IT202100005132A1 - Broad-spectrum light-absorbing material, process for its preparation and related uses - Google Patents

Description

Description of the Industrial Invention entitled:

?Broad-spectrum light-absorbing material, process for its preparation and related uses?

DESCRIPTION

The present invention refers to a broad-spectrum light-absorbing material, to the process for its preparation and to the relative uses of this material.

The prior art pertinent to the present invention includes:

- US20040208902A1: treats UV filter molecules and other organic compounds for cosmetic and pharmaceutical use adsorbed on the external surface of zeolites for controlled and prolonged release. This patent does not deal with the phases of interest of the present invention and does not provide for the encapsulation of UV filter molecules; - CN108210347: proposes the use of "zeolite imidazolate frameworks (ZIF)" containing octinoxate and/or other sunscreens. ZIFs are metal-organic complexes (Metal Organic Framework, MOF), or structures with high porosity? similar to those of zeolites, in which the channels and/or cages of the structure are made up of organic molecules coordinated with metal ions or clusters. Specifically, ZIFs are MOFs with Zn as the metal cation and imidazolate as the organic molecule. MOFs cannot be defined as zeolites according to the official, published definition of the term. In addition, ? been demonstrated? instability? MOFs for long permanence in an aqueous environment; - US-B1-6,436,375: these are sunscreens encapsulated in amorphous silica spherules, which are effective in protecting the filter-filter interactions in creams. It is therefore not about sunscreens encapsulated in zeolites. The particular properties? of the crystalline structures of the zeolites give the material of the present invention a stability? greater than an amorphous substance;

- US-A1-2008/0139507: deals with the encapsulation of non-antibiotic organic compounds within zinc zeolites for the topical treatment of skin irritations. Among the encapsulated molecules there are also UV filters. The purpose of the material produced ? the?intervention on the skin gi? conditioned, while the light-absorbing material of the present invention has the purpose of preventing irritations and the harmful effects of exposure to UV rays. Furthermore, the Zn zeolites used in US 2008/0139507 are different from the zeolites used in our hybrid material, have a different topology and do not have the characteristics highlighted here in relation to low release (i.e. in US patent 2008/0139507 the release of the encapsulated molecules);

- US-A1-2009O130154: same author as US 2008/0139507 and same material;

- US-A1-2005/0276761: this application deals with zeolites with Zn and Ti as physical screens in sunscreens, without the insertion of UV filter molecules inside the pores? of the zeolite. The material of the present invention combines the advantages of zeolites as physical filters with the advantages of chemical filter molecules encapsulated within the particles; the union of the two types of filter (physical and chemical) in a single particle results in greater efficacy than the sum of the two separate filters, given that the insertion of the filter-molecule inside the zeolite increases the stability? and consequently the effectiveness of the chemical filter molecule.

Purpose of the present invention? solve the aforementioned problems relating to the prior art, providing a broad spectrum light-absorbing material which, with respect to the technologies currently in use, provides improvements and advantages with respect to both a) the commonly used physical and/or chemical filters, and b) hybrid materials previously developed.

The organic filter-molecules degrade not only following exposure to UV radiation, but also due to reactions with other constituents of the formulations or their chemical surroundings. ? in fact demonstrated as the presence of pi? chemical filters in a cosmetic formulation can lead to a destructive interaction between these components, and therefore to the loss of effectiveness of the formulation itself. The repeated application of the product, if on the one hand solves the problem of loss of efficacy, on the other hand causes an increase in exposure to degradation products in the body, the structure and toxicity of which are different. are not currently known.

The hybrid material proposed here? therefore highly innovative because:

1) prevents the photoisomerization of the filter molecule and therefore its photodegradation;

2) avoids the interactions of the filter molecules with the other components of the formulation;

3) hinders the release of encapsulated filter molecules.

The above and other objects and advantages of the invention, as will appear from the following description, are achieved with a broad spectrum photoabsorbent material, a process for its preparation and its relative uses as claimed in the respective independent claims. Preferred embodiments and non-trivial variants of the present invention form the object of the dependent claims.

It is understood that all the attached claims form an integral part of the present description.

This invention will come better described by some preferred embodiments, provided by way of non-limiting example, with reference to the attached drawings, in which:

- Figure 1 ? a typical wash chart of the material of the present invention;

- Figure 2a ? a graph reporting the thermogravimetric analyzes of uncharged LTL zeolite and LTL/OMC hybrids at different washing levels up to the optimized sample;

- Figure 2b ? a graph showing the thermogravimetric analyzes of the FAU(silicate)/OMC hybrids at different washing levels up to the optimized sample;

- Figure 2c ? a graph reporting thermogravimetric analyzes of uncharged MFI zeolite and MFI/AVO hybrids at different washing levels up to the optimized sample;

- Figure 3 ? a graph showing the infrared spectroscopy spectra (IR, in absorbance versus wavenumber) of unencapsulated OMC and encapsulated in MOR(silicate) before and during UV irradiation;

- Figure 4 ? a graph showing the X-ray diffraction spectra (XRPD, in intensity with respect to 2?) of the dehydrated LTL zeolite and of the dehydrated LTL/OMC hybrid;

- Figures 5a and 5b show the UV spectra in vaseline of free sunscreens (5a) and encapsulated in zeolites (5b);

- Figures 6a and 6b instead show a comparison of the UV spectra of the pure filters and the hybrids in vaseline, with a content of 1% OMC (a) and AVO (b) in the measured preparation;

- Figures 7a to 7f show the UV spectra of the non-encapsulated filters (a,b), of the LTL hybrids (c,d) and FAU (e,f) before and after simulated solar irradiation.

- Figure 8 ? a schematic view of the vertical static diffusion Franz cells used for the tests;

- Figure 9 ? a graph that shows the quantity? of avobenzone found in the recipient phase of the Franz cell at different times for the MOR(silicate)/AVO hybrids;

- Figure 10 ? a graph that shows the quantity? of octinoxate found in the receiving phase of the Franz cell at different times for the MOR(silicate)/OMC hybrid;

- Figure 11 ? a graph showing the percentage of octinoxate found in the receiving phase of the Franz cell at different times for the MOR/OMC hybrid;

- Figure 12 ? a graph showing the percentage of octinoxate found in the receiving phase of the Franz cell at different times for the LTL/OMC hybrid;

- Figure 13 ? a schematic view of a simulated seawater release test apparatus;

- Figure 14a ? a graph showing the percentage of filter released versus time for various zeolite/OMC hybrids of the invention;

- Figure 14b ? a graph showing the percentage of filter released versus time for FAU/AVO and LTL/AVO;

- Table 1 represents the maximum loading possible for each hybrid zeolite/filter system;

- Table 2 represents accumulated avobenzone in porcine skin samples;

- Table 3 represents the accumulated octinoxate in porcine skin samples.

Referring to the Figures and Tables, ? illustrated and described a preferred embodiment of the present invention. will result? it is immediately obvious that innumerable variations and modifications (for example relating to shape, dimensions and parts with equivalent functions) can be made to the described without departing from the scope of protection of the invention as appears from the attached claims.

The material obtained? an inorganic-organic hybrid made up of inorganic particles with a microporous structure having a diameter between 0.01 and 300 micrometers and hosting, in the porosity, organic molecules, possibly different, and possibly cations and/or H2O molecules. The microporous particles are zeolites having precise and defined crystalline structures presenting channels with a circumference ranging from 6 to 14 TO4 tetrahedra (preferably 10 or 12 tetrahedra), T being a cation, in particular T ? a tetravalent and/or trivalent cation, usually Si and Al but also, but not limited to, P, B, Fe, Co, Ga, Ge, Be, or any combination thereof. These channels have an average free diameter between 3 and 30 ?ngstr?m, in particular between 4 and 12 ?ngstr?m. The ratio of tetrahedral-tetrahedral-travalent cations/tetrahedral-trivalent cations (T4/T3), in particular Si/Al, can vary between 1 and ?, in particular between 3 and 900, meaning T4/T3=? zeolites containing only tetravalent cations, in particular only Si. Organic molecules of the appropriate size are encapsulated inside the channels, capable of absorbing UV radiation and dissipating its energy. These molecules are permanently trapped inside the structure and are not released. The molecules encapsulated in the zeolite are possibly different from each other. H<2>O molecules, alkaline or alkaline-earth metal cations or transition metals or H<+> protons may be present inside the channels or in portions of the structure far from the channels.

