FLUORESCENT PARTICULATE MATERIAL

Abstract

The present invention relates to a fluorescent particulate material, formed from particles of an oxide of an element M, some of the atoms M of which bear a cationic group of formula (I) all or some of said cationic radicals of formula (I) being combined ionically with an anionic form of an organic compound A, which is fluorescent in the visible region, said anionic form of an organic compound A bearing at least one sulfonate group and/or at least one carboxylate group.

##STR00001##

Claims

1: Fluorescent particulate material, formed from particles of an oxide of an element M, some of the atoms M of which bear a cationic group of formula (I): ##STR00039## in which: *- representing a covalent bond with an atom M, M being chosen from titanium, iron, copper, zinc, zirconium, strontium, silicon, bismuth, cerium and mixtures thereof, Q represents a linear or branched divalent C.sub.1-C.sub.12 alkylene radical, optionally interrupted with one or more oxygen atoms, and optionally substituted, or an optionally substituted C.sub.6-C.sub.10 arylene radical, or a divalent radical RC.sub.6H.sub.4R, R and R, which may be identical or different, represent a divalent C.sub.1-C.sub.4 alkylene radical and C.sub.6H.sub.4 represents an aromatic divalent radical, X.sup.+ represents a cationic organic group, and the groups R, which may be identical or different, represent a hydrogen atom, a C.sub.1-C.sub.6 alkyl radical or a covalent bond with an atom M, all or some of said cationic radicals of formula (I) being combined ionically with an anionic form of an organic compound A, which is fluorescent in the visible region, said anionic form of an organic compound A bearing at least one sulfonate group and/or at least one carboxylate group.

2: Material according to claim 1, in which the oxide of the element M is chosen from the group formed by TiO.sub.2, Fe.sub.2O.sub.3, CuO, ZnO, ZrO.sub.2, SiO.sub.2, Bi.sub.2O.sub.3, CeO.sub.2, SrO.sub.2 and Si.sub.xO.sub.y, x and y being independently comprised between 0.1 and 2.

3: Material according to claim 1, in which the oxide of the element M is a silicon oxide.

4: Material according to claim 1, in which the particles are porous.

5: Material according to claim 1, in which the particles have a porosity of less than 1000 m.sup.2/g.

6: Material according to claim 1, in which the group X.sup.+ has the formula N.sup.+R.sub.1R.sub.2R.sub.3 in which groups R.sub.1, R.sub.2 and R.sub.3, which may be identical or different, independently represent a linear or branched C.sub.1-C.sub.6 alkyl radical, optionally interrupted with one or more oxygen atoms, and optionally substituted, or an optionally substituted C.sub.6-C.sub.10 aryl group, one of the groups R.sub.1, R.sub.2 and R.sub.3 eventually forming a linear or branched C.sub.1-C.sub.20 alkyl radical, two of the groups R.sub.1, R.sub.2 and R.sub.3 possibly forming together, with the nitrogen atom to which they are attached, an optionally substituted, 5- or 6-membered, saturated or unsaturated heterocycle.

7: Material according to claim 6, in which the groups R.sub.1, R.sub.2 and R.sub.3, which may be identical or different, independently represent a methyl or ethyl group.

8: Material according to claim 1, in which the group X.sup.+ represents an unsaturated, 5- or 6-membered heterocyclic group, comprising one or more heteroatoms including a nitrogen atom bearing a positive charge, said group being optionally substituted.

9: Material according to claim 8, in which the group X.sup.+ is chosen from the group consisting of imidazolium, oxazolium, thiazolium, pyridinium, pyrimidinium, pyrazinium, benzimidazolium, benzoxazolium and benzothiazolium groups.

10: Material according to claim 1, in which Q represents a linear or branched divalent C.sub.1-C.sub.6 alkylene radical.

11: Material according to claim 1, in which the anionic form of the organic compound A bears from 2 to 4 groups chosen from the group consisting of the sulfonate group (SO.sub.3.sup.), the carboxylate group (COO.sup.), and mixtures thereof.

