UV-resistant coating

Abstract

A filter film comprising compounds absorbing UV light in the 300 nm to 380 nm range and a binder, in which the weighted average absorbance A_380 is greater than 2, and packaging comprising a substrate that is partially or totally covered with the filter film or formed from the filter film. Also, methods for protecting consumer goods against UV light, the consumer goods being enclosed by the filter film. Abstract figure: Fig. 1

Description

Title of the invention: UV-resistant coating DOMAIN

[0001] This disclosure relates to the field of UV protection, in particular for food products, cosmetic formulations, and perfumes. BACKGROUND

[0002] It is well known that UV light can have deleterious effects on various commercial products, such as food products, cosmetic formulations and perfumes.

[0003] For example, UV light can affect the flavor of food products. In the wine and beer industries, it has been known for centuries that light, particularly sunlight, can impair the flavor of many types of beer and wine. The flavor resulting from light exposure is commonly referred to as lightstruck flavor, and this odor is particularly unpleasant for most consumers.

[0004] Moreover, many different odoriferous compounds are used in cosmetic products and perfumes. Among these, aldehydes represent a large family of compounds, including vanillin, phenylacetaldehyde, heliotropin, ionone, citronellal, or methylnonylacetaldehyde; and their derivatives.

[0005] Currently, UV stabilizers are added to cosmetics and perfumes, in particular avobenzone which is widely used despite the alleged hazardous effects of its degradation products on human health, marine life and the environment.

[0006] It is also noted that major UV stabilizers have been developed for the plastics industry, in which degradation mechanisms are simply associated with the formation of free radicals. This mechanism is, however, less relevant for protection against aldehyde derivatives.

[0007] Acetaldehydes share a common characteristic in terms of their interaction with UV light: they can absorb a UV photon to promote an electron from an n-state of the bonded carbonyl oxygen to an n*-unbonded state of the bonded carbonyl, thereby reducing the energy of the bonded carbonyl and enabling a reaction of the aldehyde functional group, for example, oxidation or the formation of a lactone or acetal. The typical energy involved in such an electronic transition corresponds to UV light in the range of 280 nm to 290 nm. This UV light range is not found naturally in sunlight, as it is filtered by the atmosphere. Nevertheless, the aldehydes in question often exhibit a conjugated structure: Unsaturations, whether ethylenic or aromatic, lead to a reduction in the energy required for the transition of electrons from the n-state to the n*-state, and UV light in the 300 nm to 340 nm range thus becomes a source of degradation. This UV light range is present in natural sunlight, but in small quantities.

[0008] Glass absorbs some UV light in the 300 nm to 340 nm range. Absorption efficiency is directly correlated with glass thickness. A current industry trend is to reduce packaging weight, leading to a reduction in glass thickness for glass containers. Therefore, the absorption properties of glass must be compensated for by additional filtering.

[0009] There is therefore a need for a light-filtering material, such as a suitable filter film for application to glass containers, enabling effective filtering of UV light in the wavelength range of approximately 300 to 340 nm while maintaining a very low color. Such an achromatic filter allows the use of clear glass containers without any risk of product degradation. Clear glass containers offer a better presentation of the liquid inside and are better suited to high-end markets. Such filters also allow for a reduction in the thickness and therefore the weight of glass containers.

[0010] The applicant has found that these needs can be met with filter films having a specific weighted average absorbance defined in relation to solar spectral irradiance ES(A) and a sensitivity function S(A) of aldehydes and other delicate organic molecules. SUMMARY

[0011] The present disclosure relates to a filter film comprising compounds absorbing UV light in a range of 300 nm to 380 nm and a binder, in which the weighted average absorbance A3gQ of the filter film is greater than 2, with A3gQ defined by the following relationship: [° 012 L _ ^ 38 ° ~ / 300 W ^ dA

[0013] where A(2) represents the absorbance of the filter film at a given wavelength, and W( A) represents a weighting function equal to the product of the solar spectral irradiance E s ( A ) and a sensitivity function S ( A ) defined as a Gaussian function with a peak centered at 300 nm and a standard deviation of 24 nm.

[0014] In one embodiment, the filter film is transparent, preferably transparent and colorless.

[0015] In one embodiment, the weighted average absorbance A3gg is greater than 2.5, preferably greater than 3.

[0016] In one embodiment, the weighted average absorbance A340 of the filter film is greater than 2, preferably greater than 2.5, with A34q defined by the following relation:

[0017] ^340 -

[0018] In one embodiment, the UV light-absorbing compounds comprise semiconductor nanoparticles having the following formula

[0019] MxEy (I),

[0020] in which:

[0021] M is chosen from the group consisting of Zn, Cd, Hg, Cu, Ag, Al, Ga, In, Si, Ge, Sn, Pb or a mixture of these;

[0022] E is chosen from the group consisting of O, S, Se, Te, N, P, As, Sb, or a mixture of these;

[0023] x and y are independently a decimal number from 0 to 5; and

[0024] x and y are not simultaneously equal to 0.

[0025] In one embodiment, the UV light-absorbing compounds include semiconductor nanoparticles having a maximum local absorbance of longer wavelength in the range of 320 nm to 360 nm, preferably from 320 nm to 350 nm, more preferably from 320 nm to 340 nm.

[0026] In one embodiment, the UV light-absorbing compounds include semiconductor nanoparticles having a maximum local absorbance at longer wavelengths in the range of 350 nm to 400 nm, preferably from 350 nm to 380 nm.

[0027] In one embodiment, the semiconductor nanoparticles are nanospheres, nanoplates or nanorods.

[0028] In one embodiment, the semiconductor nanoparticles are homostructures.

[0029] In one embodiment, the semiconductor nanoparticles are heterostructures, preferably core / shell semiconductor nanoparticles, the core being of a different material than the shell.

[0030] In one embodiment, the semiconductor nanoparticles are coated with an organic layer, an inorganic layer or a mixture thereof, and / or encapsulated in an encapsulation material.

[0031] In one embodiment, the content of semiconductor nanoparticles in the filter film is in a range of 0.5% by weight to 15% by weight, based on the weight of the filter film, for a film with a thickness of 10 pm.

[0032] In one embodiment, the UV light-absorbing compounds include organic anti-UV compounds, preferably selected from the group consisting of benzotriazoles, triazines, piperidines, benzophenones, catechol, their derivatives and mixtures thereof.

[0033] In one embodiment, the content of organic anti-UV compounds in the filter film is in a range of 2% by weight to 15% by weight, based on the weight of the filter film, for a film with a thickness of 10 pm.

[0034] In one embodiment, the content of UV light-absorbing compounds in the filter film is in a range of 3% by weight to 15% by weight, based on the weight of the filter film, for a film with a thickness of 10 pm.

[0035] In one embodiment, the UV light-absorbing compounds do not comprise more than 2.5% by weight, based on the total weight of the filter film, for a film with a thickness of 10 pm, of core-shell semiconductor nanoparticles comprising: • a core of ZnSexS(i_x) material where x is in a range from 0.60 to 0.98, and • a ZnS material shell, and exhibiting a maximum local absorbance at the longest wavelength in the range of 350 to 500 nm.

[0036] More preferably, the UV light-absorbing compounds do not comprise core-shell semiconductor nanoparticles comprising: • a core of ZnSexS(i_x) material where x is in a range from 0.60 to 0.98, and • a ZnS material shell, and exhibiting a maximum local absorbance at the longest wavelength in the range of 350 to 500 nm.

[0037] In one embodiment, the thickness of the filter film is in a range of 2 pm to 100 pm, preferably from 5 pm to 25 pm.

[0038] This disclosure also relates to packaging comprising a substrate partially or totally covered with a filter film as disclosed above; or packaging formed from a filter film as disclosed above.

[0039] This disclosure also relates to the use of a filter film as disclosed above as protection against UV light in a range of 300 nm to 340 nm, in particular for a glass container filled with a food product, a cosmetic formulation or a perfume.

[0040] This disclosure also relates to a method for protecting a consumer good against UV light in a range of 300 nm to 340 nm, comprising The enclosure of the consumer good in a filter film as disclosed above. The consumer good may be selected from food products, in solid or liquid form, cosmetic formulations, or perfumes. Said filter film may cover packaging in which the consumer good is contained. Brief description of the drawings

[0041] [Fig.1] illustrates various nanoparticles with a homostructure (A) or heterostructures: spherical core / shell (B), spherical core / shell / shell (C), plate point (D), nanoplate core / shell (E) and nanoplate core / crown (F).

[0042] [Fig. 2] shows absorbance curves as a function of wavelength for 7 different odorant molecules commonly used in perfumes (labeled SI to S7) without UV stabilizers. The curve of the sensitivity function S(Å) is represented by a dashed line.

