KR102329359B1 - Colorant-containing microcapsules - Google Patents

Abstract

Disclosed is a multi-layered microcapsule comprising a core comprising at least one pigment and at least two shells of a wall-forming polymer material, an opaque material and a fatty acid salt, which can be ruptured by rubbing or pressing on the skin. Microcapsules are characterized by improved lightness values (L*) and/or compatibility in aqueous solutions comprising the formulation. Also provided are cosmetic or cosmeceutical formulations comprising microcapsules, such as body skin care formulations or facial skin care formulations.

Description

Colorant-containing microcapsules

The present invention, in certain embodiments thereof, relates to encapsulation, and more particularly, to, but not limited to, newly designed pigment-containing microcapsules and compositions and/or formulations comprising the same, such as cosmetic formulations.

Compositions for topical application comprising various pigments are known in the art. Previous attempts to use protective pigments in dermal application have focused primarily on hydrophobic or solid color cosmetics such as make-up, lipstick, blush and powder products.

U.S. Patent Nos. 5,320,835 and 5,382,433 disclose "activatable" latent colored particles or pigments and the same, further comprising a colored base phase and a pigment trapping matrix dispersed thereon. Disclosed is a cosmetic formulation comprising particles. It can be said that the encapsulated pigment is released into the base phase when a mechanical force is applied to the cosmetic formulation and creates a dark tone to the color of the base, but the pigment-capturing matrix particles capture the released pigment and create a pale color in the color of the base. pay The encapsulated pigment is prepared according to the coacervation method.

U.S. Patent No. 5,380,485 discloses a color cosmetic composition comprising a particulate filler coated with a polymer that is mixed with a pigment and their application as color cosmetics.

U.S. Patent Publication Nos. 2005/0031558 and 2005/0276774 disclose the breakage of unique pigments microencapsulated within a polymer matrix, preferably a cross-linked polymer matrix that prevents the release of any entrapped pigment even with prolonged use. Disclosed is a personal skin care or cosmetic composition comprising microparticles containing a non-dissolving blend. The matrix polymer is preferably transparent or translucent so that the blend of encapsulated pigments provides the color of the cosmetic by itself and the color of the skin upon application of the cosmetic composition. The microparticles disclosed in 2005/0276774 further comprise a second particle (ie, a hydrophobic polymer different from the matrix polymer) distributed throughout the matrix. include

U.S. Patent No. 4,756,906 discloses a color cosmetic composition comprising microcapsules comprising a first colorant and a solvated second colorant different from the first colorant. Upon rupture of the microcapsule, the color of the encapsulated pigment is added to the composition to change its color characteristics.

US 2008/81057 discloses a composition comprising at least one encapsulated pigment and at least one skin colorant selected from self-tanning agents and melanogenesis activators. The composition exhibits a slow long-term color after application to the skin due to the biological action of the self-tanning agent or melanogenesis activator, while the encapsulated pigment provides an immediate color development of the skin. Pigments can be said to be invisible in the composition due to their encapsulation, but are released immediately from their capsule and become visible when applied to the skin through the destruction of the capsule by the pressure exerted during application of the composition to the skin.

WO 2004/075679 discloses rigid, unbreakable microcapsules comprising a blend of at least two colorants which do not change their color when applied to the skin and compositions comprising them. The microcapsules do not burst due to the use of a cross-linked polymer matrix comprising a polymer having a glass transition temperature (Tg) higher than 80°C.

U.S. Patent No. 6,932,984 to the present assignee discloses monolayer and bilayer microcapsules and methods for microencapsulation of materials by solvent removal methods using non-chlorinated solvents. The method is based on a physical process that does not cause any changes in the intrinsic physical and/or chemical properties, biological activity and safety of the raw materials during the process.

U.S. Patent No. 7,838,037 to the present assignee discloses bi- and/or tri-layer microcapsules designed to rupture with a slight mechanical force on the skin, such as rubbing or pressing, to immediately release their encapsulated contents. These microcapsules are prepared by a solvent removal method using a non-chlorinated solvent. This method provides the microcapsules with physical stability, good ability to entrap the active agent, protection of the active agent within the microcapsule and prevention of diffusion of the microencapsulated active agent into the external aqueous phase in water-based preparation.

The assignee's WO 2009/138978 discloses a cosmetic composition for dermal/topical application comprising a bilayer rupturable microcapsule containing one or more microencapsulated pigments and an active substance. When applied to the skin, such compositions produce an immediate color changing effect, suggesting the delivery of the active substances contained in the composition to the skin.

WO 2012/156965, filed by the assignee of the present application, discloses a single-layered microcapsule containing a black pigment and a cosmetic formulation comprising the same. WO 2013/107354, core; and microcapsules comprising a layered coating containing a pigment, a polymer and a lipid-based material, wherein the composition further comprises unencapsulated titanium oxide.

In a cosmetic composition or formulation, in order to maintain the visual effect of the cosmetic formulation for a long period of time, it is highly desirable to retain the pigment or dye in the capsule prior to its application. There is also a need to protect the encapsulated pigment from potentially harmful effects induced by other substances, particularly in mixed formulations comprising the active substance in admixture with the encapsulated pigment.

The effectiveness of protection or masking by a single-layer microcapsule depends on the chemical structure, molecular weight and physical properties of the microencapsulated component. For some pigments, the use of monolayer microcapsules prevents the development of color of the cosmetic composition before application to the skin, as known methods of monolayer microencapsulation do not provide adequate protection from leakage and/or satisfactory masking effect. will cause

Presently known pigment-containing microcapsules do not always provide adequate protection from leakage and/or satisfactory masking effect of color, and some undesirable color development of various formulations containing them have been reported. In addition, such microcapsules often exhibit low stability and color-retention effects in gels and other water-based formulations. Investigating microcapsules that will exhibit significant stability in water-based formulations, and improved color-masking effect and release of pigments encapsulated therein, without being limited by incompatibility with water-based formulations, we have developed a novel opaque formulation. A multi-layered microcapsule was devised and successfully implemented.

According to one aspect of any embodiment of the present invention, it comprises an inner core microcapsule and at least one outer shell surrounding the inner core microcapsule, wherein the inner core microcapsule comprises a core containing a pigment, and in the shell A multi-layered microcapsule is provided wherein the core surrounded by a first wall-forming material is made of, and the at least one outer shell comprises a second wall-forming material, a fatty acid salt and an opaque material.

According to any of the embodiments described herein, the at least one outer shell further comprises a plasticizer.

According to any of the embodiments described herein, the plasticizer is selected from the group consisting of triethyl citrate, tricapryline, trilaurin, tripalmitin, triacetin, acetyltriethyl citrate, paraffin oil, and any combination thereof. is chosen

According to any of the embodiments described herein, the plasticizer is triethyl citrate.

According to any of the embodiments described herein, the amount of plasticizer is from about 0.5 to about 10% by weight, or from about 0.5 to about 9.0% by weight, or from about 1.0 to about 8.0% by weight, or about 1.0 to about 7.0% by weight, or about 1.5 to about 7.0% by weight, or about 1.5 to about 6.0% by weight, or about 2.0 to 6.0% by weight, or about 2.5 to about 6.0% by weight, or about 3.0 to about 6.0% by weight , or from about 3.5 to about 6.0 weight percent, or from about 3.5 to about 5.5 weight percent, or from about 3.5 to about 5.0 weight percent, or from about 4.5 weight percent.

According to any of the embodiments described herein, the at least one outer shell further comprises a dispersant capable of dispersing a pigment upon application to the skin.

According to any of the embodiments described herein, the dispersant is an ester of a fatty acid.

According to any of the embodiments described herein, the content of the dispersant is from about 0.5% to about 10%, or from about 0.5% to about 9.0%, or from about 1.0% to about 8.0%, or about the total weight of the microcapsule. 1.0% to about 7.0%, or about 1.5% to about 7.0%, or about 1.5% to about 6.0%, or about 2.0% to about 6.0%, or about 2.5% to about 6.0%, or about 3.0% to about 6.0 %, or from about 3.5% to about 6.0%, or from about 4% to about 6%.

According to any of the embodiments described herein, the opaque material is _{selected from the group consisting of TiO 2} , zinc oxide, alumina, boron nitride, talc, kaolin, mica, and any combination thereof.

According to any of the embodiments described herein, the amount of opaque material is from about 1 to about 90% by weight, or from about 30 to about 90% by weight, or from about 30 to about 60% by weight relative to the total weight of the microcapsule.

According to any of the embodiments described herein, the opaque material is TiO ₂ and _{the content of TiO 2} is about 10 to about 80 wt%, or about 30 to about 80 wt%, or about 30 to about 60 wt%, based on the total weight of the microcapsule.

According to any of the embodiments described herein, the fatty acid salt is at least one selected from the group consisting of stearic acid, arachidic acid, palmitoleic acid, oleic acid, linoleic acid, linoleic acid, arachidonic acid, myristoleic acid and erucic acid. independently contain fatty acyls.

According to any of the embodiments described herein, the fatty acid salt is selected from the group consisting of magnesium stearate, magnesium oleate, calcium stearate, calcium linoleate and sodium stearate.

According to any of the embodiments described herein, the fatty acid salt is magnesium stearate.

According to any of the embodiments described herein, the content of the fatty acid salt is from about 0.05 to about 5% by weight, or from about 0.1 to about 3% by weight, or from about 0.2 to about 3% by weight relative to the total weight of the microcapsule, or from about 0.5 to about 3 weight percent, or from about 0.5 to about 2.0 weight percent, or from about 1.0 to about 2.0 weight percent.

According to any of the embodiments described herein, the multi-layered microcapsules contain from 1.0 to about 2.0 weight percent magnesium stearate, from about 30 to about 75 weight percent TiO ₂ and from about 4 to about 6 weight percent relative to the total weight of the microcapsule. % of dispersant.

According to any of the embodiments described herein, the content of the inner core microcapsules is from about 10 to about 70 weight percent, or from about 10 to about 50 weight percent, based on the total weight of the microcapsules.

According to any of the embodiments described herein, each of the first and second wall forming materials is independently a polymer or copolymer selected from the group consisting of polyacrylates, polymethacrylates, cellulose ethers, cellulose esters, and any combination thereof. include synthesis.

According to any of the embodiments described herein, the polymer or copolymer is a polyacrylate, polymethacrylate, acrylate/ammonium methacrylate copolymer, ammonium methacrylate copolymer type B, low molecular weight (about 15,000 Daltons). ) poly(methyl methacrylate)-co-(methacrylic acid), poly(ethyl acrylate)-co-(methyl methacrylate)-co-(trimethylammonium-ethyl methacrylate chloride), poly(butyl meta Copolymer of acrylate)-co-(2-dimethylaminoethyl methacrylate)-co-(methyl methacrylate), poly(styrene)-co-(maleic anhydride), octylacrylamide, cellulose ether , cellulose esters, poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol), PLA (poly lactic acid), PGA (poly glycolic acid) and PLGA copolymers.

According to any of the embodiments described herein, the second wall forming material comprises a polymer or copolymer selected from the group consisting of an acrylate/ammonium methacrylate copolymer, cellulose acetate, and combinations thereof.

According to any of the embodiments described herein, the second wall-forming material is from about 5 to about 70% by weight, or from about 5 to about 50% by weight, or from about 5 to about 40% by weight, based on the total weight of the microcapsules, or from about 5 to about 30 weight.

According to any of the embodiments described herein, the multilayer microcapsules comprise from about 10 to about 50 weight percent of the inner core microcapsule, from about 5 to about 30 weight percent of the second wall forming polymer or copolymer, relative to the total weight of the microcapsule. , about 0.5 to 1 weight percent magnesium stearate, about 25 to about 50 weight percent TiO ₂ and about 1 to 6 weight percent dispersant.

According to any of the embodiments described herein, the multilayer microcapsule is a bilayer microcapsule.

According to any of the embodiments described herein, the multilayer microcapsules are characterized by a lightness value (L*) on a lightness scale of 60-100 of the X-Rite measurement system.

According to any of the embodiments described herein, the multilayer microcapsules are stable when incubated in a gel formulation at 40° C. for at least 3 months with stirring.

According to one aspect of certain embodiments of the present invention, it comprises a plurality of multi-layered microcapsules, wherein at least a portion of the multi-layered microcapsules comprises a plurality of pigment-containing microcapsules described herein in any respective embodiment, and any combination thereof. There is provided a composition comprising.

According to any of the embodiments described herein, the multi-layered microcapsules in the plurality of pigment-containing microcapsules are the same or different.

According to any of the embodiments described herein, the plurality of multilayered microcapsules have an average size of from about 50 μm to about 350 μm.

According to one aspect of certain embodiments of the present invention,

(a) a first organic phase comprising a second wall-forming polymer or copolymer, a fatty acid salt, optionally a dispersant and a first water-miscible organic solvent; contacting a first aqueous continuous phase saturated with and comprising an emulsifier to obtain a first mixed-component emulsion, wherein either the first organic phase or the first aqueous phase comprises an opaque material and/or further comprising single-layer microcapsules, each of the single-layer microcapsules comprising a core containing a pigment or blend of pigments surrounded by a shell made of a first wall-forming material;

(b) adding to the emulsion formed a significant amount of water to initiate extraction of the organic solvent from the emulsion to obtain a bilayer microcapsule; and

(c) optionally repeating steps (a) and (b) using the second, third, etc. organic phases and several continuous phases to obtain multi-layered microcapsules, a method for producing multi-layered pigment-containing microcapsules this is provided

According to any of the embodiments described herein, the method further comprises, after step (b), isolating the microcapsules.

According to any of the embodiments described herein, the method further comprises drying and sieving the microcapsules to obtain a free flowing powder of the microcapsules.

According to any of the embodiments described herein, the wall forming polymer is an acrylate/ammonium methacrylate copolymer, ammonium methacrylate copolymer type B, cellulose ethyl ether, cellulose ethyl ester, or any combination thereof.

According to any of the embodiments described herein, the organic solvent is selected from ethyl acetate, ethanol, ethyl formate, or any combination thereof.

According to any of the embodiments described herein, the plasticizer is selected from tricapryline, trilaurin, tripalmitine, triacetin, triethyl citrate, acetyltriethyl citrate, paraffin oil, or any combination thereof. .

According to any of the embodiments described herein, the opaque material is selected from TiO ₂ , zinc oxide, alumina, boron nitride, talc, kaolin, mica, and any combination thereof.

According to any of the embodiments described herein, the wall forming polymer comprises an acrylate/ammonium methacrylate copolymer, ethyl cellulose or a combination thereof, the partially water miscible organic solvent is ethyl acetate, and the dispersant is an ester of a fatty acid, the fatty acid salt is magnesium stearate, and the opaque material includes TiO ₂ .

According to any of the embodiments described herein, the multilayered pigment-containing microcapsules obtained by the method are as defined in any one of the respective embodiments. That is, the method is for preparing the microcapsules described herein.

According to any of the embodiments described herein, the plurality of multilayered pigment-containing microcapsules described herein are prepared according to the methods described herein.

According to one aspect of certain embodiments of the present invention, there is provided a cosmetic or cosmeceutical formulation comprising a composition containing the microcapsules described herein.

According to any of the embodiments described herein, the formulation further comprises a cosmetically or cosmeceutical acceptable carrier.

According to any of the embodiments described herein, the formulation is an oil-in-water emulsion, an oil-in-water-in-oil emulsion, a water-in-oil emulsion. , water-in-oil-in-water emulsions, aqueous formulations, dry formulations, silicone-based formulations and powder formulations.

According to any of the embodiments described herein, the formulation is in the form of a gel, powder, cream, foam, lotion, ointment, spray, oil, paste, milk, suspension, aerosol or mousse.

Unless defined otherwise, all technical and/or scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although methods and reagents identical or equivalent to those described herein can be used in the practice or testing of embodiments of the invention, exemplary methods and/or reagents are described below. In case of dispute, the patent specification, including definitions, will be the reference standard. Moreover, the reagents, methods, and examples are illustrative only and not necessarily limiting.