12: Material according to claim 1, in which the organic compound A belongs to a chemical family chosen from the group consisting of xanthenes, coumarins, phenoxazines phenothiazines, naphthalimides, naphtholactams, lactamimides, quinacridones, epindolines, thio-epindolines, phthalimides, oxazolones, benzotriazoles, diphenylmaleimides, dibenzofurans, pyrimidines, triazines, 1,3,5-triazin-2-yl derivatives, pyrazines, triazoles, methines, distyrylbenzenes, distyrylbiphenyls, divinylstilbenes, triazinylaminostilbenes, stilbenyl-2H-triazoles, benzoxazoles, benzofurans, benzimidazoles, 1,3-diphenyl-2-pyrazolines, diketopyrrolopyrroles, perylenes and perylenemonoimides.

13: Material according to claim 1, in which the organic compound A belongs to a chemical family chosen from the group consisting of stilbenes, xanthenes, coumarins and naphthalimides.

14: Material according to claim 1, in which the organic compound A is a stilbene.

15: Material according to claim 1, in which the organic compound A corresponds to one of the following formulae: ##STR00040## in which R.sub.26 is a group chosen from OMe, NHMe, NHEt, NHCH.sub.2CH.sub.2OH, NH(CH.sub.3)(CH.sub.2CH.sub.2OH), N-morpholinyl and NHPh.

16: Material according to claim 1, in which the particles are of spherical shape.

17: Material according to claim 1, in which the particles have a mean size ranging from 300 nm to 100 m.

18: Material according to claim 1, in which the particles are porous silica particles having a mean pores size greater than 10 nm.

19: Process for preparing a material according to claim 1, comprising at least the steps consisting in: a) placing particles of an oxide of an element M in contact with at least one salt of formula (II): ##STR00041## in which: M, Q and X.sup.+ are as defined in claim 1, R represents a linear or branched C.sub.1-C.sub.6 alkyl group, and Y.sup. represents a monovalent anion, under reaction conditions that are suitable for establishing covalent bonds between atoms M and cations of the salt of formula (II), and b) placing in contact the grafted particles formed in step a) with at least one salt of an organic compound A as defined in claim 1, under reaction conditions that are suitable for ionic exchange between anions Y.sup. and anionic forms of said organic compound A.

20: Process according to claim 19, in which the salt of the organic compound A is an alkali metal salt.

21: Cosmetic composition comprising, in a physiologically acceptable medium, at least one fluorescent particulate material according to claim 1.

22: Composition according to claim 21, in which the content of fluorescent particulate material is from 0.0001% to 90% by weight relative to the weight of said composition.

23: Method for reducing the appearance of imperfections and/or relief irregularities of keratin materials, comprising at least the step of using as an agent the material according to claim 1.

24: Method for lightening keratin materials, comprising at least the step of using as an agent the material according to claim 1.

25: Non-therapeutic cosmetic process for treating keratin materials, comprising a step of applying a cosmetic composition according to claim 21 to said keratin materials.

26: Process according to claim 25, for lightening said keratin materials, wherein the particles of the at least one particulate fluorescent material are porous silica articles having a mean pores size greater than 10 nm.

27: Process according to claim 25, for reducing the appearance of skin imperfections, and/or skin relief irregularities.

Description

EXAMPLES

[0210] Starting Materials [0211] Silica H33 (Sunsphere H33 from AGC SI-TECH) having a porosity of 22.6 nm, [0212] Silica H53 (Sunsphere H53 from AGC SI-TECH) having a porosity of 22.4 nm, [0213] Silica H51 (Sunsphere H51 from AGC SI-TECH) having a porosity of 4.5 nm, [0214] 3-(Trimethoxysilyl)-1-chloropropyl, [0215] N-Methylimidazole, [0216] N-Trimethoxysilylpropyl-N,N,N-trimethylammonium chloride (as a solution at 50% by weight in methanol, Gelest), [0217] N-Trimethoxysilylundecyl-N,N,N-tributylammonium bromide (as a solution at 25% by weight in dimethylformamide, Gelest), [0218] 4-Trimethoxysilylethyl)benzyl-N,N,N-trimethylammonium chloride (as a solution at 60% by weight in methanol, Gelest), [0219] N-Octadecyl-N,N-dimethyl(3-trimethoxysilylpropyl)ammonium chloride (as a solution at 60% by weight in methanol, Gelest), [0220] N-Trimethoxysilylpropyl-N,N,N-tributylammonium chloride (as a solution at 50% by weight in methanol, Gelest), [0221] N-Trimethoxysilylpropyl-N,N,N-tributylammonium bromide (as a solution at 50% by weight in methanol, Gelest), [0222] 11-bromo-undecyltrimethoxysilane (Gelest), [0223] Tinopal CBS-X (disodium 2-[(Z)-2-[4-[4-[(Z)-2-(2-sulfonatophenyl)ethenyl]phenyl] phenyl]ethenyl]benzenesulfonate, BASF).