[0043] [Fig.3] represents absorbance curves as a function of wavelength A(2) for a commercial coating (comparative example in dotted line) and Ex. 1 (in double line).

[0044] [Fig.4] represents absorption curves as a function of wavelength A(A) for a commercial coating (comparative example in dotted line) and Ex.4 (solid line).

[0045] [Fig. 5] represents the UV-visible light spectrum of a fragrance (absorbance A) as a function of wavelength (X in nm) under different conditions. A0 represents a fragrance before SUNTEST. D0-6h represents the spectrum of the fragrance without UV protection after 6 hours of SUNTEST. Dref_add-6h represents a fragrance containing an additive, essentially avobenzone, after 6 hours of SUNTEST. Dref_coat-6h represents a fragrance protected by the reference coating of the comparative example after 6 hours of SUNTEST. DEx3-6h represents a fragrance protected by the filter film of Example 3 after 6 hours of SUNTEST.

[0046] [Fig. 6] represents the relative reduction (%) of absorbance at 500 nm of a reference fragrance over a time (t in hours) under SUNTEST conditions. D0 represents a fragrance without UV protection: rapid and significant degradation is observed. Dref_add represents a fragrance containing an additive, essentially avobenzone, defining the industry standard for protection. Dref_coat represents a fragrance protected by the reference coating of the comparative example. DEx3 represents a fragrance protected by the filter film of example 3. DETAILED DESCRIPTION

[0047] In the present invention, the following terms and expressions have the following meanings:

[0048] “Absorbance” is the decimal logarithm of the ratio 10 / 1, where 10 is the intensity of the Light incident on a sample and I is the intensity of the light transmitted through said sample. Absorbance is measured for wavelengths in the UV and visible light range from 300 nm to 780 nm.

[0049] “Encapsulated” refers to a state in which a material, a material encapsulation, covers, surrounds, incorporates, contains, includes, wraps, packages, or encloses a plurality of particles, which may be nanoparticles or composite particles.

[0050] “Charging rate” refers to the mass ratio between the mass of particles included in a formulation and the mass of said formulation. For example, 10 g of a particle mixed with 90 g of a matrix gives a loading rate of 10%.

[0051] “Nanometric size” refers to a size of matter in which effects Quantum phenomena arise due to confinement. For semiconductor nanoparticles, the nanometer size must be defined using the average Bohr radius of an electron-hole pair. Confinement is effective for nanoplate sizes in at least one dimension of less than 10 nm, preferably less than 5 nm. Confinement is effective for nanorod cross-sections of less than 100 nm², preferably less than 50 nm². Confinement is effective for nanosphere diameters of less than 20 nm, preferably less than 15 nm, and even more preferably less than 10 nm.

[0052] “Nanoparticle” refers to a particle having a size in at least one of its dimensions must be less than 100 nm. For a nanosphere, the diameter must be less than 100 nm. For a nanoplate, the thickness must be less than 100 nm. For a nanorod, the diameter must be less than 100 nm.

[0053] “Semiconductor nanoparticles” refers to particles made up of of a material with an electronic structure similar to semiconductor materials used in the electronics industry, but at a nanometer scale. Due to their specific electronic structure, semiconductor materials behave like high-pass absorption materials. Light with a wavelength exceeding the band gap can be absorbed by the semiconductor material, forming an electron-hole pair, an exciton, which then recombines within the material and dissipates heat, emits light, or both. Conversely, light with a wavelength below the band gap cannot be absorbed: the semiconductor material is transparent to these wavelengths. In macroscopic semiconductor materials, visible light is generally absorbed, while near / mid-infrared light is not.When semiconductor particles have a nanometric size, confinement, that is to say the shape. and the nanometric size, governs the electronic structure according to the rules of quantum mechanics and the absorption of light can be limited to the UV range or to high energy UV and visible light.

[0054] “Transparent” refers to a film with two properties. First, the Light scattering by the film must be low, generally less than 1% as measured by cloudiness measurement according to ASTM D1003-00, preferably less than 0.8%, and more preferably less than 0.5%. Second, the shape of an object viewed through the film must not be altered, meaning that a consumer can recognize an object when viewing it through the film. In this disclosure, transparency is not related to the absorbance of visible light: a film can be transparent and colored. Optionally, the film is colorless when the film's absorbance is less than 0.05 for a wavelength range of 420 nm to 780 nm, preferably from 400 nm to 780 nm, and more preferably for the entire visible range of 380 nm to 780 nm. With such low absorbance, there is no attenuation of the effect visible to the eye nor any change in color perception: the film is transparent and colorless.

[0055] “UV light” refers to electromagnetic radiation exhibiting a wavelength between 280 nm and 380 nm. This disclosure does not include UV-C light with a wavelength shorter than 280 nm.

[0056] “Visible light” refers to electromagnetic radiation exhibiting a wavelength between 380 nm and 780 nm.

[0057] “% by weight”, denoted %wds, refers to the percentage by weight of a component in a mixture or formulation, based on the weight of the solid mixture, after drying or hardening, as appropriate. Weighted average absorbance:

[0058] This disclosure relates to a filter film comprising compounds absorbing UV light in the 300 nm to 380 nm range and a binder. This filter film has a weighted average absorbance Aggg greater than 2, with Aggg defined by the following relationship: [°059] &WW ^380-

[0060] where A(2) represents the absorbance of the filter film at a given wavelength X, and W(2) represents a weighting function equal to the product of the solar spectral irradiance Es(2), in accordance with ASTM G177-03(2012), and a sensitivity function S(2).

[0061] Various analyses carried out by the applicant have indicated that odorant molecules often used in perfumes, lacking UV stabilizers, exhibit similar absorption spectra in UV light, as shown in Figure 2, for diluted perfumes. Indeed, regardless of certain amplitude variations, the absorbance can be fitted by a Gaussian function with a peak centered at 300 nm and a standard deviation of 24 nm, i.e., the right-hand side of a Gaussian function. In the following disclosure, the sensitivity function S(2) is defined as a Gaussian function with a peak centered at 300 nm and a standard deviation of 24 nm. The values ​​considered in this disclosure are presented in the following table: Wavelength (nm) Spectral irradiance ground area ES(Å) (mW / m².nm) Sensitivity SU) Weighting Function WU) 300 0.081 1.000 0.081 305 1.91 0.979 1.869 310 11 0.917 10.088 315 30 0.823 24.694 320 54 0.707 38.205 325 79.2 0.582 46.123 330 101 0.459 46.366 335 128 0.347 44.360 340 151 0.251 37.834 345 170 0.173 29,491 350 188 0.115 21,624 355 210 0.073 15,338 360 233 0.044 10,349 365 253 0.026 6,544 370 279 0.014 4.025 375 306 0.008 2.358 380 336 0.004 1.324 Table I

[0062] A weighted average absorbance (A38q) value greater than 2, meaning that 99% of photons in the 300 nm to 380 nm range are absorbed by the film, has proven beneficial in an aging test shown below in examples. Indeed, a commercial filtering solution with an A380 of 1.8 was unsatisfactory, whereas a filtering film disclosed in Example 4 with an A380 of 2.4 was satisfactory.

[0063] In one embodiment, the filter film is transparent, preferably transparent and colorless.

[0064] In one embodiment, the thickness of the filter film is in the range of 2 pm to 100 pm, preferably from 3 pm to 50 pm, and more preferably from 5 pm to 25 pm. In the disclosure, the filter films have a preferred thickness of 10 pm. It is nevertheless evident that the thickness of the filter film is not essential for absorption performance. Indeed, a low concentration of UV light-absorbing compounds in a filter film can be compensated for by a greater film thickness, in accordance with Beer-Lambert's law, independently of the nonlinear effects encountered with a high concentration of UV light-absorbing compounds. Therefore, the concentration of UV light-absorbing compounds is defined in association with a film thickness of 10 pm, in order to define the absolute quantity of UV light-absorbing compounds in the filter film.Another film thickness, greater but more diluted or less but more concentrated, can be equivalent.

[0065] In one embodiment, the weighted average absorbance A380 is greater than 2.5, preferably greater than 3. Larger values ​​for A380 are possible, for example greater than 4 or 5.

