been 20 increased to fore a solid or semi-solid by the addition of appropriate gums, resins, waxes, polymers, salts, and the like).
Examples of topical carrier systems useful in the present invention are described in the following four references:
'Sun 25 Products Formulary' ~osmetic~ il Toiletries, vol. 105, pp. 122-139 (December 1990); 'Sun Products Formulary', ~,Qseretics 8 Toiletries, vol. 102, pp. 117-136 (March 1987); U.S. Patent No. 4,960,764 to Figueroa et al., issued October 2, 1990; and U.S. Patent No.
4,25~,105 to Fukuda et al., issued Harch 3, 1981.
30 The carriers of the skin care compositions can c~nprise from about 50x to about 99x by weight of the coisposltions of the present invention, preferably fro4 about 75x to about 99x, and most preferably froo about 85x to about 95x.
Preferred cosawtically and/or pharmaceut1ca11y acceptable 35 topical carriers include hydro-alcoholic systems and oil-in-water emulsions. When the carrier is a hydro-alcoholic system, the carrier can comprise from about 1% to about 99x of ethanol, isopropanol, or mixtures thereof, and from about IX to about 9fx of eater. More preferred is a carrier comprising from about 5x to 5 about 60x of ethanol, isopropanol, or mixtures thereof, and from about 4fX to about 95x of water. Especially preferred is a carrier comprising from about 20X to about 50x of ethanol, isopropanol, or mixtures thereof, and frog about 50x to about 80%
of water. When the carrier is an oil-in-water emulsion. the 10 carrier can include any of the cortmon excipient ingredient. for preparing these emulsions. ~ Additional components useful in formulating these topical compositions are further described below.
Additional Comconents A wide variety of additional components can be employed in the hair care and topical skin compositions herein. Non-limiting examples include the following:
Pharmaceutical Actives The compositions of the present invention, especially the 20 topical skin care compositions, can eomprise a safe and effective amount of a pharmaceutical active. The phrase 'safe and effective amount', as used herein, means an amount of an active high enough to significantly or positively modify the condition to be treated, but low enough to avoid serious side effects (at a reasonable 25 benefit/risk ratio), within the scope of sound medical ,~udgea~ent.
A-safe and effective amount of the pharmaceutical active will vary with the specific active, the ability of the composition to penetrate the active through the skin, the amount of composition to be applied, the particular condition being treated, the age and 30 physical condition of the patient being treated, the severity of the condition, the duration of the treatment, the nature of concurrent therapy, and like factors.
Ths pharmaceutical actives which can be used in the coapositions of the present invention preferably comprise from 35 about O.lx to about 20% by weight of the compositions, more _28_ preferably from about O.lx to about lOx, and most preferably from about O.lx to about 5X. Mixtures of pharmaceutical actives may also be used.
Honlimiting examples of pharmaceutical actives can include the following:
Useful pharmaceutical actives in the compositions of the present invention include anti-acne drugs: Anti-acne drugs preferred for use in the present invention include the keratolytics such ~as salicylic acid, sulfur, lactic acid, 10 glycolic, pyruvic acid, urea, resorcinol, and N-acetylcysteine;
retinoids such as retinoic acid and its derivatives (e.g., cis and traps); antibiotics and antimicrobials such as benzoyl peroxide, octopirox, erythromycin, zinc, tetracyclin, triclosan, azelaic acid and its derivatives, phenoxy ethanol and phenoxy proponol, 15 ethylacetate, clindamycin and meclocycline; sebostats ,such as flavinoids; alpha and beta hydroxy acids; and bile salts such as scymnol sulfate and its derivatives, deoxycholate, and cholate.
Preferred for uss herein is salicylic acid.
Useful pharmacetuical actives in the compositions of the 20 present invention include non-steroidal anti-inflammatory drugs (NSAIDS). The NSAI05 can be selected from the following categories: propionic acid derivatives; acetic acid derivatives;
fena~ic acid derivatives; biphenylcarboxylic acid derivatives; and oxica~s. A11 of these NSAIDS are fully described in the U.S.
25 Patent 4,985,459 to Sunshine et al., issued January 15, 1991.
Most preferred are the propionic NSAIDS including but not limited to Aspiri n', acetaa~inophen, Ibuprofen, naproxen, benoxaprofen, flurbi.profen, fenoprofen, fenbufen, ketoprofen, indoprofen, pirprofen, 30 carprofen, oxaprozin, pranoprofen, ~iroprofen, tioxaprofen, suprofen, ~loinoprofen, tiaprofenic acid, fluprofen and bucioxic acid. Als4 useful are the steroidal anti-inflammatory drugs including hydrocortisone and the like.
Useful pharmaceutical actives in the compositions of the 35 present invention include antipruritic drugs. Antipruritic drugs _29_ preferred for inclusion in compositions of the present invention include pharaaceutically-acceptable salts of methdilizine and trimeprazine.
Useful pharmaceutical actives in the compositions of the 5 present invention include include anesthetic drugs. Anesthetic drugs preferred for inclusion in compositions of the present invention include pharmaceutically-acceptable salts of lidocaine, bupivacaine, chlorprocaine, dibucaine, etidocaine, mepivacaine, tetracaine, dyclonine, hexylcaine, procaine, cocaine, ketamine, 10 pramoxine and phenol.
Useful pharmaceutical actives in the compositions of the present invention include antimicrobiai drugs (antibacterial, antifungal, antiprotozoal and antiviral drugs). Antimicrobial drugs preferred for inclusion in compositions of the present 15 invention include pharmaceutically-acceptable salts of p-lactam drugs, quinolone drugs, ciprofloxacin, norfioxacin, tetracycline, erythromycin, amikacin, triclosan, doxycycline, capreomycin, chlorhexidine, chlortetracycline, oxytetracycline, clindamycin, ethambutol, metronidazole, pentamidine, gentamicin, kanamycin, ZO lineomycin, a~ethacycline, methenamine, minocycline, neomycin, netilmicin, paromomycin, streptomycin, tobramycin, miconazole and amanfadine. Antimicrobial drugs preferred for inclusion in compositions of the present invention include tetracycline hydrochloride, erythromycin estoiate, erythromycin stearate 25 (salt), amikacin sulfate, doxycyclint hydrochloride, capreoa~ycin sulfate, chlorhtxidine gluconate, chlorhexidine hydrochloride, chlortetracycline hydrochloride, oxytetracycline hydrochloride, clinda~nycin hydrochloride, tthambutol hydrochloride, metronidazole hydrochloride, pentamidine hydrochloride, gentamicin sulfate, 30 kanamycin sulfate, lineomycin hydrochloride, methacycline hydrochloride, methenaa~ine hippuratt, methenamine mandelatt, minocycline hydrochloride, ne~ycin sulfate, netilmicin sulfate, paromomycin sulfate, streptomycin sulfate, tabramycin sulfate, miconaZOie hydrochloride, amanfadine hydrochloride, amanfadine sulfate, triclosan, octopirox, parachlorometa xylenol, nystatin, tolnaftate and clotrimazole.
Also useful herein are sunscreening agents. A wide variety of sunscreenlng agents are described in U.S. Patent Ho. 5,087,445, 5 to Haffey et al., issued February 11, 1992; U.S. Patent No.
5,073,372, to Turner et al., issued December 11, 1991; U.S. Patent No. 5,073,371, to Turner et ai. issued December 17, 1991; and Segarin, et al., at Chapter VIII, pages 189 et seq., of Cosmetics Sc i ence and Iechnol a~ .
10 Preferred among those sunscreens which are useful in the compositions of the instant invention are those selected fram the group consisting of 2-ethylhexyl p-methoxycinnamate, 2-ethylhexyl N,N-dimethyl-p-aminobentoate, p-aminobenzoic acid, 2-phenyibenzimidazole-5-sulfonic acid, octocrylene, oxybenzone, 15 homomenthyl saiicylate, octyl salicylate, 4,4'-methoxy-~-butyldibenzoylmethane, 4-isopropyl dibenzoylmethane, 3-benzylidene camphor, 3-(4-methylbenzylidene) camphor, titanium dioxide, zinc oxide, silica, iron oxide, and mixtures thereof.
20 Still other useful sunscreens are those disclosed in U.S.
Patent No. 4,937,370, to Sabatelli, issued June 26, 1990: and U.S.
Patent No. 4,999,186, to Sabatelli et al., issued March 1Z, 1991.
The sunscreening agents disclosed therein have, in a single molecule, two dtstinct chromophore Aoieties which axhibit 25 different ultra-violet radiation absorption spectra. One of the chro~ophore moieties absorbs predominantly in the UVB radiation range and the other absorbs strongly in the UVA radiation range.
These sunscreening agents provide higher efficacy, broader UV
absorption, lower skin penetration and longer lasting efficacy 30 relative to conventional sunscreens. Especially preferred examples of these sunscreens include those selected from the group consisting of 4-N,N~(2~ethylhexyl)methylaminobenzoic acid ester of 2,4-dihydroxybenzophenone, 4-N,N-(2-ethylhexyl)methylaminobenzoic acid ester with 4-hydroxydibenzoylmethane, 4-ti, H- (2-ethylhexyl)-methylaminobenzoic acid ester of Z-hydroxy-4-(2-hydroxyethoxy)ben-zophenone, 4-N,N-(2-ethylhexyl)-methylamtnobenzoic acid ester of 4-(2-hydroxyethoxy)dibenzoylmethane, and o~txtures thereof.
6eneraliy, the sunscreens can comprise from about O.Sx to about ZO% of the compositions useful herein. Exact amounts will vary depending upon the 'sunscreen chosen and the desired Sun Protection Factor (SPF). SPF is a cortmonly used measure of photoprotection of a sunscreen against erythema. egg Fe ral 10 Rea-, Vol. 43, No. 166, pp. 38206-38269, August 25, 1978.
Also useful in the present invention are sunless tanning agents including dihydroxyacetone, giyceraldehyde, indoles and their derivatives, and the like. These sunless tanning agents aay also be used in combination with the sunscreen agents.
15 Other useful actives include skin bleaching (or lightening) agents including but not limited to hydro4uinone, ascorbic acid, ko,)ic acid and sodium metabisulfite.
Other useful actives which are especially useful for hair care compositions include anti-dandruff actives such as zinc 20 pyrithione, octopirox, seleniua~ disulfide, sulfur, coal tar, and the like.
Conditioners Conditioning agents useful herein, and especially useful for hair~care coaroositions, include hydrocarbons, silicone fluids, and 25 cationic materials.
The hydrocarbons can be either straight or branched chain and can contain froa about 10 to about 16, preferably frog about 12 to about 16 carbon atoa~s. Examples of suitable hydrocarbons are decane, dodecane, tetradecane, tridecane, and mixtures thereof.
30 Silicone conditioning agents useful hero n can include either cyclic or linear polydimethylsiloxanes, pheny and alkyl phenyl silicones, and silicone copolyols. The linear volatile silicones generally have viscosities of less than about 5 centistokes at 25oC, while the cylic materials have viscosities less than about centistokes.
Cationic conditioning agents useful herein can include quaternary ammonium salts or the salts of fatty amines. Preferred quaternary ammonium salts are dialkyl dimethyl ammonium chlorides, wherein the alkyl groups have from 12 to 22 carbon atoms and are derived from long-chain fatty acids. Representative examples of quaternary ammonium salts include ditallow dimethyl ammonium chloride, ditallow dimethyl ammonium methyl sulfate, dihexadecyl 10 dimethyl ammonium chloride, and di(hydrogenated tallow) ansnonium chloride. Other qauternary ammonium salts useful herein are dicationics such as tallow propane dianmonium dichloride.
Quaternary imidazolinium salts are also useful herein. Examples of such materials are those imidazolinium salts containing C12-22 15 alkyl groups such as 1-methyl-1-[(stearoylamide)ethyl]-2-heptadecyl-4, 5-dihydroimidazolinium chloride, 1-methyl-1-[(palmitoylamide)ethyl]-2-octadecyl-4,5-dihydroimidazo-linium chloride and 20 1-methyl-1-((tallowamids)-ethyl]-2-tallow-imidazolinium methyl sulfate. Also useful herein are salts of fatty amines. Examples of such compounds include stsarylamine hydrochloride, soyamine hydrochloride, and stsarylaa~ine formats. Useful conditioning agents are disclosed in U.S. Patent No. 4,387,090, to Bolich, 25 issued June 7, 1983.
Mumectants and Moisturizers The compositions of the present invention can contain one or more humectant or moisturizing materials. A variety of these maters al s can be empi oyed and each can be present at a 1 suet of 30 fros about O.lx to about 20lC, more preferably from about lx to about lOx and most preferably froa~ about 2x to about 5x. These materials include urea; guanidine; glycolic acid and glycolate salts (s. g. ammonium and quaternary alkyl ammonium); lactic acid and lactate salts (e. g. ammonium and quaternary alkyl ammonium);
35 aloe very in any of its variety of forms (e.g., aloe vera gel);
polyhydroxy alcohols such as sorbitol, glycerol, hexanetriol, propylene glycol, butylene glycol, hexylene glycol and the like;
polyethylene glycols; sugars and starches; sugar and starch derivatives (e. g., alkoxyiated glucose); hyaluronic acid;
5 lactamide monoethanolamine; acetamide monoethanolamine; and mixtures thereof. Preferred humectants and moisturizers are glycerol, butylene glycol, hexylene glycol, and mixtures thereof.