Example 1

Synthesis of the Material P1

[0224] Spherical silica particles H33 (Sunsphere), pregrafted with a ligand L1 (3-methyl-1-[3-(trimethoxysilyl)propyl]-1H-imidazol-3-ium chloride), were placed in contact with Tinopal CBS-X (BASF) to form the material P1 in accordance with the invention.

[0225] The overall synthetic scheme is represented below:

Step 1: Synthesis of the Ligand L

[0226] 40.56 g of 3-(trimethoxysilyl)-1l-chloropropane (0.2 mol, 1 eq.) and 24.89 g of N-methylimidazole (0.3 mol, 1.5 eq.) were placed in a 250 mL three-necked flask under argon.

[0227] The mixture was stirred using a magnetic bar under a stream of argon for 1 hour at room temperature. The mixture was then heated (IKA hotplate+DrySyn aluminum heating block), under a gentle stream of argon, for 24 hours at 78 C. The mixture was then allowed to cool to room temperature.

[0228] The ligand L1 was obtained in a purity of 88.8% (measured by NMR), the remaining 11.2% corresponding to the starting N-methylimidazole.

Step 2: Grafting of the Ligand L1 onto the Silica H33

[0229] 3.17 g of the crude product (at 88.8% of L1) obtained on conclusion of step 1 (i.e. 2.81 g of pure ligand L1) were placed in a 250 mL three-necked flask, followed by addition of silica H33 (5.83 g, i.e. 0.51 g of ligand L1 per g of silica) and heptane (140 mL).

[0230] The mixture was stirred using a magnetic bar, under argon, and heated (IKA hotplate+DrySyn aluminum heating block) at 90 C. for 21 hours. The mixture was then allowed to cool to room temperature. 140 mL of heptane were added and the mixture was filtered through a Bichner funnel and glass microfiber of porosity 0.3 m and diameter 70 mm. The solid filtered off was washed with 140 mL of ethanol and dried under vacuum at 40 C. in an oven (theoretical mass=7.9 g, mass obtained=7.5 g, yield=95%, grafting yield=96.6%).

Step 3: Cl.SUP../Tinopal CBS-X Ion Exchange

[0231] 2.02 g of Tinopal CBS-X and 83 ml of demineralized water were placed in a 250 mL glass flask. The mixture was stirred using a magnetic bar for 1 hour at room temperature to the point of complete dissolution of the Tinopal CBS-X. 5 g of silica grafted with the ligand L1 obtained on conclusion of step 2 were added and the mixture was stirred for 3 days at room temperature, and then filtered through a Bichner funnel and glass microfiber of porosity 0.3 m and diameter 70 mm.

[0232] The solid filtered off was washed with 100 mL of water and then dried under vacuum at 40 C. in an oven to give the material P1 in the form of particles (5.8 g, exchange yield=80.6%).

Example 2

Synthesis of the Material P2

[0233] Spherical silica particles H53, pregrafted with the ligand L1 (3-methyl-1-[3-(trimethoxysilyl)propyl]-1H-imidazol-3-ium chloride), were placed in contact with Tinopal CBS-X to form the material P2 in accordance with the invention according to a process equivalent to that described in Example 1, replacing the silica H33 with the silica H53.

Step 1: Grafting of the Ligand L1 onto the Silica H53

[0234] 2 L of heptane were placed in a jacketed 6 L reactor equipped with a reflux/distillation head and a condenser. The reactor was stirred at 100 rpm. 91.6 g of the crude product (at 87.4% of L1) obtained according to a process corresponding to step 1 of Example 1 (i.e. 80.28 g of pure ligand L1) were introduced, followed by addition of silica H53 (166.6 g, i.e. 0.51 g of ligand L1 per g of silica). Finally, 2 L of heptane were added.

[0235] The mixture was stirred under argon and heated in distillation mode (from 85 C. to 92 C.) for 7 hours. The mixture was then allowed to cool to room temperature. The product was extracted from the reactor and the reactor was washed with 4 L of ethanol. The whole (8 L) was filtered through a Bichner funnel and glass microfiber of porosity 0.3 m. The solid filtered off was taken up in 4 L of ethanol and then filtered again and dried under vacuum at 40 C. in an oven (synthetic yield=96%, grafting yield (measured by TGA)=100%).