[0066] Even though the weighting function W(2) gives more weight to absorption in the wavelength range from 300 nm to 340 nm, the contribution of longer wavelengths is not negligible. In one embodiment, the filter film has a weighted average absorbance A34q greater than 2, with A34q defined by the following relation: [OO67] ^34° -

[0068] where the functions have the same definitions as above for A38q. Indeed, A34Q is more focused on the wavelength range associated with aldehyde functions of odorant compounds and provides a better characterization of the filtering effect. A weighted average absorbance of A34Q greater than 2 means that 99% of photons in the 300 nm to 340 nm range are absorbed by the filter. In In one embodiment, the weighted average absorbance A34q is greater than 2.5, preferably greater than 3. Larger values ​​of A34q are possible, for example more than 4 or 5. UV light-absorbing compounds:

[0069] In the disclosure, the filter film comprises UV light-absorbing compounds, which can be of various types. Semiconductor nanoparticles

[0070] In one embodiment, UV light-absorbing compounds are semiconductor nanoparticles. Semiconductor nanoparticles impart particularly interesting light absorption properties to filter films containing them. In particular, with an appropriate selection of semiconductor nanoparticle composition and structure, filter films exhibiting high transmission between a range of absorbed (high-energy) light and a range of transmitted (low-energy) light can be designed.

[0071] Due to their electronic structure, semiconductor nanoparticles behave like high-pass filters: absorbance is high for high-energy wavelengths, i.e., short wavelengths. Conversely, absorbance for low-energy wavelengths, i.e., long wavelengths, is low. The transition between the two domains of high absorbance and low absorbance can be defined by the wavelength Xmax, defined as follows: Xmax corresponds to the maximum local absorbance at the longest wavelength in the range of 300 nm to 500 nm.

[0072] In other words, light with a wavelength shorter than the Xmax wavelength is not transmitted, while light with a wavelength longer than the Xmax wavelength is transmitted. Advantageously, in the present disclosure, Xmax is in the range of 320 nm to 360 nm: absorption in the range of 300 nm to 340 nm is therefore very effective in preventing aldehyde degradation, while absorption in the visible light is negligible to avoid any undesirable coloration of the filter film. Preferably, Xmax is in the range of 320 nm to 350 nm, more preferably in the range of 320 nm to 340 nm. The Xmax wavelength of the semiconductor nanoparticles can be adjusted according to the composition, shape, dimensions, and immediate environment of the semiconductor nanoparticles.

[0073] Semiconducting nanoparticles with a larger Xmax may be desirable to impart certain filtering properties to the filter film in UV light or even in visible light. For example, semiconductor nanoparticles may have an Xmax in the range of 350 nm to 400 nm. nm, preferably from 350 nm to 380 nm. The property of behavior of semiconductor nanoparticles as high-pass filters is particularly interesting since it allows to "block" all light of wavelength less than the Xmax wavelength.

[0074] Particularly suitable semiconductor nanoparticles have the following formula

[0075] MxEy (I),

[0076] in which:

[0077] M is chosen from the group consisting of Zn, Cd, Hg, Cu, Ag, Al, Ga, In, Si, Ge, Sn, Pb or a mixture of these;

[0078] E is chosen from the group consisting of O, S, Se, Te, N, P, As, Sb, or a mixture of these;

[0079] x and y are independently a decimal number from 0 to 5; and

[0080] x and y are not simultaneously equal to 0.

[0081] In a specific embodiment, semiconductor nanoparticles comprise a material chosen from the group consisting of CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, HgS, HgSe, HgTe, HgO, GeS, GeSe, GeTe, SnS, SnSe, SnTe, PbS, PbSe, PbTe, GeS2, GeSe2, SnS2, SnSe2, CuInS2, CuInSe2, CuA1S2, CuAlSe2, CuInZnS, CuInZnSe, AgInS2, AgInSe2, CuS, Cu2S, Ag2S, Ag2Se, Ag2Te, FeS, FeS2, InP, Cd3P2, Zn3P2, CdO, ZnO, A12O3, AIN, A1P, AlAs, AlSb, GaN, GaP, GaAs, GaSb, InN, InP, InAs, InSb, InAsP, or a mixture thereof.

[0082] In the present disclosure, semiconductor nanoparticles may have different shapes, provided they are of a nanometer size that results in exciton confinement within the nanoparticle. Semiconductor nanoparticles may be nanospheres, nanoplates, or nanorods.

[0083] Semiconducting nanoparticles can have nanometer-sized dimensions in three dimensions, which allows for quantum confinement in three spatial dimensions. Such semiconductor nanoparticles are, for example, nanocubes or nanospheres.

[0084] Semiconductor nanoparticles can have nanometer-sized dimensions in two dimensions, with the third dimension being larger: quantum confinement is in two spatial dimensions. Such semiconductor nanoparticles are, for example, nanorods, nanowires, or nanorings.

[0085] Semiconductor nanoparticles can have nanometer-sized dimensions in one dimension, with the other dimensions being larger: quantum confinement is in a single spatial dimension. Such semiconductor nanoparticles are, for example, nanoplates, nanosheets, nanoribbons, or nanodisks. Nanoplates are of particular interest in this disclosure because their absorption cross-section—that is, the efficiency of capturing a photon of light incident on the nanoparticle—is 10 times greater than that of a nanosphere with the same composition and structure. This larger cross-section significantly improves absorption.

[0086] The exact shape of the semiconductor nanoparticles defines the confinement properties; then the electronic and optical properties depend on the composition of the semiconductor nanoparticles, in particular the band gap; and finally, the Xmax of the final filter film. It has also been observed that nanoparticles with a nanometric size in one dimension, particularly nanoplates, exhibit a sharper transition between the two domains of high and low absorbance compared to nanoparticles of other shapes. Indeed, the width of the transition zone is increased if the nanometric size of the nanoparticles fluctuates around an average value. When the nanometric size is controlled in a single dimension, for example, in nanoplates, by a strict number of atomic layers, thickness fluctuations are practically zero, and the transition between the absorption and non-absorption states is very sharp.This results in particularly effective filtering films.

[0087] In one embodiment, semiconductor nanoparticles are homostructures. By homostructure, it is understood that the semiconductor nanoparticle is homogeneous and has the same local composition throughout its volume. A homogeneous spherical semiconductor nanoparticle (1) is illustrated in Figure IA.

[0088] In an alternative embodiment, semiconductor nanoparticles are heterostructures. By heterostructure, it is understood that the semiconductor nanoparticles are composed of several sub-volumes, each sub-volume having a composition different from that of the neighboring sub-volumes. In a particular embodiment, all the sub-volumes have a composition defined by formula (I) disclosed below, with different parameters, i.e., a different elemental composition and a different stoichiometry.

[0089] Examples of heterostructures are core / shell nanoparticles, the core (11) of which has any shape disclosed above. A shell (12) is a layer totally or partially covering the core. A particular example of a core / shell heterostructure is a multilayer structure comprising a core (11) and several successive shells (12, 13). For ease of understanding, these multilayer heterostructures are referred to as core / shell hereafter. The core (11) and the shell (12, 13) may have the same shape, for example sphere-to-sphere, or different shapes, for example sphere-to-plate. A nanoparticle A spherical core / shell nanoparticle is illustrated in Figure IB. A spherical core / shell / shell nanoparticle is illustrated in Figure IC. A spherical plate nanoparticle is illustrated in Figure 1D and is also called a plate point. A core / shell nanoparticle is illustrated in Figure 1E.

[0090] Another example of a heterostructure relates to core / crown nanoparticles, the core of which has any of the shapes disclosed above. A crown is a band of material arranged on the periphery of the core. This heterostructure is particularly useful with cores that are nanoplates and a crown arranged on the edges of the nanoplate. A core / crown nanoplate is illustrated in Figure 1F.

[0091] These heterostructures may exhibit a composition gradient from the core to the outside of the bark so as not to present a precise boundary between the core and the bark, but properties at the center of the core are different from the properties at the outer boundary of the bark.

[0092] In one configuration, semiconductor nanoparticles are of type II-VI and comprise a core based on cadmium, sulfur, and selenium and are selected from: • CdSe / CdS, CdSe / CdS / ZnS, CdSe / CdS / ZnSe, CdSe / CdS / ZnSeyS(1.y), CdSe / ZnSe / ZnS, CdSc / ZnScxS, |X) / ZnS, • CdSexS(l x) / ZnS, CdSexS(lx) / ZnSe, CdSexS(1.x) / ZnSeyS(1.y), CdSexTe(1.x) / ZnS, CdSexTe(i_x) / ZnSe, • CdSc / CdvZn, | VJS, CdSe / CdyZn(1.y)S / ZnS, CdSe / CdyZn(1.y)S / ZnSe, CdSe / CdyZn(i.y)S / ZnSezS(i.z) • CdSe / CdyZn(1.y)Se, CdSe / CdyZn(1.y)Se / ZnS, CdSe / CdyZn(1.y)Se / ZnSe, CdSe / CdyZn(i.y)Se / ZnSezS(i.z), • CdScxS(| X) / CdS, CdScxS. i x) / CdS / ZnS, CdSexS(M / CdS / ZnSe, CdSexS(M / CdS / ZnSeyS(ly), • CdSexS(1.x) / CdyZn(1.y)S, CdSexS(1.x) / CdyZn(1.y)S / ZnS, CdSexS(1.x) / CdyZn(1.y)S / ZnSe, CdSexS(i_X) / CdyZn(i_y)S / ZnSezS(i_Z), • CdSexS(i.x) / CdyZn(i.y)Se, CdScxS, | X) / CdvZn, | VJSc / ZnS, CdScxS( |X) / CdvZn, । y)Se / ZnSe, CdScxS(| X) / CdvZn(| V)Sc / ZnSczS(i z), où x, y et z sont des nombres rationnels entre 0 (exclu) et 1 (exclu).