In detail, zeolite has a crystalline structure, in particular with LTL, MOR, FAU or MFI topology and the molecules contained within the porosity are sunscreens, such as octyl methoxycinnamate -octinoxate (OMC)- and avobenzone (AVO), two of the most? used chemical filters for UV radiation, and possibly two separate sunscreens, e.g. OMC and AVO are simultaneously present in the zeolite. The metal cations in the zeolites used are preferably K<+ >or Na<+ >or H<+ >or Ca<++> cations.

The individual light-absorbing filters, which can degrade if in contact with each other, for example in a cosmetic formulation, can be encapsulated separately within zeolites, possibly even different ones, or they can be encapsulated simultaneously. The various zeolite-filter hybrid materials can therefore be mixed together to obtain a material with broad-spectrum light-absorbing characteristics made up of stable and safe components for humans and the environment.

The hybrid material obtained can have application in cosmetics as a UV filter in products such as:

- sunscreen products, self-tanning products,

- creams, emulsions, lotions, gels and oils for the skin,

- beauty masks, foundations (liquids, pastes, face powders), face powder,

- talcum powder for after-bath and body hygiene,

- beauty soaps, deodorant soaps, perfumes, toilet waters and colognes, - preparations for baths and showers (salts, foams, oils, gels),

- hair removal products,

- deodorants and antiperspirants,

- hair dyes, products for waving, straightening and fixing, products for styling, products for cleaning hair (lotions, powders, shampoos), products to keep hair in shape (lotions, creams, oils ), hair styling products (lotions, lacquers, glitter),

- shaving products (creams, foams, lotions),

- make-up and make-up remover products, products intended to be applied to the lips, - products for the hygiene of the teeth and mouth,

- nail care products and lacquers for them,

- products for external intimate hygiene, - products for lightening the skin and anti-wrinkle products.

- products for decorative cosmetics such as primers, foundations, face powders, concealers, colored moisturizers, mineral make-up, highlighters and bronzers, pigments, mascara, permanent make-up such as tattoo inks.

The product can replace UV filters commonly used in the above products as:

- maintains its functionality;

- ? more safe for health, preventing the contact of the molecules with the various components of the formulation and with the dermis and reducing/preventing the degradation of the encapsulated molecules. The encapsulation of the molecule within the porosity? of the zeolite prevents its degradation. The photoisomerization, which precedes the breaking of the bonds of the molecules, should in fact be inhibited following the constraints imposed by the confinement in the pores;

- reduces the degradative processes of the molecules encapsulated in the zeolite, with a consequent increase in efficiency, a decrease in the quantities necessary for protection and in the toxicity? resulting from by-products of degradation;

- ? more safe for the environment, preventing the dispersion of the organic molecules (which have proved to be toxic for many animal and plant species) contained in the zeolite in the surrounding environment, even in the case of prolonged persistence in environments with high physical-chemical stress such as the? Marine environment. This hybrid material is expected to address persistence and toxicity issues. of chemical sunscreens in water.

The hybrid material obtained can have applications outside the scope of cosmetics, within products intended to protect against UV exposure, or which require protection from UV radiation, such as paints and dyes, fabrics, optical lenses, paper, metals and glasses. In particular, non-exhaustive examples of such applications can be:

- Glass for window frames such as laminated glass, self-cleaning glass, thermal glass for window frames, solar control glass, anti-noise glass, double or triple glazing

- toughened or tempered glass, laminated or laminated glass, armored glass, insulating glass, structural glass

- shielding glasses, glasses for UV protection, glasses for solar protection of spaces or substances, colored glasses for containers

- optical glasses, special glasses

- ophthalmic lenses in plastic or vitreous material, contact lenses, ceramic utensils and advanced ceramic materials, for medical use, porcelain

- Pharmaceutical and veterinary products, hygienic products for medical purposes, poultices, material for dressings, materials for filling teeth and for dental impressions, disinfectants,

- products for the prevention of burns on plants and fruits, disinfestants, pesticides

- bricks and ceramic products for the building industry, - semi-finished woods, veneered woods, building glass (sheets, glass tiles), glass granules for road marking

- plastics for packaging, generic containers, food containers, containers for food liquids, containers for liquids, bottles for drinks, bottles for personal hygiene and household cleaning products, shampoo, shower gel, detergents, trays for taking away food, food packaging, expanded polystyrene for packaging and the like, nylon bags, plastic film,

- plastics for building, thermal insulation, sound-absorbing panels, UV protection films,

- rubber products,

- curtains, umbrellas and shading covers, windbreak fabrics and panels, privacy screen fabrics and panels, arelles,

- Ropes, strings, nets, tents, tarpaulins, sails, sacks, padding material, textile fibres, threads for textile use,

- fabrics for clothing,

- plastic additives, and in particular stabilizers to protect against damage from light and UV radiation,

- paper and cardboard for printing,

- printed matter, articles for bookbinding and photographs, stationery, adhesives (gluing materials) for stationery or for domestic use, materials for artists, brushes,

- Paper and cardboard for packaging,

- Paints, varnishes, lacquers, rust and wood preservatives, dyeing materials, mordants, unprocessed natural resins, metals in foil and powder form for painters, decorators, printers and artists, paints, varnishes and lacquers for industry, handicrafts and art, dyes for dyeing clothes, dyes for food and beverages,

- unprocessed artificial resins, dyes for laundry and bleaching, cosmetic dyes, paint boxes (school supplies), insulating paints and varnishes,

- bleaching preparations and other substances for washing, cleaning, polishing, scouring and abrasive preparations, soaps, perfumery, essential oils, - building materials of metal, transportable buildings of metal, materials of metal for railways, non-electric cables and wires of metal , ironmongery and metal trinkets, metal pipes, safes,

- optical, photographic, cinematographic materials and instruments, materials for electronics and their coverings/protections, apparatus for recording, transmission and reproduction of sound or images, magnetic recording supports, acoustic discs;

- adhesives (gluing materials) for industry and construction, products for insulation, sealing and waterproofing,

The product can replace commonly used UV filters or found in the above products as:

- enhances its functionality;

- ? more safe for health compared to UV filters often inserted in the above materials, preventing or reducing the release of the filter molecules into the materials, crops, soil and the environment;

- prolongs the useful life of the goods and extends the life cycle of the products, reducing the degradation due to damage from UV radiation, for longer times than conventional protective methods. Based on the data shown here (Figure 3) the encapsulation of the molecule within the porosity? of the zeolite prevents its degradation. The photoisomerization, which precedes the breaking of the bonds of the molecules, should in fact be inhibited following the constraints imposed by the confinement in the pores;

- reduces the degradative processes affecting the molecules encapsulated in the zeolite, with a consequent increase in efficiency, a decrease in the quantities used and in the toxicity? resulting from by-products of degradation; - in the plastics can? replace more of an additive, in fact by modulating the granulometry of the material it is possible to give the plastics the desired rheological characteristics together with the protection from radiation which would require the addition of further additives;

- ? more safe for the environment, thanks to the encapsulation it prevents the dispersion of organic molecules (which have proved to be toxic for many animal and plant species), even in the case of prolonged persistence of the hybrids in environments with high physical-chemical stress such as the environment marine. This hybrid material is expected to address persistence and toxicity issues. of chemical sunscreens in water.

The hybrid material obtained from the encapsulation of the UV filter molecules (in particular octinoxate and avobenzone or a mixture thereof) inside zeolites (in particular with LTL, FAU, MOR, MFI frameworks) allows to block UV radiation through two processes: 1) part of the radiation undergoes a scattering phenomenon on the external surface of the particle of the hybrid material and is therefore dissipated, as happens with the conventional physical filters used (e.g. TiO<2>, ZnO); 2) the portion of radiation that is not diffused penetrates inside the particles and interacts with the organic molecules which absorb the UV photons and dissipate their energy, without undergoing the photodegradation phenomena to which the filter molecules are subject outside the zeolite structure. Inside the zeolite, some vibrational motions and isomerizations, which contribute to the decay of the molecules making them photo-unstable and which decrease their absorption, are prevented by spatial confinement. Based on the data shown below (e.g. Figure 3), the photodegradation phenomena of these filtering materials are decidedly more? limited or absent. In addition, the electrostatic interactions between the filters and the zeolite anchor the molecules stably to the porous framework, preventing the release of the organic filters in the dermis, in the materials, and their dispersion in the environment.

Compared with the technologies currently in use, the present invention provides the following improvements and advantages.

