WO2014135915A1

WO2014135915A1 - Non bleeding and solvent resistant pigments for cosmetic applications

Info

Publication number: WO2014135915A1
Application number: PCT/IB2013/000710
Authority: WO
Inventors: Sophie GOLDBLUM; Hélène DE CLERMONT GALLERANDE
Original assignee: Chanel Parfums Beaute
Priority date: 2013-03-08
Filing date: 2013-03-08
Publication date: 2014-09-12

Abstract

The present invention pertains to a pigment which may be obtained according to a process including the steps of preparing a crosslinked resin, introducing at least one material chosen from water-soluble organic dyes and at least one water-soluble metallic salt during the manufacture of said crosslinked resin. It also relates to coating compositions, especially cosmetic compositions, comprising said pigment and to a cosmetic process for making-up skin (especially cheeks and/or eyelids) and/or lips, comprising the topical application onto said skin and/or lips of this cosmetic composition.

Description

Non bleeding and Solvent resistant pigments for cosmetic applications

The present invention relates to cosmetic pigments, and especially cosmetic colored pigments, suitable for cosmetic formulations in general and specifically for formulations demanding good solvent resistance, such as nail lacquers formulations.

BACKGROUND OF THE INVENTION

Embedding dyes into polymers to create pigments which may be used in paints, for example, has been reported among others under U.S. Pat. Nos. 2938873 and 2498592. The polymers used to make these pigments are either thermoplastic sulfonamide / formaldehyde polymers or thermoset resins which are essentially based on urea / formaldehyde polymers. The dyes may be introduced at any stage during the manufacture of the polymer, for instance before curing the thermoset resin. After grinding, the resulting pigments are introduced into coating compositions where they are said to be insoluble and to be stable against flocking.

Further, U.S. Pat. Nos. 5143723 and 5324506 report utilizing the same technology to create pigments to be used in cosmetic compositions. These pigments are said to confer more gloss and clarity of color to the lips or cheeks than the usual lakes, which are made of an insoluble, oil-dispersible aluminum hydroxide substrate on which a dye is absorbed or precipitated. Although a number of resins are listed, including crosslinked polyester resins, the examples provided in this document only use toluene sulfonamide formaldehyde resins .

It has now been found that the available polymer embedding technology does not provide suitable cosmetic pigments for solvent resistance demanding applications like nail varnish.

Document WO 2011/015906 discloses a process for obtaining insoluble pigments by introducing a dye, in particular a fluorescent dye, or a pigment in a crosslinked polyester, polyamide or polyesteramide resin. This process results in a higher solvent resistance for fluorescent dyes and for pigments, but when a soluble colored dye is encapsulated within the polymeric matrix, it has been found that the resulting colouring powder "bleeds" in water or in the solvents commonly used in cosmetic compositions such as nail enamels. This results in an undesirable coloration of the surface on which the product is applied, for example the skin or nails after removal of the makeup.

The inventors have realized that the above drawback could be overcome by using a specific kind of polymer in a specific process to make the colored pigment .

Moreover, the pigments according to this invention have also been shown to be heat resistant, which render them useful in various make-up products such as lipsticks, lip glosses, cheek blushes and eye shadows.

An object of the present invention is thus to provide pigments which don't bleed in water, in ethanol or in organic solvent used in nail enamels.

Another object of the present invention is to provide pigments which are not soluble and do not swell in the solvents used in nail enamels.

Another object of this invention is to provide pigments which can be easily grinded and dispersed into cosmetic compositions.

Still another object of this invention is to provide pigments which are heat resistant, in that they do not deteriorate until 220°C.

SUMMARY OF THE INVENTION

The present invention pertains to a pigment which may be obtained according to a process including the steps of :

1- preparing a crosslinked resin

2- introducing at least one water-soluble organic dye during the manufacture of said crosslinked resin;

3-introducing at least a water-soluble metallic salt capable of forming a water-insoluble salt with the water-soluble organic dye during the manufacture of said crosslinked resin; 4- optionally removing any solvent or suspension medium for the monomers, crosslinkers and/or materials, so as to obtain a powder; and

5- grinding said powder.

This invention also pertains to coating compositions, especially cosmetic compositions, comprising said novel pigment.

It is also directed to a cosmetic process for making-up skin (especially cheeks and/or eyelids) and/or lips, comprising the topical application onto said skin and/or lips of such a cosmetic composition.

