US 20140335138A1 (19) United States (12) Patent Application Publication (10) Pub. N0.: US 2014/0335138 A1 Goldstein et al. (43) Pub. Date: NOV. 13, 2014

(54) MICROCAPSULES COMPRISING BLACK Publication Classi?cation PIGMENTS (51) Int. Cl. (76) Inventors: Danny Goldstein, (IL); A61K 8/11 (2006.01) Yuri Yasman, Carmiel (IL); Olga A61Q 1/10 (2006.01) B01J13/12 (2006.01) Privalova, KibbutZ LeHavot HaBashan A61K 8/81 (2006.01) (IL); Lior Benaltabet, KibbutZ Dafna C09C1/56 (2006.01) (1L) C09C1/24 (2006.01) (52) US. Cl. (21) Appl. No.: 14/118,266 CPC A61K8/11 (2013.01); C09C 1/56 (2013.01); C09C1/24 (2013.01); B01J13/12 (2013.01); (22) PCT Filed: May 16, 2012 A61K8/8152 (2013.01); A61Q 1/10 (2013.01); A61K 2008/115 (2013.01); A61K 2800/65] PCT No.: PCT/IL2012/000192 (2013.01); A61K 2800/624 (2013.01); A61K (86) 2800/43 (2013.01); C01P 2004/61 (2013.01) § 371 (0X1)’ USPC ...... 424/401; 524/560; 524/555; 524/431; (2), (4) Date: Nov. 18, 2013 524/306; 524/521; 523/336; 523/322 (57) ABSTRACT Monolayered microcapsules comprising a black pigment and Related US. Application Data cosmetic formulations comprising them are provided for use (60) Provisional application No. 61/486,413, ?led on May particularly in mascara and eye liner formulations. The black 16, 201 1. pigment may be carbon black, black iron oxide, or both. Patent Application Publication Nov. 13, 2014 Sheet 1 0f 4 US 2014/0335138 A1

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MICROCAPSULES COMPRISING BLACK resulting in more area to wet and thus requiring more energy PIGMENTS than a carbon black particle having lower surface area. Addi tionally, as the carbon black aggregate becomes smaller there FIELD OF THE INVENTION is a higher volume concentration of carbon black at the same weight loading (compared to particles having larger aggre [0001] The present invention relates to microcapsules com prising black pigments and to topical compositions compris gates) resulting in smaller inter-aggregate distances and, con sequently, greater attractive forces to overcome. ing them, particularly for use in cosmetics, more particularly for use in mascara and eye liner formulations. [0009] It would be bene?cial to provide carbon black in an encapsulated form that would increase the safety of use, avoid BACKGROUND OF THE INVENTION dustiness during manufacturing of the composition, and improve dispersion of carbon black in the composition and [0002] The most popular black pigments in cosmetic prod will not be considered as a nanomaterial (1 -100 nanometer). ucts nowadays are carbon black and iron oxide black. Black [0010] US. Pat. No. 5,286,291 discloses pigments contain iron oxide pigment, also known as ferrous ferric oxide ing carbon black and having improved abrasion resistance. (Fe3O4), consists of particles with diameters between about 1 WO 2010/085689 discloses antimicrobial carbon black dis and 100 nanometers. It has no known health hazards and is persions. US. Pat. No. 7,300,512 discloses a method ofmak considered non-toxic. It is more opaque and less toxic than ing pigment dispersion containing a carrier such as castor oil other black pigments. or vegetable wax, wherein the pigment is optionally black [0003] Carbon black pigment is produced by the incom iron oxide. plete combustion of hydrocarbon gas or oil. It is an ultra black [0011] US. Pat. No. 6,932,984 andU.S. Pat. No. 7,838,037 pigment, providing the most authentic black shades available. assigned to the same applicant of the present application The bene?ts of carbon black for use in cosmetics and particu disclose a method for microencapsulation of substances by larly in mascaras include less clumping, less beading, less the solvent removal method using non-chlorinated solvents. buildup, better lash separation and better lash curling. Since The method is based on physical processes only which do not carbon black is lighter with more color effect at low use cause any change of original physical and/ or chemical prop concentrations, ?nal formulations offer maximum cosmetic erties, biological activity, and safety of raw materials during performance without caking and buildup. the process. This method affords physical stability of the [0004] However, carbon black has not been permitted for microcapsules, high ability to entrap the active agents, pro cosmetic use in the US. from 1976 to 2004. In 2004 the US. tection of the active agents inside the microcapsules, and Food and Drug Administration (FDA) approved the use in prevention of the diffusion of the microencapsulated active cosmetics of one form of carbon black: high purity furnace agents to the external water phase in a water-based prepara black (one of the ?ve types of carbon black which have been tion. In US. Pat. No. 7,838,037 the resulting microcapsules produced). The FDA named the allowed colorant D&C Black are double layer and triple layer microcapsules. WO 2009/ #2 to emphasize that the material is subject to batch certi? 138978 of the same applicant discloses cosmetic composi cation. tions comprising double layer microcapsules which contain [0005] In addition, carbon black is very dif?cult to handle black iron oxide with additional iron oxides. during the process of manufacturing formulations. It consists of ?ne amorphous particles having an average primary par BRIEF DESCRIPTION OF THE FIGURES ticle size as small as 0.05 to 0.5 pm. Due to the ?ne primary [0012] FIGS. 1A-1B show particle size distribution of car particle size, carbon black particles tend to heavily aggregate bon black microcapsules having an average particle size of 40 and can be dif?cult to disperse uniformly in vehicles or resin pm or 1-2 pm, respectively. compositions. In addition, carbon black particles have a very [0013] FIGS. 2A-2C show scanning electron microscope low bulk density (about 0.1 g/cm3) and, accordingly, can easily become airborne and contaminate the working envi (SEM) images of non-encapsulated carbon black (raw mate rial, 2A); carbon black microcapsules having an average par ronment. ticle size of 40 pm in magni?cation x1000 (2B), and carbon [0006] Pigments, especially carbon black, present prob black microcapsules having an average particle size of 1 -2 pm lems to customers trying to handle and disperse these prod in magni?cation of x5000 (2C). ucts. Customers desire to have a product which is dust free, [0014] FIG. 3 shows SEM image of black iron oxide micro can be easily handled in conventional material transferring capsules in magni?cation x1000. equipment and have the same product in a form that will easily disperse in the host formulation. Additionally, carbon DETAILED DESCRIPTION OF THE INVENTION black lacks signi?cant surface functional groups, which means that the particles are hard to wet and therefore dif?cult [0015] Among conventional black pigments, carbon black to disperse. exhibits excellent blackness. Carbon black powder consists [0007] Achieving an adequate dispersion involves impart of ?ne amorphous particles exhibiting average particle size as ing enough energy in the system to overcome attractive forces small as 0.05 to 0.5 pm. Special color effects can be achieved between particles without putting much energy in the system by incorporation of carbon black into pigments. Carbon black that can destroy or change the desired properties of the for (D&C Black #2) is approved by FDA for use in eyeliner, mulation. Achieving dispersions of particulate matter, and in mascara, eye shadow, lipstick, blush, make up and founda particular carbon black dispersions, remains the domain of tion. experience and know how. [0016] In order to get full color tone out of carbon black it [0008] The primary particle size of a carbon black particle is of paramount importance that a good dispersion is made. determines, to a large extent, its degree of dispersability. The However, it is very dif?cult to disperse carbon black uni smaller the primary particle the higher the surface area, formly in formulations. Carbon black particle size is directly US 2014/0335138 A1 Nov. 13, 2014