Step 2: Cl.SUP../Tinopal CBS-X Ion Exchange

[0236] 14.1 g of Tinopal CBS-X and 580 ml of demineralized water were placed in a 1 L reactor. The mixture was stirred for 1 hour at room temperature to the point of complete dissolution of the Tinopal CBS-X. 35 g of silica grafted with the ligand L1 obtained on conclusion of step 1 were added and the mixture was stirred for 3 days at room temperature, and then filtered through a Bichner funnel and glass microfiber of porosity 0.3 m.

[0237] The solid filtered off was washed with 500 mL of water and then 500 ml of ethanol, then dried under vacuum at 40 C. in an oven to give the material P2 in the form of particles (39.8 g).

Example 3

Synthesis of the Material P3

[0238] Spherical silica particles H51, pregrafted with the ligand L1 (3-methyl-1-[3-(trimethoxysilyl)propyl]-1H-imidazol-3-ium chloride), were placed in contact with Tinopal CBS-X to form the material P3 in accordance with the invention according to a process equivalent to that described in Example 1, replacing the silica H33 with the silica H51.

Example 4

Synthesis of the Material P4

[0239] Spherical silica particles H33 (Sunsphere H33), pregrafted with the ligand L2 (1-(trimethoxysilyl)propyl-3-N,N,N-trimethylammonium chloride), were placed in contact with Tinopal CBS-X (BASF) to form the material P4 in accordance with the invention, according to a process equivalent to that described in Example 1, replacing the ligand L1 with the ligand L2.

[0240] The overall synthetic scheme is represented below:

Step 1: Grafting of the Ligand L2 onto the Silica H33

[0241] 9.15 g of ligand L2 were placed in a 250 mL three-necked flask, followed by addition of silica H33 (17.49 g) and heptane (420 mL).

[0242] The mixture was stirred using a magnetic bar, under argon, and heated (IKA hotplate+DrySyn aluminum heating block) at 90 C. for 21 hours. The mixture was then allowed to cool to room temperature. 140 mL of heptane were added and the mixture was filtered through a Bchner funnel and glass microfiber of porosity 0.3 m and diameter 70 mm. The solid filtered off was washed with 140 mL of ethanol and dried under vacuum at 40 C. in an oven (theoretical mass=22.41 g, mass obtained=19.7 g, yield=88%, grafting yield=91.7%).

Step 2: Cl.SUP../Tinopal CBS-X Ion Exchange

[0243] 7.3 g of Tinopal CBS-X and 300 ml of demineralized water were placed in a 250 mL glass flask. The mixture was stirred using a magnetic bar for 1 hour at room temperature to the point of complete dissolution of the Tinopal CBS-X.

[0244] 18 g of silica grafted with the ligand L2 obtained on conclusion of step 2 were added and the mixture was stirred for 3 days at room temperature, and then filtered through a Bchner funnel and glass microfiber of porosity 0.3 m and diameter 70 mm.

[0245] The solid filtered off was washed with 100 mL of water and then dried under vacuum at 40 C. in an oven to give the material P4 in the form of particles (20 g, exchange yield=81.6%).

Example 5

Synthesis of the Material P5

[0246] Spherical silica particles H53, pregrafted with the ligand L2, were placed in contact with Tinopal CBS-X to form the material P5 in accordance with the invention, according to a process equivalent to that described in Example 4, replacing the silica H33 with the silica H53.

Example 6

Synthesis of the Material P6

[0247] Spherical silica particles H51, pregrafted with the ligand L2, were placed in contact with Tinopal CBS-X to form the material P6 in accordance with the invention, according to a process equivalent to that described in Example 4, replacing the silica H33 with the silica H51.

Example 7

Synthesis of the Material P7

[0248] Spherical silica particles H53, pregrafted with the ligand L3 (N-Trimethoxysilylundecyl-N,N,N-tributylammonium bromide), were placed in contact with Tinopal CBS-X to form the material P7 in accordance with the invention, according to a process equivalent to that described in Example 2, replacing the ligand L1 with the ligand L3.

Example 8

Synthesis of the Material P8

[0249] Spherical silica particles H53, pregrafted with the ligand L4 (4-(trimethoxysilylethyl)benzyltrimethylammonium chloride), were placed in contact with Tinopal CBS-X to form the material P8 in accordance with the invention, according to a process equivalent to that described in Example 2, replacing the ligand L1 with the ligand L4.

