KR101195121B1 - Shatter Resistant Encapsulated Colorants For Natural Skin Appearance - Google Patents

Abstract

The present invention relates to a personal care or cosmetic composition containing a blend resistant blend of microencapsulated colorants capable of producing a natural textured natural tone effect. Cosmetic treatment methods include the application of the personal care or cosmetic composition to at least a portion of the body.

Cosmetic Compositions, Microparticles, Colorants

Description

Shatter Resistant Encapsulated Colorants For Natural Skin Appearance

The present invention relates to compositions containing encapsulated colorants and their use for use in personal care articles. In particular, the present invention relates to compositions containing shatter resistant encapsulating colorants and their use for use in personal care articles.

There is a need to provide particles with improved shatter resistance that can be used in many applications. In particular, there is a need to provide products containing entrapped or encapsulated colorants that retain colorants for a long time and exhibit improved grinding resistance when placed in different environments. This is particularly the case when using oil soluble and water soluble dyes, in which case it is generally difficult to maintain the dye permanently. In cosmetic compositions, if the dye is not permanently retained, this may impair the aesthetics for the long term of the cosmetic.

U.S. Patent 5,234,711 discloses a method for encapsulating pigment particles to be used in ink formulations and their use for cosmetic products. Cosmetic products relate in particular to eyeliner pens.

U.S. Patent 5,382,433 and published PCT application WO 98/5002 disclose the use of cosmetic sticks containing microencapsulated pigment particles. The encapsulated pigments disclosed in the U.S. Patent No. 5,382,433 are prepared by a coacervation polymerization method. The PCT application extends the patent by including volatile solvents in cosmetic compositions. The volatile solvent is provided to minimize the sand feel of the microencapsulated material.

Several techniques are known for providing encapsulated or entrapped colorants. For example, published PCT application WO 91/06277 discloses cosmetic preparations with activatable potential pigments dispersed in anhydrous base or medium. The ground pigment or liquid carrier dispersion is microencapsulated to form a powder of stable, dry, free flowing fine sized particles. A preferred method of encapsulation is emulsification by coreceration, for example emulsifying a liquid dispersion into a continuous external aqueous phase to form microscopic droplets and adding a complex of colloidal material onto the exterior to deposit deposits on or near each droplet. By forming an external wall or shell. Microcapsules tend to rupture under physical forces, releasing potential pigments.

U. S. Patent No. 5,234, 711 relates to a method of encapsulating pigment particles useful in the manufacture of cosmetic products. The purpose of this technique is to use an encapsulation method to increase the wettability, dispersibility and heat resistance of pigment particles. This encapsulation process involves redox or free radical vinyl polymerization in an aqueous medium.

Published European Patent Application No. 225,799A3 discloses microencapsulated solid nonmagnetic colorant materials encapsulated in polymer sheaths as liquid, gel, wax or low temperature melting point solid carrier types. Absorbed in the shell is a silane or titanate coupling agent, which increases the lipophilic of the surface of the solid colorant material.

Published European Patent Application No. 445,342A1 relates to a cosmetic composition comprising a pigment formed by incorporating a solvating dye into a resin and then mixing with a cosmetic carrier. The amount of pigment present is sufficient to provide an attractive cosmetic effect when applied to skin, nails or hair. Soluble dyes that are acceptable for cosmetics can be used. Any number can be used as long as it can be ground to a fine powder. Solvated dyes are incorporated into resins by addition to the elasticized or molten resin, or by dissolving the dye in a solution of the non-polymeric resin and a common solvent for the dye and the resin and then polymerizing the resin or contacting the dye with the resin. Can be. The dyes impregnated with the resin powder are said to be used in various cosmetic compositions.

WO 02/090445 addresses the problem of color retention and provides polymer particles comprising a matrix polymer and colorants dispersed therethrough. The matrix polymer is a blend of a monomer comprising a first monomer which is an ethylenically unsaturated ionic monomer which is a salt of a volatile counterion and a monomer which is a second monomer which is an ethylenically unsaturated hydrophobic monomer capable of forming a homopolymer having a glass transition temperature of 50 ° C. or higher. It is formed from. Conventional matrix polymers include copolymers formed from styrene and ammonium acrylate. The polymer particles exhibit very good retention and can retain colorants under various conditions. However, these particles tend to overcome the disadvantages that can be crushed under certain conditions when handled roughly and result in loss of colorant.

Co-pending US patent application Ser. No. 10 / 785,208 discloses the use of blends of microencapsulated colorants and cosmetic compositions prepared as described in WO 02/090445. The blend, when used, forms a textured natural tone color or has a similar effect in the cosmetic itself. However, as mentioned above, the microcapsules are structurally different from those used according to the present invention and lack their crush resistance.

It is an object of the present invention to provide a cosmetic composition comprising polymer particles which retain colorants for a long time when placed in different environments and which contain entrapped or encapsulated colorants. This is particularly important when the colorants are oil-soluble and especially water soluble dyes, in which case it is generally difficult to permanently retain the dye. In cosmetic compositions, where the dye is not permanently retained, this may impair the visual effects of the cosmetic after long term use.

Encapsulating or capturing the colorant can visually damage the colorant. This can occur due to the polymer absorbing light of a certain wavelength or often due to the irregular morphology of the polymer particles. This is also the case when the particles are not crush resistant. Crushed or crushed particles of the particles can also result in visual damage to the colorant.

Therefore, another object of the present invention is to provide a cosmetic composition comprising a polymer-capturing colorant in which the particles are crush resistant and can withstand rough handling resulting in improved visual effects.

Summary of the Invention

A first aspect of the invention is the use of monomers comprising a first monomer which is an ethylenically unsaturated ionic monomer and a second monomer which is an ethylenically unsaturated hydrophobic monomer capable of forming a homopolymer having a glass transition temperature of at least 50 ° C. Ethylenically unsaturated hydrophobic monomers and optionally hydrophobic polymers that are entrapped in the matrix polymer formed from the blend and are capable of forming homogeneous polymers having a second particle dispersed in the matrix and having a glass transition temperature of at least 50 ° C. and other monomers other than the matrix polymer. It is to provide a microparticle containing a coloring effective amount of at least one colorant comprising a hydrophobic polymer formed from. Each individual colorant microparticle has a typical particle size of 1-60 microns.