related to the surface area of the pigment and in?uences its spherical homogeneous granules of the active substance dis color, rheology, dispersion and electrical conductivity in the persed in a polymer and are, in strict sense, spherically empty formulation. Carbon black particles tend to heavily aggre particles. gate. It can easily become airborne and contaminate work [0023] The term “wall-forming polymer” refers to a poly environments (bulk density of 0.1 g/cm3). mer or a combination of two or more different polymers as [0017] The present invention provides monolayered micro de?ned herein, which form a component of the external wall capsules comprising a core of a black pigment and a shell of or layer or shell of the microcapsules. The term “polymer a wall-forming polymeric material selected from a polyacry shell” refers to a polymer layer containing the wall-forming late, a polymethacrylate, a cellulose ether, a cellulose ester, or polymer(s). a combination thereof, wherein the microcap sules do not [0024] The dimensions and values disclosed herein are not contain a plasticizer (the plasticizer would cause softening of to be understood as being strictly limited to the exact numeri the wall-forming polymers). cal values recited. lnstead, unless otherwise speci?ed, each [0018] According to certain embodiments, the black pig such dimension is intended to mean both the recited value and ment is carbon black. Contrary to known carbon black par a functionally equivalent range surrounding that value. For ticles with size as small as 0.05 to 0.5 pm, the carbon black example, a dimension disclosed as “40 pm” is intended to microcapsules of the present invention have a size ranging mean “about 40 pm”. from about 1 to about 100 um, about 1 to about 90 um, about [0025] As used herein, numerical ranges preceded by the 1 to about 80 um, about 1 to about 70 um, about 1 to about 60 term “about” should not be considered to be limited to the um, about 1 to about 50 um, about 30 to about 50 um, about 34 recited range. Rather, numerical ranges preceded by the term to about 40 um, about 1 to about 40 um, about 1 to about 30 “about” should be understood to include a range accepted by um, about 1 to about 20 um, about 1 to about 10 um, about 1 those skilled in the art for any given element in microcapsules to about 5 pm, or about 1 to about 3 pm, preferably about 1 to or formulations according to the present invention. 2 pm. For example, microcapsules with mean particle size of [0026] The term “about” as used herein means within an 1.5 pm or 34 um have a surface area of4-5 m2/g and 0.2-0.4 acceptable error range for a particular value as determined by m2/g, respectively. The particle size of the microcapsules one of ordinary skill in the art, which will depend in part on according to the present invention provides increased safety how the value is measured or determined, i.e., the limitations and greater ease in handling the pigment during the process of the measurement system. For example, “about” can mean for manufacturing cosmetic compositions. a range of up to 10%, more preferably up to 5%, and still more preferably up to 1% of a given value. Where particular values [0019] According to certain embodiments, the amount of are described in the application and claims, unless otherwise carbon black in the microcapsules of the invention is within a stated, the meaning of the term “about” within an acceptable range selected from about 25 to about 95%, about 30 to about error range for the particular value should be assumed. 90%, about 40 to about 90%, about 50 to about 90%, about 60 [0027] The method used for the preparation of the micro to about 90%, about 70 to about 90%, about 80 to about 90%, or about 85 to about 90%, preferably about 90%, by weight. capsules of the invention as described hereinafter is based on the microencapsulation solvent removal method disclosed by [0020] According to certain embodiments, the black pig the applicant of the present application in the above-men ment is black iron oxide. Contrary to the microcapsules con tioned U.S. Pat. No. 6,932,984 and Us. Pat. No. 7,838,037. taining iron oxides disclosed in Us. Pat. No. 6,932,984, U.S. According to this technology, the active ingredient is found in Pat. No. 7,838,037 and WO 2009/138978, the microcapsules the core of the microcapsule. This technique seals each of the present invention are monolayer microcap sules and micro-capped ingredient from chemical and cross-link reac they do not contain plasticizers.According to certain embodi tions, degradation, color change or loss of potency during ments, the amount of black iron oxide in the microcapsules of production and for extended periods in storage. the invention is within a range selected from about 50 to about [0028] However, in contrast to the microcapsules of Us. 95%, about 60 to about 95%, about 75 to about 95%, about 80 Pat. No. 6,932,984, U.S. Pat. No. 7,838,037 and WO 2009/ to about 95%, about 80 to about 90%, or about 90 to about 138978, the microcapsules of the present invention do not 95%, preferably about 80%, 90% or 95%, by weight. contain plasticizers, which cause the softening of the wall [0021] According to certain embodiments, the black pig forming polymers, resulting in the release of their content ment is a mixture of carbon black and black iron oxide, upon application to the skin. The microcapsules of the present wherein the ratio between the carbon black and black iron invention are formulated to retain the black pigment, and not oxide is in a range of from 1:20 to 20:1, respectively. In to release it upon application. Furthermore, the encapsulation certain embodiments the ratio between the carbon black and does not change the color of the pigments; rather the encap black iron oxide is 1:1, 1:2, 1:3,1:4, 1:5, 1:6,1:7, 1:8, 1:9, sulated black pigments have an intense black color. 1:10,1:11,1:12,1:13,1:14,1:15,1:16,1:17,1:18,1:19,1:20, [0029] It was surprisingly found, according to the present 20:1,19:1,18:1,17:1,16:1,15:1,14:1,13:1,12:1,11:1,10:1, invention, that application ofthe technology developed by the 9:1, 8:1, 7:1, 6:1, 5:1, 4:1, 3:1, 2:1, 2:3, or 3:2, respectively. applicant for the microencapsulation of black pigments The total amount of black pigment ranges from about 50 to solves a problem in the cosmetic industry while handling about 90%, about 60 to about 90%, about 75 to about 90%, nanoparticles of said pigments. about 80 to about 90%, preferably about 80% or 90%, by [0030] The microcapsules of the invention have a particle weight. size within a range selected from about 1 to about 100 um, [0022] The term “microcapsule”, as used herein, refers to a about 1 to about 90 um, about 1 to about 80 um, about 1 to spherical microparticle consisting of a polymeric shell serv about 70 um, about 1 to about 60 um, about 1 to about 50 um, ing as a wall-forming material and encapsulated black pig about 30 to about 50 um, about 34 to about 40 um, about 1 to ment located within the core of the microcapsule. Microcap about 40 um, about 1 to about 30 um, about 1 to about 20 um, sules are distinct from microspheres, which consist of about 1 to about 10 um, about 1 to about 5 pm, or about 1 to US 2014/0335138 A1 Nov. 13, 2014

