Antioxidant and antipollution beads

Abstract

An antioxidant and antipollution composition for cosmetic and skincare formulations comprising a beads complex containing specific zeolites and antioxidants.

Description

[0001] BW1098M ANTIOXIDANT AND ANTIPOLLUTION BEADS

[0002] Fleid of invention

[0003] The present invention relates generally to an antioxidant and antipollution composition comprising a beads complex containing specific zeolites and antioxidants. More specifically, the invention is direct to a stable composition which can be easily incorporated in different cosmetic formulations.

[0004] Background

[0005] The use of cosmeceutical ingredients has experienced substantial growth over time, and there is a continuous pursuit of new active agents within the cosmetics industry. Formulating cosmetic products presents many challenges, ranging from chemical issues, regulations, product safety, performance, aesthetics, consumer trends and claim substantiation.

[0006] There are many cosmetic ingredients with multiple functions, providing benefits that meet consumer demands but simply piling ingredients into a formula does not always provide a solution to the problem. Indeed, several issues and requests can arise when a new compound is formulated such as tactile sensory, stability of the formulation and efficaciousness in order to effectively deliver the desired ingredients to the viable epidermis.

[0007] Skincare and cosmetic products can address to several skin concerns and one of the main are represented by the effect of free radicals, highly reactive molecules that can directly damage cell structures, membranes, lipids, proteins and DNA. These molecules, also called reactive oxygen species (ROS), due to having one or more unpaired electrons have the ability to capture electrons of another molecule to stabilize, causing oxidation thereof, staring the so-called “chain oxidation reactions” which can damage cells or even cause their death.

[0008] The production of these reactive species can occur during normal metabolism or by various processes of oxidative stress induced by environmental factors such as pollution and UV derived from sunlight. Moreover, during aging, the amount of oxidative damage increases exponentially.BW1098M Thus, the use of antioxidants substance that may protect against oxidative stress by neutralizing free radical in skincare products seems to be the most effective approach in this field. Antioxidants are also essential components in cosmetic formulations to increase the shelf life of the product by reducing oxidative degradation of sensitive ingredients.

[0009] However, it is well known that antioxidants are often classified as unstable molecules which bring to formulation problems and consequent loss of effectiveness. Indeed, a final product is effective for the antiaging purposes if, at the same time, both the antioxidant ingredients and the final formula are stable. The product should remain on the skin to reach the target tissue in the active form and remain in place for some time to achieve the desired effects.

[0010] Therefore, there is a need to have compositions comprising stable antioxidants ingredients, which can be used for the formulation of cosmetic products avoiding the phenomena of rancidity, degradation and separation of the formula.

[0011] In years several way of improving the stability of antioxidant ingredients have been studied; for example, ascorbic acid has been stabilized with the addition of an antioxidizing agent or with a method of inhibiting oxidization of ascorbic acid using zinc sulfate and L-tyrosine as reported in US 4938969. A further possible approach is represented by the chemical modification of the antioxidant species, such as the use of derivative as sodium ascorbylphosphate, magnesium ascorbyl phosphate, calcium ascorbylphosphate, ascorbic acid polypeptide, ethyl ascorbyl ether, ascorbyl dipalmitate, ascorbyl palmitate, ascorbyl glucoside or ascorbyl ethylsilanol pectinate.

[0012] While US20100255109 disclose the use of a coating layer formed by polymerizing a-lipoic acid or its derivative on the surface of antioxidants, in order to increase the relative stability.

[0013] In addition to the oxidative stress, an increasingly large number of clinical studies shows the direct impact of atmospheric pollution on the quality of the skin, in particular the heterogeneity of the complexion, the skin’s microrelief and also its involvement in the appearance of more reactive and more sensitive skin. The impact of atmospheric pollution may also be induced, or aggravated, by concomitant prolonged exposure to UV and oxidative stress.BW1098M One of the main pollutants which are constantly increasing is represented by heavy metals, microparticles or hydrocarbons which accumulate in the tissues of organisms following exposure to the atmosphere. Specifically, the metals that are particularly incriminated in atmospheric pollution are copper, cobalt, zinc, manganese, mercury, nickel, lead and cadmium and there is also the need to protect the skin by selecting active principles that are efficient for preventing the penetration of metals into the skin or in general into keratin materials.

[0014] Therefore, the design of new cosmetic and skincare products with antiaging purpose may increasingly require the simultaneous use of multiple active ingredients, specifically antioxidant and anti-pollution active ingredients. The typical approach is represented by the use of different stabilized antioxidant and anti-pollution molecules, with the consequent drawbacks in terms of time and cost saving related to the multiple steps to be performed during the formulation and also the possible issues related to the stability of both the single ingredients and the final formulas.

[0015] Thus, the need of alternative compositions overcoming the drawbacks of those already known in the art is still felt.

[0016] Brief description of

[0017]

[0018] Fig. 1-3 are respectively FAU type zeolites, LTA type zeolites and Niacinamide (antioxidant) as raw materials before their use according to the invention.

[0019] Fig. 4 and 5 are beads complex made of FAU type zoelite and a misture of Vitamin C and Vitamin B3 at different magnifications.

[0020] Fig. 6 is a bead made of LTA type zeolite and a mixture of Vitamin C and Vitamin B3. Fig. 7 is a bead made of LTA type zeolite and a mixture of Vitamin C, vitamin B3 and caffeine.