A second aspect of the invention relates to the use of a monomer comprising a monomer comprising a first monomer which is an ethylenically unsaturated ionic monomer and a second monomer which is an ethylenically unsaturated hydrophobic monomer capable of forming a homopolymer having a glass transition temperature of at least 50 ° C. Ethylenically unsaturated hydrophobic monomers and optionally hydrophobic polymers, which are entrapped in at least one microparticle matrix polymer formed from the blend, wherein the second particles are dispersed in the matrix and can form homopolymers having a glass transition temperature of at least 50 ° C. Is to provide a solid or liquid personal care or cosmetic composition containing a coloring effective amount of two or more colorants, comprising a hydrophobic polymer formed from other other monomers.

The colorant in the composition is selected from two or more different colors. In one embodiment a blend of two or more of the basic colors yellow, red and blue is used.

The present invention also provides a method of coloring a body by applying a liquid or solid personal care or cosmetic blend having at least a portion of the body a coloring effective amount of a blend of at least two of said microparticle colorants.

The microparticle colorants according to the invention further improved the visual performance as natural skin. Moreover, the matrix polymer is not comminuted during harsh compounding conditions or handling to maintain the desired aesthetic effect upon storage and use.

DETAILED DESCRIPTION OF THE INVENTION

The matrix polymer is formed from a blend of monomers comprising a first monomer that is an ethylenically unsaturated ionic monomer and a second monomer that is an ethylenically unsaturated hydrophobic monomer capable of forming a homopolymer having a glass transition temperature of at least 50 ° C., and a second A matrix polymer and a matrix polymer, wherein the particles comprise an ethylenically unsaturated hydrophobic monomer capable of forming a homopolymer having a glass transition temperature of at least 50 ° C. and a hydrophobic polymer, optionally comprising a hydrophobic polymer formed from other monomers different from the matrix polymer. Microparticles comprising the second particles dispersed in can be prepared by a process comprising the following steps A) to D):

A) providing an aqueous phase of a polymer salt formed from monomers comprising first and second monomers,

B) forming a second particle of the aqueous phase or mixing the second particle with the aqueous phase,

C) forming a dispersion comprising an aqueous phase in a liquid phase insoluble in water, preferably comprising an amphiphilic polymer stabilizer to form an emulsion, and

D) evaporating water from the aqueous particles to dehydrate the dispersion to form solid particles comprising second particles dispersed in the matrix polymer.

Preferably, the first monomer used to form the matrix polymer is a salt of the volatile counterion component. In the dehydration step (D) the volatile counterion component of the salt is preferably evaporated. This means that at least part of the counterion component is evaporated. For example, if the polymer matrix is an ammonium salt, the volatile component ammonia will evaporate. As a result, the matrix polymer is converted into its free acid or free base form in the distillation step.

Particles useful in the present invention include colorants. The colorant may be selected from pigments, dyes or lakes. In the particle preparation process, it is particularly preferred that the colorant be dissolved or dispersed in the aqueous phase so that it can be dispersed in the matrix polymer.

It has been found that the polymer microparticles exhibit improved grinding resistance with improved visual action. Moreover, the polymer matrix ensures that the captured colorant is not released even after prolonged use. It is particularly preferred to provide particles wherein the colorant is dispersed in the matrix polymer and the matrix polymer is impermeable to the colorant.

The polymer product can be further enhanced if the matrix polymer is crosslinked. Such crosslinking may occur because it involves a crosslinking step in the microencapsulation process. This can be accomplished by including self-crosslinking groups in the polymer, such as by including monomer repeat units having methylol functional groups. Preferably said crosslinking is achieved by introducing a crosslinking agent with the aqueous phase polymer. Crosslinkers are generally compounds that react with functional groups on the polymer chain. For example, if the polymer chain contains anionic groups, suitable crosslinkers include aziridine, diepoxide, carbodiamide, silane and polyvalent metals such as aluminum, zinc or zirconium. Particularly preferred crosslinkers are ammonium zirconium carbonate or zinc oxide. Another particularly preferred type of crosslinking agent includes compounds that form covalent bonds between polymer chains, such as silanes or diepoxides.

The crosslinking process preferably takes place during the dehydration step. Thus, if a crosslinking agent is included, the crosslinking agent is generally latent until dehydration is initiated.

Polymers formed from certain combinations of hydrophobic monomers capable of forming homopolymers having glass transition temperatures above 50 ° C., preferably above 60 or 80 ° C., have significantly improved performance in terms of impermeability to colorants as well as other active agents. Indicates. By hydrophobic monomer it is meant that the monomer has solubility in water of less than 5 g with respect to 100 ml water.

The glass transition temperature (T _g ) for polymers is described in Encyclopedia of Chemical Technology, Volume 19, 4th edition, page 891 (1) transition kinetics of whole molecules and (2) winding of 40-50 carbon atom fragment chains (coils). Both ring) and uncoiling are defined as frozen temperatures. Thus his T _g In the following the polymer will not exhibit flowability or rubber elasticity.

T _{g of} polymer Can be measured using a microscanning calorimeter (DSC).

Generally the average particle diameter of the particles is less than about 100 microns. Preferably the average particle diameter is about 1 to 60 microns, for example 1 to 40 microns, in particular 1 to 30 microns. Average particle size is measured by a Coulter particle size analyzer according to standard methods well described in the literature.

Without being bound by theory, it is believed that certain combinations of ionic monomers and hydrophobic monomers provide polymers with the correct degree of hydrophilicity and hardness that serve to improve opacity for colorants and other active agents. The presence of the second particles comprising the hydrophobic polymer appears to serve to provide the particles with improved grinding resistance.

Typically, the monomer blend for preparing the matrix polymer comprises at least 50% by weight of hydrophobic monomers, with the remainder being supplemented with ionic monomers. Generally, the hydrophobic monomer is present at least 60% by weight or more. Preferred compositions comprise 65-90% by weight of hydrophobic polymer, for example about 70 or 75%.

Specific examples of such hydrophobic monomers include styrene, methyl methacrylate, tertiary butyl methacrylate, phenyl methacrylate, cyclohexyl methacrylate and isobornyl methacrylate.