about 3 pm. In preferred embodiments, the mean particle size hydrogenated polyisobutene or butylene glycol cocoate pro of the microcapsules is from about 1 to 2 pm. vides a more intense black color. [0031] The wall-forming polymeric material may be a [0036] The microcapsules of the present invention includ polyacrylate, a polymethacrylate, a cellulose ether or ester, or ing carbon black microcapsules or black iron oxide micro a combination thereof. In certain embodiments, the polymer capsules as free ?owing powder or in slurry/paste form, con is a polymethacrylate, more preferably poly(methyl meth tain high purity grade black pigments designed to provide acrylate) co-methacrylic acid (herein referred to sometimes intense black color in cosmetic formulations for full color as PMMA) or ammonium methacrylate copolymer type B development. (poly(ethyl acrylate)-co-(methyl methacrylate)-co-(trim [0037] The advantages of the microcapsules of the present ethylammonium-ethyl methacrylate chloride), also known as invention include: Eudragit RSPO® or EuRSPO®). In other certain embodi [0038] (i) High loading (90% for both carbon black and ments, the polymer is a cellulose ether or ester such as, but not black iron oxide). limited to, methyl cellulose, ethyl cellulose, hydroxypropyl [0039] (ii) Available in both powder form and slurry/ methyl cellulose, hydroxypropyl cellulose, cellulose acetate, paste form. cellulose acetate phthalate, or hydroxypropyl methyl cellu [0040] (iii) Strong color strength. lose acetate phthalate. In other certain embodiments, the [0041] (iv) No agglomerates. wall-forming polymeric material is a combination of the [0042] (v) Less clumping, less beading and less buildup. mentioned polymers such as, but not limited to, combinations [0043] (vi) Better formulation stability. of Eudragit RSPO® with either PMMA or ethyl cellulose [0044] (vii) Reduced micro problems. (EC). The amount (weight/weight) of the polymers from the [0045] (viii) Better handling, ease of use and reduced total microcapsule weight varies according to the polymer dusting problems. and the presence of additives and can be within a range [0046] (ix) More uniformity as well as narrower particle selected from about 2 to about 50%, about 2 to about 40%, size distribution. about 2 to about 30%, or about 2 to about 25%, preferably [0047] (x) No nano issueiaverage particle size of 1-2 about 2%, 5%, 10% or 25%, by weight. micron or 40 micron. [0032] In certain embodiments of the invention, the micro [0048] (xi) Enhanced waterproof properties of the ?nal capsules contain no additives. For example, see hereinafter in formulation. Example 5 (Table 7isamples 260411L and 250111L), [0049] (xii) Can be used in mascaras, eyeliners and other wherein the black pigment is black iron oxide in an amount of water based products as well as in waterproof mascaras. about 90% or 95%, by weight, and the wall-forming material [0050] In another aspect the present invention provides a is ammonium methacrylate copolymer type B in an amount of method for the preparation of the microcap sules comprising a about 5% or 10%, by weight. black pigment described above, the method comprising: [0033] The microcapsules of the invention may further [0051] a) preparing an organic solution of a black pig comprise one or more additives including, but not limited to, ment with the wall-forming polymeric material in ethyl mineral oils such as paraf?n oil, mineral oil substitutes such acetate, optionally in the presence of one or more addi as hydrogenated polyisobutene, or castor oil, lanolin, buty tives, and subjecting the solution to homogenization or lene glycol cocoate or camauba wax. In certain embodiments, low shear mixing/ stirring until a homogenate suspen the amount of additive is within a range selected from about sion is obtained; 5 to about 50%, about 5 to about 40%, about 5 to about 30%, [0052] b) mixing said homogenate suspension with an or about 10 to about 25%, preferably about 10% or 25%. In aqueous solution containing an emulsi?er, under either certain embodiments, the additive is hydrogenated poly low or high shear stirring, to form an emulsion; isobutene used, for example, in Example 2 (Table 1) and in [0053] c) adding to the emulsion formed in (b) an excess Example 5 (Table 7isample 270411L). In other certain amount of water to initiate extraction of the organic embodiments, the additive is butylene glycol cocoate used, solvent from the emulsion, thus obtaining microcap for example, in Example 3 (Table 5). sules; [0034] In certain embodiments, the blackpigment is carbon [0054] d) optionally allowing sedimentation of the black in an amount of about 50%, by weight, the wall-forming microcapsules; and material is poly(methyl methacrylate) co-methacrylic acid in [0055] e) isolating said microcapsules of c) or d) by an amount of about 25%, by weight, and the additive is ?ltration, subsequently washing with water or with 10% hydrogenated polyisobutene, in an amount of about 25%, by alcohol, and optionally drying the wet capsules. weight (see Example 2 (Table 1)). In other certain embodi [0056] According to the method of the present invention it ments, the black pigment is carbon black in an amount of is possible to control the average particle size of the microen about 90%, by weight, the wall-forming material is poly capsulated black pigment by performing step b) of the above (methyl methacrylate) co-methacrylic acid in an amount of method either at low or high shear stirring. The term “low about 2%, by weight, and the additive is butylene glycol shear stirring” or “low shear mixing” or “low shear mixing/ cocoate, in an amount of about 10%, by weight (see Example stirring” refers to a mixing of about 300-600 revolutions per 3 (Table 5)). In certain embodiments the black pigment is minute (RPM), preferably about 400 RPM, and provides black iron oxide in an amount of about 80%, by weight, the bigger microcapsules. The term “high shear stirring” refers to wall-forming material is ammonium methacrylate copolymer a mixing at about 6000-12000 RPM, preferably about 6000 type B in an amount of about 10%, by weight, and the additive 8000 RPM, and provides smaller microcapsules. For is hydrogenated polyisobutene in an amount of about 10%, by example, black pigment microcapsules having an average weight (see Example 5 (Table 7 sample 270411L)). particle size of 40 um were obtained under stirring at 400 [0035] When the black pigments are mixed with an oily RPM as shown in Example 2 (step 2.2) and FIG. 1A, while substance it results in a richer color. Thus, the wetting agent smaller microcapsules, i.e. having an average particle size of US 2014/0335138 A1 Nov. 13, 2014