[0021] Fig. 8 is a bead made of LTA type zeolite and a mixture of Vitamin C and caffeine. Fig. 9 is a bead made of LTA type zeolite and a mixture of Vitamin C and caffeine. Fig. 10 is a bead made of FAU type zeolite and caffeine.

[0022] Fig. 11 is a bead made of LTA type zeolite and panthenol.

[0023] Fig. 12 is a bead made of FAU type zeolite and hyaluronic acid.BW1098M Fig. 13 is a bead made of FAU type zeolite and urea.

[0024] Fig. 14 is a bead made of FAU type zeolite and vitamine B6.

[0025] Fig. 15 is a bead made of FAU type zeolite and centella asiatica extract.

[0026] Fig.16 is a bead made of FAU type zeolite and a mixture of Vitamin C, vitamin B3 and caffeine.

[0027] DETAILED DESCRIPTION

[0028] After extensive experimentations, the inventors of the present invention found out that a composition comprising a beads complex containing specific zeolites and antioxidant molecules can be easily incorporated in different cosmetic formulations and can act both as antioxidant and as antipollution agent.

[0029] Indeed, as it will be shown in the experimental part, the beads object of the present invention demonstrate at the same time an increased antioxidant activity on the human skin with respect to the simple antioxidant, a chelating anti-pollutant action and a texturizing effect on the final formula in which they are incorporated.

[0030] Hence, it is clear the synergic benefic effect of the composition herein disclosed for skin issues and the advantages in terms of ease of incorporation into the formula both for the reduction of the number of steps and for the final stability.

[0031] Indeed, when an antioxidant and / or antipollution ingredient is incorporated in a formulation, for example comprising hot process emulsions, the addition of the antioxidant molecules should be done at 45-50°C, to avoid the degradation that can occur at emulsification temperature (75-80°C). This means that antioxidants should be solubilized in an extra amount of oil or water, to be added to the cold emulsion at the end of the process, resulting in a greater chance of instability or in a non-homogeneous distribution in the final product. This procedure needs to be repeated for each antioxidant, if more than one is present.

[0032] The beads or complex beads object of the present invention, can be incorporated in a powder form both in warm or cold emulsions, maintaining the benefit of antioxidants,BW1098M antipollution and texturizing activities, in a single ingredient which can be added to the formulation, in one step.

[0033] Moreover, a further demonstration of the versatility of the present composition in the field of final formulation is represented by the possibility to be easily integrated in hydrophobic products such as butters, powders, or other anhydrous products. Indeed, lot of commonly used antioxidants are typically hydrophilic, and are used only in water-based formulations. On the contrary, the complex beads according to the present invention, can be easily incorporated in anhydrous formulations, due to the good oil dispersibility. This means that hydrophilic antioxidants contained in this complex are conveyed in oil phase, resulting in the use of hydrophilic ingredients in anhydrous formulations.

[0034] Thus, object of the present invention is an antioxidant and anti-pollution composition for cosmetic formulations comprising a beads complex containing zeolites selected among Faujasite (FAU) type, Linde type or mixture thereof and at least an antioxidant selected among Vitamin C, Vitamin E, Vitamin A, Vitamins B, Vitamin D, Vitamin K, Caffeine, Quercetin, Astaxanthin (e.g. from Haematococcus algae), Resveratrol (e.g. from Polygonum cuspidatum), alpha-Lipoic acid, hydroxydecyl ubiquinone (CoQ10), ferulic acid, thioctic acid, Glutathione, Catechins (e.g. from Green Tea Extract), Polyphenols, Carotenes, and their derivatives and combinations thereof.

[0035] Said beads are typically characterized by a spherical structure, specifically defined as a structure having an average eccentricity comprised between 0 and 0.7, preferably between 0 and 0.5 composed by one of the specific zeolite, embedded in the selected antioxidant, or combinations thereof, that acts as a binder and covers at least 50% of the zeolite surface.

[0036] The beads according to the invention can present an internal cavity, and are topically charaterized by a final volume mean diameter comprised between 1 and 70 pm preferably between 10 and 40 pm as measured by a state-of-the-art laser diffraction instrument.

[0037] The present invention, therefore also refers to a composition comprising among its components:

[0038] zeolites selected among Faujasite (FAU) type, Linde type or mixture thereof andBW1098M at least an antioxidant selected in the group consisting of Vitamin C, Vitamin E, Vitamin A, Vitamins B, Vitamin D, Vitamin K, Caffeine, Quercetin, Astaxanthin, Resveratrol, alpha-Lipoic acid, hydroxydecyl ubiquinone (CoQ10), ferulic acid, thioctic acid, Glutathione, Catechins, Polyphenols, Carotenes, Urea, Hyauronic acid (various MW), sodium hyaluronate (various MW), centella asiatica extracts expecially with high content of madecassoside, asiaticoside, asiatic acid, madecassic acid, and their derivatives and combinations thereof,

[0039] wherein said composition is in form of beads characterized by:

[0040] a spherica structure essentially consisting of said zeolites,

[0041] an external binder of antioxidant covering at least 50% of the spherical structure surface, a volume mean diameter comprised between 1 and 70 pm, preferably between 10 and 40 pm. Figures (1) to (9) are scanning electron microscope (SEM) images of some raw materials shown as reference and complex beads obtained according to the present invention. The analysis has conducted using a scanning electron microspoy (SEM) equipement: Zeiss SUPRA 55VP 30-60 at various magnification from 1000X to 30000X, the image has acquired using an electron beam with a power of 15kV and the secondary electron (SE2) probe.