[0093] Dans une configuration, des nanoparticules semi-conductrices sont de type II-VI et comprennent un cœur basé sur du zinc, du soufre et du sélénium et sont choisies parmi : • ZnSe / ZnS, ZnSe / ZnSeyS(i y), ZnTe / ZnSeyS(i y) • ZnSexS(i_x) / ZnS, ZnSexS(i_x) / ZnSe, ZnSexS(i_x) / ZnSeyS(i_y), ZnSexTe(i_x) / ZnS, ZnSexTe(i_x) / ZnSe, ZnScxTc(| X) / ZnScxS(| X), • ZnSe / CdyZn(1.y)S, ZnSe / CdyZn(1.y)S / ZnS, ZnSe / CdyZn(1.y)S / ZnSe, ZnSe / CdyZn(i_y)S / ZnSezS(i_z) • ZnSe / CdyZn(i y)Se, ZnSe / CdyZn(i y)Se / ZnS, ZnSe / CdyZn(i y)Se / ZnSe, ZnSe / CdyZn(i_y)Se / ZnSezS(i_z), • ZnSexS(i_x) / ZnS, ZnSexS(i_x) / ZnS / ZnSe, ZnSexS(i_X) / ZnS / ZnSeyS(i_y), • ZnSexS(i_x) / CdyZn(i_y)S, ZnScxS( | X) / CdvZn, | VJS / ZnS, ZiiScxSdx / CclvZnd^ ZnSe, ZnSexS(i_X) / CdyZn(i_y)S / ZnSezS(i_Z), • ZnSexS(i_x) / CdyZn(i_y)Se, ZiiScxSdx / CclvZndy3^ ZnScxSd x) / CdvZnd vJSc / ZnSe, ZnSexS(i_X) / CdyZn(i_y)Se / ZnSezS(i_Z), where x, y and z are rational numbers between 0 (exclusive) and 1 (exclusive). In this configuration, x is preferably a rational number between 0 (exclusive) and 0.6.

[0094] In one configuration, semiconductor nanoparticles are of type II-VI and comprise a core based on zinc, cadmium, sulfur and selenium and are selected from: • CdwZn(1.w)Se / CdS, CdwZn(lw)Se / CdS / ZnS, CdwZn(1.w)Se / ZnSe / ZnS, CdwZn(1_ w)Se / CdS / ZnSe, CdwZn(lw)Se / CdS / ZnSeyS(ly), * CdwZn(i_w)SexS(i_x) / ZnS, CdwZnd W)ScxSd • CdwZn(i_w)Se / CdyZn(i_y)S, CdwZnd WJSc / CdvZnd vJS / ZnS, CdwZnd WJSc / CdvZnd y)S / ZnSe, CdwZn(iw)Se / CdyZn(iy)S / ZnSezS(iz) • CdwZn(iw)Se / CdyZn(iy)Se, CdwZn(iw)Se / CdyZn(iy)Se / ZnS, CdwZnd WJSc / CdyZn(iy)Se / ZnSe, CdwZnd w)Sc / CdvZnd v)Sc / ZnSczSd z), • CdwZn(i_w)SexS(i_x) / CdS, CdwZnd WJScxSd xJ / CdS / ZnS, CdwZnd WJScxSd xJ / CdS / ZnSe, CdwZn(i_w)SexS(i_X) / CdS / ZnSeyS(i_y), • CdwZn(i_w)SexS(i_x) / CdyZn(i_y)S, CdwZnd WJScxSd xJ / CdvZnd vJS / ZnS, CdwZn(i. w)SexS(i_x) / CdyZn(i_y)S / ZnSe, CdwZnd WJScxSd xJ / CdvZnd vJS / ZnSczSd ZJ, • CdwZn(i_w)SexS(i_X) / CdyZn(i_y)Se, CdwZnd WJScxSd x) / CdvZnd vJSc / ZnS, CdwZna_ w)SexS(i_x) / CdyZn(i_y)Se / ZnSe, CdwZnd WJScxSd x / CclvZnd ^ où w, x, y et z sont des nombres rationnels entre 0 (exclu) et 1 (exclu).

[0095] Les nanoparticules II-VI les plus préférées sont CdSe / CdS / ZnS, CdSexS(i_x) / CdS / ZnS, CdSe / ZnSe / ZnS, CdSe / ZnSexS(1.x) / ZnS, CdSexS(1.x) / ZnSe / ZnS, CdxZn(1.x)Se / ZnSe / ZnS, ZnSexS(i_x) / ZnS, ZnSexS(i_x) / ZnSe, ZnSexS(i_x) / ZnSeyS(i_y).

[0096] Other particularly suitable nanoparticles are IILV type semiconductor nanoparticles and are chosen from InP / ZnS, InP / ZnSe, InP / ZnScxSd K), InP / CdS / ZnS, InP / ZnSe / ZnS, InP / ZnSexS(1.x) / ZnS, InP / GaP, CuxInyZn(1.xy)S / ZnS, InxAs(i_x)P / ZnSexS(i_x), where x and y are rational numbers between 0 (excluded) and 1 (excluded).

[0097] Other particularly suitable nanoparticles are type I-III-VI2 semiconductor nanoparticles and are chosen from AgInS2, AgInSe2, CuInS2, CuInSe2, CuA1S2, CuAlSe2, CuJn(2_x)S2, CuxIn(2.x)Se2, CuxAl(2.x)S2, CuxAl(2 x)Se2, where x is a rational number between 0 (excluded) and 2 (excluded). These type I-III-VI2 semiconductor nanoparticles can form the core of the following core / shell heterostructures: AgInS2 / ZnSe, AgInSe2 / ZnSe, CuInS2 / ZnSe, CuInSe2 / ZnSe, CuA1S2 / ZnSe, CuAlSe2 / ZnSe, CuxIn(2x)S2 / ZnSe, CuxIn(2x)Se2 / ZnSe, CuxAl(2x)S2 / ZnSe, CuxAl(2x)Se2 / ZnSe, AgInS2 / ZnS, AgInSe2 / ZnS, CuInS2 / ZnS, CuInSe2 / ZnS, CuAlS2 / ZnS, CuAlSe2 / ZnS, CuxIn(2x)S2 / ZnS, CuxIn(2x)Se2 / ZnS, CuxAl(2x)S2 / ZnS, CuxAl(2x)S2 / ZnS x)Se2 / ZnS, where x is a rational number between 0 (excluded) and 2 (excluded).

[0098] Other particularly suitable nanoparticles are chosen from core-doped quantum dots, such as ZnSe:Mn / ZnS, or ZnSe:Cu / ZnS.

[0099] Other particularly suitable nanoparticles are chosen from ZnTe / ZnSeyS(iy), ZnSexTe(i_x) / ZnS, ZnSexTe(i_x) / ZnSe, ZnSexTe(i_x) / ZnSeyS(i_y), where x and y are rational numbers between 0 (excluded) and 1 (excluded).

[0100] In an advantageous embodiment, semiconductor nanoparticles have a largest dimension that is less than 100 nm, in particular less than 50 nm, ideally less than 20 nm. Small semiconductor nanoparticles do not cause light scattering when dispersed in a material having a different refractive index.

[0101] In one embodiment, the content of semiconductor nanoparticles in the filter film is in a range of 0.5% by weight to 15% by weight, based on the weight of the filter film, for a film with a thickness of 10 pm, preferably from 1% by weight to 12% by weight, more preferably from 1.5% by weight to 10% by weight.

[0102] Type II-VI semiconductor nanoparticles comprising a core based on zinc, sulfur and selenium are particularly suitable as UV light-absorbing compounds when used at a concentration of 0.5 wt% to 8 wt%.

