Chemical and physical sun protection dry compositions, emulsions and / or fluids and their uses

Abstract

The present invention relates to a dry composition for chemical and physical sun protection, comprising (a) at least one calcium carbonate and (b) at least one lignin in an amount of 0.1% to 100% by weight, based on the dry weight of the at least one calcium carbonate (a). The present invention also relates to a fluid composition containing the dry composition according to the present invention, and to an emulsion containing the dry composition according to the present invention. The present invention also relates to the use of the composition according to the present invention for sun protection of plants and plant parts, and the use of the emulsion according to the present invention for chemical and physical sun protection in cosmetic formulations.

Description

[Technical Field]

[0001] The present invention relates to a dry composition for chemical and physical sun protection, comprising (a) at least one calcium carbonate and (b) at least one lignin in an amount of 0.1% to 100% by weight, based on the dry weight of the at least one calcium carbonate (a). The present invention also relates to a fluid composition containing the dry composition according to the present invention, and to an emulsion containing the dry composition according to the present invention. The present invention also relates to the use of the composition according to the present invention for sun protection of plants and plant parts, and to the use of the emulsion according to the present invention for chemical and physical sun protection in cosmetic formulations. [Background technology]

[0002] Solar energy, primarily the ultraviolet portion of the solar spectrum, is widely known to have damaging effects on living cells, particularly plants and plant parts, as well as human skin. In particular, ultraviolet B (UV-B) radiation in the range of 280-320 nm and ultraviolet A (UV-A) radiation in the range of >320-400 nm both cause sunburn in plants and plant parts. Plants and plant parts, and especially fruit, can be damaged by sunburn, particularly when air temperatures in the shade exceed a temperature of approximately 30°C. This "fruit sunburn" results in fruit damage and a reduction in overall production yield, with economic consequences, primarily during hot summer months.

[0003] Furthermore, ultraviolet A (UV-A) and ultraviolet B (UV-B) radiation damages human DNA through the formation of free radicals and other reactive species that occur via phototoxic reactions in the epidermis and dermis of the skin. Consequently, UV-B and UV-A radiation are considered to be major factors in the development of chronic photoinduced changes such as premature skin aging and the development of skin cancer.

[0004] Therefore, it is becoming increasingly important to protect living cells from sunburn. In particular, it is becoming increasingly important to protect at least some plants and plant parts, especially fruits exposed to sunlight, from UV-B and UV-A radiation. There is also a need to protect human skin exposed to sunlight from UV-B and UV-A radiation. Several attempts have been made in the art to provide such UV protection.

[0005] One attempt to protect plants from sunburn involves covering the living cells with an opaque material such as foil or fabric to shield them from sunlight. For example, China Utility Model Registration No. 203538002 refers to a pomegranate growing bag capable of preventing sunburn, one side of which is reflective and the other side is transparent. During hot seasons, the reflective side of the pomegranate growing bag facing the sun covers the pomegranates, reflecting most of the midday sunlight to prevent sunburn, and some of the sunlight reflected by the reflective plastic film is irradiated onto the leaves on the shaded side of the fruit trees, increasing photosynthesis throughout the orchard. However, this procedure is complicated, time-consuming, and labor-intensive, as every plant or fruit must be individually handled by hand.

[0006] Another option for reducing the possibility of sunburn is to use mineral particles, usually clay or calcium carbonate, which form a thin film on plants and plant parts or on human skin and protect living cells by reflecting or absorbing damaging UV radiation. Therefore, these compounds are known as physical sunscreens. Such sunscreen compositions for application to plants are known; for example, U.S. Patent Application Publication No. 2012 / 0052187 A1 describes a sunscreen composition containing titanium dioxide (TiO), zinc oxide (ZnO), silicon dioxide (SiO), surfactants, wetting agents, dispersants (SWD), and water. This composition forms a suspension concentrate, which, when diluted in water, provides a solution that provides a uniform coating using conventional spray equipment.

[0007] WO 2010 / 008476 A1 relates to a method for increasing crop yields, which comprises controlling stress in plant tissue by at least partially coating the plant tissue with a composition comprising an agricultural sunscreen formulation and a second pesticide, the agricultural sunscreen formulation comprising 40-80% by weight calcium carbonate, 1-5% by weight bicarbonate, and 15-59% by weight water.

[0008] US Patent Application Publication No. 2016 / 037772 A1 relates to a method of treating plants to increase their tolerance to abiotic stress or to reduce the consequences of abiotic stress in plants. Kaolin or calcium carbonate, for example, can be added to the sunscreen.

[0009] U.S. Patent Application Publication No. 2017 / 333301 A1 relates to a water-in-oil emulsion sunscreen cosmetic product containing 6 to 40% by weight of a UV protection agent, an organically modified clay mineral, an oil phase thickener, and a silicone-based surfactant with an HLB of less than 8. The UV protection agent can be particles of a metal oxide such as zinc oxide, titanium oxide, iron oxide, cerium oxide, or tungsten oxide.

[0010] Inorganic UV filters such as zinc oxide and titanium dioxide are photostable and provide broad-spectrum protection covering UV-A and UV-B by blocking UV light.So-called mineral (inorganic)-only sunscreen formulations, that is, sunscreen formulations containing only inorganic UV filter materials such as zinc oxide and / or titanium dioxide, have long been recommended, especially for people with sensitive skin as well as for infants and young children.However, inorganic UV filters are mainly used in the form of nanoparticles, and recently, these nanoparticles are thought to have potentially harmful effects on natural and human skin.

[0011] The paper "TiO2 Encapsulated in Lignin-Based Colloidal Spheres for High Sunscreen Performance and Weak Photocatalytic Activity," by Yuan Yuan Li et al., ACS Sustainable Chemistry and Engineering, vol. 7, no. 6, February 18, 2019, describes nano-TiO2 particles fully entrapped in lignin colloidal spheres. However, as already mentioned above, TiO2 nanoparticles can have harmful effects on the environment and human skin. Furthermore, colloidal spheres exhibit different chemical properties than, for example, particles coated with lignin.

[0012] The paper "Lignin Coatings to Quench the Photocatalytic Activity of Titanium Dioxide Nanoparticles for Potential Skin Care Applications," by M. Morsella et al., RSC Advances, vol. 5, no. 71, January 1, 2015, concerns coatings to quench the photocatalytic activity of titanium dioxide nanoparticles for potential skin care applications. However, as already mentioned above, TiO2 nanoparticles can have harmful effects on natural and human skin. Furthermore, this paper concerns photocatalytic activity that is distinct from UV activity.

[0013] Another option for reducing the possibility of sunburn is to use organic UV filters. Organic UV filters are often transparent or translucent. Such filters provide chemical sun protection by absorbing UV-A and / or UV-B radiation. Organic UV filters can be classified into synthetically produced UV filters and naturally occurring UV filters. Synthetically produced UV filters are not found in nature and are synthetically produced, while naturally occurring UV filters occur in nature or are produced from naturally occurring compounds.

[0014] For example, synthetically produced UV filters such as octocrylene can be designed to be perfectly compatible with each system or composition that is blended with them.Furthermore, such filters can be customized for individual applications.However, synthetic organic UV filters such as octocrylene are under increasing concern, especially because they are suspected of causing dermatitis and skin allergies in people with sensitive skin, and of their potentially harmful effects on the environment.

[0015] Thus, there is a continuing need in the art for suitable formulations or compositions that provide sufficient or improved UV-B and / or UV-A protection to living cells, particularly to plants and plant parts and human skin. Summary of the Invention [Problem to be solved by the invention]

[0016] It is therefore an object of the present invention to provide compositions for providing chemical and physical sun protection. More precisely, it is an object of the present invention to provide compositions for providing sufficient or improved UV-B and / or UV-A protection to living cells, particularly plants and plant parts, and human skin, by different mechanisms, namely, by reflecting UV-B and / or UV-A radiation and by absorbing UV-B and / or UV-A radiation. A further object of the present invention is that the compounds used in these compositions are non-toxic to humans, do not have harmful effects on the environment, and are preferably approved by food regulations for plants and plant parts, particularly fruit, and by the FDA for use in cosmetics. Another object of the present invention is that the compositions should be easy and rapid to manufacture, inexpensive, and, above all, easy to handle. It is particularly preferred that these compositions adhere to plants and plant parts and human skin and are not easily washed away by rain or sweat. [Means for solving the problem]

[0017] These and other objects of the present invention are solved by a chemical and physical sun protection composition as described herein and as defined in the claims. Advantageous embodiments of the invention are defined in the corresponding dependent claims.

[0018] According to one embodiment of the present invention, there is provided a dry chemical and physical sunscreen composition comprising: (a) at least one calcium carbonate; and (b) from 0.1% to 100% by weight, based on the dry weight of the at least one calcium carbonate of (a), of at least one lignin.

[0019] The inventors have surprisingly found that the above-described compositions provide sufficient or improved chemical and physical sun protection. More precisely, the inventors have surprisingly found that the compositions of the present invention provide two distinct mechanisms for UV-B and / or UV-A protection for living cells, particularly plants and plant parts, and human skin: by reflecting UV-B and / or UV-A radiation and by absorbing UV-B and / or UV-A radiation. The combination of at least one calcium carbonate and at least one lignin provides a new and improved UV protection mechanism that is not achievable with bare minerals, particularly bare calcium carbonate. Furthermore, the compounds used in the compositions of the present invention, i.e., calcium carbonate and lignin, are non-toxic to humans and do not have a harmful effect on the environment. Furthermore, these compounds are often approved by food regulations for plants and plant parts, particularly fruit, and by the FDA for use in cosmetics. Furthermore, the inventors have surprisingly found that the composition of the present invention can be easily and quickly produced, is inexpensive and, above all, is easy to handle. Furthermore, when the composition according to the present invention is used for sun protection of plants and plant parts, another advantage is that the composition also provides calcium nutrients to the plants due to the calcium carbonate in the composition.

[0020] According to another aspect of the present invention, there is provided a fluid composition for chemical and physical sun protection, the fluid composition comprising water and 1 to 100% by weight, based on the weight of the water, of the dry composition according to the present invention. A further advantage is that when the fluid composition is applied to plants and plant parts, the layer of the composition formed on the plants and plant parts also repels insects.

[0021] According to another aspect of the present invention there is provided a chemical and physical sun protection emulsion comprising a water-in-oil or oil-in-water mixture and comprising 0.1 to 100% by weight of a dry composition according to the present invention, based on the weight of the water-in-oil or oil-in-water mixture.

[0022] According to another aspect of the invention, the compositions according to the invention are used for sun protection of plants and plant parts, wherein this sun protection includes physical and chemical protection.

[0023] According to another aspect of the invention, the emulsions of the present invention are used for chemical and physical sun protection in cosmetic formulations.

[0024] Advantageous embodiments of the above aspects are defined in the corresponding dependent claims.