The pigments according to this invention have proved to not bleed in water or solvent and to be stable upon heating and in solvents used to manufacture nail enamels, especially alkyl acetates and acetone and to be easily dispersible in cosmetic media. They also offer a better resistance to pH and light than the usual organic dyes and a newer range of colors which cannot be obtained by means of these dyes.

DETAILED DESCRIPTION OF THE INVENTION

As mentioned above, the process according to the present invention comprises the manufacture of a crosslinked resin.

Any resin may be used in the process of this invention, provided it can crosslink, is safe for application to the skin, and is compatible with the other components of the composition.

Preferred resins are those that do not absorb appreciable amounts of light. Preferably, the resins are transparent or at least translucent.

Preferred polymeric materials used as resins in the process of the invention include, but are not limited to acrylic and modified acrylic polymers such as polymethyl methacrylate ; acrylonitrile/butadiene/ styrene copolymers ; acrylonitrile/butadiene/ styrene/methyl methacrylate copolymers; acrylonitrile/styrene copolymers; acrylonitrile/styrene copolymers modified with butadiene/styrene elastomer; cellophane; cyclohexylene dimethylene terephthalate and 1 , 4-cyclohexylene dimethylene isophthalate copolymers; ethylene-acrylic acid copolymers; ethylene-1 , 4-cyclohexylene dimethylene terephthalate copolymers; ethylene-ethyl acrylate copolymers; ionomeric resins; ethylene-methyl acrylate copolymer resins; ethylene-vinyl acetate copolymers; ethylene-vinyl acetate-vinyl alcohol copolymers; fluorocarbon resins; cellulose derivatives, water- insoluble; isobutylene polymers; isobutylenebutene copolymers ; 4,4' -isopropylidenediphenolepichlorohydrin resins; melamine-formaldehyde resins; nitrile rubber modified acrylonitrile-methyl acrylate copolymers; nylon resins; olefin polymers; perfluorocarbon resins; polyarylate resins; polyarylsulfone resins; poly-1- butene resins and butene/ethylene copolymers; polycarbonate resins; polyester resin; polyesteramide resin, polyetherimide resins; polyethylene resins, carboxyl modified; polyethylene, chlorinated; polyethylene, fluorinated; polyethylene, oxidized; polyethylene phthalate polymers; poly (p-methylstyrene ) and rubber-modified poly (p-methylstyrene ) ; polystyrene and rubber-modified polystyrene; polysulfide polymer- polyepoxy resins; polysulfone resins; poly

( tetramethylene terephthalate ) ; polyvinyl alcohol films; polyurethane resins; styrene block polymers; styrene-maleic anhydride copolymers; styrene-methyl methacrylate copolymers; textryls; urea-formaldehyde resins; vinyl chloride-ethylene copolymers; vinyl chloride-hexene-1 copolymers; vinyl chloride-lauryl vinyl ether copolymers; vinyl chloride-propylene copolymers; vinylidene chloride/methyl acrylate copolymers; vinylidene chloride/methyl acrylate/methyl methacrylate polymers; ethylene polymers, chlorosulfonated; 4,4' -isopropylidenediphenol- epichlorohydrin thermosetting epoxy resins; mineral reinforced nylon resins; perflourocarbon cured elastomers; phenolic resins; polyester resins, cross- linked; polyether resins, chlorinated; polyethersulfone resins; polyamide resins such as nylon-12, polyamide- imide resins; poly ( 2 , 6-dimethyl-l , 4-phenylene ) oxide resins; polyoxymethylene copolymers; polyoxymethylene homopolymers ; polyphenylene sulfide resins; polyvinylidene fluoride resins; and styrene- divinylbenzene resins.

In a preferred embodiment, the resin can be chosen from limited to acrylic and modified acrylic polymers such as polymethyl methacrylate; cellulose derivatives, polyamide resins such as nylon-12, polyester resin and polyesteramide resin.

In another a preferred embodiment, the resin is crosslinked in an aqueous phase. Indeed, the dyes incorporated in the resins in the present invention being water-soluble, it is preferred that the resin be prepared in a water containing medium.

In another preferred embodiment, the crosslinked resin is chosen from polyester, polyamide or polyesteramide resins, from at least one bi-functional monomer Ml chosen from diols and diamines and at least one bi-functional monomer M2 chosen from dicarboxylic acids and acid anhydrides, in the presence of at least one crosslinking agent chosen from tri-functional crosslinkers CL3 and tetra-functional crosslinkers CL4, wherein :

0.3 < A/B < 1.7

1.5 < (A+B) /C < 3.5

1.7 < (A+B) /D < 4

where A = total molar content of Ml

B = total molar content of M2

C = molar content of CL3

D = molar content of CL4.