Surfactants The. compositions of the present invention, especially the 10 shampoo and conditioner compositions, can contain one or more surfactants. These surfactants are useful ad,~uncts for the carriers of the present compositions, and are not required for solubilizing or dispersing the copolymers of the present invention. For a shampoo, the level is preferably from about 15 1pX to about 30X, preferably from 12X to about 25X, of the composition. For conditioners, the preferred level of surfactant is from about O.ZX to about 3X. Surfactants useful in compositions of the present invention include anionic, nonionic, cationic, zwitterionic and amphoteric surfactants. A wide variety 20 of surfactants useful herein are disclosed in U.S. Patent No.
5,151,209, to Mc Call et al., issued September 29, 1992; U.S.
Patent No. 5,151,210, to Steuri et al., issued September 29, 1992; and U.S. Patent No. 5,120,532, to halls et al., issued June 9, 1992 .
25 Nbnlimiting examples of theca surfactants include anionic surfactants such as alkyl and alkyl ether sulfates. Theca materials typically have the respective formulae ROS03M and RO(C2N40)xS03M, wherein R is alkyl or alkenyl of from about 10 to about 20 carbon atoms, x is 1 to 10, and !i is a water-soluble 30 can on such as anraonium, sodium, potassium and triethanolamine.
Another suitable class of anionic surfactants are the water-solubla salts of the organic, sulfuric acid reaction products of the general formula:
wherein R1 is chosen from the group consisting of a straight or branched chain, saturated aliphatic hydrocarbon radical having from about 8 to about 24, preferably about 12 to about 18, carbon atoms; and M is a can on. Additional examples of anionic synthetic surfactants which come within the terms of the present invention are the reaction products of fatty acids esterified with isethionic acid and neutralized with sodium hydroxide where, for example, the fatty acids are derived from coconut oil; sodium or potassium salts of fatty acid amides of methyl tauride in which the fatty acids, for example, are derived from coconut oil. Still other anionic synthetic surfactants include the class designated as succinamates, olefin sulfonates having about 12 to about 24 carbon atoms, and B-alkyloxy alkane sulfonates. Many additional nonsoap synthetic anionic surfactants ire described in pc~~+~heon's Detergents and Emulsifiers. 1984 Annual, published by Allured Publishing Corporation.
Also U.S. Patent 3,929,678, t.aughlin et al., issued December 30, 1975, discloses many other anionic as well as other surfactant types.
Nonionic surfactants useful herein are preferably used in combination with an anionic, amphoteric or zwitterionic surfactant. Thsse nonionic surfactants can be broadly defined as compounds produced by the condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which may-be aliphatic or alkyl aromatic in naturc.
Cationic surfactants useful in compositions of the present invention are disclosed in the following documents:
M.C. Publishing Co., ~rmtcheon's Detera~~ts 8 Emulsifiers, (North Averican edition 1979); SchwartZ. et al., Surface Active Agents, Their Chemistry and Technologic, New York: Interscisnce Publishers, 1949; U.S.
Patent 3,155,591, Hilfer, issued November 3, 1964; U.S. Patent 3,929,678, Laughlin, et al., issued December 30, 1975; U.S. Patent 3,959,461, Bailey, et al., issued May 25, 1976; and U.S. Patent 4,387,090, Bolich, Jr., issued June 7, 1983. If included in the compositions of the present invention, the cationic surfactant is present at from about 0.05X to about 5x.
Zwitterionic surfactants are exemplified by those which can be broadly described as derivatives of aliphatic quaternary ammonium, phosphonium, and sulfonium compounds, in which the aliphatic radicals can be straight or branched chain, and wherein one of the aliphatic substituents contains from about 8 to about 18 carbon atoms and one contains an anionic water-solubilizing group, e.g., carboxy, sulfonate, sulfate, phosphate, or phosphonate. Other zwitterionics such as betaines are also useful in the present invention. Examples of betaines include the high alkyl betaines, such as coco dimethyl carboxymethyl betaine, - lauryl dimethyl carboxymethyl betaine, lauryl dimethyl alpha carboxyethyl betaine, cetyi dimethyi carboxymethyl betaine, lauryl bis-(2-hydroxyethyl) carboxymethyl betaine, stearyl bis-(2 hydroxypropyl) carboxymethyl betaine, oleyl dimethyl~ gamna-carboxypropyl betaine, lauryl bis-(2-hydroxypropyl)alpha-carboxyethyl betaine, coco dimethyl sulfopropyl betaine, stearyl dimethyl sulfopropyl betaine, lauryl dimethyl sulfoethyl betaine, lauryl bis-(2-hydroxyethyl) sulfopropyl betaine, and amidobetaines and amidosulfobetaines (wherein the RCONH(CH2)3 radical is at-tached to the nitrogen atom of the betaine).
Examples of amphoteric surfactants which can be used in the 2S co~ositions of the present invention are those which are broadly described as derivatives of aliphatic secondary and tertiary amines in which the aliphatic radical can be straight or branched chain and wherein one of the aliphatic substituents contains from about 8 to about 18 carbon at~os and one contains an anionic water solubilizing group, e.g., carboxy, sulfonate, sulf~tl, phosphate, or phosphonate. Examples of compounds falling Within this defini-tion are sodium 3-dodecyl-aminopropionate, sodium 3-dodecylamino-propane sulfonate, N-alkyltaurines such as the one prepared by reacting dodecylamine with sodium isethionate according to the teaching of U.S. Patent 2,658,072, H-higher alkyl aspartic acids such as those produced according to the teaching of U.S. Patent 2,438,091, and the products sold under the trade name 'Miranol' and described in U.S. Patent 2,528,378.
Carboxviic Acid Cooolvmer Thickeners Another component useful in the compositions herein is a 5 carboxylic copolymer thickener. These crosslinked polymers contain one or more monomers derived from acrylic acid, substituted acrylic acids, and salts and esters of these acrylic acids and the substituted acrylic acids, wherein the crosslinking agent contains two or more carbon-carbon double bonds and is 10 derived from a polyhydric alcohol. The preferred polymers for use herein are of two general types. The first type of polymer is a crosslinked homopolymer of an acrylic acid monomer or derivative thereof (e.g., wherein the acrylic acid has substituents on the two and three carbon positions independently selected from the 15 group consisting of C1-4 alkyl, -CN, -COOH, and mixtures thereof).
The second type of polymer is a crosslinked copolymer having a first monomer selected from the group consisting of an acrylic acid monomer or derivative thereof (as just described in the previous sentence), a short chain alcohol (i.e. a C1-4) acrylate 20 ester monomer or derivative thereof (e. g., wherein the acrylic acid portion of the ester has substituents on the two and three carbon positions independently selected from the group consisting of CI_4 alkyl, -CH, ~CODE1, and mixtures thereof), and mixtures thereof; and a second monomer which is a long chain alcohol (i.e.
25 C8-40) acrylate ester monomer or derivative thereof (e. g., wherein the acrylic acid portion of the ester has substituents on the two and three carbon positions independently selected from the group consisting of CI_4 alkyl, -CN, -COOH, and a~ixtures thereof).
Coebinations of these two types of polymers are also useful 30 herein.
In the first type of crosslinked homopolyaiers the monomers are preferably selected from the group consisting of acrylic acid, methacrylic acid, ethacryitc acid, and mixtures thereof, with acrylic acid being most preferred. In the second type of 35 crosslinked copolymers the acrylic acid monomer or derivative thereof is preferably selected from the group consisting of acrylic acid, methacrylic acid, ethacrylic acid, and mixtures thereof, with acrylic acid, methacrylic acid, and mixtures thereof being most preferred. The short chain alcohol acrylate ester 5 monooier or derivative thereof is preferably selected from the group consisting of C1_4 alcohol acrylate esters, C1_4 alcohol methacrylate esters, C1_4 alcohol ethacrylate esters, and mixtures thereof, with the C1_4 alcohol acrylate esters, C1_4 alcohol methacrylate esters, and mixtures thereof, being most preferred.
10 The long chain alcohol acrylate ester monomer is selected from C8_40 alkyl acrylate esters, with C10-30 alkyl acryiate esters being preferred.
The crosslinking agent in both of these types of polymers is a polyalkenyl polyether of a polyhydric alcohol containing more 15 than one alkenyl ether group per molecule, wherein the parent polyhydric alcohol contains at least 3 carbon atoms and at least 3 hydroxyl groups. Preferred crosslinkers ire those selected from the group consisting of allyl ethers of sucrose and allyl ethers of pentaerythritol, and mixtures thereof. These polymers useful 20 in the present invention are more fully described in U.S. Patent No. 5,087,445, to Haffey et al., issued February 11, 1992; U.S.
Patent No. 4,509,949, to Huang et al., issued April 5, 1985; U.S.
Patent No. 2,798,053, to Broom, issued July 2, 1957; which are incorporated by reference herein. ~~, CTFA International 25 c~~~t;~ Ingredient Dictionary, fourth edition, 1991, pp. 12 and 80.
Exaa~les of coaoercially availble hompolymers of the first type useful herein include the carbomers, which are homopolymers of acrylic acid crosslinked with allyl ethers of sucrose or 30 pe~taerytritol. The carbomers are available as tha CarbopolR 900 series froa~ B.F. Goodrich. Examples of commercially available copolymers of the second type useful herein include copolymers of C10-30 alkyl acrylates with one or more uonomers of acrylic acid, methacrylic acid, or one of their short chain (i.e. C1_~ aicoholj 35 esters, wherein the crosslinking agent is an allyl ether of sucrose or pentaerytritol. These copolymers are known as acrylates/C10-30 alkyl acrylate crosspolymers and are commerically available as CarbopolR 1342, Pemulen"TR-1, and Pemolen TR-2, from B.F. Goodrich. In other words, examples of carboxylic acid polymer thickeners useful herein are those selected from the group consisting of carbomers, acrylates/C10-C30 alkyl acrylate crosspolymers, and mixtures thereof.
The compositions of the present can comprise from about 0.025x to about lx,~ more preferably from about 0.05X to about 10 0.75x and most preferably from about O.IOX to about 0.50X of the carboxylic acid polymer thickeners.
Emulsifiers The compositions herein can contain various emulsifiers.
These emulsifiers are useful for emulsifying the various carrier 15 components of the compositions herein, and are not required for solubiliiing or dispersing the copolymers of the ' present invention. Suitable emulsifiers can include any of a wide variety of nonionic, cationic, anionic, and zwitterionic emulsifiers disclosed in the prior patents and other references. _Sge 20 I~IcCutcheon's, Qetergents and EmuTsifier~, North American Edition (1986), published by Allured Publishing Corporation; U.S. Patent No. S,OlI,681 to Ciotti et al., issued April 30, 1991; U.S. Patent No. 4,421,769 to Dixon et al., issued December 20, 1983; and U.S.
Patent No. 3,755,560 to Dickert et al., issued August 28, 1973.
25 Suitable eawlsifier types include esters of glycerin, esters of propylene glycol, fatty acid esters of polyethylene glycol, fatty acid esters of polypropylene glycol, esters of sorbitol, esters of sorbitan anhydrides, carboxylic acid copolymers, esters and ethers of glucose, ethoxylated ethers, ethoxylated alcohols, 30 alkyl phosphates, polyoxyethylene fatty ether phosphates, fatty acid amides, acyl lactylates, soaps and mixtures thereof.
Suitable emulsifiers can include, but are not limited to, polyethylene glycol 20 sorbitan monolaurate (PolysorbateT" 20), polyethylene glycol 5 soya sterol, Steareth 20, CetearethTH20, PPG-2 methyl glucose ether distearate, CetethT~lO, Polysorbate 80, cetyl phosphate, potassium cetyl phosphate, diethanolamine cetyl phosphate, Polysorbate 60, glyceryl stearate, PEG-100 stearate.
and mixtures thereof.
The emulsifiers can be used individually or as a mixture of two or more and can compri se from about O.1X to about 10X, more preferably from about 1X to about 7X, and most preferably from about 1X to about 5X of the compositions of the present invention.
10 Emol 1 i en~,~
The compositions useful in the methods of the present invention can also optionally comprise at least one emollient.
Examples of suitable emollients include, but are not limited to, volatile and non-volatile silicone oils, highly branched 15 hydrocarbons, and non-polar carboxylic acid and alcohol esters, and mixtures thereof. Emollients useful in the instant invention are further described in U.S. Patent No. 4,919,934, to Oeckner.et al., issued April 24 1990.
The emollients can typically comprise in total from about 1X
20 to about 50X, preferably from about 1X to about 25X, and more preferably from about lx to about lOX by weight of the compositions useful in the present invention.