Certain embodiments of the invention are described herein by way of example only in connection with the accompanying drawings. With particular reference directly to the drawings, the details presented are emphasized by way of example, for the purpose of an exemplary discussion of embodiments of the invention. In that regard, the description of the drawings clearly shows to those skilled in the art how the embodiments of the present invention may be implemented.
1 is an image showing three plates (top plate) containing powders containing commercially available microcapsules encapsulating a red, black or yellow pigment, the same red color as described in Examples 5, 6 and 7, respectively; , is an image (bottom plate) showing three plates containing powder containing exemplary microcapsules of certain embodiments of the present invention encapsulating black or yellow pigment.
2 shows an image of three pairs of vials, in each pair of which the left vial is an exemplary pigment-containing microcapsule (RedCap New, BlackCap) according to certain embodiments of the present invention, as described in Examples 8, 9 and 10; New and YellowCap), and the right vial contains commercially available microcapsules (RedCap 1, BlackCap 1 and YellowCap 1).
3 shows three plates (bottom plate) containing powder containing commercially available microcapsules encapsulating a red, black or yellow pigment and the same red, black or yellow color as described in Examples 8, 9 and 10; An image showing three plates containing powder containing exemplary microcapsules of certain embodiments of the present invention encapsulating a pigment.
4 shows an image of three pairs of vials, in each pair of which the right vial contains a basic body lotion cream containing an exemplary pigment-containing microcapsule according to certain embodiments of the present invention (CameleonYellow, CameleonRed, CameleonBlack). , the left vial contains commercially available microcapsules (RedCap 1, BlackCap 1 and YellowCap 1).
Figures 5a-b show the results obtained in X-rite measurement for an exemplary red pigment-containing microcapsule according to a certain embodiment (CameleonRed, Example 8) of the present invention compared to a commercially available microcapsule (RedCap 1), the same A comparison image obtained under photographic conditions (FIG. 5A) and a comparison graph showing reflectance as a function of wavelength (FIG. 5B) are shown.
Figures 6a-b show the results obtained in X-rite measurement for an exemplary black pigment-containing microcapsule according to a certain embodiment of the present invention (CameleonBlack, Example 9) compared to a commercially available microcapsule (BlackCap 1). A comparative image (Fig. 6a) obtained under the same photographic conditions and a comparative graph (Fig. 6b) showing reflectance as a function of wavelength are shown.
7a-b show the results obtained in the X-rite measurement for the exemplary yellow pigment-containing microcapsules according to a certain embodiment (CameleonYellow, Example 10) of the present invention compared to the commercially available microcapsules (YellowCap 1), the same A comparison image obtained under photographic conditions (FIG. 7A) and a comparison graph showing reflectance as a function of wavelength (FIG. 7B) are shown.

The present invention, in certain embodiments thereof, relates to encapsulation, and more particularly, to, but not limited to, newly designed pigment-containing microcapsules and compositions and/or formulations comprising the same, such as cosmetic formulations.

Before describing at least one embodiment of the present invention in detail, it is to be understood that the present invention is not necessarily limited in its application to the specific description set forth in the following description or by way of example by way of example. The invention is capable of other embodiments or of being implemented or practiced in various ways.

Investigating products containing encapsulated pigments that provide improved properties of capsules, such as improved stability, improved color-masking and color release, including stability in skin care, particularly cosmetics, aqueous-based formulations, the inventors devised and successfully implemented a new pigment-containing microcapsule.

We have modified known solvent-removing microencapsulation techniques to encapsulate pigments within opaque, multi-layered microcapsules, which, on the one hand, exhibit unexpected stability when synthesized in industrial processes and when maintained in an aquatic environment, which encapsulates therein. Significantly enhances the masking of pigmented pigments, provides adequate protection from the "bleeding" effect in cosmetic formulations, and on the other hand, easily ruptures and encapsulates only by applying mechanical pressure/shearing force, such as rubbing the formulation on the skin. color was allowed to be emitted.

The modified solvent removal method is based on a physical process that does not cause any change in the stability and/or intrinsic physical and/or chemical properties of the raw material during the process. This method provides the physical stability of microcapsules, good ability to capture pigments, protection of pigments in microcapsules, and prevention of diffusion of microencapsulated pigments into external media in oil-based and water-based manufacturing (prior to use). can give

Thus, the present inventors have obtained a stable formulation, effectively hiding the color of the microencapsulated pigment contained therein, an exceptional long-term visual effect before application, a smooth and good application of the microcapsule upon application, and only rubbing the formulation on the skin to remove the encapsulated pigment. A new method to exhibit immediate release was designed and successfully implemented.

For example, the inventors have found that as well as compressed powders comprising pigment-containing microcapsules prepared using a methodology as described herein, the basic body lotion formulation includes pigment-containing microcapsules prepared by the solvent removal method described previously. It was demonstrated that the color was significantly brighter and more shiny compared to the corresponding formulation. Moreover, we have demonstrated that the pigment-containing microcapsules provided herein are stable in gel formulations up to the last three months when maintained at 40° C. under continuous stirring.

The microcapsules provided in this embodiment generally consist of particles (eg, generally spherical particles) that are closed structures containing encapsulated (enveloped, entrapped) pigments or blends of pigments. Particles generally have a core-shell structural feature, ie consisting of at least two polymer shells and a core containing or consisting of a pigment and surrounded by these shells. More specifically, the multilayer microcapsules include an inner core microcapsule comprising a core containing a pigment surrounded by a shell made of a first wall-forming material, and the inner core microcapsule (a pigment-containing core and a first wall-forming material). at least one additional outer shell made of a second wall-forming material surrounding the shell of

In multi-layered microcapsules, each shell is typically and independently a wall-forming material (eg, a first, second, third, etc. wall-forming material that forms a first, second, third, etc. outer shell, respectively) It is used as a membrane for encapsulated material. In the pigment-containing microcapsules provided in this embodiment, at least one outer shell is opaque due to the opaque material contained therein, and further comprises a fatty acid salt.

The outer shell further comprises a plasticizer to control its hardness and/or a dispersant to promote smooth application of the pigment to the skin, and the microcapsules can be ruptured by rubbing or pressing on the skin.

The microcapsules of this embodiment are suitable for inclusion in topical applications such as cosmetics, cosmeceuticals and pharmaceuticals (eg, dermatology), among other uses. While applied to the skin, the microcapsules may rupture upon application of a shear force that is rubbed and pressed against the skin, but remains intact as the formulation itself prior to application, and exhibits excellent stability in water-based formulations as well as in other formulations. Microcapsules are strong enough to avoid breaking of the shell and realization of contents during production processes such as separation, drying, sieving, etc.

Microcapsules:

According to an aspect of certain embodiments of the present invention, there is provided a microcapsule comprising: an inner core microcapsule comprising a core surrounded by a first shell comprising a pigment and made of a first wall-forming material; and at least one outer shell made of a second wall-forming material surrounding the inner core microcapsule. Such multilayer microcapsules are also referred to herein as pigment-containing microcapsules.

The core of the multilayer microcapsules described herein comprises core-shell microcapsules, referred to herein as inner core microcapsules or inner core-shell microcapsules. An inner core microcapsule comprises a core comprising or consisting of a pigment or blend of pigments, and a shell surrounding the core referred to herein as a first shell or first outer shell. The shell of the inner core microcapsule comprises a first wall forming polymer, as described herein, and optionally further comprises a plasticizer, as described herein. The inner core-shell microcapsules are surrounded by a second outer shell, optionally surrounded by third, fourth, etc. outer shells each surrounding the preceding shell.

In certain embodiments, the multilayer microcapsules described herein comprise one outer shell surrounding an inner core-shell microcapsule to form a bilayer (or bilayered) microcapsule, or comprise two outer shells to form a trilayer It is referred to as a multilayer (or multilayered) microcapsule as a whole by forming (or triple-layered), or forming three or more outer shells. A bilayer microcapsule contains one outer shell surrounding an inner core microcapsule, whereas a trilayer microcapsule contains two continuous outer shells surrounding an inner core microcapsule.

In some embodiments, multilayer microcapsules comprising a pigment as described herein are prepared by a solvent removal method modified as described in the Examples section below.

In certain embodiments, the average size of the microcapsules described herein is within about 50 μm to about 350 μm, or from about 50 μm to about 150 μm, including any intermediate values or subranges therebetween.

In any of the embodiments described herein, the at least one outer shell comprises, in addition to the wall-forming material, a fatty acid salt and an opaque material as described herein.

According to any optional embodiment of the present invention, the multi-layered microcapsules may be compared to the previously described microcapsules different from the microcapsules provided herein by the absence of fatty acid salts in their wall-forming material and/or their manufacturing process. It is characterized by a significantly lighter color when

According to some embodiments of the present invention, the brightness of the microcapsules is measured using the X-Rite measurement technique, and similar microcapsules containing the same pigment but not containing fatty acid salts and prepared using the solvent removal method described previously. The L*a*b* value as the difference in lightness compared to the capsule, or alternatively, expressed as a DL* value relative to the lightness scale (L*).

According to certain embodiments of the present invention, the lightness of the microcapsules is measured using the X-Rite measurement technique, expressed as a lightness scale (L*), and is greater than 60, greater than 70, greater than 80, or greater than 90. In some embodiments, the lightness is 60-100 on the lightness scale L*.

In an exemplary embodiment, the lightness of the microcapsules of any exemplary embodiment comprising a red, yellow or black pigment is measured using an X-Rite measurement technique, e.g., as described herein in Example 13, on a lightness scale. The lightness value in (L*) was higher by 4-25 compared to the lightness of commercially available microcapsules similar to the examples prepared by using the other solvent removal method without including the same pigment but without fatty acid salt (measurement) when reflecting the DL*s value).

In a further exemplary embodiment described in Example 13 and shown in Figures 1-4, a formulation comprising either a microcapsule according to an exemplary embodiment of the invention described herein or a commercially available microcapsule, both comprising the same pigment. A visual and qualitative comparative measurement of the color brightness of Powders (Figs. 1 and 3) and basic body lotions (Figs. 2 and 4) containing microcapsules of the exemplary embodiment of the present invention were compared with powders and lotions containing commercially available microcapsules encapsulating the same black, red or yellow pigment. Significantly brighter and shinier.

These exemplified embodiments microcapsules is seems that include TiO ₂ on their outer wall-forming material and, TiO ₂ surrounds a uniform polymer shell (the first outer shell) of the inner core microcapsules, to be bound by any particular theory It doesn't, but this seems to be the reason for the brighter colors.

Without wishing to be bound by any particular theory, the use of fatty acid salts appears to be the reason for exhibiting improved adhesion of the outer polymer shell to the opaque material and optionally to the inner core microcapsules, additionally a brighter color and improved stability of the microcapsules. appears to indicate a reason for

According to any optional embodiment of the present invention, the multilayer microcapsules described herein may rupture or break when applied to the skin. That is, the microcapsules described herein remain intact in formulations, including water-based formulations, but break immediately when pressed or rubbed against the skin. The non-brittleness of microcapsules prior to their topical application allows them to withstand their size and shape when subjected to low shear mixing, for example, at 40-600 (or 80-100) rpm for 5-10 minutes at room temperature and 40°C. The stability of the microcapsules in the basal cream or lotion is routinely evaluated by monitoring (eg, using a light microscope). A change of less than 10% in microcapsule size is indicative of the non-brittleness of microcapsules in general industrial processes.

The multilayer microcapsules provided herein showed good stability in general water-based formulations and especially in gel formulations.

For example, as disclosed herein in Example 14, in an exemplary embodiment, the durability of the multilayer microcapsules provided in the exemplary embodiment of the present invention in a gel formulation was tested. The carbomer gel formulation comprising about 3% by weight of the exemplary microcapsules of this embodiment, including red, yellow or black, was incubated at 40° C. for at least 3 months under continuous stirring, but the color of the gel did not change. That is, it was observed that there was no color leakage from the microcapsules to the gel, and at least 90% of the microcapsules retained their shape and size throughout the long incubation.

Wall-forming materials :

The wall-forming material forms the shell of the multilayer microcapsules of this embodiment and serves as a film for the encapsulated material (eg, pigment). According to an embodiment of the present invention, each wall-forming material forming the shell comprises a wall-forming polymer or copolymer. In certain optional embodiments of the present invention, the at least one outer shell further comprises an opaque material and a fatty acid salt and, optionally, will further comprise a plasticizer and/or a dispersant.

The phrase "wall-forming polymer", also referred to herein as "wall-forming polymeric material", refers to a polymeric material (e.g., a polymer or copolymer) that forms a component of the outer wall or layer or shell of a microcapsule as described herein; or means a combination of two or more different polymeric materials. The term “polymer shell” means a polymeric layer composed of wall-forming polymer(s).

In some embodiments, the wall-forming polymer is selected to withstand shear forces applied when synthesized in an industrial process, but is nonetheless selected to provide microcapsules that can rupture when applied to the skin (eg, rubbed or pressed). do.

In some embodiments, each wall-forming polymeric material comprises a polymer comprising a sufficient amount of functional groups to independently form hydrogen bonds.

In certain embodiments, one or more, or each polymeric material forming the two or more shells comprises hydrogen bond forming functional groups characterized by 4-40% by weight of the total polymer weight. Hydrogen bond forming functional groups include, but are not limited to, functional groups comprising one or more electron donating atom(s) such as oxygen, sulfur and/or nitrogen.

In some embodiments, the hydrogen bond-forming group comprises a carboxylic acid, a carboxylate, a hydroxy, or any combination thereof.

In certain embodiments, the one or more, or each wall-forming polymeric material forming the two or more shells comprises a polyacrylate, polymethacrylate, cellulose ether or ester, or any combination thereof.

Exemplary wall-forming polymeric materials include, but are not limited to, polyacrylates, polymethacrylates, low molecular weight poly(methyl methacrylate)-co-(methacrylic acid) (eg, 1:0.16), poly (ethyl acrylate)-co-(methyl methacrylate)-co-(trimethylammonium-ethyl methacrylate chloride) (eg 1:2:0.1) (known as Eudragit® RSPO), poly(butyl methacrylate)-co-(2-dimethylaminoethyl methacrylate)-co-(methyl methacrylate) (eg 1:2:1), poly(styrene)-co-(maleic anhydride) , copolymers of octylacrylamide, cellulose ethers, cellulose esters, poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol), PLA(poly(lactic acid)), PGA(poly(glycolide) )), PLGA (poly(lactide)-co-poly(glycolide)), or any combination thereof.

Any combination of polymers and copolymers as described herein is contemplated for the wall forming material as described herein.

In certain embodiments, the wall-forming polymeric material of the at least one outer shell includes, but is not limited to, methyl cellulose, ethyl cellulose, hydroxypropyl methyl cellulose, hydroxypropyl cellulose, cellulose acetate, cellulose acetate phthalate, cellulose acetate butyrate. and cellulose ethers or esters such as hydroxypropyl methyl cellulose acetate phthalate. When cellulose ethers or esters are used as polymeric materials, they preferably contain about 4-20% of hydroxyl groups that are free to form hydrogen bonds (eg, alkylated or unacylated hydroxyl groups).

In any of the embodiments described herein, the first outer shell of the inner core microcapsule comprises a wall forming material as described in U.S. Patent No. 6,932,984, incorporated by reference as if fully set forth herein.

In any of the embodiments described herein, the wall forming material of the at least one second, third, etc. outer shell comprises an acrylate/ammonium methacrylate copolymer such as, for example, Eudragit® RSPO. In any other embodiment of the present invention, the wall forming material of the at least one second, third, etc. outer shell is, but is not limited to, poly(methyl methacrylate)-co-(methacrylic acid) or cellulose. combinations of the aforementioned polymers, such as the combination of either acetate with an acrylate/ammonium methacrylate copolymer (eg Eudragit® RSPO).

In some embodiments, the wall forming material of the one or more second, third, etc. outer shells comprises a cellulose ester, such as cellulose acetate. In any other embodiment of the present invention, the wall forming material of the at least one second, third, etc. outer shell is a cellulose acetate and acrylate/ammonium methacrylate copolymer (eg Eudragit® RSPO) or poly (methyl methacrylate)-co-(methacrylic acid).