Example 9

Synthesis of the Material P9

[0250] Spherical silica particles H53, pregrafted with the ligand L5 (N,N-dimethyl-N(3-(trimethoxysilyl)propyl)octadecane-1-ammonium chloride), were placed in contact with Tinopal CBS-X to form the material P9 in accordance with the invention, according to a process equivalent to that described in Example 2, replacing the ligand L1 with the ligand L5.

Example 10

Synthesis of the Material P10

[0251] Spherical silica particles H53, pregrafted with the ligand L6 (N-Trimethoxysilylpropyl-N,N,N-tributylammonium chloride), were placed in contact with Tinopal CBS-X to form the material P10 in accordance with the invention, according to a process equivalent to that described in Example 2, replacing the ligand L1 with the ligand L6.

Example 11

Synthesis of the Material P11

[0252] Spherical silica particles H53, pregrafted with the ligand L7 (11-dimethylimidazolium undecyltrimethoxysilane bromide), were placed in contact with Tinopal CBS-X to form the material P11 in accordance with the invention, according to a process equivalent to that described in Example 2, replacing the ligand L1 with the ligand L7.

Synthesis of the Ligand L7

[0253] 71.01 g of 11-bromoundecyltrimethoxysilane (0.2 mol, 1 eq.) and 24.89 g of N-methylimidazole (0.3 mol, 1.5 eq.) were placed in a 250 mL three-necked flask under argon.

[0254] The mixture was stirred using a magnetic bar under a stream of argon for 1 hour at room temperature. The mixture was then heated (IKA hotplate+DrySyn aluminum heating block), under a gentle stream of argon, for 24 hours at 78 C. The mixture was then allowed to cool to room temperature.

Example 12

Evaluation of the Haze, Transparency and Lightness Power of Materials P1 to P11

[0255] Eleven compositions were prepared comprising 3% by weight of each of the materials P1 to P11 of Examples 1 to 11 by mixing the material with the base composition B1 below (3% of the material and 97% of the base B1):

[0256] Base B1 (Weight %):

TABLE-US-00003 Cetyl alcohol 1.25% Triethanolamine 0.375% Polyethylene stearate containing 40 ethylene oxide units 3.125% 1,2-Octanediol 0.625% Hydrogenated polyisobutene 6.25% (Parleam from NOF Corporation) Isohexadecane 18.75% Mixture of glyceryl stearate and PEG-100 stearate 3.125% (Arlacel 165 FL from Croda) Carboxyvinyl polymer 0.375% (Carbopol 981 polymer from Lubrizol) Stearyl alcohol 1.25% Preserving agent qs Water qs 100%

[0257] Similar compositions were also prepared with the untreated silica Sunsphere H33 and Sunsphere H51.

[0258] Each composition was then applied onto a polyester film sold under the reference 100045425 by the company Byk, using a film spreader to deposit a coat 50 m thick, which was left to dry for 30 minutes at room temperature (25 C.). The transparency, haze and lightness measurements were taken on the dry deposit obtained, using a Hazegard Plus machine from Bye Additive & Instruments.

[0259] The following results were obtained:

TABLE-US-00004 Composition Transparency Haze Lightness B1 + P1 93.14 86 14.64 B1 + P2 92.72 83.66 11.28 B1 + P3 91.88 62.26 23.3 B1 + P4 92.76 91.76 16.28 B1 + P5 91.52 83.22 8.6 B1 + P6 92.02 72.04 21.62 B1 + P7 92.3 87.4 B1 + P8 91.6 61.9 B1 + P9 92.3 87.4 B1 + P10 91.4 71.1 B1 + P11 91.9 80.1 Silica H33 91.02 57.56 17.28 Silica H51 91.06 55.72 16.32

[0260] The results obtained show that the deposits obtained have good natural transparency (between 91 and 94).

[0261] Furthermore, the deposits obtained have a high haze value (greater than 60), which shows that the materials in accordance with the invention have a good soft-focus effect and thus good masking of imperfections. The haze value of the materials according to the invention is greater than that of the untreated silica, which shows that these materials according to the invention have a better soft-focus effect and better masking of imperfections.

[0262] The deposits also have low lightness (less than 24), thus contributing toward a natural appearance of the deposit.