The organic filter molecules degrade not only following exposure to UV radiation, but also due to reactions with other constituents of the cosmetic formulation. ? in fact, demonstrated as the presence of pi? chemical filters in a cosmetic formulation can lead to a destructive interaction between these components, and therefore to the loss of efficacy of the formulation itself. The repeated application of the product, if on the one hand it solves the problem of loss of efficacy, on the other it causes an increase in exposure to degradation products in the human body, the structure and toxicity of which are different. are not currently known.

The hybrid material proposed here? therefore highly innovative because:

1) prevents the photoisomerization of the filter molecule and therefore its photodegradation;

2) avoids interactions of the filter molecule with the other components of the formulations and materials in which UV filters are required. The interactions are limited and stabilized even in the case of the simultaneous presence of different filters in the zeolite.

3) hinders the release of encapsulated filter molecules.

The main advantages will be, in the case of cosmetic preparations:

- an increase in stability? filters (prolonged effectiveness);

- reduction of the number of applications;

- reduction of any degradation products formed and their entrapment in the hybrid material;

- reduction in the consumption of the formulation. -reduction of the dispersion of harmful filter molecules in the environment

The main advantages will be, in plastics, glass and other products not related to cosmetics:

- union of properties? rheological properties of inert particles with granulometry adjustable to the protective ones of UV filters;

- prolongation of the useful life of the goods and of the life cycle of the products, reducing the degradation due to damage from UV radiation.

-reduction of the dispersion of harmful filter molecules in the environment

In the literature there are few sporadic studies on the use of zeolitic materials for the encapsulation of photosensitive molecules, most of which focused on the role and type of compensator cation, rather than on the framework (structure) used as a host. Most of the materials made, in fact, have zinc as a compensating cation inside the zeolite, and the inserted organic molecules chelate to this cation. In our material, the choice of host is? focused on the topology/architecture of the zeolite in relation to the size and shape of the molecules to be stabilized. In particular, structures such as LTL, FAU, MOR, MFI have channels delimited by rings of 6-14 tetrahedrons, with periodically repeated enlargements which allow the insertion and stable anchoring of organic molecules inside the structure. Compared to other materials consisting of sunscreens encapsulated within MOF (CN108210347), the hybrid material proposed by the present invention is more? stable in an aqueous environment, thanks to the greater stability? of the inorganic structures of the zeolites compared to those of the MOFs. The thing that most distinguishes our materials compared to those already? present in the literature? the capacity? NOT to release the filter molecules once encapsulated in environments with high chemical-physical stress such as the marine one. By way of example, two graphs are attached where the releases of octinoxate and avobenzone from some of the hybrid systems proposed by the present invention are reported.

How can you? see from the graphs shown in Figure 14a, 14b pi? further on, the systems proposed here have a very low release when compared with other inorganic or metal-organic matrix systems presented in the literature. This characteristic ? conferred by the particular conformation and chemical composition of the LTL, FAU, MOR, MFI zeolites. The organic filters used here were also encapsulated in mesoporous materials such as MCM-41 and SBA-15. The studies carried out, however, demonstrated that the encapsulated organic molecules were released in the formulation, due to the weak bonds established between molecules and framework. To avoid the dispersion of the filter molecules incorporated in mesoporosis, an additional ?sealing of the pores? procedure is required, which in addition to being a complex operation, also precludes the use of these hybrids in a series of formulations. In fact, having the molecules used as a ?cap? lipophilic nature, and therefore being soluble in oil, the hybrids cos? made can only be used in water-based formulations.

In summary, the invention relates to a new broad-spectrum light-absorbing material that can have application as a UV filter inside cosmetic products and possibly as an additive in plastics, glasses and other industrial products not directly related to cosmetics.

Such material? a hybrid consisting of organic molecules commonly used as a UV filter (in particular octinoxate, OMC, and avobenzone, AVO), encapsulated within the porosity? structural of zeolites (in particular having LTL, MOR, FAU, MFI structure).

The materials that have to date shown the properties? the best are the hybrids resulting from the encapsulation of OMC and AVO in LTL zeolite (LTL-OMC and LTL-AVO).

None of the compounds listed here? explicitly present in the prior art. Only the document US-A1-20080139507 provides, among the various materials presented, the encapsulation of sunscreens (among which avobenzone and octinoxate) in unspecified zinc zeolites, with purposes different from ours. Furthermore, the zeolites used in the present invention do not contain zinc.

Materials

Zeolites

They are aluminosilicate or crystalline aluminophosphate materials (natural and synthetic) characterized by a porous structure with channels and cages arranged neatly in space (framework). These channels and cages, communicating with each other and with the outside, host H2O molecules and/or alkaline and/or alkaline earth cations in the natural phases. In the case of the phases obtained by synthesis, the Si/Al ratio can? be modulated to obtain completely silicate zeolites. While the aluminosilicate phases are hydrophilic and lipophobic, the silicate ones are hydrophobic and lipophilic. A zeolite? uniquely identifiable by an X-ray diffraction spectrum (XRPD) and by a chemical analysis of the major elements with loss on fire (e.g. XRF-LOI). Is the literature available? boundless, the definition of zeolite and all the known structural topologies are reported by the International Association of Zeolites (IZA) on the website www.iza-online.org. The different structural topologies are identified by a set of letters (e.g. LTL, FAU, MOR, MFI). The zeolites available on the market as pure phases, and exploitable from an industrial point of view, are of synthetic origin and sold in the form of powder or pellets.

The zeolites used for the preparation of the hybrid material have a particle size ranging between 0.05 and 300 ?m. The grain size can be selected according to the field of application. The zeolites used are indicated here by the triad of letters indicating the topology in the case of the aluminosilicate phases (LTL, FAU, MOR, MFI) or by the triad with the addition of attributes in the case of peculiar phases, as in the case of zeolites with a high Si/Al, MOR(silicate), FAU(silicate), and MFI(silicate).

Organic UV filters

The organic filters used are commonly applied as UV-B (octinoxate) and UV-A (avobenzone) filters. Chemical UV filters are organic molecules capable of absorbing UV photons and dissipating their energy in vibrational motions (thermal energy) and/or by changing their configuration (isomerization). Often these organic molecules irradiated by UV for prolonged times and/or in a complex chemical environment (such as for example that of cosmetic formulations) are subject to photodegradation of the products of which are not? always note the composition and toxicity?. Organic UV filters are known to be very persistent in the environment and their presence in the marine environment? harmful to many living species.

Preparation procedure of hybrid materials The preparation procedure developed ? reproducible and easy to perform. Furthermore, the procedure allows you to quickly explore similar systems for a first evaluation of the efficiency of the loading and therefore the possibility? to obtain hybrid materials with other encapsulated filters or with different zeolites.

The procedure is carried out by limiting the exposure of the components to light radiation (solar and artificial) to a minimum.

The production of the material involves the following stages:

- Zeolite dehydration (pre-treatment)

- Loading of the zeolite

- Washing of the hybrid

- Drying of the hybrid

In particular, although all the previous steps represent the optimal preparation process, the above procedure can exclude one or more of the previous phases, different from the zeolite loading phase, if the result obtained with or without it/s? the same. ? Is it possible, for example, to avoid the pre-treatment of the zeolite if the starting zeolite ? anhydrous, or avoid or reduce the washing procedure of the hybrid if an excess of organic filter is not used, and similarly for the drying phase. The loading phase of the zeolite with the organic filter remains mandatory.

Dehydration of the zeolite (pre-treatment) The zeolites used must first be dehydrated using a suitable method. For silicate zeolites ? sufficient to degas the powder under vacuum for an appropriate time interval. For cationic zeolites ? a heat treatment at a suitable temperature, for example between 100 and 350°C for a suitable time (generally 1-3 hours), is convenient. Temperature and dehydration time can be optimized in relation to the zeolite topology and quantity of treated material.

The zeolite what? dehydrated ? ready for the next upload.

Zeolite loading

The loading takes place by mixing the dehydrated zeolite with pure OMC (which is in the liquid state at room temperature), or pure AVO (which is solid at room temperature) or with a mixture thereof. The quantity? of filter used in the production of hybrids? been evaluated as a result of numerous loading tests carried out using quantities? of decreasing filters, in any case in excess of the one that can actually be accommodated in the porosity. Tests have shown successful loading even without excess molecules.

Loading takes place for times ranging from 1-48 h up to a week and the loading temperature varies between 15 ?C and 150 ?C. Temperature and loading time can also be optimized in relation to the zeolite topology, the organic filter and the quantity? of treated material. However, the heat treatment seems to favor encapsulation. The heat treatment at 70-120 ?C ? indispensable in the case of loading with AVO, since? ? it is necessary to melt the avobenzone to facilitate its loading (melt synthesis).