When two polymeric materials are used as the wall forming material, the weight ratio between them may be from 10:1 to 1:1, including any intermediate values and ranges therebetween, for example 5:1, 4 It can be :1, 3:1, 2:1, or 3:2.

A wall-forming material (e.g., a first wall-forming material of an inner microcapsule, a second wall-forming material of a first outer shell surrounding the inner microcapsule, and optionally a first The third wall forming material of the second outer shell surrounding the outer shell, etc.) may be the same or different.

In some embodiments, in the bilayer microcapsule, the wall-forming materials of the first and second outer shells are different. In some of these embodiments, the second wall-forming material comprises cellulose acetate, an acrylate/ammonium methacrylate copolymer (eg, Eudragit® RSPO), or a combination thereof.

The total weight/weight of the wall-forming polymer material(s) of the outer shell (excluding the inner capsule) in the microcapsule total weight is from about 5 to about 70 weight including any ranges and any intermediate values therebetween. %, about 5 to about 50 weight percent, about 5 to about 40 weight percent, or about 5 to about 30 weight percent, or about 8 to about 21 weight percent.

In embodiments wherein the wall-forming material comprises cellulose acetate, the content of the wall-forming polymer material(s) of the outer shell (excluding the inner capsule) relative to the total weight of the microcapsule is 5 to 20% by weight or 5 to 20% by weight can be

Opaque material:

The shell of the microcapsule may independently be opaque, semi-opaque or non-opaque (transparent). In the pigment-containing microcapsules provided herein with at least one outer shell, the majority of the outer shell is opaque.

In certain embodiments of the present invention, the opacity of the outer shell of the multilayer microcapsule is obtained by an opaque material.

As used herein, an “opaque material” is a material that is not transparent and blocks at least 70% of light passing through it.

Thus, the opaque outer shell blocks 70% to 100% of the light. A semi-opaque outer shell blocks up to 50% of light. A non-opaque or transparent outer shell blocks less than 30% of the light passing through it.

The terms “opacity” and “opaqueness” mean herein to ultraviolet-visible light, eg, sunlight.

Exemplary opaque materials include, but are not limited to, TiO ₂ , zinc oxide, alumina, boron nitride, talc, kaolin, mica, and any combination thereof.

The total content of opaque material in the at least one outer shell is from about 1 to about 90% by weight, or from about 10 to 90% by weight relative to the total weight of the microcapsule, including any ranges and any intermediate values therebetween, or from about 30 to about 90 weight percent, or from about 30 to about 80 weight percent, or from about 30 to about 60 weight percent.

In any of the embodiments described herein, the opaque material is TiO ₂ In certain embodiments, _{the content of TiO 2} is from about 10 to about 85% by weight, or from about 30 to about 80% by weight relative to the total weight of the microcapsule, including any ranges and any intermediate values therebetween. %, or from about 30 to about 75 weight percent, or from about 30 to about 60 weight percent.

In any of the embodiments described herein, the opaque material comprises TiO ₂ in admixture with boron nitride.

fatty acid salt :

A technical feature of the multilayer microcapsules of this embodiment, which is supposed to explain their ability to maintain opacity and remain stable in a water-based environment, is that at least one outer shell comprises a fatty acid salt.

In any of the embodiments described herein, the outer shell comprising the opaque material described herein in any one of the respective embodiments further comprises a fatty acid salt described herein in any one of the respective embodiments.

Fatty acid salts include long hydrophobic hydrocarbon chains (e.g., 4 to 30 carbon atoms in length) carboxylate anions (fatty acyls) and cations, as depicted in the formula:

(RC(=O)-O ^- ) _n M ⁽ⁿ⁺⁾

where R is a substituted or unsubstituted linear or branched hydrocarbon chain of 4 to 30 carbon atoms, M + is a cation, preferably a metal cation and n is an integer representing the number of fatty acyls reacting with the cation, It also indicates the number of charges on the cation (eg 1, 2, 3, etc.).

The fatty acid salt used in any optional embodiment of the present invention will comprise from 1 to 3 fatty acyl chains, each chain independently having 4 to 30 or 8 to 24 carbon atoms (C8-C24) in length. include Thus, the fatty acid salt may be a salt of a monovalent, divalent or trivalent metal ion or a salt of an organic cation.

Monovalent metal ions, ^{e.g., Na +, K +, Cs} +, Li ⁺ can be a, 2 a metal ion is ^{Mg 2+, Ca 2 +, Fe} (II), Co 2 +, Ni 2 +, Cu ^2+, Mn ^2+, Cd ^2+, Sr ²⁺ or Zn is selected from ^{2 +,} trivalent metal ions, e.g., Fe (III), La ^{3 +,} Eu ^{3 +,} or be a Gd ^{3 +} and the organic cation may be, for example, ammonium, sulfonium, phosphonium, or arsonium.

Fatty acyls may be derived from fatty acids such as, but not limited to, stearic acid, arachidic acid, palmitoleic acid, oleic acid, linoleic acid, linoleic acid, arachidonic acid, myristoleic acid and erucic acid. Other fatty acids are also contemplated.

While not wishing to be bound by any particular theory, it appears that the hydrocarbon chains minimize contact with the aqueous environment, while the ionic cation heads form ionic reactions with water molecules and anionic materials. Thus, in certain embodiments of the process for making multilayer microcapsules of the present invention, when the inner core microcapsule and the opaque material are brought into contact with the fatty acid salt and the wall forming polymer, long hydrophobic chains of fatty acid carboxylates are formed into the inner core microcapsule. While spontaneously enclosing the hydrophobic outer shell of Thus, the cations of the fatty acid salt presumably attract the particles of the opaque material and optionally the free carboxyl and/or hydroxyl groups of the wall-forming polymer dispersed in the aqueous emulsion, so that both the opaque material and the polymer material are in the outer layer of the inner core microcapsule. It provides effective masking of the pigment in the inner core microcapsules by allowing better adhesion, while producing multi-layered microcapsules with the end result being microcapsules characterized by a lighter color as described herein.

Fatty acid salts will be used in the preparation of monolayer microcapsules, while being added to the organic phase with the encapsulated material and wall forming polymer with or without opaque material. Upon contacting the organic phase with an aqueous phase comprising an opaque material such as TiO ₂ , the fatty chains will spontaneously wrap around the encapsulated material, and their polar/ionic heads will be oppositely charged opaque material as well as oppositely charged groups in the polymer. will enhance the formation of an opaque polymeric sheath surrounding the core comprising the encapsulated material.

Exemplary fatty acid salts include, but are not limited to, magnesium stearate, magnesium oleate, calcium stearate, calcium linoleate, sodium stearate, magnesium arachidonate, magnesium palmitate, magnesium linoleate, calcium arachidonate, calcium miri Stolate, Sodium Linoleate, Calcium Linoleate, Sodium Stearate, Potassium Stearate, Sodium Laurate, Sodium Myristate, Sodium Palmitate, Potassium Laurate, Potassium Myristate, Potassium Palmitate, Calcium Laurate, Calcium Myristate , calcium palmitate, zinc laurate, zinc myristate, zinc palmitate, zinc stearate, magnesium laurate and magnesium myristate.

In some embodiments, the fatty acid salt is magnesium stearate.

The fatty acid salt is usually from about 0.05 to about 5% by weight, or from about 0.1 to about 4.5% by weight, or from about 0.2 to about 4% by weight relative to the total weight of the microcapsule, including any ranges and any intermediate values therebetween. , or about 0.5 to about 4 weight percent, or about 0.5 to about 3.0 weight percent, or about 0.75 to about 3.0 weight percent, or about 1.0 to about 3.0 weight percent, or about 1.0 to about 2.0 weight percent, or about 1.0 weight percent %, or about 2.0% by weight.

Dispersants and/or plasticizers:

In certain embodiments, one or more outer shells of the multilayer microcapsules contain a dispersant, preferably a lower alkyl fatty acid ester, such as, but not limited to, isopropyl myristate, isopropyl butyryl myristate, propylene glycol stearate. lactate, butylene glycol cocoate, hydrogenated lecithin and jojoba oil.

In some embodiments, the dispersant is isopropyl myristate (IPM), propylene glycol stearate, or a combination thereof. It has been observed that when a dispersing agent such as IPM or propylene glycol stearate is incorporated into the outer shell of the bilayer microcapsules, more flexible and much more easily diffusible microcapsules are obtained. When the microcapsules were broken, the encapsulated pigment was released and coated with an oily dispersant, which appeared to make the skin softer and more uniformly pigmented. Such fats can be considered reactive with both plasticizers and dispersants.

The content of the dispersant is usually from about 0.5 to about 10% by weight, or from about 0.5 to about 9.0% by weight, or from about 1.0% to about the total weight of the multilayer microcapsule, including any ranges and any intermediate values therebetween. 8.0 wt%, or about 1.0 to about 7.0 wt%, or about 1.5% to about 7.0 wt%, or about 1.5 to about 6.0 wt%, or about 2.0 to about 6.0 wt%, or about 2.5 to about 6.0 wt%, or from about 3.0 to about 6.0 weight percent, or from about 4.0 to about 6.0 weight percent.

In certain embodiments of any of the embodiments of the invention, the one or more outer shells (eg, the first and/or second outer shell(s) in the bilayer microcapsule) further comprise a plasticizer.

As used herein and in the art, "plasticizer" refers to a substance that increases the plasticity or variability of a composition. In the context of this embodiment, a plasticizer is added to the wall-forming material to control the level of elasticity and physical properties of the outer shell of the microcapsule.

Exemplary plasticizers include, but are not limited to, triethyl citrate, tricapryline, trilaurin, tripalmitin, triacetin, acetyltriethyl citrate, paraffin oil, and any combination thereof. In an exemplary embodiment, the plasticizer is triethyl citrate.

The content of the plasticizer is from about 0.5% to 10% by weight, or from about 0.5% to about 9.0% by weight, or from about 1.0% to about 8.0% by weight relative to the total weight of the microcapsule, including any ranges and any intermediate values therebetween. , or from about 1.0 to about 7.0% by weight, or from about 1.5 to about 7.0% by weight, or from about 1.5 to about 6.0% by weight, or from about 2.0 to about 6.0% by weight, or from about 2.5 to about 6.0% by weight, or from about 3.0% to about 6.0 wt%, or from about 3.5 to about 6.0 wt%, or from about 3.5 to about 5.5 wt%, or from about 3.5 to about 5.0 wt%, or from about 4.5 wt%.

Color:

The terms "colorant", "color agent" and "pigment" are used interchangeably herein and are organic pigments, such as synthetic or natural dyes, selected from any of the well known FD&C or D&C dyes. ), inorganic pigments such as metal oxides, or lakes and any combination (blend) thereof. In certain exemplary embodiments, the colorant is an inorganic pigment such as, for example, a metal oxide.

The pigment will be oil-soluble or oil-dispersible or have limited solubility in water. Suitable pigments for typically microencapsulation according to any optional embodiment of the present invention include, but are not limited to, organic and inorganic pigments, lakes, natural and synthetic dyes, and any combination thereof.

In certain embodiments, the colorant includes, but is not limited to, iron oxide, titanium dioxide (TiO ₂ ), lower titanium oxide, aluminum oxide, zirconium oxide, cobalt oxide, cerium oxide, nickel oxide, chromium oxide (chromium green), zinc oxide. and metal oxides such as composite metal oxides; metal hydroxides such as calcium hydroxide, iron hydroxide, aluminum hydroxide, chromium hydroxide, magnesium hydroxide and composite metal hydroxides; other pigments such as ferric ammonium ferrocyanide, Prussian blue, iron sulfide, manganese violet, carbon black, mica, kaolin, and any combination thereof.

In any of these embodiments, the inorganic pigment is selected from iron oxide, TiO ₂ , zinc oxide, chromium oxide/hydroxide, and mixtures thereof. In a more preferred embodiment, the colorant is iron oxide of any one of the three primary colors-red, yellow or black, or most preferably a mixture thereof. Optionally, the pigment will include, in addition to the mixture of iron oxides, TiO ₂ for the purpose of providing the composition with any desired final color or shade of color. Preferably, when encapsulated in inner core microcapsules, TiO ₂ is in any of its mineral forms such as, but not limited to, anatase, brookite or rutile or any combination thereof. used as one

In some other embodiments, the pigment is a lake organic pigment produced by precipitating a natural or synthetic dye with a metal salt such as an aluminum, calcium or barium salt. Such pigments are typically oil-dispersible and are widely used in cosmetics. Examples of lake pigments include, but are not limited to, a series of well-known FD&C and D&C dyes such as, but not limited to, Indigo Lakes, Carmine Lakes, D&C Red 21 Aluminum Lake, D&C Red 7 Calcium Lake. Including rakes of origin.

As described herein, the pigment is contained in the core of the inner core microcapsule. In certain embodiments, inner core microcapsules comprising pigments, wall formers and optional additives are disclosed in US Pat. No. 6,932,984, including any embodiments and combinations thereof described herein.

The content of the inner core microcapsules comprising the pigment is usually from about 10 to about 80% by weight, or from about 10 to about 70% by weight, or from about 10 to about 60% by weight, including any ranges and any intermediate values therebetween. %, or from about 10 to about 50 weight percent, or from about 10 to about 40 weight percent. A person skilled in the art will recognize the content of the pigment as a weight ratio with respect to the total weight of the multilayer microcapsule.

In any of the embodiments described herein, the microcapsules contain only one type of pigment or a mixture of two or more pigments. Individually and/or encapsulated with either a blend of one or more pigments may be encapsulated within the core of a double- or multi-layered microcapsule. Those skilled in the art will know how to select pigments and combinations of pigments to produce the desired color effect on the skin.

Pigment-containing composition:

According to one aspect of certain embodiments of the present invention, as disclosed in any one of the embodiments described herein, it comprises a plurality of microcapsules, wherein at least a portion of the microcapsules comprises at least one pigment and a first enclosing core. A composition is provided which is a multi-layered microcapsule comprising an inner core microcapsule comprising a first shell of a wall-forming polymeric material and at least one outer shell surrounding the inner core microcapsule. Such compositions are also referred to herein as pigment-containing compositions or color compositions.

In some embodiments, at least 10%, at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% in the composition , or at least 99%, or all of the plurality of microcapsules are pigment-containing microcapsules as described in any one of the embodiments described herein.

As used herein, "composition" means a plurality of microcapsules, which may be the same or different, which may be characterized by a plurality or various characteristics. According to an embodiment of the present invention, at least a portion of the plurality of microcapsules, in any one of the embodiments thereof, for example, has at least two outer shells, encapsulates a pigment, comprises a fatty acid salt, and a dispersant It exhibits all of the technical features that characterize the microcapsules described herein, which are opaque and breakable when rubbed against the skin.

The term "at least a portion" refers to at least 20%, at least 50%, at least 70%, at least 60%, at least 80%, at least 90%, at least 95%, at least 98%, at least 99% or all.

In certain embodiments, the pigment-containing microcapsules described herein in the composition may be the same or different from each other in the number and/or type of wall-forming polymeric material comprising pigments and/or shells encapsulated therein.

In at least one part or portion of the plurality of microcapsules of the compositions provided herein, the colorant will be the same or different, and/or the microcapsules will encapsulate a mixture of pigments within their core.

In certain embodiments related to the composition of the present invention, in particular in the part of a plurality of microcapsules in the composition exhibiting a combination of technical features that characterize the multilayer microcapsules of the present invention, each microcapsule comprising one or a mixture of two or more pigments may include. In some other embodiments, microcapsules containing one pigment may be mixed with microcapsules containing other pigments or mixtures of pigments in a color composition.

Each of the microcapsules described herein can be used in any combination, and through each of the embodiments described herein for formulations/compositions comprising the same.

In certain exemplary embodiments of the present invention, the second wall-forming material comprises 1.0 to 2.0% by weight of magnesium stearate, 30 to 75% by weight of TiO ₂ and 4 to 6% by weight of a dispersant (e.g., based on the total weight of the microcapsule) for example, isopropyl myristate of propylene glycol stearate).