[0025] According to one embodiment of the present invention, the calcium carbonate is selected from the group consisting of ground calcium carbonate (GCC), preferably marble, limestone, and / or chalk; precipitated calcium carbonate (PCC), preferably vaterite, calcite, and / or aragonite; and mixtures thereof, most preferably the calcium carbonate is ground calcium carbonate.

[0026] According to another embodiment of the present invention, the at least one calcium carbonate is (a) a weight median particle size d in the range of 0.05 μm to 20 μm, preferably 0.25 μm to 10 μm, and most preferably 0.5 μm to 8 μm; 50 value, and / or (b) a top cut (d 98 ), and / or (c) 0.5-100 m measured by the BET nitrogen method 2 / g, preferably 0.5 to 50m 2 / g, more preferably 0.5 to 35m 2 / g, most preferably 0.5 to 10m 2 / g specific surface area (BET).

[0027] According to another embodiment of the present invention, the at least one lignin is a water-soluble or water-insoluble lignin selected from the group consisting of native lignin, Klason lignin, hydrolyzed lignin, ground lignin (ground wood lignin), soda lignin, organosolv lignin, Kraft lignin, sulfonated lignin, and mixtures thereof, preferably a water-insoluble lignin selected from the group consisting of Klason lignin, Kraft lignin, and mixtures thereof, most preferably Kraft lignin.

[0028] According to another embodiment of the present invention, the at least one lignin is present in the composition in an amount of 1 to 50 wt. %, preferably in an amount of 3 to 30 wt. %, and most preferably in an amount of 5 to 25 wt. %, based on the dry weight of the (a) at least one calcium carbonate.

[0029] According to another embodiment of the present invention, the composition further comprises an organic solvent, preferably in an amount of 5 to 50 wt. %, more preferably 10 to 40 wt. %, most preferably 15 to 35 wt. %, based on the dry weight of the (a) at least one calcium carbonate, and / or preferably in an amount of 100 to 500 wt. %, more preferably 150 to 450 wt. %, most preferably 200 to 300 wt. %, based on the dry weight of the (b) at least one lignin.

[0030] According to another embodiment of the present invention, the organic solvent is selected from the group consisting of hexane, toluene, methanol, ethanol, dioxane, acetone, dimethyl sulfoxide, dimethylformamide, ethylene glycol, ethyl acetate, glycerol, γ-valerolactone, polyethylene glycol, polypropylene glycol, and mixtures thereof, more preferably selected from the group consisting of ethylene glycol, ethyl acetate, glycerol, γ-valerolactone, polyethylene glycol, polypropylene glycol, and mixtures thereof, most preferably γ-valerolactone.

[0031] According to another embodiment of the invention, the at least one lignin is present in the composition in the form of a mixture with the at least one calcium carbonate or in the form of a coating on the at least one calcium carbonate, preferably as a coating on the at least one calcium carbonate.

[0032] According to another embodiment of the present invention, the at least one lignin in the coating on the at least one calcium carbonate is a water-insoluble lignin, preferably a kraft lignin.

[0033] According to another embodiment of the present invention, the fluid composition further comprises a surfactant, preferably selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic anhydride, isocrotonic acid, aconitic acid (cis or trans), mesaconic acid, sinapic acid, undecylenic acid, angelic acid, canellic acid, hydroxyacrylic acid, acrolein, acrylamide, acrylonitrile, dimethylaminoethyl methacrylate, vinylpyrrolidone, vinylcaprolactam, ethylene, propylene, isobutylene, diisobutylene, vinyl acetate, styrene, α-methylstyrene, methyl vinyl ketone, esters of acrylic and methacrylic acid, organically modified trisiloxanes, PEG, polyglycerol esters, sophorolipids, polyether monomers and / or comonomers, and mixtures thereof, most preferably poly(acrylic acid) and / or poly(methacrylic acid); and / or The surfactant is present in the composition in an amount of 0.0001 to 0.2 wt. %, preferably 0.001 to 0.1 wt. %, and most preferably 0.005 to 0.05 wt. %, based on the dry weight of the (a) at least one calcium carbonate and (b) at least one lignin.

[0034] According to another embodiment of the present invention, the plants and plant parts are fruits, vegetables, trees, seeds, leaves, wood, nuts, agricultural crops, crop plants, and flowering plants.

[0035] According to another embodiment of the invention, the at least one lignin is present in the form of a coating on the at least one calcium carbonate and / or the at least one lignin is a water-insoluble lignin, preferably a kraft lignin.

[0036] According to another embodiment of the present invention, the cosmetic formulation is a sunscreen product, a facial makeup product, a hair care product, a hair styling product, a nail care product, a hand care product, a skin care product, and mixtures thereof.

[0037] For purposes of the present invention, the following terms shall be understood to have the following meanings:

[0038] "Chemical sun protection" in the sense of the present invention refers to protection against UV-B and / or UV-A radiation by absorbing UV-B and / or UV-A radiation.

[0039] "Physical sun protection" in the sense of the present invention refers to protection from UV-B and / or UV-A radiation by reflecting said radiation.

[0040] "UV-A protection" and "UV-B protection" in the sense of the present invention refer to protection from ultraviolet B (UV-B) radiation in the range of 280-320 nm and ultraviolet A (UV-A) radiation in the range >320-400 nm, both of which cause sunburn in plants and plant parts as well as human skin.

[0041] A "water-insoluble" material is defined as a material that, when mixed with 100 g of deionized water and filtered at 20° C. under atmospheric pressure on a 0.2 μm pore size filter to recover the liquid filtrate, provides 0.1 g or less of recovered solid material after evaporation of 100 g of the liquid filtrate at 95-100° C. under ambient pressure. Accordingly, a "water-soluble" material is defined as a material that, when mixed with 100 g of deionized water and filtered at 20° C. under atmospheric pressure on a 0.2 μm pore size filter to recover the liquid filtrate, provides 0.1 g or more of recovered solid material after evaporation of 100 g of the liquid filtrate at 95-100° C. under ambient pressure.

[0042] The "particle size" of the particulate material in this specification refers to the particle size d x where the value d x is the weight percent of particles in x This refers to the diameter of the hole, e.g., d 20 A value of d means that 20% by weight of all particles are smaller than that particle size. 50 The values ​​are weight median particle diameters, i.e., 50% by weight of all particles are larger than this particle diameter and the remaining 50% by weight are smaller than this particle diameter. For the purposes of this invention, particle diameters are referred to as weight median particle diameter d unless otherwise specified. 50 Identified as d 98 is the particle size below which 98% of all particles by weight are smaller. 98 Values ​​are also specified as "top cut." Particle size was determined using a Sedigraph® 5100 instrument from Micromeritics Instrument Corporation. This method and instrument is known to those skilled in the art and is commonly used to determine particle size of fillers and pigments. Measurements were made in an aqueous solution of 0.1 wt% Na4P2O7. Samples were dispersed using a high-speed stirrer and sonication.

[0043] The "specific surface area (SSA)" of a calcium carbonate-containing filler material in the sense of the present invention is defined as the surface area of ​​the calcium carbonate-containing filler material divided by its mass. The specific surface area is measured by nitrogen gas adsorption using the BET isotherm (ISO 9277:2010) and is expressed as m 2 It is specified as / g.

[0044] The term "dry" material or "dry" composition is understood to be a material / composition having less than 5.0% by weight of water relative to the weight of the material / composition. The % water (equal to the total remaining water content) is determined according to the coulometric Karl Fischer measurement method, in which the material / composition is heated to 220°C and the water content released as vapor and isolated using a nitrogen gas flow (100 ml / min) is measured in a coulometric Karl Fischer apparatus.

[0045] "Coating" in the sense of the present invention means that one compound is located on the surface of another compound.

[0046] Where the terms "comprising" or "containing" are used in the present description and claims, it does not exclude other elements. For the purposes of the present invention, the term "consisting of" is considered to be a preferred embodiment of the term "comprising". Hereinafter, when a group is defined to include at least a certain number of embodiments, this is to be understood as also disclosing a group that preferably consists only of these embodiments.

[0047] Where an indefinite or definite article is used when referring to a singular noun, e.g. "a", "an" or "the", this includes a plural of that noun unless otherwise stated.

[0048] Terms such as "obtainable" or "defined" and "obtained" or "defined" are used interchangeably. For example, this does not mean that the term "obtained" indicates that, for example, an embodiment must be obtained by the sequence of steps that follows the term "obtained," unless the context clearly dictates otherwise, but that such a limited understanding is always included in the terms "obtained" or "defined," as a preferred embodiment.

[0049] The details and preferred embodiments of the present invention are explained in more detail below: The embodiments referring to the compositions and emulsions of the present invention also relate to the embodiments of the use of the compositions of the present invention for sun protection of plants and plant parts, and the use of the emulsions of the present invention for chemical and physical sun protection in cosmetic formulations, and the embodiments referring to the use of the compositions of the present invention for sun protection of plants and plant parts, and the use of the emulsions of the present invention for chemical and physical sun protection in cosmetic formulations also relate to the embodiments of the compositions and emulsions of the present invention.

[0050] According to the present invention, there is provided a dry composition for chemical and physical sun protection, the composition comprising: (a) at least one calcium carbonate; and (b) from 0.1% to 100% by weight, based on the dry weight of the at least one calcium carbonate of (a), of at least one lignin.

[0051] At least one calcium carbonate According to the invention, at least one calcium carbonate is present in the dry composition.

[0052] The term "at least one" calcium carbonate in the sense of the present invention means that the calcium carbonate comprises one or more calcium carbonates, preferably consists of one or more calcium carbonates.

[0053] In one embodiment of the present invention, the at least one calcium carbonate in the composition preferably comprises, and preferably consists of, one calcium carbonate. Alternatively, the at least one calcium carbonate comprises, and preferably consists of, two or more calcium carbonates. For example, the at least one calcium carbonate comprises, and preferably consists of, two or three calcium carbonates.

[0054] The amount of calcium in the calcium carbonate is at least 50 mol%, preferably at least 70 mol%, more preferably at least 90 mol%, and most preferably at least 99 mol%, based on the total amount of calcium carbonate. The calcium carbonate may contain further alkaline earth compounds such as Mg.

[0055] According to a preferred embodiment of the present invention, the calcium carbonate is selected from the group consisting of ground calcium carbonate (GCC), preferably marble, limestone, and / or chalk; precipitated calcium carbonate (PCC), preferably vaterite, calcite, and / or aragonite; and mixtures thereof.

[0056] Natural or ground calcium carbonate (GCC) is understood to be produced from naturally occurring forms of calcium carbonate mined from sedimentary rocks such as limestone or chalk, or from metamorphic marble, eggshells, or seashells. Calcium carbonate is known to exist in three types of crystalline polymorphs: calcite, aragonite, and vaterite. Calcite, the most common crystalline polymorph, is considered to be the most stable crystalline form of calcium carbonate. Aragonite is less common, having a discrete or clustered needle-like orthorhombic crystalline structure. Vaterite is the rarest calcium carbonate polymorph and is generally unstable. Ground calcium carbonate is almost exclusively the calcite polymorph, which is described as trigonal-rhombohedral and represents the most stable form of calcium carbonate polymorph. The term "source" for calcium carbonate in the sense of this application refers to the naturally occurring mineral material from which calcium carbonate is obtained. The calcium carbonate source may also contain naturally occurring components such as aluminosilicates.