Hybrid washing

In the case of loading with an excess of organic filter, it is necessary to remove the excess, ie? of the organic molecules that may possibly be found on the external surface of the zeolite grains and in the intergranular space. In fact, these molecules behave as non-encapsulated and can distort the UV absorption and release data.

Sample washing? carried out by extraction with an appropriate solvent and with appropriate methods and times. For example, can you use a Soxhlet extractor with acetone (which has been found to be superior to other solvents such as ethanol and isopropyl alcohol), or alternatively with ultrasound-assisted acetone extraction. To optimize the material and the process, so as to obtain a hybrid in which the filter molecules are only housed in the porosity, it is necessary to follow the chemical evolution of the system during washing, measuring the carbon content with suitable techniques, for example by Elemental Analysis (EA), on various aliquots of hybrid during the different washing steps. For each sample taken you can? calculate a parameter l/s, given by the ratio between the total volume of solvent in contact with the sample (expressed in ml) and the mass of washed sample (expressed in mg). Then plotting the data in a graph of C% vs l/s, ? possible to evaluate the washing effect on the basis of the slope of the curve. The initial rapid decline indicates the removal of molecules on the surface of the grains, the plateau indicates that the washing is not removing the molecules within the porosity. (content of C constant), the decrease that you can? observe excessively prolonging the washing ? index of the removal of molecules from the porosity? zeolitic, a phenomenon to be avoided. In fact, by washing excessively, the C% content reaches zero, more? or less quickly depending on the zeolite topology, the organic molecule and the quantity? of treated material. The attached Figure 1 shows a typical trend of the washing curve.

Hybrid drying

After washing, the hybrid material is subjected to drying at 30-100°C, alternatively at ambient pressure or under vacuum, to remove excess solvent. The drying time used? of 3-150 hours, but also in this case temperature and duration can be optimised.

Characterization of hybrid materials

Numerous analyzes were carried out on the materials developed, initially with the aim of verifying the encapsulation of the filter molecules within the zeolite structure and subsequently to study the effectiveness and stability of the filter molecules. of materials in terms of absorption of UV radiation and the release of molecules in conditions other than those of storage.

For the first phase of characterization, Elemental Analysis (EA), Thermogravimetry (TGA), Infrared Spectroscopy (IR) and Powder X-Ray Diffraction (XRPD) were carried out. For the second part of characterization pi? application have used UV-Vis spectroscopy, solar spectrum irradiation test, permeability test? in vitro with Franz cell and release test in simulated sea water.

Elemental Analysis (EA)

Elemental analysis measures the weight percent of C (and other elements) in a sample, and ? the most instrument effective and rapid way to evaluate the organic UV filter content of the prepared material. However, ? necessary to verify with other experimental techniques if the quantity? of filter measured ? present or not within the zeolite structure. The numerous tests carried out made it possible to determine the maximum loading for all the systems analyzed (Table 1).

Thermogravimetric Analysis (TGA)

Thermogravimetric analyzes provide information on the weight variations of a sample subjected to heating between two established temperatures. These weight variations are linked to the loss of volatile substances (e.g. water, CO2, organic substances, ammonia, etc.) or to oxidation and/or recrystallisation reactions. Tendency to lose weight at temperature pi? high indicate interactions pi? strong between the volatile component responsible for this loss and the zeolite. The graphs usually show the TG curve, which shows the percentage weight loss at each temperature, and the DTG curve, which shows the derivative of the TG curve.

To verify the successful loading of the molecule inside the zeolites, TG analyzes were performed on the unloaded zeolites and on the zeolite/filter hybrids at different washing levels up to the optimized sample. Some examples of such graphs are shown in Figure 2a, b, c. Can you? note within each system that, at lower values of the l/s parameter, greater final weight losses correspond, indicating that poorly washed samples have a higher content of organic filter (i.e. the filter is present both in the porosity and on the surface ). Pi? in detail, you can? note that the samples with low l/s show more pronounced peaks in the DTG curve at low temperature, while samples with higher l/s show a more pronounced DTG curve? structured with peaks to pi? high temperature. Sometimes ? observable the appearance, in the samples at high l/s, of a DTG peak below 100 ?C, completely similar to the one observable in the original zeolite. Such a peak ? attributable to a small percentage of water re-absorbed by the zeolite, demonstrating the successful removal of the external organic molecules that sealed the structure. The shifting of the losses in weight at high temperature as the parameter l/s increases indicates more interactions? strong between the molecules and the zeolite framework in such samples. Such interactions more? strong are due to the fact that the organic filter molecules are found inside the cavities? zeolites.

This ? the main demonstration of the effective encapsulation of the filters within the zeolite structure.

Infrared Spectroscopy (IR)

Infrared spectroscopy (IR) analyzes the interaction of the material with a beam of infrared rays, allowing to study the vibrational structure of the molecules that compose it, with particular emphasis on the nature of the chemical bonds. Thereby ? for example it is possible to discriminate between two molecules having the same chemical composition but different configuration, as in the case of isomers.

Precisely for this purpose, studies have been carried out on some hybrid zeolite-filter materials which have shown the ability of these phases to inhibit the isomerization of AVO and OMC. Figure 3 shows the spectra of unencapsulated and MOR(silicate) encapsulated OMC before and during UV irradiation as an example. Can you? note that the two spectra of unencapsulated OMC are different due to isomerization of OMC during UV exposure. In contrast, the MOR(silicate)/OMC spectra show minimal differences in their vibrational spectra indicating the absence of the isomerization process.

The differences between the non-irradiated spectra of OMC and MOR(silicate)/OMC are instead due precisely to the encapsulation.

Powder X-Ray Diffraction (XRPD)

X-ray diffraction? the main technique for the structural characterization of crystalline materials as it allows the unique identification of a compound and the definition of its structure. In fact, while two identical chemical analyzes can actually? belong to two distinct crystalline materials, the diffraction pattern, if properly collected, uniquely identifies a material. The location and? Intensity? of the diffraction peaks depends in fact on the ordered position of the atoms in the material, or rather on its structure. In the case of zeolites, the position of the peaks uniquely identifies the zeolite topology, while the composition of the zeolite scaffold and the content of the channels/cages induce variations in intensity. of the diffraction peaks. In particular, ? it is known that in zeolites the low angle diffraction peaks have intensity? inversely proportional to the contents of the channels and cages.

This principle? been used in the characterization of our materials to further confirm the encapsulation of the filters inside the zeolites.

As an example, Figure 4 shows the diffraction spectra of the dehydrated LTL zeolite and the dehydrated LTL/OMC hybrid. Both samples were dehydrated to remove the contribution of H<2>O molecules that commonly occupy the cavities. free zeolites. ? possible to observe that in parity? of intensity? of the diffraction peaks at 15 ?2?, the first diffraction peak appears noticeably more? intense in the dehydrated LTL compared to the dehydrated LTL/OMC hybrid, indicating that in the second case the channels are occupied, precisely by OMC.

UV-Vis spectroscopy

UV-Vis spectroscopy studies the interaction between a material (fluid or solid) with ultraviolet and/or visible radiation. In particular, the sample is irradiated with a certain monochromatic radiation and the spectrum of the radiation diffused and/or transmitted by the sample is studied with respect to a standard. Working in transmission, the quantity? of radiation absorbed by a sample at a given wavelength (absorbance) ? proportional to the concentration of the analyte in the sample and to the thickness of the sample. The constant of proportionality? ? called extinction coefficient of the analyte, and ? dependent on its chemical surroundings. Spectra are usually collected in transmittance (%) relative to a reference, where 100% corresponds to a completely transparent material and 0% to a completely opaque material. In the case of our material, UV-Vis spectroscopy? necessary to verify the capacity? of the material in absorbing and dissipating UV radiation.