The words "trifunctional " and "tetra-functional " are intended to refer to compounds including three or four functions, respectively, which may be chosen among hydroxy, carboxyl, epoxy and amino groups. Optionally, one anhydride group can be used instead of two carboxyl groups . The bifunctional , trifunctional and tetra- functional compounds used in this invention may be linear, branched or cyclic hydrocarbons bearing said functions or may be chosen from heterocyclic or aromatic compounds (preferably including a phenyl moiety) bearing said functions.

The monomers Ml include diols, diamines and their mixtures. Among diols, mention can be made of 1,4- cyclohexane dimethanol (CHDM) , 1 , 4-butanediol (BDO) , 1, 5-pentanediol (PDO) , 1 , 6-hexanediol (HDO) , 1,12- dodecanediol (DDO) and their mixtures. Among diamines, mention can be made of para-phenylenediamine (PPD) , isophorone diamine (IPDA), hexamethylenediamine (HMDA) , 2-methylpentane-l , 5-diamine (MPMD) , diaminododecane (DADD) and their mixtures.

Examples of monomers M2 are dicarboxylic acids, such as adipic acid (ADA) , dodecanedioic acid (DDA) , methylisophthalic acid (MIPA) , isophthalic acid (IPA) and terephthalic acid (TPA) , acid anhydrides bearing one anhydride group, such as phthalic anhydride (PA) , and their mixtures.

The trifunctional crosslinking agents CL3 may be chosen from the group consisting of: tris-(2,3- epoxypropyl ) isocyanurate (TGIC) , trimethylolpropane (TMP) , trimellitic anhydride (TMA) , dimethylolpropionic acid (DMPA) and their mixtures. The tetra-functional crosslinking agents CL4 may be chosen from the group consisting of: pentaerythritol (penta) , tris (hydroxy) aminomethane (THAM) , pyromellitic dianhydride (PMDA) , 2-amino-2- (hydroxymethyl ) propanediol, ethylenediaminetetraacetic acid (EDTA) and their mixtures.

According to this invention, the foregoing monomers and crosslinking agents should be used in specific ratios so as to obtain pigments having enough solvent resistance while avoiding gelling problems during their manufacture and preserving the ability to grind them.

Specifically, they should satisfy:

0.3 < A/B < 1.7

1.5 < (A+B) /C < 3.5

1.7 < (A+B) /D < 4

wherein A = total molar content of Ml

B = total molar content of M2

C = molar content of CL3

D = molar content of CL4

More preferably, at least one and optionally all of the following requirements could be satisfied:

A/B ranges from 0.6 to 1.4,

(A+B)/C ranges from 2 to 3,

(A+B) /D ranges from 2.2 to 3.5.

Moreover, in case a mixture of CL3 and CL4 crosslinking agents is used, it is preferred to have: 1.5 < [ (A+B+C) / (A+B+D) ] <4. In order to prepare the crosslinked resin according to this invention, the monomers (in particular monomers Ml and M2 previously described) are polymerized in the presence of the crosslinking agents (in particular CL3 and/or CL4) according to any polymerization process well-known to the skilled person, such as bulk polymerization, emulsion polymerization or suspension polymerization. The polymerization is preferably a polycondensation reaction conducted in the presence of a catalyst such as oxalic acid.

The water-soluble organic dyes are added to the resin during its formation, in particular during its polymerization or during its crosslinking. The water- soluble dye contains an ionic group that allows it to be soluble in water. The ionic groups may be chosen from a carboxylate, a sulfate, or a sulfonate. This material usually provides for an optical effect including absorbing, reflecting, transmitting, diffusing and/or refracting any portion of the light spectrum, and especially of the UV and visible wavelengths, such as providing a color for instance. Thus, the pigment obtained according to this invention is preferably a colored pigment.