1-2 m, were obtained under stirring at 6000-8000 RPM as tion thereof, in ethyl acetate, optionally with one or more shown in Example 3 (step 3.2) and FIG. 1B. additives such as wetting agents, and homogenizing or low [0057] The homogenization of the organic phase (“master shear mixing/stirring until a homogenate suspension is batch”) is an important stage in the process for preparation of obtained; the microcapsules comprising a black pigment. However, for [0065] b) mixing said homogenate suspension with an the preparation of carbon black microcapsules, the duration aqueous solution containing an emulsi?er, under low or high of this stage should be no longer than 5 min. In addition, for shear stirring, to form an emulsion; the preparation of carbon black microcapsules, the duration [0066] c) adding to the formed emulsion an excess amount of the emulsion stage is also short (5 min). Longer emulsion of water to initiate extraction of the organic solvent from the times result in a cream which can not be mixed. emulsion, thus obtaining microcapsules; [0058] In another aspect the present invention provides [0067] d) optionally leaving for a time suf?cient to allow compositions/formulations comprising microencapsulated sedimentation of the microcapsules; and carbon black, black iron oxide, or a mixture thereof. In certain [0068] e) isolating said microcapsules by ?ltration, subse embodiments the compositions/ formulations of the invention quently washing with water or with 10% alcohol (to remove comprise microcapsules selected from: (i) carbon black ethyl acetate residues) and optionally drying the wet micro microcapsules; (ii) black iron oxide microcapsules, (iii) capsules. microcapsules comprising a mixture of black iron oxide and carbon black, or (iv) a mixture of black iron oxide microcap Example 2 sules and carbon black microcapsules, preferably 3% of car bon black microcapsules and 7% of black iron oxide micro Preparation of Microcapsules Containing Carbon capsules. Black [0059] These compositions/formulations are particularly for cosmetic use and include, for example, mascara, eyeliner, [0069] 2.1 Preparation of Organic Phase (“Master Batch”): eye shadow, lipstick, blush, makeup, cream concealer, and [0070] An organic phase (herein called “master batch” foundation for makeup formulations. In some preferred (MB)) was prepared by gradually adding 25 g of the wall embodiments, the invention provides mascara formulations forming polymer poly(methyl methacrylate-co-methacrylic comprising microencapsulated carbon black and/ or iron acid), under stirring, into 566.7 g of ethyl acetate, heating to oxide black (see Examples 6 and 7). 50° C. and stirring well until the mixture was homogeneous [0060] The preparation of the formulation can be carried (about 10 min). The polymer solution was cooled to 25° C. out by mixing the black pigment microcapsules with the other The wetting agent hydrogenated polyisobutene (25 g) was ingredients of the formulation and compressing the mixture, added to this mixture and it was further stirred for about 10 wherein the other ingredients of the formulation may option min. Carbon black pigment was then gradually added to the ally be heated to obtain a homogeneous solution, and cooled mixture and it was stirred for 1 min. The mixture was then prior to the addition of the black pigment microcapsules (as homogenized for 2 min to obtain a homogenate suspension exempli?ed in Example 6). (composition detailed in Table 1). [0061] The invention will now be illustrated by the follow ing non-limiting Examples. TABLE 1 Organic phase (MB) composition EXAMPLES Material Loading component of MB (g)-(for 100 g) Materials 1 poly(methyl methacrylate—co— 25 [0062] The following materials used in the examples are methacrylic acid) listed with their abbreviations used herein and their suppliers: 2 Hydrogenated Polyisobutene 25 3 Carbon Black pigment 50 carbon black (amorphous, D&C Black#2, Amerilure Inc, 4 Ethyl Acetate 566.7 (removed) USA); black iron oxide (amorphous, Sun Chemical, USA); poly(ethyl acrylate)-co-(methyl methacrylate)-co-(trimethy lammonium-ethyl methacrylate chloride) (Eudragit RSPO® [0071] 2.2 Preparation of the Emulsion: or EuRSPO®, Evonik, Germany); poly(methyl methacry [0072] A water solution was prepared by mixing tap water late) co-methacrylic acid (PMMA; average MW ca. 15,000; (2400 g) with polyvinyl alcohol (PVA, Mowiol® 4-88, Sigma-Aldrich); hydrogenated polyisobutene (JEEN Inter Kuraray Specialities Europe (KSE) GmbH, Frankfurt am national Corporation, USA or Elementis UK Ltd, Germany); Main, Germany; 4%, 160 g) such that the water phase con ethyl acetate (Sciencelab.com, Inc., USA); polyvinyl alcohol sisted of 0.25% PVA. Ethyl acetate (106.7 g) was added to the (PVA 4%; Kuraray America, Inc., USA); butylene glycol water phase under stirring at 400 RPM for 10 min. The master cocoate (Gattefosse, France). batch of step 2.1 above (666.7 g) was gradually added into the ethyl acetate/water emulsion under stirring at 400 RPM, and Example 1 further stirred for additional 1 min (composition detailed in Table 2). General Procedure for Preparation of Microcapsules TABLE 2 Containing a Black Pigment Emulsion composition [0063] The microcapsules are prepared by the solvent removal method comprising: Material Loading for 100 g portion (g) [0064] a) preparing an organic solution of the black pig 1 Tap Water 2400 ment with a wall-forming polymeric material selected from a 2 PVA Mowiol 4—88, KSE solution 4% 160 acrylate, a polymethacrylate, a cellulose ether, or a combina US 2014/0335138 A1 Nov. 13, 2014