For the characterization of our material, UV-Vis spectroscopic analyzes were carried out in transmission on molecules such as in different solvents (ethanol, acetone, ethyl acetate) and in paraffin oil (Vaseline). Figure 5a, b show the spectra in vaseline of free sunscreens (5a) and encapsulated in zeolites (5b). From Figure 5a you can? Note that unencapsulated filter molecules exhibit a spectrum indicating total transparency in the wavelengths of visible radiation, with pronounced absorption in the UV-A (AVO) or UV-B (OMC) radiation range. By increasing the concentration of the filter in the vaseline, the transmittance in the UV field of the two filters goes to zero and the UV radiation? fully absorbed. Similarly, in Figure 5b it is noted that the transmittance of the hybrids ? zero in the respective ranges UV-A (hybrid with AVO) and UV-B (hybrid with OMC). As regards the range of visible radiation (400-700 nm), in the filters encapsulated in FAU the transmittance drops uniformly as the wavelength decreases, while MOR (silicate) shows some absorption peaks in the visible, responsible for the variable color between the pink and brown of the samples loaded with OMC. FAU(silicate) and LTL instead have a very high transmittance and almost? constant throughout the field of visible radiation and a sharp drop in transmittance in the UV. Hybrids made with LTL and FAU (silicate) show an absorption profile very similar to that of non-encapsulated filters and are therefore the best. In fact, very low transmittance profiles in the visible (as in MOR(silicate) and FAU) are reflected in a very opaque and therefore not very usable aspect in cosmetic products. The transparency in the visible can? be partly optimized by adjusting the grain size of the material.

Figure 6a, b instead show a comparison of the absorption spectra of pure filters and hybrids in vaseline with a content of 1% OMC (a) and AVO (b) in the measured sample. At parity? concentration filter in the measured sample, you can? note that the hybrid LTL/filter show a pi? high transmittance in the visible compared to the FAU hybrids and a lower transmittance (and therefore greater absorption) in the UV both compared to the FAU hybrids and the non-encapsulated filter.

? therefore demonstrated that the hybrids LTL are much more? effective in terms of UV absorption compared to non-encapsulated filters and to obtain the same UV protection ne? therefore necessary a quantity? minor.

In general, however, the encapsulation of the filters in the zeolites does not affect their effectiveness, on the contrary it improves it for all the systems explored.

Irradiance Test in Solar Simulator The hybrid materials were subjected to simulated solar irradiation to verify their stability. For this purpose, the hybrid powders and, for comparison purposes, the free sunscreens (not encapsulated and dispersed in vaseline) were irradiated in a first test for 130 minutes at 500 W/m<2 > and in a second test for 4 hours at 750 W/m<2 > (lamp power settable by instrument, ATLAS Suntest CPS/CPS+).

Following the irradiation, the powders were dispersed in vaseline and ? a UV-Vis spectrum was acquired to verify any variations with respect to non-irradiated hybrids. Figure 7a,b,c,d,e,f shows the irradiated and non-irradiated spectra of the non-encapsulated filters (a,b), of the LTL hybrids (c,d) and FAU (e,f). Can you? note that, considered a variability? experimental of 10% on the transmittance (due to minimal differences in the thickness of the samples), both the encapsulated and free filters do not show substantial differences before and after irradiation. Does this confirm the stability? of encapsulated filters under irradiation.

Further studies will be necessary for the behavior of both encapsulated and free OMC-AVO mixtures under irradiation. In these conditions the stability? of encapsulated filters? significantly increased compared to that of the free filters since the filter-filter interaction is missing, which is it ? proven to be a major source of instability.

In Vitro Permeation Test (PT)

In vitro permeation tests were performed using vertically static diffusing Franz cells (Figure 8). Franz's cell? consists of a donor compartment (CD) and a recipient compartment (CR) separated by a membrane. The capacity? of the target molecules placed in the CD to permeate the membrane is evaluated on the basis of the quantity? of molecules detected in the CR. Should you use pigskin as a biological membrane? It is also possible to study the accumulation and distribution of target molecules within the different layers of the skin.

Determination of permeability? against WTO and OVO

On the CD ? was placed an aqueous suspension of UV filter, encapsulated or not, in two successive experiments, while the receiving phase in the CR ? consists of a phosphate buffered saline containing sodium dodecyl sulfate (SDS) as a solubilizing agent. The receiving stage? taken at regular time intervals and replaced with a fresh receiving phase. The receiving phase samples were subjected to HPLC analysis to quantitatively determine the solar filter content in the receiving phase itself. In our studies, two tests with Franz cell were performed, the first using pig skin as a biological membrane and a second using a synthetic cellulose membrane.

Permeation test results for encapsulated and unencapsulated AVO.

- Using pig skin as membrane, for suspensions of: i) unencapsulated AVO, ii) encapsulated in LTL and iii) encapsulated in FAU, yes? observed AVO in the recipient phase. For MOR(silicate)/AVO hybrids, yes? instead observed a minimum quantity? of AVO in the receiving compartment, up to a maximum of 0.49 ?g/cm<2 >after 26 hours (Figure 9).

- In tests with synthetic membranes, for: i) OVO encapsulated in LTL and ii) OVO encapsulated in MOR(silicate) yes? observed AVO in the recipient phase, indicating that the filter molecules are not released from the zeolite.

Permeation test results for encapsulated and non-encapsulated OMC

Using pigskin as membrane, for suspensions of i) OMC not encapsulated, ii) encapsulated in FAU (silicate), iii) encapsulated in FAU, iv) encapsulated in LTL, yes? observed WTO in the receiving sector. For OMC/MOR(silicate) hybrids, yes? instead observed a minimum quantity? of OMC in the VR, up to a maximum of 0.07 ?g/cm<2 >after 26 hours (Figure 10).

- In tests with synthetic membrane, the quantity? of WTO issued by MOR(silicate) ? minimal, reaching 0.04% of the original filter after 26 hours (Figure 11). The quantity? of WTO issued by LTL ? even less, reaching only 0.03% of the original filter after 26 hours (Figure 12).

Determination of OMC and OVO content in pig skin

The quantity of solar filters present in pig skin? been determined at the end of the permeation test. After superficial cleansing of the skin to remove the adhered donor and recipient phases, the skin is cleansed. been dried and the stratum corneum (SC) ? been separated from epidermis and dermis (E+D) by suitable methods. In a first test, SC and E+D were subsequently subjected to solvent extraction (methanol for AVO and isopropanol for OMC). In a second test, conducted only on LTL hybrids, epidermis (E) and dermis (D) were then separated by thermal shock, minced separately and extracted with solvents, as indicated in the previous test.

All extractions were performed using a sonicator at 40°C for 15 minutes and repeated three times.

The quantity of OMC and OVO present in the extracts? was determined by HPLC analysis, using calibration lines obtained from standard solutions of sunscreens.

OVO content in pork skin

- First test. The data are reported in Table 2 and show that the observed values of OVO are very low, with a maximum of 13.06 ?g/cm<2 >accumulated in the SC and of 7.62 ?g/cm<2 >in ED+D.

- Second test. The content of OVO, deriving from LTL/AVO, in the skin layers? minimum, in particular 16.26 ?g/cm<2 >(SC), 11.02 ?g/cm<2 >(E), 0.06 ?g/cm<2 >(D).

OMC content in pig skin

- First test. The data are reported in Table 3 and show that the OMC values observed are very low, with a maximum of 33.12 ?g/cm<2 >in the SC and of 20.15 ?g/cm<2 >in ED+D.

- Second test. The content of OMC, deriving from LTL/OMC, in the layers of the skin ? minimum, in particular 2.34 ?g/cm<2 >(SC), 0.91 ?g/cm<2 >(E), 0.02 ?g/cm<2 >(D).

All the above data on permeation and accumulation of sunscreens in the receiving phase and in the layers of the skin are completely in line with those found in the literature.

Furthermore, the results obtained could be further improved by optimizing the grain size of the material.

Release test in sea water

Simulated seawater release tests were performed with a home-made experimental setup (Figure 13). The water with a marine composition? been formulated at 38? using sea salt for aquariums (Kent, Reef Salt Mix). The hybrids were dispersed in simulated seawater at a constant solid-to-liquid ratio in Falcon tubes. The test tubes were then inserted into a darkened container and placed in a water bath thermostated at 19°C. At known time intervals yes ? separate by centrifugation the sea water from the hybrid and ? The filter content in the water was quantified by UV spectroscopy on liquid, after extraction of sea water in ethyl acetate. To the dust ? fresh sea water was subsequently added and the process repeated.

The measurements carried out show very limited release trends from all hybrid materials in sea water, which after about 150 hours of testing show a release of less than 4% in the case of OMC and 1% in the case of AVO. The release graphs are shown in Figures 14a (OMC) and 14b (AVO). Can you? note that some samples show a rapid initial release that can? be due to the removal of some residual molecules outside the zeolitic grains, while following the release ? very minor.