Examples of such water-soluble organic dyes include, without any limitation: FD&C Blue No. 1, FD&C Blue No. 2, FD&C Green No. 3, FD&C Red No. 3, FD&C Red No. 4, FD&C Red No. 40, FD&C Yellow No. 5, FD&C Yellow No. 6, D&C Blue No. 4, D&C Blue No. 6, D&C Blue No. 9, D&C Green No. 5, D&C Green No. 8, D&C Orange No. 4, D&C Orange No. 5, D&C Orange No. 10, D&C Orange No. 11, D&C Red No. 6 sodium salt, D&C Red No. 19, D&C Red No. 21, D&C Red No. 22, D&C Red No. 27, D&C Red No. 28, D&C Red No. 30, D&C Red No. 31, D&C Red No. 39, Ext. D&C Yellow No. 7, D&C Yellow No. 8, D&C Brown No. 1, Ext. D&C Violet 2, natural dyes such as caramel, coffee, and chlorophyll .

In a preferred embodiment, the water-soluble organic dyes used in the present invention are colored dyes, fluorescent or non-fluorescent. Indeed, the fluorescent property of a dye is the result of its conjugated chemical structure which allows the electrons to delocalize. This delocalization of the electrons on the structure of the colorant can mainly be observed when the colorant remains in a dissolved form. Therefore, a fluorescent dye precipitated by a metallic salt according to the present invention would result in a loss of most of its fluorescent properties. In the context of the present invention, the colored dyes are used for their intense color, independently of the fluorescent property. This problem is specific to fluorescent dyes, i.e. colored fluorescent compounds such as the one exemplified in document WO 2011/015906 where a fluorescent property is researched. This is however not the case for optical brighteners which are fluorescent compounds invisible under visible light. These uncolored fluorescent compounds can be suitable water-soluble organic dyes used in the present invention since their precipitation would only lead to a limited decrease of there fluorescent properties. Therefore, in one aspect of the invention, the water- soluble organic dyes can be an optical brightener which is a fluorescent compound invisible under visible light as stilbene salt derivatives, biphenyl distyryl salt derivatives, dianaline salt derivatives, and coumarine salt derivatives.

A water-soluble metallic salt capable of forming a water-insoluble salt with the water-soluble organic dye is also added to the resin during or its formation, in particular during its polymerization or during its crosslinking .

This metallic salt is water-soluble and capable of forming a new water-insoluble salt with the organic dye when added, thus precipitating the dye.

The water-soluble salt may be formed by the reaction of a metal M and an acid.

Therefore, the water-soluble salt can be represented by the formula M-X, wherein M is the metallic cation and X is the anion from parent acid.

M can be any metal of the periodic table, and for example calcium, barium, aluminum magnesium, potassium, sodium, silver, tin, zinc, iron, lead, but preferably, M is calcium, barium or aluminum.

Anion X may be chosen from (parent acid in parentheses): chloride Cl^~ (hydrochloric acid), sulfate S0₄ ^2~ ( sulfuric acid), nitrate NC>3^~(nitric acid), acetate CH₃COO^~ (acetic acid) , carbonate CC>3^2~ (carbonic acid) , citrate HOC (COO^~) (CH₂COO^~) ₂ (citric acid), phosphate P0₄ ^3~ (phosphoric acid) Preferably, X is chosen from chloride Cl^~, sulfate SC>4^2~and nitrate NC>3^~.

The salt is preferably introduced in molar excess relative to the water-soluble organic dye to obtain complete precipitation of said dye. In particular, the molar ratio of the water-soluble salt to the water- soluble organic dye is greater than 1, and preferably around 2.

The pigment thus obtained shows an intense color and no bleeding in water or in any water-soluble solvent .

In a particular embodiment, the preparation process of the pigments of this invention further comprises a step of introducing any powdery material to the resin either before, during or after its formation, for instance during its polymerization or during its crosslinking, before the step of removal of the solvent .

Indeed, in aqueous or water-miscible solvent compositions, water-insoluble powdery materials such as fillers or UV-filters may lead to stability problems or may be dispersed non-homogeneously . It can therefore be advantageous to incorporate these powdery materials within the resin before removal of the solvent.

The powdery material can for example be chosen from fillers to opacify to the pigment such as barium sulfate, talc, kaolin, alumina, natural or synthetic mica, silica, titanium dioxide, or from inorganic UV- absorbers to protect the color of the pigment such as zinc oxide, nanofine titanium dioxide, or from optical brighteners .

After the resin has been formed, any solvent used during its formation is usually removed, for instance by evaporation. After grinding, if necessary, the powder thus obtained has a median particle size between 0.02 pm and 1000 pm, preferably between 0.2 pm and 100 pm, more preferably between 2 pm and 10 pm, for instance from 3 to 5 pm. The grinding step may be carried out by means of jet milling, high shear dispersing, ball milling or pin or sand milling, for instance .