Additional Components A variety of additional components can be incorporated into 25 the compositions herein. Hon-limiting examples of these additional components include vitamins and derivatives thereof (e. g:, ascorbic acid, vitamin E, tocopheryl acetate, retinoic acid, retinol, retinoids, and the like); low pH thickening agents (e.g. polyacrylamide and C13-14 isoparaffin and laureth-7, 30 available as Sepigel~ from Seppic Corporation; polyquaternium and mineral oil, available as Salcare SC92, from Allied Colloids;
crosslinked methyl quaternized dimethylaminomethacrylate and mineral oil, available as Salcare SC95 from Allied Colloids;
resins; gums and thickeners such as xanthan gum, carboxymethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, alkyl-modified hydroxyalkyl celluloses (e. g. long chain alkyl modified hydroxyethyl celluloses such as cetyl hydroxyethylcellulose), and magnesium aluminum silicate; cationic polymers and thickeners (e. g., cationic guar gum derivatives such as guar hydroxypropyltrimonium chloride and hydroxypropyl guar hydroxypropyltrimonium chloride, available as the Jaguar C series from Rhone-Poulenc; polymers for aiding the film-forming properties and substantivity of the composition (such as a 10 copolymer of eicosene and vinyl pyrrolidone, an example of which is available from GAF Chemical Corporation as GanexR V-220);
suspending agents such as ethylene glycol distearate and the like;
preservatives for maintaining the antimicrobial integrity of the compositions; skin penetration aids such as OMSO, 15 1-dodecylatacycloheptan-2-one (available as Atone from the Upjohn Co.) and the like; antioxidants; chelators and sequestrants; and aesthetic components such as fragrances, colorings, essential oils, skin sensates, astringents, skin soothing agents, skin healing agents and the like, nonlimiting examples of these 20 aesthetic components include panthenot and derivatives (e. g. ethyl panthenol), pantothenic acid and its derivatives, clove oil, menthol, caa~phor, eucalyptus oil, eugenol, menthyl lactate, witch hazel distillate, allantoin, bisabalol, dipotassium glycyrrhizinat~ and the like.
25 Method of Usinci Hair and Skin Care Compositions The hair care and skin care compositions of the present invention are used in conventional ways to provide the desired benefit appropriate to the product such as hair styling, holding, cleansing, conditioning and the like for hair care compositions 30 and benefits such as moisturization, sun protection, anti-acne, anti-wrinkling, artificial tanning, analgesic, and other cosmetic and pharmaceutical benefits for skin cars compositions. Such methods of use depend upon the type of composition employed but generally involve application of an effective amount of the 35 product to the hair or skin, which may then be rinsed from the hair or skin (as in the case of shampoos and some conditioning products) or al 1 owed to remai n on the hai r ( as i n the case of spray, mousse, or gel products). or allowed to remain on the skin (as in the case of the skin care compositions). By "effective amount" is meant an amount sufficient to provide the benefit desired. Preferably, hair rinse, mousse, and gel products are applied to wet or damp hair prior to drying and styling of the hair. After such compositions are applied to the hair, the hair is dried and styled in the usual ways of the user. Hair sprays are typically applied to dry hair after it has already been dried and styled. Cosmetic and pharmaceutical topical skin care compositions are applied to and rubbed into the skin.
The following examples further illustrate preferred embodiments within the scope of the present invention. The examples are given solely for the purposes of illustration and are not to be construed as limitations of the present invention as many variations of the invention are possible without departing from its spirit and scope.
EXAMPLES
The following examples further describe and demonstrate embodiments within the scope of the present invention and the parent application. The examples are given solely for the purpose of illustration and are not to be construed as limitations of the present invention, as many variations thereof are possible without departing from the spirit and scope of the invention.
Ingredients are identified by chemical or CTFA name.
S~mthesis of Poly(2-ethyl-2-oxazoline) Alcohol To a solution of 50 g (0.5044 mol) of 2-ethyl-2-oxazoline in 50 mL of acetonitrile is added 0.92 g (0.0048 mol) of methyl-p-toluenesulfonate at 0°C under a nitrogen atmosphere. The reaction mixture is heated at 80°C for 20 hours and the resulting polymer solution is then refluxed with 2.3 mL distilled water in the presence of 5.6 g (0.0528 mol) of sodium carbonate for 24 hours. The solvents are removed under vacuum. The residue is extracted with 300 mL of dichloromethane for 24 hours, and the insolubles are removed by suction filtration. The dichloromethane is then evaporated to yield about 48 g {96x yield) of poly(2-ethyl-2-oxatoline) alcohol.
EXAMPLE II
Synthesis of Acrvlate-Canoed Polvl2-ethyl-2-oxazoline) Alcohol Macromonomer To a solution of 48 g of poly(2-ethyl-2-oxazoline) alcohol (from EXAMPLE I) and 1.0 g (0.01056 mol) of triethylamine in 80 mL
10 of dichloromethane is added dropwise a solution of 0.95 g (0.01056 mol) of acryloyl chloride at OoC under a nitrogen atmosphere. The reaction mixture is then stirred at room temeprature for 36 hrs, and the resulting solution is then suction filtered to remove the insolubles. The solvent and any unreacted triethylamine are 15 removed by evaporation under vacuum. The resulting solid is then redissolved in 200 ml of dichloromethane, filtered, and evaporated under vacuum to yield about 45.6 g (95X yield) of the macromonomer.
Using an analogous procedure the methacrylate and ethacrylate 20 endcapped macromonomers are prepared by replacing the acryloyl chloride with an equivalent molar amount of methacryloyl chloride and ethacryloyl chloride, respectively.
EXAlIPLE III
c~~th.~i5 of Yinvlbenzvl-Cacced Polv(2-ethyl-2-oxazolinel Alcohol 25 Macromonomer To a solution of 50 g (0.5044 mol) of 2-ethyl-2-oxazoline in 50 ml of acetonitrite is added a mixture of 0.3816 g (0.0025 mol) of meta and paravinylbenzylchlorides (available from Aldrich Chemical Co.), 0.562 g (0.0037 mol) of sodium iodide and 0.06 g 30 (0,00023 mot) of H,H'-Biphenyl-~-phenylenediamine. The solution .is then heated at 90oC for 16 hours. To the resulting reaction product is added 100 mL of dichloromethane and the solution is filtered and then precipitated in 800 ml of ether, The precipitate product is collected by vacuum filtration and dried under vacuum at ambient temperature to yield about 45 g (90X
yield) of the macromonomer.
EXAh1 P L E I Y
5 5vnthesis of Acrvlate-Canoed Polv(ethvlene glvcol)methvl ~Fther hlacromonomer To a solution of 50 g (0.01 mol) of polyethylene glycol)methyl ether having an average molecular weight of about 5000 (commercially available from Aldrich Chemical Co.) and 4.05 g 10 (0_04 mol) of triethylamine in 400 mL of dichloromethane is added dropwise at OoC under a nitrogen atmosphere a solution of 2.26 g (0.025 mol) of acryloyl chloride dissolved in 25 ml of dichloromethane. The reaction mixture is then stirred at room temeprature for 36 hrs, and the resulting solution is then suction 15 filtered to remove the insolubles. The solvent and any unreacted triethylamine are removed by evaporation under vacuum. The resulting solid is then redissolved in 300 mL of dichloromethane, filtered, and evaporated under vacuum to yield about 50 g (100X
yield) of the macromonomer.
20 The above procedure is varied using other polyethylene glycol)alkyl ethers (e. g. methyl, ethyl, 2-sthylhexyl, decyl, dodecyl, cetyl, stearyl, lauryl, and myristyl wherein the polymer has an average molecular weight varying from about 1000 to about 200,000) to obtain the analogous acrylate-capped ~acromonomers.
25 Additionally, the methacrylate and ethacrylate endcapped macromonoaiers are prepared by replacing the acryloyl chloride with an equivalent molar amount of methacryloyl chloride and ethacryloyl chloride, respectively.
Synthesis of Polv(n-butyl acrvlate)-ql~aft-oolv(2-ethyl-2-oxazo-line) Thermoplastic Elastomeric C~yolvmer To a solution of 16.0 g (0.1248 mol) of 0-butyl acrylate, and 4 g of acrylate capped poly(2-ethyl-2-oxazoline) macromonomer (from Example II) in 100 ml of acetone is added 0.03 g (0.00018 mol) of azoisobutyronitrile (AIBN) initiator. The resulting solution is refluxed slowly for about 20 hours. The reaction is then quenched by the addition of about 5 mL of methanol. The 5 solution is then poured into a Teflon' pan and the acetone is evaporated at room temperature under a fume hood. The resulting polymer film is redissovled in ethanol, filtered, and the ethanol is then evaporated to yield about 18.4 g of the thermoplastic elastomeric copolymer.
10 Alternatively, by varying the monomers and macromoners used, this procedure is used to prepare other copolymers of the present invention.
EXAMPLE VI
15 Synthesis of Polv(n-bud,vl-co-2-methoxvethvlacrvlatel-craft-oolv(2-~,~hvl 2 oxazolinel Thermoplastic Elastomeric CoXiolvmer~ Method I
To a solution of 4.5 g (0.035 mol) of ~-butyl acrylaEe, 2.5 g (0.0192 mol) of 2-methoxy ethylacrylate and 3 g poly(2-ethyl-2-oxazoline) macromonomer (from Example II) in 40 ml 20 of acetone is added 0.05 g of AI6N irritator. The resulting solution is refluxed slowly for about 20 hours. The reaction is then quenched by the addition of about 5 ml of methanol. The solution is then poured into a teflon pin and the acetone is evaporated at room temperature under a fume hood. The resulting 25 polymer film is redissovled in ethanol, filtered, and the ethanol is then evaporated to yield about 9.5 g of the thermoplastic elastomeric copolymer.
Alternatively, by~varying the nwnomers and macromoners used, this procedure is used to prepare other copolymers of the present 30 invention.
EXAMPLE VII
Svnthe~is of Polv(n-butyl- co-2-methoxvethvla crv~iatel-oraft -oolv(2-2thv1 2 oxazolinel plastic ElastomericCopolymer: thod Thermo Me II
To a 500 ml round-bottomed flask is added 20.8 g (0.1623 mol) of n-butyl acrylate, 11.2 g (0.0861 mol) of 2-methoxyethyl acrylate, 0.30 g (0.002 mol) ~-vinylbenzyl chloride, and 0.02 g (0.0012 mol) of azoisobutyronitrile (AIBN) irritator, in 200 ml of acetone. The resulting solution is refluxed slowly for about 24 hours. The reaction is then quenched by the addition of about 5 ml of methanol and cooled to room temperature. The solvents are removed by rotary evaporation and the resulting polymer is dissolved in 250 mL of dry acetonitrile. Next 20.0 g (0.2018 mol) 0,.- 2-ethyl-2-oxazoline and 0.44 g (0.0029 mol) of sodium iodide is added and the solution is heated to 90oC for 20 hours. The . resulting solution is filtered and the solvent is evaporated to yield about 45.0 g (86X yield) of the thermoplastic elastomeric copolymer.
Alternatively, by varying the monomers used, this procedure is used to prepare other copolymers of the present invention.
EXAMPLE VIII
Synthesis of Polvln-butyl co 2 ldimethvlaminoiethvl metharrvlatel craft-oolvl2-ethyl-2-oxazolinel Thermoplastic Elast merit To a solution of 7.Z g (0.0561 mol) of 0-butyl acrylate, 4.8 g (0.0305 mol) of 2-(dimethylamino)ethyl methacrylate, and 8.0 g poly(2-ethyl-2-oxazoline) macromonomer (from Example II) in 80 ml of acetont is added 0.01 g of AIBN irritator. The resulting solution is refluxed slowly for about 24 hours. The reaction is then quenched by the addition of about 5 mL of methanol. The solution is then poured into a teflon pan snd the acetone is evaporated at room temperature under a fume hood. The resulting polymer film is redissovled in ethanol, filtered, and the ethanol is then evaporated to yield about 18.4 g of the thermoplastic elastomeric copolymer.
Alternatively, by varying the monomers and macromoners used, this procedure is used to prepare other copolymers of the present invention.
EXAMPLE IX
~ nthesis of Methyl Quaternized Polv(n-butyl-co-2-(dimethvlaminol-~~vl methacrvlatelaraft-y~olv(2-ethyl-2-oxazoline) Thermoplastic Flash Copolymer 5 To l0 grams of the copolymer from EXAMPLE VIII dissovled in 80 grmas of ethanol is added dropwise 4.32 g (0.0281 mole) of dimethylsulfate. The resulting solution is stirred for 2 hours at room temperature. The solvent is removed by rotary evorpation to yield about 10 grams of the methyl quaterniied copolymer.
Hai r~Sora_v Hair spray compositions are prepared from the following components utilising conventional mixing techniques.
15 Ingredients ~.9nc x 9 ~ ~ Q
water QS 100 QS 100 QS 100 QS 100 Ethanol (SOA 40) 79.0 79.0 79.0 90.0 Copolymer of Example VI1 4.0 4.0 3.0 3.0 20 Fragrance 0.1 0.2 --- ---These products ire prepared by first dissolving the polymer in the ethanol with stirring. The water and fragrance are then added with stirring. The resulting hsir spray compositions can 25 then be packaged .in a nonaerosol spray pump. Alternatively, the compositions can be combined with conventional propellants and packaged in an aerosol spray.
These hair sprays are useful for application to the hair to provide a styling and holding benefit.
1 Alternatively, spray compositions are prepared using the copolymers of Examples V and VIII.
geduced Volatile Organic Content Hairsorav Hair spray compositions are prepared from the following components utilizing conventional mixing techniQues.
Ingredients V~gight x Q
Water QS 100 QS 100 QS 100- QS 100 Ethanol (SDA 40) 54.0 54.0 54.0 54.0 Copolymer of Example VI1 4.0 3.0 4.0 3.0 Fragrance 0.05 O.Z --- ---These products are prepared by first dissolving the polymer in the ethanol with stirring. The water and fragrance are then added with stirring. The resulting hair spray compositions can 15 then be packaged in a nonaerosol spray pump. Alternatively, the compositions can be combined with conventional propellants and packaged in an aerosol spray.