[0103] In one embodiment, the semiconductor nanoparticles are coated with an organic layer, an inorganic layer, or a mixture thereof. Composite particles

[0104] In one embodiment, the semiconductor nanoparticles are encapsulated in an encapsulation material, generating composite particles. By encapsulation material is meant a material that covers the entire surface of the semiconductor nanoparticles. In other words, the encapsulation material forms a barrier around the semiconductor nanoparticles. Such a barrier This offers several advantages. In particular, these semiconductor particles can be protected against chemicals such as moisture or oxidants. Furthermore, semiconductor nanoparticles that are not dispersible in a medium can be encapsulated in a material with good compatibility with that medium: the barrier acts as a compatibilizing agent. In addition, encapsulated semiconductor nanoparticles can be in the form of a powder dispersible in a medium instead of a dispersion in a solvent, which facilitates handling. Finally, the encapsulation material can play a role in refractive index matching to reduce scattering or turbidity: indeed, when semiconductor nanoparticles are dispersed in a matrix, the turbidity is proportional to the difference in refractive indices between the matrix and the dispersed nanoparticles.Adding an encapsulating material with an intermediate refractive index mitigates this effect and reduces turbidity.

[0105] The encapsulation material may be an organic or an inorganic material. For example, the organic material may be selected from allyl polymers, (meth)acrylic polymers; epoxy compounds; polyurethane, polyester, or polythiourethane materials, or a mixture thereof. For example, the inorganic material may be selected from sol-gel materials, metal oxide materials, mineral oxides, or mixtures thereof.

[0106] Suitable inorganic materials may be chosen from the group consisting of SiO2, Al2O3, TiO2, ZrO2, HfO2, GeO2, SnO2, or a mixture thereof, including, for example, AlZrzO with + 2z = 1. In one embodiment, the encapsulating material does not consist of pure SiO2. Here, "pure" means an encapsulating material obtained by a synthesis protocol aimed solely at the formation of silica. The presence of impurities in the reagents, in the proportions normal to the field of inorganic synthesis, is therefore possible.

[0107] In one embodiment, the encapsulating material does not absorb UV light, and the absorbance of the filter film is defined solely by the semiconductor nanoparticles. Alternatively, the encapsulating material absorbs UV light, and the absorbance of the filter film is defined by the sum of the absorbance of the semiconductor nanoparticles and the absorbance of the encapsulating material.

[0108] In one embodiment, the charge level of the semiconductor nanoparticles in the composite particle is at least 1%, preferably at least 2.5%, more preferably at least 5%, said charge level being the mass ratio between the mass of the semiconductor nanoparticles included in a composite particle and the mass of said composite particle. Indeed, the performance of the The properties of composite particles are proportional to the concentration of semiconductor nanoparticles they contain. A high concentration of semiconductor nanoparticles is therefore advantageous. However, increasing the concentration of semiconductor nanoparticles without degrading their properties, particularly through aggregation or manufacturing processes, is not easy.

[0109] Composite particles can be in the form of a monodisperse population. Monodisperse composite particles are advantageous for various reasons depending on the application. When composite particles are used in filter films, a homogeneous size distribution prevents uncontrolled light scattering and ensures spatial homogeneity of the filter film.

[0110] In one embodiment, composite particles have a larger dimension that is less than 500 nm, in particular less than 300 nm, ideally less than 200 nm.

[0111] The average size of the composite particles is preferably in the range of 50 nm to 500 nm, more preferably from 50 nm to 250 nm. Composite particles having an average size of 50 nm to 250 nm, preferably from 50 nm to 100 nm, are particularly suitable for obtaining filter films with high transparency and low turbidity.

[0112] Composite particles can be chemically modified on their surface. Chemical modification can be achieved by grafting, by adsorption of molecules, or by physical processes such as heat, vacuum, or gas treatment. Chemical modification can utilize compatibilizing agents, allowing composite particles to be mixed into complex formulations, such as resins, varnishes, paints, colloidal dispersions, polymerizable compositions, or others, without aggregation or phase separation of the composite particles. Organic compounds that absorb UV light

[0113] As an alternative to semiconductor nanoparticles, UV light-absorbing compounds may be organic anti-UV compounds.

[0114] Particularly suitable organic anti-UV compounds may be selected from the group consisting of benzotriazoles, triazines, piperidines, benzophenones, catechol, their derivatives and mixtures thereof.

[0115] Suitable benzotriazoles are derivatives of (2H-benzotriazol-2-yl)-4-hydroxybenzene such as Sodium 3-(2H-benzotriazol-2-yl)-5-sec-butyl-4-hydroxybenzenesulfonate - CAS No. 92484-48-5 - or Polyethylene glycol mono-3-(3-(2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyphenyl)-1-oxopropyl ether - CAS No. 104810-48-2 - or Polyethylene glycol di[3-[3-(2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyphenyl]-1-oxopropyl] ether - CAS No. 104810-47-1 - or the Esters of benzenepropanoic acid and 3-(2H-benzotriazol-2-yl)-5-(l,l-dimethylethyl)-4-hydroxy-, linear and branched C7-9 alkyl - CAS No. 127519-17-9 - or 2-(2H-Benzotriazol-2-yl)-6-( 1 -methyl-1 -phenylethyl 1)-4-( 1,1,3,3-tetramethylbutyl)phenol - CAS No. 73936-91-1.

[0116] Suitable triazines are reaction products of 1,3-Benzenediol, 4-[4,6-bis(2,4-dimethylphenyl)-l,3,5-triazin-2-yl] with derivatives of [(dodecyloxy)methyl]oxirane and mono[(C10-16-alkyloxy)methyl oxirane] - CAS No. 153519-44-9 - or Isooctyl 2-[4-[4,6-bis[(l,l'-biphenyl)-4-yl]-l,3,5-triazin-2-yl]-3-hydroxyphenoxy]propanoate - CAS No. 204848-45-3 - or a triazine bearing the name TINUVIN®477 supplied by BASF.

[0117] Suitable piperidines are bis(l-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate - CAS No. 129757-67-1.

[0118] A mixture of bis(l-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate - CAS No. 129757-67-1 - and reaction products of 1,3-Benzenediol, 4-[4,6-bis(2,4-dimethylphenyl)-l,3,5-triazin-2-yl] with derivatives of [(dodecyloxy)methyl]oxirane and mono[(C10-16-alkyloxy)methyl oxirane] - CAS No. 153519-44-9 - bearing the trade name Eversorb AQ8 is particularly suitable.

[0119] Other suitable organic anti-UV compounds are avobenzones, such as 1,3-Propanedione, l-[4-(l,l-dimethylethyl)phenyl]-3-(4-methoxyphenyl) - CAS No. 70356-09-1 - or the compound bearing the trade name Parsol guard.

[0120] Among these organic anti-UV compounds, those exhibiting a primary or secondary absorption peak in the 300 nm to 340 nm range are preferred. In particular, Tinuvin 384-2, Eversorb AQ8, and Tinogard HS are suitable.

[0121] The following mixture of organic anti-UV compounds is also suitable: Tinuvin 384-2; Parsol Guard and Eversorb AQ8 in a proportion of 1:1:1.

[0122] In one embodiment, the content of organic anti-UV compounds in the filter film is in a range of 2% by weight to 15% by weight, based on the weight of the filter film, for a film with a thickness of 10 pm, preferably from 2.5% by weight to 12% by weight, more preferably from 3% by weight to 10% by weight.

[0123] In one embodiment, UV light-absorbing compounds comprise a mixture of one or more semiconducting nanoparticles and / or one or more organic anti-UV compounds. In the present embodiment, the amount of UV light-absorbing compounds in the filter film is in the range of 3% by weight to 15% by weight, based on the weight of the filter film, for a film with a thickness of 10 µm.

[0124] In one embodiment, the UV light-absorbing compounds comprise no more than 2.5% by weight, based on the total weight of the filter film, for a a 10 pm thick film of core-shell semiconductor nanoparticles comprising: • a core of ZnSexS(i_x) material where x is in a range from 0.60 to 0.98, and • a ZnS material shell, and exhibiting a maximum local absorbance at longer wavelengths in the range of 350 to 500 nm.

[0125] More preferably, the UV light-absorbing compounds do not comprise core-shell semiconductor nanoparticles comprising: • a core of ZnSexS(i_x) material where x is in a range from 0.60 to 0.98, and • a bark of ZnS material, and exhibiting a maximum local absorbance at longer wavelengths in the range of 350 to 500 nm. Link:

[0126] In the disclosure, the filter film includes a binder. This binder may be composed of various types of polymers, for example selected from poly(methyl methacrylate) (PMMA), poly(butyl methacrylate), poly(lauryl methacrylate), poly(vinyl butyral), poly(vinyl acetate), poly(ethylene vinyl acetate), thermoplastic polyurethane, cellulose, ionoplast, polycarbonate, poly(ethylene vinyl alcohol), polyester / melamine adducts, silicone, polyphenylmethylsiloxane, polyphenylalkylsiloxane, polydiphenylsiloxane, polydialkylsiloxane, fluorinated silicone, vinyl- and hydride-substituted silicone, divinylbenzene, or a mixture thereof.