In certain exemplary embodiments, the multilayer microcapsules described herein encapsulate a pigment with iron oxide, ferric trioxide, and/or tetraoxide, mixed with a cellulose ester, such as cellulose acetate, or alone, an acrylate/ammonium methacrylate copolymer. a wall-forming material comprising

In certain exemplary embodiments, the multilayer microcapsules described herein contain a pigment, or about 30-50% by weight of a pigment, 10-30% by weight of a wall-forming polymer or copolymer, 0.5-1% by weight of magnesium stearate, 25- and internal microcapsules comprising 50% by weight of TiO ₂ and 1-6% by weight of isopropyl myristate.

In certain exemplary embodiments, at least a portion of the plurality of microcapsules included in the composition of the present invention is an opaque material in an amount of about 30-45 wt % TiO ₂ , about 10-30 wt % acrylate with respect to the total weight of the capsule. /wall forming material comprising ammonium methacrylate copolymer (e.g. Udragit® RSPO), 1 wt% magnesium stearate and 36-45 wt% ferric tetraoxide (black), iron oxide (yellow) and It is a double-layered microcapsule containing an inner microcapsule containing a metal oxide pigment selected from ferric trioxide (red). Example 1 discloses an exemplary red containing composition comprising these ingredients.

In certain exemplary embodiments, at least a portion of the plurality of microcapsules included in the composition of the present invention comprises 14.5 wt % acrylate/ammonium methacrylate copolymer, 1.0 wt % magnesium stearate, 41 wt % TiO ₂ , 36% by weight of ferric trioxide, and further comprising 4.5% by weight of a plasticizer triethyl citrate. Examples 3 and 4 disclose yellow- and black-containing compositions, respectively.

In certain exemplary embodiments, at least a portion of the plurality of microcapsules comprised in the composition of the present invention is a red, yellow and black containing composition comprising bilayer microcapsules comprising 3.0% by weight of the dispersant isopropyl myristate.

In certain exemplary embodiments, the multilayer microcapsules described herein contain about 10-30% by weight of a pigment, or 5-15% by weight of a wall-forming polymer or copolymer, 1-2% by weight relative to the total weight of the composition. and inner microcapsules comprising magnesium stearate, 30-75 wt % TiO ₂ and 4-6 wt % propylene glycol stearate.

In certain exemplary embodiments, at least a portion of the plurality of microcapsules included in the composition of the present invention is an opaque material, based on the total weight of the capsule, of about 30-75 wt% TiO ₂ , about 5-15 wt% ethyl cellulose A wall forming material comprising an acrylate/ammonium methacrylate copolymer (eg Udragit® RSPO) mixed with 2 wt% magnesium stearate, and 10-30 wt% ferric tetraoxide (black) , a double-layer microcapsule containing an inner microcapsule containing a metal oxide pigment selected from iron oxide (yellow) and ferric trioxide (red). Examples 8-10 and 12 disclose exemplary color containing compositions comprising these components.

In certain exemplary embodiments, at least a portion of the plurality of microcapsules included in the composition of the present invention is an opaque material in an amount of about 70-75 wt % TiO ₂ , about 5-10 wt % ethyl cellulose with respect to the total weight of the capsule. It is a bilayer microcapsule comprising an inner microcapsule comprising a wall-forming material comprising: 2 wt % magnesium stearate and 10-15 wt % blue pigment. Example 11 discloses an exemplary color containing composition comprising these components.

In certain exemplary embodiments, at least a portion of the plurality of microcapsules included in the composition of the present invention comprises, wherein the second wall-forming material comprises or consists of cellulose acetate, and a dispersant in an amount of 4-6% by weight relative to the total weight of the microcapsules. Red, yellow, blue, green and/or black containing composition comprising bilayer microcapsules comprising propylene glycol stearate.

Manufacture process:

The process used to prepare the microcapsules of the present invention described herein is a modification of the microencapsulation solvent removal method disclosed, for example, in US Pat. is included as According to this technique, the active ingredient is found within the core of the microcapsule. This technology seals each micro-encapsulated component from chemical and cross-linking reactions, degradation, color change or loss of potency during production, and for extended shelf life. The solvent removal process is based on four main steps:

(i) preparing a homogeneous organic solution comprising an encapsulated pigment, a wall-forming polymer material, an opaque material, a plasticizer and a partially miscible organic solvent in water;

(ii) preparing an emulsion of a continuous phase comprising an emulsifier and saturated with the same organic solvent of an organic solution;

(iii) mixing the aqueous emulsion with the homogeneous organic solution under high shear agitation to form a mixed-component emulsion; and

(iv) extracting the organic solvent by adding to the emulsion formed in step (iii) an amount of water capable of initiating extraction of the organic solvent from the emulsion to obtain microcapsules.

As disclosed in U.S. Patent No. 7,838,037, bi-layer and tri-layer microcapsules are formed by first modifying the surface of the single-layer microcapsules formed according to steps (i)-(iv), and then the inner core microcapsules are formed with a wall-forming material. When dispersed in an organic solution with

However, in certain embodiments of the modified methods provided herein, TiO ₂ Dissolve or disperse the same opaque material as well as the inner core microcapsules in a continuous aqueous emulsion. In addition, a fatty acid salt such as magnesium stearate is added to the organic solution. TiO ₂ is transferred to the aqueous phase and magnesium stearate is added to the organic solution to obtain bi- and tri-layer microcapsules, where TiO ₂ uniformly coats the outer polymer shell to provide a masking layer to the inner core microcapsule . Thus, in some embodiments, multilayer microcapsules according to the present invention can be prepared by a modified solvent removal method comprising the steps of:

(a) a first organic phase comprising a second wall-forming polymer or copolymer, a fatty acid salt, optionally a dispersant and a plasticizer and a first organic solvent partially miscible in water, saturated with said organic solvent, said emulsifier, opaque contacting a first aqueous solution comprising monolayer microcapsules comprising a substance and a pigment or blend of pigments and a first wall former to obtain a first mixed-component emulsion;

(b) adding to the emulsion formed an amount of water capable of initiating extraction of the organic solvent from the emulsion to obtain bilayered microcapsules; and

(c) Optionally, repeating steps (a) and (b) using the second, third, etc. organic phase and the water continuous phase to obtain multi-layered microcapsules.

In a further step, the microcapsules are separated, dried and sieved after step (b) to obtain a free flowing powder of microcapsules.

These steps are further detailed as follows:

The homogeneous solution prepared in step (a) is an organic solution of the wall-forming polymer material in an organic solvent capable of dissolving or dispersing the wall-forming polymer and partially miscible with water as described in any one of the embodiments described herein, or It is obtained by preparing a dispersion. In an exemplary embodiment, the organic solvent is an organic solvent approved for topical application, such as, but not limited to, ethyl acetate, ethanol, ethyl formate, or any combination thereof. In some embodiments, the organic solvent is ethyl acetate.

The fatty acid salt is as described in any one of the embodiments described herein. The optional dispersant is as described in any one of the embodiments described herein.

When a plasticizer is used, it is usually selected from tricapryline, trilaurin, tripalmitin, triacetin, triethyl citrate, acetyltriethyl citrate, paraffin oil, or any combination thereof.

The components of the organic solution are mixed/stirred until a homogeneous, optionally clear solution is obtained.

The first aqueous continuous phase is saturated with an organic solvent forming an organic solution, and is typically a single containing an emulsifier, an opaque material and a blend of a pigment or pigment and a first wall forming material (inner core microcapsules, as described herein). layer microcapsules. The opaque material is as described in any one of the embodiments described herein. In a preferred embodiment, the opaque material is TiO ₂ . Internal, eg, single core microcapsules will be obtained by known solvent removal methods as described, for example, in US Pat. No. 6,932,984.

The organic solution and the first aqueous continuous phase are mixed under low shear agitation to form a mixed-component emulsion.

In step (b), a significant amount of water is added to the mixed-component emulsion prepared in (a) to extract the organic solvent and form bilayer microcapsules.

When triple or other multi-layered microcapsules are designed, steps (a) and (b) are repeated using a second, third, etc. organic phase and several continuous phases, wherein the organic solvents are the same or different, opaque substances, fats The acid and dispersant, as well as the wall forming material, the plasticizer, may be the same or different.

In the context of an embodiment of the present invention, the term “low shear agitation” means mixing at about 100-800 rpm, preferably at about 300-600 rpm.

In certain exemplary embodiments, the components used in the process are acrylate/ammonium methacrylate copolymer as the wall-forming polymer, ethyl acetate as the water-miscible organic solvent, isopropyl myristate as the dispersant, and magnesium as the fatty acid salt. _{TiO 2} as stearate and opaque material.

In any other embodiment of the methods of modification provided herein, TiO ₂ The same opaque material as well as inner core microcapsules are dissolved or dispersed in the organic phase, and fatty acid salts such as magnesium stearate are also added to the organic solution. These embodiments preferably relate to microcapsules comprising cellulose acetate in one or more outer shells (eg second and/or outermost shells). We use cellulose acetate as one of the wall-forming polymeric materials to form TiO ₂ It was also demonstrated that improved opacity was obtained when the same opaque material was included in the organic phase, and in the obtained bi- and tri-layer microcapsules, TiO ₂ uniformly coated the outer polymer shell to provide a masking layer to the inner core microcapsule. Thus, in some embodiments, multilayer microcapsules according to the present invention can be prepared by a modified solvent removal method comprising the following steps:

(a) a single layer microcapsule comprising a second wall-forming polymer or copolymer, a fatty acid salt, an opaque material and a pigment or a blend of pigments and optionally a dispersant and a plasticizer, and a first organic solvent partially miscible with water; contacting a first organic phase comprising: a first aqueous solution saturated with said organic solvent and typically comprising an emulsifier to obtain a first mixed-component emulsion;

(b) adding to the emulsion formed a significant amount of water to initiate extraction of the organic solvent from the emulsion to obtain bilayer microcapsules; and

(c) Optionally, repeating steps (a) and (b) using the second, third, etc. organic phase and the water continuous phase to obtain multi-layered microcapsules.

In a further step, the microcapsules are separated, dried and sieved after step (b) to obtain a flowable powder of microcapsules.

These steps are further detailed as follows:

The homogeneous solution prepared in step (a) is partially miscible with water as described in any one of the embodiments described herein, and in an organic solvent capable of dissolving or dispersing the second wall-forming polymer. Obtained by preparing an organic solution or dispersion of a substance. In an exemplary embodiment, the organic solvent is an organic solvent approved for topical application, such as, but not limited to, ethyl acetate, ethanol, ethyl formate, or any combination thereof. In some embodiments, the organic solvent is ethyl acetate.

The fatty acid salt is as described in any one of the embodiments described herein. The optional dispersant is as described in any one of the embodiments described herein.

The opaque material is as described in any one of the embodiments described herein. In a preferred embodiment, the opaque material is TiO ₂ , optionally mixed with boron nitride. Internal, eg, single core microcapsules will be obtained by known solvent removal methods as described, for example, in US Pat. No. 6,932,984.

When a plasticizer is used, it is usually selected from tricapryline, trilaurin, tripalmitin, triacetin, triethyl citrate, acetyltriethyl citrate, paraffin oil, or any combination thereof.

The components of the organic solution are mixed/stirred until a homogeneous, optionally clear solution is obtained.

The first aqueous phase is saturated with an organic solvent forming an organic solution and typically includes an emulsifier. The organic solution and the first aqueous continuous phase are mixed under low shear agitation to form a mixed-component emulsion.

Additional steps in these embodiments are as described above.

Exemplary microcapsules and compositions:

In certain exemplary embodiments of the present invention, the second wall-forming material comprises 1.0 to 2.0% by weight of magnesium stearate, 30 to 75% by weight of TiO ₂ and 4 to 6% by weight of a dispersant (e.g., based on the total weight of the microcapsule) for example, isopropyl myristate of propylene glycol stearate).

In certain exemplary embodiments, the multilayer microcapsules described herein comprise a wall forming material comprising an acrylate/ammonium methacrylate copolymer alone or in admixture with a cellulose ester such as cellulose acetate.

In certain exemplary embodiments, the multilayer microcapsules described herein contain about 30-50 wt % activator, 10-30 wt % wall forming polymer or copolymer, 0.5-1 wt % magnesium stearate, 25-50 wt % % TiO ₂ and 1-6% by weight isopropyl myristate containing microcapsules inside.

In certain exemplary embodiments, at least a portion of the plurality of microcapsules included in the composition of the present invention is an opaque material in an amount of about 30-45 wt % TiO ₂ , about 10-30 wt % acrylate with respect to the total weight of the capsule. Bi-layer microcapsules comprising /wall forming material comprising ammonium methacrylate copolymer (eg Udragit®RSPO), 1 wt% magnesium stearate and 36-45 wt% activator It is a capsule.

In certain exemplary embodiments, at least a portion of the plurality of microcapsules included in the composition of the present invention is a bilayer microcapsule comprising 3.0% by weight of the dispersant isopropyl myristate.

In certain exemplary embodiments, the multilayer microcapsules as described herein contain about 10-30% by weight of an activator, 5-15% by weight of a wall-forming polymer or copolymer, 1-2% by weight, based on the total weight of the composition. and inner microcapsules comprising magnesium stearate, 30-75 wt % TiO ₂ and 4-6 wt % propylene glycol stearate.

In certain exemplary embodiments, at least a portion of the plurality of microcapsules included in the composition of the present invention comprises about 30-75 wt% TiO ₂ and about 5-15 wt% ethyl cellulose as an opaque material relative to the total weight of the capsule. A bilayer microcapsule containing 2 wt% magnesium stearate and 10-30 wt% inner microcapsules, a wall forming material comprising an acrylate/ammonium methacrylate copolymer (e.g. Udragit® RSPO) in admixture with It is a capsule.

In certain exemplary embodiments, at least a portion of the plurality of microcapsules included in the composition of the present invention comprises about 70-75 wt% TiO ₂ and about 5-10 wt% ethyl cellulose as an opaque material relative to the total weight of the capsule. A bilayer microcapsule comprising a wall-forming material comprising: 2 wt % magnesium stearate and 10-15 wt % inner microcapsule.

In certain exemplary embodiments, at least a portion of the plurality of microcapsules comprised in the composition of the present invention is a color-containing composition comprising bilayer microcapsules, the second wall forming material consists of or consists of cellulose acetate, and a dispersant Propylene glycol stearate is included in an amount of 5-6% by weight based on the total weight of the microcapsule.

Manufacture process:

The process used to prepare the microcapsules of the invention described herein is a modification of the microencapsulation solvent removal method disclosed, for example, in US Pat. is included as According to this technique, the active ingredient is found in the core of microcapsules. This technology seals each micro-encapsulated component from chemical and cross-linking reactions, degradation, color change or loss of potency during production, and for extended shelf life. The solvent removal process is based on four main steps:

(i) preparing a homogeneous organic solution comprising an encapsulant, a wall-forming polymer material, an opaque material, a plasticizer and a partially water-miscible organic solvent;

(ii) preparing an emulsion of a continuous phase comprising an emulsifier and saturated with an organic solvent such as an organic solution;

(iii) mixing the uniform organic solution and the aqueous emulsion under high shear agitation to form a mixed-component emulsion; and

(iv) extracting the organic solvent by adding to the emulsion formed in step (iii) a significant amount of water to initiate extraction of the organic solvent from the emulsion to obtain microcapsules.

As disclosed in U.S. Patent No. 7,838,037, bi-layer and tri-layer microcapsules are formed by first modifying the surface of the single-layer microcapsules formed according to steps (i)-(iv), and then the inner core microcapsules form a wall. When dispersed in an organic solution together with the material, one or more cycles of steps (i)-(iv) are performed on the surface-modified inner core microcapsule.

