Cosmetic Colorant Compositions

Europaisches Patentamt European Patent Office © Publication number: 0 238 225 Office europeen des brevets A2

@ Date of filing: 26.02.87

® Priority: 18.03.86 US 840917 © Applicant: MINNESOTA MINING AND MANUFACTURING COMPANY © Date of publication of application: 3M Center, P.O. Box 33427 23.09.87 Bulletin 87/39 St Paul, Minnesota 55133-3427(US)

© Cosmetic compositions are provided which have modifiable color characteristics. A single composition may be applied, and with the application of pressure, the color of the composition may be changed. The composition contains a first pigment and microcapsules containing a second pigment. Upon rupture of the microcapsules, the coloration of the second pigment is added to the composition, altering its color characteristics.

CM < Lf) CM CM 00 CO CM

Xerox Copy Centre 1 0 238 225 2

COSMETIC COLORANT COMPOSITONS

ents 3,016,308 and 3,516,941. These patents dis- BACKGROUND OF THE INVENTION close in situ polymerization reactions in which a hydrophobic oil phase is dispersed in an aqueous 1. Field of the Invention phase containing resin precursors, particularly 5 aminoplast resin precursors (to form urea/aldehyde The present invention relates to compositions resins and the like). High shear agitation is used to useful in the application of colored cosmetics to the keep the capsule size small. Addition of an acid human body. catalyst initiates the polycondensation of the aminoplast precursors, resulting in the deposition 10 of the aminoplast resin about the dispersed 2. Background of the Art droplets of the oil phase. This produces the microcapsules. The application of decorative or masking colors Other polycondensations encapsulation tech- to the skin of humans and particularly to the face of niques are shown in U.S. Patents 3,429,827 and humans is a highly specialized technical area. 75 4,000,087. These particular techniques are more Compositions vary greatly depending upon the limited in the classes of hydrophobic inner phases specific location to which the color is to be applied. acceptable in the microcapsules because of reac- The compositions used to apply color to the lips - tion with the oil soluble monomer or poor solubility (e.g., lipstick or lip balm) require water repeliancy of the monomer in the desired hydrophobic phase. because of their repeated contact with liquids. Mas- 20 U.S. Patent 3,930,101 teaches that, to be re- cara must have very high color density and strong tained in the hydrophobic phase during high shear bonding ability to eyelashes. Rouge, blusher and dispersion of a fluid particulate dispersion, it is pancake must be very fine and easily spreadabie. necessary that the particculate be preferentially Eye shadow must also be fine and spreadabie, yet wetted by the hyrophobic phase. It is suggested to should not break down during mild abrasion as is 25 use suitable surfactants which adsorb to the par- encountered with repeated blinking and movement ticulate surface as a way to achieve the desired of eyelids. There are aiso bases and foundations preferential wetting. It has, however, been recog- for colors which require specific properties to en- nized that, in the in situ polymerization of able them to perform their unique function. aminoplast resins method for encapsulation, the In recent years, styles have become more dra- so presence of surfactants interferes with the deposi- matic, allowing the use of more color and even tion of the aminoplast resin at the hydrophobic multiple colors in the applications of makeup. For phase/water phase interface, giving poorly formed example, one portion of an eyelid may be pink and or leaky capsules. Similarly, oil soluble suspending another portion blue. The change in colors can be agents could alter the wetting of many particulates. used not only for the multicolor appearance, but 35 Since many of these materials contain carboxylate the change can give an appearance of eyes being groups, exposure to highly acidic medias often farther apart or closer together then they actually converts them to carboxylic acid groups altering are. Such make-over techniques are highly valued their adsorbability to the particulates. by the cosmetician and makeup artist. U.S. Patent 4,307,169 teaches the inclusion of There are some problems involved in blending 40 magnetic materials into a pressure fixable core colors, however. Even though separate color sour- material within a shell formed by interfacial poly- ces and separate brushes may be used to apply condensation. the individual colors, the later applied colors will U.S. Patent 3,954,666 teaches the preparation always contact the first applied colors. The brushes of semipermeable microcapsules containing cata- will then pick up colorant from the skin and trans- 45 lysts and ferromagnetic materials. port it back to the colour source. The brushes U.S. Patent 4,450,221 teaches magnetic toners themselves will also retain mixtures of colors, ren- comprising lyophilic magnetic particles and a resin dering them less useful. The intermixing of colors surrounded by a resin wall to form microcapsules. in the original source will of course diminish the Colorants such as pigments of dyes may be in- quality of the colorant. 50 eluded in the wall forming resin or the toner. The It is fairly common to find encapsulated liquid magnetic particles are rendered lyophilic by treat- materials in the marketplace. Technology has been ment with a titanate or silane coupling agent The available for many years to effectively provide microcapsules with liquid oleophilic ingredients. Representative processes are shown in U.S. Pat-