[0042] The evaluation of internal cavity, figures (4a, 10a and 16a), has been conducted with FIB accesory, witch are able to the cut of zeolite-antioxidant beads with accelerated atoms (Ga), the imaging has been conducted at various magnification from 1000X to 8000X, the images have been acquired using an electron beam with a power of 5-1 OkV and the secondary electron (SE2) probe.

[0043] Specifically, Fig. 1-3 are respectively FAU type zeolites, LTA type zeolites and Niacinamide (antioxidant) as raw materials before their use according to the invention. Fig. 4 and 5 are beads complex made of FAU type zoelite and a misture of Vitamin C and Vitamin B3 at different magnifications. Fig. 6 is a bead made of LTA type zeolite and a mixture of Vitamin C and Vitamin B3. Fig. 7 is a bead made of LTA type zeolite and a mixture of Vitamin C, vitamin B3 and caffeine. Fig. 8 is a bead made of LTA type zeolite and a mixture of Vitamin C and caffeine. Fig. 9 is a bead made of LTA type zeolite and caffeine. Fig. 10 is a bead made of FAU type zeolite and caffeine. Fig. 11 is a bead made of LTA type zeolite and panthenol. Fig. 12 is a bead made of FAU type zeolite andBW1098M hyaluronic acid. Fig. 13 is a bead made of FAU type zeolite and urea. Fig. 14 is a bead made of FAU type zeolite and vitamine B6. Fig. 15 is a bead made of FAU type zeolite and centella asiatica extract. Fig.16 is a bead made of FAU type zeolite and a mixture of Vitamin C, vitamin B3 and caffeine

[0044] The peculiar morphology of the beads object of the present invention, which differ for example from the one reported in WO2019160367, is represented by the fact that the beads structure is directly made of zeolites and organic antioxidant blend, without the use of an inert core material (glass, ceramic or plastic support); as a consequence the zeolite surface is only partially or not exposed to the surface of the bead. Indeed, as clearly shown in Figures 4 to 9, the exposed components are the antioxidants which also act as a sort of binder between the zeolites and on their surface.

[0045] The beads or the beads complex system of the invention differ for example from those reported in US20040208902A1 , since zeolites are not intended to be a carrier for the controlled release of the active materials, but this specific structure allows the stabilization of the antioxidant and - at the same time - an easier dispersion in the final formula, with a consequent increase of their activity.

[0046] The composition herein disclosed is characterized by an amount of zeolites comprised between 50 and 90%, and an amount of antioxidant comprised between 10 and 50% by weight with respect to the total weight of the composition.

[0047] The zeolites can be characterized by the presence of sodium or potassium as counterion at an ion exchange site of the framework structure

[0048] In a preferred embodiment, the antioxidant is preferably selected among ascorbyl glucoside (vitamin C derivates), niacinamide (vitamin B3), tocopherol (vitamin E), caffeine, pantenol (B5), urea, Hyauronicacid (various MW), sodium hyaluronate (various MW), centella asiatica extracts or mixtures thereof.

[0049] As reported in the below experimental part, the antioxidant and antipollution composition according to the present invention can be incorporated in a cosmetic formulation.

[0050] The present invention, therefore also refers to a cosmetic or skincare formulation comprising the composition according to any one of the embodiments disclosed therein,BW1098M preferably in an amount comprised between 0.1 and 5% by weight with respect to the total weight of the formulation. Due to the extremely versatility of the composition herein disclosed, said formulations can either be prepared as one phase water-free composition, or as two-phase composition characterized by the presence of a water-free and an aqueous phase.

[0051] The water-free phase is selected, for instance, in a group consisting of hydrocarbons, esters, ethers, silicones, waxes, butters or mixtures thereof.

[0052] In a preferred embodiment the one-phase water free formulation is prepared as homogenous anhydrous formulations, preferably in the form of pressed powder, loose powder, or other mixtures of ingredients in a cosmetic powder form, or as anhydrous oily formulation, preferably in the form of hot poured products, lipogel, oils or butters mixtures; while the two-phase formulation is prepared as a homogenous oil-in-water or water-in-oil emulsion, preferably in form of serum or cream.

[0053] The cosmetic formulation according to the invention can also comprise one or more of a cosmetically acceptable emollient, carrier fluid, pigment, humectant, vitamin, antioxidant, emulsifier, co-emulsifier, hydrophilic or hydrophobic thickeners, wax, butter, film former, silicone, surfactant, active agent, extract, fragrance, preservative, pH-adjusting agent, suspending agent and chelating agent.

[0054] As will be apparent from the following experimental section, due to its effects, the composition of the invention can be used as as an adjuvant or additive in antiaging and / or antioxidant and / or antipollution formulations.

[0055] Other advantages of the invention are as disclosed in the following.

[0056] EXAMPLES

[0057] Hereinafter, the invention will be explained in more detail with reference to the following non-limiting examples. Modifications or variations of the embodiments here exemplified, obvious to an expert in the art, are encompassed by the appended claims.