[0057] Generally, the grinding of natural ground calcium carbonate can be a dry or wet grinding process and can be carried out using any conventional grinding equipment, for example, under conditions where grinding occurs primarily as a result of impact with secondary objects, i.e., in one or more of a ball mill, rod mill, vibratory mill, roll crusher, centrifugal impact mill, vertical bead mill, attrition mill, pin mill, hammer mill, crusher, shredder, declamper, knife cutter, or other such equipment known to those skilled in the art. When the calcium carbonate-containing mineral material comprises a mineral material containing wet-ground calcium carbonate, the grinding process can be carried out under conditions where autogenous grinding occurs and / or by horizontal ball milling and / or other such processes known to those skilled in the art. The wet-processed ground calcium carbonate-containing mineral material thus obtained can be washed and dewatered by known processes, for example, by flocculation, filtration, or forced evaporation, before drying. The subsequent drying step (if necessary) can be carried out in a single step, such as spray drying, or in at least two steps. Such mineral materials also typically undergo beneficiation processes (such as flotation, bleaching, or magnetic separation processes) to remove impurities.

[0058] According to one embodiment of the present invention, the source of natural or ground calcium carbonate (GCC) is selected from marble, chalk, limestone, or mixtures thereof. Preferably, the source of ground calcium carbonate is marble. According to one embodiment of the present invention, the GCC is obtained by dry grinding. According to another embodiment of the present invention, the GCC is obtained by wet grinding and optionally subsequent drying.

[0059] According to one embodiment of the invention, the calcium carbonate comprises one type of ground calcium carbonate. According to another embodiment of the invention, the calcium carbonate comprises a mixture of two or more types of ground calcium carbonate selected from different sources.

[0060] "Precipitated calcium carbonate" (PCC) in the sense of the present invention is generally a synthesized material obtained by precipitation following the reaction of carbon dioxide with lime in an aqueous environment, or by precipitation of a calcium and carbonate ion source in water, or by precipitation from solution with a combination of calcium and carbonate ions, e.g., CaCl2 and Na2CO3. Further possible methods for producing PCC are the lime-soda process or the Solvay process, in which PCC is a by-product of ammonia production. Precipitated calcium carbonate exists in three primary crystalline forms: calcite, aragonite, and vaterite, and for each of these crystalline forms, many different polymorphs (crystal habits) exist. Calcite has a trigonal crystal structure with typical crystal habits such as scalenohedral (S-PCC), rhombohedral (R-PCC), hexagonal prismatic, tabular, colloidal (C-PCC), cubic, and prismatic (P-PCC). Aragonite has an orthorhombic structure with a typical crystal habit of twinned hexagonal prisms, but also structures with a varied assortment of thin, elongated prisms, curved blades, steeply sloped pyramids, chisel-like crystals, branched tree forms, and coral- or worm-like morphologies. Vaterite belongs to the hexagonal crystal system. The resulting PCC slurry can be mechanically dewatered and dried.

[0061] According to one embodiment of the present invention, the precipitated calcium carbonate is a precipitated calcium carbonate, preferably comprising the mineralogical crystalline forms of aragonite, vaterite, or calcite, or mixtures thereof.

[0062] According to one embodiment of the present invention, the calcium carbonate comprises one type of precipitated calcium carbonate. According to another embodiment of the present invention, the calcium carbonate comprises a mixture of two or more precipitated calcium carbonates selected from different crystalline forms and different polymorphs of precipitated calcium carbonate. For example, the at least one precipitated calcium carbonate may comprise one PCC selected from S-PCC and one PCC selected from R-PCC.

[0063] According to a preferred embodiment of the present invention, the at least one calcium carbonate-comprising material is ground calcium carbonate, preferably dry ground calcium carbonate. According to another preferred embodiment, the at least one calcium carbonate-comprising material is marble.

[0064] Preferably, the at least one calcium carbonate is a dry-ground material, a wet-ground and dried material, or a mixture of the aforementioned materials. Generally, the grinding step can be carried out using any conventional grinding equipment, for example, under conditions such that refinement occurs primarily as a result of impact with secondary objects, i.e., in one or more of a ball mill, rod mill, vibratory mill, roll crusher, centrifugal impact mill, vertical bead mill, attrition mill, pin mill, hammer mill, crusher, shredder, declamper, knife cutter, or other such equipment known to those skilled in the art.

[0065] If the at least one calcium carbonate is wet-ground calcium carbonate, the grinding step can be carried out under conditions such that autogenous grinding occurs, and / or by horizontal ball milling, and / or other such processes known to those skilled in the art. The wet-processed ground calcium carbonate thus obtained can be washed and dewatered by known processes, for example, by flocculation, filtration, or forced evaporation, before drying. The subsequent drying step can be carried out in a single step, such as spray drying, or in at least two steps, for example, by subjecting the calcium carbonate to a first heating step, thereby reducing the associated moisture content to a level not exceeding about 5% by weight, based on the total dry weight of the calcium carbonate. The residual total moisture content of the filler can be measured by Karl Fischer coulometric titration by desorbing moisture in an oven at 195°C and continuously passing the filler through a KF coulometer (Mettler Toledo Coulometric KF Titrator C30 in combination with a Mettler oven DO 0337) at 100 ml / min for 10 minutes using dry N2. The residual total moisture content can be determined using a calibration curve and can also take into account a blind 10-minute gas flow rate without a sample. The residual total moisture content can be further reduced by applying a second heating step to the calcium carbonate. If this drying is carried out by more than one drying step, the first step can be carried out by heating in a hot air stream, while the second and further drying steps are preferably carried out by indirect heating, where the atmosphere in the corresponding container contains a surface treatment agent. It is also common for calcium carbonate to undergo beneficiation steps (e.g., flotation, bleaching, or magnetic separation steps) to remove impurities.

[0066] In one embodiment of the present invention, the at least one calcium carbonate comprises dry ground calcium carbonate. In another preferred embodiment, the at least one calcium carbonate is a raw material that is wet ground in a horizontal ball mill and subsequently dried by using the well-known process of spray drying.

[0067] Depending on the at least one calcium carbonate, the at least one calcium carbonate according to the present invention has a residual total moisture content of less than 5 wt.-%, preferably less than 4 wt.-%, more preferably less than 3 wt.-%, even more preferably less than 2 wt.-%, and most preferably less than 1 wt.-%, based on the total dry weight of the at least one calcium carbonate.

[0068] Alternatively, the at least one calcium carbonate according to an embodiment may have a total residual moisture content of 0.01 to 1 wt. %, preferably 0.02 to 0.5 wt. %, more preferably 0.03 to 0.3 wt. %, even more preferably 0.04 to 0.2 wt. %, and most preferably 0.05 to 0.15 wt. %, based on the total dry weight of the at least one calcium carbonate.

[0069] For example, when wet-ground and dried calcium carbonate is used as the at least one calcium carbonate, the total residual moisture content of the at least one calcium carbonate is preferably 0.01 to 1 wt %, more preferably 0.02 to 0.1 wt %, and most preferably 0.04 to 0.08 wt %, based on the total dry weight of the at least one calcium carbonate. When PCC is used as the at least one calcium carbonate, the total residual moisture content of the at least one calcium carbonate is preferably 0.01 to 1 wt %, more preferably 0.05 to 0.2 wt %, and most preferably 0.05 to 0.15 wt %, based on the total dry weight of the at least one calcium carbonate.

[0070] According to one embodiment of the present invention, the at least one calcium carbonate is preferably in the form of a granular material and may have a particle size distribution as conventionally used for the material or materials involved in the type of product to be produced. Typically, the at least one calcium carbonate has a weight median particle size d in the range of 0.05 μm to 20 μm, preferably 0.25 μm to 10 μm, most preferably 0.5 μm to 8 μm. 50 It is preferred that the compound has the following structure:

[0071] Additionally or alternatively, the at least one calcium carbonate has a top cut (d 98 )

[0072] Additionally or alternatively, the at least one calcium carbonate has a pH of 0.5 to 100 m as measured by the BET nitrogen method. 2 / g, preferably 0.5 to 50m 2 / g, more preferably 0.5 to 35m 2 / g, most preferably 0.5 to 10m 2 / g BET specific surface area.

[0073] According to another embodiment of the present invention, the at least one calcium carbonate has: (a) a weight median particle size d in the range of 0.05 μm to 20 μm, preferably 0.25 μm to 10 μm, and most preferably 0.5 μm to 8 μm; 50 value, or (b) a top cut (d 98 ), or (c) 0.5-100 m measured by BET nitrogen method 2 / g, preferably 0.5 to 50m 2 / g, more preferably 0.5 to 35m 2 / g, most preferably 0.5 to 10m 2 / g specific surface area (BET).

[0074] According to another embodiment of the present invention, the at least one calcium carbonate has: (a) a weight median particle size d in the range of 0.05 μm to 20 μm, preferably 0.25 μm to 10 μm, and most preferably 0.5 μm to 8 μm; 50 value, and (b) a top cut (d 98 ), and (c) 0.5-100 m measured by BET nitrogen method2 / g, preferably 0.5 to 50m 2 / g, more preferably 0.5 to 35m 2 / g, most preferably 0.5 to 10m 2 / g specific surface area (BET).

[0075] At least one lignin According to the invention, the at least one lignin is present in the composition in an amount of 0.1% to 100% by weight, based on the dry weight of the at least one calcium carbonate.

[0076] The term "at least one" lignin in the sense of the present invention means that the lignin comprises one or more lignins, preferably consists of one or more lignins.

[0077] In one embodiment of the invention, the at least one lignin in the composition comprises, and preferably consists of, one lignin. Alternatively, the at least one lignin comprises, and preferably consists of, two or more lignins, for example, the at least one lignin comprises, and preferably consists of, two or three lignins.

[0078] Preferably, the at least one lignin in the composition comprises, more preferably consists of, one lignin.

[0079] "Lignin" in the sense of the present invention is defined as an organic biopolymer obtained from wood and plants. Lignin is a cross-linked polymer with a molecular weight of more than 10,000 u. Lignin is rich in hydrophobic, aromatic subunits, and mainly contains a cross-linked network of 4-hydroxy-3-methoxyphenylpropane, 3,5-dimethoxy-4-hydroxyphenylpropane, and 4-hydroxyphenylpropane.

[0080] Lignin is known to those skilled in the art and is commercially available, for example, from Domsho under the trade name Domsho Lignin DS10.