It has been found that instead of hydrophobic monomers it is not possible to use ethylenically unsaturated carboxylic acid esters which cannot form homopolymers having a glass transition temperature of at least 50 ° C. without the adverse effect of increasing the permeability of the polymer. Preferably T _g should be at least 60 ° C or at least 80 ° C. For example, it would not be suitable to use other (meth) acrylic esters such as 2-ethylhexyl acrylate in place of the hydrophobic monomers of the present invention. The best results can be obtained by using monomers capable of forming polymers with high T _g each week. Thus, ethyl acrylate or propyl acrylate will be used as hydrophobic monomers to produce less desirable products.

Ionic monomers may contain anionic or cationic groups or may be potentially ionic, such as in the form of acid anhydrides. Preferably the ionic monomer is an ethylenically unsaturated anionic or potentially anionic monomer. Suitable anionic or potentially anionic monomers include acrylic acid, methacrylic acid, ethacrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, crotonic acid, vinylacetic acid, (meth) allyl sulfonic acid, vinyl sulfonic acid and 2-acrylamido-2-methyl propane sulfonic acid. Preferred anionic monomers are carboxylic acids or acid anhydrides.

When the ionic monomer is an anion such as carboxylic acid or anhydride, the volatile counter ion may be an ammonia or volatile amine component. In general, the volatile amine component may be a liquid that can be evaporated at low to mild temperatures, for example up to 200 ° C. Preferably, the volatile amines can be evaporated under reduced pressure and below 100 ° C. The polymer can thus be produced in free acid form and neutralized by an aqueous solution of ammonium hydroxide or by volatile amines such as ethanolamine, methanolamine, 1-propanolamine, 2-propanolamine, dimethanolamine or diethanolamine. . Alternatively, the polymer may be prepared by copolymerizing ammonium or volatile amine salts of anionic monomers with hydrophobic monomers.

In general, the matrix polymer can be prepared by any suitable polymerization method. For example, the polymer may be conveniently prepared by aqueous emulsion polymerization as described in EP-A-697423 or US Pat. No. 5,070,136. This polymer can be neutralized by adding an aqueous solution of ammonium hydroxide or volatile amines.

In a typical polymerization process the mixture of hydrophobic monomers and anionic monomers is emulsified with an aqueous phase containing a suitable amount of emulsifier. Typically the emulsifier may be a commercially available emulsifier suitable for forming an aqueous emulsion. Preferably, these emulsifiers tend to exhibit a high hydrophilic lipophilic balance (HLB) because they tend to dissolve better in the aqueous phase than on monomers that are not mixed with water. The emulsification of the monomers can be carried out by known emulsification techniques, including vigorous stirring or shearing of the monomer / non-aqueous phase or passing the monomer / non-aqueous phase through a screen or mesh. The polymerization can be carried out by the use of a suitable initiator system, for example by the use of a UV initiator or a thermal initiator. A suitable technique for initiating the polymerization is to raise the temperature of the aqueous emulsion of the monomer to at least 70 or 80 ° C. and then add 50-1000 ppm ammonium persulfate per monomer weight.

In general, matrix polymers have a molecular weight of 200,000 or less (as measured by GPC using industry standard parameters). Preferably the polymer has a molecular weight of 50,000 or less, such as 2,000 to 20,000. Usually the optimum molecular weight for the matrix polymer is about 6,000 to 12,000.

Particularly preferred matrix polymers are copolymers of styrene and ammonium acrylate. More preferably, the polymer is used when the method uses a crosslinking agent that is ammonium zirconium carbonate or zinc oxide.

As another example of the process of the invention, the ionic monomer may be cationic or potentially cationic, such as ethylenically unsaturated amines. In this type of invention, the volatile counterion component is a volatile acid component. Thus, in this type of invention, the matrix polymer may be formed in a manner similar to the anionic matrix polymer described above, except that anionic monomers are used instead of cationic monomers or potential cationic monomers. In general, when the polymer is prepared in the form of a copolymer of free amine and hydrophobic monomer, the polymer is neutralized with a suitable volatile acid such as acetic acid, formic acid, propanoic acid, butanoic acid or carbonic acid. Preferably the polymer is neutralized by volatile carboxylic acids.

Suitable cationic or potentially cationic monomers include dialkyl aminoalkyl (meth) acrylates, dialkyl aminoalkyl (meth) acrylamides or allyl amines and other ethylenically unsaturated amines and their acid addition salts. Typically, dialkyl aminoalkyl (meth) acrylates are dimethyl aminomethyl acrylate, dimethyl aminomethyl methacrylate, dimethyl aminoethyl acrylate, dimethyl aminoethyl methacrylate, diethyl aminoethyl acrylate, diethyl aminoethyl Methacrylate, dimethyl aminopropyl acrylate, dimethyl aminopropyl methacrylate, diethyl aminopropyl acrylate, diethyl aminopropyl methacrylate, dimethyl aminobutyl acrylate, dimethyl aminobutyl methacrylate, diethyl aminobutyl acrylic Rate and diethyl aminobutyl methacrylate. Typically, the dialkyl aminoalkyl (meth) acrylamides are dimethyl aminomethyl acrylamide, dimethyl aminomethyl methacrylamide, dimethyl aminoethyl acrylamide, dimethyl aminoethyl methacrylamide, diethyl aminoethyl acrylamide, diethyl aminoethyl Methacrylamide, dimethyl aminopropyl acrylamide, dimethyl aminopropyl methacrylamide, diethyl aminopropyl acrylamide, diethyl aminopropyl methacrylamide, dimethyl aminobutyl acrylamide, dimethyl aminobutyl methacrylate, diethyl aminobutyl acryl Rate and diethyl aminobutyl methacrylamide. Typically, allyl amines include diallyl amines and triallyl amines.

The second particle comprises an ethylenically unsaturated hydrophobic monomer capable of forming a homopolymer having a glass transition temperature of 50 ° C. or higher and optionally a hydrophobic polymer formed from other monomers, which hydrophobic polymer is different from the matrix polymer. The ethylenically unsaturated hydrophobic monomer may be any of the monomers defined above in connection with the second monomer used to form the matrix polymer. Preferably, the hydrophobic monomer is the same as the second monomer used to form the matrix polymer. Specific examples of such hydrophobic monomers are styrene, methyl methacrylate, tertiary butyl methacrylate, phenyl methacrylate, cyclohexyl methacrylate and isobornyl methacrylate. Preferred hydrophobic monomer is styrene.