However, in certain embodiments of the variant methods provided herein, TiO ₂ Dissolve or disperse the same opaque material as well as the inner core microcapsules in a continuous aqueous emulsion. In addition, a fatty acid salt such as magnesium stearate is added to the organic solution. TiO ₂ is transferred to the aqueous phase and magnesium stearate is added to the organic solution to obtain bi- and tri-layer microcapsules, where TiO ₂ uniformly coats the outer polymer shell to provide a masking layer to the inner core microcapsule. Thus, in some embodiments, multilayer microcapsules according to the present invention can be prepared by a modified solvent removal method comprising the following steps:

(a) a first organic phase comprising a second wall-forming polymer or copolymer, a fatty acid salt, optionally a dispersant and a plasticizer and a first organic solvent partially miscible with water, saturated with said organic solvent, said emulsifier, opaque contacting a first aqueous solution comprising monolayer microcapsules comprising a substance and at least one colorant and a first wall-forming substance to obtain a first mixed-component emulsion;

(b) adding to the emulsion formed a significant amount of water to initiate extraction of the organic solvent from the emulsion to obtain bilayer microcapsules; and

(c) optionally repeating steps (a) and (b) using the second, third, etc. organic phases and the water continuous phase to obtain multi-layered microcapsules.

In a further step, the microcapsules are separated, dried and sieved after step (b) to obtain a flowable powder of microcapsules.

These steps are further specifically described as follows:

The homogeneous solution prepared in step (a) is an organic solution of the wall-forming polymer material in an organic solvent capable of dissolving or dispersing the wall-forming polymer or partially miscible with water as described in any one of the embodiments described herein. It is obtained by preparing a dispersion. In an exemplary embodiment, the organic solvent is an organic solvent approved for topical application, such as, but not limited to, ethyl acetate, ethanol, ethyl formate, or any combination thereof. In some embodiments, the organic solvent is ethyl acetate.

The fatty acid salt is as described in any one of the embodiments described herein. The optional dispersant is as described in any one of the embodiments described herein.

When a plasticizer is used, it is usually selected from tricapryline, trilaurin, tripalmitin, triacetin, triethyl citrate, acetyltriethyl citrate, paraffin oil, or any combination thereof.

The components of the organic solution are mixed/stirred until a homogeneous, optionally clear solution is obtained.

The first aqueous continuous phase is saturated with an organic solvent that forms an organic solution, and is typically a monolayer microcapsule (inner core, as described herein) comprising an emulsifier, an opaque material and one or more activators and a first wall forming material. microcapsules).

The opaque material may be present in any one of the embodiments described herein. as described. In a preferred embodiment, the opaque material is TiO ₂ .

Internal, eg, single-layered core microcapsules will be obtained by known solvent removal methods as disclosed, for example, in US Pat. No. 6,932,984.

The organic solution and the first aqueous continuous phase are mixed under low shear agitation to form a mixed-component emulsion.

In step (b), a significant amount of water is added to the mixed-component emulsion prepared in (a) to extract the organic solvent and form bilayer microcapsules.

If a trilayer or other multilayer microcapsule is designed, steps (a) and (b) are repeated using a second, third, etc. organic phase and several continuous phases, where the organic solvent will be the same or different and the opaque material , fatty acid salts and dispersants, as well as wall forming materials, plasticizers, may be the same or different.

In the context of an embodiment of the present invention, the term "low shear agitation" means mixing at about 100-800 rpm, preferably at about 300-600 rpm.

In certain exemplary embodiments, the components used in the process are wall-forming polymers, acrylate/ammonium methacrylate copolymers, water-miscible organic solvents, ethyl acetate, dispersants, isopropyl myristate, fats Magnesium stearate as an acid salt and TiO ₂ as an opaque material.

In any other embodiment of the modified methods provided herein, TiO ₂ The same opaque material as well as the inner core microcapsules are dissolved or dispersed in the organic phase, and fatty acid salts such as magnesium stearate are also added to the organic solution. These embodiments relate to microcapsules comprising cellulose acetate, preferably in one or more outer shells (eg second and/or outermost shells). We use cellulose acetate as one of the wall-forming polymer materials to use TiO ₂ Improved opacity was also obtained when the same opaque material was included in the organic phase, demonstrating that in the obtained bilayer and trilayer microcapsules, TiO ₂ uniformly coats the outer polymer shell to provide a masking layer to the inner core microcapsule. Thus, in some embodiments, multilayer microcapsules according to the present invention can be prepared by a modified solvent removal method comprising the following steps:

(a) a second wall-forming polymer or copolymer, a single-layer microcapsule comprising a fatty acid salt, an opaque material and one or more pigments, optionally comprising a dispersant and a plasticizer and a first organic solvent that is partially miscible with water contacting an organic phase with a first aqueous solution saturated with said organic solvent and typically comprising an emulsifier to obtain a first mixed-component emulsion;

(b) adding to the emulsion formed a significant amount of water to initiate extraction of the organic solvent from the emulsion to obtain bilayer microcapsules; and

(c) optionally repeating steps (a) and (b) using the second, third, etc. organic phase and the water continuous phase to obtain multi-layered microcapsules.

In a further step, the microcapsules are separated, dried and sieved after step (b) to obtain a flowable powder of microcapsules.

These steps are described in more detail as follows:

The homogeneous solution prepared in step (a) is partially miscible with water as described in any one of the embodiments described herein, and in an organic solvent capable of dissolving or dispersing the second wall-forming polymer. Obtained by preparing an organic solution or dispersion of a substance. In an exemplary embodiment, the organic solvent is an organic solvent approved for topical application, such as, but not limited to, ethyl acetate, ethanol, ethyl formate, or any combination thereof. In some embodiments, the organic solvent is ethyl acetate.

The fatty acid salt is as described in any one of the embodiments described herein. The optional dispersant is as described in any one of the embodiments described herein.

The opaque material is as described in any one of the embodiments described herein. In a preferred embodiment, the opaque material is TiO ₂ optionally mixed with boron nitride.

Internal, eg, single-layer core microcapsules will be obtained by known solvent removal methods as described, for example, in US Pat. No. 6,932,984.

When a plasticizer is used, it is usually selected from tricapryline, trilaurin, tripalmitin, triacetin, triethyl citrate, acetyltriethyl citrate, paraffin oil, or any combination thereof.

The components of the organic solution are mixed/stirred until a homogeneous, optionally clear solution is obtained.

The first aqueous phase is saturated with an organic solvent forming an organic solution and typically includes an emulsifier. The organic solution and the first aqueous continuous phase are mixed under low shear agitation to form a mixed-component emulsion.

Additional steps in these embodiments are as described above.

Topical Formulation:

In certain embodiments, the compositions provided herein are used in cosmetic, cosmeceutical or pharmaceutical formulations, e.g., skin care formulations, make-up or dermatological or other topical pharmaceutical formulations comprising the microcapsules described herein (e.g. For example, the color compositions described herein). The formulation may optionally and preferably further comprise a carrier and optionally additional activators and/or additives.

As used herein, a “formulation” refers to a pigment in association with a physiologically acceptable carrier and excipient described herein and optionally other chemical ingredients, such as a cosmetic, cosmeceutical or pharmaceutical (eg, drug). It refers to a vehicle in the form of an emulsion, lotion, cream, gel, powder, etc. containing microcapsules.

As used herein, the term "physiologically acceptable" means listed in the United States Pharmacopoeia or other generally recognized pharmacopeia or approved by a federal or state oversight agency for use in animals and more particularly in humans. do.

As used herein, the phrase "physiologically suitable carrier" means an approved carrier or diluent that does not cause significant irritation to living organisms and does not abrogate the properties of the biological activity and possible activator.

As used herein, the term “excipient” refers to an inert substance added to a pharmaceutical composition to further facilitate processing and administration of the active ingredient.

In certain embodiments of the present invention, the cosmetic or cosmeceutical formulation is formulated in a form suitable for topical application in the area of application.

As will be specifically described below, with a selection of suitable carriers and optionally other ingredients that may be included in the compositions, the compositions of this embodiment will be formulated in any form typically used for topical application.

The formulation may be water-based, oil-based or silicone-based.

The formulations described herein can be, for example, skin care products, make-up products (including eye shadows, makeup-ups, lipsticks, lacquers, etc., or any other product described herein).

In certain embodiments, the formulations described are in the form of creams, ointments, pastes, gels, lotions, milks, oils, suspensions, solutions, aerosols, sprays, foams, powders (eg, compressed powders or loose powders) or mousses.

Ointments are semi-solid preparations, typically based on petrolatum or petrolatum derivatives. The particular ointment base employed is one that provides optimal delivery for the active agent selected for a given formulation, and preferably also provides other desirable characteristics (eg, softening properties). As with other carriers or vehicles, the ointment base should be inert, stable, non-irritating and non-sensitizing. Remington : The Science and Practice of Pharmacy , 19th Ed., Easton, Pa.: Mack Publishing Co. (1995), pp. As described in 1399-1404, ointment bases will be classified into four categories: oily bases; oil base; emulsion base; and a water soluble base. Oily ointment bases include, for example, vegetable oils, animal fats and semi-solid hydrocarbons derived from petrolatum. Emulsifying ointment bases, also known as absorbable ointment bases, contain little water and include, for example, hydroxystearin sulfate, anhydrous lanolin and hydrophilic petrolatum. Emulsion ointment bases are either water-in-oil (W/O) emulsions or oil-in-water (O/W), and include, for example, cetyl alcohol, glyceryl monostearate, lanolin and stearic acid. Preferred water soluble ointment bases are prepared from polyethylene glycols of varying molecular weights.

Lotions are preparations that are applied to the skin surface without friction. Lotions are typically liquid or semi-liquid preparations, in which the solid particles, including microcapsules containing sunscreen, are present in a water or alcohol base. Lotions are preferred for covering/protecting large areas of the body as generally more fluid compositions are easier to apply. Lotions are generally solid suspensions and often contain liquid oily emulsions of the oil-in-water type. In general, it is necessary to finely distribute the insoluble substances in the lotion. Lotions generally contain a suspending agent for better dispersion, as well as a compound useful for positioning and holding the active agent in contact with the skin, such as methylcellulose, sodium carboxymethyl cellulose, and the like.

A cream is a viscous liquid or semi-solid emulsion, either oil-in-water or water-in-oil. Cream bases are typically washable and include an oil phase, an emulsifier and an aqueous phase. The oily phase is also referred to as the "internal" phase and generally consists of petrolatum and/or a fatty alcohol such as cetyl or stearyl alcohol. The aqueous phase generally, but not necessarily, exceeds the oil phase in volume and generally includes a wetting agent. Emulsifiers in cream formulations are generally nonionic, anionic, cationic or amphiphilic surfactants. For additional information, see Remington : The Science and Practice of Pharmacy , supra.

A paste is a semi-solid dosage form in which the bioactive agent is suspended in a suitable base. Depending on the nature of the base, pastes are divided into fat pastes or those made from single-phase water-soluble gels. In fat paste, the base is usually petrolatum, hydrophilic petrolatum, etc. Pastes prepared from single phase water-soluble gels generally contain carboxymethylcellulose or the like as a base. For additional information, reference may additionally be made to Remington : The Science and Practice of Pharmacy.

The gel formulation is a semi-solid suspension type system. Single phase gels comprise normally water-soluble organic macromolecules distributed fairly uniformly throughout the carrier liquid, but also preferably an alcohol and optionally an oil. Preferred organic macromolecules, ie gelling agents, are a family of carbomer polymers, for example crosslinked acrylic acid polymers such as carboxypolyalkylenes commercially available under the trade name Carbopol™. Other types of polymers preferred by the context include hydrophilic polymers such as polyethylene oxide, polyoxyethylene-polyoxypropylene copolymers and polyvinyl alcohol; cellulosic polymers such as hydroxypropyl cellulose, hydroxyethyl cellulose, hydroxypropyl methylcellulose, hydroxypropyl methylcellulose phthalate and methyl cellulose; gums such as tragacanth and xanthan gum; sodium alginate; and gelatin. To prepare a uniform gel, a dispersing agent such as alcohol or glycerin may be added, or the gelling agent may be dispersed by grinding, mechanical mixing or stirring, or a combination thereof.

Sprays generally provide the activator in an aqueous and/or alcoholic solution that can be sprayed for delivery to the skin. Such sprays include those formulated to provide a concentration of an active agent solution at the site of delivery after administration. For example, a spray solution may consist primarily of an alcohol or other similar volatile liquid in which the activator is soluble. Upon delivery to the skin, the carrier evaporates leaving the active agent concentrated at the site of administration.

Foam compositions are typically formulated in single or multiple phase liquid form, and are contained in a suitable container, optionally with a propellant to facilitate release of the composition from the container, to transform into a foam upon application. Other foaming techniques include, for example, "Bag-in-a-can" formulation techniques. As such, usually formulated compositions contain a low boiling hydrocarbon such as isopropane. When such a composition is applied and shaken at body temperature, the isopropane evaporates, creating a foam, in a manner similar to a pressurized aerosol foaming system. The foam can be water-based or hydroalcoholic, but is usually formulated with a high alcohol content when the user applies it to the skin and evaporates quickly while delivering the active ingredient through the upper skin layer to the treatment site.

Preparation of the formulation can be carried out through low shear mixing of the mixture after mixing and homogenizing all components except for the pigment-containing microcapsules, and finally adding the pigment-containing microcapsules.

The multilayer microcapsules of the present invention can be used in pharmaceutical compositions for topical application, for example, comprising a pharmaceutically active ingredient for dermatological or transdermal application.

In any of the formulations described herein, additives and/or additives may be included. These additives and/or additives may be encapsulated or non-encapsulated.

In some embodiments, one or more of these additives and/or additives are encapsulated.

In any of these embodiments, the additive and/or additive is encapsulated using microcapsules disclosed in any one of US Pat. Nos. 6,932,984 and 7,838,037 and WO 2009/138978.

Some non-limiting representative examples of additives and/or additives include wetting agents, deodorants, antiperspirants, sunless tanning agents, hair conditioning agents, pH adjusting agents, chelating agents, preservatives, emulsifying agents, occlusive agents. ), emollients, thickeners, solubilizers, penetration enhancers, anti-irritants, pigments, propellants and surfactants.

Without limiting to representative examples of wetting agents, guanidine, glycolic acid and glycolate salts (eg, ammonium slat and quaternary alkyl ammonium salts), aloe vera (eg, aloe vera gel) in any of the various forms, allantoin, ura Polyhydroxy alcohols such as sol, sorbitol, glycerol, hexanetriol, propylene glycol, butylene glycol, hexylene glycol, polyethylene glycol, sugars and starches, sugars and starch derivatives (eg alkoxylated glucose), hyaluronic acid ronic acid, lactamide monoethanolamine, acetamide monoethanolamine, and any combination thereof.

Suitable pH adjusting agents include, for example, one or more of adipic acid, glycine, citric acid, calcium hydroxide, magnesium aluminometasilicate, a buffer, or any combination thereof.

Representative examples of deodorants include, without limitation, cetyl-trimethylammonium bromide, cetyl pyridinium chloride, benzethonium chloride, diisobutyl phenoxy ethoxy ethyl dimethyl benzyl ammonium chloride, sodium N-lauryl sarcosine, sodium N- Palmityl sarcosine, lauroyl sarcosine, N-myristoyl glycine, potassium N-lauryl sarcosine, stearyl, trimethyl ammonium chloride, sodium aluminum chlorohydroxy lactate, tricetylmethyl ammonium chloride, 2,4 quaternary ammonium compounds such as ,4'-trichloro-2'-hydroxy diphenyl ether, diaminoalkyl amides such as L-lysine hexadecyl amide, heavy metal salts of citrate, salicylate and pyroctose, especially zinc salts and their acids, heavy metal salts of pyrithione, in particular zinc pyrithione and zinc phenolsulfate. Odor absorbing substances such as, but not limited to, carbonates and bicarbonate salts, such as alkali metal carbonates and bicarbonates, ammonium and tetraalkylammonium carbonates and bicarbonates, especially sodium and potassium salts, or any combination thereof include

Antiperspirants may be included in the compositions of the present invention, either in solubilized or particulate form, and include, for example, aluminum or zirconium astringent salts or complexes.

Representative examples of sunless tanning agents include, without limitation, dihydroxyacetone, glyceraldehyde, indole and derivatives thereof. Sunless tanning agents can be used in conjunction with sunscreen.

Chelating agents are optionally added to the formulation to enhance preservatives or preservative systems. Preferred chelating agents are mild agents such as, for example, ethylenediaminetetraacetic acid (EDTA), EDTA derivatives, or any combination thereof.