> 3 0 238 225 4

coupling agent is said to uniformly disperse the Pigments of various types, when dispersed in particles in the binder resin and firmly bond the water insoluble oils, and then mixed or dispersed magnetic particle to the resin. under high shear into water phases to produce oil in water dispersions, will show a variety of be- s haviors depending upon the surface characteristics BRIEF DESCRIPTION OF THE INVENTION of the pigment particles relative to the oil and water phases. In particular, pigment particles which are Conventional cosmetic formulations, with or wetted by the water phase and incompletely or without a predominant coloration in the composi- poorly wetted by the oil phase, will readily move tion, can be rendered colored, can be highlighted, 10 from the oil phase to the water phase during this or can be altered in color by the application of dispersion process. Attempts to encapsulate such a pressure to the composition after or during applica- pigment will generally be unsuccessful and lead to tion. The presence within the composition of fran- a capsule containing few, if any, pigment particles. gible microcapsules containing pigment enables Pigment particles which are completely wetted by this coloring phenomenon to occur. 75 the water phase will tend to remain in the interior of Color adjustable cosmetic composition com- the oil phase droplets during the dispersion pro- prise a first colorant, a binder, and a frangible cess. Pigment particles of this type will generally microcapsule comprising a shell , an encapsulate result in microcapsules having the pigment par- liquid and a second colorant which differs in color ticles in the oil core of the microcapsule with rela- from said first colorant. 20 tively few particles being abstracted from the oil phase or caught or immobilized in the microcapsule shell wall. Finally, pigment particles which are DETAILED DESCRIPTION OF THE INVENTION incompletely wetted by either the oil phase or by the water phase will be found concentrated at the The present invention relates to cosmetic for- 25 oil/water interface during such a dispersion pro- mulations, with or without a predominant coloration cess. Microcapsules formed from this type of pig- in the compositions, which by the application of ment will give capsules having the pigment par- differential pressure over the surface of the com- ticles more or less in the shell wall of the micro- position, during or after application, can be ren- capsule. The ability to alter the surface characteris- dered colored, can be highlighted, or can be al- 30 tics and more particularly the wetting characteris- tered in its predominant color. Conventional cos- tics of pigment particles relative to the chosen oil metic color compositions such as eye shadow, and water phase compositions provides the means lipstick, pancake, face powder, lip balm, cream to control the encapsulatability of pigment disper- rouge, mask powder, suntan lotion, and the like are sions and the means to control the ultimate location used as the basic compositions of the invention. To 35 of the majority of the pigment particles within the these basic compositions are added microcapsules microcapsule (i.e., either freely dispersed in the containing pigments of colors (including sparkling core oil phase or fixed at or within the micro- pigments) which may be different from the color in capsule shell wall). Useful products can be made the original composition. After application of the from microcapsules containing pigments of either composition, further light rubbing (as with a finger) 40 the two types. will rupture the microcapsules, highlighting or It is part of this invention that the second changing the color in the area where the composi- colorant be associated with the microcapsules. This tion was rubbed by exposing the encapsulated means that the second colorant should be on the pigment within the composition. shell, in the shell, or within the shell of the micro- In accordance with the present invention, 45 capsule. The more of the second pigment that is microcapsules are prepared by in situ such as within the shell, the greater will be the degree aminoplast polymerization. The techniques dis- change in the overall coloration of the product upon closed, generally referred to as an in situ poly- rupture of the shells. That is because any second merization reaction, yield, for example, an pigment (colorant) on the exterior of the shell will aminoplast resin capsule wall material. In the pro- so contribute to the overall color of the composition cess, a hydrophobic oil phase is dispersed in an before rupture of the microcapsules. It is therefore aqueous phase containing the aminoplast resin pre- preferred that said second colorant is predomi- cursors by applying high shear agitation. Addition nantly encapsulated by the shell. This means that of an acid catalyst initiates the polycondensation of at least 50% by weight of said second colorant is the aminoplast precursors, resulting in the deposi- 55 within the shell. Amounts as small as 25% by tion of the aminoplast resin about the dispersed weight of said second colorant within the capsules droplets of the oil phase, producing the micro- (in the shell wall and inside the shell itself) can capsules. significantly alter the color or tone of the composi-