Examples of preparation

Example 1 LTL-WTO

The LTL zeolite dehydrated at a suitable temperature and time is put in contact with a quantity of octinoxate in zeolite/filter ratios from 1:5 to 300:1, preferably between 1:1 and 100:1, in the most preferable between 4:1 to 10:1. The mixture is brought to a temperature comprised between 15 and 150°C, preferably between 25 and 120°C, for a time comprised between 1 and 360 hours, preferably between 6 and 72 hours. The mixture is subsequently cooled and subjected to washing in acetone until obtaining a composition suitable for not having the presence of a filter outside the zeolitic structure. The solvent/zeolite ratio [l/g] necessary to optimize the sample varies between 0 and 10, preferably between 0.1 and 2. The sample is then dried in an oven at a temperature between 30 and 100?C, preferably between 40 and 70 ?C, for a time ranging from 3 to 150 hours. The final sample contains between 0.5% and 40% by weight of carbon, preferably between 2.5% and 6%.

Example 2 LTL AVO

The LTL zeolite dehydrated at a suitable temperature and time is put in contact with a quantity of avobenzone in a zeolite/filter ratio from 1:5 to 300:1, preferably between 1:1 and 100:1, in the most preferable between 4:1 and 15:1. The mixture is brought to a temperature comprised between 15 and 150°C, preferably between 70 and 120°C, for a time comprised between 1 and 360 hours, preferably between 6 and 72 hours. The mixture is subsequently cooled and subjected to washing in acetone until obtaining a composition suitable for not having the presence of a filter outside the zeolitic structure. The solvent/zeolite ratio [l/g] necessary to optimize the sample varies between 0 and 10, preferably between 0 and 1. The sample is then dried in an oven at a temperature between 30 and 100?C, preferably between 40 and 70 ?C, for a time ranging from 3 to 150 hours. The final sample contains between 0.5% and 30% by weight of carbon, preferably between 3.5% and 6.5%.

Example 3 FAU-WTO

The FAU zeolite dehydrated at a suitable temperature and time is put in contact with a quantity of octinoxate in a zeolite/filter ratio from 1:2 to 1000:1, preferably between 1:1 and 500:1, in the most preferable between 3:1 and 20:1. The mixture is brought to a temperature comprised between 15 and 150°C, preferably between 25 and 120°C for a time comprised between 1 and 360 hours, preferably between 6 and 72 hours. The mixture is subsequently cooled and subjected to washing in acetone until obtaining a composition suitable for not having the presence of a filter outside the zeolitic structure. The solvent/mixture ratio [l/g] necessary to optimize the sample varies between 0 and 5, in particular between 0.1 and 1. The sample is then dried in an oven at a temperature between 30 and 100?C, preferably between 40 and 70 ?C, for a time from 3 to 150 hours. The final sample contains between 0.5% and 40% by weight of carbon, preferably between 4% and 15%.

Example 4 FAU-AVO

The FAU zeolite dehydrated at a suitable temperature and time is put in contact with a quantity of avobenzone in a zeolite/filter ratio from 1:2 to 1000:1, preferably between 1:1 and 500:1, in the most preferable between 3:1 and 20:1. The mixture is brought to a temperature comprised between 15 and 150°C, preferably between 70 and 120°C for a time comprised between 1 and 360 hours, preferably between 6 and 72 hours. The mixture is subsequently cooled and subjected to washing in acetone until obtaining a composition suitable for not having the presence of a filter outside the zeolitic structure. The solvent/mixture ratio [l/g] necessary to optimize the sample varies between 0 and 5, preferably between 0 and 1. The sample is then dried in an oven at a temperature between 30 and 100?C, preferably between 40 and 70 ?C, for a time ranging from 3 to 150 hours. The final sample contains between 0.5% and 40% by weight of carbon, preferably between 3% and 15%.

Example 5 MOR(silicate)-OMC

The MOR (silicate) zeolite dehydrated at a suitable temperature and for a suitable time is put in contact with a quantity of octinoxate in a zeolite/filter ratio from 1:5 to 500:1, preferably between 1:4 and 200:1, in the most preferable between 3:1 and 20:1. The mixture is brought to a temperature comprised between 15 and 150°C, preferably between 25 and 120°C for a time comprised between 1 and 360 hours, preferably between 6 and 72 hours. The mixture is subsequently cooled and subjected to washing in acetone until obtaining a composition suitable for not having the presence of a filter outside the zeolitic structure. The solvent/mixture ratio [l/g] necessary to optimize the sample varies between 0 and 5, preferably between 0 and 2. The sample is then dried in an oven at a temperature between 30 and 100?C, preferably between 40 and 70 ?C, for a time ranging from 3 to 150 hours. The final sample contains between 0.5% and 30% by weight of carbon, preferably between 3% and 10%.

Example 6 MOR(silicate)-AVO

The MOR (silicate) zeolite dehydrated at a suitable temperature and time is put in contact with a quantity of avobenzone in a zeolite/filter ratio from 1:5 to 500:1, preferably between 1:4 and 200:1, in the most preferable between 3:1 and 20:1. The mixture is brought to a temperature comprised between 15 and 150°C, preferably between 70 and 120°C for a time comprised between 1 and 360 hours, preferably between 6 and 72 hours. The mixture is subsequently cooled and subjected to washing in acetone until obtaining a composition suitable for not having the presence of a filter outside the zeolitic structure. The solvent/mixture ratio [l/g] necessary to optimize the sample varies between 0 and 5, preferably between 0 and 1. The sample is then dried in an oven at a temperature between 30 and 100?C, preferably between 40 and 70 ?C, for a time ranging from 3 to 150 hours. The final sample contains between 0.5% and 30% by weight of carbon, preferably between 3.5% and 10%.

Example 7 FAU(silicate)-OMC

The zeolite FAU (silicate) dehydrated at a temperature and for a suitable time is put in contact with a quantity of octinoxate in a zeolite/filter ratio from 1:5 to 1000:1, preferably between 1:4 and 200:1, in the most preferable between 3:1 and 40:1. The mixture is brought to a temperature comprised between 15 and 150°C, preferably between 25 and 120°C for a time comprised between 1 and 360 hours, preferably between 6 and 72 hours. The mixture is subsequently cooled and subjected to washing in acetone until obtaining a composition suitable for not having the presence of a filter outside the zeolitic structure. The solvent/mixture ratio [l/g] necessary to optimize the sample varies between 0 and 5, preferably between 0.1 and 1. The sample is then dried in an oven at a temperature between 30 and 100?C, preferably between 40 and 70 ?C, for a time ranging from 3 to 150 hours. The final sample contains between 0.5% and 30% by weight of carbon, preferably between 5% and 20%.

Example 8 FAU(silicate)-AVO

The zeolite FAU (silicate) dehydrated at a temperature and for a suitable time is put in contact with a quantity of avobenzone in a zeolite/filter ratio from 1:5 to 1000:1, preferably between 1:3 and 100:1, in the most preferable between 3:1 and 40:1. The mixture is brought to a temperature comprised between 15 and 150°C, preferably between 70 and 120°C for a time comprised between 1 and 360 hours, preferably between 6 and 72 hours. The mixture is subsequently cooled and subjected to washing in acetone until obtaining a composition suitable for not having the presence of a filter outside the zeolitic structure. The solvent/mixture ratio [l/g] necessary to optimize the sample varies between 0 and 5, preferably between 0 and 1. The sample is then dried in an oven at a temperature between 30 and 100?C, preferably between 40 and 70 ?C, for a time ranging from 3 to 150 hours. The final sample contains between 0.5% and 30% by weight of carbon, preferably between 1% and 20%.

Example 9 ROM-WTO

The MOR zeolite dehydrated at a suitable temperature and time is put in contact with a quantity of octinoxate in a zeolite/filter ratio from 1:5 to 1000:1, preferably between 1:3 and 300:1, in the most preferable between 5:1 and 30:1. The mixture is brought to a temperature comprised between 15 and 150 ?C, preferably between 25 ?C and 120 ?C for a time comprised between 1 and 360 hours, preferably between 6 and 72 hours. The mixture is subsequently cooled and subjected to washing in acetone until obtaining a composition suitable for not having the presence of a filter outside the zeolitic structure. The solvent/mixture ratio [l/g] necessary to optimize the sample varies between 0 and 5, in particular between 0 and 2. The sample is then dried in an oven at a temperature between 30 and 100?C, preferably between 40 and 70 ?C, for a time from 3 to 150 hours. The final sample contains between 0.1% and 30% by weight of carbon, preferably between 3% and 10%.