[0081] Plant lignins can be broadly divided into three types: coniferous (gymnosperm) lignin, broad-leaved (angiosperm) lignin, and grass or annual (grass) lignin. Three different phenylpropane units, or monolignols, are responsible for lignin biosynthesis. Guaiacyl lignin is primarily composed of coniferyl alcohol units, while guaiacyl-syringyl lignin contains coniferyl alcohol and sinapyl alcohol monomer units. Generally, guaiacyl lignin is found in conifers, while guaiacyl-syringyl lignin is found in broad-leaved trees. Grass lignin is primarily composed of p-coumaryl alcohol units. Lignin polymerization is initiated by oxidation of the phenolic hydroxyl group of phenylpropane. Stabilization of the radical occurs by coupling to another radical at any position of the unpaired electron.

[0082] According to one embodiment of the present invention, the at least one lignin is a water-soluble or water-insoluble lignin selected from the group consisting of native lignin, Klason lignin, hydrolyzed lignin, ground lignin, soda lignin, organosolv lignin, kraft lignin, sulfonated lignin, and mixtures thereof.

[0083] Natural lignin is the lignin present in plant tissues and is also known as native lignin.

[0084] Klason lignin is the acid-insoluble lignin content of natural lignin. Klason lignin is obtained by prehydrolyzing natural lignin in H2SO4, hydrolyzing the mixture at high temperature, and filtering. The residue contains Klason lignin. The Klason process is known to those skilled in the art.

[0085] Hydrolyzed lignin can be obtained by refluxing lignin or lignocellulose with HCl in a dioxane / water composition. This treatment results in the decomposition of lignin with the formation of significant amounts of allylpropane, with the majority of the acid-decomposed monomers being derived from allylglycerol β-aryl ether structures.

[0086] Ground lignin (or ground wood lignin; MWL), also known as Bjoerkman lignin, is obtained by grinding wood flour in a ball mill, either dry or in the presence of a non-swelling solvent, such as toluene, where the cellular structure of the wood is destroyed. A portion of the lignin can be obtained from the suspension by extraction with a dioxane-water mixture. The Bjoerkman process is known to those skilled in the art.

[0087] Kraft lignin is lignin obtained from the Kraft process, also known as Kraft pulping or sulfate processing. This process is known to those skilled in the art for converting wood into wood pulp, which consists of nearly pure cellulose fibers, the main component of paper. The Kraft process involves treating wood chips with a hot mixture of water, sodium hydroxide (NaOH), and sodium sulfide (NaS), known as white liquor, to break the bonds connecting lignin, hemicellulose, and cellulose. This technique involves several steps, both mechanical and chemical.

[0088] Lignosulfonates, also known as sulfonated lignins, are water-soluble anionic polyelectrolyte polymers. They are obtained from wood by treating the wood at high temperature with a solution containing sulfur dioxide and bisulfite ions. This process is known to those skilled in the art.

[0089] Soda lignin is obtained from the soda process, which involves heating fibrous wood material to high temperatures in a pressurized reactor in the presence of sodium hydroxide (i.e., soda), also known as cooking liquor. In this process, the lignin separates from the cellulose and is suspended in a liquid phase called black liquor. The black liquor therefore contains lignin and sodium hydroxide (soda), and is known as soda lignin.

[0090] Organosolv lignin is obtained by the organosolv process, which typically involves extracting lignin from lignocellulosic biomass using an organic solvent in the presence of an acid catalyst. Organosolv lignin does not contain sulfur or sulfonate groups and has a molecular weight of about 1000-2000 g / mol.

[0091] According to one embodiment of the invention, the at least one lignin is a mixture of two or more lignins, such as a mixture of two lignins, such as a sulfonated lignin and a further lignin, such as a mixture of a sulfonated lignin and a kraft lignin or a native lignin.

[0092] According to a preferred embodiment of the present invention, the at least one lignin consists of only one lignin, preferably selected from native lignin, Klason lignin, hydrolyzed lignin, ground lignin, soda lignin, organosolv lignin, kraft lignin, or sulfonated lignin, and most preferably consists of only kraft lignin.

[0093] According to one embodiment of the present invention, the at least one lignin is a water-soluble lignin. According to another embodiment of the present invention, the at least one lignin is a water-insoluble lignin. Preferably, the at least one lignin is a water-insoluble lignin, and most preferably, the at least one water-insoluble lignin is selected from the group consisting of Klason lignin, Kraft lignin, and mixtures thereof, and most preferably Kraft lignin.

[0094] According to another embodiment of the invention, the at least one lignin has a molecular weight of more than 10,000 u, preferably between 15,000 and 1,000,000 u, even more preferably between 50,000 and 800,000 u, most preferably between 100,000 and 500,000 u.

[0095] The at least one lignin is present in the composition in an amount of 0.1 to 100% by weight, based on the dry weight of the (a) at least one calcium carbonate. According to a preferred embodiment of the present invention, the at least one lignin is present in the composition in an amount of 1 to 50% by weight, preferably in an amount of 3 to 30% by weight, and most preferably in an amount of 5 to 25% by weight, based on the dry weight of the (a) at least one calcium carbonate.

[0096] Dry Composition The dry compositions of the present invention for chemical and physical sun protection include (a) at least one calcium carbonate, and (b) from 0.1% to 100% by weight, based on the dry weight of the at least one calcium carbonate of (a), of at least one lignin.

[0097] Alternatively, the dry composition of the present invention for chemical and physical sun protection comprises (a) at least one calcium carbonate and (b) from 0.1% to 100% by weight, based on the dry weight of the at least one calcium carbonate of (a), of at least one lignin.

[0098] Preferably, the dry compositions of the present invention for chemical and physical sun protection comprise (a) at least one calcium carbonate and (b) from 0.1% to 100% by weight, based on the dry weight of the at least one calcium carbonate of (a), of at least one lignin, in which case other compounds may also be present in the composition.

[0099] According to one embodiment of the present invention, the composition further comprises an organic solvent.

[0100] An "organic solvent" in the sense of the present invention is a compound that is liquid at room temperature and is different from water. Room temperature refers to a temperature of 25° C. Preferably, the organic solvent is capable of dissolving at least one lignin, preferably a water-insoluble lignin.

[0101] The organic solvent of the present invention can be any organic solvent suitable for the composition of the present invention. Those skilled in the art know how to select such an organic solvent. Organic solvents are known to those skilled in the art and are commercially available.

[0102] According to one embodiment of the present invention, the organic solvent is selected from the group consisting of hexane, toluene, methanol, ethanol, dioxane, acetone, dimethyl sulfoxide, dimethylformamide, ethylene glycol, ethyl acetate, glycerol, γ-valerolactone, polyethylene glycol, polypropylene glycol, and mixtures thereof, more preferably ethylene glycol, ethyl acetate, glycerol, γ-valerolactone, polyethylene glycol, polypropylene glycol, and mixtures thereof, and most preferably γ-valerolactone.

[0103] Hexane has the chemical formula: CH 14 Hexane is a six-carbon alkane with five structural isomers. All of them are colorless, odorless liquids when pure, with a boiling point between 50 and 70 °C.

[0104] Toluene is an aromatic hydrocarbon with the formula C6H5CH3 and is a colorless, water-insoluble liquid with an odor related to paint thinner.

[0105] Methanol, also known among other things as methyl alcohol, is a chemical with the formula CHOH. Ethanol, also known among other things as ethyl alcohol, is a chemical with the formula CH-CH-OH.

[0106] Dioxane is a heterocyclic organic compound classified as an ether. It is a colorless liquid with a slightly sweet odor. Dioxane includes the isomers 1,2-dioxane, 1,3-dioxane, and 1,4-dioxane.

[0107] Acetone or propanone is an organic compound with the formula (CH3)2CO; it is a colorless, volatile, and flammable liquid and the simplest and smallest ketone.

[0108] Dimethyl sulfoxide (DMSO) is an organosulfur compound with the formula (CH3)2SO. This colorless liquid is a polar aprotic solvent that dissolves both polar and nonpolar compounds and is miscible in a wide range of organic solvents and water.

[0109] Dimethylformamide is an organic compound with the formula: (CH)NC(O)H. Commonly abbreviated as DMF, this colorless liquid is miscible with water and most organic liquids.

[0110] Ethylene glycol, also known as ethane-1,2-diol, is an organic compound with the chemical formula: (CHOH). Ethylene glycol is an odorless, colorless, sweet-tasting, viscous liquid.

[0111] Ethyl acetate is an organic compound with the formula CH3-COO-CH2-CH3. It is a colorless liquid with a characteristic sweet odor. It is the ester of ethanol and acetic acid.

[0112] Glycerol, also known as glycerin or propane-1,2,3-triol, is a simple polyol compound. Glycerol is a colorless, odorless, viscous liquid that is sweet-tasting and non-toxic. Glycerol has the chemical formula: CH2OH-CHOH-CH2OH.

[0113] γ-Valerolactone is an organic compound with the formula C5H8O2. This colorless liquid is chiral but is usually used as a racemate. γ-Valerolactone is easily obtained from cellulosic biomass and is a potential fuel and green solvent.

[0114] Polyethylene glycol is a polyether compound with many applications, from industrial manufacturing to pharmaceuticals. PEG is also known as polyethylene oxide (PEO) or polyoxyethylene (POE), depending on its molecular weight. The structure of PEG is generally H-(OCH2-CH2). n It is represented by -OH.

[0115] Polypropylene glycol or polypropylene oxide is a polymer of propylene glycol. Chemically, it is a polyether. The structure of PPG is generally H-(O-CHCH3-CH2) n It is represented by -OH.

[0116] According to a preferred embodiment of the present invention, the solvent is gamma-valerolactone.

[0117] According to one embodiment of the present invention, the organic solvent is present in the composition in an amount of 5 to 50 wt. %, more preferably in an amount of 10 to 40 wt. %, and most preferably in an amount of 15 to 35 wt. %, based on the dry weight of the (a) at least one calcium carbonate.

[0118] Additionally or alternatively, the organic solvent is present in the composition in an amount of 100 to 500 wt. %, more preferably 150 to 450 wt. %, and most preferably 200 to 300 wt. %, based on the dry weight of the at least one lignin in (b).

[0119] According to one embodiment of the present invention, the organic solvent is present in the composition in an amount of 5 to 50 wt. %, more preferably 10 to 40 wt. %, most preferably 15 to 35 wt. %, based on the dry weight of the (a) at least one calcium carbonate, or in an amount of 100 to 500 wt. %, more preferably 150 to 450 wt. %, most preferably 200 to 300 wt. %, based on the dry weight of the (b) at least one lignin.

[0120] According to another embodiment of the present invention, the organic solvent is present in the composition in an amount of 5 to 50 wt. %, more preferably 10 to 40 wt. %, and most preferably 15 to 35 wt. %, based on the dry weight of the (a) at least one calcium carbonate, and in an amount of 100 to 500 wt. %, more preferably 150 to 450 wt. %, and most preferably 200 to 300 wt. %, based on the dry weight of the (b) at least one lignin.

[0121] According to one embodiment of the present invention, the dry composition comprises: (a) at least one calcium carbonate; (b) 0.1 wt. % to 100 wt. % of at least one lignin, based on the dry weight of the at least one calcium carbonate of (a); and (c) an organic solvent.