[0058] Preparation of samples S1-S5 and counterexamples C1-C3BW1098M Bead samples are produced by spray-drying a stock solution containing zeolites particles dispersed in a suitable suspending agent (preferably water), in which the active ingredients are dissolved.

[0059] The water-based dispersion / solution was formulated in order to reach the correct zeolite / antioxidant ratio and the desired solid content, optimized for the spray drying process. The solid content is comprised between 10 and 40% wt and preferably between 15 and 30% wt.

[0060] Before the antioxidant dissolution in the water-based dispersion of zeolites, the pH of the slurry is adjusted between 5 and 8, for example by adding organic acid (e.g. citric acid, lactic acid) or alkaline reagents (e.g. NaOH, KOH).

[0061] The solution is sprayed at high temperature to promote fast evaporation of the suspending agent (180-230 °C).

[0062] In-vitro tests have been performed in order to evaluate the efficacy of the sample in reducing the cellular production of ROS in response to UVA exposure in skin cells (immortalized human keratinocytes).

[0063] Oxidative stress occurs in cells when ROS generation is not counteracted by the cell's natural antioxidant defenses. As known, oxidative stress is one of the main causes of biological aging and is involved in the development of many diseases.

[0064] The analysis is carried out by stimulation with UVA rays in order to trigger the basic oxidative reaction. The intensity of the cellular response is then evaluated by fluorimetric analysis to verify cells stability of the samples treated with antioxidant-based formulation at different concentrations compared to an untreated negative control.

[0065] The results are reported in protection percentage according to the formula:

[0066] % protection = 100 - [(average fluorescence of the sample I average fluorescence of negative control) * 100]

[0067] Ref. Zeolite Antioxidant Concentration (mg / ml) Protection % B1 - - 0.04 7.8

[0068] C1 - Vitamin C 0.2 4.0

[0069] S1 LTA - K+Vitamin C 0.2 43.8

[0070] C2 - Vit C + Vit B3 0.04 8.5

[0071]

[0072] S2 LTA - K+Vit C + Vit B3 0.04 35.4BW1098M S3 FAU - Na+Vit C + Vit B3 0.04 29.3

[0073]

[0074] S4 FAU - Na+caffeine 0.03 21.5 Table 1.

[0075] Table 1 clearly shows the antioxidant effect of the compositions according to the present invention (see S1-S4), with respect to the same antioxidant molecules which are not comprised in the beads complex (see B1, C1 and C2). Specifically, see for example S1 with respect to C1 for Vitamin C derivatives, or S2 and S3 with resepct to C2 for an antioxidant mixture of Vitamins C and B3.

[0076] Furthermore, several beads prepared according to the present invention, have been integrated in a cosmetic formulation in order to prove the compatibility of the specific zeolite frameworks.

[0077] Ref. Zeolite Antioxidant Phase separation

[0078] B1 - - no

[0079] S5 LTA - K+Vitamin E no

[0080] S6 FAU - Na+Vitamin E no

[0081] S7 LTA - K+Vitamin C no

[0082] S8 FAU - Na+Vitamin B3 no

[0083] S9 FAU - Na+Vit C + Vit B3 no

[0084] S10 FAU - Na+Vit C + Vit B3+caffeine No

[0085] S11 FAU - Na+Panthenol No

[0086] S12 FAU - Na+caffeine No

[0087] C3 \ Caffeine yes

[0088]

[0089] C4 ZMS-5 Vitamin E yes

[0090] Table 2.

[0091] Indeed, Table 2, points out that the use of beads according to the invention, thus comprising different antioxidants and zeolites frameworks, are easily integrable in cosmetic formulations avoiding unwanted effects as the phase separation, while zeolites with a different framework with respect to the one of the claimed invention (see for example C4 using ZSM-5 type zeolites) or the use of the single antioxidant (see C3) brings to a separation of the final formula and a consequent impossibility to use the components as an ingredient.

[0092] The ability of zeolites to retain heavy metals for antipollution applications have then been evaluated by means of experimental test and ICP analysis. For each selected metal (Cr, Co, Ni, Cd, Pb), a standard ICP solution (4ppm) has been used to disperse the zeolites powder with a concentration of 3%wt; after a reaction time of 1h under mixing withBW1098M overhead shaker (max rotation speed) a separation step was performed (20 min of centrifuge at 6000rpm at RT).

[0093] The results of ICP quantification on surnatant solution are reported in the Table 3 and clearly point out that zeolite framework and counterion according to the present invention reduce the metal content over 90%, while different type of zeolites such as the natural heulandite-type (HEU) zeolites are not able to reach the same performances.

[0094] Zeolites LTA-Na LTA-K FAU-Na HEU

[0095] Cr reduction (%wt) 91.8 93.3 99.9 99.6

[0096] Co reduction (%wt) 100 100 100 74.5

[0097] Ni reduction (%wt) 100 100 100 \

[0098] Cd reduction (%wt) 100 100 100 93.4

[0099] Pb reduction (%wt) 100 100 98 100

[0100]

[0101] Table 3.

[0102] The beads complexes according to the present invention have been then tested in a dermatological institute in order to prove their efficiency for several further needs in the cosmetic fileds related to the antiaging and antioxidant purpose, hydration and support for the skin barrier.

[0103] CLINICAL EVIDENCE 1

[0104] As a result of a 3-week test conducted on 20 subjects, skin damage was induced by applying a 1% SLS patch to the test area treated with S9 cream.