These hair sprays are useful for application to the hair to provide a styling and holding benefit.
1 Alternatively, spray compositions are prepared using the copolymers of Examples V and VIII.
~XA~tPLE
~usse XII
Mousse compositions are prepared from the following coa~ohents utilizing convent ional mixingtechniques.
t Weight x s A
Ingredien Water QS 100 QS 100 QS 100 Copolymer of Example VIII1 3.00 2.50 3.50 Lauramide DEA 0.33 0.33 0.33 SodiuA Methyl Oleyl Taurate I.67 1.67 1.67 DMOM Hydantoin 0.78 0.78 0.78 pisodium DTA 0.20 0.20 0.20 Polyoxyalkylated isostearyl Alcohol2 0.10 0.10 0.10 Fragrance 0.10 0.10 0.10 Propellant3 7.0 7.0 7.0 These products are prepared by first dissolving the polymer in water with stirring. The remaining ingredients, except the propellant, are' then added with stirring.
The resulting mousse concentrate can then be combined with 10 conventional propellants (e.g., Propellant A46) and packaged in an aerosol spray.
These mousses are useful for application to the hair to provide a styling and holding benefit.
15 1 Alternatively, mousse compositions are prepared using the copolymers of Examples V and and VI.
2Available as Aerosurf~" 66-E10:
3Available as a mixture of 82.46x isobutane, I6.57X propane, and O.OOIX butane.
Hair Tonic Hair ionic compositions are prepared from the following 25 components utilizing conventional mixing techniques.
Ingredients weight ~
Ethanol (SOA 40) QS 100 QS 100 QS 100 Copolymer of Example UI1 0.75 1.00 1.25 30 Fragrance 0.10 0.20 0.30 These products are prepared by dissolving the polymer in the ethanol with stirring and then adding the fragrance and any colors.
These hair tonics are useful for application to the hair to provide a styling and holding benefit.
1 Alternatively, tonic compositions are prepared using the copolymers of Examples Y and VIII.
EXAMPLE XIY
Hair Conditioner A hair conditioner composition is prepared from the following components utilizing conventional mixing techniques.
Ingredient Weight x Stvlina Agent Premix Copolymer of Example IX 1.00 Silicone Premix Silicone gum, GE SE761 0.30 Octamethyl cyclotetrasiloxane 1.70 Main MixMix water QS100 Cetyl Alcohol 1.00 Quaternium 182 0.85 Stearyl Alcohol 0.70 Hydroxethyl cellulose 0.50 Ceteareth-20 0.35 Fragrance 0.20 Dimethicone copolyol 0.20 Citric Acid 0.13 Methylchloroisothiazolinone (and) ~thylisothiazolinone 0.04 Sodium Chloride 0.01 The product is prepared by co~aixing all the Main Mix ingredients, heating to about 60oC with mixing, and colloid milling while cooling to about 45oC. At this temperature, the two premixes are add separately with moderate agitation and the resultant conditioner is allowed to cool to room temperature.
This product is useful as a rinse off hair conditioner.
5 1 Commercially available from General Electric.
2 Dimethyl Di(Hydrogenated Tallow) Ammonium Chloride EXAMP! E XV
Shampoo Composition 10 A shampoo composition is prepared from the following components utilising conventional mixing techniques.
Ingredients Weight x ~tvlina Agent 15 copolymer from Example IX 1.00 Premi xx Silicone gum 0.50 Dimethicone, 350 cs fluid 0.50 Main Mix water OS100 Artmoniua~ lauryl sulfate 11.00 Cocamide MEA 2.00 25 Ethylene glycol distearate 1.00 Xanthan Guar 1.20 Methy-lchloroisothiaZOlinone (and) methylisothiatolinone 0.0~
Citric Acid to pH 4.5 as needed The Main Mix is prepared by first dissolving the xanthan gum in the water with conventional mixing. The remaining Main Mix ingredients are added and the Main Mix is heated to 150oF with agitation for 1/2 hour. The Styling Agent and the Premix are then 35 added sequentially with about 10 minutes of agitation between additions, and the entire mixture isstirred while the batch is cooled to room temperature. For varied particile size, the Styling AGent and Premix can be added at different times using either or both high shear mixing (high speed dispersator) or 5 normal agitation.
This shampoos is useful for cleansing the hear and for providing a styling benefit.
Example XYI
10 Anti-Acne Ccomposition An anti-acne composition is made by combining the following components using conventional mixing technology.
15 Ingredient Neiaht x hater QS100 5aiicylic Acid 2.0 Copolymer from Example VI1 2.0 Ethanol (SOA 40) 40.0 The compositon display skin penetration of the salicylic acid as well as improved skin reel and residue characteristics and is useful for the treatment of acne.
25 1 Alternatively, the anti-acne compositions are prepared using the copolymers of Examples VIII and IX.
Example XVII
Topical Anal esic Composition A topical analgesic composition is made by combining the following ingredients utilizing conventional mixing techniques.
j,naredient W, eight x Hater, Purified QS100 Ibuprofen Z.0 Copolymer from Example YII 2.0 Ethanol (SDA 40) 20.0 IO
The compositions display skin penetration of the ibuprofen active as well as improved skin feel and residue characteristics together with excellent moisturizing, emolliency, rub-in and absorption characteristics.
I Alternatively, the topical analagesic compositions are prepared using the copolymers of Examples VIII and IX.
I~camule XYIII
20 c~~nless Tannins Composition A composition for sunless tanning is made by combining the following ingredients utilizing conventional a~ixing techniques.
Pha-hater qs 100 Copolymer from Example YI1 2.00 Carbomer 9342 0.20 30 Carbomer 9803 0.15 Acrylic Acid Copolymer4 0.15 Phase B
PPG-20 Methyl Glucose Ether 35 Distearate 2.00 Tocopheryl Acetate 1.20 Mineral Oil 2.00 Stearyl Alcohol 1.00 Shea Butter 1.00 5 Cetyl Alcohol 1.00 Ceteareth-20 2.50 Ceteth-2 1.00 Ceteth-10 1.00 10 ph DEA-Cetyl Phosphate 0.75 Phase D
Dihydroxyacetone 3.00 Phase E
8utylene Glycol Z.00 OMOh Hydantoin (and) Iodopropynyl Butylcarbamate 0.25 Phase F
Fragrance 1.00 Cyclomethicone 2.00 25 In a suitable vessel the Phase A ingredients are dispersed in the water and heated to 75-85oC. In a separate vessel the Phase B
ingredients are combined and heated to 85-90oC until melted.
Next, the DEA-Cetyl Phosphate is added to the liquid Phase B and stirred until dissolved. This mixture is then added to Phase A to 30 form the emulsion. The emulsion is cooled to 40-45oC with continued mixing. Next, in a separate vessel, the dihydroxyacetone is dissolved in water and the resulting solution is mixed into the emulsion. In another vessel, the Phase E
ingredients are heated with mixing to 40-45oC until a clear 35 solution is formed and this solution is then added to the emulsion. Finally, the Phase F ingredients are added to the emulsion with mixing, which is then cooled to 30-35oC, and then to room temperature.
Thi s emul sion i s useful for topical appl ication to the skin 5 to provide an artificial tan.
1 Alternatively, the artificial tanning compositions are prepared using the copolymers of Examples VIII and IX.
2 Available as CarbopolR 934 from B.F. Goodrich.
10 3 Available as CarbopolR 980 from B.F. Goodrich.
4 Available as Pemulen TR1 from B.F. Goodrich.
EXAMPLE XIX
15 Sunscreen Com~iosition An oil-in-water emulsion is prepared by combining the following components utilizing conventional mixing techniques.
Ingredients - W_e_i hq t x ZO Phase A
Water QS100 Carbomer 9541 0.24 Carba~er 13422 0.16 Copolymer from Exmaple VII3 1.75 25 Disodium EDTA 0.05 Phase 8 Isoarachidyl Neopentanoate4 2.00 PVP Eicosene Copoiymer5 Z.00 30 Octyl Methoxycinnaa~ate 7.50 Octocryl ere 4 . 00 Oxybenzone 1.00 Titanium Dioxide 2.00 Cetyl Palmitate 0.75 35 Stearoxytrimethylsilane (and) Stearyl Alcohol6 0.5'0 Glyceryl Tribehenate7 0.75 Dimethicone 1:00 Tocopheryl Acetate 0.10 DEA-Cetyl Phosphate 0.20 Phase C
Water 2.00 Triethanolamine 99x 0.60 phase D
Water 2.00 Butylene Glycol 2.00 DMDM Hydantoin (and) 15 Iodopropynyl Butylcarbamate8 0.25 dl Panthenol 1.00 Ph Cyclomethicone 1.00 I Available as CarbopolR 954 from B.F. Goodrich.
2 Available as CarbopolR I342 from B.F. Goodrich.
3 Alternatively, the sunscreen compositions are prepared using the copolymers of Examples VIII and IX.
25 4 Available as Elefac~I-205 from 8ernel Chemical.
5 Available as GaneX Y-220 frog GAF Corporation.
30 The carriers of the skin care compositions can c~nprise from about 50x to about 99x by weight of the coisposltions of the present invention, preferably fro4 about 75x to about 99x, and most preferably froo about 85x to about 95x.
Preferred cosawtically and/or pharmaceut1ca11y acceptable 35 topical carriers include hydro-alcoholic systems and oil-in-water emulsions. When the carrier is a hydro-alcoholic system, the carrier can comprise from about 1% to about 99x of ethanol, isopropanol, or mixtures thereof, and from about IX to about 9fx of eater. More preferred is a carrier comprising from about 5x to 5 about 60x of ethanol, isopropanol, or mixtures thereof, and from about 4fX to about 95x of water. Especially preferred is a carrier comprising from about 20X to about 50x of ethanol, isopropanol, or mixtures thereof, and frog about 50x to about 80%
of water. When the carrier is an oil-in-water emulsion. the 10 carrier can include any of the cortmon excipient ingredient. for preparing these emulsions. ~ Additional components useful in formulating these topical compositions are further described below.
Additional Comconents A wide variety of additional components can be employed in the hair care and topical skin compositions herein. Non-limiting examples include the following:
Pharmaceutical Actives The compositions of the present invention, especially the 20 topical skin care compositions, can eomprise a safe and effective amount of a pharmaceutical active. The phrase 'safe and effective amount', as used herein, means an amount of an active high enough to significantly or positively modify the condition to be treated, but low enough to avoid serious side effects (at a reasonable 25 benefit/risk ratio), within the scope of sound medical ,~udgea~ent.
A-safe and effective amount of the pharmaceutical active will vary with the specific active, the ability of the composition to penetrate the active through the skin, the amount of composition to be applied, the particular condition being treated, the age and 30 physical condition of the patient being treated, the severity of the condition, the duration of the treatment, the nature of concurrent therapy, and like factors.
Ths pharmaceutical actives which can be used in the coapositions of the present invention preferably comprise from 35 about O.lx to about 20% by weight of the compositions, more _28_ preferably from about O.lx to about lOx, and most preferably from about O.lx to about 5X. Mixtures of pharmaceutical actives may also be used.
Honlimiting examples of pharmaceutical actives can include the following:
Useful pharmaceutical actives in the compositions of the present invention include anti-acne drugs: Anti-acne drugs preferred for use in the present invention include the keratolytics such ~as salicylic acid, sulfur, lactic acid, 10 glycolic, pyruvic acid, urea, resorcinol, and N-acetylcysteine;
retinoids such as retinoic acid and its derivatives (e.g., cis and traps); antibiotics and antimicrobials such as benzoyl peroxide, octopirox, erythromycin, zinc, tetracyclin, triclosan, azelaic acid and its derivatives, phenoxy ethanol and phenoxy proponol, 15 ethylacetate, clindamycin and meclocycline; sebostats ,such as flavinoids; alpha and beta hydroxy acids; and bile salts such as scymnol sulfate and its derivatives, deoxycholate, and cholate.
Preferred for uss herein is salicylic acid.
Useful pharmacetuical actives in the compositions of the 20 present invention include non-steroidal anti-inflammatory drugs (NSAIDS). The NSAI05 can be selected from the following categories: propionic acid derivatives; acetic acid derivatives;
fena~ic acid derivatives; biphenylcarboxylic acid derivatives; and oxica~s. A11 of these NSAIDS are fully described in the U.S.
25 Patent 4,985,459 to Sunshine et al., issued January 15, 1991.
Most preferred are the propionic NSAIDS including but not limited to Aspiri n', acetaa~inophen, Ibuprofen, naproxen, benoxaprofen, flurbi.profen, fenoprofen, fenbufen, ketoprofen, indoprofen, pirprofen, 30 carprofen, oxaprozin, pranoprofen, ~iroprofen, tioxaprofen, suprofen, ~loinoprofen, tiaprofenic acid, fluprofen and bucioxic acid. Als4 useful are the steroidal anti-inflammatory drugs including hydrocortisone and the like.
Useful pharmaceutical actives in the compositions of the 35 present invention include antipruritic drugs. Antipruritic drugs _29_ preferred for inclusion in compositions of the present invention include pharaaceutically-acceptable salts of methdilizine and trimeprazine.