[0122] According to another embodiment of the present invention, a dry composition comprises: (a) at least one calcium carbonate; (b) 0.1% to 100% by weight, based on the dry weight of the at least one calcium carbonate of (a), of at least one lignin; and (c) an organic solvent.

[0123] The organic solvent may further comprise water or may be used in combination with water. However, the amount of water in the organic solvent or when used in combination with the organic solvent is fairly small. More precisely, whether water is present in the organic solvent or used in combination with the organic solvent, a dry composition according to the present invention is still obtained.

[0124] As already mentioned above, a "dry" composition is understood to be a composition having less than 5.0% by weight of water relative to the weight of the composition. Preferably, a dry composition according to the invention comprises less than 4% by weight, more preferably less than 3% by weight, even more preferably less than 2% by weight, and most preferably less than 1% by weight of water, based on the total dry weight of the composition.

[0125] According to one embodiment of the present invention, the at least one lignin is present in the composition in the form of a mixture with at least one calcium carbonate, in which case the at least one lignin and the at least one calcium carbonate coexist in the composition of the invention.

[0126] According to another embodiment of the invention, the at least one lignin is present in the composition in the form of a coating on the at least one calcium carbonate, in which case the at least one lignin is located on the surface of the at least one calcium carbonate.

[0127] According to a preferred embodiment of the present invention, the at least one lignin is present in the composition in the form of a coating on the at least one calcium carbonate. Preferably, the at least one lignin in the coating on the at least one calcium carbonate is a water-insoluble lignin, preferably a kraft lignin.

[0128] Those skilled in the art know how to prepare coated particles. Preferably, these coated particles are prepared by mixing the components of the composition of the invention in the presence of an organic solvent, followed by drying the mixture.

[0129] The mixing can be performed sequentially or simultaneously in any order. For example, at least one lignin can be dissolved in an organic solvent, and then at least one calcium carbonate can be added. Alternatively, at least one calcium carbonate can be dispersed in an organic solvent, and then at least one lignin can be added. According to another embodiment, all compounds can be mixed simultaneously.

[0130] Mixing can be carried out under normal mixing conditions. Those skilled in the art will adapt these mixing conditions (such as the configuration of the mixing pallet and the mixing speed) according to their own process equipment. It is understood that any suitable mixing method can be used.

[0131] In one embodiment, mixing is carried out at a temperature in the range of 15 to 120° C., more preferably 20 to 110° C., and most preferably 30 to 100° C. Mixing can be carried out for at least 1 second, at least 10 seconds, at least 30 seconds, at least 1 minute, at least 10 minutes, or at least 1 hour.

[0132] Drying can be carried out in a single step, such as spray drying, or in at least two steps, for example by applying a first heating step to the calcium carbonate, thereby reducing the associated moisture content. The remaining total moisture content can be further reduced by applying a second heating step to the calcium carbonate. If this drying is carried out by more than one drying step, the first step can be carried out by heating in a hot air stream, while the second and further drying steps are preferably carried out by indirect heating.

[0133] The resulting at least one calcium carbonate coated with at least one lignin may be further deagglomerated, for example, during a grinding step. Generally, the grinding step can be carried out using any conventional grinding equipment, for example, under conditions such that refinement occurs primarily as a result of impact with secondary objects, i.e., in one or more of a ball mill, rod mill, vibratory mill, roll crusher, centrifugal impact mill, vertical bead mill, attrition mill, pin mill, hammer mill, crusher, shredder, declamper, knife cutter, or other such equipment known to those skilled in the art.

[0134] According to one embodiment of the present invention, the composition of the present invention is in solid form, preferably in the form of a granular material. The term "particles" in the present sense refers to a material composed of a plurality of particles, which can be defined, for example, by their particle size distribution. The expression "granular material" can include powders, particles, tablets, flakes, or crumbles.

[0135] According to another embodiment of the present invention, the composition of the present invention is in the form of a slurry. A "suspension" or "slurry" in the sense of the present invention comprises undissolved solids, a solvent as defined above, and any further additives, and usually contains a large amount of solids and may therefore be more viscous and denser than the liquid from which it is formed.

[0136] For example, the amount of the at least one calcium carbonate and the at least one lignin is 0.1 to 20 wt %, preferably 0.2 to 15 wt %, more preferably 0.5 to 10 wt %, and most preferably 1 to 5 wt %, based on the total weight of the slurry.

[0137] According to a preferred embodiment of the present invention, the dry formulation comprises at least one calcium carbonate, preferably ground calcium carbonate, and 10 wt. % of at least one lignin, preferably alkaline lignin, based on the dry weight of the at least one calcium carbonate. Preferably, the lignin is present as a coating on the at least one calcium carbonate. According to another preferred embodiment, the dry composition further comprises an organic solvent, preferably gamma-valerolactone, in an amount of 30 wt. % based on the dry weight of the at least one calcium carbonate and 300 wt. % based on the dry weight of the lignin. According to a preferred embodiment of the present invention, the dry formulation comprises, preferably consists of, ground calcium carbonate and 10 wt. % alkaline lignin, based on the dry weight of the at least one calcium carbonate, and gamma-valerolactone in an amount of 30 wt. % based on the dry weight of the at least one calcium carbonate and 300 wt. % based on the dry weight of the lignin.

[0138] fluid composition The fluid chemical and physical sunscreen compositions of the present invention comprise water and from 1 to 100% by weight, based on the weight of the water, of the dry composition of the present invention.

[0139] The dry composition has already been described in detail above.

[0140] The water of the present invention can be selected from drinking water, process water, demineralized water, distilled water, rainwater, reclaimed water, river water, and mixtures thereof. According to a preferred embodiment of the present invention, the water present in the fluid composition is drinking water.

[0141] Potable water, also known as drinking water, is water that is safe for drinking or use in food preparation. Rainwater / river water is obtained from rainwater / river. Reclaimed water is recycled water that can be used for agriculture. Process water is water that is not considered suitable for drinking and is primarily used in connection with industrial plants, industrial processes, and manufacturing facilities. Demineralized water is specially purified water that has had most or all of its mineral and salt ions removed, such as calcium ions, magnesium ions, sodium ions, chloride ions, sulfate ions, nitrate ions, and bicarbonate ions. Demineralized water is also known as deionized water. Distilled water is water that has been boiled to form steam and then condensed back into a liquid in a separate vessel.

[0142] According to one embodiment of the present invention, the fluid composition comprises water and 1 to 99.8% by weight, preferably 5 to 95% by weight, even more preferably 10 to 90% by weight, most preferably 15 to 85% by weight of the dry composition according to the present invention, based on the weight of the water.

[0143] According to one embodiment of the present invention, the fluid composition further comprises a surfactant. A "surfactant" in the sense of the present invention is a substance that reduces the surface tension (or interfacial tension) between two different compounds.

[0144] Any surfactant suitable for use in combination with calcium carbonate and / or lignin can be present in the compositions of the present invention. Such surfactants are known to those skilled in the art and are commercially available.

[0145] According to a preferred embodiment of the present invention, the surfactant is selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic anhydride, isocrotonic acid, aconitic acid (cis or trans), mesaconic acid, sinapic acid, undecylenic acid, angelic acid, canellic acid, hydroxyacrylic acid, acrolein, acrylamide, acrylonitrile, dimethylaminoethyl methacrylate, vinylpyrrolidone, vinylcaprolactam, ethylene, propylene, isobutylene, diisobutylene, vinyl acetate, styrene, α-methylstyrene, methyl vinyl ketone, esters of acrylic and methacrylic acid, organically modified trisiloxanes, PEG, polyglycerol esters, sophorolipids, polyether monomers and / or comonomers, and mixtures thereof, most preferably poly(acrylic acid) and / or poly(methacrylic acid).

[0146] Additionally or alternatively, the surfactant is present in the fluid composition in an amount of 0.0001 to 0.2 wt. %, preferably 0.001 to 0.1 wt. %, and most preferably 0.005 to 0.05 wt. %, based on the dry weight of the (a) at least one calcium carbonate and (b) at least one lignin.

[0147] According to a preferred embodiment of the present invention, the composition comprises a surfactant, preferably selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic anhydride, isocrotonic acid, aconitic acid (cis or trans), mesaconic acid, sinapic acid, undecylenic acid, angelic acid, canellic acid, hydroxyacrylic acid, acrolein, acrylamide, acrylonitrile, dimethylaminoethyl methacrylate, vinylpyrrolidone, vinylcaprolactam, ethylene, propylene, isobutylene, diisobutylene, vinyl acetate, styrene, α-methylstyrene, methyl vinyl ketone, esters of acrylic and methacrylic acid, organically modified trisiloxanes, PEG, polyglycerol esters, sophorolipids, polyether monomers and / or comonomers, and mixtures thereof, most preferably poly(acrylic acid) and / or poly(methacrylic acid), or The surfactant is present in the composition in an amount of 0.0001 to 0.2 wt. %, preferably 0.001 to 0.1 wt. %, and most preferably 0.005 to 0.05 wt. %, based on the dry weight of (a) the at least one calcium carbonate and (b) the at least one lignin.

[0148] According to another preferred embodiment of the present invention, the composition comprises a surfactant, preferably selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic anhydride, isocrotonic acid, aconitic acid (cis or trans), mesaconic acid, sinapic acid, undecylenic acid, angelic acid, canellic acid, hydroxyacrylic acid, acrolein, acrylamide, acrylonitrile, dimethylaminoethyl methacrylate, vinylpyrrolidone, vinylcaprolactam, ethylene, propylene, isobutylene, diisobutylene, vinyl acetate, styrene, α-methylstyrene, methyl vinyl ketone, esters of acrylic and methacrylic acid, organically modified trisiloxanes, PEG, polyglycerol esters, sophorolipids, polyether monomers and / or comonomers, and mixtures thereof, most preferably poly(acrylic acid) and / or poly(methacrylic acid); The surfactant is present in the composition in an amount of 0.0001 to 0.2 wt. %, preferably 0.001 to 0.1 wt. %, and most preferably 0.005 to 0.05 wt. %, based on the dry weight of (a) the at least one calcium carbonate and (b) the at least one lignin.

[0149] Such surfactants are known to those skilled in the art and are commercially available. According to an exemplary embodiment, the surfactant is polyether trisiloxane (Break-Thru S200), commercially available from Evonik Nutrition & Care GmbH.

[0150] According to a preferred embodiment of the present invention, the fluid composition of the present invention comprises, in addition to water, an organic solvent as defined above.

[0151] Preferably, the organic solvent is miscible with water in any ratio, and preferably the ratio of water:organic solvent is 100:0.1 to 100:200, preferably 100:1 to 100:150, more preferably 100:5 to 100:120, and most preferably 100:10 to 100:100, based on the weight of water and the dry weight of the organic solvent.

[0152] According to one embodiment of the present invention, the fluid composition consists solely of calcium carbonate, lignin, and water. According to another preferred embodiment of the present invention, the fluid composition consists solely of calcium carbonate, lignin, an organic solvent, and water. According to another preferred embodiment of the present invention, the fluid composition consists solely of calcium carbonate, lignin, an organic solvent, a surfactant, and water.