[0105] Skin roughness, transepidermal water loss (TEWL), and erythema (a-value) were evaluated. The test sample was applied to the test area for 2 weeks prior to SLS application, and after 24 hours of 1% SLS patching, the test sample was continuously applied for an additional 6 days.

[0106] The roughness has been evaluated with a high-resolution, three-dimensional (3D) imaging device that analyzes skin conditions by capturing reflected signals generated when visible light of varying wavelengths is projected onto the skin. The system utilizes a combination of optical techniques and mathematical algorithms to construct 3D surfaceBW1098M images of the skin, from which quantitative data can be extracted to assess skin improvements and monitor changes over time.

[0107] Sample A after 48h SLS A after 6 days

[0108] treatment SLS treatment

[0109] Zeolite antiox beads (S9) cream -1,44 -1,50

[0110] Placebo sample -0,91 -0,80

[0111] Comparison sample -0,92 -0,99

[0112]

[0113] Control area -0,82 -0,79

[0114] Transepidermal water loss has evaluated with a device designed to measure transepidermal water loss (TEWL), which refers to the amount of water vapor passively evaporating through the skin. The instrument detects the presence of a water vapor gradient between the skin surface and the surrounding air within the microenvironment around the skin using sensors housed in an open chamber. This allows for the quantification of TEWL in units of grams per square meter per hour (g / m2 / h).

[0115] Sample A after 48h SLS A after 6 days

[0116] treatment SLS treatment

[0117] Zeolite antiox beads (S9) cream -3,12 -4,40

[0118] Placebo sample -0,94 -1,60

[0119] Comparison sample -0,64 -1,08

[0120]

[0121] Control area 0,04 0,01

[0122] Erythema (a-value) has evauated whit a specific tool it measures the colors recognized by humans through reflective colors (rate) according to reflected light using a three primary colors (red, blue, and green) filter on three sensors. This is called the Tristimulus method. As a device that converts the color of measured surfaces into digital codes consisting of L, a and b factors, it is a high-definition and multi-functional device widely used to measure skin color in cosmetic research.

[0123] Sample A after 48h A after 6 days

[0124] SLS treatment SLS treatment

[0125] Zeolite antiox beads (S9) cream -0,73 -1,20

[0126] Placebo sample 0,16 -0,46

[0127] Comparison sample 0,46 -0,56

[0128] Control area 1,04 -0,17

[0129]

[0130] BW1098M

[0131] As a result, the increased skin roughness, transepidermal water loss (TEWL) and erythema (a-value) sample, with zeolite antioxidant beads, showed a statistically significant (p<0.05) decrease after 48 hours of the test sample application compared to the control areas using placebo, comparison sample and non-treated area, it was confirmed that the test sample has the promoted skin self-recovery potential after damage caused by external irritation (chemical damage).

[0132] CLINICAL EVIDENCE 2

[0133] As a result of testing on 20 subjects during the 1-week test period, the test area using a cream comprising materials described in present patent was evaluated in the test area where skin roughness , transepidermal water loss (TEWL) and erythema (a-value) have increased by damaging the skin barrier through patching of 1% SLS.

[0134] The roughness has evaluated with a high-resolution, three-dimensional (3D) imaging device that analyzes skin conditions by capturing reflected signals generated when visible light of varying wavelengths is projected onto the skin. The system utilizes a combination of optical techniques and mathematical algorithms to construct 3D surface images of the skin, from which quantitative data can be extracted to assess skin improvements and monitor changes over time.

[0135] Samples A after 48h A after 72h A after 6 days SLS SLS SLS treatment treatment treatment

[0136] Zeolite antiox beads (S9) cream -0,83 -1,05 -1,05

[0137] Placebo sample -0,56 -0,72 -0,73 Comparison sample -0,41 -0,73 -0,70

[0138] Control area -0,28 -0,24 -0,31

[0139]

[0140] Transepidermal water loss has been evaluated with a device designed to measure transepidermal water loss (TEWL), which refers to the amount of water vapor passively evaporating through the skin. The instrument detects the presence of a water vapor gradient between the skin surface and the surrounding air within the microenvironment around the skin using sensors housed in an open chamber. This allows for the quantification of TEWL in units of grams per square meter per hour (g / m2 / h).BW1098M Samples A after 48h A after 72 h A after 6 days SLS treatment SLS SLS treatment treatment

[0141] Zeolite antiox beads (S9) cream -2,57 -4,25 -6,16

[0142] Placebo sample -1,70 -2,57 -3,78 Comparison sample -1,60 -2,50 -3,71

[0143]

[0144] Control area -0,51 -0,88 -1,39

[0145] Erythema (a-value) has been evaluated whit a specific tool which measures the colors recognized by humans through reflective colors (rate) according to reflected light using a three primary colors (red, blue, and green) filter on three sensors. This is called the Tristimulus method. As a device that converts the color of measured surfaces into digital codes consisting of L, a and b factors, it is a high-definition and multi-functional device widely used to measure skin color in cosmetic research.