Useful pharmaceutical actives in the compositions of the 5 present invention include include anesthetic drugs. Anesthetic drugs preferred for inclusion in compositions of the present invention include pharmaceutically-acceptable salts of lidocaine, bupivacaine, chlorprocaine, dibucaine, etidocaine, mepivacaine, tetracaine, dyclonine, hexylcaine, procaine, cocaine, ketamine, 10 pramoxine and phenol.
Useful pharmaceutical actives in the compositions of the present invention include antimicrobiai drugs (antibacterial, antifungal, antiprotozoal and antiviral drugs). Antimicrobial drugs preferred for inclusion in compositions of the present 15 invention include pharmaceutically-acceptable salts of p-lactam drugs, quinolone drugs, ciprofloxacin, norfioxacin, tetracycline, erythromycin, amikacin, triclosan, doxycycline, capreomycin, chlorhexidine, chlortetracycline, oxytetracycline, clindamycin, ethambutol, metronidazole, pentamidine, gentamicin, kanamycin, ZO lineomycin, a~ethacycline, methenamine, minocycline, neomycin, netilmicin, paromomycin, streptomycin, tobramycin, miconazole and amanfadine. Antimicrobial drugs preferred for inclusion in compositions of the present invention include tetracycline hydrochloride, erythromycin estoiate, erythromycin stearate 25 (salt), amikacin sulfate, doxycyclint hydrochloride, capreoa~ycin sulfate, chlorhtxidine gluconate, chlorhexidine hydrochloride, chlortetracycline hydrochloride, oxytetracycline hydrochloride, clinda~nycin hydrochloride, tthambutol hydrochloride, metronidazole hydrochloride, pentamidine hydrochloride, gentamicin sulfate, 30 kanamycin sulfate, lineomycin hydrochloride, methacycline hydrochloride, methenaa~ine hippuratt, methenamine mandelatt, minocycline hydrochloride, ne~ycin sulfate, netilmicin sulfate, paromomycin sulfate, streptomycin sulfate, tabramycin sulfate, miconaZOie hydrochloride, amanfadine hydrochloride, amanfadine sulfate, triclosan, octopirox, parachlorometa xylenol, nystatin, tolnaftate and clotrimazole.
Also useful herein are sunscreening agents. A wide variety of sunscreenlng agents are described in U.S. Patent Ho. 5,087,445, 5 to Haffey et al., issued February 11, 1992; U.S. Patent No.
5,073,372, to Turner et al., issued December 11, 1991; U.S. Patent No. 5,073,371, to Turner et ai. issued December 17, 1991; and Segarin, et al., at Chapter VIII, pages 189 et seq., of Cosmetics Sc i ence and Iechnol a~ .
10 Preferred among those sunscreens which are useful in the compositions of the instant invention are those selected fram the group consisting of 2-ethylhexyl p-methoxycinnamate, 2-ethylhexyl N,N-dimethyl-p-aminobentoate, p-aminobenzoic acid, 2-phenyibenzimidazole-5-sulfonic acid, octocrylene, oxybenzone, 15 homomenthyl saiicylate, octyl salicylate, 4,4'-methoxy-~-butyldibenzoylmethane, 4-isopropyl dibenzoylmethane, 3-benzylidene camphor, 3-(4-methylbenzylidene) camphor, titanium dioxide, zinc oxide, silica, iron oxide, and mixtures thereof.
20 Still other useful sunscreens are those disclosed in U.S.
Patent No. 4,937,370, to Sabatelli, issued June 26, 1990: and U.S.
Patent No. 4,999,186, to Sabatelli et al., issued March 1Z, 1991.
The sunscreening agents disclosed therein have, in a single molecule, two dtstinct chromophore Aoieties which axhibit 25 different ultra-violet radiation absorption spectra. One of the chro~ophore moieties absorbs predominantly in the UVB radiation range and the other absorbs strongly in the UVA radiation range.
These sunscreening agents provide higher efficacy, broader UV
absorption, lower skin penetration and longer lasting efficacy 30 relative to conventional sunscreens. Especially preferred examples of these sunscreens include those selected from the group consisting of 4-N,N~(2~ethylhexyl)methylaminobenzoic acid ester of 2,4-dihydroxybenzophenone, 4-N,N-(2-ethylhexyl)methylaminobenzoic acid ester with 4-hydroxydibenzoylmethane, 4-ti, H- (2-ethylhexyl)-methylaminobenzoic acid ester of Z-hydroxy-4-(2-hydroxyethoxy)ben-zophenone, 4-N,N-(2-ethylhexyl)-methylamtnobenzoic acid ester of 4-(2-hydroxyethoxy)dibenzoylmethane, and o~txtures thereof.
6eneraliy, the sunscreens can comprise from about O.Sx to about ZO% of the compositions useful herein. Exact amounts will vary depending upon the 'sunscreen chosen and the desired Sun Protection Factor (SPF). SPF is a cortmonly used measure of photoprotection of a sunscreen against erythema. egg Fe ral 10 Rea-, Vol. 43, No. 166, pp. 38206-38269, August 25, 1978.
Also useful in the present invention are sunless tanning agents including dihydroxyacetone, giyceraldehyde, indoles and their derivatives, and the like. These sunless tanning agents aay also be used in combination with the sunscreen agents.
15 Other useful actives include skin bleaching (or lightening) agents including but not limited to hydro4uinone, ascorbic acid, ko,)ic acid and sodium metabisulfite.
Other useful actives which are especially useful for hair care compositions include anti-dandruff actives such as zinc 20 pyrithione, octopirox, seleniua~ disulfide, sulfur, coal tar, and the like.
Conditioners Conditioning agents useful herein, and especially useful for hair~care coaroositions, include hydrocarbons, silicone fluids, and 25 cationic materials.
The hydrocarbons can be either straight or branched chain and can contain froa about 10 to about 16, preferably frog about 12 to about 16 carbon atoa~s. Examples of suitable hydrocarbons are decane, dodecane, tetradecane, tridecane, and mixtures thereof.
30 Silicone conditioning agents useful hero n can include either cyclic or linear polydimethylsiloxanes, pheny and alkyl phenyl silicones, and silicone copolyols. The linear volatile silicones generally have viscosities of less than about 5 centistokes at 25oC, while the cylic materials have viscosities less than about centistokes.
Cationic conditioning agents useful herein can include quaternary ammonium salts or the salts of fatty amines. Preferred quaternary ammonium salts are dialkyl dimethyl ammonium chlorides, wherein the alkyl groups have from 12 to 22 carbon atoms and are derived from long-chain fatty acids. Representative examples of quaternary ammonium salts include ditallow dimethyl ammonium chloride, ditallow dimethyl ammonium methyl sulfate, dihexadecyl 10 dimethyl ammonium chloride, and di(hydrogenated tallow) ansnonium chloride. Other qauternary ammonium salts useful herein are dicationics such as tallow propane dianmonium dichloride.
Quaternary imidazolinium salts are also useful herein. Examples of such materials are those imidazolinium salts containing C12-22 15 alkyl groups such as 1-methyl-1-[(stearoylamide)ethyl]-2-heptadecyl-4, 5-dihydroimidazolinium chloride, 1-methyl-1-[(palmitoylamide)ethyl]-2-octadecyl-4,5-dihydroimidazo-linium chloride and 20 1-methyl-1-((tallowamids)-ethyl]-2-tallow-imidazolinium methyl sulfate. Also useful herein are salts of fatty amines. Examples of such compounds include stsarylamine hydrochloride, soyamine hydrochloride, and stsarylaa~ine formats. Useful conditioning agents are disclosed in U.S. Patent No. 4,387,090, to Bolich, 25 issued June 7, 1983.
Mumectants and Moisturizers The compositions of the present invention can contain one or more humectant or moisturizing materials. A variety of these maters al s can be empi oyed and each can be present at a 1 suet of 30 fros about O.lx to about 20lC, more preferably from about lx to about lOx and most preferably froa~ about 2x to about 5x. These materials include urea; guanidine; glycolic acid and glycolate salts (s. g. ammonium and quaternary alkyl ammonium); lactic acid and lactate salts (e. g. ammonium and quaternary alkyl ammonium);
35 aloe very in any of its variety of forms (e.g., aloe vera gel);
polyhydroxy alcohols such as sorbitol, glycerol, hexanetriol, propylene glycol, butylene glycol, hexylene glycol and the like;
polyethylene glycols; sugars and starches; sugar and starch derivatives (e. g., alkoxyiated glucose); hyaluronic acid;
5 lactamide monoethanolamine; acetamide monoethanolamine; and mixtures thereof. Preferred humectants and moisturizers are glycerol, butylene glycol, hexylene glycol, and mixtures thereof.
Surfactants The. compositions of the present invention, especially the 10 shampoo and conditioner compositions, can contain one or more surfactants. These surfactants are useful ad,~uncts for the carriers of the present compositions, and are not required for solubilizing or dispersing the copolymers of the present invention. For a shampoo, the level is preferably from about 15 1pX to about 30X, preferably from 12X to about 25X, of the composition. For conditioners, the preferred level of surfactant is from about O.ZX to about 3X. Surfactants useful in compositions of the present invention include anionic, nonionic, cationic, zwitterionic and amphoteric surfactants. A wide variety 20 of surfactants useful herein are disclosed in U.S. Patent No.
5,151,209, to Mc Call et al., issued September 29, 1992; U.S.
Patent No. 5,151,210, to Steuri et al., issued September 29, 1992; and U.S. Patent No. 5,120,532, to halls et al., issued June 9, 1992 .
25 Nbnlimiting examples of theca surfactants include anionic surfactants such as alkyl and alkyl ether sulfates. Theca materials typically have the respective formulae ROS03M and RO(C2N40)xS03M, wherein R is alkyl or alkenyl of from about 10 to about 20 carbon atoms, x is 1 to 10, and !i is a water-soluble 30 can on such as anraonium, sodium, potassium and triethanolamine.
Another suitable class of anionic surfactants are the water-solubla salts of the organic, sulfuric acid reaction products of the general formula:
wherein R1 is chosen from the group consisting of a straight or branched chain, saturated aliphatic hydrocarbon radical having from about 8 to about 24, preferably about 12 to about 18, carbon atoms; and M is a can on. Additional examples of anionic synthetic surfactants which come within the terms of the present invention are the reaction products of fatty acids esterified with isethionic acid and neutralized with sodium hydroxide where, for example, the fatty acids are derived from coconut oil; sodium or potassium salts of fatty acid amides of methyl tauride in which the fatty acids, for example, are derived from coconut oil. Still other anionic synthetic surfactants include the class designated as succinamates, olefin sulfonates having about 12 to about 24 carbon atoms, and B-alkyloxy alkane sulfonates. Many additional nonsoap synthetic anionic surfactants ire described in pc~~+~heon's Detergents and Emulsifiers. 1984 Annual, published by Allured Publishing Corporation.
Also U.S. Patent 3,929,678, t.aughlin et al., issued December 30, 1975, discloses many other anionic as well as other surfactant types.
Nonionic surfactants useful herein are preferably used in combination with an anionic, amphoteric or zwitterionic surfactant. Thsse nonionic surfactants can be broadly defined as compounds produced by the condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which may-be aliphatic or alkyl aromatic in naturc.
Cationic surfactants useful in compositions of the present invention are disclosed in the following documents:
M.C. Publishing Co., ~rmtcheon's Detera~~ts 8 Emulsifiers, (North Averican edition 1979); SchwartZ. et al., Surface Active Agents, Their Chemistry and Technologic, New York: Interscisnce Publishers, 1949; U.S.
Patent 3,155,591, Hilfer, issued November 3, 1964; U.S. Patent 3,929,678, Laughlin, et al., issued December 30, 1975; U.S. Patent 3,959,461, Bailey, et al., issued May 25, 1976; and U.S. Patent 4,387,090, Bolich, Jr., issued June 7, 1983. If included in the compositions of the present invention, the cationic surfactant is present at from about 0.05X to about 5x.
Zwitterionic surfactants are exemplified by those which can be broadly described as derivatives of aliphatic quaternary ammonium, phosphonium, and sulfonium compounds, in which the aliphatic radicals can be straight or branched chain, and wherein one of the aliphatic substituents contains from about 8 to about 18 carbon atoms and one contains an anionic water-solubilizing group, e.g., carboxy, sulfonate, sulfate, phosphate, or phosphonate. Other zwitterionics such as betaines are also useful in the present invention. Examples of betaines include the high alkyl betaines, such as coco dimethyl carboxymethyl betaine, - lauryl dimethyl carboxymethyl betaine, lauryl dimethyl alpha carboxyethyl betaine, cetyi dimethyi carboxymethyl betaine, lauryl bis-(2-hydroxyethyl) carboxymethyl betaine, stearyl bis-(2 hydroxypropyl) carboxymethyl betaine, oleyl dimethyl~ gamna-carboxypropyl betaine, lauryl bis-(2-hydroxypropyl)alpha-carboxyethyl betaine, coco dimethyl sulfopropyl betaine, stearyl dimethyl sulfopropyl betaine, lauryl dimethyl sulfoethyl betaine, lauryl bis-(2-hydroxyethyl) sulfopropyl betaine, and amidobetaines and amidosulfobetaines (wherein the RCONH(CH2)3 radical is at-tached to the nitrogen atom of the betaine).