Suitable preservatives include, without limitation, one or more of alkanols, disodium EDTA (ethylenediamine tetraacetate), EDTA salts, EDTA fatty acid conjugates, isothiazolinones, parabens such as methylparaben and propylparaben, propylene glycol, sorbate, diazoline urea derivatives such as dinyl urea, or any derivative thereof.

Suitable emulsifiers, for example, one or more of sorbitan, alkoxylated fatty alcohols, alkylpolyglycosides, soaps, alkyl sulfates, monoalkyl and dialkyl phosphates, alkyl sulfonates, acyl isothionates or any thereof includes a combination of

Suitable sealants include, for example, petrolatum, mineral oil, beeswax, silicone oil, lanolin and oil-soluble lanolin derivatives, saturated and unsaturated fatty alcohols such as behenyl alcohol, hydrocarbons such as squalene, and almond oil, peanut oil, wheat germ. Oil, linseed oil, jojoba oil, apricot seed oil, walnut, palm nut, pistachio nut, sesame, rapeseed, cad oil, corn oil, peach seed oil, poppy seed oil, pine oil, castor oil, soybean oil, avocado oil, various animal and vegetable oils such as safflower seed oil, coconut oil, hazelnut oil, olive oil, grapeseed oil and sunflower seed oil.

Suitable emollients include, for example, dodecane, squalene, cholesterol, isohexadecane, isononyl isononanoate, PPG ether, petrolatum, lanolin, safflower oil, castor oil, coconut oil, cottonseed oil, palm kernel oil, palm oil, peanut oil , soybean oil, polyol carboxylic acid esters, derivatives thereof and mixtures thereof.

Suitable thickening agents include, for example, non-ionic water-soluble polymers such as hydroxyethylcellulose (commercially available under the trade name Natrosol.RTM. 250 or 350), Polyquat 37 (commercially available under the trade name Synthalen®CN). ) such as cationic water-soluble polymers, fatty alcohols, fatty acids and alkali salts thereof and mixtures thereof.

Representative examples of solubilizing agents that can be used in the context of the present invention include, without limitation, citric acid, ethylenediamine-tetraacetate, sodium meta-phosphate, succinic acid, urea, cyclodextrin, polyvinylpyrrolidone, diethylammonium -complex-forming solubilizers such as ortho-benzoate, and micellar-forming solubilizers such as TWEENS and Span, eg TWEEN 80. Other solubilizing agents that may be used in the compositions of the present invention include, for example, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene n-alkyl ethers, n-alkyl amine n-oxides, poloxamers, organic solvents, phospholipids and cyclos. It is dextrin.

Suitable penetration enhancers include, but are not limited to, dimethyl sulfoxide (DMSO), dimethyl formamide (DMF), allantoin, urazole, N,N-dimethylacetamide (DMA), decylmethylsulfoxide (C ₁₀ MSO) ), polyethylene glycol monolaurate (PEGML), propylene glycol (PG), propylene glycol monolaurate (PGML), glycerol monolaurate (GML), lecithin, 1-substituted azacycloheptan-2-ones, in particular, 1-n-dodecylclazacycloheptan-2-one ( ^{available under the trade name Azone RTM} from Whitby Research Incorporated, Virginia, USA), alcohol, and the like. The penetration enhancer may also be a vegetable oil. Such oils include, for example, safflower oil, cottonseed oil and corn oil.

Suitable anti-irritants, for example, steroidal and non-steroidal anti-inflammatory agents or aloe vera, chamomile, alpha-bisabolol, kola tree extract, green tea extract, tea tree oil, licorice extract, allantoin, caffeine or other xanthines, gly other substances such as series acids and derivatives thereof.

Exemplary additional active agents according to these embodiments of the present invention include, without limitation, antibiotics, antimicrobial agents, anti-acne agents, anti-aging agents, wrinkle reducing agents, skin lightening agents, sebum reducing agents, antibacterial agents, antifungal agents, antiviral agents. , one or more steroidal anti-inflammatory agents, non-steroidal anti-inflammatory agents, anesthetics, antipruritic agents, antiprotozoal agents, antioxidants, antitumor agents, immunomodulators, interferons, antidepressants, antihistamines, vitamins, hormones and antidandruff agents, or any combination thereof includes

Examples thereof include alpha-hydroxy acids and esters, beta-hydroxy acids and esters, polyhydroxy acids and esters, kojic acids and esters, ferulic acid and ferulate derivatives, vanillic acid and esters, dioic acids (e.g. sebaside and azole acid) and esters, retinol, retinal, retinyl esters, hydroquinone, t-butyl hydroquinone, mulberry extract, licorice extract and resorcinol derivatives.

In the context of the present invention, suitable anti-acne agents that may be used include, without limitation, keratolytic agents such as salicylic acid, sulfuric acid, glycolic acid, pyruvic acid, resorcinol and N-acetylcysteine, and retinoic acid and its derivatives (e.g. for example, cis and trans, esters) such as retinoids.

In the context of the present invention, suitable antibiotics that may be used include, without limitation, benzoyl peroxide, octopirox, erythromycin, zinc, tetracycline, triclosan, azelaic acid and its derivatives, phenoxyethanol and phenoxy. propanol, ethyl acetate, clindamycin and meclocycline; sevostats such as flavonoids; alpha and beta hydroxy acids; and bile salts such as skimnol sulfate and its derivatives, deoxycholate and cholate.

Representative examples of nonsteroidal anti-inflammatory agents that may be used in the context of the present invention include, without limitation, oxicams such as piroxicam, isoxicam, tenoxicam, sudoxicam and CP-14,304; salicylates such as aspirin, disalside, benorylate, trilysate, safariin, solfrin, diflunisal and pendosal; Diclofenac, penclofenac, indomethacin, sulindac, tolmetin, isocepac, furofenac, thiopinac, zidomethacin, acematacin, pentiazak, zomepirac, clindanac, oxepinac, felvinac and acetic acid derivatives such as ketorolac; phenamates, such as mefenamic, meclofenamic, flufenamic, niflumic and tolfenamic acid; Ibuprofen, naprosen, benoxaprofen, flubiprofen, ketoprofen, fenoprofen, fenbufen, indoprofen, pirprofen, carprofen, oxaprozin, pranoprofen, miroprofen , propionic acid derivatives such as thioxaprofen, suprofen, aluminopropene and thiapropenic; pyrazoles such as phenylbutazone, oxyfebutazone, peprazone, azapropazone and trimetazone. Dermatologically acceptable salts and esters of these agents as well as mixtures of these non-steroidal anti-inflammatory agents will also be used. For example, etofenamate, a derivative of flufenamic acid, is particularly useful for topical application.

Representative examples of steroidal anti-inflammatory drugs include, without limitation, hydrocortisone, hydroxytriamcinolone, alpha-methyl dexamethasone, dexamethasone-phosphate, beclomethasone dipropionate, clobetazole valerate, desonide, disoxymetha Son, disoxycorticosterone acetate, dexamethasone, dichlorisone, diflorasone diacetate, diflucotolone valerate, fluadrenolone, fluchlorolone acetonide, fludrocortisone, flumethasone pivalate, fluoro Sinolone Acetonide, Fluosinonide, Flucortin Butyl Ester, Fluorocortolone, Fluprednidene (Fluprednylidene) Acetate, Flurandrenolone, Halsinonide, Hydrocortisone Acetate, Hydrocortisone Butyrate, Methylprednisolone , triamcinolone acetonide, cortisone, cortodoxone, flucetonide, fludrocortisone, difluorosone diacetate, fluradrenolone, fludrocortisone, diflurosone diacetate, fluradrenolone acetonide, medrisone, Amcinafel, Amcinapide, Betamethasone and its esters balance, chloroprednisone, chlorprednisone acetate, clocortelone, clecinolone, dichlorisone, difluprednate, fluchloronide, flunisolide, fluorometallone corticosteroids such as fluferolone, fluprednisolone, hydrocortisone valerate, hydrocortisone cyclopentylpropionate, hydrocortamate, meprednisone, paramethasone, prednisolone, prednisone, beclomethasone dipropionate, triamcinolone and mixtures thereof Includes steroids.

Suitable antipruritic agents include, without limitation, pharmaceutically acceptable salts of metdylazine and trimeprazine.

Non-limiting examples of anesthetic drugs that may be used in the context of the present invention include lidocaine, bupivacaine, chlorprocaine, dibucaine, etidocaine, mepivacaine, tetracaine, diclonaine, hexylcaine, pharmaceutically acceptable salts of procaine, cocaine, ketamine, pramoxine and phenol.

Suitable antimicrobial agents that may be used in the context of the present invention, including, without limitation, antibacterial, antifungal, antiprotozoal and antiviral agents, beta-lactam drugs, quinolone drugs, ciprofloxacin, norfloxacin, tetracycline, erythr Romaycin, amikacin, triclosan, doxycycline, capreomycin, chlorhexidine, chlortetracycline, oxytetracycline, clindamycin, ethambutol, metronidazole, pentamidine, gentamicin, kanamycin, lineomycin, metacycline, methenamine, minocycline, neomycin, netylmycin, streptomycin, tobramycin and miconazole. In addition, tetracycline hydrochloride, farnesol, erythromycin estolate, erythromycin stearate (salt), amikacin sulfate, doxycycline hydrochloride, chlorhexidine gluconate, chlorhexidine hydrochloride, chlorhexidine hydrochloride , oxytetracycline hydrochloride, clindamycin hydrochloride, ethambutol hydrochloride, metronidazole hydrochloride, pentamidine hydrochloride, gentamicin sulfate, kanamycin sulfate, lineomycin hydrochloride, metacycline hydrochloride, methenamine hyporate, methenama phosphorus mandelate, minocycline hydrochloride, neomycin sulfate, netylmycin sulfate, paromomycin sulfate, streptomycin sulfate, tobramycin sulfate, miconazole hydrochloride, amanfadine hydrochloride, amanfadine sulfate, triclosan, octopirox, parachloromethasilenol, nystatin, tolnaftate and clotrimazole and mixtures thereof.

Non-limiting examples of antioxidants that may be used in the context of the present invention include ascorbic acid (vitamin C) and its salts, ascorbyl esters of fatty acids, ascorbic acid derivatives (e.g. magnesium ascorbyl phosphate, sodium ascorbyl phosphate, ascorbyl sorbate), tocopherol (vitamin E), tocopherol sorbate, tocopherol acetate, other esters of tocopherol, butylated hydroxybenzoic acid and salts thereof, 6-hydroxy-2,5, 7,8-tetramethylchroman-2-carboxylic acid ( ^{commercially available under the trade name Trolox R} ), gallic acid and its alkyl esters, in particular propyl gallate, uric acid and its salts and alkyl esters, sorbic acid and its alkyl esters salts, lipoic acid, amines (eg N,N-diethylhydroxylamine, amino-guanidine), sulfhydryl compounds (eg glutathione), dihydroxy fumaric acid and salts thereof, lysine pidolate, arginine pyrrolate, nordihydroguaiaretic acid, bioflavonoids, curcumin, lysine, methionine, proline, superoxide dismutase, silymarin, tea extract, grape skin/seed extract, melanin and rosemary extract.

Non-limiting examples of anti-tumor agents that may be used in the context of the present invention include daunorubicin, doxorubicin, idarubicin, amrubicin, pyrarubicin, epirubicin, mitoxantrone, etoposide, teni. Forside, vinblastine, vincristine, mitomycin C, 5-FU, paclitaxel, docetaxel, actinomycin D, colchicine, topotecan, irinotecan, gemcitabine cyclosporine, verapamil, valspodor, probenecid, MK571, GF120918, LY335979, viricodar, terfenadine, quinidine, ferbilin A and XR9576.

Non-limiting examples of antidepressants that may be used in the context of the present invention include, but are not limited to, amitriptyline, desmethylamitriptyline, clomipramine, doxepin, imipramine, imipra norepinephrine-reuptake inhibitors such as mine-oxide, trimipramine; Adinazolam, amyltriptylinoxide, amoxapine, desipramine, maprothyline, nortriptyline, protriptyline, aminephthine, butriptyline, dimexiftyline, dibenzepine, dimethacrine , dothiepin, fluasizine, ifrindol, iopepramine, melitracene, metapramine, norchloripramine, noxiptyline, opipramol, perrapine, pizotilin, propizepine, quinupramine, Reboxetine, tianeptine and, but not limited to, binedaline, m-chloropiperzine, citalopram, duloxetine, etoperidone, pemoxetine, fluoxetine, fluvoxamine, indalphine, indeloxazine, wheat Norepinephrine-reuptake inhibitors (“NRIs”), as well as serotonin-reuptake inhibitors such as nacipran, nefazodone, oxaplazone, paroxetine, prolintan, ritanserine, sertraline, tandospiron, venlafaxine and zimeldin , selective-serotonin-reuptake inhibitors (SSRIs), monoamine-oxidase inhibitors (MAOIs), serotonin-and-noradrenaline-reuptake inhibitors ("SNFIs), corticotropin-releasing factor (CRF) antagonists, α- adrenoreceptor antagonists, NKI-receptor antagonists, 5-HT _1A -receptor agonists, antagonists and partial agonists and atypical antidepressants.

Exemplary anti-dandruff agents include, without limitation, zinc pyrithione, shale oil and derivatives thereof such as sulfonated shale oil, selenium sulfide, sulfur; Salicylic acid, coal tar, povidone-iodine, imidazoles such as ketoconazole, dichlorophenyl imidazolodioxalane, clotrimazole, itraconazole, miconazole, climbazole, thioconazole, sulconazole, butoconazole, fluconazole, miconazolenitrite and any possible stereoisomers and derivatives thereof such as anthralin, piroctone olamine (octopirox), selenium sulfide and ciclopirox olamine and mixtures thereof.

Non-limiting examples of vitamins include vitamin A and analogs and derivatives thereof; Retinol, retinal, ritenyl palmitate, retinoic acid, tretinoin, iso-tretinoin (collectively known as retinoids), vitamin E (tocophenol and its derivatives), vitamin C (L-ascorbic acid and its esters and other derivatives) , vitamin B ₃ (niacinamide and its derivatives), alpha hydroxy acids (such as glycolic, lactic, tartaric, malic, citric, etc.) and beta hydroxy acids (such as salicylic acid).

Non-limiting examples of dermatologically active ingredients that may be used in the context of the present invention include ammonium phenolsulfonate, bismuth subgallate, zinc phenolsulfonate and zinc salicylate, as well as jojoba oil and methyl salicylate, aromatic oils such as wintergreen, peppermint oil, bay oil, eucalyptus oil and citrus oil. Non-limiting examples of antifungal agents include miconazole, clotrimazole, butoconazole, penticonazole, thioconazole, terconazole, sulconazole, fluconazole, haloprogine, ketonazole, ketoconazole, oxinazole. , econazole, itraconazole, terbinafine, nystatin and grithafulvin.

Non-limiting examples of antihistamines that may be used in the context of the present invention include, but are not limited to, chlorpheniramine, brompheniramine, dexchlorpheniramine, tripolidine, clemastine, diphenhydramine, promethazine, piperazine, piperidine. , astemizole, iolatadine and terfenadine.

Many related pigments, wall forming materials and opaque materials will be developed from this application during the patent expiry period, and the scope of the terms "colorant", "wall forming polymer" and "opaque material" is intended to include all such new technologies a priori. it is expected

The terms “comprise”, “comprising”, “contains”, “comprising”, “having” and their conjugations mean “including, but not limited to,”.

The term “comprising” means “including, but not limited to”.

The term “consisting essentially of” means that a composition, method, or structure includes additional components, steps and/or members, but the additional components, steps and/or members are fundamental and novel to the composition, method, or structure in which they are claimed. This means that the features are not substantially changed.

As used herein, the singular forms “a”, “an” and “the” include plural references unless the context clearly dictates otherwise. For example, the term “a compound” or “at least one compound” shall include a plurality of compounds, including mixtures thereof.