Example 10 MOR-AVO

The MOR zeolite dehydrated at a suitable temperature and time is put in contact with a quantity of avobenzone in a zeolite/filter ratio from 1:5 to 1000:1, preferably between 1:4 and 300:1, in the most preferable between 5:1 and 30:1. The mixture is brought to a temperature comprised between 15 and 150°C, preferably between 70°C and 120°C for a time comprised between 1 and 360 hours, preferably between 6 and 72 hours. The mixture is subsequently cooled and subjected to washing in acetone until obtaining a composition suitable for not having the presence of a filter outside the zeolitic structure. The solvent/mixture ratio [l/g] necessary to optimize the sample varies between 0 and 5, preferably between 0 and 2. The sample is then dried in an oven at a temperature between 30 and 100?C, preferably between 40 and 70 ?C, for a time ranging from 3 to 150 hours. The final sample contains between 0.1% and 30% by weight of carbon, preferably between 3% and 15%.

Example 11 MFI(silicate)-OMC

The MFI (silicate) zeolite dehydrated at a suitable temperature and time is put in contact with a quantity of octinoxate in a zeolite/filter ratio from 1:5 to 1000:1, preferably between 1:3 and 400:1, in the most preferable between 3:1 and 40:1. The mixture is brought to a temperature comprised between 15 and 150°C, preferably between 25°C and 120°C, for a time comprised between 1 and 360 hours, preferably between 6 and 72 hours. The mixture is subsequently cooled and subjected to washing in acetone until obtaining a composition suitable for not having the presence of a filter outside the zeolitic structure. The solvent/mixture ratio [l/g] necessary to optimize the sample varies between 0 and 5, preferably between 0 and 2. The sample is then dried in an oven at a temperature between 30 and 100?C, preferably between 40 and 70 ?C, for a time ranging from 3 to 150 hours. The final sample contains between 0.1% and 40% by weight of carbon, preferably between 1.5% and 20%.

Example 12 MFI(silicate)-AVO

The MFI (silicate) zeolite dehydrated at a suitable temperature and time is put in contact with a quantity of avobenzone in a zeolite/filter ratio from 1:5 to 1000:1, preferably between 1:4 and 400:1, in the most preferable between 3:1 and 40:1. The mixture is brought to a temperature comprised between 15 and 150°C, preferably between 70°C and 120°C for a time comprised between 1 and 360 hours, preferably between 6 and 72 hours. The mixture is subsequently cooled and subjected to washing in acetone until obtaining a composition suitable for not having the presence of a filter outside the zeolitic structure. The solvent/mixture ratio [l/g] necessary to optimize the sample varies between 0 and 5, preferably between 0 and 2. The sample is then dried in an oven at a temperature between 30 and 100?C for a time from 3 to 150 hours. The final sample contains between 0.1% and 40% by weight of carbon, preferably between 2% and 20%.

Example 13 MFI-WTO

The MFI zeolite dehydrated at a suitable temperature and time is put in contact with a quantity of octinoxate in a zeolite/filter ratio from 1:5 to 1000:1, preferably between 1:3 and 400:1, in the most preferable between 3:1 and 40:1. The mixture is brought to a temperature comprised between 15 and 150°C, preferably between 25°C and 120°C, for a time comprised between 1 and 360 hours, preferably between 6 and 72 hours. The mixture is subsequently cooled and subjected to washing in acetone until obtaining a composition suitable for not having the presence of a filter outside the zeolitic structure. The solvent/mixture ratio [l/g] necessary to optimize the sample varies between 0 and 5, preferably between 0 and 2. The sample is then dried in an oven at a temperature between 30 and 100?C, preferably between 40 and 70 ?C, for a time ranging from 3 to 150 hours. The final sample contains between 0.1% and 40% by weight of carbon, preferably between 1.5% and 15%.

Example 14 MFI-AVO

The MFI zeolite dehydrated at a suitable temperature and time is put in contact with a quantity of avobenzone in a zeolite/filter ratio from 1:5 to 1000:1, preferably between 1:4 and 400:1, in the most preferable between 3:1 and 40:1. The mixture is brought to a temperature comprised between 15 and 150°C, preferably between 70°C and 120°C for a time comprised between 1 and 360 hours, preferably between 6 and 72 hours. The mixture is subsequently cooled and subjected to washing in acetone until obtaining a composition suitable for not having the presence of a filter outside the zeolitic structure. The solvent/mixture ratio [l/g] necessary to optimize the sample varies between 0 and 5, preferably between 0 and 2. The sample is then dried in an oven at a temperature between 30 and 100?C for a time from 3 to 150 hours. The final sample contains between 0.1% and 40% by weight of carbon, preferably between 2% and 20%.

Example 15 cosmetic formulation with FAU-OMC hybrid

The FAU-OMC hybrid is prepared as in example 3 and selected with a suitable grain size, for example between 0.5 and 10 micrometres. An oil-in-water emulsion is prepared with standard technique using: oil:hydrophilic surfactant:lipophilic surfactant:water = 20:3:2:75. The oil can possibly be petroleum jelly. Hybrid and emulsion are mixed in a ratio of 1:99 to 40:60, for example 20:80. The compound is homogenized with an appropriate method and for an appropriate time. A suitable thickener is added to the compound in a quantity suitable with a suitable method, for example with a thickener:compound ratio of 2:98. Further additives can be added to improve the properties? of the formulation. What is the formulation? obtained ? rheologically stable.

Example 16 cosmetic formulation with FAU-AVO hybrid

The FAU-AVO hybrid is prepared as in example 4, and selected with a suitable grain size, for example between 0.5 and 10 micrometres. An oil-in-water emulsion is prepared with standard technique using: oil:hydrophilic surfactant:lipophilic surfactant:water = 20:3:2:75. The oil can possibly be petroleum jelly. Hybrid and emulsion are mixed in a ratio of 1:99 to 40:60, for example 20:80. The compound is homogenized with an appropriate method and for an appropriate time. A suitable thickener is added to the compound in a quantity suitable with a suitable method, for example with a thickener:compound ratio of 2:98. Further additives can be added to improve the properties? of the formulation. What is the formulation? obtained ? rheologically stable.

Example 17 cosmetic formulation with LTL-OMC hybrid

The LTL-OMC hybrid is prepared as in example 1, and selected with a suitable grain size, for example between 0.5 and 10 micrometres. An oil-in-water emulsion is prepared with standard technique using: oil:hydrophilic surfactant:lipophilic surfactant:water = 20:3:2:75. The oil can possibly be petroleum jelly. Hybrid and emulsion are mixed in a ratio of 1:99 to 40:60, for example 20:80. The compound is homogenized with an appropriate method and for an appropriate time. A suitable thickener is added to the compound in a quantity suitable with a suitable method, for example with a thickener:compound ratio of 3:97. Further additives can be added to improve the properties? of the formulation. What is the formulation? obtained ? rheologically stable.

Example 18 cosmetic formulation with LTL-AVO hybrid

The LTL-AVO hybrid is prepared as in example 2, and selected with a suitable grain size, for example between 0.5 and 10 micrometres. An oil-in-water emulsion is prepared by standard technique, for example using oil:hydrophilic surfactant:lipophilic surfactant:water = 20:3:2:75. The oil can possibly be petroleum jelly. Hybrid and emulsion are mixed in a ratio of 1:99 to 40:60, for example 20:80. The compound is homogenized with an appropriate method and for an appropriate time. A suitable thickener is added to the compound in a quantity suitable with a suitable method, for example with a thickener:compound ratio of 3:97. Further additives can be added to improve the properties? of the formulation. What is the formulation? obtained ? rheologically stable.

Some preferred embodiments of the present invention have been illustrated and described above: obviously, numerous variants and modifications, functionally equivalent to the previous ones, which fall within the scope of protection of the invention as highlighted in the attached claims, will obviously be immediately apparent to those skilled in the art.