Examples of amphoteric surfactants which can be used in the 2S co~ositions of the present invention are those which are broadly described as derivatives of aliphatic secondary and tertiary amines in which the aliphatic radical can be straight or branched chain and wherein one of the aliphatic substituents contains from about 8 to about 18 carbon at~os and one contains an anionic water solubilizing group, e.g., carboxy, sulfonate, sulf~tl, phosphate, or phosphonate. Examples of compounds falling Within this defini-tion are sodium 3-dodecyl-aminopropionate, sodium 3-dodecylamino-propane sulfonate, N-alkyltaurines such as the one prepared by reacting dodecylamine with sodium isethionate according to the teaching of U.S. Patent 2,658,072, H-higher alkyl aspartic acids such as those produced according to the teaching of U.S. Patent 2,438,091, and the products sold under the trade name 'Miranol' and described in U.S. Patent 2,528,378.
Carboxviic Acid Cooolvmer Thickeners Another component useful in the compositions herein is a 5 carboxylic copolymer thickener. These crosslinked polymers contain one or more monomers derived from acrylic acid, substituted acrylic acids, and salts and esters of these acrylic acids and the substituted acrylic acids, wherein the crosslinking agent contains two or more carbon-carbon double bonds and is 10 derived from a polyhydric alcohol. The preferred polymers for use herein are of two general types. The first type of polymer is a crosslinked homopolymer of an acrylic acid monomer or derivative thereof (e.g., wherein the acrylic acid has substituents on the two and three carbon positions independently selected from the 15 group consisting of C1-4 alkyl, -CN, -COOH, and mixtures thereof).
The second type of polymer is a crosslinked copolymer having a first monomer selected from the group consisting of an acrylic acid monomer or derivative thereof (as just described in the previous sentence), a short chain alcohol (i.e. a C1-4) acrylate 20 ester monomer or derivative thereof (e. g., wherein the acrylic acid portion of the ester has substituents on the two and three carbon positions independently selected from the group consisting of CI_4 alkyl, -CH, ~CODE1, and mixtures thereof), and mixtures thereof; and a second monomer which is a long chain alcohol (i.e.
25 C8-40) acrylate ester monomer or derivative thereof (e. g., wherein the acrylic acid portion of the ester has substituents on the two and three carbon positions independently selected from the group consisting of CI_4 alkyl, -CN, -COOH, and a~ixtures thereof).
Coebinations of these two types of polymers are also useful 30 herein.
In the first type of crosslinked homopolyaiers the monomers are preferably selected from the group consisting of acrylic acid, methacrylic acid, ethacryitc acid, and mixtures thereof, with acrylic acid being most preferred. In the second type of 35 crosslinked copolymers the acrylic acid monomer or derivative thereof is preferably selected from the group consisting of acrylic acid, methacrylic acid, ethacrylic acid, and mixtures thereof, with acrylic acid, methacrylic acid, and mixtures thereof being most preferred. The short chain alcohol acrylate ester 5 monooier or derivative thereof is preferably selected from the group consisting of C1_4 alcohol acrylate esters, C1_4 alcohol methacrylate esters, C1_4 alcohol ethacrylate esters, and mixtures thereof, with the C1_4 alcohol acrylate esters, C1_4 alcohol methacrylate esters, and mixtures thereof, being most preferred.
10 The long chain alcohol acrylate ester monomer is selected from C8_40 alkyl acrylate esters, with C10-30 alkyl acryiate esters being preferred.
The crosslinking agent in both of these types of polymers is a polyalkenyl polyether of a polyhydric alcohol containing more 15 than one alkenyl ether group per molecule, wherein the parent polyhydric alcohol contains at least 3 carbon atoms and at least 3 hydroxyl groups. Preferred crosslinkers ire those selected from the group consisting of allyl ethers of sucrose and allyl ethers of pentaerythritol, and mixtures thereof. These polymers useful 20 in the present invention are more fully described in U.S. Patent No. 5,087,445, to Haffey et al., issued February 11, 1992; U.S.
Patent No. 4,509,949, to Huang et al., issued April 5, 1985; U.S.
Patent No. 2,798,053, to Broom, issued July 2, 1957; which are incorporated by reference herein. ~~, CTFA International 25 c~~~t;~ Ingredient Dictionary, fourth edition, 1991, pp. 12 and 80.
Exaa~les of coaoercially availble hompolymers of the first type useful herein include the carbomers, which are homopolymers of acrylic acid crosslinked with allyl ethers of sucrose or 30 pe~taerytritol. The carbomers are available as tha CarbopolR 900 series froa~ B.F. Goodrich. Examples of commercially available copolymers of the second type useful herein include copolymers of C10-30 alkyl acrylates with one or more uonomers of acrylic acid, methacrylic acid, or one of their short chain (i.e. C1_~ aicoholj 35 esters, wherein the crosslinking agent is an allyl ether of sucrose or pentaerytritol. These copolymers are known as acrylates/C10-30 alkyl acrylate crosspolymers and are commerically available as CarbopolR 1342, Pemulen"TR-1, and Pemolen TR-2, from B.F. Goodrich. In other words, examples of carboxylic acid polymer thickeners useful herein are those selected from the group consisting of carbomers, acrylates/C10-C30 alkyl acrylate crosspolymers, and mixtures thereof.
The compositions of the present can comprise from about 0.025x to about lx,~ more preferably from about 0.05X to about 10 0.75x and most preferably from about O.IOX to about 0.50X of the carboxylic acid polymer thickeners.
Emulsifiers The compositions herein can contain various emulsifiers.
These emulsifiers are useful for emulsifying the various carrier 15 components of the compositions herein, and are not required for solubiliiing or dispersing the copolymers of the ' present invention. Suitable emulsifiers can include any of a wide variety of nonionic, cationic, anionic, and zwitterionic emulsifiers disclosed in the prior patents and other references. _Sge 20 I~IcCutcheon's, Qetergents and EmuTsifier~, North American Edition (1986), published by Allured Publishing Corporation; U.S. Patent No. S,OlI,681 to Ciotti et al., issued April 30, 1991; U.S. Patent No. 4,421,769 to Dixon et al., issued December 20, 1983; and U.S.
Patent No. 3,755,560 to Dickert et al., issued August 28, 1973.
25 Suitable eawlsifier types include esters of glycerin, esters of propylene glycol, fatty acid esters of polyethylene glycol, fatty acid esters of polypropylene glycol, esters of sorbitol, esters of sorbitan anhydrides, carboxylic acid copolymers, esters and ethers of glucose, ethoxylated ethers, ethoxylated alcohols, 30 alkyl phosphates, polyoxyethylene fatty ether phosphates, fatty acid amides, acyl lactylates, soaps and mixtures thereof.
Suitable emulsifiers can include, but are not limited to, polyethylene glycol 20 sorbitan monolaurate (PolysorbateT" 20), polyethylene glycol 5 soya sterol, Steareth 20, CetearethTH20, PPG-2 methyl glucose ether distearate, CetethT~lO, Polysorbate 80, cetyl phosphate, potassium cetyl phosphate, diethanolamine cetyl phosphate, Polysorbate 60, glyceryl stearate, PEG-100 stearate.
and mixtures thereof.
The emulsifiers can be used individually or as a mixture of two or more and can compri se from about O.1X to about 10X, more preferably from about 1X to about 7X, and most preferably from about 1X to about 5X of the compositions of the present invention.
10 Emol 1 i en~,~
The compositions useful in the methods of the present invention can also optionally comprise at least one emollient.
Examples of suitable emollients include, but are not limited to, volatile and non-volatile silicone oils, highly branched 15 hydrocarbons, and non-polar carboxylic acid and alcohol esters, and mixtures thereof. Emollients useful in the instant invention are further described in U.S. Patent No. 4,919,934, to Oeckner.et al., issued April 24 1990.
The emollients can typically comprise in total from about 1X
20 to about 50X, preferably from about 1X to about 25X, and more preferably from about lx to about lOX by weight of the compositions useful in the present invention.
Additional Components A variety of additional components can be incorporated into 25 the compositions herein. Hon-limiting examples of these additional components include vitamins and derivatives thereof (e. g:, ascorbic acid, vitamin E, tocopheryl acetate, retinoic acid, retinol, retinoids, and the like); low pH thickening agents (e.g. polyacrylamide and C13-14 isoparaffin and laureth-7, 30 available as Sepigel~ from Seppic Corporation; polyquaternium and mineral oil, available as Salcare SC92, from Allied Colloids;
crosslinked methyl quaternized dimethylaminomethacrylate and mineral oil, available as Salcare SC95 from Allied Colloids;
resins; gums and thickeners such as xanthan gum, carboxymethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, alkyl-modified hydroxyalkyl celluloses (e. g. long chain alkyl modified hydroxyethyl celluloses such as cetyl hydroxyethylcellulose), and magnesium aluminum silicate; cationic polymers and thickeners (e. g., cationic guar gum derivatives such as guar hydroxypropyltrimonium chloride and hydroxypropyl guar hydroxypropyltrimonium chloride, available as the Jaguar C series from Rhone-Poulenc; polymers for aiding the film-forming properties and substantivity of the composition (such as a 10 copolymer of eicosene and vinyl pyrrolidone, an example of which is available from GAF Chemical Corporation as GanexR V-220);
suspending agents such as ethylene glycol distearate and the like;
preservatives for maintaining the antimicrobial integrity of the compositions; skin penetration aids such as OMSO, 15 1-dodecylatacycloheptan-2-one (available as Atone from the Upjohn Co.) and the like; antioxidants; chelators and sequestrants; and aesthetic components such as fragrances, colorings, essential oils, skin sensates, astringents, skin soothing agents, skin healing agents and the like, nonlimiting examples of these 20 aesthetic components include panthenot and derivatives (e. g. ethyl panthenol), pantothenic acid and its derivatives, clove oil, menthol, caa~phor, eucalyptus oil, eugenol, menthyl lactate, witch hazel distillate, allantoin, bisabalol, dipotassium glycyrrhizinat~ and the like.
25 Method of Usinci Hair and Skin Care Compositions The hair care and skin care compositions of the present invention are used in conventional ways to provide the desired benefit appropriate to the product such as hair styling, holding, cleansing, conditioning and the like for hair care compositions 30 and benefits such as moisturization, sun protection, anti-acne, anti-wrinkling, artificial tanning, analgesic, and other cosmetic and pharmaceutical benefits for skin cars compositions. Such methods of use depend upon the type of composition employed but generally involve application of an effective amount of the 35 product to the hair or skin, which may then be rinsed from the hair or skin (as in the case of shampoos and some conditioning products) or al 1 owed to remai n on the hai r ( as i n the case of spray, mousse, or gel products). or allowed to remain on the skin (as in the case of the skin care compositions). By "effective amount" is meant an amount sufficient to provide the benefit desired. Preferably, hair rinse, mousse, and gel products are applied to wet or damp hair prior to drying and styling of the hair. After such compositions are applied to the hair, the hair is dried and styled in the usual ways of the user. Hair sprays are typically applied to dry hair after it has already been dried and styled. Cosmetic and pharmaceutical topical skin care compositions are applied to and rubbed into the skin.
The following examples further illustrate preferred embodiments within the scope of the present invention. The examples are given solely for the purposes of illustration and are not to be construed as limitations of the present invention as many variations of the invention are possible without departing from its spirit and scope.
EXAMPLES
The following examples further describe and demonstrate embodiments within the scope of the present invention and the parent application. The examples are given solely for the purpose of illustration and are not to be construed as limitations of the present invention, as many variations thereof are possible without departing from the spirit and scope of the invention.
Ingredients are identified by chemical or CTFA name.
S~mthesis of Poly(2-ethyl-2-oxazoline) Alcohol To a solution of 50 g (0.5044 mol) of 2-ethyl-2-oxazoline in 50 mL of acetonitrile is added 0.92 g (0.0048 mol) of methyl-p-toluenesulfonate at 0°C under a nitrogen atmosphere. The reaction mixture is heated at 80°C for 20 hours and the resulting polymer solution is then refluxed with 2.3 mL distilled water in the presence of 5.6 g (0.0528 mol) of sodium carbonate for 24 hours. The solvents are removed under vacuum. The residue is extracted with 300 mL of dichloromethane for 24 hours, and the insolubles are removed by suction filtration. The dichloromethane is then evaporated to yield about 48 g {96x yield) of poly(2-ethyl-2-oxatoline) alcohol.
EXAMPLE II
Synthesis of Acrvlate-Canoed Polvl2-ethyl-2-oxazoline) Alcohol Macromonomer To a solution of 48 g of poly(2-ethyl-2-oxazoline) alcohol (from EXAMPLE I) and 1.0 g (0.01056 mol) of triethylamine in 80 mL
10 of dichloromethane is added dropwise a solution of 0.95 g (0.01056 mol) of acryloyl chloride at OoC under a nitrogen atmosphere. The reaction mixture is then stirred at room temeprature for 36 hrs, and the resulting solution is then suction filtered to remove the insolubles. The solvent and any unreacted triethylamine are 15 removed by evaporation under vacuum. The resulting solid is then redissolved in 200 ml of dichloromethane, filtered, and evaporated under vacuum to yield about 45.6 g (95X yield) of the macromonomer.
Using an analogous procedure the methacrylate and ethacrylate 20 endcapped macromonomers are prepared by replacing the acryloyl chloride with an equivalent molar amount of methacryloyl chloride and ethacryloyl chloride, respectively.