[0127] The filter film can be obtained from a thermoplastic polymer in which UV light-absorbing compounds are dispersed, generally during the melting / extrusion / stretching process. The thickness of the filter film is governed by the manufacturing process.

[0128] Alternatively, the filter film can be obtained from a polymerizable composition in which UV light-absorbing compounds are dispersed. The polymerizable composition is then cured, thermally, actinically, or by any other curing method, or dried to form a film. In this case, the polymerizable composition may include a solvent.

[0129] In one embodiment, the film is obtained by hardening a polymerizable Sol-Gel composition and has a thickness in a range of 1 pm to 15 pm, preferably from 1 pm to 10 pm, more preferably from 2 pm to 6 pm.

[0130] In one embodiment, the film is obtained by hardening a composition comprising (meth)acrylic monomers or oligomers, epoxy monomers or oligomers, or mixtures thereof. In particular, the thickness of the coating obtained by hardening said polymerizable composition is in a range of 2 pm to 100 pm, preferably from 3 pm to 50 pm, more preferably from 4 pm to 30 pm. Packaging :

[0131] This disclosure also relates to packaging, for example packaging selected from the group consisting of glass containers, glass bottles, plastic containers and plastic bottles, particularly a light-filtering glass container.

[0132] In the disclosure, the filter film may be a self-supporting material or may be deposited on a substrate to form a package. Particularly interesting substrates are glass containers, in order to form light-filtering glass containers.

[0133] For this purpose, a filter film can be deposited on the surface of the substrate. Adhesion between the substrate and the filter film can be ensured by an adhesive or by the adhesive properties of the filter film itself.

[0134] Alternatively, a polymerizable composition can be coated onto the surface of the substrate, by any process such as spray coating or dip coating, and cured or dried to obtain the filter film.

[0135] Finally, the filter film can be used directly to form a package. In this case, the thickness of the filter film can be in the range of 50 µm to 3 mm. Use - Protection method:

[0136] This disclosure also relates to the use of a filter film, disclosed above, as protection against UV light in a range of 300 nm to 340 nm.

[0137] For example, a substrate can be covered with a filter film, as disclosed above. The substrate can then be placed around the product to be protected. In particular, the substrate can be a glass container, and the product, such as a food, cosmetic, or perfume, can be placed inside the glass container to be protected from UV light.

[0138] Alternatively, the filter film can be formed in a package, in which the product is filled, wrapped or otherwise contained.

[0139] This disclosure also relates to a method for protecting a consumer good against UV light in the 300 nm to 340 nm range, comprising enclosing the consumer good in a filter film as disclosed above. The consumer good may be food products, in solid or liquid form, cosmetic formulations, or perfumes. The filter film may cover packaging in which the consumer good is contained. This protection process is particularly suitable for perfume / fragrance bottles. EXAMPLES

[0140] The present invention is illustrated in more detail by the following examples. Absorption curve of filter films:

[0141] A filter film is prepared by applying a liquid composition to a 250 pl glass plate with a cube coating device, to obtain a coating with a thickness of 100 pm, then hardening for 12 minutes in an oven at 180 °C, which gives a dry film with a thickness of 10 pm.

[0142] The film thickness is controlled by a profilometer, and then the film's absorbance is measured. The absorbance of the glass plate is subtracted to obtain the absorbance of the filter film only. Aging test:

[0143] To evaluate the protection of the filter films, the following protocol is used.

[0144] A bottle is coated with a polymerizable composition and then hardened. After hardening, the filter film has a thickness of 10 µm.

[0145] The UV-visible light absorbance spectrum of a studied composition, food product, cosmetic formulation or perfume, is measured.

[0146] Next, the bottle is filled with the composition under study and the bottle is placed under constant lighting corresponding to a D65 illuminant, which includes UV light from a wavelength of 300 nm, with a total power of 550 W / m2 for 24 hours at a temperature of 40 °C, which is called SUNTEST.

[0147] During SUNTEST, the UV-visible light absorbance value at 500 nm of the aged composition is measured and compared to the spectrum before SUNTEST.

[0148] Comparing the spectra before and during SUNTEST makes it possible to determine whether the composition studied has been protected by the filter film or not.

[0149] Figure 5 represents the UV-visible light spectrum A0 of a fragrance before SUNTEST. D0-6h represents the spectrum of the fragrance without UV protection after 6 hours. Dref_add-6h represents a fragrance containing an additive, essentially avobenzone, after 6 hours, defining the industry standard for protection. Note that the spectrum below 430 nm is slightly different due to the presence of the additive. Dref_coat-6h represents a fragrance protected by the reference coating of the comparative example: the protection is not adequate. Finally, DEx3-6h represents a fragrance protected by the filter film of Example 3: the protection is better than the reference coating and approaches the industry standard.

[0150] Figure 6 shows the relative reduction in absorbance at 500 nm of a fragrance during a SUNTEST. DO represents a fragrance without UV protection: rapid and significant degradation is observed. Dref_add represents a fragrance containing an additive, essentially avobenzone, defining the industry standard for protection. Dref_coat represents a fragrance protected by the reference coating of the comparative example: the protection is inadequate. DEx3 represents a fragrance protected by the filter film of Example 3: the protection is similar to the industry standard.

[0151] In addition, a visual comparison of the composition's color before and after SUNTEST is used for colored samples. A visually detectable color change results in a "FAIL" classification for the filter film. Comparative example:

[0152] Two commercial bottles used for a perfume and containing a filter film are used. The first bottle is cleaned to remove the filter film. The second bottle is used without any intervention.

[0153] The absorption of the filter film is measured by the difference in absorption between the second bottle and the first bottle. The absorption curve is represented by the dashed line in Figures 3 and 4. The corresponding values ​​for A30Q and A340 are 1.8 and 1.8, respectively.

[0154] In SUNTEST, the commercial bottle is not satisfactory: changes in the UV-visible light absorption spectrum, see [Fig.5], and in the color of the perfume are observed. Example 1:

[0155] 5% by weight of organic absorbent Tinuvin 384-2 and 5% by weight of nanoparticles Semiconductor core / shell SC#1 nanoparticles are added to an aqueous polyester resin (75 parts) and a polymerizable hexamethoxymethyl melamine composition (25 parts), hereinafter referred to as the reference binder or ref. binder, and then cured. After curing, the filter film has a thickness of 10 µm. The core of the semiconducting nanoparticles has a diameter of 3.0 nm and a formula of ZnSexS(i_x) with x equal to approximately 0.94, and a ZnS shell with an average thickness of 1.3 nm. Xmax for SC#1 is approximately 400 nm.

[0156] The absorption curve is shown in Figure 3. The corresponding values ​​for Aggg and A34Q are respectively 2.8 and 2.8.

[0157] In SUNTEST, the bottle in example 1 is satisfactory: a perfume without UV stabilizer is not degraded, see [Fig.5]. Examples 2 to 7:

[0158] Example 1 is reproduced, but the composition of the UV light-absorbing compounds is modified according to the following table (in % by weight, based on the weight of the filter film): Semiconductor Nanoparticles %wt Organic Anti-UV Compounds %wtt ^380 A340 SUNTEST 1 SC#1 5 Tinuvin 384-2 5 2.8 2.8 PASS (success) 2 SC#1 1.1 Tinuvin 384-2 5 PASS (success) 3 SC#1 1.1 Tinuvin 384-2 7.5 3.6 3.7 PASS (success) 4 - - Tinuvin 384-2 5 2.4 2.4 PASS (success) 5 SC#1 4.6 Tinogard HS 1.3 3 3.2 PASS (success) 6 SC#1 1.1 Tinuvin 384-2 Tinuvin 249 5 1.3 PASS (success) 7 SC#1 1.1 Tinuvin 384-2 Tinuvin 249 10 2.6 PASS (success) Table II Examples 10 to 133:

[0159] Additional examples are reproduced, but the composition of the UV light-absorbing compounds is modified according to the following Table III (in % by weight, based on the weight of the filter film). The film thickness is also modified to be 10 µm, 12 µm, or 15 µm. All these films exhibit Aggg values ​​greater than 2 and pass the SUNTEST.