3 5 0 238 225 6 tion on being ruptured. It is preferred that at least 2. Addition of the coupling agent directly to 50% by weight of all second colorant be inside the the oil phase of the pigment dispersion. shell (on the wall, or in the liquid carrying medium, 3. Having the coupling agent present in the or in the wall). More preferably at least 70% is water phase at the time of dispersing of the inside the shell, and most preferably more than 5 oil/pigment dispersion. 90% of said second colorant is inside the shell. The first process is the most universally useful The preferred method of forming capsules for as the pretreatments are usually accomplished by use in the present invention is a process whereby exposure of the pigments to solutions of the cou- the surface of non-magnetic colorant particulates, pling agents. Selection of solvents according to the by the addition of surface adsorbabfe agents, are 10 nature of the coupling agent is more readily ac- rendered oleophilic and can maintain their complished. For example, the preferred solvent, oleophilicity in water (at pH's encountered in en- and sometimes the required solvent, for use with capsulation processes). This may mean pH's of 10 many of the siiane coupling agents is water. In or more for some interfacial encapsulation pro- other cases, the solubility of a chosen coupling cesses or pH 4-1.8 for in-situ aminoplast encapsula- is agent in the desired oil phase for encapsulation tion. The additive must remain on the surface of may not be satisfactory for effective pigment treat- the particle for a period of at least five minutes at a ment, or it may be undesirable to have free cou- pH representative of the extreme pH to be encoun- pling agent present in the oil phase of the encap- tered in the encapsulation process under the fol- sulated pigment dispersion. Treatment of the pig- lowing conditions: 20 ment in solutions of 0.05% to 10% of the coupling 1. The oil phase used as the interior phase of agent will usually produce acceptable results, with the capsule (e.g., diethyl phthalate) is placed in the 0.25% to 2.0% being most desirable. same flask with the pigment. The pigment is either The second method is restricted to coupling pretreated with the additive or the pigment is treat- agents of the two classes that have solubility in the ed in-situ by incorporation of additive into the oil 25 oil phase composition to be used in the micro- phase. capsule. Usually an excess of the coupling agent 2. One part of the oil phase dispersion to ten over that necessary for the surface treatment of the parts of an aqueous phase at the required pH are pigment will be used. This will result in some combined in a flask. residual soluble coupling agent present in the 3. The combination in the flask is shaken 30 oil/pigment dispersion. The addition of .05% to 5% vigorously for at least five (and preferably ten) by weight of the particulate will usually produce minutes. The phases are microscopically examined acceptable results. to determine the location of the pigment. If at least The third method is restricted to those coupling 20%, preferably no more than at least 10%, and no agents which are soluble in water. It is most useful more than at least 5% of the pigment is in the 35 with pigments which are wettable by water. Addi- water phase (unassociated with oil phase), the ad- tions of 0.05% to 10% of the coupling agent by ditive has failed. This test procedure defines the weight of the particulate will usually produce ac- functional ability of an oleophilic additive according ceptable results, with 0.25% to 2.0% being the to the present invention. Any material that passes most desired range. this test (no more than 20% in the water phase) is 40 Pigments as used in the present invention refer referred to as a functional oleophilic additive. exclusively to solid materials. Dyes or pigments It has been found that two main classes of carried in solid polymeric or waxy phases can pigment surface modifying agents are particularly constitute pigments in the present invention, but useful for controlling the wetting characteristics of a dyes dissolved in liquid media are not solids and variety of pigment types. These materials are usu- 45 therefore not within the definition of pigments. ally described as titanate or silan coupling agents. Chemisorption of the additives to the par- Judicious selection of the coupling agents from ticulates is preferred, but not essential. Adsorption these classes allows the control of the en- of the additives to the particulates (e.g., pigments) capsulatability and particulate location of a variety by Van der Waals forces, dipole-dipole attraction, of pigment types, associated with a variety of dif- so or hydrogen bonding are also useful. Chemisorp- ferent oil phase compositions. Three methods for tion requires an actual chemical bond to be formed the use of these surface modifying agents are between a part of the additive and the particulate possible depending upon the specific agent chosen surface. The pigments for which this process is and on other restrictions dictated by the micro- most useful are those which have hydrophilic sur- capsule use. They are: 55 faces initially and require increased oleophilicity of I. Pretreatment of the pigment particles prior their surfaces. The pigments may be a single, solid to dispersion in the oil phase.