EXAlIPLE III
c~~th.~i5 of Yinvlbenzvl-Cacced Polv(2-ethyl-2-oxazolinel Alcohol 25 Macromonomer To a solution of 50 g (0.5044 mol) of 2-ethyl-2-oxazoline in 50 ml of acetonitrite is added a mixture of 0.3816 g (0.0025 mol) of meta and paravinylbenzylchlorides (available from Aldrich Chemical Co.), 0.562 g (0.0037 mol) of sodium iodide and 0.06 g 30 (0,00023 mot) of H,H'-Biphenyl-~-phenylenediamine. The solution .is then heated at 90oC for 16 hours. To the resulting reaction product is added 100 mL of dichloromethane and the solution is filtered and then precipitated in 800 ml of ether, The precipitate product is collected by vacuum filtration and dried under vacuum at ambient temperature to yield about 45 g (90X
yield) of the macromonomer.
EXAh1 P L E I Y
5 5vnthesis of Acrvlate-Canoed Polv(ethvlene glvcol)methvl ~Fther hlacromonomer To a solution of 50 g (0.01 mol) of polyethylene glycol)methyl ether having an average molecular weight of about 5000 (commercially available from Aldrich Chemical Co.) and 4.05 g 10 (0_04 mol) of triethylamine in 400 mL of dichloromethane is added dropwise at OoC under a nitrogen atmosphere a solution of 2.26 g (0.025 mol) of acryloyl chloride dissolved in 25 ml of dichloromethane. The reaction mixture is then stirred at room temeprature for 36 hrs, and the resulting solution is then suction 15 filtered to remove the insolubles. The solvent and any unreacted triethylamine are removed by evaporation under vacuum. The resulting solid is then redissolved in 300 mL of dichloromethane, filtered, and evaporated under vacuum to yield about 50 g (100X
yield) of the macromonomer.
20 The above procedure is varied using other polyethylene glycol)alkyl ethers (e. g. methyl, ethyl, 2-sthylhexyl, decyl, dodecyl, cetyl, stearyl, lauryl, and myristyl wherein the polymer has an average molecular weight varying from about 1000 to about 200,000) to obtain the analogous acrylate-capped ~acromonomers.
25 Additionally, the methacrylate and ethacrylate endcapped macromonoaiers are prepared by replacing the acryloyl chloride with an equivalent molar amount of methacryloyl chloride and ethacryloyl chloride, respectively.
Synthesis of Polv(n-butyl acrvlate)-ql~aft-oolv(2-ethyl-2-oxazo-line) Thermoplastic Elastomeric C~yolvmer To a solution of 16.0 g (0.1248 mol) of 0-butyl acrylate, and 4 g of acrylate capped poly(2-ethyl-2-oxazoline) macromonomer (from Example II) in 100 ml of acetone is added 0.03 g (0.00018 mol) of azoisobutyronitrile (AIBN) initiator. The resulting solution is refluxed slowly for about 20 hours. The reaction is then quenched by the addition of about 5 mL of methanol. The 5 solution is then poured into a Teflon' pan and the acetone is evaporated at room temperature under a fume hood. The resulting polymer film is redissovled in ethanol, filtered, and the ethanol is then evaporated to yield about 18.4 g of the thermoplastic elastomeric copolymer.
10 Alternatively, by varying the monomers and macromoners used, this procedure is used to prepare other copolymers of the present invention.
EXAMPLE VI
15 Synthesis of Polv(n-bud,vl-co-2-methoxvethvlacrvlatel-craft-oolv(2-~,~hvl 2 oxazolinel Thermoplastic Elastomeric CoXiolvmer~ Method I
To a solution of 4.5 g (0.035 mol) of ~-butyl acrylaEe, 2.5 g (0.0192 mol) of 2-methoxy ethylacrylate and 3 g poly(2-ethyl-2-oxazoline) macromonomer (from Example II) in 40 ml 20 of acetone is added 0.05 g of AI6N irritator. The resulting solution is refluxed slowly for about 20 hours. The reaction is then quenched by the addition of about 5 ml of methanol. The solution is then poured into a teflon pin and the acetone is evaporated at room temperature under a fume hood. The resulting 25 polymer film is redissovled in ethanol, filtered, and the ethanol is then evaporated to yield about 9.5 g of the thermoplastic elastomeric copolymer.
Alternatively, by~varying the nwnomers and macromoners used, this procedure is used to prepare other copolymers of the present 30 invention.
EXAMPLE VII
Svnthe~is of Polv(n-butyl- co-2-methoxvethvla crv~iatel-oraft -oolv(2-2thv1 2 oxazolinel plastic ElastomericCopolymer: thod Thermo Me II
To a 500 ml round-bottomed flask is added 20.8 g (0.1623 mol) of n-butyl acrylate, 11.2 g (0.0861 mol) of 2-methoxyethyl acrylate, 0.30 g (0.002 mol) ~-vinylbenzyl chloride, and 0.02 g (0.0012 mol) of azoisobutyronitrile (AIBN) irritator, in 200 ml of acetone. The resulting solution is refluxed slowly for about 24 hours. The reaction is then quenched by the addition of about 5 ml of methanol and cooled to room temperature. The solvents are removed by rotary evaporation and the resulting polymer is dissolved in 250 mL of dry acetonitrile. Next 20.0 g (0.2018 mol) 0,.- 2-ethyl-2-oxazoline and 0.44 g (0.0029 mol) of sodium iodide is added and the solution is heated to 90oC for 20 hours. The . resulting solution is filtered and the solvent is evaporated to yield about 45.0 g (86X yield) of the thermoplastic elastomeric copolymer.
Alternatively, by varying the monomers used, this procedure is used to prepare other copolymers of the present invention.
EXAMPLE VIII
Synthesis of Polvln-butyl co 2 ldimethvlaminoiethvl metharrvlatel craft-oolvl2-ethyl-2-oxazolinel Thermoplastic Elast merit To a solution of 7.Z g (0.0561 mol) of 0-butyl acrylate, 4.8 g (0.0305 mol) of 2-(dimethylamino)ethyl methacrylate, and 8.0 g poly(2-ethyl-2-oxazoline) macromonomer (from Example II) in 80 ml of acetont is added 0.01 g of AIBN irritator. The resulting solution is refluxed slowly for about 24 hours. The reaction is then quenched by the addition of about 5 mL of methanol. The solution is then poured into a teflon pan snd the acetone is evaporated at room temperature under a fume hood. The resulting polymer film is redissovled in ethanol, filtered, and the ethanol is then evaporated to yield about 18.4 g of the thermoplastic elastomeric copolymer.
Alternatively, by varying the monomers and macromoners used, this procedure is used to prepare other copolymers of the present invention.
EXAMPLE IX
~ nthesis of Methyl Quaternized Polv(n-butyl-co-2-(dimethvlaminol-~~vl methacrvlatelaraft-y~olv(2-ethyl-2-oxazoline) Thermoplastic Flash Copolymer 5 To l0 grams of the copolymer from EXAMPLE VIII dissovled in 80 grmas of ethanol is added dropwise 4.32 g (0.0281 mole) of dimethylsulfate. The resulting solution is stirred for 2 hours at room temperature. The solvent is removed by rotary evorpation to yield about 10 grams of the methyl quaterniied copolymer.
Hai r~Sora_v Hair spray compositions are prepared from the following components utilising conventional mixing techniques.
15 Ingredients ~.9nc x 9 ~ ~ Q
water QS 100 QS 100 QS 100 QS 100 Ethanol (SOA 40) 79.0 79.0 79.0 90.0 Copolymer of Example VI1 4.0 4.0 3.0 3.0 20 Fragrance 0.1 0.2 --- ---These products ire prepared by first dissolving the polymer in the ethanol with stirring. The water and fragrance are then added with stirring. The resulting hsir spray compositions can 25 then be packaged .in a nonaerosol spray pump. Alternatively, the compositions can be combined with conventional propellants and packaged in an aerosol spray.
These hair sprays are useful for application to the hair to provide a styling and holding benefit.
1 Alternatively, spray compositions are prepared using the copolymers of Examples V and VIII.
geduced Volatile Organic Content Hairsorav Hair spray compositions are prepared from the following components utilizing conventional mixing techniQues.
Ingredients V~gight x Q
Water QS 100 QS 100 QS 100- QS 100 Ethanol (SDA 40) 54.0 54.0 54.0 54.0 Copolymer of Example VI1 4.0 3.0 4.0 3.0 Fragrance 0.05 O.Z --- ---These products are prepared by first dissolving the polymer in the ethanol with stirring. The water and fragrance are then added with stirring. The resulting hair spray compositions can 15 then be packaged in a nonaerosol spray pump. Alternatively, the compositions can be combined with conventional propellants and packaged in an aerosol spray.
These hair sprays are useful for application to the hair to provide a styling and holding benefit.
1 Alternatively, spray compositions are prepared using the copolymers of Examples V and VIII.
~XA~tPLE
~usse XII
Mousse compositions are prepared from the following coa~ohents utilizing convent ional mixingtechniques.
t Weight x s A
Ingredien Water QS 100 QS 100 QS 100 Copolymer of Example VIII1 3.00 2.50 3.50 Lauramide DEA 0.33 0.33 0.33 SodiuA Methyl Oleyl Taurate I.67 1.67 1.67 DMOM Hydantoin 0.78 0.78 0.78 pisodium DTA 0.20 0.20 0.20 Polyoxyalkylated isostearyl Alcohol2 0.10 0.10 0.10 Fragrance 0.10 0.10 0.10 Propellant3 7.0 7.0 7.0 These products are prepared by first dissolving the polymer in water with stirring. The remaining ingredients, except the propellant, are' then added with stirring.
The resulting mousse concentrate can then be combined with 10 conventional propellants (e.g., Propellant A46) and packaged in an aerosol spray.
These mousses are useful for application to the hair to provide a styling and holding benefit.
15 1 Alternatively, mousse compositions are prepared using the copolymers of Examples V and and VI.
2Available as Aerosurf~" 66-E10:
3Available as a mixture of 82.46x isobutane, I6.57X propane, and O.OOIX butane.
Hair Tonic Hair ionic compositions are prepared from the following 25 components utilizing conventional mixing techniques.
Ingredients weight ~
Ethanol (SOA 40) QS 100 QS 100 QS 100 Copolymer of Example UI1 0.75 1.00 1.25 30 Fragrance 0.10 0.20 0.30 These products are prepared by dissolving the polymer in the ethanol with stirring and then adding the fragrance and any colors.
These hair tonics are useful for application to the hair to provide a styling and holding benefit.
1 Alternatively, tonic compositions are prepared using the copolymers of Examples Y and VIII.
EXAMPLE XIY
Hair Conditioner A hair conditioner composition is prepared from the following components utilizing conventional mixing techniques.
Ingredient Weight x Stvlina Agent Premix Copolymer of Example IX 1.00 Silicone Premix Silicone gum, GE SE761 0.30 Octamethyl cyclotetrasiloxane 1.70 Main MixMix water QS100 Cetyl Alcohol 1.00 Quaternium 182 0.85 Stearyl Alcohol 0.70 Hydroxethyl cellulose 0.50 Ceteareth-20 0.35 Fragrance 0.20 Dimethicone copolyol 0.20 Citric Acid 0.13 Methylchloroisothiazolinone (and) ~thylisothiazolinone 0.04 Sodium Chloride 0.01 The product is prepared by co~aixing all the Main Mix ingredients, heating to about 60oC with mixing, and colloid milling while cooling to about 45oC. At this temperature, the two premixes are add separately with moderate agitation and the resultant conditioner is allowed to cool to room temperature.
This product is useful as a rinse off hair conditioner.
5 1 Commercially available from General Electric.
2 Dimethyl Di(Hydrogenated Tallow) Ammonium Chloride EXAMP! E XV
Shampoo Composition 10 A shampoo composition is prepared from the following components utilising conventional mixing techniques.
Ingredients Weight x ~tvlina Agent 15 copolymer from Example IX 1.00 Premi xx Silicone gum 0.50 Dimethicone, 350 cs fluid 0.50 Main Mix water OS100 Artmoniua~ lauryl sulfate 11.00 Cocamide MEA 2.00 25 Ethylene glycol distearate 1.00 Xanthan Guar 1.20 Methy-lchloroisothiaZOlinone (and) methylisothiatolinone 0.0~
Citric Acid to pH 4.5 as needed The Main Mix is prepared by first dissolving the xanthan gum in the water with conventional mixing. The remaining Main Mix ingredients are added and the Main Mix is heated to 150oF with agitation for 1/2 hour. The Styling Agent and the Premix are then 35 added sequentially with about 10 minutes of agitation between additions, and the entire mixture isstirred while the batch is cooled to room temperature. For varied particile size, the Styling AGent and Premix can be added at different times using either or both high shear mixing (high speed dispersator) or 5 normal agitation.
This shampoos is useful for cleansing the hear and for providing a styling benefit.
Example XYI
10 Anti-Acne Ccomposition An anti-acne composition is made by combining the following components using conventional mixing technology.
15 Ingredient Neiaht x hater QS100 5aiicylic Acid 2.0 Copolymer from Example VI1 2.0 Ethanol (SOA 40) 40.0 The compositon display skin penetration of the salicylic acid as well as improved skin reel and residue characteristics and is useful for the treatment of acne.