[0153] According to one embodiment of the present invention, water is present in the fluid composition in an amount of 0.1 to 50 wt. %, more preferably in an amount of 0.5 to 40 wt. %, and most preferably in an amount of 1 to 35 wt. %, based on the dry weight of the (a) at least one calcium carbonate and the (b) at least one lignin.

[0154] Those skilled in the art know how to prepare such fluid compositions. Preferably, these fluid compositions are prepared by mixing water with the dry composition according to the invention. Alternatively, these fluid compositions are prepared by mixing water with the components of the dry composition according to the invention.

[0155] The mixing can be carried out sequentially or simultaneously in any order. For example, the dry composition can be added to water in one or several portions. Alternatively, the at least one calcium carbonate, the at least one lignin, and the optional organic solvent can be added to water in any order. According to another embodiment, all of these compounds can be mixed simultaneously.

[0156] Mixing can be carried out under normal mixing conditions. Those skilled in the art will adapt these mixing conditions (such as the configuration of the mixing pallet and the mixing speed) according to their own process equipment. It is understood that any suitable mixing method can be used.

[0157] In one embodiment, mixing is carried out at a temperature in the range of 15 to 100° C., more preferably 20 to 95° C., and most preferably 30 to 90° C. Mixing can be carried out for at least 1 second, at least 10 seconds, at least 30 seconds, at least 1 minute, at least 10 minutes, or at least 1 hour.

[0158] The fluid composition of the present invention is in the form of a slurry. A "suspension" or "slurry" in the sense of the present invention comprises undissolved solids, a solvent as defined above, and any further additives, and usually contains a large amount of solids and may therefore be more viscous and denser than the liquid from which it is formed.

[0159] For example, the amount of the at least one calcium carbonate and the at least one lignin is 0.1 to 20 wt %, preferably 0.2 to 15 wt %, more preferably 0.5 to 10 wt %, and most preferably 1 to 5 wt %, based on the total weight of the slurry.

[0160] According to a preferred embodiment, the fluid composition comprises about 5 wt.% of a dry composition based on the weight of water and about 0.05 wt.% of a surfactant based on the dry weight of the (a) at least one calcium carbonate and (b) at least one lignin. According to a preferred embodiment of the present invention, the fluid composition comprises, or preferably consists of, about 5 wt.% of a dry composition based on the weight of water and about 0.05 wt.% of a surfactant based on the dry weight of the (a) at least one calcium carbonate and (b) at least one lignin, wherein the dry composition comprises, or preferably consists of, ground calcium carbonate, 10 wt.% of an alkaline lignin based on the dry weight of the at least one calcium carbonate, and gamma-valerolactone in an amount of 30 wt.% based on the dry weight of the at least one calcium carbonate and 300 wt.% based on the dry weight of the lignin. Preferably, the surfactant is a polyether trisiloxane.

[0161] emulsion The chemical and physical sunscreen emulsions of the present invention comprise a water-in-oil or oil-in-water mixture and contain from 0.1 to 100% by weight of the dry composition of the present invention, based on the weight of the water-in-oil or oil-in-water mixture.

[0162] The dry composition has already been described in detail above, and the water has also been described above.

[0163] An emulsion in the sense of the present invention is a mixture of two or more liquids, which are usually immiscible and in which one liquid (dispersed phase) is dispersed in the other (continuous phase). An oil-in-water emulsion according to the present invention is an emulsion in which oil is the dispersed phase and water is the continuous phase. A water-in-oil emulsion according to the present invention is an emulsion in which water is the dispersed phase and oil is the continuous phase.

[0164] Oil in the sense of the present invention is liquid or solid silicone and / or hydrocarbon-containing compound.Oil of the present invention can be any oil suitable for the composition of the present invention.Those skilled in the art know how to select such oil.Oil is known to those skilled in the art and is commercially available.

[0165] Any oil known to those skilled in the art as suitable for cosmetic formulations can be used.For example, the oil can be selected from the group including alkane coconut esters, polydimethylsiloxanes, polyalkylmethylsiloxanes, silicones, petroleum jellies such as petrolatum, vegetable oils such as palm oil, vegetable oil esters, and mixtures thereof.Preferably, at least one oil is alkane coconut esters or petrolatum.

[0166] Preferably, the emulsion according to the present invention comprises water and oil in a ratio of 100:0.1 to 100:1000, preferably 100:1 to 100:700, more preferably 100:5 to 100:500, most preferably 100:10 to 100:300, based on the weight of water and dry oil.

[0167] The emulsions according to the invention may contain further compounds such as dispersants, emulsifiers, preservatives, active agents, cosmetic ingredients, colour pigments, skin active substances and the like.

[0168] According to one embodiment of the invention, the emulsion consists exclusively of calcium carbonate, lignin, and a water-in-oil or oil-in-water mixture. According to another preferred embodiment of the invention, the emulsion consists exclusively of calcium carbonate, lignin, an organic solvent, and a water-in-oil or oil-in-water mixture. According to another preferred embodiment of the invention, the emulsion consists exclusively of calcium carbonate, lignin, an organic solvent, a skin active agent, and a water-in-oil or oil-in-water mixture.

[0169] According to one embodiment of the present invention, the emulsion comprises a water-in-oil or oil-in-water mixture and 0.1 to 15% by weight, preferably 0.25 to 10% by weight, more preferably 0.5 to 5% by weight, most preferably 1 to 3% by weight, of the dry composition according to the invention, based on the water-in-oil or oil-in-water mixture.

[0170] Alternatively, the amount of the at least one calcium carbonate and the at least one lignin is in an amount of 0.1 to 15 wt. %, preferably 0.25 to 10 wt. %, more preferably 0.5 to 5 wt. %, and most preferably 1 to 3 wt. %, based on the total weight of the emulsion.

[0171] Those skilled in the art know how to prepare such emulsions. Preferably, these emulsions are prepared by first preparing a water-in-oil or oil-in-water mixture and then mixing the dry composition according to the present invention with these emulsions. Alternatively, these emulsions are prepared by mixing all the ingredients and then emulsifying the mixture.

[0172] The mixing and emulsification can be carried out sequentially or simultaneously in any order. For example, the dry composition can be added to the water-in-oil or oil-in-water mixture in one or several portions. Alternatively, at least one calcium carbonate, at least one lignin, and any organic solvent can be added to the water-in-oil or oil-in-water mixture in any order. According to another embodiment, all of these compounds can be mixed simultaneously. Alternatively, the dry composition can be mixed with water and oil in any order or simultaneously in one or several portions, and then the mixture is emulsified.

[0173] The mixing and / or emulsification can be carried out under conventional mixing and / or emulsification conditions. Those skilled in the art will adapt these mixing and / or emulsification conditions (such as the configuration of the mixing tray and the mixing speed) according to their own process equipment. It is understood that any suitable mixing and / or emulsification method can be used.

[0174] In one embodiment, the mixing and / or emulsifying is carried out at a temperature in the range of 15 to 100° C., more preferably 20 to 95° C., and most preferably 30 to 90° C. The mixing and / or emulsifying can be carried out for at least 1 second, at least 10 seconds, at least 30 seconds, at least 1 minute, at least 10 minutes, or at least 1 hour.

[0175] According to a preferred embodiment of the present invention, the emulsion is a water-in-oil emulsion and contains 0.25 to 10% by weight, preferably about 5% by weight, of the dry composition according to the present invention, based on the weight of the water-in-oil mixture. Preferably, the emulsion according to the present invention contains water and oil in a ratio of 100:10 to 100:300, preferably about 100:200, based on the weight of water to dry oil. The dry composition according to the present invention preferably contains about 10% by weight, based on the dry weight of the at least one calcium carbonate, of at least one lignin, preferably an alkaline lignin.

[0176] The inventors have surprisingly found that the above-mentioned compositions, i.e., dry and fluid compositions and emulsions, provide sufficient or improved chemical and physical sun protection. More precisely, the inventors have surprisingly found that the compositions of the present invention provide two different mechanisms for UV-B and / or UV-A protection to living cells, in particular plants and plant parts, and human skin, by reflecting UV-B and / or UV-A radiation and by absorbing UV-B and / or UV-A radiation.

[0177] UV-B and / or UV-A protection can be measured by measuring transmittance and absorbance. Ultraviolet-visible spectroscopy or ultraviolet-visible spectrophotometry and near-infrared spectroscopy (UV-Vis or UV / Vis and NIR) refers to absorption or reflectance spectroscopy in the ultraviolet-visible and near-infrared spectral regions. This means that the method uses light in the visible and adjacent regions. Absorption or reflectance in this range directly affects the perceived color of the chemicals involved. In this region of the electromagnetic spectrum, atoms and molecules undergo electronic transitions. As used herein, transmittance and absorbance are measured with a double-beam PerkinElmer Lambda 950 UV / Vis / NIR spectrometer equipped with a 150 mm integrating sphere with a PMT and InGaAs detector.

[0178] According to one embodiment of the present invention, the compositions / emulsions of the present invention have improved UV-B and / or UV-A protection for living cells, such as plants and plant parts, in particular fruits, and human skin, compared to the same compositions / emulsions containing only at least one calcium carbonate or at least one lignin.

[0179] "Identical composition / identical emulsion" in the sense of the present invention refers to a composition / emulsion that consists of the same ingredients in the same amounts as the composition / emulsion of the present invention, except that this composition does not contain both at least one calcium carbonate and at least one lignin, but only calcium carbonate or only lignin, the missing ingredients being replaced by other ingredients.

[0180] According to one preferred embodiment of the present invention, the compositions / emulsions of the present invention have improved transmittance and absorbance in the range of 280 nm to 320 nm, or >320 nm to 400 nm, most preferably in the range of 280 nm to 400 nm, compared to the same compositions / emulsions containing only at least one calcium carbonate.

[0181] Furthermore, the inventors have surprisingly found that the compositions / emulsions of the present invention are easy and fast to prepare, are cheap and, above all, easy to handle. More precisely, the compositions / emulsions of the present invention can be easily prepared by mixing and / or emulsifying the components of the compositions / emulsions of the present invention as described above.

[0182] Furthermore, when at least one lignin is present in the composition / emulsion in the form of a coating on at least one calcium carbonate, the inventors have found that these coated particles provide two distinct mechanisms for UV-B and / or UV-A protection to living cells, particularly plants and plant parts, and human skin by reflecting UV-B and / or UV-A radiation and absorbing UV-B and / or UV-A radiation. Because calcium carbonate and lignin are non-toxic to humans and have no harmful effects on the environment, these coated particles are non-toxic to humans and have no harmful effects on the environment. Furthermore, when the at least one lignin in the coating on the at least one calcium carbonate is a water-insoluble lignin, such as kraft lignin, the inventors have surprisingly found that the coating remains attached to the calcium carbonate even after the coated calcium carbonate particles are redispersed in water. Therefore, the coating layer remains intact even when the particles are dispersed in water. For example, when such compositions are on plants and plant parts, the lignin cannot be easily washed away by rain or by irrigation water. When such compositions are incorporated into water-based cosmetic formulations, the lignin adheres to the surface of the calcium carbonate and therefore cannot be easily washed off human skin by sweat.