Hydrophobic monomers can be polymerized alone or optionally polymerized with one or more other hydrophobic monomers as defined above. It may include other monomers other than hydrophobic monomers capable of forming homopolymers having a glass transition temperature of 50 ° C. or higher, provided these monomers have no adverse action. Other monomers are hydrophobic monomers such as long chain alkyl and esters of acrylic or methacrylic acid, such as 2-ethylhexyl acrylate or stearyl acrylate. Typically, when such a monomer is included, the monomer should be present in an amount of up to 20% by weight, based on the weight of the monomer used for the second particle. Preferably, these monomers are present in an amount of less than 10% by weight, more preferably less than 5% by weight.

In addition, a hydrophilic monomer may be sufficient as another monomer. The hydrophilic monomer may be nonionic, such as acrylamide, or may be ionic as defined above in connection with the first monomer used to form the matrix polymer. In general, such monomers tend to be used in small proportions so that the polymer becomes hydrophobic. If such a monomer is included, the monomer should be present in an amount of up to 20% by weight, based on the weight of the monomer used for the second particle. Preferably, these monomers are present in an amount of less than 10% by weight, more preferably less than 5% by weight.

It is particularly preferred that the second particles comprise a hydrophobic polymer formed entirely from at least one ethylenically unsaturated hydrophobic monomer capable of forming a homopolymer having a glass transition temperature of at least 50 ° C. Particularly suitable hydrophobic polymers are copolymers of styrene and methyl methacrylate or homopolymers of styrene. Polymers of styrene and methyl methacrylate generally comprise at least 40% by weight of styrene and up to 60% by weight of methyl methacrylate. Preferably, the copolymer has a weight ratio of styrene to methyl methacrylate 50:50 to 95: 5, more preferably 60:40 to 80:20, particularly preferably 70:30 to 75:25.

Generally, the second particles have an average particle diameter of 1 micron or less, usually an average particle size of 750 nm or less. Preferably, the second particles have an average particle diameter of 50 to 500 nm. The second particle can be produced by any known method. Typically, the particles can be prepared by aqueous emulsion polymerization. Preferably, the particles are prepared by an aqueous microemulsion polymerization process according to known microemulsion polymerization processes as described in the known art, such as EP-A-531005 or EP-A-449450.

Typically, the second particles comprise a microemulsion comprising a continuous aqueous phase (20-80% by weight), a dispersed oil phase comprising monomers (10-30% by weight), and surfactants and / or stabilizers (10- 70 wt%)). In general, surfactants and / or stabilizers are mainly present in the aqueous phase. Preferred surfactants and / or stabilizers are aqueous solutions of the polymers used to form the polymer matrix. Particularly preferred surfactants / stabilizers are copolymers of ammonium acrylate and styrene as defined above in connection with the matrix polymer.

The polymerization of the monomers in the microemulsion can be carried out by a suitable initiation system, such as a UV initiator or a thermal initiator. Suitable techniques for initiating the polymerization include, for example, raising the temperature of the aqueous emulsion of the monomer up to 70 or 80 ° C. or higher, followed by 50 to 1000 ppm ammonium persulfate or azo compound, such as azodiisobutyro, by weight of the monomer. Nitrile is added. On the other hand, suitable peroxides, such as. Room temperature cure peroxides, or photoinitiators may be used. The polymerization is preferably carried out at about room temperature with a photoinitiator.

Generally, the second particle comprises a polymer having a molecular weight of 2,000,000 or less (measured by GPC using standard industrial parameters). Preferably, the polymer has a molecular weight of 500,000 or less, such as 5,000-300,000. Usually, the optimal molecular weight for the polymerizable second particles is 100,000 to 200,000.

It is preferred that the second particles have a core shell structure wherein the core comprises a hydrophobic polymer surrounded by a polymer shell. More preferably, the second particles comprise a core comprising a hydrophobic polymer and an envelope comprising a matrix polymer. Particularly preferably, the shell of the matrix polymer is formed around the core of the hydrophobic polymer and during the polymerization reaction.

As mentioned above, the particles of the present invention comprise a colorant. They may further comprise active ingredients such as UV absorbers, UV reflectors, flame retardants or active dye tracer materials.

The particles may capture one or more colorants, which may be any colorant, such as dyes, pigments or lakes. Typically suitable colorants are organic or inorganic pigments approved for cosmetic use by CTFA and FDA, such as conventional pigments used in rakes, iron oxides, titanium dioxide, iron sulfide or other cosmetic formulations or include colorants.

Examples of pigments include carbon black, D & C red 7, calcium lake, D & C red 30, talc lake, D & C red 6, barium lake, red brown oxide, yellow iron oxide, brown iron oxide, talc, kaolin, mica, mica titanium, red iron oxide, silicic acid Inorganic pigments such as magnesium and titanium oxide; And organic pigments such as red number 202, red number 204, red number 205, red number 206, red number 219, red number 228, red number 404, yellow number 205, yellow number 401, orange number 401 and blue number 404. do. Examples of vat dyes are red number 226, blue number 204 and blue number 201. Examples of rake dyes include various acid dyes that are rake by aluminum, calcium or barium.

In one embodiment the colorant is an aqueous solution of a water soluble dye. These dyes include FD & C Blue No. 11, FD & C Blue No. 12, FD & C Green No. 13, FD & C Red No. 13, FD & C Red No. 140, FD & C Yellow No. 15, FD & C Yellow No. 16, D & C Blue No. 14, D & C Blue No. 19, D & C Green No. 15, D & C Green No. 16, D & C Green No. 18, D & C Orange No. 14, D & C Orange No. 15, D & C Orange No. 110, D & C Orange No. 111, D & C Orange No. 117, FD & C Red No. 14, D & C Red No. 16, D & C Red No. 17, D & C Red No. 18, D & C Red No. 19, D & C Red No. 117, D & C Red No. 119, D & C Red No. 121, D & C Red No. 122, D & C Red No. 127, D & C Red No. 128, D & C Red No. 130, D & C Red No. 131, D & C Red No. 134, D & C Red No. 139, FD & C Red No. 140, D & C Violet No. 12, D & C Yellow No. 11, Ext. D & C violet number 12, D & C blue number 16 and D & C yellow number 110.