[0146] Samples A after 48h A after 72 h A after 6 days SLS treatment SLS treatment SLS treatment Zeolite antiox beads (S9) cream -1,11 -1,52 -1,91 Placebo sample -0,69 -0,98 -1,43 Comparison sample -0,56 -0,99 -1,26

[0147]

[0148] Control area -0,47 -0,68 -0,81

[0149] As a result, the increased skin roughness, transepidermal water loss (TEWL) and erythema (a-value) sample showed a statistically significant (p<0.05) decrease after 48 hours of the zeolite + antioxidant beads cream application compared to the control area using placebo, comparison sample (AA2G) cream and non treated area.

[0150] It was confirmed that the test sample has a calming effect on the skin whose barrier was damaged by external irritation (chemical damage).

[0151] CLINICAL EVIDENCE 3

[0152] An evaluation over the catalase enzyme activity has been conducted after using a cream comprising materials of the invention. The test has been conducted on 20 subjects during the 4-week test period, the test area is 3 cm below the exact center of the cubital fossa. Catalase acts as a defense mechanism against reactive oxygen (together with other antioxidant enzymes such as superoxide dismutase and glutathione peroxidase) so sa to protect the organism against reactive oxygen.BW1098M Improvement rate % week 0 week 2 week 4

[0153] Zeolite antiox beads (S9) cream 0% 21,06% 36,86%

[0154] Placebo 0% 2,42% 8,51%

[0155]

[0156] The test showed a statistically significant (p <0.05) anti-oxidant increase by 21 ,06% after 2 weeks and 36,86% after 4 weeks in catalase activity compared to before the sample application.

[0157] CLINICAL EVIDENCE 4

[0158] An evaluation of skin tone, melanin distribution and melasma appearance has been conducted on 20 subjects during the 4-weeks of test period in a test area treated with a cosmetic formulation containing zeolite beads according to the present invention.

[0159] Skin tone (L-value) has been evaluated whit a specific tool which measures the colors recognized by humans through reflective colors (rate) according to reflected light using a three primary colors (red, blue, and green) filter on three sensors. This is called the Tristimulus method. As a device that converts the color of measured surfaces into digital codes consisting of L, a and b factors, it is a high-definition and multi-functional device widely used to measure skin color in cosmetic research.

[0160] Improvement % week 0 week 2 week 4

[0161] Zeolite antiox beads (S9) cream 0% 2,10% 3,54%

[0162] Placebo 0% 0,61% 0,48%

[0163]

[0164] The melanin distribution has been measured with a particular equipment which evaluates the skin topography and the chromophores’ concentration by analyzing the spatial and spectral analysis of the acquired image data obtained by illuminating the skin with light emitting diodes (LEDs) of different wavelengths, shining from different directions.

[0165] Improvement rate % week 0 week 2 week 4

[0166] Zeolite antiox beads (S9) cream 0% -8,17% -10,44%

[0167] Placebo 0% -0,62% 1,30%

[0168]

[0169] BW1098M The melasma appearance has been evaluated with a device for a high-definition digital image analysis.

[0170] Improvement rate % week 0 week 2 week 4

[0171] Zeolite antiox beads (S9) cream 0% -11,03% -13,31%

[0172] Placebo 0% 10,12% 4,94%

[0173]

[0174] The test sample containing Zeolite antioxidant beads was confirmed to help improving skin whitening (skin tone, melanin distribution, melasma) and to be superior to the control sample.

[0175] CLINICAL EVIDENCE 5

[0176] An evaluation of Wrinkle and Epidermal Density has been conducted on 20 subjects during the 4-weeks of test period in a test area (crow’s feet and lateral canthus zone) treated with a cosmetic formulation containing zeolite beads according to the invention. Wrinkle depth has been evaluated with an instrument which measures the skin topography and the chromophores’ concentration by analyzing the spatial and spectral analysis of the acquired image data obtained by illuminating the skin with light emitting diodes (LEDs) of different wavelengths shining from different directions.

[0177] Improvement rate % week 0 week 2 week 4

[0178] Zeolite antiox beads (S9) cream 0% -9,09% -16,20%

[0179] Placebo 0% -1,86% -3,84%

[0180]

[0181] Skin tone has been monitored during the test period with a high-resolution ultrasound skin measurement device that utilizes 20MHz ultrasound energy to analyze skin structures at a depth of 3.37mm and a width of 17.6mm from the skin surface. It enables the visualization of the stratum corneum, epidermis, dermis, and subcutaneous tissue. The skin imaging process is based on measuring signals reflected from the skin when ultrasound waves are transmitted. The reflected signals generate a visualized cross-sectional image through amplitude analysis. Darker colors indicate lower reflection, meaning that the skin structure in that area has low or no density, whereas brighter colors indicate stronger reflection, signifying higher density in the skin structure.BW1098M

[0182] Improvement rate % week 0 week 2 week 4

[0183] Zeolite antiox beads (S9) cream 0% 2,71% 6,59%

[0184] Placebo 0% 0,84% 2,19%

[0185]

[0186] Therefore, the test sample containing Zeolite antioxidant beads was confirmed to improve wrinkles and epidermal density and was superior to the control sample.

[0187] CLINICAL EVIDENCE 6

[0188] A study has been conducted over the excessive sebum regulation, a test has been carried out on 20 subjects during the 4week test period, the test area is ascribable to glabella zone.