[0183] Use of the composition and emulsion The composition of the invention and the emulsion of the invention are used for sun protection.

[0184] More precisely, the compositions of the present invention, including the dry compositions of the present invention and the fluid compositions of the present invention, are used for sun protection of plants and plant parts, where this sun protection includes physical and chemical protection.

[0185] This can be easily accomplished by applying the composition of the present invention to the plants and plant parts by any suitable method known to those skilled in the art, such as spraying, painting, or dipping. According to a preferred method, the composition of the present invention is sprayed onto the plants and plant parts. Equipment for spraying the composition is known to those skilled in the art and is commercially available.

[0186] According to one embodiment of the present invention, the plants and plant parts are fruits, vegetables, trees, seeds, leaves, wood, nuts, agricultural products, crop plants, and flowers, in particular fruits such as apples, oranges, citrons, cherries, pears, plums, bananas, or mangoes.

[0187] As already mentioned above, the present inventors have surprisingly found that the above-mentioned compositions provide sufficient sun protection for plants and plant parts, especially fruits. In particular, the present inventors have surprisingly found that when a composition comprising (a) at least one calcium carbonate and (b) at least one lignin in an amount of 0.1% to 100% by weight, based on the dry weight of the at least one calcium carbonate (a), is used, the composition provides improved sun protection, i.e., sun protection including physical and chemical protection for plants and plant parts. Furthermore, when the composition according to the present invention is used for sun protection of plants and plant parts, another advantage is that, due to the calcium carbonate in the composition, the composition also provides calcium nutrients to the plants. Furthermore, another advantage is that when the fluid composition is used on plants and plant parts, the layer of the composition formed on the plants and plant parts also repels insects.

[0188] Furthermore, the present invention relates to the use of an emulsion according to the invention, more precisely to the use of an emulsion comprising a water-in-oil or oil-in-water mixture and 1 to 100% by weight, based on the weight of the water-in-oil or oil-in-water mixture, of a dry composition according to the invention, for chemical and physical sun protection in cosmetic formulations.

[0189] This can be easily achieved by applying the emulsion of the present invention to the cosmetic formulation by any suitable method known to those skilled in the art, for example by mixing, dispersing, or emulsifying. According to a preferred method, the ingredients of the cosmetic formulation are mixed with the emulsion of the present invention. Equipment for this purpose is known to those skilled in the art and is commercially available.

[0190] According to one embodiment of the present invention, the cosmetic formulation is a sunscreen product, a facial makeup product, a hair care product, a hair styling product, a nail care product, a hand care product, a skin care product, and mixtures thereof.

[0191] According to another preferred embodiment, the at least one lignin is present in the cosmetic formulation in the form of a coating on the at least one calcium carbonate. Additionally or alternatively, the at least one lignin in the cosmetic formulation is a water-insoluble lignin, preferably a kraft lignin.

[0192] According to another preferred embodiment, the at least one lignin is present in the cosmetic formulation in the form of a coating on the at least one calcium carbonate, and the at least one lignin in the cosmetic formulation is a water-insoluble lignin, preferably a kraft lignin.

[0193] According to another preferred embodiment, the at least one lignin is present in the cosmetic formulation in the form of a coating on the at least one calcium carbonate, or the at least one lignin in the cosmetic formulation is a water-insoluble lignin, preferably a kraft lignin.

[0194] As already mentioned above, the inventors have surprisingly found that the above-mentioned compositions provide sufficient sun protection to living cells, in particular to human skin. The inventors have surprisingly found that when using an emulsion containing a water-in-oil or oil-in-water mixture and 1 to 100% by weight, based on the water-in-oil or oil-in-water mixture, of a dry composition according to the invention, this composition provides improved sun protection, i.e. sun protection including physical and chemical protection for human skin.

[0195] Furthermore, the present invention relates to a cosmetic preparation comprising the emulsion of the present invention as described above. More precisely, the present invention relates to a cosmetic preparation comprising an emulsion comprising a water-in-oil or oil-in-water mixture and 1 to 100% by weight, based on the weight of the water-in-oil or oil-in-water mixture, of a dry composition according to the present invention.

[0196] According to one embodiment, the at least one lignin is present in the cosmetic formulation in the form of a coating on the at least one calcium carbonate and / or the at least one lignin is a water-insoluble lignin, preferably a kraft lignin.

[0197] According to another embodiment of the present invention, the cosmetic formulation is a sunscreen product, a facial makeup product, a hair care product, a hair styling product, a nail care product, a hand care product, a skin care product, and mixtures thereof.

[0198] The scope and benefits of the present invention can be better understood based on the following examples, which are intended to illustrate certain specific embodiments of the invention and are not limiting. [Brief explanation of the drawings]

[0199] [Figure 1] Figure 1 shows a schematic diagram of a diffuse reflectance measurement with a sample placed at the reflectance port of an integrating sphere. [Figure 2] Figure 2 is a schematic diagram of an absorbance measurement with the sample placed in the center of the integrating sphere. [Figure 3]FIG. 3 is a schematic diagram of a transmittance measurement with the sample placed at the transmission port of the integrating sphere. [Figure 4] FIG. 4 shows the diffuse reflectance derived absorbance using the Kubelka-Munk function for a dry composition comprising at least one ground calcium carbonate (GCC) coated with at least one lignin and a dry composition comprising ground calcium carbonate (GCC). [Figure 5] FIG. 5 shows the absorbance of a fluid composition containing 0.1 wt. % ground calcium carbonate (GCC) used as a reference and a fluid composition having 0.1 wt. % ground calcium carbonate (GCC) coated with at least one lignin. [Figure 6] FIG. 6 shows the transmittance as a function of coating density at 300 nm, 360 nm, and 550 nm for coatings achieved with a fluid composition comprising 5 wt. % ground calcium carbonate (GCC) and a fluid composition comprising 5 wt. % ground calcium carbonate (GCC) coated with at least one lignin. [Figure 7] FIG. 7 shows the transmittance at 300 nm and 360 nm of a water-in-oil emulsion containing 5 wt. % ground calcium carbonate (GCC) alone and a water-in-oil emulsion containing 5 wt. % ground calcium carbonate (GCC) coated with at least one lignin. [Example]

[0200] 1.Measurement method The measurement methods used in the examples are described below.

[0201] Reflectance, absorbance, and transmittance measurements Reflectance, absorbance and transmittance analyses were performed using a double beam PerkinElmer Lambda 950 UV / Vis / NIR spectrophotometer equipped with a 150 mm integrating sphere with a PMT and InGaAs detector.

[0202] The dry compositions were measured by diffuse reflectance spectroscopy, as shown in Figure 1. The analysis was performed using powder samples loaded into an aluminum cup placed flush with the reflectance port of an integrating sphere. To obtain a proxy for the absorption spectrum of the dry composition, the measured diffuse reflectance spectrum was calculated using the Kubelka-Munk equation: K / S = (1 - R) 2 The conversion was performed using / 2R, where R is the reflectance, and K and S are the absorption and scattering coefficients, respectively. The spectrophotometer was scanned from 280 nm to 800 nm in 2 nm steps. A Spectralon® white standard was used as the 100% baseline.

[0203] Fluid compositions were measured by absorbance analysis. The fluid compositions were diluted with deionized water to a final solids content of 0.1 wt. % based on the total weight of the fluid composition. The diluted sample was poured into a quartz cuvette with a 1 cm path length and placed inside an integrating sphere using a centrally mounted holder, as shown in Figure 2. This arrangement allows simultaneous measurement of both the transmittance (T) and reflectance (R) of the sample, thus deriving the absorbance (A) from a single measurement as A = -log(T + R). This technique is also known as transflectance analysis. A 0.1 wt. % suspension of ground calcium carbonate (GCC) in deionized water was used as a reference. The spectrophotometer scanned from 280 nm to 800 nm in 2 nm steps. Three replicates were prepared and measured for each sample, and the average absorbance spectrum was calculated.

[0204] The fluid composition was also analyzed using a transmittance technique. The fluid composition was applied onto a quartz plate (50 x 50 x 3 mm) using an airbrush. The coated plate was dried in an oven at 50°C. A coating of 0.4 g / m2 was obtained by spraying an appropriate amount of the fluid composition. 2 ~16.4g / m 2Coating densities in the range of 0.01 to 0.01 were achieved. The samples thus obtained were placed at the entrance of an integrating sphere, as shown in Figure 3. Transmittance measurements were performed in 2-nm steps from 280 nm to 700 nm. Four repeats were performed for each sample at different sample positions obtained by rotating the coated plate 90° around the axis of the incident beam. The average transmittance spectrum of the sample was then calculated. Finally, the average transmittance spectrum of the sample was normalized to the average transmittance of the bare quartz plate.

[0205] The emulsions were analyzed using the transmittance technique. Samples were prepared by applying 30 mg of emulsion to a roughened PMMA plate (HD6 Helioplate, Helioscreen). The coated plate was allowed to dry at room temperature for 30 minutes in the dark. The resulting sample was placed at the entrance of an integrating sphere, as shown in Figure 3. Transmittance measurements were performed in 2 nm steps over the range of 280 nm to 700 nm. Four replicate samples were prepared, and four repeats were performed for each sample at different sample positions obtained by rotating the coated plate 90° around the axis of the incident light beam. The average transmittance spectrum of the sample was then calculated. Finally, the average transmittance spectrum of the sample was normalized to the average transmittance of the bare PMMA plate.

[0206] Particle size distribution Median particle size by weight d 50 The particle size distribution (wt) was measured by the sedimentation method, which is an analysis of sedimentation behavior in a gravitational field. The measurement was performed using a Sedigraph® 5100 from Micromeritics Instrument Corporation, USA. This method and instrument are known to those skilled in the art and are commonly used to determine particle size distribution of fillers and pigments. The measurement was performed in an aqueous solution of 0.1 wt% Na4P2O7. The sample was dispersed using a high-speed stirrer and ultrasonic treatment.

[0207] BET specific surface area (SSA) of the material BET specific surface area was measured via the BET procedure according to ISO 9277:2010 using nitrogen following conditioning of the sample by heating at 250°C for 30 minutes. Prior to such measurement, the sample was filtered, rinsed and dried in an oven at 110°C for at least 12 hours.