TABLE 2-continued TABLE 5

Emulsion composition MB composition with high loading of carbon black

Material Loading for 100 g portion (g) Loadingcomponent of Material MB (g)-(for 100 g) 3 Ethyl Acetate 106 .7 4 MB 666.7 1 poly(methyl methacrylate—co— 2 methacrylic acid) 2 Butylene glycol cocoate 10 [0073] 2.3 Procedure of Extraction: 3 Carbon Black pigment 88 [0074] The extraction phase was composed of 13600 g tap 4 Ethyl Acetate 566.7 water. The emulsion of step 2.2 (3333 g) above was gradually added into the extraction phase under stirring at 130 RPM and [0080] 3.2 Preparation of the Emulsion: was further stirred for additional 15 min (composition [0081] A water solution was prepared by mixing tap water detailed in Table 3). (2400 g) with polyvinyl alcohol (PVA, Mowiol® 4-88, KSE GmbH, Frankfurt am Main, Germany; 4%, 160 g) such that TABLE 3 the water phase consisted of 0.25% PVA. Ethyl acetate (106.7 Extraction content g) was added to the water phase under stirring at 6000-8000 RPM for 10 min. The master batch of step 3.1 above (666.7 g) Material Loading for 100 g portion (g) was gradually added into the ethyl acetate/water emulsion 1 Tap Water 13600 under stirring at 6000-8000 RPM, and further stirred for 2 Emulsion 3333 additional 1 min (composition detailed in Table 6).