The pigments thus obtained might be mixed in applications to supply a special effect, like being reflective or absorbing only at a narrow range of the visible or invisible light wavelengths, as an example but not limited to, when being reflective or absorbing only between 400 and 500 nm or between 600 and 700 nm or 400 and 460 nm or having a cascading effect as when one colorant fluoresces whereas the other(s) absorb(s). It is easy to the one skilled in the art to find out the percentage of the needed colorant in the targeted special effect mixtures based on the reflection, absorption and emission curves of the single components. As an example, but not limited too, targeting a cascading effect at 560 nm might be achieved by 2 pigments, one absorbing at 430 nm and fluorescing at 500 nm and the other absorbing at 500 nm and fluorescing at 560 nm.

The pigments obtained with the process of the invention can be characterized by an improved non- bleeding property that can be easily observed visually since the compositions in which they are introduced do not stain the surface on which they are applied compared to the same compositions containing classical lakes .

The "bleeding" may also be tested by mixing 3 % of the pigment in water, or ethanol, or any other solvents used in enamels during 10 minutes. The water soluble organic dye entrapped in the polymer matrix may solubilize in the solvent. After filtration, the absorbance of the solvent can be measured with UV- Visible Spectrophotometer and leads to the concentration C (mol.LT¹) of dye having bled, through the Beer-Lambert law A= e*l*C, where ε (L.mol^.cm^-1) is the molar extinction coefficient of the dye and l(cm) is the length of the "cuve". The percentage of bleeding can be obtained by the formula :

% bleeding = (Cdye in solvent) / (Cdye in the pigment) *100

This calculation is well known for the skilled person .

The pigments are considered non-bleeding when their % bleeding is less than 0.5 %, preferably less than 0.1%, and more preferably less than 0.05%. The pigments are characterized by a high resistance to solvents such as alkyl acetates and acetone. Solvent resistance may be tested by leaving 1 g of the pigment, pulverized to a median particle size of 5 pm, in 10 ml of said solvent for 30 minutes at 37- 38°C or 24h at 40°C. The solvent attack on the pigment indicates the resistance or the solubility of said pigment and it is classified from 5 (insoluble) to 1 (completely soluble) . Pigments are regarded as solvent- resistant in case their grade is 5. Moreover, one checks that the pigment particles remain free flowing in the solvent after applying the test.

Usually, the pigments of this invention also have a melting point of 210-240°C and a decomposition temperature of more than 300°C, which enables them to be processed up to a temperature of 220°C.

They can thus be used in all applications requiring pigments having non bleeding properties, a good solvent and/or heat resistance.

These pigments may thus be used to color cosmetic or non cosmetic coating products or to provide a color to a substrate onto which these cosmetic or non- cosmetic products are applied. This invention is thus also directed to coating compositions comprising at least one pigment as defined above. In particular, this invention is also directed to coating compositions comprising at least one pigment and containing water, ethanol and/or in organic solvent such as those used in nail enamels

Among cosmetic products, mention can be made of: lipsticks, lip glosses, nail enamels, mascaras, cheek blushes, eye shadows and hair sprays, without limitation. Non cosmetic products are among others polymer articles such as PVC, PU or PE films ; modeling clay ; sand ; inks ; spray cans; paints ; LCDs ; textiles ; electronic devices ; electrical devices ; and mechanical devices.

When used in cosmetic compositions, the pigments of this invention are included in a cosmetically acceptable medium. By this expression, it is intended to mean a physiologically acceptable medium, which is compatible with the keratin materials such as the skin and/or lips and/or nails and/or hair and which does not provide the consumer with any unacceptable discomfort such as stinging.

This cosmetic medium usually includes at least one solvent which may be chosen from water and polar and apolar organic solvents such as alkyl acetates or acetone and oils. Examples of oils include: linear or branched hydrocarbons of mineral or synthetic origin, synthetic (poly) esters and (poly) ethers and in particular (poly) esters of C6-C20 acids and of C6-C20 alcohols that are advantageously branched, such as isononyl isononanoate, plant oils, branched and/or unsaturated fatty acids, branched and/or unsaturated fatty alcohols, fluoro oils, and also mixtures thereof.

The resulting composition may be anhydrous or it may be in the form of an oil-in-water , water-in-oil or multiple (W/O/W, 0/W/O, etc.) emulsion or in the form of a hydrodispersion (dispersion of oil in a polar phase, especially an aqueous phase, in the absence of emulsifier) .