[0160] Compositions suspended in a solvent are based on the reference binder of Example 1. Aqueous compositions are based on saturated polyesters with a dry extract of 30% in water and less than 10% polar co-solvents.

[0161] An Ecotox assessment is also carried out for these compositions. Examples that comply with Ecotox do not require labeling. %9'^ '^Z % 8'0 %8'£ %0 ro £ £> £1 — •JOJ JU Bn 61 %9'^ '^Z %8'£ %0 ro 8 9> £1 — •JOJ JU Bn 81 %V^ '^Z %8'Z %o ro t £1 9 JOJ u JOJU JOJU • LA %V^ ?8'Œ ?8'O %9'£ %o ro £ rt £1 — •JOJ JU Bn 91 %V^ oCX %9'£ %o ro £ I't £1 — •JOJ JU Bn £1 %r^ ?O'Z %8'Z %o ro £ I't £1 JOJ o JOJO JU Bn • % rt %8'Z %o ro Z 8'£ £1 OUI JOJ uoo •JOJ JU Bn £1 %r^ ?8'Z %8'Z %o ro t £> £1 OUI JOJ uoo •JOJ JU Bn ? •JOJ JU Bn II %Z '01 %o ro 9 O'£ £1 — •JOJ JU Bn 01 □+ V s -I 2 0£ III 8 £611 ZI a □9 -H 0 OtI 6 OIH L LVIL 6 II zt 8£I i #5§ V (oJOjOj) XOjOO oxh vz 20 Lia nt ref. ___ 15 4,3 2 0,1 0% 6,7% 1,4^ S,2% 21 Lia nt ref. — 15 4,5 0 0,1 0% 6,7% 0,6^ »,8% 22 Lia nt ref. — 15 4,4 7 0,1 0% 4,1% 2,0^ &,1% 23 Lia nt ref. — 15 4,3 9 0,1 0% 5,4% 1,4^ a,2% 24 Lia nt ref. — 15 3,8 6 0,1 0% 4,1% 2,2 % 2,2^ c 25 Lia nt ref. — 15 4,7 5 0,1 0% 5,4% 2,0 % 1,7^ c 26 Lia nt ref. — 15 4,2 3 0,1 0% 5,4% 2,0 % 2,0^ c 27 Lia nt ref. — 15 5,4 4 0,1 0% 4,1% 2,8 % 2,8^ c 28 Lia nt ref. — 15 4,5 3 0,1 0% 4,4% 2,0 % 2,8^ a,8% 29 Lia nt ref. — 15 3,9 3 0,1 0% 4,1% 2,8^ S,4% 30 Lia nt ref. — 15 4,9 3 0,1 0% 5,4% 2,2^ &,i% 31 Lia nt ref. ___ 15 4,9 6 10, 3% 32 Lia nt ref. con for me 15 3,8 8 2,8% 2,8 % 2,8^ c 33 Lia nt ref. con for me 15 4,2 5 2,8% 2,8^ &,1% 34 Lia nt ref. con for me 15 3,7 5 2,8% 4,1 % 2,2^ c 35 Lia nt ref. con for me 15 4,0 5 2,8% 2,0^ &,1% 36 Lia nt ref. — 15 4,0 7 3,6% 1,7^ S,4% 37 Lia nt ref. — 15 4,3 6 3,6% 0,8< ©,8< S,4% 38 Lia nt ref. con for me 15 4,1 6 2,8% 2,0^ S,4% 39 Lia nt ref. — 15 4,5 8 3,8% 2,0^ &,6% 40 Lia nt ref. — 15 4,2 6 3,8% 0,8 % 2,0^ &,6% 41 Lia nt ref. — 15 4,2 3 6,7% 1,4^ a,2% 42 Lia nt ref. ___ 15 4,4 1 6,7% 0,6^ »,8% 43 Lia nt ref. — 15 4,3 8 1% 4,1% 2,0^ &,1% 44 Lia nt ref. — 15 4,3 0 1% 5,4% 1,4^ a,2% 45 Lia nt ref. — 15 3,7 9 1% 4,1% 2,2 % 2,2^ c 46 Lia nt ref. — 15 4,6 6 1% 5,4% 2,0 % 1,7^ c 47 Lia nt ref. — 15 4,1 4 1% 5,4% 2,0 % 2,0^ c 48 Lia nt ref. — 15 5,3 3 1% 4,1% 2,8 % 2,8^ c 49 Lia nt ref. — 15 4,4 4 1% 4,4% 2,0 % 2,8^ a,8% 50 Lia nt ref. — 15 3,8 5 5% 4,1% 2,8^ S,4% 51 Lia nt ref. — 15 4,8 3 5% 5,4% 2,2^ &,i% 52 Lia nt ref. — 15 5,2 1 5% 10, 2% 53 Lia nt ref. con for me 15 7,0 8 5% 2,7% 2,7 ¾7^ 'c 54 Lia nt ref. con for me 15 4,4 7 5% 2,7% 2,7< &,1% 55 Lia nt ref. — 15 4,8 2 5% 3,8% 1,9^ ^,6% 56 Lia nt ref. — 15 4,4 5 5% 6,6% 1,4^ 2,2% 57 Lia nt ref. — 15 4,0 5 4,1% 2,7< 8,3% 58 Lia nt ref. — 15 5,0 8 5,3% 2,2^ &,1% 59 Lia nt ref. — 15 6,3 2 9,8% 60 Lia nt ref. con for me 15 8,5 9 2,6% 2,6 %,6^ 'c 61 Lia nt ref. con for me 15 5,4 2 2,6% 2,6^ 8,9% 62 Lia nt ref. — 15 5,8 5 3,6% 1,9^ &,4% 63 Lia nt ref. — 15 5,4 0 6,3% 1,3^ 2,1% 64 Lia nt ref. ___ 15 4,9 2 3,9% 2,6^ 8,1% 65 Lia nt ref. — 15 6,1 7 5,1% 2,K 8,9% 66 Lia nt ref. con for me 10 2,4 5 3,3 % 67 Lia nt ref. — 10 2,6 5 5,4< 'c 68 Lia nt ref. — 10 2,4 1 5,4^ c 69 Lia nt ref. — 10 2,6 8 6,7% 70 Lia nt ref. — 10 2,8 7 6,7% 71 Lia nt ref. — 10 2,9 2 7,9< 'c 72 Lia nt ref. con for me 10 3,2 1 2,8% 2,8 % 73 Lia nt ref. con for me 10 3,0 1 2,2% 1,4 %2C. 'c 74 Lia nt ref. con for me 10 2,9 8 2,8% 2,2e, 2,2% 75 Lia nt ref. ___ 10 3,4 5 6,7 % 76 Lia nt ref. con for me 10 3,8 6 7,9< 'c 77 Lia nt ref. — 10 2,4 5 5,4 78 Lia nt ref. — 10 2,6 5 6,7 % 79 Lia nt ref. con for me 10 3,1 7 2,8 % 80 Lia nt ref. con for me 10 2,6 4 4,1% 1,4^ 'c 81 Lia nt ref. con for me 10 3,0 9 2,8 % 1,4^ 'c 82 Lia nt ref. con for me 10 3,3 9 2,8 ¾8^ 'c 83 Lia nt ref. con for me 10 2,5 6 1,4 % 3,3^ 'c 84 Lia nt ref. con for me 10 2,3 8 2,2% 3,3^ 'c 85 Lia nt ref. con for me 10 2,6 0 2,8< 'c 2,8< 'c 86 Lia nt ref. con for me 10 3,0 7 2,8% 4, H 'c 87 Lia nt ref. con for me 10 2,7 3 2,8% 1,4 % 88 Lia nt ref. con for me 12 5,5 6 2,8% 6,7 % 0,0 % 89 Lia nt ref. con for me 12 2,9 2 2,8% 2,8< 'c 90 Lia nt ref. con for me 12 6,2 1 10, 3% 91 Lia nt ref. con for me 12 5,1 4 1,4 %,4< 'c 5,4< 'c 92 Lia nt ref. con for me 12 6,7 0 2,8% 2,8^ c 2,8 % 93 Lia nt ref. con for me 12 6,8 5 2,8% 2,8< 'c 2,8 % 94 Lia nt ref. con for me 12 4,7 9 2,8^ c 5,4 % 95 Lia nt ref. con for me 12 4,9 3 2,8< 'c 5,4 % 96 Lia nt ref. con for me 12 4,5 6 2,8^ c 5,4< 'c 97 Lia nt ref. con for me 12 4,7 0 2,8< 'c 5,4< 'c 98 Lia nt ref. — 12 2,6 4 10, 3% 99 Lia nt ref. — 12 4,2 5 5,4^ c 5,4< 'c 100 Lia nt ref. — 12 5,5 7 10, 3% 101 Lia nt ref. con for me 12 6,2 1 10, 3% 102 Lia nt ref. con for me 12 4,5 4 2,8% 2,8< 'c 2,8< 'c 103 Lia nt ref. con for me 12 5,8 1 5,4< 'c 5,4% 104 Lia nt ref. con for me 12 7,1 8 2,8^ S,4% 5,4< 'c 105 Lia nt ref. — 12 5,6 5 7,9% 2,8^ c 106 Lia nt ref. con for me 12 6,1 2 2,8^ c 7,9< 'c 107 Lia nt ref. con for me 12 6,2 7 2,8< 'c 7,9< 'c 108 Binder ref. con for me 12 7.4 0 5.4%,L 109 Binder ref. con for me 12 7.0 7 2.8 < 7.9% 2.8 < 110 Aqu eux con for me 10 2.4 5 3.3 % 111 Aqu eux con for me 10 2.6 5 5.4 < 112 Aqu eux con for me 10 2.4 1 5.4^ c 113 Aqu eux con for me 10 2.6 8 6.7% 114 Aqu eux ___ 10 2.8 7 6.7% 115 Aqu eux con for me 10 3.3 9 2.8 ¾8^ 116 Aqu eux con for me 10 3.2 1 2.8% 2.8 % 117 Aqu eux con for me 10 3.0 1 2.2% 1.4 %2C. 118 Aqu eux con for me 10 2.9 8 2.8% 2.2e, a.2% 119 Aqu eux con for me 10 2.5 6 1.4% 3.3^ 120 Aqu them compliant 10 2.3 8 2.2% 3.3^ 'c 121 Aqu them compliant 10 2.6 0 2.8< 'c 2.8< 'c 122 Aqu them compliant 10 3.0 7 2.8% 4, H 'c 123 Aqu them compliant 10 2.7 3 2.8% 1.4% 124 Binder ref. — 10 4.6 3 10.3% 125 Binder ref. con for me 10 5.1 5 10.3% 126 Binder ref. con for me 10 3.7 7 2.8% 2.8< 'c 2.8< 'c 127 Binder ref. con for me 10 4.8 2 5.4< 'c 5.4% 128 Binder ref. con for me 10 5.9 6 2.8^ S.4% 5.4< 'c 129 Binder ref. — 10 4.6 9 7.9% 2.8^ c 130 Binder ref. con for me 10 5.0 8 2.8^ c 7.9< 'c 131 Binder ref. con for me 10 5.2 0 2.8< 'c 7.9^ 'c 132 Link ref. con for me 10 6.1 5 5.4%,L 'c 133 Binder ref. con for me 10 5.8 7 2.8< 'c 7.9% 2.8< 'c Table III