TABLE 6 [0075] 2.4 Washing and Drying Procedure: [0076] The microcapsules of step 2.3 above were separated Emulsion composition by ?ltration as a “cake”. The “cake” was washed on a ?lter Material Loading for 100 g portion (g) paper under vacuum with tap water (1 L) followed by deion ized water (0.2 L) to obtain a wet “cake” with 50-60% water 1 Tap Water 2400 content. The “cake” of microcapsules was then dried in a 2 PVA Mowiol 4—88, KSE solution 4% 160 3 Ethyl Acetate 106.7 vacuum drying oven under Silica Gel (500 g) for 48 hr, 4 MB of 3.1 666.7 vacuum 30 mbar, temperature ~40° C. The dry capsules were sifted with an automatic sifter for 10 min. [0077] The mean particle size of the obtained carbon black The extraction, washing and drying procedures are identical microcapsules was 34 um (see FIG. 1). The yield of produc to the extraction, washing and drying procedures described tion of encapsulated carbon black was 90%. The bulk density above in 2.3 and 2.4 of Example 2. of the microencapsulated carbon black was higher than that of the raw material in both loose and packed forms (see Table 4). Example 4

TABLE 4 Scanning Electron Microscopy Images of the Carbon Black Microcapsules Bulk density microencapsulated black iron oxide vs raw material [0082] Scanning electron microscopy (SEM) images of Loose gcm3 Packed gcm3 carbon black (raw material) and the carbon black microcap Carbon Black-Raw material 0.20 0.22 sules prepared as detailed above in Example 2 or Example 3 CarbonCapl—Capsules 0.31 0.38 were taken using Zeiss Ultra Gemini® (Zeiss, Germany, FIGS. 2A-2C). The SEM image of the microcapsules shows that the microcap sules have an indeterminate form (FIG. 2B). Example 3 Example 5 Preparation of Microcapsules Containing a High Percentage of Carbon Black Pigment Preparation of Microcapsules Containing Black Iron Oxide [0078] 3.1 Preparation of Master Batch: [0079] A master batch was prepared by gradually adding 2 [0083] 5.1 Preparation of Organic Phase (“Master Batch”): g of the wall-forming polymer poly(methyl methacrylate-co [0084] An organic phase was prepared by gradually adding methacrylic acid), under stirring, into 566.7 g of ethyl acetate, 10 g of the wall-forming polymer ammonium methacrylate heating to 50° C. and stirring well until the mixture was copolymer type B (EuRSPO®), under stirring, into 122.2 g of homogeneous (about 10 min). The polymer solution was ethyl acetate, until the mixture was homogeneous (about 10 cooled to 25° C. Butylene glycol cocoate (10 g) was added to min). The wetting agent hydrogenated polyisobutene (10 g) the polymer solution and it was further stirred for about 10 was added to this mixture and it was further stirred for about min. Carbon black pigment (88 gr) was then gradually added 10 min. Black iron oxide (80 gr) was then gradually added to to the mixture and it was stirred for 1 min. The mixture was the mixture and it was further stirred for 1 min. The mixture then homogenized for 2 min to obtain a homogenate suspen was then homogenized for 7 min to obtain a homogenate sion (composition detailed in Table 5). suspension (composition detailed in Table 7). US 2014/0335138 A1 Nov. 13, 2014

TABLE 7 BlackM Cap 260411Li91%; and Black Cap Inner produc tioni85%, see Table 7). The bulk density of the microencap MB (organic phase) composition sulated black iron oxide was similar to that of the raw material Loading component in the loose form and lower than that of the raw material in the ofMB for 100 g portion (g) packed form (see Table 10). BlackM Cap BlackM Cap BlackM Cap No Raw material 270411L 260411L 250111L TABLE 10