This composition may include from 0,1 to 50wt. % of the pigments according to this invention. In addition, it may include at least one additive chosen from:

• plant, animal, mineral or synthetic waxes, the latter advantageously possibly being hydrocarbon-based waxes or silicone waxes ;

• a pasty fatty substance or a butter characterized by a melting point of between 25 and 45°C;

• lipophilic and/or hydrophilic gelling agents;

• film-forming polymers;

• surfactants;

• fillers;

• dyestuffs chosen from water-soluble or liposoluble dyes, pigments, nacres and lakes;

• active agents such as humectants and/or anti^¬ oxidants ;

• organic and/or inorganic UV-screening agents; and • their mixtures.

Examples of such adjuvants are mentioned especially in the Personal Care Product Council (PCPC) On-line Infobase (http :/ /online . personalcarecouncil . org/ sp/Home . sp ) .

The invention will now be illustrated by the nonlimiting examples that follow.

EXAMPLES

EXAMPLE 1

8 g D&C Orange 5, 1.4 g aluminium chloride, 60 g isophoronediamine, 50 g 2-amino-2- (hydroxymethyl ) -1 , 3- propanediol and 170 g of isophthalic acid are added and mixed in 1 liter reactor. The mixture is heated under mixing for 3 hours between 100 and 250°C. After cooling to room temperature, the mix is crushed and processed via a laboratory jet mill to get fine orange pigment with particles of 5 pm median particle size. The pigment has good solvent resistance and high reflection, and shows no bleeding.

EXAMPLE 2

The same pigment as described in Example 1 is prepared, except that D&C Orange 5 is replaced with solvent Yellow 135. Grinding resulted in a greenish yellow pigment with particles of 5 pm median particle size. The pigment has good solvent resistance and high reflection . EXAMPLE 3

The preparation method of Example 1 is repeated, except that D&C Orange 5 is replaced with 4 g of D&C Red 22 and 3 g D&C Red 17. Grinding results in a bluish red pigment with particles of 5 pm median particle size. The pigment has good solvent resistance and high reflection .

EXAMPLE 4

The preparation method of Example 1 is repeated, except that D&C Orange 5 is replaced with 8 g of D&C Violet 2. Grinding results in a bluish violet pigment with particles of 5 pm median particle size with good solvent resistance and high reflection.

EXAMPLE 5

The preparation method of Example 1 is repeated, except that D&C Orange 5 is replaced with 8 g of disodium distyrylbiphenyl disulphonate . Grinding results in a white to colorless pigment with particles of 5 pm median particle size with good solvent resistance and high reflection. The pigment fluoresces and becomes blue when illuminated with UV-light.

EXAMPLE 6

Five colored pigments were made according to the preparation method described in Example 1, except that they contained the following colorants:

EXAMPLE 6A: D&C Yellow 7 and D&C Yellow 8

EXAMPLE 6B: D&C Yellow 7, D&C Orange 5 and D&C

Red 28 EXAMPLE 6C: D&C Orange 5 and D&C Red 28 EXAMPLE 6D: D&C Red 28 and D&C Red 21.

These pigments were tested for assessing their solvent resistance in various solvents: they were completely insoluble in acetone, MEK, water, isopropyl alcohol, DMF and in mixtures of DIDP/acetone (1/1) and Butyl/propyl/ethyl acetates (1/1/1).

EXAMPLE 7

This example illustrates a lipstick composition containing the pigments of this invention.

Octyldodecanol : 10-20%

Pentaerythrityl tetraisostearate : 5-15%

Sucrose tetrastearate triacetate : 5-15%

Dipentaerythrityl/hexahydroxystearate/

hexastearate/hexarosinate : 5-12%

Diisostearyl malate : 5-12%

Hydrogenated polydecene : 4-10%

Phenylpropyldimethylsiloxysilicate : 4-10%

Mica : 2-7%

Polyethylene : 2-6%

Synthetic wax : 2-6%

Preservatives : 0-1%

Anti-oxidants : 0-1%

Fragrance : 0-1%

Pigments and pearls : 0-20%

Pigments of Example 6B: 0.1-20%

EXAMPLE 8 This example illustrates an aqueous lipgloss emulsion containing a pigment according to this invention .