Such dyes are known and commercially available and their chemical structures are described, for example, in " 21 C. FRPart 74 " (April 1, 1988) and in " CTFA Cosmetic Ingredient Handbook, (1988) " Publication). These documents are incorporated herein by reference.

The validated dye may be a water soluble dye, or preferably a rake. Lakes are organic pigments made by depositing a water soluble dye onto a reactive or adsorbent stratum that is an integral part of the pigment composition. Most rakes are derived from aluminum, barium or calcium. These insoluble pigments are mainly used in powder or liquid make-up products when they require a temporary color that does not contaminate the skin (fat-soluble dyes tend to do so). Lakes are used in these products with inorganic colors such as iron oxide, zinc oxide and titanium dioxide (whitest white pigment).

The colorant may also be a material that is a latent colorant, such as a color former, that exhibits color upon exposure to a suitable triggering mechanism, such as heat or irradiation. Appropriate color formers thus captured can be coated or incorporated into a suitable substrate and then treated to exhibit color. The advantage of providing color formers as polymer particles is that they can be processed more easily and incorporated into the substrate in a preferred manner. Color formers can be activated even if entrapped within the polymer particles.

The table below lists currently available dyes and colorants licensed for use in foods, drugs and / or cosmetics. The colorant selected for use herein is preferably selected from the list exemplified below.

Dyes proven for use in food, drugs and cosmetics (FDC color) FD & C Blue Number 1 FD & C Green Number 3 FD & C Red Number 4 FD & C Red Number 40 FD & C Yellow Number 5 FD & C Yellow Number 6

Topically proven dyes in used drugs and cosmetics Ext. DC purple # 2 Ext. D & C Yellow Number 7 Ext. D & C Purple Number 2 D & C Brown 1 FD & C Red Number 4 D & C Red Number 17 D & C Red Number 31 D & C Red No. 34 D & C Red No. 39 D & C Purple Number 2 D & C Blue No. 4 D & C Green No. 6 D & C Green No. 8 D & C Yellow Number 7 D & C Yellow Number 8 D & C Yellow Number 11 D & C orange number 4 D & C orange number 10 D & C orange number 11

Dyes proven only for drug and food D & C Blue No. 4 D & C Brown 1 D & C Green Number 5 D & C Green No. 6 D & C Green No. 8 D & C Orange Number 4 D & C Orange Number 5 D & C Orange Number 10 D & C Orange Number 11 D & C Red No. 6 D & C Red Number 7 D & C Red Number 17 D & C Red No. 21 D & C Red Number 22 D & C Red Number 27 D & C Red Number 28 D & C Red No. 30 D & C Red Number 31 D & C Red Number 33 D & C Red No. 34 D & C Red Number 36 D & C Purple Number 2 D & C Yellow Number 7 D & C Yellow Number 8 D & C Yellow Number 10 D & C Yellow Number 11

Some color additives are exempt from verification and are permanently listed in cosmetic applications and include aluminum powder, anato, bismuth oxychloride, bronze powder, caramel, carmine, beta-carotene, chromium hydroxide, chromium oxide green copper (metallic powder) ), Dihydroxyacetone, disodium EDTA-copper, ferric ammonium ferrocyanide, ferric ferrocyanide, guanine (pearl essence), guiazulene (azulene), iron oxide, luminescent zinc sulfide, manganese violet, mica, Pyrophyllite, silver (for colored nail polish), titanium dioxide, ultramarine (blue, green, pink, red and purple) and zinc oxide.

The process of the present invention involves dispersing an aqueous solution of a matrix polymer containing colorant in a liquid that is not mixed with water. Typically liquids that do not mix with water are organic liquids or mixtures of organic liquids. Preferred organic liquids are mixtures of nonvolatile paraffin oils and volatile paraffin oils. The two oils can be used in the same weight ratio, but it is generally preferred to use non-volatile oils in excess, such as in an amount of from 50 to 75 parts by weight of nonvolatile oil to 25 to 50 parts by weight of volatile oil.

In the process of the present invention, it is preferred to include a polymerizable amphiphilic stabilizer in a liquid that is not mixed with water. Amphiphilic stabilizers can be suitable commercially available amphiphilic stabilizers such as HYPERMER ^® (manufactured by ICI). Suitable stabilizers include the stabilizers described in WO-A-97 / 24179.

In addition to amphiphilic stabilizers, other stabilizer materials may be included, such as surfactants, but the only stabilizing material is generally preferred to be an amphipathic stabilizer.

In the process of the invention, the dehydration step can be carried out by conventional means. Preferably, dehydration can be carried out by vacuum distillation of the dispersion in oil. Generally this will require elevated temperatures, such as 30 ° C. or higher. Although much higher temperatures may be used, such as 80-90 ° C., it is generally preferred to use temperatures of 60 or 70 ° C. or less.

It may be desirable to dehydrate by spray drying instead of vacuum distillation. Suitably this can be achieved by the spray drying method described in WO-A-97 / 34945.

The dehydration step removes water from the aqueous solution and volatile counterion components of the matrix polymer to produce a dry polymer matrix that is insoluble in water and non-swellable and contains colorants dispersed throughout the polymer matrix.

The encapsulated colorant microspheres have an average diameter of 0.1 to 60 microns, preferably 1 to 40 microns, particularly preferably 1 to 30 microns.

The preferred average diameter depends on the intended use. For example, one embodiment of the present invention may be a liquid facial cosmetic formulation comprising at least two encapsulated colorants and having a preferred particle size of 10-30 microns. Another embodiment may be a lipstick formulation comprising at least two encapsulated colorants having a preferred particle diameter of 1-10 microns.

It has been found that applying a personal care or cosmetic formulation composition comprising a (micro) encapsulated colorant has a desirable effect upon application. Compositions containing two or more mixtures of microencapsulated colorants, in particular one or more primary colors, with a unique and noticeable color are effective means of producing a natural weave skin tone effect. Primary color means red, yellow and blue. An additional feature of the encapsulation in the present invention will eliminate the grinding or grinding commonly found in unencapsulated colorants.