[0189] The evaluation has been conducted using a particular equipment - Sebumeter® -measures the oil contents of the skin surface using a Sebumeter-mounted oil cassette. The special semi-transparent lipid absorption tape adheres to the skin for more than 15 seconds to absorb the sebum and uses photometric reflection to measure the oil amount ( g / cm) contained in the absorbed tape. When measuring, the pressing force must be constantly maintained, using units of g / cm. This means that the lower the measurement values, the less the oil amount on the skin. The oil content of normal skin is 100 to 220 g / cm in the T-zone and 70 to 180 jug / cm in the U-zone.

[0190] sebum level (pg / cm2) Improvement rate % week 0 week 2 week 4

[0191] Zeolite antiox beads (S9) cream 0% -23,93% -36,84%

[0192] Placebo 0% -1,22% -3,56%

[0193]

[0194] It is appreciable how the area treated with the Zeolite antiox beads (S10) cream sample showed a statistically significant ( p <0.05) decrease by 23.93 % after 2 weeks and 36.84% after 4 weeks in skin sebum level compared to before the sample application.

[0195] In order to prove the wide versatility of the complex beads for the formulation of cosmetic products, we herein report some examples of cosmetic products containing the beads according to the present invention.BW1098M Oil in Water Emulsion preparation

[0196] Methodology:

[0197] Mix and heat phase A until 75-80°C. Mix and heat phase B until 75°C.

[0198] Add phase B to phase A and homogenize until emulsion is formed.

[0199] Cool under stirring then add phase C (below 45-50°C) using homogenizer, then add phase D.

[0200] Phase Ingredients INCI % wt

[0201] A. Purified water Water 70.50 Glycerin Glycerin 2.00 Propanediol Propanediol 1.00 Xanthan gum Xanthan gum 0.30

[0202] B. Simulsol 165 PEG- 100 Stearate, Glyceryl Stearate 3.00 Ceterayl alcohol Ceterayl alcohol 3.00 Dicaprylyl carbonate Dicaprylyl carbonate 3.00 Emosmart L15 C13-C15 alkane 5.00 Capryly capric Capryly capric trigliceride 2.00 trigliceride

[0203] Shea Butter Butyrospernum parkii butter 0.50 Mimic Beeswax Oryza sativa bran wax, Shorea robusta 1.00 resin, Rhus succedanea fruit cera,

[0204] Squalene

[0205] Dimethicone 350 Dimethicone 1.00

[0206] C. Complex beads Zeolite, Ascorbyl Glucoside, 6.70 Niacinamide, citric acid

[0207] D. Preservative Phenoxyethanol, Ethylhexylglycerin 1.00

[0208]

[0209] TOTAL 100 Table 4.

[0210] The use of the beads in emulsions allow the formulator to introduce in one step, different antioxidants, an antipollution and a texturizing agent. The formulation is more cushioning and presents a dry after feel, compared to the one without beads, moreover, antioxidant activity of the formulation containing complex beads has been tested and confirmed.

[0211] Anhydrous ButterBW1098M Methodology:

[0212] Weigh the ingredients of phase A and heat to a temperature of 75-80°C under stirring. Mix components of phase B under stirring and heat to a temperature of 40-45°C.

[0213] Mix together ingredients of phase B and A under mixing until the product is homogeneous, maintaining the temperature not above 65°C.

[0214] Pour quickly the product in the container, avoiding prolonged exposure to heat.

[0215] Phase Ingredients INCI %wt A. Deodorized Theobroma Cacao Seed Butter 15.0 Cocoa Butter

[0216] Shea Butter Butyrospermum parkii butter 5.0 Mimic Beeswax Oryza sativa bran wax, Shorea robusta resin, 5.0

[0217] Rhus succedanea fruit cera, Squalene

[0218] Rice Wax Oryza sativa bran wax 15.0 B. Caprylic / Capric Caprylic / Capric Triglyceride 37.3 Triglyceride

[0219] Coco-caprylate Coco-caprylate 16.0 Complex beads Zeolite, Ascorbyl Glucoside, Niacinamide, citric 6.7 acid

[0220]

[0221] TOTAL: 100 Table 5.

[0222] Powders

[0223] Methodology:

[0224] Grind together the powders of Phase A using a suitable mixer or blender.

[0225] Add ingredients of Phase B and continue grinding until homogeneous mixture is obtained.

[0226] Compact the final product in the pan at 40-50 bar.

[0227] % A Vegetal Zinc Stearate Zinc Stearate 1,50 Titanium Dioxide Cl 77891 15,00

[0228]

[0229] SynthMica WM9 Synthetic Fluorphlogopite 59,50BW1098M Complex beads Zeolite, Ascorbyl Glucoside, Citric Acid 2,50 Colorona Oriental Beige Mica, Cl 77891, Cl 77491 10,00 B SymDiol 68 1,2-Hexanediol, Caprylyl Glycol 0,50

[0230] Coco-caprylate Coco-Caprylate 3,50 Ethyhexyl Stearate Ethyhexyl Stearate 7,00 Tocopheryl Acetate Tocopheryl Acetate 0,50

[0231]

[0232] TOTALE: 100,00

[0233] The use of the beads in pressed or loose powders allow the formulator to introduce vitamins together with a texturizing agent in this type of formulations.

[0234] Aqueous Lotions

[0235] Methodology:

[0236] Mix the ingredients of Phase A until the gel is formed.

[0237] Add Phase B to Phase A, using an homogenizer if needed.

[0238] Add the ingredients of phase C while stirring, then add phase D and E.