I- 7 0 238 225 8 particulate, colorant materials carried in a solid The above listed titanate coupling agents are medium or colloidal materials which in gross or commercially available. bulk form appear gelatinous (e.g., colloidal, hy- Illustrative silane coupling agents have the for- drated iron oxide) and thus act as a solid. mulas below: Titanate coupling agents that are illustrative of s RSiX3 those used in the present invention as agents to RR'SiX, modify the wettability of the particulates have for- RR'R"SiX mulas shown in Table I. Where X is CI, alkoxy of 1-4 carbon atoms (e.g. OCH3, OC2H5) alkoxy ethers (e.g., [0(CH2)n0(CHa)- 70 mCH3] where n is 1 to 4, and m is 0 to 4 or TABLE I OCH2CH20 CH3 and R, R', R" are alkyl or substituted alkyls (e.g., of I to 20 carbon atoms and 1. Isopropyl triisostearoyl titanate allowing for ether linkages), aryls or substituted 2. Isopropyl methacryl diisostearoyl titanate aryl, (e.g., of 6 to 20 carbon atoms) vinyl, acrylate 3. Isopropyl dimethacryl isostearoyl titanate 75 or methacrylate groups. Substituted alkyls include, 4. Isopropyl tridodecylbenzenesulfonyl but are not limited to: titanate 5. Isopropyl diacryl isostearoyl titanate NH2-CH2CH2NH-CH2CH2CH2- 6. Isopropyl tri(dioctylphosphato) titanate 7. Isopropyl 4-aminobenzenesulfonyl di- 20 (dodecylbenzenesulfonyi titanate 8. Isopropyl trimethacryl titanate CHo-VCH-CHo-0-CHoCHoCH„- 9. Isopropyl tricumylphenyl titanate 10. Isopropyl di(4-aminobenzoyl) isostearoyl titanate HS-CH2CH2CH2- 11. Isopropyl tri(dioctylpyrophosphato) titanate 12. Isopropyl triacryl titanate 13. Isopropyl tri(N ethyiamino-ethylamino) titanate 14. Isopropyl tri(2-aminobenzoyl) titanate 30 15. Isopropyl tri(butyl, octyl pyrophosphato) titanate di(dioctyl, hydrogen) phosphate These coupling agents are commercially available. 16. Di(butyl, methyl pyrophosphato) isopropyl The particulates or pigments useful in the titanate di(dioctyl, hydrogen) phosphite present invention are preferably finely divided ma- 17. Titanium isostearate methacrylate ox- terials having particle sizes of less than 25 microns yacetate and preferably less than 10 microns and most pref- 18. Titanium acrylate isostearate oxyacetate erably less than 2 microns. Suitable materials are 19. Titanium dimethacrylate oxyacetate non-magentic titanium, iron, aluminum, chromium, 21. Titanium di(cumylphenylate) oxyacetate copper and cobalt oxides, water insoluble materials 22. Titanium di(dioctylpyrophosphate) ox- such as barium sulfate, a variety of silicates, silica, yacetate talcs, carbon black, micas and treated micas, 23. Titanium diacrylate oxyacetate phthalocyanine complexes, and particularly essen- 24. Titanium di(butyl, octyl pyrophosphate) tially oil and water insoluble cosmetic colorants. di(dioctyl, hydrogen phosphite) oxyacetate The hydrophobic inner phase for the capsule 25. Diisostearoyl ethylene titanate may be any in situ aminoplast encapsulatable com- 26. Di(dioctylphosphato) ethylene titanate position as discussed in U.S. Patent 3,516,941. The 27. 4-aminobenzenesulfonyl dodecylben- material or the dispersion produced by incorpora- zenesulfonyl ethylene titanate tion of the particulate may be fluid, semi-solid (e.g., 28. Di(dioctylpyrophosphato) ethylene gel), or low melting (less than 100 °C) solid titanate waxy carrier phase. Typical materials may be fragrance 29. Di(butyl, methyl pyrophosphato)ethylene oils, mineral oils, emollients such as isopropyl titanate di(dioctyl, hydrogen phosphite) myristate, plasticizers such as the phthalate esters, 30. Tetraisopropyl di(dioctylphosphito) waxes such as found in lipstick, etc. titanate When the microcapsule is prepared by inter- 31. Tetraoctyloxytitanium di- facial polycondensation, the capsule skin may be (ditridecylphosphite) composed of any condensation polymer or addition 32. Tetra(2,diallyoxymethyl-l butoxy titanium polymer, e.g., polyamide, polyurethane, polysul- ji(di-tridecyl)phosphite fonamide, polyurea, polyester, polycarbonate, etc.