Example 13

Evaluation of the Lightening Effect of Materials P1, P4 and P5 to P11

[0263] Eight compositions were prepared comprising each of the materials P1, P4 and P5 to P11 by mixing the material with the base composition B2 below.

[0264] Base B2 (Weight %):

TABLE-US-00005 Acetylated ethylene glycol stearate 0.51% Cyclopentadimethylsiloxane 10.35% Propylene glycol 5% Smectite in cyclopentadimethylsiloxane and ethanol 5.82% (18/77/5) (BENTONE GEL VS 5 V from Elementis) Magnesium sulphate 0.7% Mixture of Oxyethylenated Poly 6.55% methylcetyldimethylsiloxane, Poly glycerol isostearate and Hexyl laurate (Abil WE 09 from Evonik Goldschmidt) Polydimethylsiloxane (10 cSt) 2.91% N-oleyl dihydrosphingosine 0.03% Isododecane 1.89% Preserving agent qs Water qsp 100%

[0265] Compositions are prepared with such a material content that the amount of fluorescent Tinopal CBS-X molecules is equal to 1.5 mmole, corresponding for example to weight contents of 3.22% for material P1 and 2.59% for material P4.

[0266] Two compositions comprising respectively 1.5% by weight of a mixture of Sunsphere H33+Tinopal CBS-X and 1.5% by weight of a mixture of Sunsphere H53+Tinopal CBS-X were also prepared.

[0267] Each composition, and also the base B2 alone, was then applied onto a glossy multizone cosmetic chart sold under the reference 25C by the company Leneta, using a film spreader to deposit a coat 50 m thick, which was left to dry for 30 minutes at room temperature (25 C.). The multizone chart Leneta comprises 7 zones of different colours going from white (zone 1) to black (zone 7) going through different colours corresponding to different skin complexions (zones 2 to 6).

[0268] L a b colorimetry measurements were taken on each zone of the dry deposit obtained, using a Nikon D7000 camera, aperture 6.3, speed , with a D65 angular light.

[0269] For each colorimetric measurement, the difference A between the value obtained by applicating of the material and the value obtained by application of the base B2. The lightening properties of the applied materials is thus evaluated.

[0270] The following results were obtained for zones 2, 3 and 4, which are the most relevant.