In one embodiment, the personal care or cosmetic composition comprises a blend of microencapsulated colorants individually provided in at least two separate matrix polymeric materials. In another embodiment at least two microencapsulated colorants are present in a single matrix polymeric material.

The personal care or cosmetic composition according to the invention is based on the total weight of the composition, from 0.1 to 70% by weight, such as from 1 to 50% by weight, in particular from 5 to 35% by weight of at least two encapsulated colorants, as well as cosmetically acceptable carriers. Or adjuvants. While water is acceptable in cosmetics and present in most cases, "acceptable carriers or auxiliaries for cosmetics" means one or more substances other than water conventionally used in personal care or cosmetic compositions.

Personal care or cosmetic preparations according to the invention are w / o (water-in-oil) or o / w (oil-in-water) emulsions, vesicular dispersions of ionic or nonionic amphiphilic lipids As a gel or a solid stick. Preferably the cosmetic preparation is in liquid form.

As w / o or o / w emulsions, personal care preparations or cosmetic preparations preferably contain 5 to 50% oil phase, 5 to 20% emulsifier and 30 to 90% water. The oily phase may contain any oil suitable for cosmetic formulations, for example one or more hydrocarbon oils, waxes, natural oils, silicone oils, fatty acid esters or fatty alcohols.

Cosmetic liquids may contain small amounts of mono- or polyols, such as up to 10% by weight, such as ethanol, isopropanol, propylene glycol, hexylene glycol, glycerol or sorbitol.

Cosmetic preparations according to the invention can be contained in a variety of cosmetic preparations. In particular, examples of the following formulations may be considered:

Skin care preparations such as skin emulsions, multi-emulsions or skin oils and body powders;

Cosmetic preparations for personal protection, such as lipsticks, lip gloss, eye shadows, liquid makeup, day creams or powders, facial lotions, creams and powders (loose powder or compressed); And

Light-blocking preparations such as tanning lotions, creams and oils, sun blocks and pretanning preparations.

Depending on the form of the personal care preparation, additional ingredients besides encapsulated colorants, such as sequestering agents, additional non-encapsulated colorants, flavorings, clouding agents or solidifying agents (hardening agents), emollients, UVs Absorbents, skin protectants, antioxidants and preservatives.

The composition according to the invention can be prepared by physically mixing a suitable encapsulated colorant into a personal care formulation in a known manner. The examples disclose some of these methods.

The present invention also provides a method of coloring a body comprising applying to at least a portion of a body a liquid or solid personal care or cosmetic combination having a coloring effective amount of the at least two encapsulating colorant blends described above.

In one embodiment of the method, the personal care or cosmetic formulation comprises, based on the total weight of the formulation, from 0.1 to 70% by weight of the two or more microencapsulated colorants, such as from 1 to 50% by weight, in particular from 5 to 35% by weight.

In another embodiment of the method, the personal care or cosmetic composition comprises a blend of two or more microencapsulated colorants individually provided in separate polymer matrix materials. In another embodiment at least two microencapsulated colorants are present in a single matrix polymeric material.

In another embodiment of the method, the personal care or cosmetic composition is a w / o or o / w emulsion, as an alcoholic or alcohol-containing formulation, as an antifoam dispersion of an ionic or nonionic amphiphilic liquid, as a gel or a solid It is compounded as a stick.

In another embodiment of the method, the personal care or cosmetic composition is in the form of a skin care preparation, a personal care cosmetic preparation or a photoprotective preparation.

The following examples disclose certain embodiments of the invention, but the invention is not limited thereto. It will be appreciated that many modifications may be made in accordance with the teachings of the invention without departing from the spirit and scope of the invention. These examples are not intended to limit the scope of the invention. Rather, the scope of the present invention is limited only by the appended claims and their equivalents. All parts in these examples are by weight unless otherwise indicated.

Example  One

Grinding resistant yellow-colored micro-beads comprising 60% by weight colorant and 40% by weight crosslinked polymer are prepared as follows.

46 containing 32% by weight of styrene-methyl methacrylate copolymer (70/30% by weight monomer ratio, molecular weight 200,000) and 14% by weight of styrene-acrylic acid copolymer (65/35% by weight monomer ratio, molecular weight 6,000) The aqueous phase is prepared by diluting 488 g of% polymer microemulsion with 790 g of water and then mixing 313 g of Yellow # 10 Al lake powder (ex-Kingfisher) and 56 g of titanium dioxide with a high speed mixer. 19 g of a 50% aqueous solution of ammonium zirconium carbonate are added to the aqueous pigment dispersion.

Separately, 76 g of 20% amphiphilic stabilizer (90 wt% stearyl methacrylate, 10 wt% methacrylic acid copolymer, molecular weight 40,000) was diluted with 1,800 g of Isopar G solvent (manufactured by Exxon Mobil). Prepare the phase. The aqueous phase is added to the oil phase by a high shear homogenizer to form a water-in-oil emulsion having an average particle diameter of 20 microns of aqueous droplet particles. The emulsion thus formed is placed in a 1-liter reactor installed for vacuum distillation. The emulsion is warmed to 60 ° C. and then vacuum distilled to remove the water / Isopar G solvent mixture. Continue vacuum distillation to 100 ° C until water is no longer collected in the distillate. The contents of the reactor are then held for an additional hour to terminate the crosslinking reaction between the zirconium crosslinker and the carboxylated support resin.

After this heat treatment step, the contents of the reactor are cooled to 25 ° C. and then the colored micro beads formed are filtered off and then oven dried at 90 ° C.

The final product is free flowing yellow micro beads with an average particle diameter of 20 microns.

Example  2

Red microbeads were prepared in the same manner as in Example 1 except for using 313 g of Red # 7 calcium rake powder (ex-Kingfisher) instead of Yellow # 10 aluminum rake powder.

Example  3

Blue microbeads were prepared in the same manner as in Example 1 except for using 313 g of Blue # 1 aluminum lake powder (ex-Kingfisher) instead of Yellow # 10 aluminum lake powder.

Example  4

This example shows the crush resistance of the colored microbeads obtained by the present invention.

30 g of the yellow microbeads of Example 1 are added to 270 g of isopropyl myristate. The resulting microbead slurry is warmed to 75 ° C. and then homogenized with a high shear mixer for 30 minutes at 6,000 rpm. After this treatment the mixture is cooled to room temperature and the microbeads are examined under a light microscope. Light microscopy showed that the colored particles produced according to the invention remained intact after such harsh treatment.