Claims (17)

1. Broad-spectrum light-absorbing material consisting of an inorganic-organic hybrid consisting of inorganic particles, with a microporous structure, having a diameter between 0.01 and 300 micrometers and hosting, in the porosity, organic molecules and possibly cations and/or H<2> molecules OR. 2. Material according to claim 1, wherein the microporous particles are zeolites having crystalline structures presenting channels, within which and/or in portions of the structure distant from the channels alkaline and/or alkaline-earth metal cations are present and/ or transition metals and/or H<2>O molecules, organic molecules, possibly different, being encapsulated inside the channels, capable of absorbing UV radiation and dissipating its energy. 3. Material according to claim 2, wherein the channels are delimited by rings from 6 to 14, preferably of 10 or 12 tetrahedra TO4, T being constituted by tetravalent and/or trivalent cations, preferably by Si and Al or by Al and Co , P, B, Fe, Ga, Ge, Be, or any combination of the above. 4. Material according to claim 2 or 3, wherein said channels have an average free diameter between 3 and 30 ?ngstr?m, in particular between 4 and 12 ?ngstr?m. 5. Material according to claim 2, 3 or 4, wherein the molar ratio tetrahedral tetravalent cations/tetrahedral trivalent cations, in particular Si/Al, varies between 1 and ?, in particular between 3 and 900, being ? corresponding to materials with only tetravalent cations in tetrahedral position. The material according to claim 2, wherein, relative to the weight of the material, the components are present in the following concentrations: - zeolite (including the zeolite scaffold and all alkaline, alkaline-earth or transition extra-scaffold cations), from 99.5% to 20%; in particular from 99.5% to 70%; - water, from 0% to 30%; in particular from 0% to 20%; - organic molecules, from 0.5% to 80%; in particular from 0.5% to 30%. 7. Material according to claim 2 or 3, wherein the zeolite has a crystalline structure with LTL, MOR, FAU or MFI topology and the phases encapsulated within the porosities? are they sunscreens (i.e. chemical filters for UV radiation), of the octyl methoxycinnamate type? octinoxate, OMC and avobenzone, AVO or a mixture thereof, the metal cations of the zeolites used being K<+ >and/or Na<+ >and/or Ca<++ >and/or H<+> cations. 8. Material according to claim 7, wherein the hybrids result from the encapsulation of OMC and AVO in the zeolite LTL, LTL-OMC and LTL-AVO, or from the encapsulation of OMC and AVO in the zeolite FAU, FAU-OMC and FAU- AVO, or from the encapsulation of OMC and AVO in the zeolite FAU(silicate), FAU(silicate)-OMC and FAU(silicate)-AVO, or from the encapsulation of OMC and AVO in the zeolite MOR, MOR-OMC and MOR-AVO , or from the encapsulation of OMC and AVO in the MOR(silicate), MOR(silicate)-OMC and MOR(silicate)-AVO zeolite, or from the encapsulation of OMC and AVO in the MFI, MFI-OMC and MFI-AVO zeolite, or from the encapsulation of OMC and AVO in the MFI(silicate), MFI(silicate)-OMC and MFI(silicate)-AVO zeolite. 9. Use of the broad-spectrum light-absorbing material according to any one of the preceding claims in cosmetics as a UV filter in products such as: sunscreen products, self-tanning products, creams, emulsions, lotions, gels and oils for the skin, beauty masks, foundation, what? liquids, pastes, face powders, talcum powder for after-bath and body hygiene, beauty soaps, deodorant soaps, perfumes, toilet waters and colognes, preparations for baths and showers, i.e. salts, foams, oils, gels, depilatories, deodorants and antiperspirants, hair dyes, products for waving, straightening and fixing, styling products, hair cleaning products, i.e. lotions, powders, shampoos, products to keep the hair in shape, that is? lotions, creams, oils, hair styling products, that is? lotions, lacquers, brilliantines, shaving products, that is? creams, foams, lotions, preparations for make-up and removing make-up, preparations intended to be applied to the lips, preparations for dental and oral hygiene, preparations for nail care and nail lacquers, hygiene preparations outer skin, and skin lightening and anti-wrinkle products, decorative cosmetic products such as primers, foundations, face powders, concealers, tinted moisturizers, mineral makeup, highlighters and bronzers, pigments, mascara, permanent makeup such as tattoo inks, dyes cosmetics. 10. Use of the broad-spectrum photo-absorbent material according to any one of the preceding claims from 1 to 8, as an additive for the preparation of pigments and plastics for various purposes where resistance to solar or artificial or UV radiation is required, or for the purpose of protection from solar or artificial or UV radiation, in particular: plastic ophthalmic lenses, contact lenses, pharmaceutical and veterinary products, hygiene products for medical purposes, poultices, material for dressings, materials for filling teeth and for dental impressions, disinfectants, products for the prevention of burns on plants and fruits, disinfestants, pesticides, UV protection films, curtains, umbrellas and shading covers, windbreak fabrics and panels, synthetic fabrics and privacy screen panels, plastic additives, and in particular stabilizers for the protection against damage from light and UV radiation, plastic material trays, plastics for packaging, general containers, food containers, containers for food liquids, containers for liquids, bottles for drinks, bottles for personal hygiene and household cleaning products, bottles for shampoo bottles for shower gel, containers for detergents, trays for taking away food, food packaging, expanded polystyrene for packaging and the like, nylon bags, plastic film, plastic for building, thermal insulation, sound-absorbing panels, rubber products, ropes, strings, nets, tents, tarpaulins, sails, sacks, padding material, textile fibers, threads for textile use, adhesives, i.e. adhesive materials for stationery or for domestic use, artificial resins in the raw state, insulating paints and varnishes, adhesives, cio? adhesives for industry and building, insulating, sealing and waterproofing preparations, bleaching preparations and other substances for laundry, cleaning, polishing, scouring and abrasive preparations, soaps, perfumery, essential oils, additives for materials, including non-plastic ones, such as clothing fabrics, paper and cardboard for printing, printed matter, bookbinding items, photographs, stationery, materials for artists, brushes, paper and cardboard for packaging, additives for typographical pigments and natural resins at the same raw state, metals in foil and powder for painters, decorators, printers and artists, paints, varnishes, lacquers, preservatives against rust and wood deterioration, dyeing materials, mordants, colours, varnishes and lacquers for industry , crafts and art, dyes for dyeing clothing, dyes for food and beverages, dyes for laundry and bleaching, boxes of paint, that is? school supplies. 11. Use of the broad-spectrum light-absorbing material according to any one of the preceding claims from 1 to 8, within products aimed at protecting against UV exposure, such as paints and dyes, fabrics or optical lenses or materials which need protection from solar radiation , in particular: ophthalmic lenses in vitreous material, glass for window frames, glass for laminated window frames, self-cleaning glass, thermal glass, solar control glass, anti-noise glass, double or triple glazing, tempered or tempered glass, laminated or laminated glass, armored glass , insulating glass, structural glass, shielding glass, glass for UV protection, glass for solar protection of spaces or substances, colored glass for containers, optical glass, special glass, building glass, that is? slabs, glass tiles, granulated glass for road signs, bricks and ceramic products for building, ceramic tools and advanced ceramic materials, for medical use, porcelains, semi-finished woods, veneered woods, arelle, metal construction materials, metal materials for railways, non-electric cables and metal wires, ironmongery and small metal hardware, metal pipes, safes, optical, photographic, cinematographic materials and instruments, materials for electronics and their covers/protections, apparatus for recording, transmission, reproduction of sound or images, magnetic data carriers, recording discs. 12. Process for the production of the light-absorbing material according to any one of the preceding claims from 1 to 8, the process comprising the following steps: - dehydration of the zeolite, i.e. pretreatment; - zeolite loading; - washing of the hybrid; - drying of the hybrid. 13. Process according to claim 12, wherein one or more of the previous phases, other than the phase of loading the zeolite, if the material obtained with or without it/s ? the same. 14. Process according to claim 12, wherein the zeolite dehydration step for silicate zeolites, if carried out, takes place under vacuum by degassing the powder for a certain amount of time, while for cationic zeolites it takes place via a heat treatment at temperatures between 100 and 350 ?C for a time equal to 1-3 hours in general, the zeolite cos? dehydrated being ready for subsequent loading. 15. Process according to claim 12 or 14, wherein the step of loading the zeolite takes place by mixing the dehydrated zeolite with pure OMC, which at room temperature? in the liquid state, or pure AVO than at room temperature? solid, or with a mixture of the two, the loading taking place for times varying between 1-48 h up to a week, the loading temperature being between 15 and 150 ?C, the heat treatment at 70-100 ?C being indispensable in case of loading with AVO, since? ? it is necessary to melt the avobenzone to facilitate its loading, as a synthesis via melt. 16. Process according to claim 12, 14 or 15, wherein, in the washing step of the hybrid, in the case of loading with an excess of organic filter, it is necessary to remove the excess, i.e. of the organic molecules which may possibly be found on the external surface of the zeolitic grains and in the intergranular space, the washing of the sample being carried out by solvent extraction, in particular by means of a Soxhlet extractor with acetone, or alternatively with ultrasound-assisted extraction in acetone. 17. Process according to any one of claims 12 to 16, wherein the drying step of the hybrid takes place at 30-100°C, in particular at 40-60°C, alternatively at ambient pressure or under vacuum, for the removal of excess solvent, with a drying time of 3-150 hours, in particular for a drying time of 12-72 hours.