Acrylates Copolymer & Aqua

& Phenoxyethanol :

Styrene/Acrylates /Ammonium

Methacrylate Copolymer & Aqua :

Ethylcellulose & Sodium Lauryl Sulfate

& Cetyl Alcohol & Aqua :

Sorbitan Stearate & Sucrose Cocoate :

Octyldodecanol :

Phenyltrimethicone :

Diisostearyl Malate :

Hydrogenated polydecene &

ethylene/propylene/styrene copolymer &

butylene/ethylene/styrene copolymer :

Pigments of Example 6B :

EXAMPLE 9

This example illustrates a pressed powder blush containing a pigment according to this invention.

Talc : 20-75%

Boron nitride : 5-15%

Magnesium myristate : 0-5%

Magnesium stearate : 0-6%

Methylmethacrylate crosspolymer : 2-8%

Mica : 0-10%

PTFE : 0-8% Nylon-12 : 2--10%

Polymethylmethacrylate : 0- -3%

Octyldodecyl neopentanoate : 1- -6%

PPG-2 myristyl ether propionate : 1- -6%

Preservatives : 0- -1%

Anti-oxidants : 0-

Fragrance : 0- -1%

Pigments of Example 6C 0. .1-20%

EXAMPLE 10

This example illustrates a procedure for making a nail varnish containing a pigment of this invention.

Butyl acetate : 25-35%

Ethyl acetate : 23-29%

Nitrocellulose : 11-15%

Styrene / acrylates copolymer : 4-10%

Acetyl tributyl citrate : 3-7%

Isophorone diamine / isophthalic

acid / tromethamine copolymer : 3-11%

Phthalic anhydride / trimellitic

anhydride / glycol copolymer : 0-6%

Isoporpyl alcohol : 4-6%

Isobutyl acetate : 0-5%

Adipic acid / neopentyl glycol /

trimellitic anhydride copolymer : 0-2%

Stearalkonium bentonite : 0.1-3%

Stearalkonium hectorite : 0.1-3%

Propylene carbonate : 0.2-2%

Colorants : 0-0.5%

Phosphoric acid : 0.1 % Silica 0.2

Pigments of Example 0.1-20%

This nail varnish is prepared as follow.

Procedure: nitrocellulose (lOg) is dissolved in a solvent mixture (20g of ethyl acetate and qs butyl acetate for lOOg) and then lOg of a plasticizer (Ethyl

Tosylamide and/or Adipic Acid/Neopentyl glycol/trimellitic anhydride copolymer) and 5g of a resin ( Styrene/acrylates copolymer) are added to the combination. 1.5g of a thickening agent ( stearalkonium hectorite) , other solvents (lg of diacetone alcohol and 5g of isopropyl alcohol) and the pigments of Example 4 are added slowly (over 5 minutes) in order to get good wetting while stirring with a spatula and mixing till a homogenous mixture is obtained.

EXAMPLE 11

This example illustrates an aqueous nail varnish containing a pigment of this invention

Acrylates Copolymer & Aqua

& Phenoxyethanol : 30-95%

Styrene/Acrylates /Ammonium

Methacrylate Copolymer & Aqua : 30-95%

Ethylcellulose & Sodium Lauryl Sulfate

& Cetyl Alcohol & Aqua : 30-95 %

Sodium Polyacrylate : 0,5-1%

Pigments of Example 6D : 0.1-20%

EXAMPLE 12 A gloss is prepared, which is fluorescent when exposed to UV light and vivid colored when exposed to day light comprising 2 pigments according to the invention : one uncolored fluorescent pigment and one colored pigment. Its formula is the following:

Polybutene: 50-80%

Diisostearyl malate: 10-20%

Octyldodecanol : 5-20%

Glyceryl Behenate/eicosadioate 0.5-5%

Tocopheryl acetate 0.1-1%

Pigments of Example 5 0.01-2%

Pigments of Example 6D : 0.1-20%

The pigments are grinded into the diisostearyl malate and added to the other raw materials already mixed and melted at 80°C. The full composition is mixed for 30 minutes before cooling at room temperature and filled in appropriate containers.

Claims

What we claim is:

1. Pigment which may be obtained according to a process including the steps of:

1- preparing a crosslinked resin;

2- introducing at least one water soluble organic dye, during the manufacture of said crosslinked resin;

3-introducing at least a water-soluble metallic salt capable of forming a water-insoluble salt with the water-soluble organic dye, during the manufacture of said crosslinked resin;

4- optionally removing any solvent or suspension medium for the monomers, crosslinkers and/or materials, so as to obtain a powder; and

5- grinding said powder.