Throughout this application, various embodiments of the invention will be presented in scope format. It is to be understood that the description in range format is for convenience and brevity only, and should not be construed as an unalterable limitation on the scope of the invention. Accordingly, range statements are to be considered as specifically reciting each numerical value within that range, as well as all possible subranges. For example, a range such as 1 to 6 includes each number within that range, such as 1, 2, 3, 4, 5, and 6, as well as 1 to 3, 1 to 4, 1 to 5, 2 to 4 , 2 to 6, 3 to 6, etc. are to be considered as having specifically disclosed subranges.

Whenever a numerical range is recited herein, it is meant to include any recited number (fractional or integer) within the indicated range. The phrases "before/before" the first designated number and the second designated number and "to/before" the first designated number "from" the second designated number" Used interchangeably herein, it is meant to include first and second designated numbers and all fractions and integers therebetween.

The terms “weight ratio” or “wt%” or “% wt.” are used interchangeably herein.

As used herein, the term “method” includes, but is not limited to, those manners, means, known to those skilled in the art of chemistry, pharmacy, biology, biochemistry and medicine, or readily developed from known manners, means, techniques and procedures. means methods, means, techniques and processes for achieving a given task, including , techniques and processes.

As used herein, the term "treating" refers to abrogating, substantially inhibiting, slowing or reversing the progression of a condition, substantially ameliorating the clinical or aesthetic symptoms of a condition, or the appearance of clinical or aesthetic symptoms of a condition. substantially inhibiting.

It is understood that certain features of the invention, which are described for clarity in the context of individual embodiments, will also be provided in combination in a single embodiment. Conversely, various features of the invention, which are described for brevity in the context of a single embodiment, will be provided individually, in any suitable subcombination, or suitably in any other described embodiment of the invention. Certain features recited in the context of various embodiments are not considered essential features of the embodiment if the embodiment did not work without those elements.

Various embodiments and aspects of the invention precisely described above and claimed in the claims below are finding experimental support in the following examples.

Example

In addition to the above description, the following examples, illustrating certain embodiments of the invention in a non-limiting manner, are now arranged for reference.

Example One

containing red pigment double layer Preparation of microcapsules

Preparation of Organic Phase/Master Batch (MB):

The organic phase (referred to herein interchangeably as “master batch, MB”) was slowly added to 117.4 g of ethyl acetate by ^{10 g of wall-forming polymer, acrylate/ammonium methacrylate copolymer (EUDRAGIT ® RSPO) at room temperature.} and the resulting mixture was stirred (about 10 minutes) until a homogeneous and transparent mixture was obtained. 1 g of magnesium stearate was added to the solution with stirring for 2 minutes, and finally 3 g of boron nitride was added during an additional 2 minutes of stirring. MB components are shown in Table 1 below.

Masterbatch Ingredients reagent Loading amount (100g MB) One Acrylate/ammonium methacrylate copolymer
(Udragit RSPO, Evonik Industries, Germany) 10.0 2 boron nitride
(Dandong, Chemical Engineering Institute Co., Ltd, China) 3.0 3 magnesium stearate
(Faci Asia pacific Pte Ltd, Singapore) 1.0 4 ethyl acetate
(Gadot, Israel) 117.4

Preparation of the emulsion:

An aqueous solution was prepared by mixing water (550 g) and a polyvinyl alcohol 4% solution (PVA 4%; 36.7 g) so that the final concentration of PVA in the aqueous phase was 0.25 wt%. Then, an opaque material, titanium dioxide (TiO ₂ ; 41 g) was added while stirring (450 rpm), followed by stirring for the first 5 minutes and then homogenized for an additional 8 minutes (2500 rpm). Ethyl acetate (65.2 g) was added to the aqueous phase with stirring at 450 rpm for 2 min. Then, single-layer microcapsules containing a red pigment (ferric trioxide; 45 g), designated herein as "Red Inners", were prepared as described in US Pat. No. 6,932,984 (with or without plasticizer), and aqueous phase was stirred for 2 minutes was added slowly. While stirring at 450 rpm, the above-described MB containing the dissolved or dispersed polymer was slowly added to the ethyl acetate/water emulsion and stirred for an additional 2 minutes such that these microcapsules were covered or surrounded by an additional layer of wall-forming material. . The ratio of MB:emulsion (w/w) is 1:3. The components of the emulsion are shown in Table 2.

Emulsion Ingredients reagent Loading amount (g) One water 550.0 2 PVA (Mowiol 4-88, kSE solution 4%; Kuraray America, Inc., USA) 36.7 3 ethyl acetate 65.2 4 TiO ₂ (RC402, Sachtleben, Germany) 41.0 5 red ferric trioxide 45.0 6 MB 131.4

of organic solvents extraction:

In a 10 L cylindrical vessel, extraction medium consisting of 3,796 g of water was slowly added to the emulsion described above (869.6 g) using a hand pump while stirring at 150 rpm. The extract phase was stirred for an additional 15 minutes. The resulting mixture was left as a precipitate at room temperature for about 5 hours. The components of the extraction medium are shown in Table 3.

Components of the extraction medium reagent Loading amount (g) One emulsion 869.6 extract 2 water 3,796.0

Washing, drying and sieving :

The microcapsules obtained in step 1.3 were separated through vacuum filtration. The upper liquid phase was poured from the cylindrical vessel, the remaining suspension was shaken and filtered, and the precipitate was washed with 400 mL of water in the filter. The suspension was transferred to a dry container and the microcapsules were stored at 4°C. In the drying step, the microcapsules were lyophilized for 48 hours.

In the sieving step, the dried microcapsules were subjected to an automatic sieving machine "Ari j-Levy", Sifter MIC. 300 was used for sieving. The sieved microcapsules were stored in a suitable container in a refrigerator.

Example 2

containing red pigment double layer Preparation of plasticizer-containing microcapsules

Bi-layered microcapsules comprising an inner core microcapsule comprising an outer shell containing a red pigment and a plasticizer (triethyl citrate) were prepared as described in Example 1 above, except that a plasticizer was used.

Thus, the wall-forming polymer, acrylate/ammonium methacrylate copolymer (EUDRAGIT ^® RSPO; 14.5 g) is slowly added to 117.4 g of ethyl acetate at room temperature while stirring well until the mixture is uniform and transparent to master batch (MB) was prepared. Next, a plasticizer, triethyl citrate (4.5 g) was added to the mixture with stirring. Then, 1 g of magnesium stearate was added to the solution with stirring for 2 minutes, and finally, 3 g of boron nitride was added during an additional 2 minutes of stirring.

As described in Example 1, water (550 g) and a polyvinyl alcohol 4% solution (PVA 4%; 36.7 g) were mixed so that the final concentration was 0.25% PVA, followed by stirring (450 rpm) with TiO ₂ (41 g) ) was added, but first stirred for 5 minutes and then homogenized (2500 rpm) for an additional 8 minutes to prepare an emulsion. Then, ethyl acetate (65.2 g; stirred at 450 rpm for 2 minutes) was added, and Red Inners (monolayer microcapsules containing 36 g of red pigment ferric trioxide) were slowly added. The MB from the previous step was slowly added while stirring at 450 rpm and stirred for an additional 2 minutes so that these microcapsules were covered or surrounded by an additional layer of wall-forming material comprising a plasticizer. The ratio of MB:emulsion (w/w) was 1:3.

Extraction of ethyl acetate and formation of bilayer microcapsules followed by washing, drying and sieving of microcapsules were performed as described in Example 1. The main components of the obtained microcapsules are shown in Table 4.

reagent Loading amount (100g MB) One Acrylate/ammonium methacrylate copolymer
(Udragit RSPO, Evonik Industries, Germany) 14.5 2 triethyl citrate 4.5 3 boron nitride
(Dandong Chemical Engineering Institute Co., Ltd, China) 3.0 4 magnesium stearate
(Faci Asia Pacific Pte Ltd, Singapore) 1.0 5 TiO ₂ (RC402, Sachtleben, Germany) 41 6 red ferric trioxide 36

Example 3

containing yellow pigment double layer , Preparation of plasticizer-containing microcapsules:

Bi-layered microcapsules comprising an inner core microcapsule comprising an outer shell containing a yellow pigment (iron oxide) and a plasticizer (triethyl citrate) are described in U.S. Pat. No. 6,932,984 (with or without plasticizer) instead of red inners. Prepared as described in Examples 1 and 2 above using yellow pigmented iron oxide capsules (yellow inners) as described. The main components of the obtained microcapsules are shown in Table 5.

reagent Loading amount (100g MB) One Acrylate/ammonium methacrylate copolymer
(Udragit RSPO, Evonik Industries, Germany) 20.5 2 triethyl citrate 4.5 3 boron nitride
(Dandong Chemical Engineering Institute Co., Ltd, China) 3.0 4 magnesium stearate
(Faci Asia Pacific Pte Ltd, Singapore) 1.0 5 TiO ₂ (RC402, Sachtleben, Germany) 35 6 yellow iron oxide 36

Example 4

containing black pigment double layer , Preparation of plasticizer-containing microcapsules:

A double-layered microcapsule comprising an inner core microcapsule comprising an outer shell containing a black pigment (triferric tetraoxide) and a plasticizer (triethyl citrate) is disclosed in U.S. Patent No. 6,932,984 using black inners instead of red inners. Prepared as described in Examples 1 and 2 above, as described in paragraph (with or without plasticizer). The main components of the obtained microcapsules are shown in Table 6.

reagent Loading amount (100g MB) One Acrylate/ammonium methacrylate copolymer
(Udragit RSPO, Evonik Industries, Germany) 14.5 2 triethyl citrate 4.5 3 boron nitride
(Dandong Chemical Engineering Institute Co., Ltd, China) 3.0 4 magnesium stearate
(Faci Asia Pacific Pte Ltd, Singapore) 1.0 5 TiO ₂ (RC402, Sachtleben, Germany) 41 6 black iron oxide 36

Example 5

isopropyl Myristate and a red pigment. double layer Preparation of microcapsules

The present inventors have found that by including isopropyl myristate (IPM) as the wall-forming material of the double-layered microcapsules, soft, much more easily spreadable microcapsules are obtained. Upon application to the skin, the microcapsules containing the IPM break and release their contents much more readily. In the exemplary microcapsules, IPM was used in an amount of about 5% by weight based on the total weight of the microcapsules. When the microcapsule is broken, the encapsulated pigment is released and coated with an oily IPM, which is the reason for a smoother and more uniform application of the pigment on the skin. Thus, isopropyl myristate is considered to act as both a plasticizer and a dispersant.

According to the exemplary encapsulation procedure provided herein, IPM is added to the master batch (MB) while consuming _{TiO 2 added to the emulsion.}

Thus, for the preparation of pigment- and IPM-containing microcapsules, the master batch was prepared by ^{slowly adding a wall-forming polymer, an acrylate/ammonium methacrylate copolymer (UDRAGIT ®} RSPO; 14.5 g) to ethyl acetate at room temperature so that the mixture was It was prepared with good stirring (about 10 minutes) until uniform and transparent. A plasticizer, triethyl citrate (4.5 g) was added with stirring. Then IPM was added and the organic phase was stirred for 2 minutes. Then, 1 g of magnesium stearate was added to the solution with stirring for 2 minutes, and finally, 3 g of boron nitride was added during an additional 2 minutes of stirring.

Formation of an emulsion of MB and its mixture followed by extraction with an organic solvent was carried out as described in Examples 1 and 2. Washing, drying and sieving of the microcapsules were performed as described in Example 1. The main components of the obtained microcapsules are shown in Table 7.

reagent Loading amount (100g MB) One Acrylate/ammonium methacrylate copolymer
(Udragit RSPO, Evonik Industries, Germany) 14.5 2 triethyl citrate 4.5 3 Isopropyl Myristate 5 4 boron nitride
(Dandong Chemical Engineering Institute Co., Ltd, China) 3.0 5 magnesium stearate
(Faci Asia Pacific Pte Ltd, Singapore) 1.0 6 TiO ₂ (RC402, Sachtleben, Germany) 36 7 red ferric trioxide 36

Example 6

isopropyl Myristate and a yellow pigment. double layer Preparation of microcapsules

Bi-layered microcapsules comprising an inner core microcapsule comprising an outer shell comprising a yellow pigment (iron oxide) and an IPM and a plasticizer (triethyl citrate) as described in Example 3 were prepared as described in Example 5 above. prepared together. The main components of the obtained microcapsules are shown in Table 8.

reagent Loading amount (100g MB) One Acrylate/ammonium methacrylate copolymer
(Udragit RSPO, Evonik Industries, Germany) 20.5 2 triethyl citrate 4.5 3 Isopropyl Myristate 5 4 boron nitride
(Dandong Chemical Engineering Institute Co., Ltd, China) 3.0 5 magnesium stearate
(Faci Asia Pacific Pte Ltd, Singapore) 1.0 6 TiO ₂ (RC402, Sachtleben, Germany) 30 7 yellow iron oxide 36

Example 7

isopropyl Myristate and a black pigment double layer Preparation of microcapsules

As described in Example 4, bilayered microcapsules comprising an inner core microcapsule comprising an outer shell comprising a black pigment (triferric tetraoxide), an IPM and a plasticizer were prepared as described in Example 5 above. did. The main components of the obtained microcapsules are shown in Table 9.

reagent Loading amount (100g MB) One Acrylate/ammonium methacrylate copolymer
(Udragit RSPO, Evonik Industries, Germany) 14.5 2 triethyl citrate 4.5 3 Isopropyl Myristate 5 4 boron nitride
(Dandong Chemical Engineering Institute Co., Ltd, China) 3.0 5 magnesium stearate
(Faci Asia Pacific Pte Ltd, Singapore) 1.0 6 TiO ₂ (RC402, Sachtleben, Germany) 36 7 black ferric tetraoxide 36

Example 8

containing red iron oxide double layer cellulose Acetate microcapsules ( Cameleon Preparation of red microcapsules)

Preparation of organic phase/master batch:

The wall forming polymer, cellulose acetate, is slowly added to ethyl acetate at room temperature, then the acrylate/ammonium methacrylate copolymer is added with stirring and stirred until the mixture is homogeneous and transparent to the organic phase (herein interchangeably referred to as "Master Batch, MB") was prepared. Then, as described herein for IPM, propylene glycol stearate, acting as a dispersant/plasticizer, was added to the solution and stirred for about 5 minutes, then magnesium stearate (MgSt) was added and stirred for about 5 minutes. . Then, titanium dioxide (TiO ₂ ) was added to the mixture and stirred for about 5 minutes, and the obtained mixture was homogenized for about 8 minutes. Then, Red inner capsules (as described in Example 1) were added and stirred for about 5 minutes.

Each content of the component and MB component is shown in Table 10 below.

Master Batch Ingredients reagent Loading amount (100g MB) Cellulose Acetate 7.5 Acrylate/ammonium methacrylate copolymer 4 Propylene glycol stearate 4 magnesium stearate 2 TiO ₂ 54.5 red inner capsule 28 ethyl acetate 233.3

Preparation of the emulsion:

A 4% aqueous solution of polyvinyl alcohol (PVA) is added to water, followed by a 4% aqueous solution of Ceteareth 25 (polyoxyethylene ether acting as an emulsifier), then added to aqueous ethyl acetate for about 1-2 minutes. An emulsion was prepared by stirring. Then, the MB described above was slowly added to the emulsion with stirring at about 400 rpm for 2 minutes. The ratio (w/w) of master batch and emulsion was 1:3. The components and each content of the emulsion are shown in Table 11.

Emulsion Ingredients reagent Loading amount (g) water 808 PVA 90 Ceteareth 25 2.25 ethyl acetate 100 MB 333.3

of organic solvents extraction:

The extraction medium consisted of a mixture of water and a 4% aqueous PVA solution (ie, the final concentration of PVA in the extract was 0.2% PVA). The emulsion described above was slowly added to the extract in a 15 L cylindrical vessel using a hand pump while stirring at 150 rpm, and the resulting mixture was stirred for an additional 15 minutes. The resulting mixture was left as a precipitate at 25° C. for about 24 hours. The components and contents of the extraction medium are shown in Table 12.