1 Black Iron Oxide 80 95 90 Bulk density microencapsulated black iron oxide vs raw material 2 EuRSPO (ammonium 10 5 10 methacrylate copolymer No Samples Loose gcm3 Packed 9cm3 WPe B) 3 Hydrogenated 10 i i 1 Black Iron Oxide— 0.7 1.1 Polyisobutene raw material 4 Ethyl Acetate 122. 2 (removed) 2 BlackM Cap-270411L 0.64 0.75 3 BlackM Cap 260411L 0.68 0.77 4 BlackM Cap 250111L 0.55 0.65 [0085] 5.2 Preparation of the Emulsion: [0086] A water solution was prepared by mixing tap water (562.5 g) with polyvinyl alcohol (PVA, Mowiol® 4-88, KSE Example 6 GmbH, Frankfurt am Main, Germany; 4%, 37.5 g) such that the water phase consisted of 0.25% PVA. Ethyl acetate (66.7 g) was added to the water phase under stirring at 400 RPM for Preparation of Mascara Oil in Water Formulation 10 min. The master batch of step 5.1 above (235.8 gr) was gradually added into the ethyl acetate/water emulsion under [0092] Mascara formulations were prepared using the stirring at 400 RPM, and further stirred for additional 7 min ingredients listed in Table 11 below, as follows: Phase 1 was (composition detailed in Table 8). prepared by mixing the water with a marine or anchor pro peller at 800-1200 RPM, dispersing a thixotropic agent TABLE 8 Thickagent LCTM (xanthan gum & hectorite & cellulose; Les Colorants, France) at room temperature till complete disper Emulsion composition sion was achieved. Heating to 75° C. with mixing, adding Euxyl® PE 9010 (a liquid cosmetic preservative based on Material Loading for 100 g portion (g) phenoxyethanol and ethylhexylglycerin; Shulke, Norderstedt 1 Tap Water 5 62.5 Germany), and triethanolamine (TEA; , ) till pH 2 PVA Mowiol 4—88, KSE solution 4% 37.5 is 7.2-7.4 and the gel viscosity decreases. Phase 2 was pre 3 Ethyl Acetate 66 .7 4 MB 235.8 pared by mixing all the ingredients while heating to 750 C. Phase 3 was prepared by mixing Covacryl E-14TM and Covacryl E-15TM (acrylate ?lm formers and texturisers; Les [0087] 5.3 Procedure of Extraction: Colorants, France) and Phenonip® (a liquid preservative; [0088] The extraction phase was composed of 3933 g tap Sharon Laboratories, Israel), and heating to 50-550 C. Phase water. The emulsion of step 5.2 above (902.5 gr) was gradu 2 was added to phase 1 under mixing with marine/anchor ally added into the extraction phase under stirring at 130 RPM propeller at 800-1200 RPM at 750 C. The mixing was con and was further stirred for additional 15 min (composition tinued for additional 10 min followed by cooling to 55° C. detailed in Table 9). Phase 3 was added to the combined phases 1+2 while mixing for 10 min at 550 C., followed by cooling to room tempera TABLE 9 ture. 4-10% of the microencapsulated black pigment can be incorporated to the above formulation at the end of the for Extraction content mulation preparation using either low or high shear mixing. Material Loading for 100 g portion (g) TABLE 11 1 Tap Water 3933 2 Emulsion 902.5 Ingredients for mascara formulation containing carbon black microencapsules

[0089] 5.4 Washing and Drying Procedure: Ingredient % (weight) [0090] The microcapsules of step 5.3 above were separated Phase 1 by ?ltration as a “cake”. The “cake” was washed on a ?lter paper under vacuum with tap water (0.5 L) to obtain a wet Water 48.67 “cake” with 50-60% water content. The “cake” of microcap Thickagent LC TM (Xanthan gum & Hectorite & Cellulose) 0.45 sules was then dried in a vacuum drying oven under Silica Gel Euxyl ® PE 9010 (Phenoxyethanol and Ethylhexylglycerin) 1 Triethanolamine 0.3 (500 g) for 48 hr, vacuum 30 mbar, temperature ~40° C. The Phase 2 dry capsules were sifted with an automatic sifter for 10 min. [0091] Scanning electron microscopy (SEM) images of the Base RW 135 (Synthetic beeswax & Camauba & Stearic 15.125 acid & Ceteareth 25 & PEG—2 stearate & black iron oxide microcapsules taken using Zeiss Ultra Paraf?num liquidum & Hydrogenated Gemini® (Zeiss, Germany), show that the microcapsules coconut oil & Cethyl alcohol; Les Colorants, France) have a spherical form with single nucleus (FIG. 3). The yield Dimethicone 350 (dimethyl—bis(trimethylsilyloxy)silane; Dow) 1.505 of production was 85 to 91% (BlackM Cap 270411Li89%; US 2014/0335138 A1 Nov. 13, 2014