[0162] The organic UV compounds used in Examples 10 to 133 are referenced below: Ref. Brand CAS Active Ingredient T384-2 Tinuvin 384-2 127519-17-9 Esters of benzenepropanoic acid, of 3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl-1)-4-hydroxy-, linear and C7-9 branched alkyl T477 Tinuvin 477 ___ Derivatives of ethyl 1-isoctyloxycarbonyl 2,4,6-tris(2,4-hydroxyphenyl)-1,3,5-triazine T479 Tinuvin 479 ___ Hydroxyphenyl-triazine T234 Tinuvin 900 70321-86-7 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol T928 Tinuvin 928 73936-91-1 2-(2H-Benzotriazol-2-yl)-6-(l-methyl-l-phenylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol T1130 Tinuvin 1130 104810-47-1 [3-[3-(2-H-Benzotriazole-2-yl)-4-hydroxy-5-tert.butylphenyl]-propionic acid-poly(ethylene glycol) 300-ester / Bis{[3-[3-(2-H-Benzotriazole-2-yl)-4-hydroxy-5-tert.butylphenyl]-propionic acid}-poly(ethylene glycol) 30 O-ester T400 Tinuvin 400 153519-44-9 1,3-Benzenediol, 4-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl] E109 Eversorb 109 83044-89-7 / 83044-90-0 Octyl 3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate E-BL1 B Eversorb BL1 B 131-55-5 2,2',4,4'-Tetrahydroxybenzo-phenone A+0 Parsol Guard 70356-09-1 / 6197-30-4 1,3-Propanedione, 1 - [4-( 1,1 -dimethylethyl)p henyl]-3-(4-methoxyphenyl) / 2-cyano-3,3-diphenylacrylate of 2-ethylhexyl TM Tinosorb M 103597-45-1 2,2'-methylenebis(6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol) TS Tinosorb S 187393-00-6 5 - [(2-ethylhexyl)oxy ] -2-(4- {4- [(2-ethylhexyl)oxy]-2-hydroxyphenyl}-6-(4-methoxyphenyl)-1,3,5-triazin-2-yl)phenol . Table IV

Claims

Demands

1. A filter film comprising compounds absorbing UV light in a range of 300 nm to 380 nm and a binder, wherein the weighted average absorbance A3gQ of the filter film is greater than 2, preferably greater than 2.5, with A33q defined by the following relation: / “«WW A380“ where A (.A) represents the absorbance of the filter film at a given wavelength, and W( A) represents a weighting function equal to the product of the solar spectral irradiance Es(A) and a sensitivity function S(2) defined as a Gaussian function with a peak centered at 300 nm and a standard deviation of 24 nm.

2. Filter film according to claim 1, wherein the weighted average absorbance A340 of the filter film is greater than 2, with A340 defined by the following relation: 340 “

3. A filtering film according to claim 1 or 2, wherein the UV light-absorbing compounds comprise semiconducting nanoparticles having the following formula MxEy (I), in which: M is selected from the group consisting of Zn, Cd, Hg, Cu, Ag, Al, Ga, In, Si, Ge, Sn, Pb and a mixture thereof; E is selected from the group consisting of O, S, Se, Te, N, P, As, Sb, and a mixture thereof; x and y are independently a decimal number from 0 to 5; and x and y are not simultaneously equal to 0.

4. Filter film according to claim 3, wherein the content of semiconductor nanoparticles in the filter film is in a range of 0.5% by weight to 15% by weight, based on the weight of the filter film, for a film with a thickness of 10 pm.

5. A filter film according to any one of claims 1 to 4, wherein the UV light-absorbing compounds comprise semiconductor nanoparticles having an absorbance maximum local peak of longest wavelength in the range of 320 nm to 360 nm.

6. Filtering film according to any one of claims 1 to 5, wherein the UV light-absorbing compounds comprise organic anti-UV compounds, preferably selected from the group consisting of benzotriazoles, triazines, piperidines, benzophenones, catechol, their derivatives and mixtures thereof.

7. Filter film according to claim 6, wherein the content of organic anti-UV compounds in the filter film is in a range of 2% by weight to 15% by weight, based on the weight of the filter film, for a film with a thickness of 10 pm.

8. Filter film according to any one of claims 1 to 7, wherein the content of UV light-absorbing compounds in the filter film is in a range of 3% by weight to 15% by weight, based on the weight of the filter film, for a film with a thickness of 10 pm.

9. Filter film according to any one of claims 1 to 8, wherein the filter film is transparent, preferably transparent and colorless.

10. A filter film according to any one of claims 1 to 9, wherein the UV light-absorbing compounds do not comprise more than 2.5% by weight, based on the total weight of the filter film, for a film with a thickness of 10 pm, of core-shell semiconductor nanoparticles comprising: • a core of ZnSexS(i_x) material where x is in a range of 0.60 to 0.98, and • a shell of ZnS material, and having a maximum local absorbance at longer wavelengths in the range of 350 nm to 500 nm.

11. A filtering film according to any one of claims 1 to 9, wherein the UV light-absorbing compounds do not comprise core-shell semiconductor nanoparticles comprising: • a core of ZnSExS(i_x) material where x is in a range of 0.60 to 0.98, and • a shell of ZnS material, and exhibiting a maximum local absorbance at longer wavelengths in the range of 350 nm to 500 nm.

12. Packaging comprising a substrate partially or totally covered with a filter film according to any one of claims 1 to 11 or formed from a filter film according to any one of claims 1 to 11.

13. Packaging according to claim 12, wherein the packaging is selected from the group consisting of glass containers, glass bottles, plastic containers and plastic bottles.

14. A method for protecting a consumer good against UV light in a range of 300 nm to 340 nm, comprising enclosing the consumer good in a filter film according to any one of claims 1 to 11.

15. A protection method according to claim 14, wherein the consumer good is selected from food products, cosmetic formulations and perfumes.

16. A protection method according to claim 15, wherein the consumer good is contained in a package covered with the filter film.

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