Example  5

The aqueous phase is prepared by diluting 200 g of 46% polymer microemulsion (styrene-methyl methacrylate copolymer microemulsion stabilized with styrene-acrylic acid copolymer) with 100 g of water. 31 g of Blue # 1 Al lake powder (ex Kingfisher) are dispersed with a high shear mixer. To the dispersion thus formed, a slurry containing 20 g of zinc oxide hydrate and 80 g of water is added.

Separately, oil was obtained by diluting 44 g of 20% amphiphilic stabilizer [consisting of stearyl methacrylate (90 wt.%)-Methacrylic acid copolymer (10 wt.%)] With 600 g of Isopar G (ex Exxon Mobil). Prepare the phase.

The aqueous phase is dispersed with an oil phase with the aid of a high shear homogenizer to form a water-in-oil emulsion having an average particle diameter of 20 microns. The emulsion is transferred to a set of devices installed for distillation. The emulsion is warmed to 50 ° C. and then vacuum distilled and heated (maximum temperature 100 ° C.) until no more water is collected in the distillate. After this treatment, the crosslinking reaction is terminated by further maintaining the reactor components at about 100 ° C for 1 hour. At the end of the crosslinking reaction, the reaction mass is cooled to 25 ° C. and then filtered to recover the colored beads. Finally, the beads are dried in an oven at 90 ° C. to obtain free flowing blue powder with an average particle diameter of 20 microns.

The following examples illustrate the use of the colorants of the invention in various cosmetic or personal care formulations.

1.lipstick

Prize INCI persons  Brand name producer Weight portion A Castor oil Lipovol co Lipo 33.25 A Triethylhexanoin Schercemol GTO Scher 7.50 A Triisostearyl
Trilinoleate Schercemol TIST Scher 15.00 A Triisostearyl
Citrate Schercemol TIST Scher 17.50 A Euphorbia serifera
(Candelilla) Wax Refined Candelilla Wax Frills Ross Waxes 7.00 A Copernicia
Serifera
(Carnauba) wax Yellow Carnauba Wax Flakes Ross Waxes 1.80 A Ozokerite White Ozokerite Wax 77W Ross Waxes 1.80 A Microcrystalline wax Microcrystalline Wax 1275W Ross Waxes 3.50 A Hydroxylated lanolin Ritahydrox Rita 1.00 A Methyl paraben Nipagin M Clariant 0.20 A Propylparaben Nipasol M Clariant 0.10 B coloring agent Encapsulated Red Pigment Shiva Specialty
Chemicals 5.70 B coloring agent Encapsulated Yellow Pigment Shiva Specialty
Chemicals 1.10 B coloring agent Encapsulated Blue Pigment Shiva Specialty
Chemicals 0.20 B mica Cosmetic Mica # 280 Whittacker,
Clark & Daniels 4.35 gun 100.00

Process :

Phase A was mixed, heated at 90-105 ° C. and mixed until uniform. Phase B is added with stirring to homogenize. The lipstick was poured into the mold while maintaining the temperature above 70 ° C.

Medium protection Sunscreen

Prize INCI persons Brand name producer Weight portion A Deionized water DI Water N / A 84.86 A Propylene glycol (and)
Diazolidinyl Urea (and)
Methylparaben (and)
Propylparaben Germaben ii ISP 1.00 A Aloe Barbadensis Leaf Juice Aloe Gel 1: 1 natural Tri-K Industries 1.00 A Propylene glycol Propylene glycol Dow Chemical 2.50 A Butylene Glycol (and) Water (and)
Juglans Nigra (Black Walnut)
Cortex extract Black walnut
Cortic Actiphyte Active organics 0.04 A Ethylhexyl salicylate Escalol 587 ISP 5.00 A Ethylhexyl
Methoxycinnamate Escalol 557 ISP 3.00 B Sodium acrylate copolymer
(And) paraffinium liquid (and)
PPG-1 Trideces-6 Ciba®SALCARE®
SC91 Shiva Specialty
Chemicals 2.00 C coloring agent Encapsulated Red Pigment Shiva Specialty
Chemicals 0.20 C coloring agent Encapsulated Blue Pigment Shiva Specialty
Chemicals 0.10 D Spices Gypsophila Belle Ayre
Fragrants 0.30 gun 100.00

Process :

Place Part A in a suitable vessel and begin to stir slowly. Part B was added and mixed until uniform. Part C was added, then part D was added and mixed to mix well.

Talc Ruth  Face powder

Prize INCI persons Brand name producer Weight portion A mica Sericite PHN Presperse 81.45 A Polymethyl
Methacrylate Ganzpearl GM-0600W Presperse 5.00 A Synthetic wax and corn
Gluten protein Microease 110XF Presperse 2.00 A Titanium dioxide Titanium dioxide 3228 Whittaker, Clark & Daniels 5.00 A Methyl paraben Nipagin M Clariant 0.20 A Propylparaben Nipsol M Clariant 0.10 A Imidazolidinyl urea Germall 115 ISP 0.25 B coloring agent Encapsulated Red Pigment Shiva Specialty Chemicals 1.00 B coloring agent Encapsulated Yellow Pigment Shiva Specialty Chemicals 5.00                   100.00 total

Process :

A was ground together until uniformly dispersed. B was added to A and mixed uniformly.