TABLE-US-00006 Material content Composition (wt %) Zone L* a* b* L a b Base B2 1 95.12 1.71 4.67 0.26 0.15 0.05 Base B2 7 7.87 4.52 3.46 3.14 4.54 0.71 Base B2 2 79.00 10.13 15.73 0.28 0.36 0.29 Base B2 3 66.37 15.03 21.64 0.57 1.37 0.31 Base B2 4 71.36 18.87 31.53 0.19 0.09 1.83 P1 (ex 1; 3.22 1 95.97 0.47 1.47 0.85 1.24 6.14 H33-L1- TCBSX) P1 (ex 1) 3.22 7 21.50 3.73 9.55 13.64 8.25 13.01 P1 (ex 1) 3.22 2 79.87 8.45 10.52 0.87 1.68 5.21 P1 (ex 1) 3.22 3 67.72 13.82 13.81 1.35 1.21 7.84 P1 (ex 1) 3.22 4 72.84 18.17 24.93 1.48 0.69 6.61 P4 (ex 4; 2.59 1 96.57 0.58 1.14 1.45 1.13 5.81 H33-L2- TCBSX) P4 (ex 4) 2.59 7 20.63 3.74 8.44 12.77 8.26 11.90 P4 (ex 4) 2.59 2 80.48 8.75 11.74 1.48 1.38 3.99 P4 (ex 4) 2.59 3 68.20 16.12 15.38 1.83 1.09 6.26 P4 (ex 4) 2.59 4 73.09 19.86 25.72 1.73 1.00 5.82 Sunsphere 1.5 1 96.67 1.60 2.26 1.55 0.11 2.41 H33 + TCBS-X Sunsphere 1.5 7 22.79 3.03 8.13 14.92 7.55 11.59 H33 + TCBS-X Sunsphere 1.5 2 80.74 9.41 14.26 1.74 0.72 1.47 H33 + TCBS-X Sunsphere 1.5 3 68.43 14.62 16.93 2.05 0.41 4.72 H33 + TCBS-X Sunsphere 1.5 4 73.57 19.28 27.33 2.21 0.42 4.20 H33 + TCBS-X P5 (ex 5; 1 95.95 0.32 1.55 0.85 0.05 4.54 H53 L2 TCBS-X) P5 (ex 5) 7 22.56 0.58 5.12 3.28 0.81 5.48 P5 (ex 5) 2 82.17 7.82 9.63 3.31 1.43 5.74 P5 (ex 5) 3 68.95 13.19 14.36 3.59 0.07 6.51 P5 (ex 5) 4 73.81 18.32 23.07 2.29 0.63 4.44 Sunsphere 1 95.61 0.77 1.85 0.51 0.5 1.14 H53 + TCBS-X Sunsphere 7 25.03 1.45 3.82 0.80 0.05 4.18 H53 + TCBS-X Sunsphere 2 81.09 8.33 13.00 2.24 0.92 2.36 H53 + TCBS-X Sunsphere 3 69.07 12.56 17.33 3.72 0.7 3.54 H53 + TCBS-X Sunsphere 4 73.68 18.51 25.41 2.16 0.43 2.11 H53 + TCBS-X P7 ( ex 7; 1 95.40 0.30 2.22 0.31 0.57 5.2 H53 L3 TCBS-X) P7 (ex 7) 7 22.81 1.48 5.02 3.02 0.09 5.38 P7 (ex 7) 2 81.63 8.27 9.52 2.77 0.98 5.84 P7 (ex 7) 3 68.97 13.27 14.18 3.62 0.01 6.68 P7 (ex 7) 4 73.51 18.21 22.75 1.99 0.74 4.76 P8 (ex 8; 1 95.14 0.11 1.32 0.25 0.15 4.32 H53 L4 TCBS-X) P8 (ex 8) 7 22.76 1.08 3.56 2.63 0.31 3.92 P8 (ex 8) 2 81.5 7.96 10.42 0.63 1.29 4.94 P8 (ex 8) 3 68.81 12.87 15.12 0.58 0.38 5.75 P8 (ex 8) 4 73.50 18.15 23.5 0.17 0.80 4.02 P9 (ex 9; 1 95.15 0.18 0.722 0.06 0.45 3.72 H53 L5 TCBS-X) P9 (ex 9) 7 23.67 1.64 1.95 2.16 0.25 2.32 P9 (ex 9) 2 81.53 8.46 11.16 2.68 0.8 4.20 P9 (ex 9) 3 69.00 12.81 16.21 3.65 0.44 4.66 P9 (ex 9) 4 73.61 18.36 24.25 2.09 0.59 3.26 P10 (ex10; 1 99.28 0.03 0.53 0.19 0.24 3.52 H53 L6 TCBS-X) P10 (ex10) 7 22.24 1.23 3.46 3.59 0.16 3.82 P10 (ex10) 2 81.65 8.47 11.36 2.79 0.78 4.01 P10 (ex10) 3 68.85 13.00 16.56 3.49 0.25 4.31 P10 (ex10) 4 73.46 18.66 24.77 1.94 0.29 2.74 P11 (ex11; 1 96.23 0.01 2.01 1.14 0.28 5.01 H53 L7 TCBS-X) P11 (ex11) 7 23.09 1.15 4.98 2.75 0.23 5.35 P11 (ex11) 2 82.31 7.94 9.61 3.45 1.31 5.75 P11 (ex11) 3 69.83 13.09 14.25 4.48 0.16 6.62 P11 (ex11) 4 74.43 18.28 23.06 2.91 0.67 4.46 BN 1 94.23 0.65 2.84 BN 7 29.27 0.24 2.00 BN 2 80.01 8.72 15.73 BN 3 66.92 12.69 19.06 BN 4 72.03 19.17 28.07 BN: Bore Nitride sold under the tradename BORON NITRIDE POWDER TRES BN PUHP 3002 from Saint-Gobain Ceramics. TCBS-X: Tinapol CBS-X

[0271] The results obtained show that the decrease of Ab is greater for the materials according to the invention than for the mixtures Sunsphere H33+TCBS-X and Sunsphere H53+TCBS-X, which means a greater decrease of the yellow tint.

[0272] An increase of L means an increase of the lightness of the material and thus a lightening of the tint after the composition containing said material is applied.

[0273] Thus, these measurements show that the application of the materials according to the invention confer a lightening effect to the skin when applied, while having a natural appearance.

[0274] It has further been noticed that materials P1 and P6 both prepared with Sunsphere H51 (having a porosity of 4.5 nm) do not confer a lightening effect to the skin.