25 1 Alternatively, the anti-acne compositions are prepared using the copolymers of Examples VIII and IX.
Example XVII
Topical Anal esic Composition A topical analgesic composition is made by combining the following ingredients utilizing conventional mixing techniques.
j,naredient W, eight x Hater, Purified QS100 Ibuprofen Z.0 Copolymer from Example YII 2.0 Ethanol (SDA 40) 20.0 IO
The compositions display skin penetration of the ibuprofen active as well as improved skin feel and residue characteristics together with excellent moisturizing, emolliency, rub-in and absorption characteristics.
I Alternatively, the topical analagesic compositions are prepared using the copolymers of Examples VIII and IX.
I~camule XYIII
20 c~~nless Tannins Composition A composition for sunless tanning is made by combining the following ingredients utilizing conventional a~ixing techniques.
Pha-hater qs 100 Copolymer from Example YI1 2.00 Carbomer 9342 0.20 30 Carbomer 9803 0.15 Acrylic Acid Copolymer4 0.15 Phase B
PPG-20 Methyl Glucose Ether 35 Distearate 2.00 Tocopheryl Acetate 1.20 Mineral Oil 2.00 Stearyl Alcohol 1.00 Shea Butter 1.00 5 Cetyl Alcohol 1.00 Ceteareth-20 2.50 Ceteth-2 1.00 Ceteth-10 1.00 10 ph DEA-Cetyl Phosphate 0.75 Phase D
Dihydroxyacetone 3.00 Phase E
8utylene Glycol Z.00 OMOh Hydantoin (and) Iodopropynyl Butylcarbamate 0.25 Phase F
Fragrance 1.00 Cyclomethicone 2.00 25 In a suitable vessel the Phase A ingredients are dispersed in the water and heated to 75-85oC. In a separate vessel the Phase B
ingredients are combined and heated to 85-90oC until melted.
Next, the DEA-Cetyl Phosphate is added to the liquid Phase B and stirred until dissolved. This mixture is then added to Phase A to 30 form the emulsion. The emulsion is cooled to 40-45oC with continued mixing. Next, in a separate vessel, the dihydroxyacetone is dissolved in water and the resulting solution is mixed into the emulsion. In another vessel, the Phase E
ingredients are heated with mixing to 40-45oC until a clear 35 solution is formed and this solution is then added to the emulsion. Finally, the Phase F ingredients are added to the emulsion with mixing, which is then cooled to 30-35oC, and then to room temperature.
Thi s emul sion i s useful for topical appl ication to the skin 5 to provide an artificial tan.
1 Alternatively, the artificial tanning compositions are prepared using the copolymers of Examples VIII and IX.
2 Available as CarbopolR 934 from B.F. Goodrich.
10 3 Available as CarbopolR 980 from B.F. Goodrich.
4 Available as Pemulen TR1 from B.F. Goodrich.
EXAMPLE XIX
15 Sunscreen Com~iosition An oil-in-water emulsion is prepared by combining the following components utilizing conventional mixing techniques.
Ingredients - W_e_i hq t x ZO Phase A
Water QS100 Carbomer 9541 0.24 Carba~er 13422 0.16 Copolymer from Exmaple VII3 1.75 25 Disodium EDTA 0.05 Phase 8 Isoarachidyl Neopentanoate4 2.00 PVP Eicosene Copoiymer5 Z.00 30 Octyl Methoxycinnaa~ate 7.50 Octocryl ere 4 . 00 Oxybenzone 1.00 Titanium Dioxide 2.00 Cetyl Palmitate 0.75 35 Stearoxytrimethylsilane (and) Stearyl Alcohol6 0.5'0 Glyceryl Tribehenate7 0.75 Dimethicone 1:00 Tocopheryl Acetate 0.10 DEA-Cetyl Phosphate 0.20 Phase C
Water 2.00 Triethanolamine 99x 0.60 phase D
Water 2.00 Butylene Glycol 2.00 DMDM Hydantoin (and) 15 Iodopropynyl Butylcarbamate8 0.25 dl Panthenol 1.00 Ph Cyclomethicone 1.00 I Available as CarbopolR 954 from B.F. Goodrich.
2 Available as CarbopolR I342 from B.F. Goodrich.
3 Alternatively, the sunscreen compositions are prepared using the copolymers of Examples VIII and IX.
25 4 Available as Elefac~I-205 from 8ernel Chemical.
5 Available as GaneX Y-220 frog GAF Corporation.
6 Available as DC 580 Wax from Dow Corning.
7 Available as SynchrowaX NRC from Croda.
8 Available as GlydantT~Plus from LonZa.
In a suitable vessel tha Phase A ingredients are dispersed in the water and heated to 75-85oC. In a separate vessel the Phase B
ingredients (except OEA-Cetyl Phosphate) are combined and heated to 85-90oC until melted. Next, the DEA-Cetyl Phosphate is added to the liquid Phase B and stirred until dissolved. This mixture is then added to Phase A to form the emulsion. The Phase C
ingredients are combined until dissolved and then added to the emulsion. The emulsion is then cooled to 40-45oC with continued mixing. In another vessel, the Phase 0 ingredients are heated 5 with mixing to 40-45oC until a clear solution is formed and this solution is then added to the emulsion. Finally, the emulsion is cooled to 35oC and the Phase E ingredient is added and mixed.
This emulsion is useful for topical application to the skin to provide protection from the harmful effects of ultraviolet 10 radiation.
EXAMPLE XX
Facial Moisturizer A leave-on facial emulsion composition containing a cationic 15 hydrophobic surfactant is prepared by combining the following components utilizing conventional mixing techniques.
Ingredient l~gi~ t x Mater QS100 ZO Copolymer from Example VI1 1.00 Glycerin 3.00 Cetyl Palmitate 3.00 Cetyl Alcohol 1.26 Quaternium22 1.00 25 Glyceryl Monohydroxy Stearate 0.74 Dimethicons 0.60 Stearic Acid 0.55 Octyldodecyl hyristate 0.30 Potassium Hydroxide 0.20 30 Carbomer 1342 0.125 Tetrasodius EDTA 0.10 OMDM Hydantoin and Iodopropynyl Butyl Carbamate 0.10 Carboaier 951 0.075 This emulsion is useful for application to the skin as a moisturizer.
Alternatively, the moisturizers are prepared using the copolymers of Examples VIII and IX.
In a suitable vessel tha Phase A ingredients are dispersed in the water and heated to 75-85oC. In a separate vessel the Phase B
ingredients (except OEA-Cetyl Phosphate) are combined and heated to 85-90oC until melted. Next, the DEA-Cetyl Phosphate is added to the liquid Phase B and stirred until dissolved. This mixture is then added to Phase A to form the emulsion. The Phase C
ingredients are combined until dissolved and then added to the emulsion. The emulsion is then cooled to 40-45oC with continued mixing. In another vessel, the Phase 0 ingredients are heated 5 with mixing to 40-45oC until a clear solution is formed and this solution is then added to the emulsion. Finally, the emulsion is cooled to 35oC and the Phase E ingredient is added and mixed.
This emulsion is useful for topical application to the skin to provide protection from the harmful effects of ultraviolet 10 radiation.
EXAMPLE XX
Facial Moisturizer A leave-on facial emulsion composition containing a cationic 15 hydrophobic surfactant is prepared by combining the following components utilizing conventional mixing techniques.
Ingredient l~gi~ t x Mater QS100 ZO Copolymer from Example VI1 1.00 Glycerin 3.00 Cetyl Palmitate 3.00 Cetyl Alcohol 1.26 Quaternium22 1.00 25 Glyceryl Monohydroxy Stearate 0.74 Dimethicons 0.60 Stearic Acid 0.55 Octyldodecyl hyristate 0.30 Potassium Hydroxide 0.20 30 Carbomer 1342 0.125 Tetrasodius EDTA 0.10 OMDM Hydantoin and Iodopropynyl Butyl Carbamate 0.10 Carboaier 951 0.075 This emulsion is useful for application to the skin as a moisturizer.
Alternatively, the moisturizers are prepared using the copolymers of Examples VIII and IX.
Claims (4)
1. A water or alcohol soluble or dispersible thermoplastic elastomeric copolymer having a backbone and one or more polymeric side chains, said copolymer formed from the copolymerization of randomly repeating A and B units and corresponding to the formula [A]a [B]b wherein (i) A is at least one polymerizable monomer unit corresponding to the formula wherein X is selected from the group consisting of -OH, -OM, -OR4, -NH2, -NHR4, and -N(R4)2; M is a cation selected from the group consisting of Na+, K+, Mg++, Ca++, Zn++, NH4+, alkylammonium, dialkylammonium, trialkylammonium, and tetraalkylammonium; each R4 is selected from the group consisting of H, C1-C8 straight or branched chain alkyl, and N,N,-dimethylaminoethyl, 2-hydroxyethyl,
2-methoxyethyl, 2-ethoxyethyl; and R5 and R6 are independently selected from the group consisting of H, C1-C8 straight or branched chain alkyl, methoxy, ethoxy, and 2-hydroxyethoxy, 2-methoxyethyl, 2-ethoxyethyl;
(ii) B is at least one hydrophilic macromonomer unit copolymerizable with A corresponding to the formula wherein R and R' are independently selected from the group consisting of H and C1-C8 straight or branched chain alkyl;
and m is an integer from about 10 to about 2000; and (iii) a is an integer of about 100 or greater and b is an integer of about 2 or greater: and wherein said copolymer has a weight average molecular weight greater than about 10,000, and wherein said copolymer exhibits two distinct Tg values, said first Tg corresponding to said backbone and having a value less than about 0°C, and said second Tg corresponding to said side chains and having a value greater than about 25°C.
2. A copolymer according to Claim 1 wherein said A monomer units are selected from the group consisting on n-butyl acrylate, 2-ethylhexyl acrylate, N-octyl acrylamide, 2-methoxyethyl acrylate, 2-hydroxyethyl acrylate, N,N-dimethylaminoethyl acrylate, and mixtures thereof: R is selected from the group consisting of H and methyl, R' is ethyl, m is an integer from about 10 to about 2000, a is an integer from about 100 to about 3000, and b is an integer from about 2 to about 50.
(ii) B is at least one hydrophilic macromonomer unit copolymerizable with A corresponding to the formula wherein R and R' are independently selected from the group consisting of H and C1-C8 straight or branched chain alkyl;
and m is an integer from about 10 to about 2000; and (iii) a is an integer of about 100 or greater and b is an integer of about 2 or greater: and wherein said copolymer has a weight average molecular weight greater than about 10,000, and wherein said copolymer exhibits two distinct Tg values, said first Tg corresponding to said backbone and having a value less than about 0°C, and said second Tg corresponding to said side chains and having a value greater than about 25°C.
2. A copolymer according to Claim 1 wherein said A monomer units are selected from the group consisting on n-butyl acrylate, 2-ethylhexyl acrylate, N-octyl acrylamide, 2-methoxyethyl acrylate, 2-hydroxyethyl acrylate, N,N-dimethylaminoethyl acrylate, and mixtures thereof: R is selected from the group consisting of H and methyl, R' is ethyl, m is an integer from about 10 to about 2000, a is an integer from about 100 to about 3000, and b is an integer from about 2 to about 50.
3. A hair care composition useful for styling hair, comprising the copolymer of Claim 1 and a carrier suitable for application to the hair.
4. A composition for topical application to the skin comprising the copolymer of Claim 1 and a carrier suitable for application to the skin.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US8660593A | 1993-07-01 | 1993-07-01 | |
| US086,605 | 1993-07-01 | ||
| US25796294A | 1994-06-16 | 1994-06-16 | |
| US257,962 | 1994-06-16 | ||
| CA002165767A CA2165767A1 (en) | 1993-07-01 | 1994-06-30 | Thermoplastic elastomeric copolymers and hair and skin care compositions containing the same |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002165767A Division CA2165767A1 (en) | 1993-07-01 | 1994-06-30 | Thermoplastic elastomeric copolymers and hair and skin care compositions containing the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2319800A1 true CA2319800A1 (en) | 1995-01-12 |
Family
ID=27170110
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002319800A Abandoned CA2319800A1 (en) | 1993-07-01 | 1994-06-30 | Thermoplastic elastomeric copolymers and hair and skin care compositions containing the same |
| CA002319799A Abandoned CA2319799A1 (en) | 1993-07-01 | 1994-06-30 | Thermoplastic elastomeric copolymers and hair and skin care compositions containing the same |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002319799A Abandoned CA2319799A1 (en) | 1993-07-01 | 1994-06-30 | Thermoplastic elastomeric copolymers and hair and skin care compositions containing the same |
Country Status (1)
| Country | Link |
|---|---|
| CA (2) | CA2319800A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111991244A (en) * | 2020-09-07 | 2020-11-27 | 广州市白云区金利工艺用品厂 | Spray-foaming adhesive cement containing modified organic silicon and preparation method thereof |
-
1994
- 1994-06-30 CA CA002319800A patent/CA2319800A1/en not_active Abandoned
- 1994-06-30 CA CA002319799A patent/CA2319799A1/en not_active Abandoned
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111991244A (en) * | 2020-09-07 | 2020-11-27 | 广州市白云区金利工艺用品厂 | Spray-foaming adhesive cement containing modified organic silicon and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CA2319799A1 (en) | 1995-01-12 |
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