[0239] Check chemical-physical parameters.

[0240] PHASE INGREDIENTS INCI %

[0241] A Purified Water Aqua 83,20

[0242] Propylene Propylene Glycol 4,00

[0243] Glycol

[0244] Xanthan Gum Xanthan Gum 0,35 Carragenan 389 Carragenan, Glucose 0,30

[0245] B Complex beads Zeolite, Caffeine, Citric Acid 5,00

[0246] C Ethyl Alcohol Ethyl alcohol 5,00

[0247] Fragrance Parfum 0,05

[0248] Acnibio PE9010 Phenoxyethanol, Ethyl hexylglycerin 1,00

[0249]

[0250] BW1098M E Lactic Acid 90% Lactic Acid, Aqua 0,10

[0251]

[0252] solution

[0253] PHASE INGREDIENTS INCI % A Purified Water Aqua 86,25

[0254] Hydrolite 5 green Pentylene Glycol 4,00 Xanthan Gum Xanthan Gum 0,40 Carragenan 389 Carragenan, glucose 0,20

[0255] B Complex beads Zeolite, Niacinamide, Ascorbyl 2,00 glucoside, Caffeine, Citric Acid

[0256] C Ethyl Alcohol Ethyl alcohol 5,00

[0257] PEG-40 Hydrogenated PEG-40 Hydrogenated Castor Oil 1,00 Castor Oil

[0258] Fragrance Parfum 0,05 D Acnibio PE9010 Phenoxyethanol, Ethyl hexylglycerin 1,00

[0259] E Sodium Hydroxide 30% Water, Sodium hydroxide 0,10 solution

[0260]

[0261] TOTAL: 100,0

[0262] The use of beads containing hot water soluble ingredients, allow the formulator to add these components without heating, using cold process production. Additionally, the formulator can use an ingredient usually soluble in hot water together with temperature sensitive elements at the same time.

Claims

22BW1098M CLAIMS1. A composition for cosmetic and skincare formulations comprising among its components:zeolites selected among Faujasite (FAU) type, Linde type or mixture thereof andat least an antioxidant selected in the group consisting of Vitamin C, Vitamin E, Vitamin A, Vitamins B, Vitamin D, Vitamin K, Caffeine, Quercetin, Astaxanthin, Resveratrol, alpha-Lipoic acid, hydroxydecyl ubiquinone (CoQ10), ferulic acid, thioctic acid, Glutathione, Catechins, Polyphenols, Carotenes, Urea, Hyauronic acid, sodium hyaluronate, centella asiatica extracts expecially with high content of madecassoside, asiaticoside, asiatic acid, madecassic acid and their derivatives and combinations thereof, wherein said components are in form of beads characterized by:a spherical structure essentially consisting of said zeolites,an external binder of antioxidant covering at least 50% of the spherical structure surface,a volume mean diameter comprised between 1 and 70 pm, preferably between 10 and 40 pm.

2. The composition according to claim 1 , wherein the amount of zeolite is comprised between 50 and 90% by weight with respect to the total weight of the composition.

3. The composition according to any of the previous claims, wherein the amount of antioxidant is comprised between 10 and 50 % by weight with respect to the total weight of the composition.

4. The composition according to any of the previous claims, wherein the zeolites are characterised by the presence of sodium or potassium as counter-ion at an ion exchange site of the framework structure.

5. The composition according to any of the previous claims, wherein the antioxidant is selected in the group consisting of ascorbyl glucoside, niacinamide, tocopherol, caffeine, panthenol, Urea, Hyauronic acid, sodium hyaluronate, centella asiatica extractsand mixtures thereof.BW1098M 6. A cosmetic or skincare formulation comprising the composition according to any one of claims 1 to 6 in an amount comprised between 0.1 and 5% by weight with respect to the total weight of the formulation.

7. The cosmetic or skincare formulation according to claim 7, comprising a water- free phase and / or an aqueous phase.

8. The cosmetic or skincare formulation according to claim 8, wherein the water- free phase is selected in a group consisting of hydrocarbons, esters, ethers, silicones, waxes, butters, powders or mixtures thereof.

9. The cosmetic or skincare formulation according to claims 7 to 9, wherein the composition is a homogenous oil-in-water emulsion, preferably in form of serum or cream.

10. The cosmetic or skincare formulation according to claims 7 to 9, wherein the composition is a homogenous anhydrous formulation, preferably in the form of pressed powder, loose powder, or other mixtures of ingredients in a cosmetic powder form, or as anhydrous oily formulation, preferably in the form of hot poured products, lipogel, oils or butters mixtures.

11. The cosmetic or skincare formulation according to claims 7 to 11, further comprising one or more of a cosmetically acceptable emollient, carrier fluid, pigment, humectant, emulsifier, co-emulsifier, hydrophilic or hydrophobic thickeners, wax, butter, film former, silicone, surfactant, active agent, extract, fragrance, preservative, pH-adjusting agent, suspending agent and chelating agent.

12. The cosmetic or skincare formulation of claims 6 to 11, wherein said formulation is an antiaging, antioxidant and / or antipollution formulation.

13. Composition according to any one of claims 1 to 5, for use in the prevenzione and / or treatment of skin damage, eritema, and melasma.

14. Cosmetic use of the composition according to any one of claims 1 to 5 for improving wrinkles, epidermal density and sebum regulation.

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