Components of the extraction medium reagent Loading amount (g) emulsion 1333.3 water 4180 4% PVA solution 144

Washing, drying and sieving :

The obtained microcapsules were isolated through either precipitation or vacuum filtration. During the precipitation process, the upper liquid phase of the cylindrical vessel was discarded, the remaining suspension was shaken and transferred to a drying vessel. During the filtration process, the upper liquid phase was discarded in a cylindrical vessel, the remaining suspension was shaken and filtered, and the precipitate was washed in the filter with 400 mL of water. In the drying step, the microcapsules were lyophilized for up to 48 hours.

In the sieving step, the dried microcapsules were subjected to an automatic sieving machine "Arj j-Levy", Sifter MIC. 100 was used for sieving. The sieved microcapsules were stored in a suitable container at room temperature.

The main components of the obtained microcapsules are shown in Table 13.

reagent Loading amount (100g) One Cellulose Acetate 7.5 2 Acrylate/ammonium methacrylate copolymer 4.0 3 Propylene glycol stearate 4.0 4 magnesium stearate 2.0 5 TiO ₂ 54.5 6 red inner capsule 28

Example 9

Double layer containing black iron oxide cellulose Preparation of acetate microcapsules (Cameleon Black microcapsules)

MB was prepared as described in Example 9 using black inner capsules prepared as described in Example 4. Then, bi-layered microcapsules containing a black inner core were prepared using an emulsion, extraction medium and procedure as described herein in Example 8. The main components of the obtained microcapsules are shown in Table 14.

reagent Loading amount (100g) One Cellulose Acetate 7.5 2 Acrylate/ammonium methacrylate copolymer 4.0 3 Propylene glycol stearate 4.0 4 magnesium stearate 2.0 5 TiO ₂ 54.5 6 black inner capsule 28

Example 10

double layer containing yellow iron oxide cellulose Preparation of acetate microcapsules ( Cameleon yellow microcapsules)

MB was prepared as described in Example 8 using yellow inner capsules prepared as described in Example 3. Then, bi-layered microcapsules containing a black inner core were prepared using an emulsion, extraction medium and procedure as described herein in Example 8.

The main components of the obtained microcapsules are shown in Table 15.

reagent Loading amount (100g) One Cellulose Acetate 7.5 2 Acrylate/ammonium methacrylate copolymer 4.0 3 Propylene glycol stearate 4.0 4 magnesium stearate 2.0 5 TiO ₂ 54.5 6 yellow inner capsule 28

Example 11

ferric ammonium Ferrocyanide (Iron Blue) containing with double layer old cellulose Preparation of acetate microcapsules ( Cameleon Blue microcapsules )

Preparation of organic phase/master batch steps:

Cellulose acetate was added slowly with stirring to ethyl acetate at room temperature and stirred well until the mixture was homogeneous and transparent to prepare an organic phase (referred to herein interchangeably as "master batch"). Then, magnesium stearate (MgSt) was added to the solution and stirred for about 5 minutes, and then boron nitrite (BN) was added and stirred for about 5 minutes. Then, titanium dioxide (TiO ₂ ) was added to this solution and stirred for about 5 minutes, and the obtained mixture was homogenized for about 8 minutes. An inner core of iron blue prepared as described in US Pat. No. 6,932,984 (with or without plasticizer) was added to the mixture and stirred for about 5 minutes. The components and contents of MB components are shown in Table 16.

Master Batch Ingredients reagent Loading amount (100g MB) Cellulose Acetate 6 magnesium stearate 2 boron night light 8.8 TiO ₂ 72 Royal blue inner capsule 11.2 ethyl acetate 233.3

Preparation of the emulsion:

A 4% aqueous solution of polyvinyl alcohol (PVA) is added to water with stirring, followed by a 4% aqueous solution of Ceteareth 25 (polyoxyethylene ether acting as an emulsifier), which is then added to aqueous phase ethyl acetate to about 1 An emulsion was prepared by stirring for -2 minutes. Then, the MB described above was slowly added to the emulsion and stirred at about 400 rpm for 2 minutes. The ratio (w/w) of master batch and emulsion was 1:3. The components and each content of the emulsion are shown in Table 17.

Emulsion Ingredients reagent Loading amount (g) water 910 PVA 90 ethyl acetate 100 MB 333.3

of organic solvents extraction:

The extraction medium consisted of a mixture of water and a 4% aqueous solution of PVA (ie, the final concentration of PVA in the extract was 0.2% PVA). The emulsion described above was slowly added to the extract using a hand pump while stirring at 150 rpm in a 15 L cylindrical vessel, and the resulting mixture was stirred for an additional 15 minutes. The resulting mixture remained as a precipitate at 25° C. for about 24 hours. The components and contents of the extraction medium are shown in Table 18.

Extraction Media Components reagent Loading amount (g) emulsion 1333.3 water 4178 4% PVA solution 144

Washing, drying and sieving of the microcapsules were performed as described in Example 8.

The main components of the obtained microcapsules are shown in Table 19.

reagent Loading amount (100g) One Cellulose Acetate 6 2 magnesium stearate 2 3 boron night light 8.8 4 TiO ₂ 72 5 Royal Blue Inner Capsule 11.2

Example 12

chrome oxide containing green double layer cellulose Preparation of acetate microcapsules (Cameleon Green microcapsules )

MB was prepared as described in Example 8 using a green inner capsule comprising chromium oxide green prepared as described in US Pat. No. 6,932,984 (with or without plasticizer). Then, bilayer microcapsules containing a green inner core were prepared using an emulsion, extraction medium and procedure as described herein in Example 8.

The main components of the obtained microcapsules are shown in Table 20.

reagent Loading amount (100g) One Cellulose Acetate 5 2 Acrylate/ammonium methacrylate copolymer 4 3 Propylene glycol stearate 6 4 magnesium stearate 2 5 TiO ₂ 49 6 green inner capsule 34

Example 13

Color test results (X-Rite)

As listed here, encapsulating either red, black or yellow pigments different from the instant microcapsules free of fatty acid salts and the process used for their manufacture (herein named RedCap New, BlackCap New and YellowCap New, respectively) The colors of the microcapsules of this embodiment and commercial microcapsules encapsulating the same pigment (herein named RedCap 1, BlackCap 1 and YellowCap 1) were measured and specifically described.

Visual and qualitative comparative measurements of color brightness of microcapsules according to an exemplary embodiment of the present invention, both containing the same pigment, or formulations comprising any one of the commercial microcapsules mentioned herein are shown in FIGS. 1-4 . It was.

1 shows three plates containing powder containing commercial microcapsules (top plate) encapsulating black, red or yellow pigments known as “TagraCap1” (BlackCap1, RedCap1 and YellowCap1), and Examples 5, 6 and As described in 7, three plates containing powder containing microcapsules of the present invention (bottom plate) encapsulated with the same black, red or yellow pigment are shown.

2 is a left vial containing a basic body lotion cream comprising exemplary pigment-containing microcapsules (YellowCap New, RedCap New, BlackCap New) according to certain embodiments of the present invention, as described in Examples 5, 6 and 7; and three pairs of vials with the right vial containing the commercial microcapsules described herein (RedCap 1, BlackCap 1 and YellowCap 1).

As is clearly shown in both Figures 1 and 2, powder formulations comprising exemplary microcapsules according to certain embodiments of the present invention, particularly formulations comprising red and black pigments, are significantly higher than formulations comprising commercial microcapsules. brighter and more radiant

Figure 3 shows three plates (top plate) containing powders containing commercial microcapsules encapsulating black, red or yellow pigments known as “TagraCap1” (RedCap1, BlackCap1 and YellowCap1), each run named CameleonCaps. As described in Examples 8, 9 and 10, three plates (bottom plate) containing powders containing microcapsules of the present invention encapsulating the same red, black or yellow pigment are shown.

4 is a left vial containing a basic body lotion cream comprising exemplary pigment-containing microcapsules (Cameleon Red, Cameleon Black, Cameleon Yellow) according to certain embodiments of the present invention, as described in Examples 8, 9 and 10; and the three pairs of vials on the right containing the commercial microcapsules (RedCap 1, BlackCap 1 and YellowCap 1) described herein are shown.

3 and 4 further demonstrate that powder formulations comprising exemplary microcapsules according to certain embodiments of the present invention, in particular formulations comprising red and black pigments, are substantially brighter and more luminous than formulations comprising commercial microcapsules. did.

For quantitative measurement of color, X using a CIE colorimeter (based on the CIE L*a*b* color scale, where L* is lightness, a* is red/green values and b* is yellow/blue values) -Rite measurement technique was used. The standard light source used for color measurements was sunlight.

Quantitative values of color were obtained by integrating measured values/data for three visual components of color: hue (i.e., how we perceive the colors of an object—red, orange, green, blue, etc.), chroma (i.e., , the vividness or dullness of a color, how to approach whether the color is gray or pure color), and the degree of lightness (i.e., classifying whether a color is light or dark ). By using these three characteristics to describe a color, it is possible to accurately identify a particular color and distinguish it from others.

Quantitative numerical values (L*) of lightness for exemplary microcapsules and commercial microcapsules of this embodiment are shown in Tables 21 and 22, and compared to commercial microcapsules in lightness for the lightness scale L* of the microcapsules of the present invention Shifts are indicated by (DL*). Positive DL* numbers shown in Tables 21 and 22 indicate shifts in the brightness scale in the direction of substantially brighter, more luminous colors for the microcapsules of the present invention compared to commercial microcapsules.

L* (brightness value) pigment/microcapsule 56.1 RedCap 1 Red

66.93 RedCapNew (Example 5) 10.83 DL* 58.25 BlackCap1 Black color

72.17 BlackCapNew (Example 6) 13.92 DL* 76.52 YellowCap1 yellow

80.08 YellowCapNew (Example 7) 4.28 DL*

L* (brightness value) pigment/microcapsule 59.83 RedCap1 Red

82.17 CameleonRed (Example 8) 22.34 DL* 59.91 BlackCap1 Black color

82.58 CameleonBlack (Example 9) 22.67 DL* 80.77 YellowCap1 yellow

86.85 Cameleon Yellow (Example 10) 6.08 DL*

5-7 show data obtained from X-rite measurement.

5a, 6a and 7a are similarly obtained images of different powders containing the same pigment obtained in the X-rite apparatus (in photographed conditions) and of brighter and more luminous powders containing microcapsules according to certain embodiments of the present invention. show visibility.

5B, 6B and 7B are comparative graphs showing the reflectance (R%) by wavelength, and demonstrate the higher color-masking effect obtained by the powder comprising microcapsules according to certain embodiments of the present invention.

Example 14

Stability test of gel formulation

To evaluate the stability of the pigment-containing microcapsules of certain exemplary embodiments of the present invention, water and carbomer (1-1.5% by weight of carbomer) were mixed and red, respectively, as disclosed in Examples 5, 6 and 7 , microcapsules containing yellow or black pigment (3% by weight of the formulation) were added to the carbomer gel and mixed together. The preparation was incubated at 40° C. for at least 3 months with stirring at 2500 rpm. The color of the gel was observed during the incubation, and a gel sample was obtained and observed under a light microscope. Thus, it was found that at least 90% of the microcapsules retained their shape even after 3 months of incubation, and there was no leakage of pigment into the gel of the microcapsules.

Although the present invention has been described in combination with specific embodiments thereof, it will be apparent that many alternatives, modifications and variations will be apparent to those skilled in the art. Accordingly, all such alternatives, modifications and variations that fall within the spirit and broad scope of the appended claims should be embraced.

All publications, patents, and patent applications mentioned in this specification are herein incorporated by reference in their entirety to the same extent as if each publication, patent or patent application was specifically and individually indicated to be incorporated herein by reference. Moreover, citation or identification of any reference in this application may be used in the art to which this invention pertains. In the sense that section headings are used, they should not necessarily be construed as limiting.

Claims (42)

an inner core microcapsule and at least one outer shell surrounding the inner core microcapsule, wherein the inner core microcapsule comprises a core containing a pigment, wherein the core surrounded by the shell is formed of a first wall-forming material and wherein the at least one outer shell comprises a second wall-forming material, a fatty acid salt and an opaque material,
wherein the second wall forming material comprises a polymer or copolymer selected from the group consisting of acrylate/ammonium methacrylate copolymers, cellulose acetate, and combinations thereof;
The amount of the second wall-forming material is in the range of 5 to 50% by weight of the total weight of the microcapsules,
The amount of the fatty acid salt is in the range of 0.5 to 3% by weight of the total weight of the microcapsule,
The microcapsule is a multilayer microcapsule, characterized in that the lightness value (L*) is in the range of 60-100 on the lightness scale of the X-Rite measurement system.
According to claim 1,
wherein the at least one outer shell further comprises a plasticizer.
According to claim 1,
The at least one outer shell further comprises a dispersing agent capable of dispersing the pigment when applied to the skin, multi-layered microcapsules.
4. The method of claim 3,
The dispersant is an ester of a fatty acid, multi-layered microcapsules.
5. The method of claim 4,
wherein the dispersant is selected from isopropyl myristate, propylene glycol stearate, and combinations thereof.
4. The method of claim 3,
The content of the dispersant is 2.0 to 6.0% by weight based on the total weight of the microcapsule, multi-layered microcapsules.
According to claim 1,
The content of the opaque material is 30 to 90% by weight based on the total weight of the microcapsule, multi-layered microcapsules.
8. The method of claim 7,
The opaque material includes TiO ₂ , and _{the content of TiO 2} is 30 to 80% by weight based on the total weight of the microcapsule.
According to claim 1,
The fatty acid salt is magnesium stearate, multi-layered microcapsules.
10. The method of claim 9,
A multi-layered microcapsule comprising an opaque material comprising 1.0 to 2.0% by weight of magnesium stearate, 30 to 75% by weight of TiO ₂ , and 4 to 6% by weight of a dispersant based on the total weight of the microcapsule.
11. The method of claim 10,
Multilayer microcapsules wherein the dispersing agent is propylene glycol stearate.
10. The method of claim 9,
10 to 50% by weight of the inner core microcapsule, 10 to 30% by weight of the second wall forming polymer or copolymer, 0.5 to 1% by weight of magnesium stearate, 25 to 50% by weight relative to the total weight of the microcapsule A _{multilayer microcapsule comprising TiO 2} and 1 to 6% by weight of a dispersant.
13. The method of claim 12,
wherein the dispersant is isopropyl myristate.
14. The method of claim 13,
A multi-layer microcapsule, which becomes a double-layer microcapsule.
14. The method according to any one of claims 1 to 13,
Stable, multi-layered microcapsules when incubated in a gel formulation for at least 3 months at 40° C. with stirring.
A composition comprising a plurality of multi-layered microcapsules, wherein at least one portion of the multi-layered microcapsules contains a plurality of pigment-containing microcapsules according to any one of claims 1 to 13.
17. The method of claim 16,
The plurality of multi-layered microcapsules have an average size of 50 μm to 350 μm.
(a) a first organic phase comprising a second wall-forming polymer or copolymer, a fatty acid salt, optionally a dispersant, and a first water-miscible solvent; contacting a first aqueous continuous phase saturated with an organic solvent and comprising an emulsifier to obtain a first mixed-component emulsion, wherein either the first organic phase or the first aqueous phase comprises an opaque material and / or further comprising monolayer microcapsules, each of said monolayer microcapsules comprising a core containing a pigment or blend of pigments surrounded by a shell of a first wall-forming material;
(b) adding to the emulsion formed a significant amount of water to initiate extraction of the organic solvent from the emulsion to obtain a bilayer microcapsule; and
(c) optionally repeating steps (a) and (b) using the second, third, etc. organic phases and several continuous phases to obtain multi-layered microcapsules, a method for producing multi-layered pigment-containing microcapsules .
A cosmetic or cosmeceutical formulation comprising the composition according to claim 16 .
20. The method of claim 19,
Oil-in-water emulsion, oil-in-water-in-oil emulsion, water-in-oil emulsion, water-in-oil-in -water) emulsions, aqueous formulations, dry formulations, silicone-based formulations and powder formulations, cosmetic or cosmeceutical formulations. delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete

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