3 9 0 238 225 10

Polyamides prepared by interracial polycondensa- Eye Shadow (Compact Powder): 30-70% talc - tion of an amine with an acid chloride or polymers (as powder base), 2-12% metal carboxylate (e.g., formed by reaction of isocyanate prepolymer with zinc stearate) as adherent, 0-3% perfume carrier, polyamines are preferred. Microcapsules formed 2-10% wax or lipid binder, 0-12% titanium dioxide by coacervation processes are afso useful in for- 5 for covering power, 4-30% primary pigment, and 3- ming microcapsule shells according to the present 30% microcapsules invention. Coacervation is the well known process talc 38% of forming higher molecular weight gelatin poly- zinc stearate 6% mers as taught in U.S. Patents 2,800,458 and lipid binder 5% 2,800,457. io titanium dioxide 5% The compositions of the present invention are primary pigment (ultramarine (Color Index prepared by making the microcapsules and the 77007) 30% cosmetic compositions separately and then mixing microcapsules (litholrubin B, barium lake, Color the two under conditions which wilt not rupture a Index 15850) 16% significant (e.g., greater than 5% or 10%) portion of 15 Lipstick: 30-70% lipid-wax mixture (e.g., car- the capsules. Preferably, fewer than l% of the nauba wax, beeswax), 15-40% lipid solvent (e.g., capsules will be broken during preparation of the ricinus oil, 3-15% primary pigment, 3-15% micro- final composition. In the case of wax or liquid base capsules compositions, intermediate temperatures can be The capsules used in these constructions and used to soften the compositions prior to mixing 20 generally in the practice of the present invention with the microcapsules. In powder compositions, have average diameters between 4 and 100 the microcapsules and powder can be gentiy sifted microns. Preferably the average diameters are be- together. In cakes, the pigment and microcapsules tween 10 and 80 microns. The capsules preferably may be mixed when dry and then the binder com- constitute from 20 to 60% by volume or weight of position added to the mixture. The percentage of 25 the composition layer, most preferably between 25 capsules and pigments in the composition can vary and 50% by weight or volume of said composition widely depending on the intensity of the desired layer. effect, the optical intensity of the various pigments, and other aesthetic objectives. Generally, the microcapsules should comprise from 10-90% dry 30 Claims weight of the composition, preferably between 25 and 75% dry weight of the composition. Below are 1. A color adjustable cosmetic composition given some particularly preferred ranges in weight comprising a first colorant, a binder, and a frangible percent of useful components and specifically de- microcapsule comprising a shell, an encapsulated sired compositions for various cosmetic uses. 35 liquid and a second colorant which differs in color Face Powder (loose): primary pigment 20-75%, from said first colorant. secondary pigment 25-80% 2. A composition according to claim I wherein Brilliant lake red (Color Index 15800) 45% said second colorant is predominantly encapsu- fused silica (flow agent) 1% lated by said shell. Capsule (10-30 microns, 85% payload of ferric 40 3. A composition according to either of claims I ferrocyanide, Color Index 77510 and diethyl and 2 being a compact face powder comprising 2- phthalate 54% 25% by weight binder, 20-75% by weight first Face Powder (compact): Binder (2-25%), pri- colorant, and 10-80% by weight of microcapsules. mary pigment 20-75%, Microcapsules 78-10% 4. A composition according to either of claims I Carmine (Color Index 75470) 75% 45 and 2 being a cream rouge comprising 35-65% lipid (as binder) 5% cream base, 15-50% first coiorant, and 15-50% encapsulated titanated mica (glitter) in diethyl- microcapsules. phthalate 20% 5. A composition according to either of claims I Cream Rouge: 35-65% Cream Base (e.g., wa- and 2 being a compact eye shadow comprising 30- ter, poiyol, lipid, sufactant-emulsifier, preservative 50 70% talc, 2-12% metal carboxylate, 2-10% of a and perfume), 15-50% primary pigment, 15-50% binder selected from waxes and lipids, 4-30% first microcapsules colorant, and 3-30% microcapsules. Ultramarine (Color Index 77007) 35% 6. A composition according to claim 5 further Cream base 45% comprising up to 12% by weight of a white pig- microcapsules (sunset yellow aluminum lake 55 ment Color Index 15985) in diethylphthalate 20% 7. A composition according to claim 6 wherein said white pigment is titanium dioxide.

3 11 0 238 225 12

8. A composition according to any one of claims I to 7 further comprising a perfume carrier. 9. A composition according to either of claims I and 2 being a lipstick comprising 30-70% by weight of a binder selected from lipids and waxes, 5 15-40% by weight of a solvent for said binder, 3- 15% by weight of first colorant, and 3-15% by weight of microcapsules. 10. A process for coloring the skin of a human being comprising applying the composition of any io10 one of claims I to 9 to a surface and subsequently applying pressure to said composition to rupture microcapsules and change the apparent color of the composition.