2. Pigment according to Claim 1, wherein the resin is chosen from limited to acrylic and modified acrylic polymers such as polymethyl methacrylate ; cellulose derivatives, polyamide resins such as nylon-12, polyester resin and polyesteramide resin.

3. Pigment according to Claim 1 or 2, wherein the resin is crosslinked in an aqueous phase.

4. Pigment according to anyone of Claims 1 to 3, wherein the resin is chosen from polyester, polyamide or polyesteramide resins, from at least one bi- functional monomer Ml chosen from diols and diamines and at least one bi-functional monomer M2 chosen from dicarboxylic acids and acid anhydrides, in the presence of at least one crosslinking agent chosen from tri- functional crosslinkers CL3 and tetra-funct ional crosslinkers CL4,

wherein :

0.3 < A/B < 1.7

1.5 < (A+B) /C < 3.5

1.7 < (A+B) /D < 4

where A = total molar content of Ml

B = total molar content of M2

C = molar content of CL3

D = molar content of CL4monomers Ml are chosen from the group consisting of: 1 , 4-cyclohexane dimethanol (CHDM) , 1 , 4-butanediol (BDO) , 1,5- pentanediol (PDO) , 1 , 6-hexanediol (HDO) , 1,12- dodecanediol (DDO) , para-phenylenediamine (PPD) , isophorone diamine (IPDA), hexamethylenediamine (HMDA) , 2-methylpentane-l , 5-diamine (MPMD) , diaminododecane (DADD) and their mixtures.

5. Pigment according to Claim 4, wherein the monomers M2 are chosen from the group consisting of: adipic acid (ADA) , dodecanedioic acid (DDA) , methylisophthalic acid (MIPA) , isophthalic acid (IPA), terephthalic acid (TPA) , phthalic anhydride (PA) and their mixtures.

6. Pigment according to claims 4 or 5, wherein the trifunctional crosslinking agents CL3 are chosen from the group consisting of: tris-(2,3- epoxypropyl ) isocyanurate (TGIC) , trimethylolpropane (TMP) , trimellitic anhydride (TMA) , dimethylolpropionic acid (DMPA) and their mixtures.

7. Pigment according to any of Claims 4 to 6, wherein the tetra-functional crosslinking agents CL4 are chosen from the group consisting of: pentaerythritol (penta) , tris (hydroxy ) aminomethane (THAM) , pyromellitic dianhydride (PMDA) , 2-amino-2- (hydroxymethyl ) -propanediol, ethylenediaminetetra- acetic acid (EDTA) and their mixtures.

8. Pigment according to any of Claims 1 to 7, wherein the water-soluble dye contains an ionic group that allows it to be soluble in water, said ionic group being a carboxylate, a sulfate, or a sulfonate.

9. Pigment according to any of Claims 1 to 8, wherein the water-soluble metallic salt is formed by the reaction of a metal M and an acid.

10. Pigment according to the preceding claim, wherein the water-soluble salt can be represented by the formula M-X, wherein M is the metallic cation preferably chosen from calcium, barium or aluminum and X is the anion from parent acid, preferably chosen from chloride Cl^~, sulfate SC>4^2~and nitrate NC>3^~.

11. Pigment according to any of Claims 1 to 10, wherein the molar ratio of the water-soluble salt to the water-soluble organic dye is greater than 1, and preferably around 2.

12. Pigment according to any of Claims 1 to 11, wherein the preparation process further comprises a step of introducing any powdery material to the resin either before, during or after its formation, for instance during its polymerization or during its crosslinking, before the step of removal of the solvent .

13. Pigment according to the preceding claim, wherein the powdery material is chosen from fillers to opacify to the pigment such as barium sulfate, talc, kaolin, alumina, natural or synthetic mica, silica, titanium dioxide, or from inorganic UV-absorbers to protect the color of the pigment such as zinc oxide, nanofine titanium dioxide, or from optical brighteners

14. Coating compositions, especially cosmetic compositions, comprising the pigment according to any of Claims 1 to 13.

15. Coating compositions, especially cosmetic compositions containing water, ethanol and/or in organic solvent used in nail enamels, comprising the pigment according to any of Claims 1 to 13.

16. Cosmetic process for making-up skin (especially cheeks and/or eyelids) and/or lips, comprising the topical application onto said skin and/or lips of the cosmetic composition according to Claim 15.