[0208] Materials and sample preparation used in the examples Calcium Carbonate: Marble-type ground natural calcium carbonate (GCC) with a calcium carbonate content of greater than 97.5% by weight. This ground calcium carbonate has a weight median particle size d of 0.95 μm. 50 value, and 5.7 m measured by the BET nitrogen method 2 / g BET specific surface area. Lignin: alkaline lignin commercially available from Sigma-Aldrich under number 370959-100G Organic solvent: gamma-valerolactone (GVL) commercially available from Sigma-Aldrich under the number V403-100G Water: Distilled water Oil-in-water mixture: Unguentum Alcoholum Lanae aquosum commercially available from Caelo under item number 3074, batch number 181705 Surfactant: Polyether trisiloxane available from Evonik under the trade name Break-thru S200

[0209] The following dry compositions were prepared: 20 g of GCC was dried overnight at 100°C. 2 g of at least one lignin was solubilized in 6 g of organic solvent. Both components were maintained at ambient temperature with mixing using a standard magnetic stirrer until complete solubilization of the alkaline lignin. For a homogeneous coating, the lignin solution was added dropwise to the GCC while the GCC was mixed manually. The lignin-coated GCC was dried overnight at 100°C. If necessary, the GCC was manually deagglomerated using a standard laboratory mortar.

[0210] The following fluid compositions were prepared: Water was mixed with the dry composition so that the composition contained 5 wt % of the dry composition based on the total weight of the slurry and 0.05 wt % of a surfactant based on the total weight of the slurry.

[0211] The following emulsions were prepared: For this composition, a commercially available water-in-oil mixture was used to which the above dry composition was added with stirring in an amount of 5% by weight based on the weight of the water-in-oil mixture.

[0212] Diffuse reflectance test 01 The diffuse reflectance of the dry compositions prepared above was measured and converted to an absorption spectrum using the Kubelka-Munk function. As can be seen from Figure 4, the dry composition containing lignin-coated GCC (filled circles) clearly shows significantly greater UV absorption compared to the dry composition containing GCC alone (open circles, reference). From Figure 4, it can be concluded that the lignin coating applied onto GCC provides improved UV absorption within the claimed range.

[0213] Absorbance test 01 The absorbance of the fluid compositions prepared above was measured. As can be seen from Figure 5, the fluid composition containing lignin-coated GCC (black circles) clearly exhibits significantly greater UV absorption compared to the fluid composition containing GCC alone (white circles, reference). From Figure 5, it can be concluded that the lignin coating applied onto GCC provides improved UV absorption within the scope of the claims.

[0214] Transmittance test 01 Figure 6 shows the average transmittance curves as a function of coating density for the lignin-coated GCC and standard GCC used in the fluid compositions prepared above. The reported transmittance values ​​are evaluated at wavelengths of 300 nm (UVB), 360 nm (UVA), and 550 nm (Vis). As an example, a coating density of approximately 5 g / m² is used because lignin absorbs a portion of the UV radiation that impinges on it. 2At a coating density of 1000 nm, the transmittance of the lignin-coated GCC is approximately 36% (UVB) and 29% (UVA) lower than that of standard GCC. This same effect is much less pronounced or not observed in the Vis region, where light is primarily attenuated by reflection mechanisms from the GCC particles in this wavelength range. Thus, the combination of at least one lignin and at least one calcium carbonate provides better UV attenuation due to two different mechanisms for UV-B and / or UV-A protection: reflection and absorption.

[0215] Transmittance test 02 Figure 7 shows the average transmittance, evaluated at 300 nm (UVB) and 360 nm (UVA), of a water-in-oil emulsion containing 5 wt% of lignin-coated GCC (hatched bars) and a water-in-oil emulsion containing 5 wt% of standard GCC (open bars). The transmittance values ​​are clearly lower for the lignin-coated GCC compared to the standard GCC. From Figure 7, it can be concluded that cosmetic emulsions containing the dry formulation according to the present invention provide improved UV absorption. The invention disclosed herein includes the following aspects: [1] A dry composition for chemical and physical sun protection, comprising: (a) at least one calcium carbonate, and (b) 0.1% to 100% by weight of at least one lignin, based on the dry weight of the at least one calcium carbonate of (a). [2] The composition according to [1] above, wherein the calcium carbonate is selected from the group consisting of ground calcium carbonate (GCC), preferably marble, limestone, and / or chalk; precipitated calcium carbonate (PCC), preferably vaterite, calcite, and / or aragonite; and mixtures thereof, and most preferably, the calcium carbonate is ground calcium carbonate. [3] The composition according to [1] or [2] above, wherein the at least one calcium carbonate has: (a) a weight median particle size d of 0.05 μm to 20 μm, preferably 0.25 μm to 10 μm, and most preferably 0.5 μm to 8 μm 50 value, and / or (b) a top cut (d 98 ), and / or (c) 0.5-100 m measured by the BET nitrogen method 2 / g, preferably 0.5 to 50m 2 / g, more preferably 0.5 to 35m 2 / g, most preferably 0.5 to 10m 2 / g specific surface area (BET). [4] The at least one lignin is a water-soluble or water-insoluble lignin selected from the group consisting of native lignin, Klason lignin, hydrolyzed lignin, ground lignin, soda lignin, organosolv lignin, kraft lignin, sulfonated lignin, and mixtures thereof; Preferably, the at least one lignin is a water-insoluble lignin selected from the group consisting of Klason lignin, Kraft lignin, and mixtures thereof; Most preferably, the at least one lignin is kraft lignin. The composition according to any one of the above [1] to [3]. [5] The composition according to any one of [1] to [4] above, wherein the at least one lignin is present in the composition in an amount of 1 to 50 wt. %, preferably 3 to 30 wt. %, and most preferably 5 to 25 wt. %, based on the dry weight of the at least one calcium carbonate of (a). [6] the composition further comprises an organic solvent; Preferably in an amount of 5 to 50% by weight, more preferably in an amount of 10 to 40% by weight, most preferably in an amount of 15 to 35% by weight, based on the dry weight of said at least one calcium carbonate of (a); and / or Preferably, in an amount of 100 to 500 wt. %, more preferably in an amount of 150 to 450 wt. %, and most preferably in an amount of 200 to 300 wt. %, based on the dry weight of the at least one lignin of (b), The composition according to any one of the above [1] to [5], which contains an organic solvent. [7] The organic solvent is selected from the group consisting of hexane, toluene, methanol, ethanol, dioxane, acetone, dimethyl sulfoxide, dimethylformamide, ethylene glycol, ethyl acetate, glycerol, γ-valerolactone, polyethylene glycol, polypropylene glycol, and mixtures thereof; More preferably, it is selected from the group consisting of ethylene glycol, ethyl acetate, glycerol, gamma-valerolactone, polyethylene glycol, polypropylene glycol, and mixtures thereof; Most preferably, it is gamma-valerolactone. The composition described in [6] above. [8] The composition according to any one of [1] to [7] above, wherein the at least one lignin is present in the composition in the form of a mixture with the at least one calcium carbonate or in the form of a coating on the at least one calcium carbonate, preferably as a coating on the at least one calcium carbonate. [9] The composition according to [8] above, wherein the at least one lignin in the coating on the at least one calcium carbonate is a water-insoluble lignin, preferably a kraft lignin.

[10] A fluid composition for chemical and physical sun protection, comprising water and 1 to 100% by weight of the dry composition according to any one of [1] to [9] above, based on the weight of the water.

[11] The composition further comprises a surfactant; and / or a surfactant selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic anhydride, isocrotonic acid, aconitic acid (cis or trans), mesaconic acid, sinapic acid, undecylenic acid, angelic acid, canellic acid, hydroxyacrylic acid, acrolein, acrylamide, acrylonitrile, dimethylaminoethyl methacrylate, vinylpyrrolidone, vinylcaprolactam, ethylene, propylene, isobutylene, diisobutylene, vinyl acetate, styrene, α-methylstyrene, methyl vinyl ketone, esters of acrylic and methacrylic acid, organically modified trisiloxanes, PEG, polyglycerol esters, sophorolipids, polyether monomers and / or comonomers, and mixtures thereof, most preferably poly(acrylic acid) and / or poly(methacrylic acid); and / or the surfactant is present in the composition in an amount of 0.0001 to 0.2 wt. %, preferably 0.001 to 0.1 wt. %, and most preferably 0.005 to 0.05 wt. %, based on the dry weight of (a) the at least one calcium carbonate and (b) the at least one lignin; The composition according to

[10] above.

[12] A chemical and physical sunscreen emulsion comprising a water-in-oil or oil-in-water mixture and 0.1 to 100% by weight of the dry composition according to any one of [1] to [9] above, based on the weight of the water-in-oil or oil-in-water mixture.

[13] Use of the composition according to any one of [1] to

[11] above for sun protection of plants and plant parts, wherein the sun protection includes chemical and physical protection.

[14] The use according to

[13] above, wherein the plants and plant parts are fruits, vegetables, trees, seeds, leaves, wood, nuts, agricultural crops, crop plants, and flowering plants.

[15] Use of the emulsion according to

[12] above for chemical and physical sun protection in cosmetic formulations.

[16] The use according to

[15] above, wherein the at least one lignin is present in the form of a coating on the at least one calcium carbonate and / or the at least one lignin is a water-insoluble lignin, preferably a kraft lignin.

[17] The use according to

[15] above, wherein the cosmetic preparation is a sunscreen product, a facial makeup product, a hair care product, a hair styling product, a nail care product, a hand care product, a skin care product, or a mixture thereof.

Claims

1. 1. A dry chemical and physical sun protection composition comprising: (a) at least one calcium carbonate; and (b) 0.1% to 100% by weight of at least one lignin, based on the dry weight of the at least one calcium carbonate of (a); wherein the at least one lignin is present in the composition in the form of a coating on the at least one calcium carbonate, and the at least one lignin in the coating on the at least one calcium carbonate is a water-insoluble lignin. Dry compositions for chemical and physical sun protection.

2. 2. The composition of claim 1, wherein the calcium carbonate is selected from the group consisting of ground calcium carbonate (GCC), precipitated calcium carbonate (PCC), and mixtures thereof.

3. 3. The composition of claim 1 or 2, wherein the at least one calcium carbonate comprises: (a) Weight median particle size d of 0.05 μm to 20 μm ５０ value, and / or (b) Top cut (d ９８ ), and / or (c) 0.5 to 100 m, measured by the BET nitrogen method ２ / g specific surface area (BET).

4. 4. The composition of claim 1, wherein the at least one lignin is a water-insoluble lignin selected from the group consisting of native lignin, Klason lignin, hydrolyzed lignin, ground lignin, soda lignin, organosolv lignin, kraft lignin, sulfonated lignin, and mixtures thereof.

5. 5. The composition of any one of claims 1 to 4, wherein the at least one lignin is present in the composition in an amount of 1 to 50 wt.%, based on the dry weight of the at least one calcium carbonate of (a).

6. A fluid chemical and physical sun protection composition comprising water and 1 to 100% by weight, based on the weight of the water, of the dry composition of any one of claims 1 to 5.

7. 10. A chemical and physical sunscreen emulsion comprising a water-in-oil or oil-in-water mixture and 0.1 to 100% by weight, based on the weight of the water-in-oil or oil-in-water mixture, of the dry composition of any one of claims 1 to 5.

8. Use of a composition according to any one of claims 1 to 6 for sun protection of plants and plant parts, said sun protection comprising chemical and physical protection.

9. 10. Use of the emulsion according to claim 7 for chemical and physical sun protection in cosmetic formulations.

Images