TABLE 1 1 -continued 1. Monolayered microcapsules comprising a core of a black pigment and a shell of a wall-forming polymeric mate Ingredients for mascara formulation containing carbon black rial selected from a polyacrylate, a polymethacrylate, a cel microencapsules lulose ether, a cellulose ester, or a combination thereof, Ingredient % (weight) wherein the microcapsules do not contain a plasticizer. 2. The microcapsules according to claim 1, wherein the Phase 3 black pigment is carbon black, black iron oxide, or a mixture Covacryl E-14 TM (acrylates copolymer, Les Colorants, France) 11 thereof. Covacryl E—15 TM (acrylates copolymer, Les Colorants, France) 22 3. (canceled) Phenonip ® (Sharon Labs, Israel) 0.65 Phase 4 4. The microcapsules according to claim 2, wherein the black pigment is carbon black, and the amount of carbon Microencapsulated black pigrnent 4-10% black in the microcapsules is within a range selected from about 25 to about 95% by weight. 5. (canceled) Example 7 6. The microcapsules according to claim 2, wherein the black pigment is black iron oxide, and the amount of black Preparation of Eye Liner Formulations iron oxide in the microcapsules is within a range selected from about 50 to about 95% by weight. [0093] Eye liner formulations were prepared by using the ingredients listed in Table 12, as follows: Phase 1 was pre 7. The microcapsules according to claim 1, wherein said pared by mixing the water with a marine propeller at 800 microcapsules have a mean particle size within a range 1200 RPM, dispersing at room temperature Thickagent selected from about 1 to about 100 um, about 1 to about 90 LCTM, followed by addition of glycerin (Gadot, Israel), eth um, about 1 to about 80 um, about 1 to about 70 pm, 1 about ylenediaminetetraacetic acid (EDTA; Sigma-Aldrich), Der to about 60 um, about 1 to about 50 um, about 30 to about 50 macryl LTTM (National Starch, USA) and Euxyl® PE 9010 um, about 34 to about 40 um, about 1 to about 40 um, about 1 and heating the phase to 75° C. Phase 2 was prepared by to about 30 um, about 1 to about 20 um, about 1 to about 10 mixing all the ingredients and heating to 750 C. Phase 2 was um, about 1 to about 5 pm, or about 1 to about 3 pm. poured into phase 1 followed by homogenization of the com bined phases by high shear homogenizer for 10 min at 750 C. 8. (canceled) The mixing was continued while cooling the mixture to 50° 9. The microcapsules of claim 2, wherein the black pig C. Ingredients of Phase 3 were gradually added and the mix ment is a mixture of carbon black and black iron oxide, and ture/formulation was cooled to room temperature. 4-10% of the ratio between the carbonblack andblack iron oxide in said the microencap sulated black pigment was incorporated to the mixture is in a range of from 1:20 to 20: 1, respectively. above formulation at the end of the formulation preparation 10. The microcapsules of claim 9, wherein said black pig using either low or high shear mixing. ment is in an amount from about 50 to about 90%, about 60 to about 90%, about 75 to about 90%, about 80 to about 90%, by TABLE 12 weight. Ingredients for eye liner formulation containing 11. The microcapsules according to claim 1, wherein said microencapsulated black pigment wall-forming material is poly(methyl methacrylate) co-meth acrylic acid, ammonium methacrylate copolymer type B, cel Ingredient % (weight) lulose ethyl ether, cellulose ethyl ester, or a combination Phase 1 thereof. 12. The microcapsules according to claim 11, wherein the Water 83.812 wall-forming material is poly(methyl methacrylate) co-meth Thickagent LC TM 0.3 Glycerin 3.45 acrylic acid or ammonium methacrylate copolymer type B Ethylenedialninetetraacetic acid (EDTA) 0.81 and the amount of the polymer in the microcapsules is within Dermacryl LT TM (acrylates/octylacrylarnide 2.3 a range selected from about 2 to about 50% by weight. copolymer) Euxyl ® PE 9010 1 13. The microcapsules according to claim 12, wherein the Phase 2 black pigment is black iron oxide in an amount of about 90% or 95%, by weight, and the wall-forming material is ammo PerformaV ®825 polymer (hyper—branched 1.15 nium methacrylate copolymer type B in an amount of about polyalphaole?n) (New Phase technologies, USA) Camauba wax (Zifroni, Israel) 0.128 5% or 10%, by weight. Candellila wax (Zifroni, Israel) 1.05 14. The microcapsules according to claim 11, further com Laurex ® C16 (linear alcohols) (Croda, UK) 0.65 prising one or more additives. Stearic acid TP (Croda, UK) 1.05 Ozokerite (Zifroni, Israel) 0.5 15-16. (canceled) Phase 3 17. The microcapsules according to claim 14, wherein the black pigment is carbon black in an amount of about 90%, by Silicone Dow Corning ®—556 (phenyl 1.15 weight, the wall-forming material is poly(methyl methacry trimethicone) Zoharsyl L—30 (sodium lauroyl sarcosinate, 2.875 late) co-methacrylic acid in an amount of about 2%, by Zohar—Dalia, Israel) weight, and the additive is butylene glycol cocoate, in an Phenonip ® 0.575 amount of about 10%, by weight. Phase 4 18. The microcapsules according to claim 14, wherein the Microencapsulated black pigments 4— 10 black pigment is black iron oxide in an amount of about 80%, by weight, the wall-forming material is ammonium meth acrylate copolymer type B in an amount of about 10%, by US 2014/0335138 A1 Nov. 13, 2014

weight, and the additive is hydrogenated polyisobutene in an methacrylic acid, ammonium methacrylate copolymer type amount of about 10%, by weight. B, cellulose ethyl ether, cellulose ethyl ester, or a combination 19. A method for the preparation of microcapsules accord thereof. ing to claim 1, comprising: 22. (canceled) a) preparing an organic solution of a black pigment with the 23. The method according to claim 19, wherein the steps of wall-forming polymeric material in ethyl acetate, homogenization or mixing/ stirring in step a) and stirring in optionally in the presence of one or more additives, and step b) are carried out for no longer than 5 minutes. subjecting the solution to homogenization or low shear mixing/ stirring until a homogenate suspension is 24. A cosmetic formulation comprising black pigment obtained; microcapsules according to claim 1. b) mixing said homogenate suspension with an aqueous 25. The cosmetic formulation according to claim 24, solution containing an emulsi?er, under low or high wherein the microcapsules are selected from: (i) carbon black shear stirring, to form an emulsion; microcapsules; (ii) black iron oxide microcapsules, (iii) c) adding to the emulsion formed in (b) an excess amount microcapsules comprising a mixture of black iron oxide and of water to initiate extraction of the organic solvent from carbon black, or (iv) a mixture of black iron oxide microcap the emulsion, thus obtaining microcapsules; sules and carbon black microcapsules. d) optionally allowing sedimentation of the microcapsules; 26. The cosmetic formulation according to claim 25, which and is a mascara, an eyeliner, an eye shadow, a lipstick, a blush, a e) isolating said microcapsules of c) or d) by ?ltration, makeup, a cream concealer, or a foundation for makeup for subsequently washing with water or with 10% alcohol, mulation. and optionally drying the wet capsules. 27. (canceled) 20. The method according to claim 19, wherein said low shear stirring in step a) or step b) ranges from 300 to 600 28. The cosmetic formulation according to claim 24, pre revolutions per minute (RPM); and said high shear stirring in pared by mixing the black pigment microcapsules with the step b) ranges from 6000 to 12000 RPM. other ingredients of the formulation and compressing the 21. The method according to claim 19, wherein the wall mixture. forming polymeric material is poly(methyl methacrylate) co