O / W Facial Foundation

Prize INCI name Brand name producer Weight portion A Deionized water DI Water N / A 53.94 A 10% KOH Solution 10% KOH Solution N / A 1.30 A PEG-12 dimethicone DC 193 Surfactant Dow Corning 0.10 A talc mica Whittaker, Clark &
Daniels 0.72 B 1,3-butylene glycol Jeechem BUGL Jeen Int. 4.00 B Magnesium aluminum
Silicate Veegum Granules RT
Vanderbilt 1.00 C 1,3-butylene glycol Jeechem BUGL Jeen Int. 2.00 C Cellulose sword CMC 7MF Hercules 0.12 C Methyl paraben Nipagin M Clariant 0.02 D Di-PPG-3 Myristyl Ether
Adipate Cromollient DP3-A Croda 14.00 D Diethyl hexyl maleate Pelemol DOM Phoenix 4.00 D Steareth-10 Lipocol S-10 Lipo 2.00 D Stearet-2 Lipocol s-2 Lipo 0.50 D Cetyl alcohol Crodacol C-95 NF Croda 0.62 D Dicetyl phosphate and
Seteth-10 phosphate and
Ceteryl alcohol Crodafos ces Croda 4.00 D Profile paraben Nipasol M Clariant 0.10 E coloring agent Encapsulated TiO2 Shiva Specialty Chemicals 7.50 E coloring agent Encapsulated Yellow Pigment Shiva Specialty Chemicals 2.50 E coloring agent Encapsulated Red Pigment Shiva Specialty Chemicals 1.20 E coloring agent Encapsulated Blue Pigment Shiva Specialty Chemicals 0.20 F DMDM Hydantoin Mackstat DM Mclntyre group 0.18 gun 100.00

Process :

The components of phase A were combined using a homogenizer and started to heat to 80 ° C. Add phases B and C and homogenize for 1 hour. In a separate beaker the components of phase D were combined, heated to 80 ° C. and mixed until uniform. After all the components of phase D were homogenized, the homogenization was continued while gradually adding to the main phase portion. After complete addition of phase D, the mixture was homogenized at 80 ° C. for 15 minutes and then the mixture began to cool. The paddle mixing was switched to medium stirring at 60 ° C. Phase E was added and mixed until a homogeneous mixture was obtained. Phase F was added at 50 ° C. The mixture was cooled until room temperature was reached.

1. Compressed Powder Eye Shadow (Purple)

INCI persons Brand name producer Weight portion mica Sericite PHN Presperse 75.60 Zinc stearate Zinc stearate Witco 5.00 coloring agent Encapsulated TiO ₂ Shiva Specialty Chemicals 6.00 coloring agent Encapsulated Red Pigment Shiva Specialty Chemicals 2.00 coloring agent Encapsulated Blue Pigment Shiva Specialty Chemicals 0.60 Methyl paraben Nipagin M Clariant 0.20 Propylparaben Nipasol M Clariant 0.10 Calcium aluminum
Borosilicate Luxsil Presperse 5.00 PEG-4 diheptanoate Liponate 2-DH Lipo 5.50 gun 100.00

Process :

The ingredients were combined and mixed well. Heated to 100 ° C. and compressed at 2,000 psi.

Claims (21)

The coloring agent is a first monomer which is an ethylenically unsaturated ionic monomer selected from the group consisting of acrylic acid and methacrylic acid, styrene, methyl methacrylate, tertiary butyl methacrylate, phenyl methacrylate, cyclohexyl methacrylate and Entrapped in a matrix polymer formed from a blend of monomers comprising a second monomer which is an ethylenically unsaturated hydrophobic monomer capable of forming a homopolymer having a glass transition temperature of at least 50 ° C. selected from the group consisting of isobornyl methacrylate, The second particles are dispersed in the matrix and have a glass transition of at least 50 ° C. selected from the group consisting of styrene, methyl methacrylate, tertiary butyl methacrylate, phenyl methacrylate, cyclohexyl methacrylate and isobornyl methacrylate Hydrophobic polymers formed from ethylenically unsaturated hydrophobic monomers capable of forming homopolymers having a temperature, Hydrophobic polymers are different from matrix polymers, A microparticle containing a color effective amount of one colorant selected from pigments, dyes or lakes. The microparticle of claim 1 having a particle size of 1 to 60 microns. delete The microparticle of claim 1 wherein the colorant is an organic or inorganic pigment, a lake or a mixture thereof. The microparticle of claim 1 further comprising an active ingredient. The coloring agent is a first monomer which is an ethylenically unsaturated ionic monomer selected from the group consisting of acrylic acid and methacrylic acid, styrene, methyl methacrylate, tertiary butyl methacrylate, phenyl methacrylate, cyclohexyl methacrylate and Is trapped in at least one matrix polymer formed from a blend of monomers comprising a second monomer which is an ethylenically unsaturated hydrophobic monomer capable of forming a homopolymer having a glass transition temperature of at least 50 ° C. selected from the group consisting of isobornyl methacrylate , The second particles are dispersed in the matrix and have a glass transition of at least 50 ° C. selected from the group consisting of styrene, methyl methacrylate, tertiary butyl methacrylate, phenyl methacrylate, cyclohexyl methacrylate and isobornyl methacrylate Hydrophobic polymers formed from ethylenically unsaturated hydrophobic monomers capable of forming homopolymers having a temperature, Hydrophobic polymers are different from matrix polymers, A solid or liquid cosmetic composition comprising a color effective amount of two colorant blends selected from pigments, dyes or lakes, as well as a carrier or adjuvant acceptable for cosmetics. 7. The composition of claim 6, wherein the colorant trapped in the composition is selected from two different colors. 7. The composition of claim 6, wherein the colorant trapped in the composition is selected from two primary colors of red, yellow and blue which are primary colors. The composition of claim 6, wherein the colorant trapped in the composition is provided in two separate matrix polymeric materials. The composition of claim 6, wherein the two captured colorants are in a single matrix polymeric material. 7. The composition of claim 6 comprising from 0.1 to 70% by weight of a blend of colorants captured on a total weight of the composition. 7. The composition of claim 6, formulated as a water-in-oil (w / o) or oil-in-water (o / w) emulsion, as an antifoam dispersion of ionic or nonionic amphiphilic lipids, as a gel or as a solid stick. The composition of claim 6 in the form of a skin care preparation, a cosmetic preparation or a photoprotective preparation. The composition of claim 6 incorporated into a facial makeup cosmetic formulation in the form of a lipstick, eye shadow, liquid makeup, day cream or powder, face lotion, cream or powder. The composition of claim 6 comprising at least one additional component selected from the group consisting of sequestrants, non-encapsulated colorants, flavorings, clouding agents, hardeners, emollients, UV absorbers, skin protectants, antioxidants and preservatives. The microparticle of claim 1, wherein the second monomer is styrene and the second particle comprises a hydrophobic polymer formed from ethylenically unsaturated hydrophobic monomers selected from the group consisting of styrene, methyl methacrylate. delete delete delete delete delete